10.1007@978 3 030 26145 0

Engineering Materials
T. Daniel Thangadurai
N. Manjubaashini
Sabu Thomas
Hanna J. Maria
Nanostructured
Materials
This series provides topical information on innovative, structural and functional
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T. Daniel Thangadurai N. Manjubaashini
• •
Sabu Thomas Hanna J. Maria

•
Nanostructured Materials
123
T. Daniel Thangadurai N. Manjubaashini
Department of Nanoscience Department of Nanoscience
and Technology and Technology
Sri Ramakrishna Engineering College Sri Ramakrishna Engineering College
Coimbatore, Tamil Nadu, India Coimbatore, Tamil Nadu, India
Sabu Thomas Hanna J. Maria

IIUCNN IIUCNN
Mahatma Gandhi University Mahatma Gandhi University
Kottayam, Kerala, India Kottayam, Kerala, India
ISSN 1612-1317 ISSN 1868-1212 (electronic)

ISBN 978-3-030-26144-3 ISBN 978-3-030-26145-0 (eBook)
https://doi.org/10.1007/978-3-030-26145-0
© Springer Nature Switzerland AG 2020
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Contents
1 Nanotechnology and Dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Fundamentals of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Dimensions of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1 2D Confinement . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.2 1D Confinement . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.3 Zero Dimensional Confinement . . . . . . . . . . . . . . . . 3
1.3 Features of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.1 Activation of Particle Surface . . . . . . . . . . . . . . . . . 4
1.3.2 Particle Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.3 Particle Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.4 Two-Dimensional Particle Projection Image . . . . . . . 5
1.3.5 Three-Dimensional Particle Image . . . . . . . . . . . . . . 5
1.4 Significances of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . 7
1.5 Basic Concept of Nanotechnology . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2 Nanomaterials, Properties and Applications . . . . . . . . . . . . . . . . . . 11
2.1 Brief Notes on Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Nanomaterial Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.1 Structural Properties . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.3 Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.4 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.5 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.6 Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.7 Electronic Properties . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.8 Physiochemical Properties of Nanomaterials . . . . . . . 18
2.2.9 Specific Surface Area and Pore . . . . . . . . . . . . . . . . 23
2.3 Nanomaterial Synthesis Process . . . . . . . . . . . . . . . . . . . . . . . 23
2.3.1 Top-Down Approach . . . . . . . . . . . . . . . . . . . . . . . 23
2.3.2 Bottom-Up Approach . . . . . . . . . . . . . . . . . . . . . . . 24
v
vi Contents
2.4 Applications of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . 25

2.4.1 Environmental Sector . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.2 Health Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4.3 Energy Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3 Fundamentals of Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.1 Nanostructures Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.2 Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.2.1 1D Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3 Features of Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.4 Theoretical Substantiation of the Approaches Proposed . . . . . . 34
3.5 Types of Nanostructured Material . . . . . . . . . . . . . . . . . . . . . 36
3.5.1 Nanostructures in Plants . . . . . . . . . . . . . . . . . . . . . 37
3.5.2 Nanostructures in Insects . . . . . . . . . . . . . . . . . . . . . 39
3.5.3 Nanostructures in the Human Body . . . . . . . . . . . . . 40
3.5.4 Ceramic Nanostructures . . . . . . . . . . . . . . . . . . . . . 42
3.5.5 Polymer Nanostructures . . . . . . . . . . . . . . . . . . . . . 42
3.5.6 Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.5.7 Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.5.8 Nanostructure Computation . . . . . . . . . . . . . . . . . . . 43
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4 Physics and Chemistry of Nanostructures . . . . . . . . . . . . . . . . . . . . 47
4.1 Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5 Quantum Effects, CNTs, Fullerenes and Dendritic Structures . . . . 55
5.1 Fullerenes Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.2 Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
5.3 Laser-Assisted Metal-Catalyzed Nanowire Growth . . . . . . . . . 59
5.4 Hierarchal Complexity in 1-D Nanostructures . . . . . . . . . . . . . 60
5.5 Mechanical and Thermal Properties . . . . . . . . . . . . . . . . . . . . 63
5.6 Electronic Properties of Nanowires . . . . . . . . . . . . . . . . . . . . 64
5.7 Optical Properties of Nanowires . . . . . . . . . . . . . . . . . . . . . . . 66
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6 Semiconductors, Organic and Hybrid Nanostructures . . . . . . . . . . 69
6.1 Semiconductor Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . 69
6.1.1 Quasi-One-Dimensional Systems . . . . . . . . . . . . . . . 69
6.1.2 Double Quantum Well . . . . . . . . . . . . . . . . . . . . . . 70
6.1.3 The Size of Semiconductor Nanostructures . . . . . . . 70
6.1.4 Electrostatics of a GaAs/AlGaAs Heterostructure . . . 71
6.1.5 Applications of Semiconductor Nanostructures . . . . . 71
Contents vii
6.2 Organic Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . ..... 72

6.2.1 Structures and Applications of Organic
Nanostructures . . . . . . . . . . . . . . . . . . . . . . . ..... 73
6.2.2 Miscellaneous Application of Organic
Nanostructures . . . . . . . . . . . . . . . . . . . . . . . ..... 73
6.3 Hybrid Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . ..... 74
6.3.1 Physical Deposition to Synthesize the Hybrid
Nanostructures of Metal NPs/2D Materials . . . ..... 74
6.3.2 Chemical Reduction to Synthesize the Hybrid
Nanostructures of Metal NPs/2D Materials . . . ..... 75
6.3.3 Applications of Hybrid Nanostructures . . . . . . ..... 75
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 76
7 Properties of Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . 77
7.1 Unique Properties of Nanostructures . . . . . . . . . . . . . . . . . . . 77
7.2 Physical Properties of Nanowires . . . . . . . . . . . . . . . . . . . . . . 78
7.2.1 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.2.2 Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.2.3 Electronic Properties . . . . . . . . . . . . . . . . . . . . . . . . 79
7.2.5 Field Emission Properties . . . . . . . . . . . . . . . . . . . . 80
7.3 Grain Boundaries in Nanostructured Materials . . . . . . . . . . . . 80
7.4 Multifunctional Properties of Nanostructured Metallic
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.4.2 Strength Measurement . . . . . . . . . . . . . . . . . . . . . . . 83
7.4.3 Superstrength and Ductility . . . . . . . . . . . . . . . . . . . 87
7.4.4 Electrical Conductivity . . . . . . . . . . . . . . . . . . . . . . 88
7.4.5 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . 89
7.4.6 Corrosion Resistance . . . . . . . . . . . . . . . . . . . . . . . 90
7.4.7 Reliability of Nanostructured Materials . . . . . . . . . . 91
7.4.8 Thermal Properties of Nanostructures . . . . . . . . . . . . 92
7.4.9 Thermal Conductance . . . . . . . . . . . . . . . . . . . . . . . 93
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8 Nanostructured Materials—Design and Approach . . . . . . . . . . . . . 97
8.1 Synthesis of Nanostructured Materials . . . . . . . . . . . . . . . . . . 97
8.2 Nanostructure Synthesis and Fabrication Methods . . . . . . . . . . 98
8.2.1 Physical Vapor Deposition . . . . . . . . . . . . . . . . . . . 99
8.3 Chemical Vapor Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . 102
8.3.1 Thermal Chemical Vapor Deposition . . . . . . . . . . . . 103
8.3.2 Metal–Organic Chemical Vapor Deposition
(MOCVD) . . . . . . . . . . . . . . . . . . . . . . . . ....... 105
8.4 Solution-Based Chemistry . . . . . . . . . . . . . . . . . . . . ....... 106
8.4.1 Hydrothermal Synthesis . . . . . . . . . . . . . . ....... 106
viii Contents
8.4.2 Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

8.4.3 Aqueous Chemical Growth . . . . . . . . . . . . . . . . . . . 107
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
9 Functionalization of Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . 109
9.1 Aspects of Nanostructure System . . . . . . . . . . . . . . . . . . . . . . 109
9.2 Chemistry of Nanostructure Functionalization . . . . . . . . . . . . . 110
9.3 Need for Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . 110
9.4 Methods of Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . 111
9.5 Class of Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
9.5.1 Thiol/Aminothiol . . . . . . . . . . . . . . . . . . . . . . . . . . 112
9.5.2 Bio-functionalization . . . . . . . . . . . . . . . . . . . . . . . . 112
9.5.3 Asymmetric Group . . . . . . . . . . . . . . . . . . . . . . . . . 113
9.5.4 Polymers in Functionalization . . . . . . . . . . . . . . . . . 114
9.5.5 Functionalization of Metals . . . . . . . . . . . . . . . . . . . 114
9.5.6 Rare-Earth in Functionalization . . . . . . . . . . . . . . . . 114
9.6 Miscellaneous Functionalized Nanostructures . . . . . . . . . . . . . 117
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
10 Characterization and Technical Analysis of Nanostructured
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
10.1 Atomic Force Microscopy (AFM) . . . . . . . . . . . . . . . . . . . . . 120
10.2 X-Ray Diffraction (XRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
10.3 Scanning Probe Microscopies (SPM) . . . . . . . . . . . . . . . . . . . 121
10.4 Field Ion Microscopy (FIM) . . . . . . . . . . . . . . . . . . . . . . . . . 121
10.5 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
10.6 Absorption Spectroscopy (UV-Vis) . . . . . . . . . . . . . . . . . . . . 123
10.7 Photoluminescence Spectroscopy (PL) . . . . . . . . . . . . . . . . . . 123
10.8 Field Emission Scanning Electron Microscopy (FESEM) . . . . 124
10.9 Confocal Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
10.10 Transmission Electron Microscope (TEM) . . . . . . . . . . . . . . . 125
10.11 X-Ray Photoelectron Spectroscopy (XPS) . . . . . . . . . . . . . . . 126
10.12 Auger Electron Spectroscopy (AES) . . . . . . . . . . . . . . . . . . . 127
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
11 Fabrication of Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
11.1 Lithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
11.1.1 Photolithography . . . . . . . . . . . . . . . . . . . . . . . . . . 129
11.1.2 Contact-Mode Photolithography (CMP) . . . . . . . . . . 131
11.1.3 Deep Ultra-Violet Lithography (DUV) . . . . . . . . . . . 132
11.1.4 Phase-Shifting Photolithography . . . . . . . . . . . . . . . 132
11.1.5 Electron Beam Lithography . . . . . . . . . . . . . . . . . . . 133
11.1.6 X-Ray Lithography . . . . . . . . . . . . . . . . . . . . . . . . . 135
11.1.7 Focused Ion Beam (FIB) Lithography . . . . . . . . . . . 136
11.1.8 Neutral Atomic Beam Lithography . . . . . . . . . . . . . 136
Contents ix
11.2 Nanolithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

11.2.1 AFM Based Nanolithography . . . . . . . . . . . . . . . . . 139
11.2.2 Soft Lithography . . . . . . . . . . . . . . . . . . . . . . . . . . 139
11.2.3 Microcontact Printing . . . . . . . . . . . . . . . . . . . . . . . 139
11.2.4 Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
11.2.5 Nanoimprint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
11.2.6 Dip-Pen Nanolithography . . . . . . . . . . . . . . . . . . . . 144
11.3 Etching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
12 Nanostructured Materials for Optical and Electronic
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 149
12.1 Applications of Nanostructured Materials in Solar Cells . . . .. 149
12.1.1 Dye-Sensitized Nanostructured ZnO Electrodes
for Solar Cell Applications . . . . . . . . . . . . . . . . . .. 150
12.2 Photoconductive Oxide Nanowires as Nanoscale
Optoelectronic Switches . . . . . . . . . . . . . . . . . . . . . . . . . . .. 150
12.3 Energy Storage, Batteries, Fuel Cells . . . . . . . . . . . . . . . . . .. 152
12.4 Nanostructured Semiconductor Materials for Optoelectronic
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 153
12.5 Carbon-Based Sensors and Electronics . . . . . . . . . . . . . . . . .. 155
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 159
13 Nanostructured Materials for Bioapplications . . . . . . . .......... 161
13.1 Nanostructured Ti and Ti Alloys for Biomedical
Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
13.2 Nanostructured Materials for Biosensors . . . . . . . . . . . . . . . . . 162
13.3 Nanobiotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
13.4 Gene Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
13.5 Bioimaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
13.6 Tissue Engineering and Regenerative Medicine . . . . . . . . . . . 165
13.7 Bone Implant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
13.8 Modulated Drug Delivery System . . . . . . . . . . . . . . . . . . . . . 166
13.9 DNA Biosensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
13.10 Glucose Biosensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
13.11 Therapies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
13.11.1 Photodynamic Therapy . . . . . . . . . . . . . . . . . . . . . . 168
13.11.2 Chemotherapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
13.11.3 Photothermal Therapy . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
14 Nanostructured Materials for Photonic Applications . . . . . . . . . . . 171
14.1 Optical Waveguides Based on Small Organic Molecules . . . . . 172
14.2 Optically Pumped Organic Lasers . . . . . . . . . . . . . . . . . . . . . 173
14.3 3D Photonic Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
14.4 Photonic LEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
x Contents
14.5 Photonic Crystal Filters . . . . . . . . . .................... 174

14.6 Photonic Crystals: Bright Structural Colour from Functional
Morphology . . . . . . . . . . . . . . . . . .................... 176
References . . . . . . . . . . . . . . . . . . . . . . . . .................... 178
15 Nanostructured Materials for Environmental Remediation . . . . . . . 179
15.1 Gas Treatment: Nano-Array Based Catalytic Converters . . . . . 180
15.2 Remediation of Organohalides by Dye Sensitized TiO2 . . . . . . 180
15.3 Water Split Application of the Nanostructure Photocatalyst . . . 181
15.4 Nanostructure Photocatalyst for Water and Wastewater
Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 181
15.5 Sensing the Chemical Environment with Semiconductor
Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
15.6 Pollution Control Using Nanostructures . . . . . . . . . . . . . . . . . 183
15.6.1 Air Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
15.6.2 Water Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
15.7 Field-Effect Transistor (FET) Sensors . . . . . . . . . . . . . . . . . . . 184
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
16 Miscellaneous Applications of Nanostructures . . . . . . . . . . . . . . . . 187
16.1 Nanostructures in Aerospace Application . . . . . . . . . . . . . . . . 187
16.2 Nanostructures in RADAR Application . . . . . . . . . . . . . . . . . 188
16.3 Nanostructures in Stealth Application . . . . . . . . . . . . . . . . . . . 188
16.4 Nanostructured Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
16.5 Nanostructures in Antimicrobial Application . . . . . . . . . . . . . . 191
16.6 Nanostructures in Cosmetic Application . . . . . . . . . . . . . . . . . 192
16.6.1 Chitin Nanofibril . . . . . . . . . . . . . . . . . . . . . . . . . . 192
16.6.2 Nanoparticles as UV Protective Filters in Sun
Screens . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 192
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 193
17 Nanostructured Materials Life Time and Toxicity Analysis . . . . .. 195
17.1 Impact of Nanomaterials to Human Health
and Ecosystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
17.2 Nanomaterial Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
17.3 A Consideration of All Pertinent Sources of Nanomaterials . . . 198
17.4 Nanoparticle Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
17.4.1 Mechanisms of Toxicity . . . . . . . . . . . . . . . . . . . . . 200
17.5 Interference of Nanoparticles with in Vitro Toxicity
Assays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 200
17.6 Nanotoxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 200
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 201
Contents xi
18 Nanomaterials Research and Development . . . . . . . . . . . . ....... 203

18.1 LCA—Life Cycle Assessment of Nanomaterials . . . . ....... 203
18.2 The Role of Life Cycle Assessment in the Field
of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
18.3 LCA Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
18.4 Life-Cycle Assessment of Engineered Nanomaterials . . . . . . . 205
18.5 LCA of an Emerging Technology . . . . . . . . . . . . . . . . . . . . . 206
18.6 Life Cycle Inventory (LCI) . . . . . . . . . . . . . . . . . . . . . . . . . . 207
18.7 Life Cycle Impact Assessment (LCIA) . . . . . . . . . . . . . . . . . . 208
18.8 LCA of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Chapter 1
Nanotechnology and Dimensions
Abstract The role of nanotechnology towards different field of application

emphases by nanomaterials size, dimensions and properties. Varying nanometer size
and dimensions leads to different nanostructures with unique properties, and the fea-
tures of nanoparticles was identified by their synthesis route and analyses techniques.
Also the chapter briefly discussed about significances and concepts of nanoscience
and technology.
1.1 Fundamentals of Nanomaterials
The design, construction and utilization of functional structures with at least one
characteristic dimension measured in nanometers are designated as nanomaterials.
Thus, the nanomaterials emphasize in the field of science, engineering and technol-
ogy, which produces the way for nanotechnology founding. These nanomaterials
show dramatic change in their physical, chemical and biological properties due to
its reduced size and shape [1].
Nanoscience and nanotechnology predominantly deal with the synthesis, char-
acterization, investigation, and use of nanostructured materials. These materials
are characterized by at least one dimension in the nanometer (1–100 nm) range.
Nanostructures create a link between molecules and bulk materials. The nanostruc-
tures include clusters, quantum dots, nanocrystals, nanowires, nanotubes, arrays,
assemblies, and superlattices of the specific nanostructures. The physical and chem-
ical properties of nanomaterials can change significantly from those of the atomic-
molecular or the bulk materials of the same structure. The uniqueness of the structural
characteristics, energetics, response, dynamics, and chemistry of nanostructures cre-
ates the basis of nanoscience. Appropriate control of the properties and reaction
of nanostructures can lead to new devices and technologies [2]. Thus, the electron
states of nanostructures are leading to new electrical, thermal, magnetic, optical,
and mechanical properties at the nanoscale. Nanostructures physico-chemical prop-
erties are tuned by governing their size and shape at the nanoscale, which leads to
unique applications. But, the physico-chemical properties of the nanostructures are
limited only by the precision of the experimental techniques used for the fabrication
© Springer Nature Switzerland AG 2020 1

T. D. Thangadurai et al., Nanostructured Materials, Engineering Materials,
https://doi.org/10.1007/978-3-030-26145-0_1
2 1 Nanotechnology and Dimensions
of the low-dimensional structures. The energy spectrum of a quantum well, quantum

wire, or quantum dot can be engineered by controlling (i) the size and shape of the
confinement region and (ii) the strength of the confinement potential [3].
1.2 Dimensions of Nanomaterials
Nanotechnology deals with materials in zero, one, two and three dimensions as
nanometers and the nanostructured materials. The physical and chemical properties
of materials undergo exciting changes in their sizes of nanometer dimension. Most
biomolecules and bioentities are of nanometer size; thus the nanoscale provides the
great prospect to study such bioentities and their interactions with other materials
[4]. Another invitation is semiconductor industry for its ever-lasting demand for
miniaturization, has been compelled deeply into the nano-realm.
The concept of quantum confinement arises from the size reduction of material
leading to the electronic wave functions being more tightly confined and resulting
in changes associated with electronic and optical properties of the nanomaterial.
A smaller (or bigger) particle size results in a stronger (or weaker) confinement
which gives rise to enhancement (or decrease) of the band gap and modifies the band
structure of the material. This results in changes in the electron mobility and effective
mass, relative dielectric constant, optical properties to name a few. For the reason
of quantum confinement effect metallic nanoparticles show interesting properties
like variations in color of colloidal suspensions with changing particle size, UV
photoemission, enhanced photoluminescence, etc. The light-induced UV emission
in Ag nanoparticles has prompted the use of nano-Ag coatings for antimicrobial
purposes in the healthcare sector [5].
1.2.1 2D Confinement
Thin films with thickness of few nanometers are usually deposited on a bulk material.
Their properties may be dominated by surface and interface effects or they reflect
the confinement of electrons in the direction perpendicular to the film. In the two
dimensional confinement which is parallel to the film the electrons behave like in a
bulk material [6].
1.2.2 1D Confinement
Nanolaminated or compositionally modified materials, Grain boundary films, Clay

platelets, Semiconductor quantum wells and superlattices, Magnetic multilayers and
spin valve structures, Langmuir–Blodgett films, Silicon inversion layers in field
1.2 Dimensions of Nanomaterials 3
Fig. 1.1 Schematic illustration of quantum effects from bulk, quantum well, quantum wire to
QD. Reprinted with permission from © Journal of Semiconductors and Semimetals, 101, 305–354
(2019)
effect transistors, Surface-engineered materials for increased wear resistance or cor-

rosion resistance [7]. The size of nanoparticles becomes smaller than the de Broglie
wavelength, the mean free path of electrons acts as quantum dots. The band gap
increases, and a continuous density of states (DOS) appear in the case of bulk mate-
rials (Fig. 1.1a) there are discrete energy levels, similar to the case of atoms. This
has a considerable influence the optical properties of nanoparticles, as the absorp-
tion shifts from the infrared to the visible range. Quantum confinement in quan-
tum wells (one-dimensional), quantum wires (two-dimensional) and quantum dots
(three-dimensional) and the resulting changes of the energy spectrum as shown in
figure has serious implications for the optoelectronic properties of nanostructured
semiconductors, and is currently utilized in optoelectronic devices [8].
1.2.3 Zero Dimensional Confinement
In a zero-dimensional structure, the exciton states are determined by a competition

between the confinement effects and the correlation of the electron-hole pair induced
by the coulomb interaction. The single-particle levels, with splittings which scale as
1/L2 where L is the size of the quantum box, which are determined by the confinement.
The coulomb energies scale as l/L. As the confinement in a zero-dimensional structure
increases, the coulomb-induced mixing of states becomes more difficult, even though
the Coulomb energies increase, and electrons and holes become frozen in the lowest
energy single-particle states. Freeze-out of motion in the confined dimensions also

occurs in quantum wells and quantum-well wires when the confinement is increased.
However, coulomb induced correlation of the unconfined motion in a well or wire is
enhanced by the confinement [9].
1.3 Features of Nanoparticles
1.3.1 Activation of Particle Surface
All the solid particles consist of the atoms or molecules. When they are micronized,
they tend to be affected by the behavior of atoms or molecules by themselves and
show different properties from those of the bulk solid of the same material. It is
attributable to a change of bonding state of the atoms or the molecules constructing
the particles. For example, if a cube with a side length of 1 cm is divided into a cube of
1 µm, the particle number increases to 1012 and being divided into the one of 10 nm,
then it amounts to 1018 , where the fraction of the atoms or the molecules located at the
surface on the particles plays a great role, since they are more active than those inside
the solid particles because of the free hand, which leads to easy bonding with the
contacting materials and causes various changes in particle properties. The diameter
of the smallest hydrogen atom is 0.074 nm, and that of the relatively large lead atom is
0.35 nm. From these sizes, it is estimated that the particle with a size of 2 nm consists
of only several tens to thousands atoms. When the particle is constructed by larger
molecules, the number decreases furthermore. On the other hand, as the micronization
of solid particles, the specific surface area increases generally in reversal proportion to
the particle size. In the above-mentioned case, when the particle of 1 cm is micronized
to 1 µm and 10 nm, the specific surface area becomes ten thousand times and million
times, respectively. As the increase in the specific surface area directly influences
such properties like the solution and reaction rates of the particles, it is one of major
reasons for the unique properties of the nanoparticles different from the bulk material
together with the change in the surface properties of the particles itself.
1.3.2 Particle Size
Particle size is tenure to represent the three-dimensional particle in one-dimensional

scalar value. The size of any spherical particle can be signified by its diameter with no
obscurity. The geometric size is obtained through three dimensional measurements of
a particle to get its width, thickness and length, and then calculating one-dimensional
value such as arithmetic mean. In practice, one-dimensional value obtained based on
the two dimensional-projected outlines is utilized such as diameter of a circle having
the same area as the projected area. Statistical diameter based on one-dimensional
1.3 Features of Nanoparticles 5
measurement is also well applied in practice such as a Feret diameter, which is deter-
mined as the distance between pairs of parallel tangents to the particle silhouette in
some fixed direction. As for the equivalent size in relation to practical methods of
particle size measurements, there are many different definitions such as sieve diam-
eter based on sieving, equivalent light-scattering diameter, Stokes diameter based on
particle motion in fluid, and the equivalent diameter based on the Brownian motion.
These equivalent diameters give, usually, different values depending on the measure-
ment principles unless the particles are spherical. Specific surface area of powder or
equivalent-specific surface diameter is well applied to the evaluation of nanopow-
ders. However, in this case, the particles should not be porous. Besides, the method
cannot be applied to get particle size distribution.
1.3.3 Particle Shape
The essential properties such as particle diameter, particle shape of nano-size or

fine particles influence the character of the particle-packed bed. In these properties,
the particle diameter measurement equipment based on various principles can be
promoted, and it is easy to measure particle diameter distribution. But a particle shape
analyzer for nanoparticle cannot be easily found and the shape index of nanoparticles
can be calculated from particle images observed using various types of microscopes.
1.3.4 Two-Dimensional Particle Projection Image
In order to measure the particle shape, the outline of particle shape of two-dimensional
projection images captured from microscopic photograph is analyzed. Since the
diameter of a nanoparticle is smaller than the wavelength of visible light, a nano-size
particle cannot be observed by an optical microscope. Usually, the two-dimensional
projection image of nanoparticles is captured by scanning electron microscope (SEM)
or transmission electron microscope (TEM), and the particle shape indices can be
calculated from the captured images by image analysis software. For the shape anal-
ysis of fine particle over micrometer order, automatic particle shape analyzers using
two-dimensional image of particles in a sheath flow are available. This analyzer
captures particle images automatically by an optical microscope with CCD camera
under stroboscope flush lighting.
1.3.5 Three-Dimensional Particle Image
In the particle shape measurement of flaky particle or porous particle including hole or
space inside the particle, the shape analysis of a two-dimensional particle projection
picture is inadequate, and three-dimensional shape analysis is necessary. Although
it is difficult to measure the thickness of a particle by the ordinary electron micro-

scope, the thickness or surface roughness can be measured by three-dimensional
scanning electron microscope (3D-SEM). 3D-SEM takes two microscopic pictures
from slightly different angles and obtains the three dimensional information includ-
ing thickness and surface roughness geometrically. However, if one of the pictures
has the hidden area in the shadow of a particle, the three-dimensional information of
the area is hidden. When well dispersed nanoparticles adhere on a flat substrate, the
height difference between the particle surface and the flat substrate can be measured
accurately, and the thickness of nanoparticle is obtained. Using the TEM, 120 trans-
mission images are taken when a sample is rotated 1° interval from −60° to +60°.
This three-dimensional imaging technique called TEM-CT, which is similar to the
computer aided tomography, is expected to be applied for detailed three-dimensional
shape measurement of nanoparticles. Using the scanning probe microscope (SPM)
including atomic force microscope (AFM), the surface roughness can be measured
by tiny probe with the high resolution under nano-meter order. SPM are very effec-
tive for thickness measurement of nanoparticles. The vertical direction length such as
particle thickness can be measured accurately by SPM, but the measured horizontal
length becomes bigger about the diameter of the probe. It means that the particle
diameter in horizontal direction measured by SPM is bigger than real particle size.
Moreover, for a soft particle or an adhesive particle, a particle position changes by
contact of probe or a particle adheres to probe, and an accurate image is not obtained
[10]. The major interest in nanoparticles has been generated in the research and the
industry sector mostly due to its physical and chemical properties which differ quite
a lot from the bulk (large scale) materials. At present almost all branches of applied
science and technology are being advanced in some way or the other with the advent
of nanotechnology.
The surface to volume ratio (S/V) is simply the surface area of an object divided
by its volume. For symmetrical objects like a spherical particle this ratio is inversely
proportional to the radius, and for a cube it is inversely proportional to its sides. The
increasing S/V more and more atoms/molecules of the material become exposed
to the surroundings and a larger number of the so-called “dangling bonds” become
available at the surface, thus making the particle more active chemically. For a very
simple example a spherical particle of ~100 nm diameter has only a very small per-
centage ~2% of its total constituent atoms exposed to the surface, if we go down
to particle diameters of ~10 nm 20–25% of the atoms become exposed to the sur-
roundings, while a further size reduction say down to 3 nm increases the fraction of
atoms exposed at the particle surface to a 45–60%. In such conditions the behavior
of the particle becomes altered in terms of its chemical activity. This is precisely
the reason behind certain noble metals like Ag, Au, Pt, etc., behaving as highly
potent catalysts in their particulate, especially nanoparticulate form. The presence
of large number of unsaturated dangling bonds on the graphene (a two-dimensional
sp3 bonded honeycomb-like sheet of carbon atoms, which is the building block of
graphite) surface which has a very high S/V makes it an excellent sensing material for
chemical and gas detection. Such high S/V ratio is also responsible for the lowering
of melting point in nanocrystals [11].
1.4 Significances of Nanotechnology 7
1.4 Significances of Nanotechnology
The nanotechnology exactly means any expertise performed on a nanoscale that has
applications in the real world. The nanotechnology incorporates the production and
application of physical, chemical, and biological systems at scales ranging from indi-
vidual atoms or molecules to submicron dimensions as well as the combination of the
resulting nanostructures into larger systems. The nanotechnology is possible to have
an intense impression on our economy and society in the early twenty first century,
similar to that of semiconductor technology, information technology or cellular and
molecular biology. Science and technology research in nanotechnology potentials
advances in areas as materials and manufacturing, medicine and healthcare, energy,
biotechnology, information technology and national security. It is widely felt that
nanotechnology will be the next industrial revolution [12].
Nanometer scale structures are primarily built up from their elemental con-
stituents. Chemical synthesis—the spontaneous self-assembly of molecular clus-
ters from simple reagents in solution or biological molecules are used as building
blocks for the production of three-dimensional nanostructures, including quantum
dot of arbitrary diameter. A variety of vacuum deposition and nonequilibrium plasma
chemistry techniques are used to produce layered nanocomposites and nanotubes.
Atomically controlled structures are produced using molecular beam epitaxy and
organo-metallic vapor phase epitaxy. Micro and nanosystem components are fabri-
cated using top-down lithographic and non-lithographic fabrication techniques and
range in size from micro to nanometers. Continued improvements in lithography
for use in the production of nano components have resulted in line widths as small
as 10 nm in experimental prototypes. The nanotechnology field, in addition to the
fabrication of nanosystems provides the impetus to development of experimental and
computational tools.
The micro and nanosystems contain micro/nano electromechanical systems, micro
mechatronics, optoelectronics, and microfluidics and systems integration. These sys-
tems can sense, control and activate on the micro/nanoscale and function individually
or in arrays to generate effects on the macroscale. Due to the permitting nature of
these systems and major influence they can have on the commercial and defense
applications, venture capitalists, industry, as well as the federal government have
taken a distinct attention in nurturing growth in this field. Micro and nanosystems
are likely to be the next logical step in the silicon revolution. Science and technol-
ogy continue to move forward in making the fabrication of micro/nano devices and
systems possible for a variety of industrial, consumer, and biomedical applications.
A range of MEMS devices have been produced, some of which are commercially
used. A variety of sensors are used in industrial, consumer, and biomedical applica-
tions. Various microstructures or micro components are used in micro instruments
and other industrial applications such as micro mirror arrays. Integrated capaci-
tive type, silicon accelerometers have been used in airbag deployment in automo-
biles. Other major industrial applications include pressure sensors, inkjet printer
heads, and optical switches. Silicon-based piezoresistive pressure sensors for man-
ifold absolute pressure sensing for engines were launched in 1991 by Nova-Sensor
and their annual sales were about 25 million units in 2002. Annual sales of inkjet
printer heads with microscale functional components were about 400 million units in
2002. Capacitive pressure sensors for tire pressure measurements were launched by
Motorola. Other applications of MEMS devices include chemical sensors, gas sen-
sors, infrared detectors, and focal plane arrays for earth observations, space science
and missile defense applications, pico-satellites for space applications, and many
hydraulic, pneumatic, and other consumer products. MEMS devices are also being
pursued in magnetic storage systems, where they are being developed for super-
compact and ultrahigh recording-density magnetic disk drives. Several integrated
head/suspension micro devices have been fabricated for contact recording applica-
tions. High bandwidth, servo-controlled micro actuators have been fabricated for
ultrahigh track density applications which serve as the fine position control ele-
ment of a two-stage, coarse/fine servo system coupled with a conventional actuator.
Millimeter-sized wobble motors and actuators for tip based recording schemes have
also been fabricated [13].
1.5 Basic Concept of Nanotechnology
The nanotechnology is a study of structure between 1 and 100 nm in size. The nan-
otechnology is concerned with materials and systems whose structure component
exhibit novel and significantly improved physical, chemical, and biological proper-
ties, phenomena and process because of their nanoscale size. The structural features
in the range of ~10−9 to 10−7 m i.e. 1–100 nm determine important changes as com-
pared to the behavior of isolated molecules or of bulk materials. It is an interdisci-
plinary science involving physics, chemistry, biology, engineering materials science,
computer science etc. [14].
Nanostructures are described as novel materials whose size of elemental struc-
ture has been plotted as nanometer scale. Nanomaterials may be classified on the
basis of dimensionality and modulation. Some special nanostructures like nanotubes,
nanoporous materials, aerogels, zeolites, core-shell structures have also come up with
their novel characteristics. A number of methods have been used for the synthesis of
nanostructure with various degrees of success and many direct and indirect techniques
are employed for their characterization. The fact, which makes the nanostructures
interesting, is that the properties become size dependent in nanometer range because
of surface effect and quantum confinement effect. The geometric structure, chemi-
cal bonds, ionization potential, electronic properties, optical properties, mechanical
strength, thermal properties, magnetic properties etc. are all affected by particle sizes
in nanometer range [15]. Nanomaterials exhibit properties often superior to those of
conventional coarse-grained materials. These include increased strength, enhanced
diffusivity, improved ductility, reduced density, reduced elastic modulus, higher elec-
trical resistivity, increased specific heat, higher thermal expansion coefficient, lower
1.5 Basic Concept of Nanotechnology 9
thermal conductivity, increased oscillator strength, blue shifted absorption, increased

luminescence and superior soft magnetic properties in comparison to conventional
bulk materials. Use of nanostructured materials has produced transistors with record
low speed and lasers with low threshold current. These are being used in compact disk
player systems, low noise amplification in satellite receivers as sources for fiber optic
communication etc. Beneficial applications of nanomaterials include self-cleaning
glass, UV resistant wood coating etc. Nanoscale devices are being used in medical
field also for diagnosis, treatment and prevention of diseases and in drug delivery
system, magnetic resonance imaging, radioactive tracers etc. [16].
References
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England
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standards community. JAI 2:1–21
3. Kurzydlowski KJ (2006) Physical, chemical, and mechanical properties of nanostructured
materials. Mater Sci 42:85–94
4. Kaur G, Singh T, Kumar A (2012) Nanotechnology: a review. IJEAR 2:50–53
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271:933–937
6. Mu P, Zhou G, Chen CL (2018) 2D nanomaterials assembled from sequence-defined molecules.
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8. Altavilla C, Ciliberto E (2011) Inorganic nanoparticles: synthesis, applications, and perspec-
tives. Taylor and Francis Group, LLC, Boca Raton, FL
9. Bryant GW (1990) Understanding quantum confinement in zero-dimensional nanostructures:
optical and transport properties. In: Beaumont SP, Torres CMS (eds) Science and engineering
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10. Hosokawa M, Nogi K, Naito M et al (2007) Nanoparticle technology handbook. Elsevier,
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Springer, Heidelberg, New York
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Stanford Publishing, Singapore
13. Purohit K, Khitoliya P, Purohit R (2012) Recent advances in nanotechnology. IJSER 3:1–10
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photosciences. Indian J Phys 85:1229–1245
Chapter 2
Nanomaterials, Properties
and Applications
Abstract Nanomaterials size range from 1 to 100 nm with unique optical, electrical,
magnetic, mechanic and structural properties. There are some naturally occurring
nanomaterials (viruses, protein, lotus leaf, spider-mite silk, and butterfly wings etc.)
and more engineered nanomaterials (Au NPs, Ag NPs, etc.) with top-down and
bottom-up approaches. The chapter detailed about properties and applications of
nanomaterials.
2.1 Brief Notes on Nanomaterials
Nanomaterials are keystones of nanoscience and nanotechnology. Nanostructure sci-

ence and technology is a wide and interdisciplinary area of research and development
activity that has been rising explosively worldwide in the past few years. It has the
potential for revolutionizing the ways in which materials and products are created
and the range and nature of functionalities that can be accessed [1]. It already has
important viable influence, which will certainly increase in the future. Nanoscale
materials are defined as a set of substances where at least one dimension is less
than approximately 100 nm. A nanometer is one millionth of a millimeter—approx-
imately 100,000 times smaller than the diameter of a human hair. Nanomaterials
are of interest because at this scale unique optical, magnetic, electrical, and other
properties emerge. These emergent properties have the potential for great impacts in
electronics, medicine, and other fields [2].
Some nanomaterials occur naturally, but of particular interest are Engineered
Nanomaterials (EN), which are designed and being used in many commercial prod-
ucts and processes. They can be found in sunscreens, cosmetics, sporting goods,
stain resistant clothing, tires, electronics, and used in medicine for purposes of diag-
nosis, imaging and drug delivery. The nanoparticles are actually a fairly common
type of material in many different environments, and they can pass by almost unde-
tected unless you are looking for them. The physical and chemical processes produce
nanoparticles. Naturally occurring nanoparticles can be found in volcanic ash, ocean
spray, fine sand and dust, and even biological matter [3] (Fig. 2.1).

https://doi.org/10.1007/978-3-030-26145-0_2
12 2 Nanomaterials, Properties and Applications
Fig. 2.1 Naturally occurring and man-made nanoparticles
Synthetic nanoparticles are derived from two general categories, incidental and
engineered nanoparticles. Incidental nanoparticles are the byproducts of human activ-
ities, generally have poorly controlled sizes and shapes, and may be made of a hodge-
podge of different elements. Many of the processes that generate incidental nanopar-
ticles are common every day activities: running diesel engines, large-scale mining,
and even starting a fire. Engineered nanoparticles on the other hand, have been specif-
ically designed and deliberately synthesized by human beings. Not surprisingly, they
have very precisely controlled sizes, shapes, and compositions. They may even con-
tain layers with different chemical compositions. Although engineered nanoparticles
get more sophisticated with each passing year, simple engineered nanoparticles can
be created by relatively simple chemical reactions that have been within the scope
of chemists and alchemists for many centuries [4] (Fig. 2.2).
Fig. 2.2 Incidental and engineered nanoparticle

2.2 Nanomaterial Properties 13
2.2 Nanomaterial Properties
2.2.1 Structural Properties
The increase in surface area and surface free energy with decreasing particle size leads
to changes in interatomic spacing. For Cu metallic clusters the interatomic spacing
is detected to decrease with decreasing cluster size. This effect can be described by
the compressive strain induced by the internal pressure arising from the small radius
of curvature in the nanoparticle. Equally, for semiconductors and metal oxides there
is indication that interatomic spacings increase with decreasing particle size. The
apparent stability of metastable structures in small nanoparticles and clusters, such
that all traces of the usual bulk atomic arrangement become lost. Metallic nanopar-
ticles, such as gold, are known to adopt polyhedral shapes such as cubeoctahedra,
multiply twinned icosahedra and multiply twinned decahedra. These nanoparticles
may be regarded as multiply twinned crystalline particles in which the shapes can
be understood in terms of the surface energies of various crystallographic planes,
the growth rates along various crystallographic directions and the energy required
for the formation of defects such as twin boundaries. However, there is convincing
indication that such particles are not crystals but are quasiperiodic crystals or crys-
talloids. These icosahedral and decahedral quasicrystals form the basis for further
growth of the nanocluster, up until a size where they will switch into more regular
crystalline packing arrangements [5].
Crystalline solids are different from amorphous solids in that they possess long
range periodic order and the patterns and symmetries which occur correspond to
those of the 230 space groups. Quasiperiodic crystals do not possess such long-range
periodic order and are distinct in that they exhibit fivefold symmetry, which is forbid-
den in the 230 space groups. In the cubic close-packed and hexagonal close-packed
structures, exhibited by many metals, each atom is coordinated by 12 neighbouring
atoms. All of the coordinating atoms are in contact, although not evenly distributed
around the central atom. However, there is an alternative arrangement in which each
coordinating atom is situated at the apex of an icosahedron and in contact only with
the central atom. The rigid atomic sphere model allow the central atom to reduce in
diameter by 10%, the coordinating atoms come into contact and the body now has
the shape and symmetry of a regular icosahedron with point group symmetry 235,
indicating the presence of 30 twofold, 20 threefold and 12 fivefold axes of symmetry.
This geometry represents the nucleus of a quasiperiodic crystal which may grow
in the forms of icosahedra or pentagonal dodecahedra. These are dual solids with
identical symmetry, the apices of one being replaced by the faces of the other. Such
quasiperiodic crystals are known to exist in an increasing number of aluminium-
based alloys and may be stable up to microcrystalline sizes. It should be noted that
their symmetry is precisely the same as that of the fullerenes C20 and C60 . Hence, as
fullerenes, quasiperiodic crystals are expected to have an important role to play in
nanostructures. The size-related instability characteristics of quasiperiodic crystals
Fig. 2.3 Geometrical shapes of cubo-octahedral particles and multiply twinned decahedral and
icosahedral particles. Reprinted with permission from © Advances in Natural Sciences: Nanoscience
and Nanotechnology, 1 (2010)
are not well assumed. An often detected process appears to be that of multiple twin-
ning, such crystals being distinguished from quasiperiodic crystals by their electron
diffraction patterns. Here the five triangular faces of the fivefold symmetric icosa-
hedron can be mimicked by five twin-related tetrahedral through relatively small
atomic movements [6] (Fig. 2.3).
2.2.2 Thermal Properties
The large increase in surface energy and the change in interatomic spacing as a
function of nanoparticle size have an effect on material properties. For instance, the
melting point of gold particles, which is really a bulk thermodynamic characteristic,
has been observed to decrease rapidly for particle sizes less than 10 nm, as shown in
Fig. 2.4. There is evidence that for metallic nanocrystals embedded in a continuous
matrix the opposite behavior is true; i.e., smaller particles have higher melting points
[7].
Fig. 2.4 Schematic diagram

of the variation in melting
point of gold nanoparticles
as a function of particle size.
Reprinted with permission
from © Handbook of
Nanoparticles, Springer,
Cham (2016)
2.2.3 Chemical Properties
The change in structure as a function of particle size is intrinsically linked to the

changes in electronic properties. The ionization potential is generally higher for small
atomic clusters than for the corresponding bulk material. Furthermore, the ionization
potential exhibits marked fluctuations as a function of cluster size. Such effects appear
to be linked to chemical reactivity, such as the reaction of Fen clusters with hydrogen
gas (Fig. 2.5). Nanoscale structures such as nanoparticles and nanolayers have very
high surface area to volume ratios and potentially different crystallographic struc-
tures which may lead to a radical alteration in chemical reactivity. Catalysis using
finely divided nanoscale systems can increase the rate, selectivity and efficiency of
chemical reactions such as combustion or synthesis whilst simultaneously signifi-
cantly reducing waste and pollution. Gold nanoparticles smaller than about 5 nm
in diameter are known to adopt icosahedral structures rather than the normal face
centered cubic arrangement. This structural change is accompanied by an extraor-
dinary increase in catalytic activity. Furthermore, nanoscale catalytic supports with
controlled pore sizes can select the products and reactants of chemical reactions
based on their physical size and thus ease of transport to and from internal reaction
sites within the nanoporous structure. Additionally, nanoparticles often exhibit new
chemistries as distinct from their larger particulate counterparts; for example, many
new medicines are insoluble in water when in the form of micron-sized particles but
will dissolve easily when in a nanostructured form [8].

of the dependence of the
electron binding energy and
relative chemical reactivity
of iron clusters to hydrogen
gas as a function of cluster
size. Reprinted with
permission from ©
Condensed Matter &
Biological Systems, 1, 1–36
(2010)
2.2.4 Mechanical Properties
The mechanical properties like toughness are highly dependent on the ease of for-
mation or the presence of defects within a material. As the system size decreases,
the ability to support such defects becomes increasingly more difficult and mechan-
ical properties will be altered accordingly. Novel nanostructures, which are very
different from bulk structures in terms of the atomic structural arrangement, will
obviously show very different mechanical properties. For example, single and multi-
walled carbon nanotubes show high mechanical strengths and high elastic limits that
lead to considerable mechanical flexibility and reversible deformation. As the struc-
tural scale reduces to the nanometer range, for example, in nanolayered composites,
different scale dependence from the usual Hall–Petch relationship for yield strength
often becomes apparent with large increases in strength reported. In addition, the
high interface to volume ratio of consolidated nanostructured materials appears to
enhance interface-driven processes such as plasticity, ductility and strain to failure.
Many nanostructured metals and ceramics are observed to be superplastic, in that
they are able to undergo extensive deformation without necking or fracture. This is
presumed to arise from grain boundary diffusion and sliding, which becomes increas-
ingly significant in a fine-grained material. Overall these effects extend the current
strength–ductility limit of conventional materials, where usually a gain in strength
is offset by a corresponding loss in ductility [9].
2.2.5 Magnetic Properties
Magnetic nanoparticles are used in many applications, like ferro-fluids, colour imag-
ing, bioprocessing, refrigeration as well as high storage density magnetic memory
media. The large surface area to volume ratio results in a substantial proportion of
atoms having a different magnetic coupling with neighbouring atoms, leading to
differing magnetic properties. Figure 2.6 shows the magnetic moments of nickel
nanoparticles as a function of cluster size. Whilst bulk ferromagnetic materials usu-
ally form multiple magnetic domains, small magnetic nanoparticles often consist of

of the variation in magnetic
moments of clusters as a
function of cluster size.
from © Scientific Reports, 7,
Article No. 9894 (2017)
only one domain and exhibit a phenomenon known as superparamagnetic. In this

case the overall magnetic coercivity is then lowered: the magnetizations of the vari-
ous particles are randomly distributed due to thermal fluctuations and only become
aligned in the presence of an applied magnetic field.
Giant magnetoresistance (GMR) is a spectacle perceived in nanoscale multilayers
consisting of a strong ferromagnet (e.g., Fe, Co) and a weaker magnetic or non-
magnetic buffer (e.g., Cr, Cu); it is generally engaged in data storage and sensing.
In the absence of a magnetic field the spins in alternating layers are oppositely
aligned through antiferromagnetic coupling, which gives maximum scattering from
the interlayer interface and hence a high resistance parallel to the layers. In an oriented
external magnetic field the spins align with each other and this decreases scattering
at the interface and hence resistance of the device [10].
2.2.6 Optical Properties
The nanoclusters has effect of reduced dimensionality on electronic structure has

the most profound effect on the energies of the highest occupied molecular orbital
(HOMO), essentially the valence band, and the lowest unoccupied molecular orbital
(LUMO), essentially the conduction band. Optical emission and absorption depend
on transitions between these states; semiconductors and metals, in particular, show
large changes in optical properties, such as colour, as a function of particle size. Col-
loidal solutions of gold nanoparticles have a deep red colour which becomes progres-
sively more yellow as the particle size increases; indeed gold colloids have been used
as a pigment for stained glass since the seventeenth century. Figure 2.7 shows optical
absorption spectra for colloidal gold nanoparticles of varying sizes. Semiconductor
nanocrystals in the form of quantum dots show similar size-dependent behavior in
the frequency and intensity of light emission as well as modified non-linear optical
properties and enhanced gain for certain emission energies or wavelengths. Other
Fig. 2.7 Size dependence of

the optical absorption
wavelength for gold
nanoparticles and (inset) the
corresponding value of the
full width at half maximum
(FWHM) of the absorption
peak. Reprinted with
permission from ©
Nanophotonics, 6, 153–175
(2019)
properties which may be affected by reduced dimensionality are photocatalysis,

photoconductivity, photoemission and electroluminescence [11].
2.2.7 Electronic Properties
The changes which occur in electronic properties are due to reduction in system length
scale and increase in wave-like property of the electrons and the scarcity of scattering
centers. As the size of the system becomes similar with the de Broglie wavelength of
the electrons, the discrete nature of the energy states becomes apparent once again,
although a fully discrete energy spectrum is only observed in systems that are con-
fined in all three dimensions. In certain cases, conducting materials become insulators
below a critical length scale, as the energy bands cease to overlap. Owing to their
intrinsic wave-like nature, electrons can tunnel quantum mechanically between two
closely adjacent nanostructures, and if a voltage is applied between two nanostruc-
tures which aligns the discrete energy levels in the density of state (DOS), resonant
tunneling occurs, which abruptly increases the tunneling current. In macroscopic
systems, electronic transport is determined primarily by scattering with phonons,
impurities or other carriers or by scattering at rough interfaces. The path of each
electron resembles a random walk, and transport is said to be diffusive. When the
system dimensions are smaller than the electron mean free path for inelastic scat-
tering, electrons can travel through the system without randomization of the phase
of their wave functions. This gives rise to additional localization phenomena which
are specifically related to phase interference. If the system is sufficiently small so
that all scattering centers can be eliminated completely, and if the sample boundaries
are smooth so that boundary reflections are purely specular, then electron transport
becomes purely ballistic, with the sample acting as a waveguide for the electron
wavefunction [12]. Conduction in highly confined structures, such as quantum dots,
is very sensitive to the presence of other charge carriers and hence the charge state
of the dot. These coulomb blockade effects result in conduction processes involving
single electrons and as a result they require only a small amount of energy to operate a
switch, transistor or memory element. All these phenomena are used to produce com-
pletely different types of components for electronic, optoelectronic and information
processing applications, such as resonant tunneling transistors and single-electron
transistors [8].
2.2.8 Physiochemical Properties of Nanomaterials
2.2.8.1 Melting Point
The number of surface atoms to that of bulk atoms increases with decrease in particle
size. Hence, the melting point of nanoparticle falls as much as equivalent surface
energy. Some examples of melting points of nanoparticles are shown in Figs. 2.8 and
2.9. A melting point of Au declines suddenly when a particle size is less than 15 nm
and a decrease of almost 200 K can be observed at about 6 nm. As shown in Fig. 2.9,
it has been reported that there is a linear relationship between a ratio of a melting
point of nanoparticle (T m ) to that of bulk material (T o ) and a reciprocal number of a
particle diameter.
Fig. 2.8 Relationship between melting point of gold and its particle size. Reprinted with permission
from © Handbook of Nanoparticles. Springer, Cham (2016)
Fig. 2.9 Relationship

between inverse of particle
size of various metal and
T m /T o . T m , measured
melting point; T o , melting
point of bulk material
(Elsevier Nanoparticle
Technology Handbook,
Third Edition 2018,
pages 3–47)
2.2.8.2 Surface Tension
Researchers calculated a change in liquid drop diameter with an evaporation of a

liquid drop at a constant temperature based on a molecular dynamics and obtained
an equation
ln(dr/dt) = ln A + B(σ/r )
where r is the radius of liquid drop, σ the surface tension, t the time, and A and B are
constants. As can be seen from above equation, when the surface tension value of
liquid drop remains constant, ln(dr/dt) should be proportional to (1/r). Figure 2.10,
shows changes of particle sizes of Au and Pb with time by evaporation. It can be found
that ln(dr/dt) and (1/r) does not show linear relationship when particle sizes of Au
Fig. 2.10 Relationship between particle size change of evaporating metal drop and particle size.
Reprinted with permission from © Elsevier Nanoparticle Technology Handbook, 3rd (eds.), 3–47
(2018)
Fig. 2.11 Effect of particle size of surface tension of Au and Pb. σm , surface tension of nanopar-
ticle; σb , surface tension of bulk metal. Reprinted with permission from © Elsevier Nanoparticle
Technology Handbook, 3rd (eds.), 3–47 (2018)
and Pb drops are less than 2 and 5 nm, respectively. The theoretical and experimental
approach on surface energies of nanoparticles of metals reports the results of Au and
Pb particles [13] (Fig. 2.11).
2.2.8.3 Wettability
As shown in Fig. 2.12, a contact angle value is used as a criterion for wettability of
solid by liquid. Generally, the contact angle is larger than 90°, is known as non-wetting
system and if the contact angle is smaller than 90°, is known as wetting system. The
contact angle of a liquid drop as the result of the equilibrium of mechanical energy
between the drop and a solid surface under the action of three interfacial free energies,
σL cos θ = σS − σSL
where θ is the contact angle, σL the surface free energy of liquid, σS the surface free
energy of solid and σSL the interface free energy between solid and liquid. Since the
surface free energy of liquid depends on a liquid drop size as mentioned above, the
contact angle also depends on the liquid drop size. Figure 2.13 shows particle size
dependence of contact angles of various liquid metals on carbon substrate. It can be
Fig. 2.12 Changes in contact angle with roughness. On a hydrophilic surface (above), the contact
angle observed is θ 90° while on a flat surface it is only θ < 90°. On a hydrophobic surface
(below), the contact angle observed is θ 90z, while on a flat surface it is only θ > 90°. Reprinted
with permission from © Progress in Organic Coatings, 65, 77–83 (2009)
Fig. 2.13 Relationship between contact angles of liquid metals on graphite and particle sizes.
Reprinted with permission from © Elsevier Nanoparticle Technology Handbook, 3rd (eds.), 3–47
(2018)
found that the contact angles of all liquid metals decrease at less than 40 nm and a
remarkable decrease of the contact angles is observed when particle radius is less
than 10 nm [14].
2.2.9 Specific Surface Area and Pore
Nanoparticles have large specific surface area, which enhance their surface prop-
erties than bulk materials. The specific surface area is boost for the properties of
nanoparticles. It is significant to access the effect of particle shapes and particle size
distribution for measuring particle size from specific surface area. By using electron
microscopic observations or other particle size measurements are preferable in com-
bination with the measurement of specific surface area. Comprehensive analysis for
these measurements would enable to estimate reasonable and meaningful particle
size [15].
2.3 Nanomaterial Synthesis Process
Atoms and molecules are vital building blocks of every object. The way in which
things are constructed with these basic units is extremely important to understand
their properties and their reciprocal interactions. An efficient control of the synthetic
pathways is essential during the preparation of nanobuilding blocks with differ-
ent sizes and shapes that can lead to the creation of new devices and technologies
with improved performances. By the way we have two opposite, but complemen-
tary approaches are followed. One is a top-down strategy of miniaturizing current
components and materials, while the other is a bottom-up strategy of building ever-
more-complex molecular structures atom by atom or molecule by molecule. These
two different methods highlight the organization level of nanosystems as the crossing
point hanging between the worlds of molecular objects and bulk materials.
The top-down approach has been advanced by Richard Feynman in his often-
cited 1959 lecture stating that “there is plenty of room at the bottom” and it is ideal
for obtaining structures with long-range order and for making connections with
macroscopic world. Conversely, the bottom-up approach is best suited for assembly
and establishing short-range order at the nanoscale [16].
2.3.1 Top-Down Approach
The top-down method is based on miniaturizing techniques, such as machining,

templating or lithographic techniques. Top-down methods usually start from patterns
generated at larger scale and then they are reduced to nanoscale. A key advantage
of the top-down approach is that the parts are both patterned and built in place, so
that no further assembly steps are needed. By means of electronic, ionic or X-ray
lithography, a monolith can be cut step by step in order to generate a quantum well
at first, then a quantum, and a quantum. Recent short-wavelength optical lithography
methods can reach dimensions not less than 100 nm. Extreme ultraviolet and X-
ray sources are being developed to allow lithographic printing techniques to reach
dimensions from 10 to 100 nm, but the principal limits are still due to the difficulty
of beam focalization. Likewise, scanning beam techniques such as electron-beam
lithography provide patterns down to about 20 nm and still-smaller features are
obtained by using scanning probes to deposit or remove thin layers [17].
The general procedure of mechanical printing techniques consist on making a
master stamp by a high-resolution lithographic technique, as described above, and
then applying this stamp, or subsequent copies of it, to a surface to mould the pat-
tern. The last step is to remove the thin layer of the masking material under the
stamped regions. These nanoscale printing techniques offer several advantages due
to the possibility to use a wide variety of materials with curved surfaces. As a general
drawback, these techniques are not cheap and require a complex manufacturing. In
addition, top-down methodologies: (1), even if they work well at the microscale, they
collide with some difficulties at nanoscale dimensions and (2) they usually lead to the
formation of bidimensional structures and hence, as they are carried out by the addi-
tion or subtraction of patterned layers, they cannot easily give rise to the production
of arbitrary three-dimensional objects. It is worth underlining that the development
in the top-down methodology was mainly driven from the traditional disciplines of
materials engineering and physics, whereas the role of inorganic chemists has been
minor in the exploitation of these techniques.
2.3.2 Bottom-Up Approach
Bottom-up approaches to nanofabrication involve gradual additions of atoms or

groups of atoms. This technique uses chemical or physical forces operating at the
nanoscale to assemble basic units into larger structures. The chemical growth of
nanometer-sized materials often implies colloidal or supramolecular systems and
it frequently passes through phase transformations, such as vapor deposition on
surfaces or precipitation of a solid phase from solution. Inspiration for bottom-up
approaches comes from biological systems, where nature has employed chemical
forces to create essentially all the structures needed by life. Researchers try to
mimic nature’s ability to produce small clusters of specific atoms, which can then
self-assemble into more-elaborated structures [18].
2.4 Applications of Nanomaterials 25
2.4 Applications of Nanomaterials
2.4.1 Environmental Sector
Nanotechnology offers a low-cost and effective solution to the challenge of access

to clean and safe water. The technology holds the potential to radically reduce the
number of steps, materials and energy needed to purify water. Depending on the
kind of water to be purified ground, surface or waste water; nanomaterials can be
tailor-made with specific pore sizes and large enhanced surface areas to filter out
certain unwanted pollutants, such as heavy metals or biological toxins. For example,
titanium oxide at nanoscale can be used to degrade organic pollutants. And silver
nano-particles have the ability to degrade biological pollutants such as bacteria. Also,
the testing are made with different kinds of membranes and filters based on carbon
nanotubes, nanoporous ceramics, magnetic nanoparticles and other nanomaterials
which could be used to remove water-borne diseases such as typhoid and cholera, as
well as toxic metal ions, organic and inorganic solutes. Another, important concern is
nanofiltration, were nanofiltration membranes are already being applied for removal
of dissolved salts from salty water, removal of micro pollutants, water softening,
and wastewater treatment. These membranes selectively reject substances, which
enables the removal of harmful pollutants and retention of nutrients present in water
that are required for the normal functioning of the body. Attapulgite clay, zeolite,
and polymer filters are source materials for nanofilters and can now are manipulated
on the nanoscale to allow for greater control over pore size of filter membranes [19].
Using catalytic particles could chemically degrade pollutants instead of simply
moving them somewhere else, including pollutants for which existing technologies
are inefficient or cost prohibitive. Magnetic nanoparticles, when coated with differ-
ent compounds could be used to remove pollutants, including arsenic, from water.
The Self-cleaning process includes photo-catalysis and hydrophobicity. These two
processes are used in coating of titanium dioxide on the outside surface of the glass
Titanium dioxide is an inorganic pigment which is widely used in a whole variety of
products and in this case is a very thin coating (25 nm) on the outside surface of the
glass [20].
2.4.2 Health Sector
Nanotechnology applications are in development and that will radically improve

medical imaging techniques. For example, gold and silver nanoparticles have optical
properties which make them extremely effective as contrast agents. Quantum dots
which are brighter than organic dyes and need only one light source for excitation,
when used in conjunction with magnetic resonance imaging, can produce exceptional
images of tumour sites. Nanomaterials are also used in therapeutics or treatment.
2.4.2.1 Targeted Drug Delivery Systems
Nanostructures can be used to recognize diseased cells and to deliver drugs to the
affected areas to combat cancerous tumour, for example, without harming healthy
cells. In obesity, nanoparticles can target and inhibit the growth of fat deposits.
2.4.2.2 Drug Therapy
Research shows that nano-sized biodegradable polymer capsules containing drugs

for tuberculosis treatment are effectively taken up by the body’s cells. The effect is a
slower release of the drug into the body and a reduction in the frequency with which
(Tuberculosis) TB patients need to take his or her medication.
2.4.2.3 Photothermal and Hypothermal Destruction
Nanoparticles like gold (Au) possess therapeutic properties based on their magnetic
wavelength or optical properties. They absorb light and heat up the surrounding area,
killing the cancer cells. Silver has been used for its ability to destroy bacteria from
ancient Romans treating their water with silver coins to NASA using the metal to
purify water aboard the Space Shuttle. Silver (Ag) nanoparticles are embedded in
sticking plasters for their ability to inhibit the transmission of viruses. Pancreatic
cancer has a devastatingly low survival rate because it is usually diagnosed at an
advanced stage. Scientists have created tools for the early diagnosis of pancreatic
cancer by attaching a molecule that binds specifically to pancreatic cancer cells to
iron oxide nanoparticles that are clearly visible under magnetic resonance imaging
(MRI). The drug is encapsulated in a nanoparticle which helps it pass through the
stomach to deliver the drug into the bloodstream.
2.4.3 Energy Sector
Research based on nanotechnology deals a practical substitute to non-renewable

fossil-fuel consumption and provides a chance to realize a hydrogen economy. Nano
applications in the above field contain: solar cells; fuel cells and new energy pro-
duction, conversion and storage processes. In all areas, the results are energy that
is cheaper, cleaner, more efficient and renewable. In future, nano holds the poten-
tial to produce hybrid vehicles with reduced fuel consumption and a lighter motor
weight. Using nanoparticles in the manufacture of solar cells is beneficial due to their
reduce manufacturing costs by using a low temperature process instead of the high
temperature vacuum deposition process typically used to produce conventional cells
made with crystalline semiconductor material. They can reduce installation costs
by producing flexible rolls instead of rigid crystalline panels. Currently available
2.4 Applications of Nanomaterials 27
nanotechnology solar cells are not as efficient as traditional; however their lower
cost offsets this. In the long term nanotechnology versions should both be lower cost
and, using quantum dots, should be able to reach higher efficiency levels than con-
ventional ones [21]. Nanostructured devices have the potential to serve as the basis
for next-generation energy systems that make use of densely packed interfaces and
thin films. Researchers have developed metal-insulator-metal nanocapacitors. It is
possible to accommodate one million such tiny capacitors on one square centimeter
area. The use of such capacitors in battery and other energy storage devices may
increase the efficiency and capacity of such devices enormously [22].
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Chapter 3
Fundamentals of Nanostructures
Abstract Nanostructures may define by its dimensions as one dimension, two

dimension and three dimensions based on quantum confinement effects. Nanostruc-
tures are made of nanoparticles using atom by atom or electron arrangement with the
help of deposition and lithography techniques. This chapter briefly describe about
nanostructured materials, approach towards nanostructured materials and various
types of nanostructural materials.
3.1 Nanostructures Definition
Nanostructures are related to a human hair which is ~50,000 nm thick whereas

the diameters of nanostructures are ~0.3 nm for a water molecule, 1.2 nm for a
single-wall carbon nanotube, and 20 nm for a small transistor. DNA molecules are
2.5 nm wide, proteins about 10 nm, and an ATPase biochemical motor about 10 nm.
This is the ultimate manufacturing length scale at present with building blocks of
atoms, molecules, and supramolecules as well as integration along several length
scales. In addition, living systems work at the nanoscale [1]. Nanostructure can be
defined as a system in the order of 1–100 nm in size. Also, the nanostructures have
intermediate size between a nano dimension and a micro dimension, which can be
developed as various forms. It is basically structured using soft/hard templates to
form micro-level structures. Nanostructure means it represents the structure of the
nanomaterials, like sphere, rod, hollow cylinder, rectangle, cube, etc. nanomaterial
means materials in nano size. It represents each and every material present in nano
size and it may be biological or non-biological, artificial or natural, anything comes
under nano size or nanomaterials. Actually nanostructured materials are a right way
to represents a material in nano size. e.g.: nano tubes, nano rods, nanoparticles,
nanofibers, nanosheets etc. Nanostructures are the building blocks of nanomaterials
[2, 3].

https://doi.org/10.1007/978-3-030-26145-0_3
30 3 Fundamentals of Nanostructures
3.2 Nanostructured Materials
Nanostructured materials are condensed material, in whole or in part composed of

structural elements with the characteristic dimensions from several nanometers to
several tens of nanometers; the long-range order in the structural elements is highly
disturbed and therefore the short-range order determines multiparticle correlations in
the arrangement of atoms in these elements; all macroscopic properties of the material
are determined by the size and/or mutual arrangement of structural elements [4]. One
way to classify nanostructures is based on the dimensions in which electrons move
freely:
Quantum well: electrons are confined in one dimension (1D), free in other 2D.
It can be realized by sandwiching a narrow-bandgap semiconductor layer between
the wide-gap ones. A quantum well is often called a 2D electronic system. Quan-
tum wires: confined in two dimensions, free in 1D. Real quantum wires include
polymer chains, nanowires and nanotubes. Quantum dots: electrons are confined in
all dimensions, as in clusters and nano-crystallites. Zero-dimensional nanomaterials
include nanocluster materials and nanodispersions, i.e. materials in which nanopar-
ticles are isolated from each other. One-dimensional nanomaterials are nanofibre
(nanorod) and nanotubular materials with fibre (rod, tube) length from 100 nm to
tens of microns. Two-dimensional nanomaterials are films (coatings) with nanometer
thickness. Structural elements in 0D, 1D and 2D nanomaterials can be distributed in
a liquid or solid macroscopic matrix or be applied on a substrate. Three-dimensional
nanomaterials include powders, fibrous, multilayer and polycrystalline materials in
which the 0D, 1D and 2D structural elements are in close contact with each other and
form interfaces. An important type of three-dimensional nanostructured materials is
a compact or consolidated (bulk) polycrystal with nanosize grains, whose entire vol-
ume is filled with those nanograins, free surface of the grains is practically absent,
and there are only grain interfaces. The formation of such interfaces and disappear-
ance of the nanoparticle (nanograin) surface is the fundamental difference between
three-dimensional compact nanomaterials and nanocrystalline powders with various
degrees of agglomeration that consist of particles of the same size as the compact
nanostructured materials [5].
Nanostructured materials made of nanosized grains or nanoparticles as building
blocks, have a significant fraction of grain boundaries with a high degree of disorder
of atoms along the grain boundaries, and a large ratio of interface area to volume.
Chemical composition of the phases and the interfaces, between nano-grains, must be
controlled as well. One of the most important characteristics of nanostructured mate-
rials is the dependence of certain properties upon the size in nanoscale region. For
example, electronic property, with quantum size effects, caused by spatial confine-
ment of delocalized valence electrons, is directly dependent on the particle size. Small
particle size permits conventional restrictions of phase equilibrium and kinetics to be
overcome during the synthesis and processing by the combination of short diffusion
distances and high driving forces of available large surfaces and interfaces. A wide
range of materials, including metals and ceramics in crystalline, quasi-crystalline, or
3.2 Nanostructured Materials 31
amorphous phases have been synthesized as nanosized or nanostructured materials.

The large surface area gives higher reactivity. Thus novel properties may result from
surface defects. In addition, there are other structural features in the nanostructured
materials that depend on the manner in which these materials are synthesized and
processed, such as surface pores, grain boundary junctions, and other crystal lattice
defects. Some examples are lowered melting temperatures, improved wear resis-
tance of nanostructured ceramics, increased strength of metals, and transformation
of magnetic state from ferromagnetic to paramagnetic or superparamagnetic state as
a function of size. The changes in lattice parameter can be attributed to changes in
surface stress, while the reduction in melting temperature results from the increase
in surface free energy. This opens the doors for tailoring given properties by careful
synthesis of the building blocks and their assembly to fabricate functional materials
with improved properties [6].
Ultrafine microstructures having an average phase or grain size on the order of a
nanometer (10−9 m) are classified as nanostructured materials (NSMs). The interest
in these materials has been stimulated by the fact that, owing to the small size of the
building blocks (particle, grain, or phase) and the high surface-to-volume ratio, these
materials are expected to demonstrate unique mechanical, optical, electronic, and
magnetic properties. The properties of NSMs depend on the following four common
microstructural features: (1) fine grain size and size distribution (<100 nm); (2) the
chemical composition of the constituent phases; (3) the presence of interfaces, more
specifically, grain boundaries, heterophase interfaces, or the free surface; and (4)
interactions between the constituent domains. In nanophase materials, a variety of
size-related effects can be incorporated by controlling the sizes of the constituent
components. For example, nanostructured metals and ceramics can have improved
mechanical properties compared to conventional materials as a result of the ultrafine
microstructure. In addition, NSMs have the capability to be sintered at much lower
temperatures than conventional powders, enabling the full densification of these
materials at relatively lower temperatures [7]. Semiconductor NSMs are currently
also considered to have technological applications in optoelectronic devices such as
semiconductor quantum dots and photodiodes, owing to the quantum size effects
caused by the spatial confinement of delocalized electrons in confined grain sizes.
Magnetic applications of NSMs include fabrication of devices with giant magnetore-
sistance (GMR) effects, the property used by magnetic heads to read data on computer
hard drives, as well as the development of magnetic refrigerators that use solid mag-
nets as refrigerants rather than compressed ozone-destroying chlorofluorocarbons.
In addition, nanostructured metals and ceramics seem to be candidates for new cat-
alytic applications [8]. The development of semiconductor nanoclusters is an area
of intense research efforts. These nanoclusters are often referred to as quantum dots,
nanocrystals, and Q-particles. In the nanometer size regime, electron-hole confine-
ment in nanosized spherical semiconductor particles results in three-dimensional size
quantization. Band gap engineering by size and dimension quantization is important
because it leads to electrical, optical, magnetic, optoelectronic and magneto optical
properties substantially different from those observed for the bulk material. As an
example, quantum dots can be developed to emit and absorb a desired wavelength
of light by changing the particle diameters [9].
3.2.1 1D Nanostructures
One-dimensional (1D) nanostructures are ideal systems for investigating the depen-
dence of electrical transport, optical properties and mechanical properties on size and
dimensionality. They are expected to play an important role as both interconnects and
functional components in the fabrication of nanoscale electronic and optoelectronic
devices. Nanoscale one-dimensional (1D) materials have stimulated great interest
due to their importance in basic scientific research and potential technology applica-
tions. Other than carbon nanotubes, 1D nanostructures (nanowires or quantum wires)
are ideal systems for investigating the dependence of electrical transport and mechan-
ical properties on size and dimensionality. They are expected to play an important
role as both interconnects and functional components in the fabrication of nanoscale
electronic and optoelectronic devices. Many unique and fascinating properties have
already been proposed or demonstrated for this class of materials, such as superior
mechanic toughness, higher luminescence efficiency, enhancement of thermoelectric
figure of merit and lowered lasing threshold. Nanowires are anisotropic nanocrys-
tals with large aspect ratios. Generally, they would have diameters of 1–200 nm and
length up to several tens of micrometers. Nanowires differ significantly from spher-
ical nanocrystals by their morphology as well as physical properties. An important
issue in the study and application of these 1D materials is how to assemble indi-
vidual atoms into 1D nanostructure in an effective and controllable way. Although
1D nanostructures could be fabricated using a number of advanced nanolithography
techniques, such as e-beam writing, proximal-probe patterning, and x-ray lithogra-
phy, these processes, however, generally are slow and the cost is high, the develop-
ment of these techniques into practical routes for fabricating large numbers of 1D
nanostructures rapidly and at low-cost still requires great ingenuity [10].
2D nanostructures have two dimensions outside of the nanometric size range. In

recent years, a synthesis 2D NSMs have become a focal area in materials research,
owing to their many low dimensional characteristics different from the bulk proper-
ties. In the quest of 2D NSMs, considerable research attention has been focused over
the past few years on the development of 2D NSMs. 2D NSMs with certain geome-
tries exhibit unique shape-dependent characteristics and subsequent utilization as
building blocks for the key components of nanodevices. In addition, a 2D NSMs
are particularly interesting not only for basic understanding of the mechanism of
nanostructure growth, but also for investigation and developing novel applications in
sensors, photocatalysts, nanocontainers, nanoreactors, and templates for 2D struc-

tures of other materials. The 2D NSMs, are junctions (continuous islands), branched
structures, nanoprisms, nanoplates, nanosheets, nanowalls, and nanodisks [11].
Owing to the large specific surface area and other superior properties over their bulk
counterparts arising from quantum size effect, 3D NSMs have attracted considerable
research interest and many 3D NSMs have been synthesized in the past years. It
is well known that the behaviors of NSMs strongly depend on the sizes, shapes,
dimensionality and morphologies, which are thus the key factors to their ultimate
performance and applications. Therefore it is of great interest to synthesize 3D NSMs
with a controlled structure and morphology. In addition, 3D nanostructures are an
important material due to its wide range of applications in the area of catalysis,
magnetic material and electrode material for batteries. Moreover, the 3D NSMs have
recently attracted intensive research interests because the nanostructures have higher
surface area and supply enough absorption sites for all involved molecules in a small
space. The typical 3D NMSs are nanoballs, nanocoils, nanocones, nanopillers and
nanoflowers [12].
3.3 Features of Nanostructures
Nanostructures are unique as compared with both individual atoms/molecules at a

smaller scale and the macroscopic bulk materials. They are also called mesoscopic
structures. Nanoscience research focuses on the unique properties of nanoscale struc-
tures and materials that do not exist in structures of same material composition but
at other scale ranges. By controlling the construction of the materials on the atomic
level, new and improved mechanical, chemical and optical properties may be devel-
oped. Both surface structure and particle size on the nanoscale are of great importance
in this context. Developments of new theories and models, as well as characteriza-
tion methods are important in order to understand the relationship between structure
and function. Nanostructure materials are often in a metastable state. Their detailed
atomic configuration depends sensitively on the kinetic processes in which they are
fabricated. Therefore, the properties of nanostructures can be widely adjustable by
changing their size, shape and processing conditions [13]. Nanoscale materials offer
larger surface area (A) to volume (V) ratios (A/V) than the bulks. Thus nanostruc-
tures are believed to have better performances than materials in the micro- or larger
scales for sensing applications. The most example for nanostructures are Zinc Oxide,
which can appear as nanowires, nanobelts, nanopropellers, nanocombs, nanotubes,
nanoswords, nanotripods, nanotetrapods, nanosquids, nanorods, nanotips, etc.
3.4 Theoretical Substantiation of the Approaches Proposed
The activity of nanostructures in self-organization processes is defined by their sur-

face energy thus corresponding to the energy of their interaction with the surround-
ings. It is known that when the size of particles decreases, their surface energy and
particle activity increase. The following ratio is proposed to evaluate their activity:
a = ε S /εV (3.1)
where, ES —nanoparticle surface energy, εV —nanoparticle volume energy. Naturally

in this case εS εV conditioned by the greater surface “defectiveness” in comparison
with nanoparticle volume. To reveal the dependence of activity upon the size and
shape we take εS as ε0S S, and εV = ε0V V, where ε0S —average energy of surface unit, S—
surface, ε0V —average energy of volume unit, V—volume, then Eq. (3.1) is converted
to:
ε0S
a =d. S/V (3.2)
εV0
Substituting the values of S and V for different shapes of nanostructures, we see

that in general form the ratio S/V is the ratio of the number whose value is defined
by the nanostructure shape to the linear size connected with the nanostructure radius
or thickness. Equation (3.2) can be given as,
ε0S ε0S
a =d. N /r (h) = 1/B (3.3)
εV0 εV0
where, B equals r(h)/N, r—radius of bodies of revolution including hollow ones,

h—film thickness depending upon its “distortion from plane”, N—number varying
depending upon the nanostructure shape. Parameter d characterizes the nanostruc-
ture surface layer thickness, and corresponding energies of surface unit and volume
unit are defined by the nanostructure composition. For the corresponding bodies of
revolution the parameter B represents an effective value of the interval of nanostruc-
ture linear size influencing the activity at the given interval r from 1 to 1000 nm.
For nanofilms the surface and volume are determined by the defectiveness and shape
of changes in conformations of film nanostructures depending upon its crystallinity
degree. However, the possibilities of changes in nanofilm shapes at the changes in the
medium activity are higher in comparison with nanostructures already formed. At the
same time, the sizes of nanofilms formed and their defectiveness play an important
role [14].
To determine the possibility of nanostructure existence and forecasting the forma-
tion of different nanosystems it is necessary to develop the corresponding theoretical
and computation apparatus. The creation of such an apparatus is possible based on
3.4 Theoretical Substantiation of the Approaches Proposed 35
corresponding ideas of quantum chemistry, molecular mechanics and thermodynam-

ics. Apparently, in developing the overall theory of nanosystems the symbiosis of
similar theoretical trends in physics, chemistry, biology, and computer modeling
will be found. The processes of nanostructure formation, the subject investigated by
chemical physics, are of great interest. Therefore, apparently, it is more appropriate to
discuss the creation of computational apparatus of chemical physics of nanostructure
formation processes. In recent years, a lot of investigations connected with the devel-
opment of different software products have been carried out in quantum chemistry,
molecular dynamics and molecular mechanics of cluster and nanosystems. These
investigations are fulfilled using semi-empirical and ab initio methods. Basically,
paired interactions were used in all the methods, although there are works discussing
collective interactions on atomic and molecular levels [15]. It is advisable to arrange
a hierarchical scheme for predicting nanostructure formation. First, the stability of
interacting particles and reaction centers should be determined. Under reaction cen-
ter we understand the group of atoms being changed during the reaction. Potential
reactivity centers, that is, groups of atoms able to participate in reactions, are usually
called functional groups. This terminology can mainly be found in organic and poly-
mer chemistry. The stability of particles and interaction energy are evaluated with
methods of quantum chemistry. After reactivity centers are selected possible reac-
tions with their participation are assumed, this operation for finding reaction options
is similar to the isolation of reaction series in physical organic chemistry. Here,
under reaction series we understand the directivity of processes in reactivity centers
or similar nanosystems with the formation of nanoparticles of certain structure and
composition.
The advantage of one or another reaction series when compared with the others
is determined based on energy consumption for performing successive acts of the
process and the rate with which these acts are performed [16]. Computational exper-
iment can be carried out using apparatuses of quantum chemistry and molecular
dynamics, in some cases in combination with semi-empirical methods of thermody-
namics in the frameworks of activated complex theory or spatial energy concept. At
previous two stages of nanosystems modeling and formation single chemical parti-
cles, reaction centers or fragments of complex nano components of the systems were
discussed. The changes of nanostructures during the action of various fields, such as
thermal, electrical, magnetic, field of particles, gravitation upon nanosystems, and
nanoparticles are also determined at the aforesaid stages. Therefore, at third and the
following stages collective interactions of nanoparticles with the help of apparatuses
of molecular mechanics and thermodynamics are discussed. The transitions from one
method of computational experiment to another one represent certain terminological
and conceptual difficulties. This can be explained not only by the time frames when
the corresponding notions, ideas and definitions appeared [17]. The complete positive
material accumulated in reactivity theory and reactions of chemical particles with the
formation of nanosystems should be used in a new nanoscience. Therefore, modular
construction should be introduced into the scheme of basic notions of nanosystems
and nanostructure modeling together with hierarchical structure (Fig. 3.1).
Fig. 3.1 Scheme of nanosystems consideration. Reprinted with permission from © CRC, Taylor
& Francis Group (2014)
3.5 Types of Nanostructured Material
The type of nanostructures includes nanotubes, fullerenes, nanowires, nanorods,

nanoonions, and nanobulbs. Thin films with thicknesses below 100 nm, which itself
can consist of nanomaterials, and Nanocomposites (Table 3.1).
3.5 Types of Nanostructured Material 37
Table 3.1 Nanostructured materials by size dependence

Nanostructure Size Material
Clusters, nanocrystals Radius, 1–10 nm Insulators, semiconductors,
quantum dots metals, magnetic materials
Other nanoparticles Radius, 1–100 nm Ceramic oxides
Nanobiomaterials, Radius, 5–10 nm Membrane protein
photosynthetic reaction
Nanowires Diameter, 1–100 nm Metals, semiconductors,
oxides, sulfides, nitrides
Nanotubes Diameter, 1–100 nm Carbon, layered
chalcogenides, BN, GaN
Nanobiorods Diameter, 5 nm DNA
Two-dimensional arrays of Area, several nm2 —μm2 Metals, semiconductors,
nanoparticles magnetic materials
Surfaces and thin films Thickness, 1–100 nm Insulators, semiconductors,
metals, DNA
Three-dimensional Several nm in three Metals, semiconductors,
superlattices of nanoparticles dimensions magnetic materials
The nanoparticle dimensions are determined by its formation conditions. When

the energy consumed for macroparticle destruction or dispersion over the surface
increases, the dimensions of nanomaterials are more likely to decrease. Several
researchers consider nanomaterials to be aggregations of nanocrystals, nanotubes, or
fullerenes. Simultaneously, there is a lot of information available that nanomaterials
can represent materials containing various nanostructures. Some of the nanostruc-
tures are fullerenes, gigantic fullerenes, fullerenes filled with metal ions, fullerenes
containing metallic nucleus and carbon shell, one-layer nanotubes, multi-layer nan-
otubes, fullerene tubules, scrolls, conic nanotubes, metal-containing tubules, onions,
Russian dolls, bamboo-like tubules, beads, welded nanotubes, bunches of nanotubes,
nanowires, nanofibers, nanoropes, nano semispheres, nanobands and various deriva-
tives from enlisted structures [18, 19]. Nanoflowers, these small plants can only be
seen properly through an electron microscope. Actually flower shape crystals rather
than actual flowers; they build themselves one molecule at a time using an underwater
chemical reaction (Figs 3.2 and 3.3).
3.5.1 Nanostructures in Plants
Plant surfaces like leaves; contain nanostructures that are used for abundant resolves
such as insects sliding, mechanical stability, and increased visible light and harmful
UV reflection and radiation absorption. The well-known nanostructure property in
plants is the super hydrophobicity in lotus leaves that helps in self-cleaning and super-
wettability of the leaves. Many studies in the literature have suggested that stacks of
Fig. 3.2 a Nanoflower—p153 ‘nanoflower’ grown from chemical solution and p44 ‘nanoflowers’
created using carbon dioxide gas, b Nanoflower—p152 Nanoflowers grown from chemical solution,
c Nanospheres, and d Nanoflakes. Reprinted with permission from © NanoScience: Giants of the
Infinitesimal by Peter Forbes and Tom Grimsey and published by Papadakis
Fig. 3.3 a Nanofibers, b Nanosheets, and c Close-up of the nanostructures grown on cotton textiles.
Reprinted with permission from © RMIT University researchers
Fig. 3.4 a Photograph of a lotus leaf; b SEM image of the lotus leaf surface. The inset is a SEM
image of typical 5–9 μm micropapillae covering the surface with fine branch-like nanostructures,
copyright 2002 Wiley-VCH. c Photograph of a red rose and d SEM image of a rose petal surface.
The inset is a magnified SEM image of the microcapillary arrays. Reprinted with permission from
© American Chemical Society (2008)
nanostructures are responsible for the circular layer in plants and insects which allows
them to float on water without sinking. Based on these reports, many artificial super
hydrophobic materials with self-cleaning ability have been manufactured through
electrodeposition, photolithography and colloidal systems with unique morphology
and roughness. These super hydrophobic materials were useful in applications such
as water treatment, wettability switchers, smart actuators, transparent coatings and
electrodes [20] (Fig. 3.4).
3.5.2 Nanostructures in Insects
Insect wing membranes are comprised of building materials with 0.5 μm–1 mm
thickness. Additionally, the insect wings are formed by a complex vein system which
gives superior stability to the entire wing structure. Long chain crystalline chitin
polymer is the basic framework of insect wings that provides membrane support and
allows for bearing forces on them during flight. Resilin enhances the wing’s flexibility
and is a unique component that is found in between the junctions of the vein and
the wing. The routine and longer colonization flights were supported by the vein
system along with their weightless wing material. Insect wing surfaces demonstrate
a rough and highly ordered structure comprised of micro- and nanoscale properties
to minimize their mass and protect them against wetting and pollutants.
Animals such as flies, spiders, and geckos with varying body weight can attach
along ceilings and move along vertical walls. The interaction of their patterned sur-
face structure with the substrate profile gives efficient ability and mechanism for
attachment to the insect’s legs. An intense inverse scaling effect in these attachment
devices are exposed via an extensive microscopic study. It has been shown that adhe-
sion is ensured by sub-micrometric devices whereas flies and beetles rely on terminal
setae that are of micrometer dimensions. The principle of contact mechanics, which
shows that the adhesion leads to the splitting of contacts into finer subcontacts, helps
to clearly explain the insect body weight to set a trend. The natural adhesive sys-
tem uses this principle for their design and may be incorporated in future practical
applications. Electrostatic forces, sticking fluids, and microsuckers are the proposed
reasons that explain the insect’s attachment mechanism. Some of these theories have
been rejected based on experimental data and combination of secretion-mediated
capillary attractive forces and molecular interactions or van der Waals interactions
leads to adhesion. This may be due to the production of secretory fluids in the contact
area by some animals, which makes the basic force in the physical form contribute
to their adhesion. The reason for adhesion of gecko setae is due to van der Waals
interaction through strong evidence and rejects the capillary adhesion mechanisms.
It was predicted that application of contact mechanics may help in smaller set an
array endings by releasing greater adhesive strength [21].
3.5.3 Nanostructures in the Human Body
The human body consists of nanostructures without which normal function of the
body is impossible. It is formed by nanostructures such as bones, enzymes, proteins,
antibodies and DNA. Even some works categorize bone as a nanomaterial com-
prised of hierarchical inorganic nano hydroxyapatite and organic collagen. Addi-
tionally, microorganisms such as viruses and bacteria are nanostructures that can
cause diseases in humans [2, 3].
3.5.3.1 DNA Nanostructures
DNA is the genetic blueprint repository of living organisms. It helps in the syn-
thesis of protein, which is essential for the activities of living organisms. Mono-
phosphorylated deoxyribose sugar attached with nitrogenized aromatic nucleobase
is called a nucleotide, and this is the basic structural unit of DNA. DNA possesses
diverse sequence information storage mechanisms with 2.86 bits per linear nanometer
density. A-DNA, B-DNA, and Z-DNA are three types of DNA classification based on
the base-paring between the strands. B-DNA is a right handed double-helical DNA
structure whereas A-DNA is a comparatively short, more-compact, right handed
double-helical structure, and Z-DNA is a left-handed double-helical DNA formed
with long polypurine stretches. These DNAs are nanostructures in organisms and
their interactions with other NMs play a major role in nanomaterial drug formu-
lations [22]. Thus, in recent years, research on artificial DNA nanostructures has
escalated in the field of bionanotechnology.
A phosphate backbone with negative charge, nucleobase with metal chelates, and
the hydrophobic core with aromatic rings are the chemical handles that are respon-
sible for the formation of self-assembled nanostructures through interaction with
inorganic NMs. The formation of DNA-templated metal nanostructures is possible
by localizing transition metal cations on DNA to act as precursors and chemical
handles. DNA nanostructures and DNA attached to NPs have been synthesized for
various applications including nano barcoding and DNA sensors. Research in this
area has advanced to include active self-reconfiguration of 1, 2 or 3-dimensional
DNA-based nanoscale architectures for drug delivery, molecular electronics and log-
ics. Recent developments in DNA technologies such as Holliday junction elucidation
and crossovers help in the virtual assemblage of any DNA structures through DNA
origami. An extensive review on DNA origami, their functions and potential has been
reported in. They mentioned that NP-templated DNA and hybridization- based DNA
are revolutionary particles that will create a positive impact on future biomedical
fields [23].
3.5.3.2 Protein Nanostructures
Antibodies, enzymes, proteins and most organelles within cells are smaller than the
micrometer-scale and are considered nanostructures. Recently, lipids, self-assembled
peptides, and polysaccharides were also included in the list of nanostructures present
in the human body. These nanostructures are artificially manipulated for use in phar-
maceutical industries. Nanozyme, which is an example of such nanostructures, is an
engineered nanometer-scaled artificial enzyme. The enzyme functions to mimic the
general natural enzyme principles. Cyclodextrins, porphyrins, supramolecules, poly-
mers and biomolecules, which include antibodies, nucleic acids and proteins, have
been widely investigated to imitate the structure and function of natural enzymes.
Nanozymes are already under research for applications in biosensing, immunoas-
says, stem cell growth and environmental rehabilitation via pollutant removal. The
viral protein capsids are extensively under research investigation as self-assembling
NPs. Aside from that, manipulation of natural proteins and antibodies with NPs as
well as individual proteins/antibodies are gaining positive biomedical applications.
It is believed that these biomolecular NPs will be highly beneficial for efficient
biomolecule delivery and in therapies and diagnostics for complex diseases and
genetic disorders [2, 3].
3.5.4 Ceramic Nanostructures
Nanostructured ceramics are one class of materials that can successfully be densified
by dynamic compaction, but the technique is certainly not limited to these materi-
als. Magnetic pulse compaction is a commercially used technique for near-net-shape
densifying metal powders into all kinds of shapes with densities close to the theoret-
ical density [24, 25]. The most widespread application is the shaping of gear wheels
for the automotive industry, but also connecting different metals (cold welding) and
polymer-metal connections are performed commercially using MPC. The advantage
of commercial equipment is the ability to compact one sample per second.
3.5.5 Polymer Nanostructures
Recently, the nanostructured metal-polymer and metal oxide—polymer composites

are the subject of increased attention of researchers in different areas of science and
technology. Among the perspectives for using these materials are novel types of solar
cells and chemical gas sensors. The electrical, mechanical, and optical properties of
the nanocomposites are improved by dispersing a metallic phase in a polymeric
matrix. Nanostructured metal (Pd, Sn, Cu, Al)-polymer (poly-para-xylylene) and
metal-oxide-polymer composites reveal synergism of properties of the initial com-
ponents, which gives rise to specific electrical, mechanical, optical and chemical
properties related to an ordered distribution of nanoparticles over the matrix volume
[26]. Various methods of preparing a metal-polymer nanocomposite exist and from
the point of view of homogeneity, methods where polymerization and formation of
the nanoparticles are performed simultaneously are very promising.
3.5.6 Nanocomposites
Composite materials are engineered materials made from two or more constituent
materials with significantly different physical or chemical properties, which remain
separate and distinct on a macroscopic level within the finished structure. One of the
most successful composites in history is concrete; other well-known examples are
plywood and carbon fiber reinforced plastics. By combining two materials to a com-
posite, physical or chemical properties are achieved which are not possible with a
single, homogeneous material. It should not be concealed that also cost aspects have
played a role in the development of nanocomposites, as one can combine an expen-
sive material of distinct properties with a low cost filler material. Nanocomposites
are nanotechnology’s logical progression of composite materials. In nanocompos-
ites, at least one of the constituents is of nanometer size. Thus, in a certain sense
nanocomposites also include porous materials, gels, co-polymers and colloids. By
this approach, a new class of materials with extraordinary optical, magnetic, electrical
and mechanical properties can be achieved. Another important aspect of nanocom-
posites is the fact that—compared to macroscopic composites—the surface to volume
ratio is much higher, typically by at least one order of magnitude. As, for example,
the mechanical properties of nanocomposites are to a large extent determined by the
interface between the two components, this means that much stronger effects can be
obtained by nanocomposites, or that much less amounts of the expensive reinforce-
ment material (e.g. nanotubes, nanofibers) are necessary to obtain the same effect.
One special group of nanocomposites are nanostructures glasses (glasses are per def-
inition amorphous, non-crystalline solids). In fact, glasses containing nanoparticles
are probably the oldest man-made nanocomposites: medieval stained church glasses
contain gold or silver nanoparticles with diameters of 50–100 nm. At the present
time, nanocomposite and other nanostructured glasses are owing to their outstanding
optical, electrical, mechanical and chemical properties again intensively investigated
[27].
3.5.7 Thin Films
Mostly, thin films are used to render the surface properties of a bulk material in those
cases where a change of the bulk properties is too expensive or simply impossible
to achieve for physical or chemical reasons. In addition, combinations of thin films
may serve to achieve complex combinations of surface properties. Thin films are two-
dimensional nanostructures by definition. In the field of optics, thin films are defined
as structures in which interferences effects don’t play a role, i.e. they must be on the
order of the wavelength of the light or even thinner. In the field of semiconductor
electronics, active and passive layers of about 1.2 nm are currently investigated.
Here, the films are moreover meanwhile structured laterally to dimensions of a few
tens of nanometers. In recent times, besides homogeneous films also nanostructured
films play an ever increasing role. Types of films, (i) Multilayer films consisting of
stacks of individual films each of which possesses a thickness of a few nm only, (ii)
Nanocomposite films consisting of nanocrystals embedded in an amorphous matrix,
(iii) Nanocomposite films consisting of nanoparticles, nanotubes etc. embedded in
an amorphous matrix [28].
3.5.8 Nanostructure Computation
Nanostructures also offer opportunities for meaningful computer simulation and

modeling since their size is sufficiently small to permit considerable rigor in treat-
ment. In computations on nanomaterials, one deals with a spatial scaling from 1 Å
to 1 μm and temporal scaling from 1 fs to 1 s, the limit of accuracy going beyond
1 kcal/mol. There are many examples to demonstrate current achievements in this
area: familiar ones are STM images of quantum dots and the quantum corral of
48 Fe atoms placed in a circle of 7.3-nm radius. Ordered arrays or superlattices of
nanocrystals of metals and semiconductors have been prepared by several workers.
Nanostructured polymers formed by the ordered self-assembly of triblock copoly-
mers and nanostructured high-strength materials are other examples. Prototype cir-
cuits involving nanoparticles and nanotubes for nanoelectronics devices have been
fabricated [29].
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Chapter 4
Physics and Chemistry of Nanostructures
Abstract Nanostructural materials are often in a metastable state. Their detailed

atomic configuration depends on nanomaterial fabrication. Therefore, the properties
of nanostructures can be widely adjustable by changing their size, shape and pro-
cessing conditions. The below chapter discuss briefly about physics and chemistry
of nanostructured materials.
4.1 Nanostructured Materials
Nanostructures are unique materials whose size of primary structure has been engi-
neered at the nanometer scale. By the demands of miniaturization, increasing efforts
are being made to synthesize, understand and apply the materials with reduced dimen-
sions. The interest in nanomaterials is growing at a dramatic rate due to realization
that reduced dimensions in nanometer regime can alter and improve the properties
of materials. Nanomaterials have attracted widespread attention because of their
specific features that differ from bulk materials. This has opened up with tailor-
made materials enormous possibilities to meet challenges in different disciplines
like medicine, biotechnology, optoelectronics, engineering etc. of new, effective and
efficient devices, drugs or tools. It is expected that the emerging technology will focus
on challenges of miniaturization and energy saving, covering different technologies
that are existing today [1].
Nanostructured materials are a new class of materials which provide one of the
greatest potentials for improving performance and extended capabilities of prod-
ucts in a number of industrial sectors, including the aerospace, tooling, automo-
tive, recording, cosmetics, electric motor, duplication, and refrigeration industries.
Encompassed by this class of materials are multilayers, nanocrystalline materials and
nanocomposites [2]. Their uniqueness is due partially to the very large percentage of
atoms at interfaces and partially to quantum confinement effects. For bulk materials,
the intrinsic physical properties, such as density, conductivity and chemical reactiv-
ity, are independent of their sizes. For example, if a one-meter Cu wire is cut into
a few pieces; those intrinsic properties of the shorter wires remain the same as in
the original wire. If the dividing process is repeated again and again, this invariance

https://doi.org/10.1007/978-3-030-26145-0_4
48 4 Physics and Chemistry of Nanostructures
cannot be kept indefinitely. Certainly, the properties are changed greatly when the
wire is divided into individual Cu atoms [3]. Significant property changes often start
when we get down to the nanoscales. The following phenomena critically affect the
properties of nanostructural materials:
Quantum confinement: the confinement of electrons in the nanoscale dimen-
sions result in quantization of energy and momentum, and reduced dimensionality
of electronic states.
Quantum coherence: certain phase relation of wave function is preserved for
electrons moving in a nanostructure, so wave interference effect must be considered.
But in nanostructures, generally the quantum coherence is not maintained perfectly as
in atoms and molecules. The coherence is often disrupted to some extent by defects
in the nanostructures. Therefore, both quantum coherent and de-coherent effects
have to be considered, which often makes the description of electronic motion in a
nanostructure more complicated than in the extreme cases.
Surface/interface effects: a significant fraction (even the majority) of atoms in
nanostructure is located at and near the surfaces or interfaces. The mechanic, ther-
modynamic, electronic, magnetic, optical and chemical states of these atoms can
be quite different than those interior atoms [4]. These factors play roles to various
degrees (but not 100%) of importance. For example, the confinement and the coher-
ent effects are not as complete as that in an atom. Both the crystalline (bulk) states
and the surface/interface states cannot be ignored in nanoscale structures. The differ-
ent mixture of atomic/molecular, mesoscopic and macroscopic characters make the
properties of nanostructures vary dramatically. Nanostructural materials are often in
a metastable state. Their detailed atomic configuration depends sensitively on the
kinetic processes in which they are fabricated. Therefore, the properties of nanos-
tructures can be widely adjustable by changing their size, shape and processing
conditions. The situation is similar to molecular behavior in chemistry (e.g., N vs.
N2 ) in certain aspect. Because of the rich and often surprising outcomes, it will be
extremely interesting and challenging to play with nanostructural systems [5].
Only a proper understanding of the dependence of a given property on the particle
size can lead to design of the nanostructured material for the related application. It is
also important to understand when a material could be considered as nanostructured.
Although one can in principle classify materials with grain size less than 100 nm
as nanostructured, several properties such as optical and vibrational properties do
not differ much from the corresponding bulk value unless the grain/particle size is
less than typically 20 nm [6]. In view of this it is reasonable to treat a material with
a grain size smaller than a certain value as nanostructured only if the property of
interest differs from the bulk value at least by a few percent. It is also possible that
a material with nanometer grain size may behave as nanostructured for a specific
property while it could act like bulk for other properties. In addition to the grain
size, the properties of the nanostructured materials may sometimes depend on the
method of their synthesis. Generally nanostructured materials are synthesized in one
of the three forms: (a) as isolated or loosely connected nanoparticles in the form
of powder, (b) as composites of nanoparticles dispersed in another host, or (c) as
compact collection of nanograins as pellets or thin films [7].
The physical and chemical properties of nanostructures are distinctly different

from those of a single atom and bulk matter with the same chemical composition.
These differences between nanomaterials and the molecular and condensed-phase
materials pertain to the spatial structures and shapes, phase changes, energetics,
electronic structure, chemical reactivity, and catalytic properties of large, finite sys-
tems, and their assemblies. Some of the important issues in nanoscience relate to
size effects, shape phenomena, quantum confinement, and response to external elec-
tric and optical excitations of individual and coupled finite systems. Size effects are
an essential aspect of nanomaterials. The effects determined by size pertain to the
evolution of structural, thermodynamic, electronic, spectroscopic, and chemical fea-
tures of these finite systems with increasing size. Size effects are of two types: one
is concerned with specific size effects and the other with size-scaling applicable to
relatively larger nanostructures [8] (Fig. 4.1).
For nanostructured materials, like nanomaterials, morphology has special signifi-
cance since form, in this case, dictates physical and chemical properties. Unlike bulk
materials, properties of nanomaterials are strongly correlated to shape. This shape is
attained during growth through a self-assembling process dictated by the interplay
of size and molecular interactions. Deviations from bulk properties become promi-
nent as the size of nanomaterials starts to be comparable to the size of constituent
molecules or to some other characteristic length scale like electron mean-free path.
In a typical application, one deals with a collection of nanomaterials, which may
be dispersed in a matrix forming a composite material. Properties of this nanocom-
posite are controlled not only by morphology of individual nanomaterials, but also
by the nature of interactions, which, in turn, is determined by the distribution of the
nanomaterials in the matrix [9]. Thin films and multilayer structures may introduce
a 1D confinement effect in addition to the confinement effect arising due to size of
Fig. 4.1 Density of states for metal and semiconductor nanocrystals compared to those of the bulk
and of isolated atoms. Reprinted with permission from © Basics of Nanocrystals, Springer, Berlin,
Heidelberg (2007)
individual nanomaterials in these films. For example, in a thin film, the presence
of different nanomaterials such as nanodots, nanowires, and nanosheets can intro-
duce an additional 3D, 2D, and 1D confinement effect, respectively. In a multilayer
structure, apart from atomic arrangements of deposited materials, the presence of
interfaces defines an additional 1D periodicity.
The additional 1D potential and associated interfaces of a multilayer modify all
physical properties of the deposited materials considerably, and the properties can
be tuned by controlling the shape of the 1D potential. In semiconductors, the direc-
tional nature of chemical bonds causes formation of extremely high quality epitaxial
multilayers. In metals, however, bonding is less directional, and it is more difficult
to achieve comparable perfection. Nevertheless, advanced crystal growth methods
such as molecular beam epitaxy (MBE) and low-pressure metal organic vapor phase
epitaxy (MOVPE) have now made possible the sequential monolayer-by-monolayer
deposition not only of semiconductors but also for metals and insulators, and prac-
tically any combinations thereof [10]. Multilayered organic and metal-organic films
are being studied actively to form model systems for biophysical application and to
understand the self-assembling mechanism observed in physics and biology. One of
the easiest ways to achieve such a film with good ordering in the direction of growth
is the Langmuir–Blodgett (LB) technique. The LB films are very convenient systems
for studying melting of 2D solids, which is expected to be a continuous transition
as opposed to melting of conventional 3D solids. Nanometer-sized semiconductor
particles that exhibit quantum confinement effect in band structure can be formed by
exposing suitable LB films to reactive gases [11].
The development of nanostructured materials has led to a new class of materials
that are single- or multiphase polycrystals with microstructural features, i.e., particle
or grain sizes, layer thicknesses, or domain sizes, in the nanometer range. Owing
to the extremely small dimensions, nanostructured materials have an appreciable
fraction of their atoms in defect environments such as grain or interface boundaries.
For example, nanocrystalline material with an average grain size of 5 nm has about
50% of its atoms within the first two nearest-neighbor planes of a grain boundary,
in which distinct atomic displacements from the normal lattice sites are exhibited.
These unique features have an important impact on their physical and chemical
properties, which may be significantly different compared to conventional coarse
grained polycrystals of the same chemical composition. For example, nanostructured
materials may exhibit enhanced diffusivity, superior soft or hard magnetic properties,
enhanced catalytic activity, ultrahigh strength or hardness, or improved ductility and
toughness in comparison with conventional polycrystals [12].
Superlattices and quantum wells were introduced as man-made quantum struc-
tures to engineer the quantum states for electrical and optical applications. In analysis,
the idea relies heavily on the availability of good heterojunctions, lattice matched
systems, and later, the strained layered systems. To realize quantum states in a given
geometry, the size must be smaller or comparable to the coherence length of electrons,
in order to exhibit quantum interference. This requirement eliminates doping as an
effective means to achieve confinement, except at low temperatures, because dop-
ing comes from charge separation which results in barriers generally far exceeding
the coherence length of electrons at room temperatures. On the other hand, band-
edge alignment of a heterojunction provides abrupt barrier height. This short range
potential is the consequence of higher orders multiples in the atomic potentials [13].
The advent of reliable production of nanostructures has opened a frontier in mate-
rial science. As the size of these structures or devices approaches the nano-meter
scale, the laws of quantum mechanics come into play. Quantum dot structures are
being considered for a variety of technological applications ranging from semi-
conductor electronics to biological applications including optical devices, quantum
communications and quantum computing. The understanding of the quantum struc-
ture’s electronic properties and quantum confinement is of paramount importance.
The basic concept of quantum confinement comes from the interplay of two funda-
mental principles of quantum mechanics; namely the electronic system must obey
the Schrodinger equation and also follow the de Broglie momentum-wavelength
relationship. It is desirable to be able to position the quantum dots in space in a deter-
mined order or pattern. Nucleation site engineering can be used to achieve the spatial
ordering of self-assembled quantum dots. For example, selective area epitaxy and the
anisotropic indium mobility have been used to create narrow ridges and promote the
formation of quantum dots positioned in a single row on such ridges [14] (Fig. 4.2).
Nanostructured materials of varying composition continue to entice the materials
research community with the promise of innumerable practical applications as well
as advancing an understanding of their fundamentals. The exploration of size and
Fig. 4.2 Scaling laws of quantum coefficient. Reprinted with permission from © Nature
Communication (2013)
structure influences on materials properties such as dielectric constant, conductivity,

and luminescence has developed into a burgeoning new subdiscipline of materi-
als science Synthetic strategies routinely achieve complex subarchitectures, sending
pore sizes plummeting into the nanoscale regime, where the ratio of surface atoms to
bulk increases to significant proportions. It is in this size regime that the surface prop-
erties of these materials become of paramount significance. The chemical properties
of the interfacial atoms directly influence the stability, reactivity, and overall utility
of a material in a given application. Although the interfacial regions have proven to
play such a dominant role in the materials properties of these systems, only recently
has their chemical reactivity and stability been intricately explored [15].
The nanostructures have higher surface areas than do conventional materials. The
impact of nanostructure on the properties of high surface area materials is an area
of increasing importance to understanding, creating, and improving materials for
diverse applications. High surface areas can be attained either by fabricating small
particles or clusters where the surface-to-volume ratio of each particle is high, or by
creating materials where the void surface area is high compared to the amount of
bulk support material. Materials such are highly dispersed supported metal catalysts
and gas phase clusters fall into the former category and microporous (nanometer-
pored) materials such as zeolites, high surface area inorganic oxides, porous carbons,
and amorphous silica. The use of the nanostructure approach to high surface area
materials may have significant impact:
• Microporous materials for energy storage and separations technologies, including
nanostructured materials for highly selective adsorption/separation processes such
as H2 O, H2 S, or CO2 removal.
• High Capacity, low volume gas storage of H2 , and CH4 for fuel cell applications
and high selectivity; high permeance gas separations such as O2 enrichment; and
H2 separation and recovery.
• Thermal barrier materials for use in high temperature engines understanding
certain atmospheric reactions.
• Incorporation into construction industry materials for improved strength or for
fault diagnostics.
• Battery or capacitor elements for new or improved operation.
• Biochemical and pharmaceutical separations.
• Product-specific catalysts for almost every petrochemical process [16].
The mechanical behavior of nanostructured materials originates from the unique
mechanical properties first observed and/or predicted for the materials prepared by
the gas condensation method. Among these early observations/predictions were the
following:
• Lower elastic moduli than for conventional grain size materials-by as much as
30–50%.
• Very high hardness and strength-hardness values for nanocrystalline pure metals
are 2–7 times higher than those of larger grained (>111) metals.
• A negative Hall-Petch slope, i.e., decreasing hardness with decreasing grain size
in the nanoscale grain size regime.
• Ductility-perhaps superplastic behavior-at low homologous temperatures in brittle
ceramics or intermetallics with nanoscale grain sizes, believed due to diffusional
deformation mechanisms [17].
References
1. Harik VM, Salas MD (2003) Trends in nanoscale mechanics. ICASE LaRC interdisciplinary
series in science and engineering, 9th edn. Springer
2. Champion Y, Fecht HJ (2004) Nano-architectured and nanostructured materials. WILEY-VCH
Verlag GmbH & Co, KGaA, Weinheim
3. Nalwa HS (2000) Handbook of nanostructured materials and nanotechnology. Academic Press
4. Lockwood DJ (2004) Nanostructure science and technology. Kluwer Academic Publishers,
Boston
5. Yan H, Yang P (2003) Semiconductor nanowires: functional building blocks for nanotechnol-
ogy. World Scientific Publishing Co. Pte. Ltd., Singapore
6. Ramrakhiani M (2012) Nanostructures and their applications. Recent Res Sci Technol 4:14–19
7. Arora AK, Rajalakshmi M, Ravindran TR (2004) Phonon confinement in nanostructured
materials. Encyclopedia Nanosci Nanotechnol 8:499–512
8. Biener J, Wittstock A, Baumann TF (2009) Surface chemistry in nanoscale materials. Materials
2:2404–2428
9. Hollingsworth MD (2002) Crystal engineering: from structure to function. Science 295:2410–
2413
10. Weissbuch C, Vintner B (1991) Quantum semiconductor structures: fundamentals and
applications. Academic, Boston
11. Sanyal MK, Datta A, Hazra S (2002) Morphology of nanostructured materials. Pure Appl
Chem 74:1553–1570
12. Eckert J (2007) Structure formation and mechanical behavior of two-phase nanostructured
materials. In: Nanostructured materials, pp 423–526
13. Tsu R, Zhang Q (2007) Nanostructured electronics and optoelectronic materials. In: Nanos-
tructured materials, pp 527–568
14. Denison AB, Hope-Weeks LJ, Meulenberg RW et al (2004) Quantum dots. In: Introduction to
nanoscale science and technology. Kluwer Academic Publishers, New York
15. Porter LA, Buriak JM (2003) Harnessing synthetic versatility toward intelligent interfacial
design: organic functionalization of nanostructured silicon surfaces. In: The chemistry of
nanostructured materials. World Scientific Publishing Co. Pte. Ltd., Singapore
16. Siegel RW, Hu E, Roco MC (1999) Nanostructure science and technology. WTEC panel on
nanoparticles, nanostructured materials, and nanodevices. Springer, Dordrecht
17. Gleiter H (2000) Nanostructured materials: basic concepts and microstructure. Acta Mater
48:1–29
Chapter 5
Quantum Effects, CNTs, Fullerenes
and Dendritic Structures
Abstract Nanostructural materials have wide classification of structures based on

their fabrication methods. Fullerenes are close-caged molecules containing only
hexagonal and pentagonal interatomic bonding networks. Carbon nanotubes are
large, linear fullerenes with aspect ratios as large as 103 –105 . Nanotubes as many
derivatives like nanocones, nanosprings, etc. The chapter detailed about different
nanostructures and its properties.
5.1 Fullerenes Structures
Fullerenes a interrelated research field including organic transformations of these

all-carbon hollow-cluster materials has emerged. C60 has been the most thoroughly
studied member of fullerenes because it (1) is produced abundantly in the carbon soot
by the arc discharge of graphite electrodes, (2) has high symmetry, (3) is less expen-
sive, (4) is relatively inert under mild conditions, and (5) shows negligible toxicity.
Electronically, C60 is described as having a closed-shell configuration consisting of
30 bonding molecular orbitals with 60p electrons, which give rise to a completely
full fivefold degenerated highest occupied molecular orbital that is energetically
located approximately 1.5–2.0 eV lower than the corresponding antibonding lowest
unoccupied molecular orbital (LUMO) one [1]. The first electron in the reduction
of C60 is added to a triply degenerate t1u unoccupied molecular orbital and is highly
delocalized. This threefold-degeneracy, together with the low-energy possession of
the LUMO, makes C60 a fairly good electron acceptor with the ability of reversibly
gaining up to six electrons upon reduction. The facile reduction contrasts with its dif-
ficult oxidation. Only the first three reversible oxidation waves have been observed.
This high degree of symmetry in the arrangement of the molecular orbitals of C60
provides the foundation for a plethora of intriguing physicochemical, electronic, and
magnetic properties. Semiconducting, magnetic, and superconducting properties of
unmodified C60 have been intensively investigated; however, these properties remain

https://doi.org/10.1007/978-3-030-26145-0_5
56 5 Quantum Effects, CNTs, Fullerenes and Dendritic Structures
to be explored for functionalized fullerenes. On the other hand, nonlinear optical

and photophysical properties of functionalized fullerene materials have been already
under investigation. The skeleton of C60 consists of 20 hexagonal and 12 pentagonal
rings fused all together.
The chemical reactivity of C60 is that of a strained electron deficient polyalkene,
with rather localized double bonds. Cyclo addition reactions have been widely
applied for the functionalization of fullerenes. Usually, addition occurs across ring
junctions where electron density is much higher than at the ones. Other reactions
that take place on the spherically shaped carbon core of fullerenes involve additions
of nucleophiles, free radicals, and carbenes as well as η2 -complexation with vari-
ous transition metal elements. In such fullerene adducts, the functionalized carbon
atoms change their hybridization from a trigonal sp2 to a less strained tetrahedral
sp3 configuration; thus, the primary driving force for addition reactions is the relief
of strain in the fullerene cage. Furthermore, the regiochemistry of the addition is
governed by the minimization of the 5,6-double bonds within the fullerene skeleton
[2]. Therefore, any 1,2-addition reactions occur to produce ringclosed 6,6-adducts,
having two sp3 carbon atoms on the fullerene framework. However, sometimes ring-
opened 6,5-adducts (fulleroids) are formed, keeping all fullerene carbon atoms sp2 -
hybridized. The main advantage gained upon functionalization of fullerenes is a
substantial increase in their solubility. The existence of a great diversity of synthetic
protocols combined with the high number of chemical reactions that have been mainly
applied to C60 has led to the formation of a wide variety of functionalized fullerenes.
The special characteristics of the added groups, coupled with the unique structural,
physicochemical, and electronic properties of fullerenes (which in most of the cases
are retained after functionalization), have aided the development of new materials
with tremendous potential in fascinating and widespread technological applications
such as electronic and optoelectronic devices, light-emitting diodes, photovoltaics,
and thermotropic liquid crystals [3].
New supramolecular motifs of fullerenes with concave–convex structures have
been developed very recently by π-stack interactions. It comprises interactions
between fullerenes and different curved carbon structures, such as nanorings or nan-
otubes. Both structures have π-orbitals oriented radially, as well as the fullerenes.
Nanorings are closed loops formed by conjugated π-orbitals. They are very inter-
esting from the point of view that they can host different molecules depending on
the size of the ring. Fullerenes can be hosted by nanorings. They prepared [6]-
and [8]paraphenyleneacetylene and studied their complexation with C60 and with
bis(ethoxycarbonyl)methanofullerene.
The experiments with C60 showed the formation of a 1:1 supramolecular com-
plex with [6]paraphenyleneacetylene (Fig. 5.1) and the association constant was
determined (Ka = 16,000 M−1 ). The same measurements were attempted with
bis(ethoxycarbonyl)methanofullerene but the changes in absorption were too small to
measure a reliable association constant. On the other hand, it was possible to obtain an
X-ray structure from the fullerene monoadduct and [6]paraphenyleneacetylene, con-
firming the structure of the complex. The experiments with [8]paraphenyleneacety-
lene showed none or very small complexation with C60 . In a different article from
5.1 Fullerenes Structures 57
Fig. 5.1 C60 -nanoring complex
the same authors, the complexation of C60 and C70 with [6]- and [7]paraphenyle-
neacetylene was studied. Also other complexation studies were carried out with
the novel isomers of [7]paraphenyleneacetylene that have 1,4- or 2,6-naphtylene
units diametrically opposed [4]. The calculation of the association constants was
attempted but they were too large to be determined precisely (>5 × 104 ), which
indicated that very stable complexes were formed. Fluorescent measurements were
carried out from these complexes, providing a lot of information about the esti-
mated relative stability of the whole series of rings with C60 and C70 . The results
were consistent with the values of the association constants and also showed that
the new naphtylene nanorings are very efficient fluorescent sensors for fullerenes.
During the synthesis and purification of the different paraphenyleneacetylene and
1,4-naphtyleneacetylene nanorings, it was found that big rings could form inclusion
complexes with smaller rings. [6]Paraphenyleneacetylene could be inserted within
the larger [9]paraphenyleneacetylene, the association constant could only be deter-
minates at −60 °C (Ka = 340 ± 45 M−1 ). The same behavior was observed with
the analogous 1,4-naphtyleneacetylene nanorings showing much higher association
constants at −60 °C (Ka = 11,000 ± 1400 M−1 ) because of the larger contact area.
In order to prepare complexes including fullerenes, C60 was first included within the
smaller ring as done in previous experiments and subsequently these complexes were
then assembled with the larger ring. NMR experiments proved the formation of these
onion-type complexes (Fig. 5.2). The association constants could only be calculated
for the [9]paraphenyleneacetylene ([6]paraphenyleneacetylene C60 ) complex at −
Fig. 5.2 C60 Onion type

complex
Fig. 5.3 Carbon peapods
60 °C (Ka = 410 ± 80 M−1 ). Other interesting structures known as carbon peapods

have been developed in the last years. Carbon peapods are single-walled carbon nan-
otubes (SWCNTs) that are filled with fullerenes (Fig. 5.3). They are considered as a
new supramolecular carbon allotrope.
Carbon peapods were first reported in 1998, when they were detected by high-
resolution transmission electron microscopy (HRTEM) as side products during the
production of carbon nanotubes. Since then, several methods for the efficient filling
of empty SWCNTs have been developed. Carbon peapods were prepared from raw
nanotubes produced by pulsed laser vaporization. Several defects were introduced on
the surface of the nanotubes by refluxing the material in nitric acid, thus facilitating
the insertion of fullerenes. Subsequently they were annealed at high temperatures
and low pressures. C60 was only inserted in 1.3–1.4 nm diameter SWCNTs that are
the only ones that permit the preferred graphitic 0.3 nm van der Waals separation
between the fullerene and the nanotube [5].
5.2 Nanostructures
Common to the synthesis or deposition of bulk and nanocrystalline solids—whether

from the liquid or vapor phase—are the concepts of nucleation and growth. Nucle-
ation of the solid phase on a surface or in solution, by definition involves the initial
formation of clusters of atoms due to supersaturation and subsequent precipitation
of a selected elemental species or compound. Viewing synthesis of nanostructures
as the early stage of bulk crystal growth, it should be emphasized that in contrast to
0-D and 2-D growth, the formation of 1-D structures is far less likely to occur in the
absence of a symmetry-breaking event, of interfacial strain between the substrate and
the nuclei, or of differences among crystallographic surfaces that can lead to strongly
anisotropic growth rates [6]. Some 1-D nanostructured materials may be grown using
methods in which there is inherent growth rate anisotropy to the crystalline structure.
However, for other technologically important materials (e.g., Si, GaAs) crystalline
structure alone often does not typically provide the necessary driving force to over-
come more energetically favorable growth modes. Thus, a central challenge in the
rational synthesis of 1-D nanostructured materials is to employ growth conditions,
which employ a symmetry-breaking feature. Additionally, for some applications and
5.2 Nanostructures 59
fundamental studies, methods that permit dislocation and twin-free structures or pre-
cise control of diameter and length, and size dispersion may be important. In some
situations, methods that produce periodic or non-periodic arrays of aligned nanostruc-
tures may be desired. Finally, the need to adapt a process for other material systems or
compositions to carry out growths at lower temperatures, to have compatibility with
existing processes, and adaptability for multi-component architectures, are important
considerations. The methods of synthesizing single-crystalline 1-D nanostructured
materials from the bottom-up may be classified into those that employ inherent crys-
talline anisotropy, those that exploit a metal nanoclusters catalyst to facilitate 1-D
growth, those that rely on templates, and those that rely on kinetic control and capping
agents. Specifically, kinetic control is gained by monomer concentration or by mul-
tiple surfactants, bringing about conditions that strongly favor anisotropic growth.
Though not discussed here, self- or directed-assembly of 0-D nanostructures into 1-D
nanostructures, and size reduction of 1-D structures are additional process routes.
Alternatively, one can classify the strategies into chemical solution-based syntheses,
and those via vapor condensation routes, by metal organic-vapor phase, by thermal
means, or by laser ablation [7].
5.3 Laser-Assisted Metal-Catalyzed Nanowire Growth
In laser-assisted metal-catalyzed nanowire growth (LCG), laser ablation of a target

containing the desired NW material(s) provides the source; the process is based, in
part, on pulsed laser deposition (PLD), a common route for producing a wide variety
of different classes of inorganic thin-film materials. The LCG method involves the
flowing of an inert or carrier gas through a furnace, and the use of a laser-ablation
target and of a growth substrate with metal nanocluster-catalyst particles. Alterna-
tively, the catalyst material may be contained within the target, and may be prepared
by sintering appropriate components. In general, laser wavelengths λe for LCG are
chosen so that the optical absorption depth is shallow in order to maximize the effect
of heating over a relatively small volume. Often, for growth of semiconductor NWs,
an Nd:YAG (λe = 1064 nm, or frequency doubled or tripled) or an excimer laser (e.g.,
ArF, KrF, or XeF) is used. Ablation targets are typically placed at the upstream end,
and in cases where heating of the target is needed, within the hot zone. Alternatively,
if the required selected NW growth and furnace temperature is higher than the melt-
ing point of the target, targets are placed just outside the furnace. The LCG method is
a highly versatile route for obtaining a wide range of NW materials—many materials
can be prepared via laser ablation. It is also attractive in that the laser ablation route
eliminates the need for gaseous precursors, many of which are toxic and, in some
cases, also pyrophoric. Many of the target materials are widely available or can be
prepared, for example, by sintering of particle components. Moreover, the method
can be used in conjunction with a vapor deposition process to yield NWs having solid
solutions and periodic segments of different composition. The LCG methods can be
pursued as a synthesis route even in the absence of detailed phase diagrams. Despite
its versatility, a shortcoming of the LCG method for the growth of semiconducting
NWs (when used alone) is that the targets themselves typically must contain all of
the components required for the NW. This limits the ability to control the introduc-
tion of dopants or other dilute impurities during growth, or the ability to adjust the
composition. Moreover, to date, precise control of diameter, diameter dispersion,
and synthesis of ultra-narrow (below ~10 nm) NWs has not been demonstrated with
LCG [8].
5.4 Hierarchal Complexity in 1-D Nanostructures
The important features of inorganic-nanomaterial synthesis by surfactant-mediated

chemical routes are the possibility of controlling the size and shape of nanostruc-
tures, thereby effectively manipulating their properties. The growth range of nanos-
tructures by varying the relative concentrations of two types of surfactants–TOPO
and hexylphosphonic acid (HPA) and systematically varying the monomer concen-
tration with time. The HPA serves to accentuate the difference between growth rates
on different crystal faces. Different systematic variations yield long rods, arrow-
shaped NCs, teardrop-shaped NCs, tetrapods, and dendritic tetrapods. The differ-
ences between wurtzite and rocksalt free energies and surface energetics govern the
evolution of some of these structures-particularly stacking faults in the tetrapods.
This explains the topology in terms of abrupt changes in the crystal structure, from
wurtzite in the rod segments to rock salt in the sphere-like vertices.
The investigations indicated that multiphase description of the tetrapod, and the
corresponding model of their formation may not be valid: rather, it seems that the
tetrapod nanostructures may consist of single phase, and that it is likely that the for-
mation of twins plays a significant role in the unique evolution of their topologies.
The control of the relative axial and radial growth rates is the basis for the synthesis of
coaxial or core–shell nanostructures as discussed above. In our laboratory at Drexel,
we have demonstrated the growth of apex-angle-controlled crystalline Si nanocones
(Si NCs) and Ge nanocones (Ge NCs) of diamond-hexagonal phase through simul-
taneous control of axial and radial growth rates using metal catalyzed CVD; we have
also synthesized single-crystalline Ge nanosprings and characterized its composi-
tion and crystallinity with electron microscopy and Raman scattering. As shown in
Fig. 5.4, the Si NCs are tapered polyhedral, possessing hexagonal cross-sections.
They are typically several microns in base diameter, and the radius of curvature at
the tip is as small as 1–2 nm. Significantly, these nanocones are of the diamond
hexagonal polymorph, and the taper angles can be tuned during growth. These Si
NCs may offer new opportunities as scanning probes and as central components in
single-molecule sensing [9] (Fig. 5.5).
The integration of two or more semiconductor or other materials and the con-
trolled incorporation of dopants within individual components of nanostructures are
essential characteristics of the advancing development of nanowires (NWs) as build-
ing blocks for nanotechnology. Homo- and heterojunctions within individual NWs
5.4 Hierarchal Complexity in 1-D Nanostructures 61
Fig. 5.4 Different phases of NW growth. Reprinted with permission from © Top Curr Chem, 226,
119–172 (2003)
enable fabrication of bipolar devices within individual NWs, opening up possibilities

for light-emitting diodes, photodetectors, and band gap-engineered devices within
individual NWs, and even NW-based superlattices. Some synthesis methods permit
formation of hierarchal nanostructures, including NWs with segments composed of
different materials. For most electronic or photonic device applications, synthesis of
single-crystalline components with some degree of control of composition at inter-
faces is desired. The synthesis of hierarchal nanostructures via metal-catalyzed and
catalyst-free VLS and solid–liquid–solid methods has been demonstrated success-
fully in several semiconducting and functional-oxide material systems. Specifically,
Fig. 5.5 Silicon nanocones (Si NCs) formed by metal nanocluster-catalyzed CVD. The left panel
shows an array of nanocones, which are tapered polyhedral, possessing hexagonal cross-sections.
These Si NCs are typically several microns in base diameter. As shown in the panel on the right,
the radius of curvature at the tip is as small as 1–2 nm. Reprinted with permission from © Taylor
& Francis Group, CRC press (2006)
modulation of composition and doping in axial and radial directions in a number of

material systems has been achieved [10] (Figs. 5.6 and 5.7).
Fig. 5.6 Representative polar surface-dominated, single-crystalline, zinc oxide 1-D nanostructures.
Reprinted with permission from © Thin Solid Films, 562, 291–298 (2014)
5.5 Mechanical and Thermal Properties 63
Fig. 5.7 Scanning electron micrograph of crystalline germanium nanosprings. The formation of
nanosprings having inversion symmetry may generate further debate on the formation mechanisms
of these and similar structures, in both polar and nonpolar crystalline materials. Reprinted with
permission from © Applied Physics Letters, 88, 193105–193107 (2006)
5.5 Mechanical and Thermal Properties
The mechanical properties of materials are not scale-invariant. For example, the
materials that undergo plastic deformation, the so-called Hall and Petch behavior—
the increase in the hardness and yield strength of a polycrystalline material with
reduction in grain size—involves the relative increase in the area of grain boundaries
and the associated piling up of dislocations. The reduction in grain size leads to
more impediments to dislocation motion and results in a scale-dependent toughness,
though there exists a finite nanoscale size for which the toughness reaches a maxi-
mum. With respect to ceramic nanomaterials, relatively little has been reported on the
scaling of mechanical properties in the semiconducting and oxide NW or nanobelt
materials [11].
Thermal conduction via phonons is expected to be significantly reduced in narrow
NWs. When the dimensions of a NW approach the mean free path of phonons, the
thermal conductivity is reduced relative to bulk values by scattering of phonons
by surfaces and interfaces. The miniaturization of electronic and photonic devices,
e.g., the higher number density of transistors, is accompanied by new challenges
in effective thermal management. A figure of merit for thermoelectric materials,
however, involves the unusual combination of poor thermal conductivity with high
electrical conductivity. Yang and his group at Berkeley have demonstrated that axial
periodicity in Si/SiGe axial superlattice NWs may be highly effective in tuning NW

thermal conductivities for thermoelectric applications; they reported the reduction
in the thermal conductivity of Si/SiGe superlattice NWs by five times, compared
with elemental undoped Si NWs of the same diameter. Raman scattering is one
of the most powerful experimental tools for characterizing lattice dynamics and
corresponding thermodynamic properties in solids. A number of investigations have
been performed to characterize the effects of finite size and wire-like geometry on
the confinement of phonons. Theoretical predictions indicate that for Si NWs of
diameters <~20 nm, phonon dispersions become altered and group velocities are
lowered relative to bulk values. Reduction in NW diameter is accompanied by a
downshifting and asymmetric broadening of the Raman line shape, and has been
attributed to the confinement of optical phonon(s). In perfect bulk single crystals
with no loss of translational symmetry, first-order Raman scattering is restricted to
q = 0 phonons in accordance with momentum selection rules.
The reduction of size, leads to the relaxation of these selection rules and necessi-
tates an inclusion of a larger fraction of the dispersion curves away from the point.
A model for including and averaging q → 0 phonons was developed and applied by
Richter et al. and by Herman and coworkers. This Gaussian-correlation model has
been used to describe the sampling of the phonon dispersion, and is widely used to
model phonon confinement in nanostructures, including NWs. Enhancements of the
model is included to incorporate known-size dispersion and the effects of strain via
a Gruneisen parameter. In addition, the effects of lattice strain at and near the NW
surface defects, and coupling of free carriers to longitudinal optical phonons in degen-
erately doped semiconductors may also affect the Raman line shapes and zone-center
phonon energies. The use of hierarchal nanostructures becomes more prevalent in
nanoelectronics and nanophotonics, Raman scattering will continue to play a unique
role in the evaluation of 1-D nanostructure materials and devices, including, for
example, crystal structure and quality, interfacial strain, thermal management, and
strongly correlated electron behavior [12].
5.6 Electronic Properties of Nanowires
Since the invention of modulation doping and the higher electron mobility transistors
by, precise control of the composition in semiconductors remains a critical compo-
nent to 2-D electronic and photonic devices. In a seminal 1980 publication, pointed
out that the restriction of electronic carriers to 1-D from 2-D or 3-D would result in
significantly reduced carrier-scattering rates, owing to the reduction in the possible
k-space points accessible to carriers. In general, electronic-carrier mobility in real
systems can be affected by the scattering of carriers in a number of ways: scatter-
ing by other carriers, by surfaces, by interfacial roughness, by acoustic phonons,
optical phonons, impurities, and by plasmons. Significant theoretical and experi-
mental work involving electronic transport in CNTs has helped in distinguishing
5.6 Electronic Properties of Nanowires 65
ballistic and diffusive modes of transport. However, for free-standing semiconduc-

tor NWs, experimental and theoretical consensus of carrier-scattering mechanisms
that are most significant in single- and multicomponent coaxial semiconductor NWs
is less clear. In some cases, carrier mobilities in Si NW-field effect transistors and
transconductance values have been reported to exceed those associated with conven-
tional Si planar technology devices. Even if the mobility of carriers in semiconductor
NWs in a given device is lower than that in the corresponding bulk material, there
are a number of other possible advantages to 1-D transistor devices over their 2-D
counterparts. With respect to electronic properties, NWs represent an important link
between bulk and molecular materials. The electronic properties of many bulk semi-
conductors, including oxide semiconductors, are well known, and the electronic-band
structures have, in many cases, been modeled in great detail [13]. Systematic control
of NW diameter enables systematic investigation of the effects of dimensionality
on electronic transport. In general, the diameter below which electronic transport
is significantly altered is related to the degree of confinement of carriers and exci-
tons, the Fermi wavelength and Coulomb interactions, although NWs with larger
diameters still possess significant surface-to-volume ratios that can affect electronic
transport via surface scattering. Semiconductor NWs, like CNTs, are currently being
investigated for elements in nanoscale spintronic devices by introducing dilute con-
centrations of magnetic dopants. Several groups have reported successful doping of
semiconductor NWs with manganese, using different methods. There are numer-
ous reports on the field emission properties of transition metal oxide nanowires and
semiconductor nanocones. There have been a number of simulations reported of the
electronic transport and properties of semiconductor NWs. The strategies can be
classified into effective mass and k · p methods, tight-binding theory, and pseudo
potential approaches. In the past, the sizes of unit cells required to describe NWs,
using first-principles density functional theoretical (DFT) methods, were too com-
putationally expensive to pursue; this has changed of late. DFT study of the struc-
tural and electronic properties of [111]-oriented Si-Ge core–shell interface in very
small-diameter (1–2 nm) NWs. Significantly, the authors found positive and negative
deviations from Vegard’s law for compressively strained Ge and tensile-strained Si
cores respectively. They also found that the direct-to-indirect transition for the fun-
damental band gap is found in Ge-core/Si-shell NWs, while Si-core/Ge-shell NWs
preserve a direct energy gap almost over the whole compositional range. The ear-
lier study reported the density-functional theoretical simulations of electronic-band
structure and optical properties of Si NWs, predicting that NWs having a principal
axis along [110] possess a direct gap at the point for wires modeled up to 4.2 nm
in diameter. These findings hold significant promise for the potential application of
such Group IV single component and coaxial NW heterostructures for a broader
range of photonic applications. The formation of addressable 0-D semiconductor
structures is important for fundamental studies of electronic transport phenomenon,
and for future applications in single-electron transistors, quantum computing, and
metrology.
Axial modulation of the composition of NWs may be used to produce precisely
located 0-D and 1-D segments within NWs. The authors reported the fabrication of
single-electron transistors and resonant-tunneling diodes by producing heterostruc-

tural interfaces separated by as few as several monolayers or as many as large as
hundreds of nanometers. In addition, the authors have recently used these so-called
1-D/0-D/1-D structures to fabricate nanowire-based, single-electron memory devices
[14]. Superlattices in NWs based on these structures may enable extension of the
quantum cascade laser as pioneered. Addressability of individual NWs for elec-
tronic and optical devices is an important consideration for practical applications:
among the developments in this area, reported on the use of NW-crossbar arrays
as address decoders. Electronic transport in semiconductor-NW devices has been
shown to be a highly sensitive means of selective binding and detection of molecules
on NW surfaces functionalized with receptors. Nanowire-based detection of a num-
ber of analytes, including the prostate-specific antigen (pSA), label-free, single virus
detection has been demonstrated. NW arrays with selectively functionalized NW sur-
faces represent one of the frontiers in high-sensitivity detection of a broad range of
chemical and biological molecules and other species. An overview of this work has
been presented in a recent review. Among the most significant recent achievements
pertaining to electronic transport are reports of coherent transport in molecular scale
semiconductor NWs and the report of formation of a 1-D hole gas in a Ge/Si NW
heterostructure. The authors reported room-temperature ballistic hole transport in
semiconductor NWs with electrically transparent contacts, opening important fur-
ther possibilities for new fundamental studies in low-dimensional, strongly correlated
carrier gases and high-speed, high-performance nanoelectronic devices based on
semiconductor NWs. The proximal superconductivity was reported in semiconduc-
tor NWs, in which the electronic transport characteristics of InAs NWs with closely
spaced aluminum electrodes were measured at temperatures below the supercon-
ducting transition temperature of Al. The NW-electrode interfaces act as mesoscopic
Josephson junctions with electrically tunable coupling [15].
5.7 Optical Properties of Nanowires
In NWs, like their 0-D nanostructure and 2-D ultrathin film counterparts, confinement
of electronic carriers leads to altered electronic-band structures that are manifested
as changes in band-to-band transition emission and absorption energies, and changes
in other optical properties according to the degree of confinement. In order to provide
a basic description of the effect of the confinement of electronic carriers to within a
NW, the electronic wave functions and bound-state energies are obtained by solving
the Schrodinger equation under the effective mass model and with the assumption
that the NW has a circular cross-section. One of the most exciting developments
involving the optical properties of NWs is the demonstration of room-temperature
lasing emission in the ultraviolet from individual NWs. The well-faceted ZnO and
GaN NWs produced using VLS growth methods and having diameters from 100
to 500 nm support predominantly axial Fabry–Perot waveguide modes, which are
separated by λ = λ2 /[2Ln(λ)], where L is the cavity length and n(λ) the group
5.7 Optical Properties of Nanowires 67
index of refraction. Structures with smaller diameters are prevented from lasing due
to diffraction, and photoluminescence emission is lost in the form of surrounding
radiation. The lasing in CdS NW optical cavities was also reported. The flexibility of
the hierarchal structure of NWs has also been applied to NW lasers. Using the core–
shell GaN/Al0.75 Ga0.25 N configuration, others works provide simultaneous exciton
and photon confinement in NW cores having diameters as small as 5 nm much smaller
than the normal minimum to avoid the diffraction effects that prevent lasing. The
Berkeley group has extended these concepts to a family of NW photonic components,
and taken advantage of the ability of these NWs to sustain significant deformation
without fracture in order to develop NW-based optical networks and devices. In fact,
the large nonlinear optical response of ZnO NWs may enable these to be used in
optical frequency conversion for nanoscale optical circuitry. Semiconductor nanos-
tructures with wide band gaps (e.g., TiOx ) have emerged as important components
in a new class of photovoltaic devices. Highly conductive wide band gap transition
metal oxide nanostructures have been used in dye-sensitized solar cells to provide
a conductive path for the collection of photoexcited carriers. The dye-sensitized
solar cells based on aligned ZnO NWs offer features of a large specific surface area,
connectivity for carriers, and the desired optical response [16].
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Chapter 6
Semiconductors, Organic and Hybrid
Nanostructures
Abstract Nanostructures vary according to their materials used as organic, inor-

ganic or hybrid structures. The nanostructured material has at least one dimension
confinement and has intermediate size between macro and microscale materials.
This chapter describes about the semiconductor nanostructures, organic and hybrid
nanostructures and its types, also their fabrication techniques explained in detail.
6.1 Semiconductor Nanostructures
6.1.1 Quasi-One-Dimensional Systems
In nanotubes, the screened potential can be expanded into a series in terms of cylindri-
cal harmonics. The behavior of the zero and all other harmonics is qualitatively differ-
ent. The zero harmonic, i.e., the axially symmetric part of the potential, experiences
logarithmically weak screening:
V0 (z) ∼ e2 /z ln2 [z/a]
(a is the nanotube radius). All higher harmonics are screened in accordance with
the dielectric type, and the effective permittivity depends on the harmonic number
as:
2
π kn
εn = 1 +
ma ∗ n
where κ n is the polarization operator of electrons at the zero frequency and zero
longitudinal momentum corresponding to virtual transition with a change of the
azimuthal quantum number by n [1].

https://doi.org/10.1007/978-3-030-26145-0_6
70 6 Semiconductors, Organic and Hybrid Nanostructures
6.1.2 Double Quantum Well
The matrix elements of the bare and screened potentials are related by a matrix
dielectric function. Its form follows from the system at zero frequency. In the case of
a two-component plasma (two parallel plasma layers), the potential of the Coulomb
centrum located in one of the layers decreases at large distances as 1/ρ3 , i.e., in the
same manner as it happens in a single layer of two-dimensional electrons. However,
the coefficient at ρ−3 now depends on the population of the layers, and it is no longer
a universal constant e~2 a*2 .
6.1.3 The Size of Semiconductor Nanostructures
The physics of semiconductor nanostructures has a lot in common with other areas of
physics. Figure 6.1 is an attempt to illustrate some of these links. The relations with
materials science and electronics have already been mentioned above. Beyond that,
modern semiconductor electronics is an integrated part of measurement equipment
that is being used for the measurement of the physical phenomena. The physics of low
temperatures is very important for experimental apparatus such as cryostats which
are necessary to reveal quantum phenomena in semiconductor nanostructures. The
world of nanostructures starts below a characteristic length of about 1 μm and ends at
about 1 nm. Of course, these limits are not strict and not always will all dimensions
of a nanostructure be within this interval. For example, a ring with a diameter of
5 μm and a thickness of 300 nm would certainly still be called a nanostructure. The
special property of structures within this size range is that typically a few length
Fig. 6.1 The physics of semiconductor nanostructures is related to many other areas of physics
6.1 Semiconductor Nanostructures 71
Fig. 6.2 Layer sequence in a

typical GaAs/AlGaAs
heterostructure with remote
doping
scales important for the physics of these systems are of comparable magnitude. In
semiconductor nanostructures this could, for example, be the mean free path for
electrons, the structure size, and the phase-coherence length of the electrons [2].
6.1.4 Electrostatics of a GaAs/AlGaAs Heterostructure
Consider a GaAs/AlGaAs heterostructure as it is depicted schematically in Fig. 6.2.

As a first step we are interested in the electrostatic description of this structure. For
simplicity we assume that the relative dielectric constants of GaAs and AlGaAs are
identical. We choose the z axis in the growth direction of the crystal, normal to the
hetero interface with its origin, z = 0, at this interface. The AlGaAs barrier material
is in the region z < 0, GaAs fills the half space z > 0. On top of the GaAs cap layer a
thick metal layer has been deposited.
6.1.5 Applications of Semiconductor Nanostructures
The applications of semiconductor nanocrystals in biotechnology have been high-

lighted recently by a broad variety of applications in the study of subcellular processes
of fundamental importance in biology. These applications include the use quantum
dots as a new type of fluorescent probes as well as their use as active electronic and
optical components in nanostructure–biomolecule complexes of potential utility in
influencing bimolecular processes in cells.
Likewise, carbon nanotubes (CNTs) portend many applications in nanobiotech-
nology as a result of their nanoscale diameters and as a result of the fact that they
may be produced as metallic or semiconducting nanostructures. The potential appli-
cations of carbon nanotubes in bioengineering were reviewed by its basic structural
and electronic properties of carbon nanotubes. Advances in nanomaterials have pro-
duced a new class of fluorescent probes by conjugating semiconductor quantum
dots (QDs), also known as semiconducting nanocrystals, with biomolecules that
have affinities for binding with selected biological structures. These inorganic dyes
have great advantages over conventional organic dyes; such advantages include the
option for continuously and precisely tuning the emission wavelength of quantum
dots by changing the size of the nanocrystal; narrow symmetric emission spectra;
a single light source can be used for simultaneous excitation of multiple semicon-
ductor quantum dots with different emission spectra of longer wavelengths than the
source; ability to function through repeated cycles of excitation and fluorescence for
hours; and extreme stability of coated quantum dots against photobleaching as well as
changes in the pH of the biological electrolytes that are ubiquitous in biological envi-
ronments. These novel optical properties render quantum dots ideal fluorophores for
ultrasensitive, multicolor, and multiplexing applications in cell and molecular biol-
ogy as well as in bioengineering. Similar studies with carbon nanotubes (CNTs)
have emphasized the use of chemically functionalized CNTs to achieve specificity
in binding to biological structures and how an electrolyte facilitates the control of
the electrical properties of a CNT [3].
6.2 Organic Nanostructures
Organic electronic material’s has made remarkable technological breakthroughs for

the last decade, enabling the realization of viable devices such as organic light-
emitting diodes (OLEDs), organic field-effect transistors (OFETs), organic solar
cells as well as memory circuits. Some products such as medium resolution emissive
OLED displays are already commercially available and others are now in various
stages of commercialization. On the other hand, nanoscale technology has clear
advantages to be gained from exploiting self-organized growth, as it avoids the need
for highly sophisticated patterning of surfaces with nanometer size objects.
Preferably, in organic applications the functional properties can be obtained essen-
tially in one self-assembled molecular layer, so that organic electronics in principle
would offer a maximum degree of miniaturization. Aniosotropic molecule especially
p-sexiphenyl shows a typhical solid state herring bone structure (Fig. 6.3). π–con-
jugated polymers combine properties of classical semiconductors with the inherent
processing advantages of plastics and therefore play a major role in low cost, large
area optoelectronic applications. Unfortunately, polymers are highly disordered in
the solid state. Consequently, carrier transport is dominantly influenced by localiza-
tion resulting in low charge carrier mobilities (μ 1 cm2 V−1 s−1 ). Therefore, an
important part of research aims toward significant improvement in the performance of
organic devices and deeper understanding of physical processes using small molec-
ular systems, in which highly ordered or even crystalline states can be obtained.
Two different approaches towards well-ordered small molecular systems are distin-
guished, namely (1) the growth of free-standing single crystals of high purity and (2)
thin film growth by epitaxial vacuum preparation techniques. Unfortunately, bulk
organic single crystals showing very high mobilities are basically technologically
irrelevant because of their poor mechanical stability. Therefore, there is a great inter-
est in the second alternative, which can lead to highly ordered self-organized films
with well-defined orientation of the molecules [4].
6.2 Organic Nanostructures 73
Fig. 6.3 Schematic of para-sexiphenyl ρ-sexiphenyl C36 H26 (a) and C60 (b) molecules indicating
single and double C–C bonds
6.2.1 Structures and Applications of Organic Nanostructures
In contrast to oligo-phenylenes, fullerene C60 represents the class of highly symmet-

rical molecules. The closed-cage nearly spherical molecule C60 and related fullerene
molecules (C70 , C84 , C60 derivatives, etc.) have attracted a great deal of interest in
recent years because of their unique structure and properties. In particular, upon
photoexcitation C60 is known as excellent electron acceptor relative to conjugated
polymers and oligomers, capable of taking on as many as six electrons. In the case of
donor–acceptor (D–A) blends or bilayers, this leads to ultrafast photoinduced charge
transfer with subsequent long-lived charge separated states. Such D–A systems were
successfully used in fabricating organic solar cells and photosensitive OFETs. On
the other hand, C60 is a very good material for highly ordered thin films, showing
well-aligned epitaxial growth with the {111} planes of C60 parallel to the surface of
layered substrates and especially of mica [5, 6].
6.2.2 Miscellaneous Application of Organic Nanostructures
Due to the prospective performances in photonic integrations, one-dimensional sin-

gle crystalline nanostructures constructed from organic luminescent molecules have
generated wide research interests like: Inspired by the existing optically and elec-
trically pumped inorganic semiconductor and polymer nanowire lasers, researchers
show increasing interest in organic-based lasers, for their unique features, such as
a high degree of spectral tunability, large stimulated emission cross-sections, and
the potential for simple high-throughput fabrication. Moreover, the ease of fabrica-
tion has made it possible to produce 1D organic laser with a wide variety of optical
microcavities. Therefore, the fabrication of 1D organic nanolasers is of great scientific
interest and technological significance.
Optical waveguides can lead to some properties of laser light, because waveguides
have common laser geometries. 1D waveguiding nanostructures with optically flat
end facets can function as miniature optical cavities, which apply feedback. As the
light passes backwards and forwards, it is amplified by the stimulated emission, and if
the amplification exceeds the losses of the resonator, lasing begins. Nanolasers with
strong polarized output are able to offer great opportunities in future applications
such as nanooptical routing, emission, detection, data storage, sensing and near-field
optics. Organic semiconductors have been successfully adopted as optically driven
lasers, while direct electrical pumping of organic lasers is a very challenging problem,
mostly relating to the low mobilities of the materials. However, in consideration of the
advances in molecular design and synthesis, as well as the development in fabricating
single-crystalline organic nanowires, which exhibit excellent performances of photon
confinement and propagation and high charge-carrier mobilities, it is reasonable to
consider that organic lasers show great promise in the future of electrically pumped
laser devices [7].
6.3 Hybrid Nanostructures
The hybrid nanostructures of metal NPs/2D materials are commonly used in SERS
and photocatalytic reactions, and as the interlayers of solar cells. There are certain
preparation requirements for specific applications, such as a large surface area for
SERS and photocatalytic reactions, and solution processing for the interlayers of
solar cells.
6.3.1 Physical Deposition to Synthesize the Hybrid

Nanostructures of Metal NPs/2D Materials
Physical deposition is a convenient method that can rapidly and efficiently deposit
metal NPs on 2D nanosheets. Sputter deposition, electron-beam evaporation, and
thermal evaporation are three main physical deposition methods. 2D materials need
to be synthesized first, followed by conversion of the bulk metal into small metal
NPs in a vacuum or an inert atmosphere to construct the hybrid nanostructures of
metal NPs/2D materials. Hybrids of metal NPs/2D materials with different densities,
shapes, and thicknesses of metal NPs can be obtained using this method, which is
very beneficial for tuning the plasmonic effect. The deposition of Au or Ag NPs
on GO was patterned using sputter deposition technique. Sometimes, an annealing
treatment is needed to obtain nanospheres. For example, by adjusting the annealing
temperature and time, Au nanospheres can be obtained on graphene sheets. The
Ag NPs/graphene composite nanostructures fabrication using thermal evaporation
was made, in that sandwiched graphene hybrid nanostructures were fabricated by
6.3 Hybrid Nanostructures 75
transferring a monolayer of graphene on top of an Ag film, followed by placing Ag

NPs on the graphene surface through thermal evaporation [8].
6.3.2 Chemical Reduction to Synthesize the Hybrid

Nanostructures of Metal NPs/2D Materials
Chemical reduction is the simplest and most efficient method for anchoring metal
NPs onto 2D materials with the assistance of various chemical reagents in a solution.
From a broad point of view, the hybrid nanostructures of metal NPs/2D materials can
usually be described as various metal NPs (Au, Ag, Cu, etc.) with uniform or different
shapes that are decorated on graphene or other 2D materials. Technically, the hybrid
nanostructures of metal NPs/graphene are prepared via two routes: (1) mixing and
reducing either the metal precursors or GO precursors and (2) simultaneously mixing
and reducing the metal precursors and GO precursors.
6.3.3 Applications of Hybrid Nanostructures
A plasmon-enhanced laser is also an important research direction. By transferring

graphene to the top of an Au film absorber mirror, stable mode-locking bulk lasers
with wavelengths of 1, 2, and 2.4 mm have been fabricated. Plasmon enhanced
near-infrared absorption in graphene with metal gratings. In addition, the hybrid Ag
nanowire/graphene nanostructure can be used as a highly transparent and stretchable
FET sensor for detecting some biomolecules.
The hybrid system of metal NP/graphene also shows an amplified photoa-
coustic effect, suggesting its implementation as an imaging probe. Based on the
enhanced near-infrared absorption and enhanced photothermal stability in the Au
nanorod/RGO composite, an extraordinarily high photoacoustic effect in the 4–
11 MHz operating frequency of an ultrasound transducer has been demonstrated
in in vitro and in vivo systems. Under light irradiation, especially near-infrared light,
metal nanomaterials can produce thermal energy via nonradiative decay. In addition,
2D materials such as RGO can also absorb light in the broadband region ranging
from UV to near-infrared wavelengths. Based on its nonradiative decay, GO can also
serve as a photothermal source. By combining metal NPs and GO, the metal NPs
enhance the light absorption of GO via the plasmonic near-field effect, and simulta-
neously, improved infrared absorption and photothermal effects are produced by the
hybrid system. A strong photothermal effect has been achieved in a GO coated Au
nanorod hybrid system, which shows promise for biomedical applications, such as
killing cells [9].
References
1. Latyshev AV, Dvurechenskii AV, Aseev AL (2017) Advances in semiconductor nanostructures,

growth, characterization, properties and applications. Elsevier, Amsterdam
2. Majumdar A (2004) Thermoelectricity in semiconductor nanostructures. Science 303:777–778
3. Alexson D, Chen H, Cho M et al (2005) Semiconductor nanostructures in biological applications.
J Phys: Condens Matter 17:R637–R656
4. Park JG, Kim GT, Park JH et al (2001) Quantum transport in low dimensional organic
nanostructures. Thin Solid Films 393:161–167
5. Atwood JL, Steed JW (2008) Organic nanostructures. Wiley, Weinheim
6. Andreev A, Teichert C, Singh B et al (2008) Fabrication and characterization of self-organized
nanostructured organic thin films and devices. Organic nanostructures for next generation
devices. Springer, Heidelberg, pp 263–300
7. Cui QH, Zhao YS, Yao J (2012) Photonic applications of one-dimensional organic single-
crystalline nanostructures: optical waveguides and optically pumped lasers. J Mater Chem
22:4136–4140
8. Lu G, Li H, Liusman C et al (2011) Surface enhanced Raman scattering of Ag or Au nanoparticle-
decorated reduced graphene oxide for detection of aromatic molecules. Chem Sci 2:1817–1821
9. Li X, Zhu J, Wei B (2016) Hybrid nanostructures of metal/two-dimensional nanomaterials for
plasmon-enhanced applications. Chem Soc Rev 45:3145–3187
Chapter 7
Properties of Nanostructured Materials
Abstract Nanostructured materials are becoming of major significance, and their

investigations require a comprehensive approach. Depending on the size of the small-
est feature, the interaction of light with structured materials can be very different. The
chapter identifies the nanostructures unique properties that make the nanostructure
for varying applications and detailed about the properties.
7.1 Unique Properties of Nanostructures
The buckyballs and buckytubes have sincerely significant properties: especially

their high electrical conductivity and unique mechanical strength. The properties of
surfactant-stabilized colloids are the basis for many bioanalytical systems. Fluores-
cent CdSe quantum dots, unlike fluorescent organic dyes, photobleach only slowly,
and show interesting optical phenomena such as blinking [1].
Quantum behavior becomes increasingly prominent as structures become smaller.
Many of the behaviors of atoms and molecules are, of course, only explicable on
the basis of quantum mechanics. The properties of objects and structures larger
than a few microns are usually classical. In the intermediate region-the region of
nanometer-scale structures quantum and classical behaviors mix. This mixture offers
the promise of new phenomena and/or new technologies. The fluorescent behavior
of semiconductor quantum dots can only be explained quantum mechanically; as
can the tunneling currents that characterize scanning tunneling microscopes, and
electron emission from the tips of buckytubes. The response of electrical resistance
to magnetic field in giant magnetic resonance (GMR) materials is already useful in
magnetic information storage, and the behavior of spin-polarized electrons in mag-
netic semiconductors forms one foundation for the emerging field of spintronics.
The ability to make structures in the region where quantum behavior emerges, or
where classical and quantum behaviors merge in new ways, is one with enormous
opportunity for discovery. And because quantum behavior is fundamentally counter-
intuitive, there is the optimistic expectation that nanostructures and nanostructured
materials will found fundamentally new technologies. The ability to fabricate small
cantilevers, tips, and wires, opens the possibility of making nanoscale sensors [2].

https://doi.org/10.1007/978-3-030-26145-0_7
78 7 Properties of Nanostructured Materials
7.2 Physical Properties of Nanowires
7.2.1 Thermal Stability
While Comparing with bulk materials, the low-dimensional nanoscale materials,

with their large surface area and possible quantum confinement effect, exhibit dis-
tinct electric, optical, chemical and thermal properties. Thermal stability of the semi-
conductor nanowires is of critical importance for their potential implementation as
building blocks for the nanoscale electronics. Size-dependent melting recrystalliza-
tion process of the carbon-sheathed semiconductor Ge nanowires has been recently
studied by the Yang group using an in situ high temperature transmission electron
microscope.
The silicon-based nanostructures have different morphologies and microstructures
at different formation and annealing temperature. The synthetic method is thermal
evaporation of Si/SiO2 mixture in an alumina tube. It was observed that besides
Si nanowires, many other kinds of Si based nanostructures such as octopuslike,
pinlike, tadpolelike, and chainlike structures were also formed. The formation and
annealing temperature was found to play a dominant role on the formation of these
structures. It is demonstrated that a control over the temperature can precisely control
the morphologies and intrinsic structures of the silicon-based nanomaterials. This is
an important step toward design and control of nanostructures using the knowledge
of nanowire thermal stability [3].
7.2.2 Optical Properties
7.2.2.1 Photoluminescence and Stimulated Emission
Due to quantum confinement effect, the nanowires exhibit distinct optical properties
when their size is below certain critical dimension. For example, the absorption edge
of the Si nanowires synthesized and shows blue-shift from the bulk indirect band
gap of 1.1 eV. Sharp discrete absorbance features and relatively strong band edge
photoluminescence (PL) were also observed. These optical properties likely result
from quantum confinement effects, although they cannot rule out the possibility of
additional surface states as well. The <110> oriented nanowires exhibited distinctly
molecular-type transitions. The <100> oriented wires exhibited a significantly higher
exciton energy than the <110> oriented wires, are among the first to show that the
tunability of the lattice orientation in the silicon nanowires can lead to different
optical properties [4].
7.2 Physical Properties of Nanowires 79
7.2.3 Electronic Properties
Miniaturization in electronics through improvements in established top-down fabri-

cation techniques is approaching the point where fundamental issues are expected
to limit the dramatic increases in computing speed. Semiconductor nanowires have
recently been used as building blocks for assembling a range of nanodevices includ-
ing FETs, p-n diodes, bipolar junction transistors, and complementary inverters.
In contrast to carbon nanotubes, the nanowire devices can be assembled in a pre-
dictable manner because the electronic properties and sizes of the nanowires can be
precisely controlled during synthesis and methods are being developed for their par-
allel assembly. Researchers explored the possibility of assembling various devices
at the nanometer scale using their n- and p-type Si, InP nanowires. It is believed that
bottom-up approach to nanoelectronics has the potential to go beyond the limits of
the traditional top-down manufacturing techniques. As the critical dimension of an
individual device becomes smaller and smaller, the electron transport properties of
their components become an important issue to study. As for semiconductors, recent
measurements on a set of nanoscale electronic devices indicated that GaN nanowires
as thin as 17.6 nm could still function properly as a semiconductor. Another issue
related to the electronic applications of chemically synthesized nanowires is the
assembly of these building blocks into various device architectures. It is worth not-
ing that the Lieber group has been able to assemble semiconductor nanowires into
cross-bar p-n junctions and junction arrays having controllable electrical character-
istics with a yield as high as 95%. These junctions have been further used to create
integrated nanoscale field-effect transistor arrays with nanowires as both the con-
ducting channel and gating electrode. In addition, OR, AND, and NOR logic-gate
structures with substantial gain have been configured and tested to implement some
basic computation. There are several appealing features for bottom-up approach to
nanoelectronics. First, the size of the nanowire building blocks can be readily tuned to
sub-100 nm and smaller, which should lead to high density of devices on a chip. Sec-
ond, the material systems for the nanowires are essentially unlimited, which should
give researchers great flexibility to select the right materials for the desired device
functionality. For example, the GaN nanowire based nanodevices which would be of
interest for their high power/high temperature electrical applications [5].
The mechanical properties of small, rodlike materials are of considerable interest.

For example, small whiskers can have strengths considerably greater than those
observed in corresponding macroscopic single crystals, an effect that is attributed to
a reduction in the number of structural defects per unit length that lead to mechanical
failure. The researchers used atomic force microscopy to determine the mechanical
properties of individual, structurally isolated silicon carbide (SiC) nanowire that
were pinned at one end to molybdenum disulfide surfaces. The bending force was
measured versus displacement along the unpinned lengths. Continued bending of
the SiC nanowires ultimately led to fracture. They calculated Young’s modulus of
610–660 Gpa based on their AFM measurement. These results agree well with the
600 GPa value predicted theoretically for [111]-oriented SiC and the average values
obtained previously for micrometer-diameter whiskers. The large Young’s modulus
values determined for SiC nanowires make these materials obvious candidates for
the reinforcing element in ceramic, metal, and polymer matrix composites [6].
7.2.5 Field Emission Properties
It is well-known that nanotubes and nanowires with sharp tips are promising materials
for applications as cold cathode field emission devices. Field emission characteristics
of the β-SiC and Si nanowires have been investigated using current-voltage measure-
ments. The silicon carbide nanorods exhibited high electron field emission with high
stability. Both Si and SiC nanowires exhibit well-behaved and robust field emission.
The turn-on fields for Si and SiC nanowires were 15 and 20 V μm−1 , respectively
and current density of 0.01 mA cm−2 which are comparable with those for other field
emitters including carbon nanotubes and diamond. Along with the ease of prepara-
tion, these silicon carbide and Si nanowires are believed to have potential application
in electron field emitting devices [7].
7.3 Grain Boundaries in Nanostructured Materials
With grain sizes in a submicron (100–1000 nm) or nanocrystalline (<100 nm) range,
(Ultrafine-grained materials) UFG materials contain in their microstructure a very
high density of grain boundaries, which can play a significant role in the development
and exhibition of novel properties. For this reason, UFG materials can be typically
considered as interface-controlled materials. In pioneered nanocrystalline materials
it was suggested that grain boundaries can possess a number of peculiar features in
terms of their atomic structure in contrast to grain boundaries in conventional poly-
crystalline materials. This is of particular importance for UFG materials produced
by (Severe Plastic Deformation) SPD methods. Depending on the regimes of SPD
processing, different types of grain boundaries can be formed in the UFG materi-
als (high- and low-angle, special and random, and equilibrium and so-called non-
equilibrium grain boundaries containing extrinsic dislocations), which paves the way
to grain boundary engineering of UFG materials, i.e., to the control of their properties
by means of varying the grain boundary structure. The notions on non-equilibrium
grain boundaries were first introduced in the scientific literature in the 1980s, reason-
ing from investigations of interactions of lattice dislocations with grain boundaries.
7.3 Grain Boundaries in Nanostructured Materials 81
Fig. 7.1 Phenomenological engineering of grain boundaries via thought cuts: (a) → (b) equilibrium
grain boundary (bunches of deformation are connected without mesoscopic strain); (c) → (d) and
(a) → (f) non-equilibrium grain boundaries (deformation is required for crystal joint – bending and
tension – compression, respectively); (e) and (g) schemes of grain boundary dislocation (GBD) com-
plexes initiating the same character of mesoscopic elastic distortions as in (d) and (f) Reprinted with
permission from © In: Bulk Nanostructured Materials with Multifunctional Properties. Springer
Briefs in Materials. Springer, Cham (2015)
According to, the formation of a non-equilibrium grain boundary state is character-

ized by three main features, namely excess grain boundary energy, the presence of
long-range elastic stresses, and enhanced free volume. Discontinuous distortions of
crystallographically ordered structures, which may come about by accommodation
problems of differently oriented crystallites of finite sizes or by high densities of
lattice dislocations and their interaction with grain boundaries, can be considered as
sources of elastic stress fields that modify the atomic structure of high-angle grain
boundaries so that their excess free energy becomes enhanced. These unusual grain
boundaries are known as non-equilibrium grain boundaries, each grain boundary is
non-equilibrium defect if segregation effects are not to be considered [8] (Fig. 7.1).
7.4 Multifunctional Properties of Nanostructured Metallic

Materials
The mechanical and functional properties of all polycrystalline metallic materials are
determined by several factors, the grain size of the material generally plays the most
significant and often a dominant role. Thus, the strength of different polycrystalline
materials is related to the grain size, d, through the Hall–Petch equation which states
that the yield stress, σy , is given by
σ y = σo + k y d −1/2 (1.1)
where σo is termed the friction stress and ky the Hall–Petch constant. It follows from
Eq. 1.1 that the strength increases with a reduction in the grain size and this has led to
an ever-increasing interest in fabricating materials with extremely small grain sizes
[9].
The mechanical properties like flexural strength and the fracture toughness have
been studied on a sintered silicon carbide, which is prepared by the pressure less
sintering route from the nano crystalline silicon carbide particles of an Acheson type
α-SiC that is processed by high energy attrition grinding route. The average flexural
strength is found to be 390 MPa and the average fracture toughness is found to be
4.3 MPa m1/2 . The sintering behavior of nano particles of SiC is very interesting
indeed. The non-oxide ceramics are attractive candidates for structural materials
because of their high temperature strength, which makes them highly suitable for the
applications in ceramic engines and gas turbines.
The silicon carbide seems to be particularly well suited because of its high temper-
ature strength and intrinsic resistance to oxidation. However, silicon carbide ceramic
has a strong covalent bonding character and a small amount of sintering aids such
as AlN or B4 C are usually necessary to make dense materials. Usually, the dense
silicon carbide materials have lower strength compared to silicon nitride materials.
The latter experience of a degradation of strength at 1200–1300 °C, while silicon car-
bide materials do not show any decrease of strength up to 1500 °C [10]. The silicon
carbide, like other ceramics, shows a wide scattered distribution in flexural strength.
This distribution of strength is a matter of concern and hence an important topic to
be studied. The strength distribution of silicon carbide varies typical for many other
ceramic materials. Most of earlier work is based on a 4-point bending test. Depending
on the manufacturer and the type of silicon carbide, the average room temperature
strength varies between 350 and 550 MPa. For such cases, the Weibull modulus
which is a measure of the dispersion in strength varies between 6 and 15 depending
on the strength of the ceramic materials. The observed behavior in metals, the room
temperature strength of the sintered α-silicon carbide increases, as the exaggerated
grain growth is intentionally introduced by a suitable heat treatment. However, the
comparisons between the grain sizes should be made between two different materials
having a uniform distribution of small grain sizes versus a uniform distribution of
large grain sizes. The isolated rise of a mixed grain-size matrix, it should be pointed
out that the mechanical strength of the sintered silicon carbide remains unaltered at
temperatures up to 1500 °C, which has a definite advantage in the high temperature
applications such as gas turbines and ceramic engines. A further increase of strength
has been observed in this material, when heated in the argon atmosphere the effect of
the dopants on the flexural strength. They observed that the materials doped with alu-
minum had a higher strength than that doped with boron, and with the improvement
in the processing parameters, it would be as strong as the ‘hot-pressed’ SiC materials.
They also found that the production of the materials with ultrafine grains occurred in
a very narrow range of sintering temperature (2050–2075 °C). The exaggerated grain
growth at temperatures above 2075 °C was the cause of the reduction in strength of
7.4 Multifunctional Properties of Nanostructured Metallic Materials 83
boron doped materials. The materials sintered with aluminum nitride, which acted
as a grain growth inhibitor, showed a higher strength. The silicon carbide, like other
ceramics, shows a wide distribution in strength.
One common way of characterizing the variability of strength of brittle materials
is by using the Weibull modulus. A high Weibull modulus material (i.e. m > 20)
will give a narrow distribution of fracture strength, whereas a low Weibull modulus
material (i.e. m < 5) has a wide distribution in fracture strength, and hence a low
reliability. However, a number of workers indicated that the structural reliability of
ceramics is primarily dependent on the flaw size distribution during the processing
[11].
7.4.2 Strength Measurement
7.4.2.1 Flexural Strength
The measurement of flexural strength requires the following steps:

1. Preparation of the Samples,
2. Introduction of 4-Point Bending Samples, and
3. Measurement of the Fracture Load.
7.4.2.2 Fracture Toughness
A large number of methods of measurement of fracture toughness and such other

parameters have been standardized for metals and alloys in recent years. These meth-
ods are normally suitable for ambient laboratory conditions. Different methods utilize
different configurations. In sintered nano-crystalline particles of silicon carbide, the
measurement of fracture toughness was made by 4-point Single Edge Notch Bend
(SENB) specimen technique. The load required for causing the fracture of the sample
was measured by the above high temperature Bending Strength Tester (BST), having
a length 1600 mm × width 750 mm × height 2100 mm. The bars of size (45 mm
× 4.5 mm × 3.5 mm) were notched with a diamond blade of 0.2 mm thickness
(100 μm diameter), after grinding in a 25 μ diamond wheel. The notch dimensions
were measured with the help of a traveling microscope. As a result of using 0.2 μm
thick blade for notching, the notch width varied from 0.31 to 0.39. The value of a/w
≈ 0.25–0.40 mm, where a = notch length and w = notch width. The notched samples
were put into the furnace. On attainment of the desired temperature, the load was
applied on the Bending Strength Tester at the speed of 1.25 N/s, and the fracture load
was noted [12].
7.4.2.3 Flexural Strength of α-SiC
There are many factors which affect the strength of ceramic materials such as poros-
ity, grain size, grains shape and surface conditions etc. Figure 7.2 shows a SEM
micrograph of a polished and etched surface of the dense α-silicon carbide. The
grains had mostly tabular shapes. The average grain size was found to be 5700 nm.
Figure 7.3 shows the flexural strength as a function of temperature. No variation
of strength data with temperatures was found up to 1400 °C. The average flexural
strength was found to be 390 MPa. Figures 7.3 and 7.4 show the flexural strength
Fig. 7.2 SEM photo of

etched and polished surface
of a dense α-silicon carbide
(dopant: 0.5 wt% boron
carbide + 1 wt% carbon)
Fig. 7.3 Flexural strength as

a function of temperature of
α-silicon carbide (dopant:
0.5 wt% boron carbide + 1
wt% carbon)
Fig. 7.4 Weibull modulus of flexural strength at room temperature for α-silicon carbide (dopant:
0.5 wt% boron carbide + 1 wt% carbon)
as Weibull modulus (m) at room temperature and at 1400 °C. The number of speci-
mens was 30 in each case. The Weibull modulus was 11.3 at room temperature and
13.3 at 1400 °C. The Weibull modulus is found to increase at higher temperature
presumably due to healing of surface cracks, which were induced during the cutting
of the samples by high speed diamond blades, i.e. the curing of the surface damages
at higher temperature. The Weibull modulus for β-silicon carbide (not shown here)
was found to be 10.9 and 12.9 at room temperature and 1400 °C respectively. The
low value of ‘m’ for β-silicon carbide could be due to the presence of pores of differ-
ent sizes and also due to a relatively wider distribution of flexural strength at room
temperature. The increase of Weibull modulus by about 20% for both these materials
from room temperature to 1400 °C might be due to the ‘healing of surface cracks’
and possibly due to the ‘release of residual stresses’. Figure 7.6 shows the fracture
toughness of α-silicon carbide as a function of temperature. The average fracture
toughness was found as 3.95 MPa m1/2 . The value for β-silicon carbide was found
to be 3.55 MPa m1/2 . A higher value of fracture toughness for α-silicon carbide is
obtained due to the fine grained microstructures obtained after sintering and due to
higher level of densification compared to that of β-silicon carbide [13] (Fig. 7.5).
Fig. 7.5 Weibull modulus of flexural strength at 1400 °C for α-silicon carbide (dopant: 0.5 wt%
boron carbide + 1 wt% carbon)
Fig. 7.6 Fracture toughness

as a function of temperature
of α-silicon carbide (dopant:
0.5 wt% boron carbide + 1
wt% carbon)
7.4.2.4 Microstructures
The fracture mainly originates from the crack generated due to pores. This type of
fracture, which is caused by an intergranular pore, was observed during this investi-
gation. Figure 7.7 shows a SEM micrograph of the fracture surface of the α-silicon
Fig. 7.7 SEM photo showing the presence of a large void (the origin of the crack)
Fig. 7.8 SEM photo

showing crack propagation
through the sintered sample
carbide in terms of the propagation of cracks and the fracture caused by the inter-
granular pores. The presence of pores is expected to cause the formation of tiny
cracks. The propagation of cracks requires the rupture of the inter-atomic bonds at
the tip of the crack [14] (Fig. 7.8).
7.4.3 Superstrength and Ductility
The influence of grain size reduction to nanometer range on the materials strength
has been explored in multiple works. The enhancement of strength with grain size
reduction in compliance was observed in many studies, but for nanosized grains
(20–50 nm), this relations reported to be typically violated so that the Hall–Petch
plot deviates from linear dependence at lower stress values and its slope ky often
becomes negative (the curve 1 in Fig. 7.9). The Hall–Petch relationship breakdown
is not observed in ultrafine-grained materials with a mean grain size of 100–1000 nm
Fig. 7.9 The Hall–Petch slopes within different characteristic length scales
produced by SPD processing. Moreover, recently it was shown that UFG alloys can
exhibit a considerably higher strength than the Hall–Petch relationship predicts for
the range of ultrafine grains. The nature of such superstrength may be associated
with another nanostructural features which could be observed in the SPD-processed
metals and alloys [15].
7.4.4 Electrical Conductivity
Electrical conductivity is an important functional property of metallic materials.

Electrical conductivity in metals is a result of the movement of electrically charged
particles. The atoms of metal elements are characterized by the presence of valence
electrons—electrons in the outer shell of an atom that are free to move about. These
free electrons allow metals to conduct an electric current. Because valence elec-
trons are free to move, they can travel through the lattice that forms the physical
structure of a metal. Under an electric field, free electrons move through the metal
much like billiard balls knocking against each other, passing an electric charge as
they move. The transfer of energy is strongest when there is little resistance. On a
billiard table, this occurs when a ball strikes against another single ball, passing most
of its energy onto the next ball. If a single ball strikes multiple other balls, each of
those will carry only a fraction of the energy. By the same token, the most effective
conductors of electricity are metals that have a single valence electron that is free
to move and causes a strong repelling reaction in other electrons. This is the case in
the most conductive metals, such as Ag, Cu, and Au, which have a single valence
electron that moves with little resistance and causes a strong repelling reaction. Al
with three valence electrons comes as the fourth most conductive metal. Mechanical
Fig. 7.10 Room temperature electrical conductivity (in IACS) versus yield strength for CG pure Cu
and Cu-based alloys and their nanostructured counterparts obtained via SPD processed Reprinted
with permission from © Journal of Minerals, 64, 1134–1142 (2012)
strength and electrical conductivity are the most important properties of conduct-
ing materials. However, high strength and high electrical conductivity are mutually
exclusive in metallic materials, and trade-off between strength and conductivity is
always encountered in developing conducting materials. Pure Cu and Al having high
electrical conductivity show very low mechanical strength. The alloying of pure
metals, strain hardening, or introduction of precipitates dramatically improves their
mechanical strength due to suppression of dislocation glide. But all strengthening
methods lead to a degradation of electrical conductivity, since the latter is deter-
mined by the scattering of conductive electrons due to disturbances in the crystal
structure including thermal vibrations, solute atoms, and crystal defects [16]. This is
clearly seen from the electrical conductivity—yield strength plot for coarse-grained
pure Cu and its alloys presented in (Fig. 7.10). The electrical conductivity of most
conventional Cu alloys ranges from ~30 to ~85% of International Annealed Copper
Standard (IACS).
7.4.5 Magnetic Properties
Ferromagnetic materials with the demagnetized state do not show magnetization

although they have spontaneous magnetization. This is because the ferromagnetic
materials are divided into many magnetic domains. Within the magnetic domains,
the direction of magnetic moment is aligned. However, the direction of magnetic
moments varies at magnetic domain walls so that it can reduce the magnetostatic
energy in the total volume. When domain wall can easily migrate, the ferromagnetic
material can be easily magnetized at low magnetic field. This type of ferromagnetic
materials is referred to as soft magnetic material and is suitable for applications of

magnetic cores or recording heads. When domain wall is difficult to migrate, mag-
netization of the ferromagnetic material occurs only when high magnetic field is
applied. In other words, this type of ferromagnetic materials is difficult to magne-
tize, but once magnetized, it is difficult to demagnetize. These materials are referred
to as hard magnetic materials and are suitable for applications such as permanent
magnets and magnetic recording media. Soft magnetic materials are one of the most
investigated classes of functional materials. Their microstructure can be amorphous
or crystalline with grain sizes ranging from some nanometers in nanocrystalline soft
magnetic materials to several centimeters in transformer steels. Most of them are
available as powders, ribbons, and thin films and are used in a huge variety of indus-
trial applications such as motors, generators, transformers, sensors, or microelec-
tronic devices. Earlier investigations showed the strong influence of nanostructuring
via SPD on magnetic hysteresis characteristics of soft magnetic metals, such as Ni,
Co, Fe, and Fe–Si. A sharp increase in the coercivity Hc was revealed in pure metals
after SPD processing. It was demonstrated that coercivity in nanostructured pure Ni
strongly depends on grain size, dislocation structure, and the non-equilibrium state of
the grain boundaries. For example, SPD-processed specimens subjected to recovery
annealing at 100 and 200 °C had different values of coercivity by ~ 40%, though their
grain sizes were nearly the same. At the same time, at 200°C, an intense recovery
of non-equilibrium grain boundaries was observed. As the temperature of annealing
increased, a further decrease in the value of Hc was correlated with increasing grain
size. An analogous regularity was revealed in Co processed via (high pressure tor-
sion) HPT. TEM investigations of the domain structure of nanostructured Co with
a grain size of about 100 nm used the Lorentz method. It was established that the
magnetic domain sizes were significantly larger than the grain sizes and remagneti-
zation was conditioned by the movement of domain walls, but at the same time, this
movement was hampered by non-equilibrium grain boundaries [17].
7.4.6 Corrosion Resistance
Corrosion, the property of a material to deteriorate its properties due to interaction

with the environment, especially chemically aggressive one, is an old problem for
the industry since the very beginning. The embrittlement of a metal, leading to crack-
ing of metallic materials inducing catastrophic failures of constructions, inspired the
challenge to modify microstructures to survive hostile conditions. Materials required
by different branches of industry are generally described by corresponding stan-
dards, but they are not flexible enough to reflect the industry needs. Development
of corrosion-resistant metallic materials for advanced applications is a topical task
for modern materials science with attention to both effectiveness and security of the
cutting-edge technologies and ecological security taking into consideration risks of
global warming and industrial disasters. The problem of utmost importance is devel-
opment of new functional materials with reasonable corrosion resistance to be used
in new-generation applications. Corrosion resistance was shown to be significantly

enhanced in several nanocrystalline metals and alloys as compared to their coarse-
grained counterparts. A tendency for localized corrosion was observed to be lower for
electrodeposited (ED) nanocrystalline Ni. The origin of better corrosion resistance
for nanocrystalline metals was a subject of discussion and was attributed to increased
breakdown potential and a better resistance to anodic dissolution as a result of lower
porosity. Evidence provided to substantiate these hypotheses or cogent reasons for
not observing a higher localized corrosion even in the presence of such a high volume
fraction of grain boundaries has not been conclusive. The discovery of grain bound-
aries in ED nanocrystalline Ni to be predominantly coherent low-sigma coincidence
site lattices (3 CSLs) has been attributed to the possible origin of its superior corro-
sion resistance. Recently, it has been demonstrated that grain refinement, independent
of the processing route, leads to the formation of high-angle boundaries and provides
corrosion resistance to down-hole alloys. This breakthrough and recent advances in
processing technology to engineer high-strength corrosion-resistant metallic nano-
materials will enable the design of nanostructured metallic materials specifically for
the oil and gas industry. However, for the case of bulk nanostructured materials pro-
cessed via SPD, it is necessary to note that up to now, there is no unified opinion on
their corrosion properties. In case of nanostructured (Unalloyed Commercially Pure)
CP Ti, it was shown that simultaneous enhancement of both mechanical strength and
corrosion properties in aggressive environments, such as HCl and H2 SO4 solutions,
are possible. Corrosion resistance of SPD-processed Ti is determined not only by
grain size, but also by the crystallographic texture developed during SPD processing.
Particularly, basal planes of CP Ti offer higher corrosion resistance independently
of grain size. Dislocation density can also significantly affect corrosion properties of
this material. Very recently, it was demonstrated that corrosion resistance of the SPD-
processed CP Ti can be further improved without any loss of mechanical strength
via proper annealing treatments due to reduction of dislocation density and residual
stresses. Very similar results were reported for SPD-processed Mg alloy AZ61 tested
in 0.1 M NaCl solution [18] (Fig. 7.11).
7.4.7 Reliability of Nanostructured Materials
Reliability is the probability of survival in service of a component at a predetermined

property level for a given length of time. Therefore, it is primarily concerned with
the statistics of failure time, which may be regarded as the most important variable
in Reliability Theory. It establishes an absolute limit to the lifetime of a component.
For example, in the case of structural nanomaterials, parameters like strength and
ductility have to be related to the failure time. Concepts associated with reliability
are applied in all fields of engineering design and have been used extensively in the
case of electronic and structural components and in materials assemblies that may
comprise several dissimilar materials. It is self-evident that other considerations like
materials selection, economics, productivity, strength-to-weight ratio and flexibility
Fig. 7.11 Weight loss measurement test results of the CG Ti and UFG Ti in a 0.5 M H2 SO4
solution before and after annealing at different temperatures for 2 h Reprinted with permission
from © Corrosion Science, 89, 331–337 (2014)
become relevant only if the reliability of components in service can be ensured.

Reliability of advanced materials is even more difficult to accomplish because they
are used in the most demanding conditions, where conventional materials will prove
to be inadequate. The ability of nanostructured materials to display properties that
are different from those of their conventional analogues or are entirely new has made
the currently available databases irrelevant. Therefore, reliability of nanostructured
materials is primarily concerned with structure–property correlations with a view to
ensuring the retention of the assumed design values of properties during the service
life of a component and the capacity to predict its residual life at any given point
in time. This suggests the need for a multidisciplinary, systems-oriented approach
to producing nanostructures that function reliably in service. Common features that
need to be addressed in order to increase the reliability of nanostructures are: surface
quality, fracture, fatigue, creep, interface stability, phase stability and thermal stability
[19].
7.4.8 Thermal Properties of Nanostructures
The second law of thermodynamics states that for large systems and over long times
the entropy production rate is necessarily positive. However, the fluctuation theo-
rem predicts measurable violations of the second law for small systems over short
timescales. This has been shown experimentally by following the trajectory of a col-
loidal particle in an optical trap. An optical trap is formed when the micron sized
particle with a refraction index higher than that of the surrounding medium is located
within a focused laser beam; the refracted rays eventually exert a force on the par-
ticle which can be resolved to 2 × 10−15 N. From observing the particle’s position
and the optical forces acting on the particle, the entropy production rate can be
determined. It turns out that entropy consuming, i.e., second law-defying events, can
be discerned for micron-sized particles on the timescales of seconds. This is partic-
ularly important to applications of nanomachines and molecular motors. As these
nanomachines become smaller, the probability that they will run thermodynamically
in reverse inescapably increases [20].
7.4.9 Thermal Conductance
In nanosystems the classical picture of a diffusive heat flow mechanism is often

not applicable because the phonons or electrons that carry heat have mean free paths
similar to or larger than the nanoscale feature size. This is a challenge for heat removal
in microelectronic devices which already involve features with sizes of the order of
the mean free path. The thermal conductance κ(V g) of electrons in a semiconductor
quantum wire at low temperatures shows a quantized behavior in dependence of
a gate voltage V g. This originates from the plateaus in the electrical conductance
G(V g) quantized in units of GO = 2e2 /h.
7.4.9.1 Lattice Parameter
The lattice parameter of Pd nanoparticles in a polymer matrix decreases by about 3%

when the particle size decreases from 10 to 1.4 nm. A similar behavior is observed
for Ag nanoparticles.
7.4.9.2 Phase Transitions
Phase transitions in confined systems differ, as shown in the case of the melting
transition above, from those of bulk materials and strongly depend on particle size,
wetting, as well as the interaction of a nanoscale system with a matrix or a substrate.
Phase transitions in nanosized systems have been investigated for superfluidity where
the critical behavior of superfluid He in an aerogel deviates from that of bulk He. In
superconductivity the superconducting transition temperatures of Ga or In nanopar-
ticles in vycor glass are shifted to values higher than in the bulk materials. The Curie
temperature T C of ferromagnetic nanolayers decreases with decreasing layer thick-
ness. Liquefaction in nanopores or order—disorder phase transitions near surfaces
was also found to differ from that of bulk systems. Two examples of solid–solid
phase transitions on the nanoscale will be sketched in the following. Under elevated
pressures PbS undergoes a B1-to-orthorhombic structural phase transition. For PbS
nanoparticles in a NaCl matrix, the transition is shifted to higher pressures when
the particle size is reduced. The stability of crystal structures at ambient conditions
depends on the size of ZrO2 nanocrystals which exhibit a tetragonal structure for
small sizes and the bulk orthorhombic structure for larger sizes. In this oxide, the
lattice strain varies with the grain sizes giving rise to a variation of the Landau free
energy so that for small grain sizes the tetragonal phase is stabilized whereas for
grain sizes d > 54 nm the bulk orthorhombic phase appears [21].
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Chapter 8
Nanostructured Materials—Design
and Approach
Abstract Nanostructured material handling, properties and applications are widely

important for promptly advancing field. This chapter focuses on important synthe-
sis methods for production of nanostructural materials and selected properties of
synthesized materials.
8.1 Synthesis of Nanostructured Materials
The nanostructural design of materials is schematically illustrated in Fig. 8.1 the

scheme modifies and further develops a well-known concept of contemporary cre-
ation of novel materials through the integration of theory and modeling, structure
characterization, processing and synthesis, as well as the properties of studies. In
addition, nanostructuring of bulk materials deals with a far larger number of struc-
tural parameters related to the grain size and shape, lattice defects in the grain interior,
as well as with the grain boundary structure, and also the presence of segregations
and second-phase nanoparticles. This provides an opportunity to vary the trans-
port mechanisms and therefore can drastically increase the properties. For example,
nanostructuring of bulk materials by super plasmon diffusion (SPD) processing not
only permits a considerable enhancement of many mechanical and physical prop-
erties but also contributes to the appearance of multifunctional materials. In this
respect, one can anticipate that already in the near future, nanostructuring of materi-
als by various processing and synthesis techniques may provide many new examples
in the development of materials with superior properties for advanced structural and
functional applications [1].
Two broad strategies are commonly employed for generating nanostructures. The
first is bottom-up: that is, to use the techniques of molecular synthesis, colloid chem-
istry, polymer science, and related areas to make structures with nanometer dimen-
sions. These nanostructures are formed in parallel and can sometimes be nearly
identical, but usually have no long-range order when incorporated into extended
materials. The second strategy is top-down: that is, to use the various methods of
lithography to pattern materials. Currently, the maximum resolution of these patterns
is significantly coarser than the dimensions of structures formed using bottom-up

https://doi.org/10.1007/978-3-030-26145-0_8
98 8 Nanostructured Materials—Design and Approach
Fig. 8.1 Principles of nanostructural design of bulk nanostructured material
methods. Materials science needs an accessible strategy to bridge these two methods
of formation, and to enable the fabrication of materials with the fine resolution of
bottom-up methods and the longer-range and arbitrary structure of top-down pro-
cesses. This bridging strategy is self-assembly: that is, to allow structures synthesized
bottom-up to organize themselves into regular patterns or structures by using local
forces to find the lowest-energy configuration, and to guide this self-assembly using
templates fabricated top-down [2].
Quantum confinement has become a powerful tool for creating new structures with
extraordinary properties. In creation, quantum-confined structures have been widely
used in optoelectronic device technology. Then sensor applications based on quantum
dots experiments existed in the field with the help of semiconductor nanocrystals.
The possibility of having high quality, industrially scaled-up, biocompatible quantum
dot nanocrystals has made a real breakthrough in the biological and medical fields.
Quantum dots significantly improve the sensing property in applications such as
cellular assays, cancer detection, or DNA sequencing. There are different techniques
for fabricating quantum dot structures depending on the material and also on the
confinement strategy has two different categories; (i) QDs made by semiconductor
growth techniques onto wafers and other, (ii) Synthesis of QD nanocrystal colloidal
suspensions [3].
8.2 Nanostructure Synthesis and Fabrication Methods
There is various growth techniques employed for the fabrication of nanostructures,

and to synthesis nanowires, nanobelts, nanocombs, nanotubes, and nanosquids.
8.2 Nanostructure Synthesis and Fabrication Methods 99
1. Physical Vapor Deposition (PVD)
a. Laser-Assisted Catalytic Growth

b. Thermal Evaporation
c. Radiofrequency Magnetron Sputtering.
2. Chemical Vapor Deposition (CVD)
a. Thermal Chemical Vapor Deposition

b. Metal–Organic Chemical Vapor Deposition (MOCVD).
3. Solution based synthesis methods
a. Hydrothermal Synthesis
b. Hydrolysis
c. Aqueous Chemical Growth
d. Electrospinning.
8.2.1 Physical Vapor Deposition
Physical vapor deposition (PVD) is vapor–solid (VS) deposition techniques that

involve the generation of reactant vapors by physical processes such as heats,
plasmas, and lasers.
8.2.1.1 Laser-Assisted Catalytic Growth
Laser-assisted catalytic growth (LCG) was among the earlier approaches for the
growth of semiconducting nanowires. This technique involves the use of a pulsed
laser to ablate a target that containing the element(s) desired in the nanowires
and the metal catalyst component. In this technique the target was kept inside the
growth chamber of a tube furnace. The vaporized compounds were then grown
into nanowires of Si, GaN, InP, and GaP, through the vapor–liquid–solid (VLS)
mechanism. This approach was used to prepare bulk quantities of single-crystalline
nanowires with diameters of as small as 3 nm and lengths as long as 30 mm.
This technique was similar to the growth of single-wall carbon nanotubes by laser
vaporization [4] (Fig. 8.2).
8.2.1.2 Thermal Evaporation
Thermal evaporation was one of the most widely used techniques for the growth of
alternative nanostructures. In most cases, horizontal furnaces are used with a tubular
reaction chamber constructed by an alumina tube or a quartz tube. This was the
Fig. 8.2 ZnO nanostructures as nanobelts, nanopropellers, nanocombs, nanotubes, nanoswords,

nanotripods, nanotetrapods, nanosquids, nanorods, and nanotips (left to right, top to bottom), scale
bar 1 µm. Reprinted with permission from © Sensors Based on Nanostructured Materials, Springer,
59–78 (2009)
technique used for the growth of nanobelts of SnO2 , ZnO, In2 O3 , and CdO. For
example, the growth of SnO2 nanobelts was conducted in a horizontal tube furnace
with an alumina tube chamber. SnO2 powders were used as the source material that
was evaporated at 1350 °C under a pressure of ~200–300 Torr and Ar gas flow rate of
50 sccm. These vapors were then condensed as belt-like nanostructures in a narrow
region downstream where the temperature was ~900 to 950 °C. This vapor–solid
condensation process did not involve the use of other metal catalysts, although Sn
itself could have mediated the formation of SnO2 nanobelts.
This approach was used for the growth of interesting diskettes of SnO2 in a hori-
zontal tube furnace as shown in Fig. 8.3. In this case SnO2 powders were vaporized
at 1050 °C under a pressure of 500–600 Torr with the flow of Ar gas. SnO2 diskettes
were deposited at the low temperature (LT) region (200–400 °C). By using the same
approach, Ga2 O3 nanoribbons and nanosheets were produced by thermal evapora-
tion of GaN powders in a horizontal alumina tube furnace at 1100 °C. These Ga2 O3
8.2 Nanostructure Synthesis and Fabrication Methods 101
Fig. 8.3 Various appearances of SnO2 diskettes (a–e). (Down) Schematic diagram for a horizontal
tube furnace for the growth of various oxide nanostructures by thermal vaporization. Nanostructures
can be condensed at high (H.T.), medium (M.T.), and low temperature (L.T.) regions downstream.
Reprinted with permission from © Progress in Materials Science, 66, 112–255 (2014)
nanostructures were condensed at 800–850 °C under a pressure of 300 Torr created

by the flow of Ar gas at a rate of 50 sccm. Various ZnO nanostructures can be pro-
duced by thermal evaporation of Zn powders. ZnO nanotetrapods were synthesized
in a horizontal tube furnace with a fused-quartz tube chamber at 900 °C. A quartz
plate held with a few spherical Zn pellets (~3 mm in diameter) was inserted into the
tube and vaporized in air ambient. After heating for about 2 min, ZnO nanotetrapods
were found on the surface of the quartz plate. These ZnO nanotetrapods were used
for humidity sensors. On the other hand, ZnO nanobelts can be grown by evaporation
of Zn powder at 600 °C. Results indicate that the control of gas flow rates and partial
pressures of Ar, O2 , and Zn vapors are important for the growth of ZnO nanobelts.
Finally, the growth of ZnO nanowires in quantity of several grams was demonstrated
by heating the mixture of Zn powders and NaCl to 600–700 °C in the flow of Ar
(25 sccm) and O2 (20 sccm) gases that create a pressure of 2 Torr. About 70–80% of
the Zn powders were converted to ZnO nanowires when NaCl was used, otherwise
5–10% without NaCl [5].
8.2.1.3 Radiofrequency Magnetron Sputtering
Vapor–solid growth of nanostructured materials can also be obtained by other phys-

ical vapor deposition technique such as radiofrequency (rf) magnetron sputtering.
For example, ZnO nanobelts were grown by using rf magnetron sputtering of a ZnO
target. These nanobelts were deposited on sapphire substrates without the use of cat-
alyst at relatively low pressure of 40 mTorr and an rf power of 300 W for 60 min. The
sputtering gas used in this technique is not indicated in this report. The deposition
of these nanobelts was carried out without external heating to the substrates. This
approach usually results in the formation of ZnO films but nanobelts were deposited
when sapphire substrates were used [6].
8.3 Chemical Vapor Deposition
Chemical vapor deposition (CVD) techniques involved chemical decomposition or

chemical reaction in the formation of nanostructured materials. These chemical reac-
tions required to either create the growth species or form nanostructures by the use of
catalyst through the vapor–liquid–solid (VLS) mechanism. The two types of CVD
techniques are, namely thermal CVD and metal–organic chemical vapor deposition
(MOCVD).
8.3 Chemical Vapor Deposition 103
8.3.1 Thermal Chemical Vapor Deposition
Various ZnO nanostructures can be grown by carbothermal reduction of ZnO pow-

ders either with or without the use of catalyst such as Au. In this case, the precursor
ZnO and graphite powders were mixed and loaded into a ceramic boat, which was
placed in a small quartz reaction tube. This reaction tube was then inserted into
a larger quartz tube of a horizontal tube furnace. This approach was sometimes
referred as double-tube thermal CVD. Oxidized Si substrates (or other substrates)
were usually placed downstream to the source materials at the lower temperature
zones. In most cases, these precursor powders were combusted at 1100 °C so that
ZnO powders will be reduced into Zn and ZnOx vapors in the presence of graphite
powders. These Zn and ZnOx vapors were then condensed as ZnO nanostructures
in O2 gas at a pressure of several Torrs. ZnO appeared as nanowires, nanobelts,
nanopropellers, nanocombs, nanotubes, nanoswords, nanotripods, nanotetrapods,
nanosquids, nanorods, nanotips, etc. We found that nanorods can be grown without
Au catalyst. These ZnO nanorods can be transformed into nanotubes and nanosquids
with appropriate cooling during the growth. These nanorods can also be transformed
into long nanowires by placing an Au-coated substrate beside the sampling substrates
during the growth, a so-called side-catalyst approach.
This technique was applied for the growth of ZnO nanocombs by heating the tube
furnace at 900 °C for 30 min. Argon (100 sccm) and oxygen (1 sccm) were used in this
case without Au catalyst. Under this oxygen-deficient ambient, Zn vapors/droplets
might be formed that functions as a catalyst for the growth of ZnO nanocombs.
These nanocombs were tested as the biosensors for glucose detection. ZnO nanowires
can also be grown by using ZnO and graphite powders with germanium (Ge) as
the catalyst. The Ge catalysts were supplied in two ways. In one method, GeO2
powders were reduced by the graphite powders together with the ZnO powders.
In the other method Ge dots were patterned on the SiO2 -coated silicon wafer by
photolithography. ZnO nanowires were condensed at the temperature zone of 500–
650 °C with diameters and lengths of 50–400 nm and 50–200 mm, respectively.
It is interesting to note that the Ge catalysts remain at the tips of these nanowires
with diameters much larger than those of the nanowires. In addition to ZnO, other
nanostructured metal oxides were grown by this vapor–liquid–solid approach. For
example, SnO2 nanowires were grown directly on the electrodes of sensors and
tested for NO2 gas sensing. The synthesis of these SnO2 nanowires was carried out
by thermal evaporation of Sn metal powders at low temperatures of 600–700 °C. This
was performed in the flows of O2 gas at a flow rate of 10 sccm and growth pressure
of 1–10 Torr. Gold films of 0.2–0.3 nm were used as the catalyst for the growth of
these nanowires. The diameters of the resulted SnO2 nanowires were ranged from 50
to 100 nm, which was determined by the growth temperatures. The growth of silicon
oxide (SiOx ) nanowires was demonstrated by a simple thermal CVD approach. In
this case, GaN powders were used as the Ga source, i.e., the metal catalyst. The Si
sources can be the Si wafers, SiO powders, or silane (SiH4 ) gas. The GaN powders
were placed at the location with temperature around 1150 °C, no matter what Si source
Fig. 8.4 Badminton-like SiOx nanowire at different magnification (a, b), c TEM image of a
badminton-like structure. Reprinted with permission from © Tsinghua Science and Technology,
10, 718–728 (2005)
was used. This technique was based on the VLS process. In fact, bundles of these SiOx
nanowires can be grown from a micrometer-sized Ga droplet. They can assemble into
gourdlike, spindle-like, badminton-like, and octopus-like morphologies at different
temperature zones. For example, the badminton-like structures can be formed at 980–
1010 °C (Fig. 8.4a, b). These SiOx nanowires exhibit branching growth features with
a height of ~10 to 15 mm (Fig. 8.4c).
Thermal CVD was used for the growth of doped nanostructures. For example,
Sb-doped SnO2 nanowires were grown for gas sensor application. In this case, metal
Sn and Sb powders mixed in the weight ratio of 10:1 were used as the evaporation
sources in a thermal CVD system. Si substrates coated with 5 nm gold were placed
downstream in the furnace.
8.3 Chemical Vapor Deposition 105
The temperature at the center of quartz tube was 900 °C, and a constant flow of
1% oxygen and 99% nitrogen was maintained at a flow rate of 5 l/min. The as-grown
nanowires have a diameter of 40–100 nm and lengths up to several tens of microm-
eters. The CVD has been a very useful and versatile technique. Nanostructures that
were initially grown by other techniques have later been successfully grown by CVD.
For example, instead of laser-assisted catalytic growth, silicon nanowires are now
commonly grown by thermal CVD. This was carried out using Au nanoparticles as
the catalyst and Silane (SiH4 , 10% in He) gas as the Si source [7].
8.3.2 Metal–Organic Chemical Vapor Deposition (MOCVD)
Thermal CVD techniques discussed so far are not always the suitable approach for
the growth of certain nanostructures. For example, GaN nanowires have been grown
by laser ablation and thermal CVD. High temperatures were needed to generate Ga
vapor source in the thermal CVD technique, and Ni, Fe, and Au were used as the
catalysts. The use of a solid Ga is technically simple but often leads to nonconstant
vapor pressures for continuous growth of GaN nanowires. Metal–organic chemi-
cal vapor deposition (MOCVD) was found to be a more versatile technique for the
growth of GaN nanowires. The MOCVD technique seems to overcome the vapor
pressure problem and yield high-quality GaN nanowires. In the MOCVD approach,
trimethylgallium (TMG) and ammonia gas were used as Ga and N precursors. Silicon
substrates or c-plane and a-plane sapphire substrates coated with 2–10 nm thin film
of Ni, Fe, or Au were used for the growth at 800–1000 °C. The reaction was carried
out in an oxygen-free environment at atmospheric pressure. TMG was kept cool in
a—10 °C temperature bath. Nitrogen was used as a carrier gas and percolated through
the TMG precursor and coupled with a second nitrogen line to give a total nitrogen
flow rate of 250 sccm. Hydrogen and ammonia gases were supplied at a total flow
rate of 155 sccm. The as-grown GaN nanowires were having diameters of 15–100 nm
and lengths of 1–5 mm, oriented predominantly along the [210] or [110] direction.
MOCVD technique was also used for growing nanostructured IrO2 crystals. The
nanostructured crystals were grown on a gold-coated quartz substrate and their gas-
sensing properties were studied by quartz crystal microbalance (QCM) technique.
The growth of these nanostructures was performed by using (methylcyclopentadi-
enyl) (1,5-cyclooctadiene) iridium, (MeCp)Ir(COD), as the precursor. The quartz
substrate temperature (Ts) was kept between 350 and 500 °C. High-purity oxygen
was used as carrier gas at a flow rate of 100 sccm, which leads to a growth pressure of
7.2 Torr. The temperature of the precursor reservoir (Tp) was varied between 95 and
1058C. Different morphologies, such as nanoblades, layered columns, incomplete
nanotubes, and square nanorods, were observed at various combinations of Ts and
Tp [8].
8.4 Solution-Based Chemistry
In addition to the vapor phase growth techniques discussed so far, several solution
phase deposition techniques have been used for the growth of various alternative
nanostructures.
8.4.1 Hydrothermal Synthesis
Tungsten oxide nanowires (WO2.72 ) were grown by hydrothermal technique and

were tested for hydrocarbon sensing. Sensors based on WO2.72 nanowires show high
sensitivity for 50–2000 ppm of LPG (propane–butane mixture) at 200 °C as well
as relatively short recovery and response times. These WO2.72 nanowires were pre-
pared by solvothermal synthesis. Tungsten hexachloride (1 g) was loaded into a 25 ml
autoclave filled with ethanol up to 90% of its volume. Hydrothermal synthesis was
carried out at 200 °C for 24 h. The product obtained by centrifugation was washed
with ethanol. The as-grown nanowires were having diameters of 5–15 nm and lengths
of 100–200 nm. ZnO nanorods can also be grown by hydrothermal techniques. Zinc
and cetyltrimethylammonium bromide (CTAB) were used as the precursors. CTAB
(1.5 g) was dissolved in deionized water (35 ml) to form a transparent solution. Then,
zinc powders (1.8 g) were added to the above solution under continuous stirring. The
resulting suspension was transferred into a teflonlined stainless steel autoclave (vol-
ume 40 ml) and sealed tightly. Hydrothermal treatments were carried out at 182 °C
for 24 h. The autoclave was then cooled down. Next precipitates were collected,
washed with deionized water for several times, and dried in air. The lengths of the
ZnO nanorods are usually shorter than 1 mm and their diameters ranging from 40 to
80 nm. These nanorods were used for the sensing of various vapors including alcohol,
LPG, gasoline, ammonia, etc. Vanadium oxide (V2 O5 ) nanobelts coated with Fe2 O3 ,
TiO2 , and SnO2 nanoparticles have been prepared by mild hydrothermal reaction. For
the growth of the V2 O5 nanobelts, nitric acid was added dropwise to a 0.1 M ammo-
nium metavanadate solution until the final pH value of the solution reached about 2–3
under stirring. Solution obtained was transferred to a Teflon-lined autoclave and filled
with deionized water up to 80% of the total volume. Then the autoclave was kept at
180 °C for 24 h. The final product was washed with deionized water and pure alcohol
several times to remove any possible remnants. The as-grown nanobelts were tens of
micrometers long with smooth surfaces, typically 60–100 nm wide and 10–20 nm
thick. These nanobelts were then coated with the oxide nanoparticles for the sens-
ing of alcohol, benzene, cyclohexane, gasoline, ammonia, etc. NiFe2 O4 nanospheres,
nanocubes, and nanorods were prepared by a hydrothermal method. For synthesizing
these NiFe2 O4 nanostructures, Ni(NO3 )2 ·6H2 O and Fe(NO3 )3 ·9H2 O were dissolved
in deionized water to form a mixed solution with [Na2+ ] = 0.10 mol/l and [Fe3+ ] =
0.20 mol/l. NaOH solution (6.0 mol/l) was added dropwise under stirring into 20.0 ml
of the mixed solution until the desired pH value was attained to form an admixture.
8.4 Solution-Based Chemistry 107
In the next step, the admixture was transferred to a Teflon autoclave (50 ml volume)
with a stainless steel shell up to 80% of the total volume. The autoclave was kept
at 120–200 °C for 24–96 h and then cooled down. The final product was washed
with deionized water and alcohol for several times and then dried. The length and
diameter of the nanorods were about 1 mm and 30 nm, respectively; the side length
of the nanocubes was about 60–100 nm. It was found that sensors based on NiFe2 O4
nanorods were relatively sensitive and selective to triethylamine [9].
8.4.2 Hydrolysis
The growth of Fe2 O3 /ZnO core/shell nanorods was reported by a solution phase-
controlled hydrolysis process of Zn2+ ions in the presence of Fe2 O3 nanorods. One
hundred milligram of Fe2 O3 nanorods (~100 nm long, 25 nm in diameter) were
dispersed in 200 ml deionized water by ultrasonication. Then 20 mg of zinc acetate
(Zn(Ac)2 ·6H2 O)) was introduced to the solution, and the suspension was heated in
an oil bath at 40 °C under vigorous stirring. Twenty milliliters of 5% ammonia was
then added into the suspension for 30 min, and the reaction was maintained at the
temperature for 1 h. The colloidal suspension was then centrifuged and sintered
at 400 °C for 2 h to obtain Fe2 O3 /ZnO nanorods. These core/shell structures have
diameters of ~30 nm.
8.4.3 Aqueous Chemical Growth
ZnO nanostructures were deposited on glass substrates by the aqueous chemical

growth technique at ~95 °C. The growth process involves the use of an equimolar
(0.01 M) aqueous solution of Zn(NO3 )2 ·6H2 O and C6 H12 N4 as the precursors. The
solution and the substrates were then placed in glass bottles and heated at 95 °C for
1, 5, 10, and 20 h. After each induction time, the substrates were thoroughly washed
with deionized water and dried in air. Flower-like aggregations of ZnO nanorods
were deposited in all cases. The diameters of these nanorods are relatively big (~500
to 1000 nm) and increased with the deposition duration. Their lengths are usually
<10 mm [10].
References
1. Whitesides GM, Kriebel JK, Mayers BT (2005) Self-assembly and nanostructured materials.
In: Nanoscale assembly. Nanostructure science and technology. Springer, Boston, MA
2. Fiorani D, Sberveglieri G (1994) Fundamental properties of nanostructured materials. World
Scientific Publishing Co. Pte. Ltd, Italy
3. Arregui FJ (2009) Sensors based on nanostructured materials. Springer, Spain
4. Horprathum M, Eiamchai P, Kaewkhao J et al (2014) Fabrication of nanostructure by physical

vapor deposition with glancing angle deposition technique and its applications. AIP Conf Proc
7:1617–1624
5. Khanh LD, Binh NT, Binh LTT et al (2008) SnO2 nanostructures synthesized by using a thermal
evaporation method. J Korean Phys Soc 52:1689–1692
6. Hernandez MA, Alvaro R, Serrano S et al (2011) Catalytic growth of ZnO nanostructures by
r.f. magnetron sputtering. Nanoscale Res Lett 6:437–444
7. Shariffudin SS, Herman SH, Rusop M (2014) Self-catalyzed thermal chemical vapor deposited
ZnO nanotetrapods. Adv Mater Res 832:670–674
8. Fu K (2009) Growth dynamics of semiconductor nanostructures by MOCVD. Universitetsser-
vice US AB, Stockholm, Sweden
9. Xu X, Wu M, Asoro M et al (2012) One-step hydrothermal synthesis of comb-like ZnO
nanostructures. Cryst Growth Des 12:4829–4833
10. Nair SS, Forsythe J, Winther-Jensen B (2015) Directing the growth of ZnO nano structures on
flexible substrates using low temperature aqueous synthesis. RSC Adv 5:90881–90887
Chapter 9
Functionalization of Nanostructures
Abstract Presently, coating on nanostructural materials is preferred for exact release

of biological entities into human system for varies desired application like drug deliv-
ery system, and thus the functionalization is an important concept for nanostructural
material development. The functionalization is made by coating the material surface,
tuning the material size etc.
9.1 Aspects of Nanostructure System
Nanotechnology allows for a unique control of the material world, and any material
comprising an average phase or grain size in the order of a nanometer (10−9 m)
is defined as a nanostructured material. At this scale, man-made objects are able to
gain access to cells as nanostructured materials have enhanced mechanical properties
compared to conventional materials due to their ultrafine microstructure and ability
to interface with living cells. Nanostructured materials of varying compositions play
important roles in cancer therapeutics due to their passive tumor targeting property.
In this context, inorganic metal complexes occupy a pioneer niche as they offer a
multipurpose platform for drug design and development, and the nanostructures used
in the functionalization of metallodrugs act as transport vehicles to deliver the met-
allodrugs to the biological target. Nanostructured systems, such as macromolecular
systems, carbon nanotubes, dendrimers, metallacages, ceramic materials, liposomes,
and lipid nanocapsules, as well as metal and polymeric nanoparticles are commonly
used for drug delivery. In addition, the optimum loading and sustained release of
metallodrugs from nanostructures are essential requirements for every drug delivery
system. Therefore, it is important to ensure that metallodrugs are attached to the sur-
face of nanoparticles with adequate strength to withstand the wear and tear during
the passage to the target site. However, it is also crucial to ensure that the bond is
weak enough to release the metallodrugs at the target site [1].
Nanostructured surfaces can be produced on conventional biomaterials by surface
modification. Depending on the ways surfaces are modified, nano-functionalization

https://doi.org/10.1007/978-3-030-26145-0_9
110 9 Functionalization of Nanostructures
techniques can be categorized into two groups, namely nano coating and film deposi-
tion as well as in situ surface nano-functionalization. These two types of techniques
are often combined to produce surfaces with hybrid nanostructures such as a coating
and a nanostructured zone.
Typical coating and film deposition techniques are plasma spraying, plasma
immersion ion implantation & deposition (PIII&D), sol–gel, chemical vapor deposi-
tion (CVD), physical vapor deposition (PVD), cold spraying, self-assembly, and so
on, whereas in situ surface modification techniques include laser etching, shot blast-
ing, acid and alkali treatments, anodic oxidation, micro-arc oxidation, ion implanta-
tion, etc. The nano-functionalized surfaces also possess promising biological prop-
erties and therefore, the biological properties and clinical applications of titanium,
titanium alloys, and related materials can be improved and widened by producing a
nanostructured surface [2].
9.2 Chemistry of Nanostructure Functionalization
Nanostructuration may produce surfaces with controlled topography and chem-

istry that could help developing of novel implant surfaces with predictable tissue-
integrative properties. It was indicated that the implant surface nanostructuration is
a decisive factor in surface cell adhesion and growth, by modulating cell behavior
and protein adsorption. Surface chemical composition and local atomic charges are
also critical for protein adsorption and cell attachment. Recently, Calcium phos-
phate compounds CaPs have been widely used as coatings for metallic prostheses
to improve their biological properties. Once the integration of titanium implants
coated with biomimetic calcium phosphate has been investigated in pre-clinical com-
parative models. Studies have demonstrated a higher bone-to-implant contact for
biomimetic calcium phosphate coatings than for uncoated ones. A common method
of adding functionality to silica nanoparticles is by installing amino groups onto the
surface. Amination is an ideal method to install functionality because amino groups
react specifically and spontaneously with other functional groups. Installing amino
groups on the surface of the particles, followed by conjugation of water-soluble
molecules, increases biocompatibility. Silica nanoparticles themselves are biocom-
patible, but certain molecules such as PEG can enhance biocompatibility, stability,
cell penetration, and water solubility [3].
9.3 Need for Functionalization
Functionalization has been used to conjugate drug molecules, polymers and organic
groups to NPs. In addition, functionalization has also been shown to protect NPs
against agglomeration and render them compatible in other phases. Functionaliza-
tion also improves the physical, chemical and mechanical properties of NPs, which
9.3 Need for Functionalization 111
are synergetic. Functionalization of the NPs can be defined as the addition of a chem-
ical functional group on their surface in order to achieve surface modification that
enables their self-organization and renders them compatible. NPs have mainly been
functionalized with thiols, disulfides, amines, nitriles, carboxylic acids, phosphine
and biomolecules. The main goal of functionalizing NPs is to cover their surface
with a molecule that possesses the appropriate chemical functionality for the desired
application. In all cases, functionalization of the particles produces a drastic change
in their surface properties. The surface chemistry of NPs is already an important
aspect of their synthesis, since this property can be exploited to control their size
and self-organization during formation. This can be achieved by complexing groups
that bind on the surfaces during their formation and complex formation should not
promote agglomeration [4].
9.4 Methods of Functionalization
There are two strategies for introducing functional groups to surfaces and NPs.
The first method is direct functionalization, where the whole functional ligand is
a bi-functional organic compound. In this approach, one of the functionally reactive
groups is used to attach to the NPs surface and the second group contains the required
active functionality. Direct functionalization is preferred because it only requires a
single conjugation step. One limitation of the direct functionalization method is the
incompatibility of the functional group F with the preparation process, for instance
the modifying group may react with the particle surface.
The second method is post-functionalization, which is generally preferred because
this strategy is more versatile and the nature of the functionalizing moieties may not be
fully compatible with good control over the size and dispersion state of the particles in
the solvent used for their synthesis. This describes a bifunctional compound where
a binding chelating group is reacted first and the group of coupling site can be
converted, in a second step, to the final functional group F. Post-functionalization
of the particles requires a molecule to be grafted on the surface such that it has a
structure that can be described as N-C-F (Nanoparticle-Chelating agent-Functional
group). For post-functionalization, silane like compounds has been generally used.
Hydrolysis reactions lead to the formation of a silane like coating around the particles
with a fraction of the functional group orientated towards the outside of the particle.
This process has been used in many systems, mostly in oxide systems, but it has also
been investigated in the case of chalcogenides [5] (Fig. 9.1).
Fig. 9.1 Schematic representations of functionalization methods. Reprinted with permission from
© Current Medicinal Chemistry, 17, 4559–4577 (2010)
9.5 Class of Functionalization
9.5.1 Thiol/Aminothiol
Thiol chemistry is one of the most developed functionalization methods used for the
fabrication of functional NPs. Figure 9.2 describes the chemical functionalization
reaction of thiols. Sulfur compounds naturally form strong coordination bonds with
many metals including Ag, Cu, Pt, Hg, Fe, Si, and Au. Sulfur and organosulfur have a
high affinity for metal surfaces and thus will adsorb spontaneously. Thiol or disulfide
capped NPs can be prepared by either the direct functionalization method where
the metal precursor and the protective ligand are reacted simultaneously. Another
method based on thiol chemistry is the post functionalization method, where the
sulfur compounds are grafted on the surface of presynthesized NPs that are covered
by solvent molecules and are thus replaced by sulfur containing ligands [6].
9.5.2 Bio-functionalization
NPs functionalized with biomolecules have recently attracted great interest because
the resulting hybrid materials have proven to be useful as drug carriers. Small bio-
logical molecules such as amino acids can be anchored to the surface of the NPs,
9.5 Class of Functionalization 113
Fig. 9.2 Schematic of the thiol group based functionalization. Reprinted with permission from ©
Current Medicinal Chemistry, 17, 4559–4577 (2010)
opening the possibility of attaching functional biomolecules to bio FNPs. Au NPs

functionalized with proteins and investigated the mechanical properties of the result-
ing NPs, which could be used to tune the properties of biomolecular films. The use
of N-(2-aminoethyl)-APS (AEAPS) for the surface modification of iron oxide NPs
have become a popular method for the covalent attachment of antibodies such as
anti-CD34. NPs modified with molecules such as organosilane, vinyl alcohol/vinyl
amine co-polymer were used for subsequent conjugation of antibodies, which could
then be utilized for targeting specific biological cells and tissues. molecular target-
ing camptothecin (anticancer) drug delivery system using BH3 and LHRH peptides
functionalized polymeric NPs to treat ovarian cancer [7].
9.5.3 Asymmetric Group
Asymmetric nanostructures are more versatile building blocks compared to their

symmetric counterparts. For example, Au NPs were asymmetrically modified with
single strand DNA, which can be used as the building block to prepare more com-
plex structures such as dimers and trimmers, also asymmetric diblock Au-polymer
nanorods can self-assemble into bundles, tubes, and sheets Similarly, Au shell struc-
tures were grown on a silica surface to produce Au cups or caps. The asymmetric
structure in the nano rod system has also been realized using the chemical vapor
deposition technique, which is known as the direct functionalization method. Like-
wise, asymmetric rods can be synthesized using template directed growth. However,
when this approach is used, relatively large particles are produced. For example, the
Au-metal oxide asymmetric dimers can only be prepared from metal oxide particles
larger than 200 nm. The Au-polymer asymmetric nanorods have diameters around
200 nm and lengths over 1 μm. As a result, they can only be used to prepare particles
with dimensions of μm or larger. To synthesize nanometer sized assemblies, smaller
asymmetric building blocks are needed. Furthermore, it is desirable to develop a
range of methods that can yield such structures. The structure of the tetrapod is topo-
logically similar to that of a sp3 hybridized carbon atom. This kind of structure can
serve as a building block to prepare superstructures, especially 3D superstructures,
by mimicking the bonding between carbon atoms and organic molecules [8].
9.5.4 Polymers in Functionalization
The polymer matrix embedded in the NPs plays a major role in dictating the compat-
ibility of the NPs for applications in harsh environments such as in acidic and alkali
solutions. Also polymer NPs are widely used in pharmaceuticals application particu-
larly cancer therapy and drug targeting. In polymeric nanocomposites synthesis, NPs
or nanofibers have been used as fillers to improve the properties of the nanocom-
posites such as strength, which is very important in tissue engineering applications
[9].
9.5.5 Functionalization of Metals
The main purpose of surface functionalization of pure Mg or Fe and alloys is to

control their degradation rate. In the particular case of Mg, the degradation after
surface functionalization can be highly mitigated but not stopped. Contrary, when
considering Fe, the surface functionalization aims an increased corrosion rate. The
underneath substrate degradation process will be constrained by the presence of
cracks or defects on the coating. Therefore, the durability and integrity of the coating
is crucial in biomedical applications. An improved surface biocompatibility and/or
drug vehicle for controlled release can be regarded as a plus for pure Mg, Fe or
Zn and alloys, although in the specific case of Zn, the surface functionalization of
Zn should induce no more than slight changes in the corrosion rate of this metallic
biomaterial [10].
9.5.6 Rare-Earth in Functionalization
The design of nanostructured materials containing (Rare Earth) RE elements, either

as major components or as dopants, has paved the way for the development of new
applications. In particular, nanoparticles (NPs) possess the size (ranging from 1 to
9.5 Class of Functionalization 115
100 nm) in which most of the biomolecular interactions take place, so the incorpo-
ration of RE into NPs allows their use in many different biomedical applications,
including bioimaging, biosensing, targeting, drug delivery and other therapies.
9.5.6.1 Functionalization of RE-Based Nanostructures
Solvothermal-based methods are those carried out in closed vessels under autogenous
pressure above the boiling point of the solvent. They have been applied for the
synthesis of many different nanomaterials. RE chlorides and nitrates are normally
used as precursors. When using water as solvent (hydrothermal synthesis), in some
cases, no additives are required to control particle size and shape, as in the synthesis
of NaREF4 (RE = Pr, Sm, Gd, Tb, Dy, Er) nanotubes, which were obtained using a
two-step procedure. Firstly, RE(OH)3 nanotubes of dimensions of 300 × 50 nm were
synthesized after submitting at 120 °C a aqueous solution of the corresponding RE
nitrates at pH 14. Such RE(OH)3 nanotubes were then treated at 120 °C with aqueous
solutions containing HF and NaF to obtain NaREF4 nanotubes. CePO4 nanotubes
were also prepared without additives after hydrothermal reaction of Ce(NO3 )3 ·6H2 O
and (NH4 )2 HPO4 solutions at pH 1 and 180 °C. Likewise, REPO4 (RE = La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) nanotubes with diameters ranging
from 5 to 120 nm were obtained after treatment at 150 °C of aqueous basic solutions
containing the corresponding RE nitrates and NH4 H2 PO4 . Finally, CePO4 :Tb3+ and
LaPO4 :Eu3+ nanorods were also synthesized in a water/ethanol mixture at 120 °C
from the lanthanide chloride and H3 PO4 . In all these examples, an optimization of the
reaction pH was carried out. In most hydrothermal syntheses, however, hydrophilic
additives are needed to produce uniform NPs. Among them, the most common is
sodium citrate, which is able to form strong complexes with the REs, as previously
commented. Several examples can be cited in which these complexes have been
used in aqueous solutions such as the synthesis of NaGdF4 nanorods (100 nm) at
180 °C from solutions containing Gd(NO3 )3 and NaF, and the synthesis of BaGdF5
porous nanospheres of sizes ranging from 65 to 119 nm from solutions containing
gadolinium and barium nitrate and NaBF4 at 180 °C in butyl amine, which was used
to increase the pH. Some RE phosphates have been also synthesized in this way as it
is the case of YPO4 :Ln3+ (Ln = Tb, Eu, Dy) nanorods (60 × 35 nm), synthesized at
180 °C from acid aqueous solutions of the corresponding RE chloride, sodium citrate
and Na5 P3 O10 , and YPO4:Ln3+ (Ln = Tb, Eu) spherical-like NPs obtained after
hydrothermal treatment at 180 °C of basic aqueous solutions of Y(NO3 )3 , sodium
citrate and Na3 PO4 .
Other hydrophilic additives used for the hydrothermal synthesis of RE-based NPs
are PEG, Ethylenediaminetetraacetic acid (EDTA), PEI, PAA and polyvinylpyrroli-
don (PVP). PEG has been used, for example, for the hydrothermal synthesis
at 190 °C of BaLuF5 NPs (24 nm) from solutions containing PEG, BaCl2 ,
Lu(NO3 )3 and NH4 F. Likewise, BaGdF5 nanospheres have been synthesized from
aqueous basic solutions containing EDTA BaCl2 , GdCl3 and NaBF4 at 180 °C. PEI
has been used for the solvothermal synthesis in EG at 200 °C of NaGdF4 :Yb3+ ,
Ln3+ (Ln = Er, Tm, Ho) cubic NPs (40 nm) from the corresponding RE chloride,
NH4 F and PEI; KGdF4 :Ln3+ (Ln = Gd, Eu, Tb, Dy) roughly spherical NPs (25 nm)
were obtained from KCl, RE chloride and NH4 F solutions in EG at 200 °C. Eu3+
doped calcium apatite 191 × 40 nm nanospindles have been synthesized in water
at 180 °C from calcium nitrate, sodium phosphate monobasic and PAA at basic pH.
Finally, PVP has been used for the synthesis of 50 × 10 nm GdPO4 :Ln3+ (Ln =
Ce + Tb, Eu, Yb + Er) nanorods by treatment at 180 °C of aqueous solutions of
Gd(NO3 )3 and Na2 HPO4 . Organic hydrophobic additives such as linoleic or oleic
acid, often in presence of sodium linoleate or oleate, are also frequently used for the
solvothermal synthesis of highly uniform RE-based NPs in organic media, mostly in
alcohol and in alcohol/water solutions. Typical examples are the synthesis of highly
uniform REF3 and NaREF4 fluorides from the corresponding RE acetate and NaF in
water/ethanol-containing linoleic acid or sodium linoleate solutions at temperatures
ranging from 100 to 200 °C. This procedure yields rounded NPs of NaYF4 , YbF3
and LaF3 of around 4–12 nm diameter and rice-like YF3 NPs of 500 × 100 nm.
Other RE fluoride systems synthesized following this strategy are LaF3 :Ln3+ (Ln
= Ce/Tb and Yb/Er) and NaLaF4 nanorods, obtained from the corresponding RE
nitrate, NaOH, NaF and oleic acid in a water/ethanol solution treated at 190 °C
and NaYb1−x Gdx F4 :Ln3+ (Ln = Eu3+ , Tb3+ , Ce3+ /Eu3+ , Ce3+ /Tb3+ , Ce3+ /Eu3+ /Tb3+ ,
Ho3+ , Er3+ , Tm3+ and Er3+ /Tm3+ ) NPs obtained from the corresponding RE nitrate,
NaOH and NH4 F at temperatures ranging from 130 to 230 °C. In the last case the
Gd content played a key role in the final morphology of the NPs, which ranged from
NaYbF4 nanocubes to NaYb1−x Gdx F4 nanorods.
Round-shaped NPs for REF3 (RE = La to Eu) and rice-like NPs for REF3 (RE
= Gd to Yb) have also been obtained at temperatures ranging from 100 to 200 °C
from solutions of RE nitrates in water and ethanol with sodium linoleate and linoleic
acid as additives. Some amines have also been employed instead of fatty acid deriva-
tives. For example, GdF3 nanowires (length ≤ 40 nm) were synthesized at 240 °C
from a solution of Gd(NO3 )3 ·xH2 O and HF in octylamine/ethanol, and rice-like
YF3 and YbF3 NPs have been obtained from ethanol/water solutions of RE nitrates,
linoleate acid, octadecylamine and NH4 HF2 treated at 100–200 °C. Other RE-based
phases have also been synthesized following this method. For example, YPO4 :Eu3+
hexagonal-like NPs of around 16 nm were obtained from the RE nitrates, NaH2 PO4 ,
NaOH and oleic acid in a water/ethanol solution at temperatures ranging from 100 to
140 °C. Likewise, REPO4 ·H2 O (RE = Y, La-Nd, Sm–Lu) of different morphologies
(sphere-like, rod-like and polygon-like, with sizes ranging from 8 to 60 nm, depend-
ing on the RE) were synthesized from RE nitrate, NaH2 PO4 , oleic acid, and NaOH
solutions in water and ethanol treated at 140 °C. However, the use of hydrophobic
additives finally produces hydrophobic NPs, thus demanding further functionaliza-
tion treatments. The main advantages of hydrothermal methods with or without
hydrophilic additives over the solvothermal method using hydrophobic additives are
the final hydrophilic character of the NPs, their high level of crystallinity and the fact
that in contrast to most organic solvents water is not toxic. However, these methods
also present some drawbacks such as the larger particle size that usually results in
comparison with that produced by the organic solvent-based methods [11] (Fig. 9.3).
9.6 Miscellaneous Functionalized Nanostructures 117
Fig. 9.3 (a) YF3 NPs synthesized from yttrium acetylacetonate and the IL [BMIM] BF4 in ethylene
glycol at 120 °C. (b) Ca5 (PO4 )3 )(OH):Eu3+ nanospindles synthesized through a microwave-assisted
hydrothermal method at 180 °C in the presence of PAA. (c) NaYF4 NPs synthesized through a
solvothermal method in ethanol with linoleic acid and sodium linoleate as additives. Reprinted with
permission from © Nanophotonics, 6, 881–921, (2017)
9.6 Miscellaneous Functionalized Nanostructures
Functionalization of the liquid media in which self-assembled monolayers are

deposited to nanostructured high surface area materials has resulted in several
improvements in the process and the product materials. The processing time has
been reduced by three orders of magnitude. The monolayers produced from Super-
critical fluids (SCFs) demonstrate the ability to “heal” over time, resulting in nearly
defect-free coatings. This lack of defects allows greater coverage, and has redefined
what is meant as fully dense monolayer. Depositions of covalently bound functional
groups to extremely small pore spaces (i.e., <10 Å zeolites) are possible in super-
critical media. Functionalizing the internal surfaces of aerogel materials is likewise
enabled using super critical fluids (SCFs), and circumvents the structural collapse of
such materials brought about by surface tension. The coated aerogel materials so pro-
duced are strengthened by the coating, and have been shown to withstand immersion
in aqueous solutions [12].
Functionalized Peptide Nanostructures containing bioactive signals that com-
bine bioactivity for multiple targets with biocompatibility, improve the possibility to
deliver proteins, nucleic acids, drugs and cells. Their chemical design versatility leads
to a variety of possible secondary, tertiary and quaternary structures through folding
and hydrogen bonding. In particular, β-sheet forming peptides have demonstrated the
extraordinary ability to use intermolecular hydrogen bonding for the assembly of one-
dimensional nanostructures. Furthermore, the design of self-assembly peptides for
targeted functions can also include their modification with other biomolecular units
such as sugars, lipid components and nucleic acid monomers. These oligopeptides,
whilst designed for supramolecular self-assembly, could also serve to functionally
mimic large proteins. For these reasons, self-assembling, nonimmunogenic peptides
project as promising new therapeutics for human disease [13].
References
1. Thangavel P, Viswanath B, Kim S (2017) Recent developments in the nanostructured materials

functionalized with ruthenium complexes for targeted drug delivery to tumors. Int J Nanomed
12:2749–2758
2. Xuanyong L, Chu PK, Ding C (2010) Surface nano-functionalization of biomaterials. Mater
Sci Eng R 70:275–302
3. Issa S, Azevedo C, Pires R et al (2015) Functionalization of nanostructured TiO2 surfaces with
electrodeposited strontium doped calcium phosphate and evaluation of BSA adsorption for
dental implant design. J Nanomed Nanotechnol 6:344–355
4. Doty RC, Tshikhudo TR, Brust M et al (2005) Extremely stable water-soluble Ag nanoparticles.
Chem Mater 17:4630–4635
5. Philipse AP, Nechifor AM, Pathmamanoharan C (1994) Isotropic and birefringent dispersions
of surface modified silica rods with a boehmite-needle core. Langmuir 10:4451–4458
6. Gooding JJ, Mearns F, Yang W et al (2003) Self-assembled monolayers into the 21st century:
recent advances and applications. Electroanalysis 15:81–96
7. Dharap SS, Qiu B, Williams GC et al (2003) Molecular targeting of drug delivery systems to
ovarian cancer by BH3 and LHRH peptides. J Control Release 91:61–73
8. Park S, Lim JH, Chung SW et al (2004) Self-assembly of mesoscopic metal-polymer
amphiphiles. Science 303:348–351
9. Mammeri F, Le Bourhis E, Rozes L et al (2005) Mechanical properties of hybrid organic-
inorganic materials. Mater Chem 15:3787–3811
10. Santos C, Alves MM, Montemor MF et al (2017) Bioresorbable metallic implants: surface
functionalization with nanoparticles and nanostructures. In: Advanced materials and their
applications—micro to nano scale, pp 219–242
11. Escudero A, Becerro AI, Carrillo-Carrion C et al (2017) Rare earth based nanostructured
materials synthesis functionalization properties and bioimaging and biosensing applications.
Nanophotonics 6:881–921
12. Zemanian TS, Fryxell GE, Liu J et al (2001) Chemical functionalization of nanostructured
materials using supercritical reaction media. In: Proceedings of the 1st IEEE conference on
nanotechnology, pp 288–292
13. Peran M, Garcia MA, Lopez-Ruiz E et al (2012) Functionalized nanostructures with application
in regenerative medicine. Int J Mol Sci 13:3847–3886
Chapter 10
Characterization and Technical Analysis
of Nanostructured Materials
Abstract The morphology, structural and other properties of nanostructured mate-

rials are analyzed by different characterization techniques. In the below characteri-
zation studies, the shapes, sizes, and structures of nanostructured materials and their
distribution are investigated. This chapter discuss briefly on analysis techniques.
In order to realize the correlation between structure and properties, nanocrystalline

materials need to be characterized on both atomic and nanometer scales. The charac-
teristic of above involves determining the shapes and sizes of nanoparticles and under-
standing of the inter-particle interactions [1]. A number of experimental techniques
have been employed to yield structural information on nanocrystalline materials.
1. Atomic force microscopy (AFM)
2. Transmission electron microscopy (TEM)
3. Scanning electron microscopy (SEM)
4. Field ion microscopy (FIM)
5. Absorption spectra
6. Diffraction of X-rays, electrons or neutrons
7. Rutherford back scattering (RBS)
8. Raman spectroscopy
9. Auger electron spectroscopy (AES)
10. Photoluminescence and Photoluminescence excitation.
Techniques such as scanning electron microscopy (SEM) or transmission elec-
tron microscopy (TEM) are prominent examples of these approaches; with the latter
atomic resolution is possible but sample preparation is time consuming and may
introduce artefacts. Two other examples of characterization techniques based on
high energy ions and electrons, which yield not only images but other, e.g. chemi-
cal information, are Nano-SIMS (secondary ion mass spectrometry) with a spatial
resolution of about 50 nm, and XPS (X-ray photoelectron spectroscopy) and PEEM
(photoemission electron microscopy) using synchrotron radiation, which in contrast
to hard-to-focus conventional X-rays can be focused to yield spatial resolutions of
100 nm or even lower [2].

https://doi.org/10.1007/978-3-030-26145-0_10
120 10 Characterization and Technical Analysis of Nanostructured …
10.1 Atomic Force Microscopy (AFM)
Atomic-force microscope (AFM) allows obtaining the three-dimensional images of

a surface of solid state with nanoscale resolution. However in a usual mode with
the help of AFM it is possible to obtain data only about surface of solid samples,
because AFM cantilever tip cannot glance in deeper near-surface layers of substance.
The level-by-level removal of superficial layers, for example with the help of their
dissolution or chemical etching in liquid environment, allows taking off this restric-
tion. This method is especially effective for study of nanostructured materials which
have different rate of dissolution of separate nanofragments. The selective chemical
etching of the surface of such sample can reveal thin structure of such substance in
this case. It is essential, that as it is possible to carry out researches with AFM in
liquid environment so there is an opportunity to observe transformation of the surface
during etching in in situ mode in a real time scale [3].
10.2 X-Ray Diffraction (XRD)
XRD pattern from nanostructured materials is similar to that from nanocrystalline

materials. If the lattice orientations of particular entities forming a solid, nanostruc-
tured material are distributed at random, the interference functions are identical.
The nanostructured materials can be multiphase. The phases can all be nanocrys-
talline or a nanocrystalline phase can be embedded inside a polycrystalline and/or
amorphous matrix. Thus besides the influence of nanocrystal size, also the grain
boundaries, defects and microstrains are to be considered. Simple modeling of XRD
pattern from material with different density and arrangement of dislocations in the
grain boundaries show that the different methods of its analysis (Scherrer’s equa-
tion, Williamson-Hall method, Warren-Averbach), based on different assumptions
can bring about significantly different results. In many instances the method of mate-
rial preparation and its history can suggest which factors can mostly influence the
observed diffraction pattern. The measurements of XRD profiles on nanocrystalline
palladium, depending on the history of the preparation of the sample shows that
there is a different structure of grain boundaries and the number of atoms at the
grain boundaries being not on crystal lattice side, i.e. in disordered state. A partic-
ular example of nanostructured materials can be supported metal catalysts in which
the prevailing part of a mass is a support, and interest is mostly in the structure of a
small fraction of the highly dispersed nanocrystalline metal. Due to the high specific
surface of the support and usually low loading of the metal, the nanocrystals of the
metal phase are distanced each from other. The XRD pattern of the catalyst is usu-
ally a superposition of two: from the metal phase and, usually predominant, from the
support. The contribution to the pattern originating from the distances between the
support and the metal in most cases can be neglected. The simplest case can be when
the background is from amorphous (or quasi-amorphous) phase which can be e.g. for
10.2 X-Ray Diffraction (XRD) 121
silica. In such a case the background can easily be modeled with smooth analytical
function and subtracted from the measured pattern and the resulting profile fitted to
an analytical function [4].
10.3 Scanning Probe Microscopies (SPM)
The new class of characterization techniques has to be emphasized, which allows the
characterization of surfaces on the nanometer scale with respect to their topography,
but also to a wide variety of other properties. These are the scanning probe micro-
scopies (SPM), which have been rapidly developed after the invention of the scanning
tunneling microscopy (STM) by Binnig and Rohrer in 1982, and subsequently that
of the atomic force microscope (AFM) by Binnig et al. in 1986. All SPM techniques
rely on the same principle: A probe or tip with an apex of nanometer dimensions is
rastered by means of piezoelectric scanners with nanometer precision over a surface,
while the interaction between tip and surface is measured. The difference between
all the various techniques can be found in the type of interaction between tip and
surface exploited which can rely e.g. on electrical, mechanical, optical, magnetic or
thermal effects. In the original SPM tunneling currents between a conductive surface
and the atoms at the very end of a sharp metal tip are measured; as a consequence, the
lateral resolution is extremely high; it is possible to observe the electron distribution
around single surface atoms [5].
10.4 Field Ion Microscopy (FIM)
The utility of the FIM for preparing and characterizing tips destined for SPM experi-
ments, the main advantage of an atomically defined tip apex is that if the exact atomic
arrangement of the apex is known, the electronic structure of the tip and the lateral
resolution of the STM are predetermined. The same detailed knowledge of the apex
termination, as well as the tip radius, is useful for atomic force microscopy (AFM)
experiments and important in the interpretation of results from combined STM and
AFM experiments. Largely unknown, the atomic-scale tip structure is directly respon-
sible for image contrast, as well as the details of the measured electronic properties
by scanning tunneling spectroscopy, chemical bonding forces by force spectroscopy,
and yield point of materials by indentation. In order to obtain quantitative and repro-
ducible data, which could be considered as a benchmark for computational simula-
tions, one requires a tip with known atomic structure. For example, FIM characterized
tips could act as atomically defined electrodes to build junctions to single molecules,
where transport properties are sensitive to the atomic arrangement of the contact
electrodes.
The FIM is the study of diffusion of single atoms or clusters on crystal surfaces,
and this technique has generated most of the existing experimental data about the
diffusion of atoms and clusters on metal surfaces. Another unique feature of the FIM
is the possibility of integrating a time-of-flight (ToF) mass spectrometer to enable
chemical analysis with single-atom sensitivity and a spatial resolution of several
angstroms. The combined technique is known as atom probe field ion microscopy
(AP-FIM) or more simply as the atom probe. In AP-FIM, a pulsed field is applied
to the FIM specimen to field evaporate a small amount of material from its surface
to be chemically analyzed in the ToF unit; it is a destructive technique, consuming
the sample as data is collected. Applications of AP-FIM include the investigation of
chemical segregation of elements at crystalline defects (steels and semiconductors),
local studies of grain boundaries in nanocrystalline materials [with grains too small
for techniques like electron backscatter diffraction (EBSD)], and short-range order
in materials (e.g., in high-temperature superconductors) [6].
10.5 Raman Spectroscopy
Raman spectroscopy is a powerful tool for the characterization of nano-sized mate-

rials and structures. It is widely used for the study of phonon confinement effects,
the effect of the increase in local temperature, strain and substitutional effects, lattice
distortion, the presence of structural defects and nonstoichiometric in different kinds
of nanomaterial. Several factors like phonon confinement, strain, non-homogeneity
of the size distribution, defects and nonstoichiometric, as well as an harmonic effects
due to temperature increases can contribute to the changes in the peak position, line,
width and shape of the Raman modes in nanostructures [7].
The grain size and its distribution, the existence of mixed phases, the value and
type of the strain, deviations from stoichiometry as well as type of stoichiometric
defects, etc. also have great influence on the Raman spectra of nanomaterials. The
Raman spectroscopy method can be used for the characterization of nano-powdered
oxides like TiO2 , CeO2 and ZnO, as well as nanostructured ZnSe/SiOx multilayers.
The shift, broadening and asymmetric shape of the Raman modes, observed in the
nanomaterials, are compared to spectra obtained from the phenomenological model,
which takes into account disorder effects through the breakdown of the k = 0 Raman-
scattering selection rule, as well as the an harmonicity, which is incorporated through
the 3- and 4-phonon decay processes. The application of a three-dimensional (3D)
confinement model appropriate to isolated or loosely connected nanoparticles shows
that the shift and broadening of the Raman peak in some nanopowders are dominated
by the strong confinement and inhomogeneous strain (CeO2 ), while in the others an
harmonic effects (TiO2 ) or tensile strain (ZnO) plays the main role. On the other
hand, the shift and asymmetric broadening of the Raman mode in nanostructured
ZnSe/SiOx multilayers is analyzed by a one-dimensional (1D) confinement model,
appropriate for very thin films or quantum wells. Due to the low dimensionality
of these structures, the surface phonon modes are also observed. The infrared (IR)
spectra of nanocrystalline solids differ from the spectra of monocrystals, due to the
polycrystalline character and island structure of nanoparticles. From IR spectra, it is
10.5 Raman Spectroscopy 123
possible to get information about the energy gap, grain size, porosity, nature of the
surface bonds, and chemical reactions occurring at the nanoparticle surface [8].
10.6 Absorption Spectroscopy (UV-Vis)
The optical absorption spectrum of ZnO nanorods and nanotubes are shown at room
temperature. The UV-visible spectrum shows a strong exciton absorption peak at 366
and 362 nm for ZnO nanorods and nanotubes, respectively and blue shifted relative to
the bulk exciton absorption (380 nm) as a result of the quantum size effect. According
to the quantum confinement theory, the electrons in the conduction band and holes
in the valance band are confined spatially by the potential barrier of the surface.
Because of the confinement of electrons and holes, the optical transition energy from
the valence top to the conduction bottom increases and the absorption maximum shifts
to the shorter wavelength region. The stronger exciton effect is an important character
of quantum confinement in nano semiconductors, in which the electrons, holes and
excitons have limited space to move and their motion is possible for definite values
of energies. The continuum of states in conduction and valence bands are broken
down into discrete states with an energy spacing relative to band edges which is
approximately inversely proportional to the square of the particle size and reduced
mass. The highest occupied valence band and the lowest unoccupied conduction
band are shifted to more negative and positive values respectively resulting in the
widening of band gap, which leads to the effective band gap larger than its bulk value.
Thus, there will be a blue shift in the absorption spectra with reduction in crystallite
size. The highly confined carriers in the nanotubes enhance the coupling interaction
with each other, thus the excitons bounded becomes very stronger. This is the reason
why the absorption peak of ZnO nanotubes has a slight blue shift compared with that
of nanorods [9].
10.7 Photoluminescence Spectroscopy (PL)
Photoluminescence (PL) spectroscopy is a useful technique for the study and char-
acterization of materials and dynamical processes occurring in materials, specifi-
cally the optical properties of the materials. This technique involves measuring the
energy distribution of emitted photons after optical excitation. This energy distri-
bution is then analyzed in order to determine the properties of material, including
defect species, defect concentrations, possible stimulated emission etc. It is widely
recognized as a useful tool for characterizing the quality of semiconductor materials
as well as for elucidating the physics which may accompany radiative recombina-
tion. PL is useful in quantifying (1) optical emission efficiencies, (2) composition of
the material, (3) impurity content, and (4) layer thickness etc. It is well known that
the radiative transition between the band-gap in semiconductors is the most impor-
tant one. So the PL measurement not only helps us determine the band gap of a
semiconductor especially for a new compound semiconductor, but also guides us to
accomplish the band gap engineering, which is particularly significant for prompting
the practical applications of a semiconductor in the industry [10].
10.8 Field Emission Scanning Electron Microscopy

(FESEM)
A field emission cathode in the electron gun of a SEM provides narrower probing
beams resulting in both improved spatial resolution and less sample charging. Such
systems are designated as field emission scanning electron microscopes (FESEM).
To achieve this increased electron focusing a different gun design is required. In
this design, electrons are expelled by applying a high electric field very close to the
filament tip. The size and proximity of the electric field to the electron reservoir in
the filament controls the degree to which electrons tunnel out of the reservoir. One
type of field emission gun commonly used is known as the Schottky in-lens thermal
FESEM electron gun. Cold gun alternatives are available for even finer FESEM res-
olution; however, these suffer rapid degradation and can therefore lead to expensive
operation due to relatively frequent placement. The field emission guns have higher
stability, can allow higher current and hence provide a smaller spot size. Under good
operating conditions, a typical FESEM resolution of 1 nm is achievable. Elements
that add to improved operation and FESEM resolution include designs with a beam
booster to maintain high beam energy, an electromagnetic multi hole beam aperture
changer, a magnetic field lens and a beam path which has been designed to prevent
electron beam crossover [11]. Nanostructures have been characterized by FESEM
in different morphological formations including nanoflowers, nanosheets, nanopar-
ticles and thin films. Molybdenum disulphide (MoS2 ) nanosheets exhibit interesting
conductive/semiconductive, magnetic, photoluminescence, and photocatalytic and
field effect transistor properties. The properties of MoS2 nanosheets depend upon
the method used to generate them, and depending upon the structural properties,
these nanosheets can be used for applications in optoelectronics, energy harvesting,
spinelectronics, etc. [12].
10.9 Confocal Microscopy
In confocal microscopy two focusing arrangements are used to focus on the point in a
sample to be imaged. One focuses laser light through an objective lens to the point of
interest, and the other focuses the reflected light to the imaging sensor. Light from the
point to be imaged is passed through a pinhole such that all extraneous out of focus
10.9 Confocal Microscopy 125
light is removed. This allows lateral resolutions approximately 1.4 times greater
than in conventional microscopes to be achieved with confocal microscopy. The
depth of the focal plane depends on the specimen optical properties and importantly
on the squared value of the objective lens numerical aperture. Three dimensional
reconstructions of cells and surfaces can be achieved with this technique. To achieve
this, the sample is scanned such that one 2D slice is recorded, the focal plane of the
sample is then moved a prescribed amount where the next 2D slice is recorded and this
sequence is repeated until the required volume is scanned. Image processing software
is then used to process the collected data to reconstruct the 3D object. Confocal
microscopes are most often used to image biological systems and semiconductor
surfaces. Three variations of scanning are available in confocal microscope systems
[13].
In the conventional confocal laser scanning microscope, the sample is raster
scanned which results in a scanning rate of about three frames per second. Such
systems provide the highest spatial resolution; however for higher temporal reso-
lution, the spinning disc (Nipkow) and the programmable array microscope (PAM)
systems can provide rates of 30 frames per second. In a Nipkow disc system, a thin
disc with hundreds of spirally patterned pinholes is spun in the light path to the objec-
tive lens. The pinholes only allow perpendicularly oriented rays of light to penetrate
which allows high scanning speeds independent of the laser scanning speed. PAM
is a variation on this whereby an acousto- or electro-optical filter can be patterned
to automatically produce the pinhole pattern required. Such a system can allow for
up to 1000 beams to simultaneously scan the entire field at millisecond scan speeds.
High-frequency scanning has the added advantage of reducing exposure of sensitive
samples to photons which may cause damage due to photobleaching or phototoxicity
[14].
10.10 Transmission Electron Microscope (TEM)
TEM is an established characterization technique, which can provide both image

mode and diffraction mode information from a single sample. It is regarded as one of
the main techniques for nanomaterial characterization, largely due to its high lateral
spatial resolution in the region of 0.08 nm. A feature of nanomaterials is that specific
properties, for example, colour, can be related to a particle size. Agglomeration
of nanoparticles or failure to isolate individual nanostructures is likely to result
in anomalous property characterization. Characterizing the elastic or mechanical
properties of individual nanoparticle is a challenge to many existing testing and
measurement techniques. It is difficult to pick up samples and difficult to clamp
samples, in order to test for tensile strength or creep, for example [15].
The modern TEM are capable of formatting nanometer size electron probes hav-
ing diameters ranging from 2 to 5 nm. This formation is possible by employing a
multistage condenser lens system. This lens system makes scanning transmission
mode possible, and the resulting electron probe diameter defines the resolution of
the system. Therefore, in addition to thin samples, specimens with higher degree
of crystallinity and thickness can be imaged by TEM. Multistage condenser lens
systems enable recording of secondary and backscattered electrons. This has advan-
tages for imaging thick or crystalline specimens and for recording secondary elec-
trons and backscattered electrons. The inhomogeneity in cathode luminescence can
also be recorded using complex multistage condenser lens system for correlation
with structural defects. Cathodoluminescence microscopy is a useful characteriza-
tion technique in various fields related to optoelectronics, energy, geology, cellular
biology and healthcare. Traditionally scanning electron microscopy (SEM) has been
used to study the cathodoluminescence of bulk samples as well as nanoparticles. The
limited resolution of SEM up to 20 nm in the most advanced systems restricts the
use of SEM for microstructure correlation with the cathodoluminescence. Therefore
high-resolution cathodoluminescence microscopy is possible using TEM [16].
10.11 X-Ray Photoelectron Spectroscopy (XPS)
When excess electromagnetic energy is transferred to an electron that is in an outer

shell, it is called an Auger electron. An analysis of these electrons for chemical
identification is known as Auger electron spectroscopy (AES). X-ray photoelectron
spectroscopy (XPS) analyses electron emission of similarly high energy. XPS can be
used to measure the chemical or electronic state of surface elements, detect chemi-
cal contamination or map chemical uniformity of biomedical implant surfaces. For
XPS the material to be examined is irradiated with aluminium or magnesium X-
rays. Monochromatic aluminium Kα X-rays are normally produced by diffracting
and focusing a beam of non-monochromatic X-rays off of a thin disc of crystalline
quartz. Such X-rays have a wavelength of 8.3386 Å, corresponding photon energy of
1486.7 eV, and provide a typical energy resolution of 0.25 eV. Non-monochromatic
magnesium X-rays have a wavelength of 9.89 Å, corresponding photon energy of
1253 eV and a typical energy resolution of 0.90 eV. The kinetic energy of the emitted
electrons is recorded. This kinetic energy of the ejected electrons is directly related to
the element-specific atomic binding energy of the liberated. A plot of these energies
against the corresponding number of electron counts provides the spectrum which
indicates the qualitative and quantitative elemental composition [17]. At these higher
energies, XPS only analyses to a depth of 10 nm into the surface. Electrons emitted at
greater depths are recaptured or trapped in various excited states within the material.
Spectral profiles up to 1 μm deep can however be obtained by continuous spectral
recording during ion etching or from consecutive ion etching and XPS measurement
steps.
XPS is usually performed in UHV and typically provides resolutions down to
1000 ppm. With optimum settings and long recording times, resolutions down to
100 ppm can be achieved. Non-monochromatic X-ray sources can produce a sig-
nificant amount of heat (up to 200 °C) on the surface of the sample as the anode
producing the X-rays is typically only a few centimeters from the sample. This level
10.11 X-Ray Photoelectron Spectroscopy (XPS) 127
of heat when combined with high-energy Bremsstrahlung X-rays can degrade the sur-
face. Organic chemicals are therefore not routinely analyzed by non-monochromatic
X-ray sources [18].
10.12 Auger Electron Spectroscopy (AES)
When an electron or ion is incident on a semiconductor, it may transfer enough

energy to an inner shell electron to eject it from its parent atom. The atom is in an
excited state, and, to lower its energy, an electron from a less tightly bound shell
may fill the hole while simultaneously emitting a third electron from the atom. This
ejected atom is known as an Auger electron. Its energy is related specifically to the
electron energy levels involved in the process and, therefore, is characteristic of the
atom concerned. Since the Auger process is not a three-electron process, hydrogen
nor helium can be detected since both have less than three electrons [19].
AES has two distinct advantages over EDX analysis. It is a far more surface-
sensitive technique. Escape depths range from less than a nanometer to a few nanome-
ters. In EDX it can be difficult to analyze small particles on a substrate, because the
electron beam passes through the particles and spreads out in the substrate below
it. There is the potential for chemical-state information in Auger spectroscopy, for
example, the oxidation state of silicon at a Si–SiO2 interface may be ascertained. EDX
does not provide chemical state information. AES has found applications in mea-
suring semiconductor composition, oxide film composition, silicide’s, metallization,
particle analysis and the effects of surface cleaning. AES measurements are made in
a high vacuum environment (10−12 –10−10 torr) to retard the formation of hydrocar-
bon contamination layers on the sample surface. Scanning Auger microscopy (SAM)
allows surfaces to be mapped for one selected element at a time. In this mode the
electron beam is scanned over a selected area. The Auger intensity is measured at
each point of the area. SAM requires higher beam currents and is much slower than
SEM/EDX [20].
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85:919–923
Chapter 11
Fabrication of Nanostructures
Abstract This chapter explains the techniques that are available for fabricating
nanostructures and also explain the substrates and wafers, modification of materials,
lithography, film deposition, wet and dry etching, wafer bonding and packaging.
With a bottom-up approach, nanostructures are formed molecule by molecule, using

methods such as chemical vapor deposition or self-assembly. By contrast, top-down
fabrication can be likened to sculpting from a base material, and typically involves
steps such as deposition of thin films, patterning, and etching [1].
11.1 Lithography
Lithography is referred as photoengraving, and is the process of transferring a pattern

into a reactive polymer film, termed as resist, which will subsequently be used to
replicate that pattern into an underlying thin film or Many techniques of lithography
have been developed in the last half a century with various lens systems and exposure
radiation sources including photons, X-rays, electrons, ions and neutral atoms. In
spite of different exposure radiation sources used in various lithographic methods
and instrumental details, they all share the same general technical approaches and
are based on similar fundamentals [2].
11.1.1 Photolithography
Typical photolithographic process consists of producing a mask carrying the req-

uisite pattern information and subsequently transferring that pattern, using some
optical technique into a photoactive polymer or photoresist. There are two basic
photolithographic approaches: (i) shadow printing, and proximity printing, (ii) pro-
jection printing. Figure 11.1 outlines the basic steps of the photolithographic process,

https://doi.org/10.1007/978-3-030-26145-0_11
130 11 Fabrication of Nanostructures
Fig. 11.1 Schematic representation of the photolithographic process sequences, in which images
in the mask are transferred to the underlying substrate surface. Reprinted with permission from ©
Journal of Nanomaterials, Article. No. 486301, p. 21 (2012)
in which the resist material is applied as a thin coating over some base and subse-
quently exposed in an image-wise fashion through a mask, such that light strikes
selected areas of the resist material. The exposed resist is then subjected to a devel-
opment step. Depending on the chemical nature of the resist material, the exposed
areas may be rendered more soluble in some developing solvent than the unexposed
areas, thereby producing a positive tone image of the mask. Conversely, the exposed
areas may be rendered less soluble, producing a negative tone image of the mask.
The effect of this process is to produce a three-dimensional relief image in the resist
material that is a replication of the opaque and transparent areas of the mask. The
areas of resist that remain following the imaging and developing processes are used
to mask the underlying substrate for subsequent etching or other image transfer steps.
The resist material resists the etchant and prevents it from attacking the underlying
substrate in those areas where it remains in place after development. Following the
etching process, the resist is removed by stripping to produce a positive or negative
tone relief image in the underlying substrate. Diffraction sets the limit of the maxi-
mum resolution or the minimum size of the individual elements by photolithography,
which can be obtained [3].
Diffraction refers to the apparent deviation of light from rectilinear propagation
as it passes an obstacle such as an opaque edge and the phenomenon of diffraction
can be understood qualitatively as follows. According to geometrical optics, if an
opaque object is placed between a point light source and a screen, the edge of the
object will cast a sharp shadow on the screen. No light will reach the screen at
11.1 Lithography 131
points within the geometrical shadow, whereas outside the shadow the screen will be
uniformly illuminated. In reality, the shadow cast by the edge is diffuse, consisting of
alternate bright and dark bands that extend into the geometrical shadow. This apparent
bending of light around the edge is referred to as diffraction, and the resulting intensity
distribution is called a diffraction pattern. Obviously diffraction causes the image of
a perfectly delineated edge to become blurred or diffused at the resist surface. The
theoretical resolution capability of shadow photolithography with a mask consisting
of equal lines and spaces of width b is given by:

2bmin = 3 λ(S + d/2)
where 2b is the grating period (1/2b is the fundamental spatial frequency ν), s the gap
width maintained between the mask and the photoresist surface, λ the wavelength of
the exposing radiation and d the photoresist thickness. For hard contact printing, s is
equal to 0, and from the equation, the maximum resolution for 400 nm wavelength
light and a 1 pm thick resist film will be slightly less than 1 km [4].
11.1.2 Contact-Mode Photolithography (CMP)
In contact-mode photolithography, the mask and wafer are in intimate contact, and
thus this method can transfer a mask pattern into a photoresist with almost 100%
accuracy and provides the highest resolution. Other photolithographic techniques can
approach but not exceed its resolution capabilities. However, the maximum resolution
is seldom achieved because of dust on substrates and non-uniformity of the thickness
of the photoresist and the substrate. Such problems can be avoided in proximity
printing, in which, a gap between the mask and the wafer is introduced. However,
increasing the gap degrades the resolution by expanding the penumbral region caused
by diffraction. The difficulties in proximity printing include the control of a small
and very constant space between the mask and wafer, which can be achieved only
with extremely flat wafers and masks [5]. Projection printing differs from shadow
printing. In projection printing techniques, lens elements are used to focus the mask
image onto a wafer substrate, which is separated from the mask by many centimeters.
Because of lens imperfections and diffraction considerations, projection techniques
generally have lower resolution capability than that provided by shadow printing. The
resolution limit in conventional projection photolithography is determined largely
by the well-known Rayleigh’s equation. The resolution, i.e. the minimum resolvable
feature, R, and the corresponding depth of focus (DOF) are given by the following:
k1 λ
R=
NA
k2 λ
DO F =
N A2
Here A is the exposure wavelength, k1 and k2 are constants that depend on the
specific resist material, process technology and image-formation techniques used,
and NA is the numerical aperture of the optical system and is defined as
NA = n Sin θ
where n is the index of refraction in image space and is usually equal to 1 (air or vac-
uum), and θ is the maximum cone angle of the exposure light beam. The diffraction
limit is a very basic law of physics directly related to Heisenberg’s uncertainty rela-
tion. It restricts any conventional imaging process to a resolution of approximately
λ/2 [6].
11.1.3 Deep Ultra-Violet Lithography (DUV)
The Deep Ultra-Violet Lithography is based on exposure at wavelengths below

300 nm, presents far more difficult technical challenges. Classical UV sources have
lower output power in the DUV Excimer lasers can provide 10–20 W of power at any
one of several wavelengths in the DUV. Of particular interest are the KrCl and KrF
excimer lasers, which have outputs at 222 and 249 nm, respectively. High intensity,
microwave powered emission sources provide substantially higher DUV output than
classical electrode discharge mercury lamps Light sources with shorter wavelengths
exploited for optical lithography include: KrF excimer laser with a wavelength of
249 nm, ArF excimer laser of 193 nm, F2 excimer laser of 157 nm. Optical lithog-
raphy allows one to obtain patterns with a minimal size of ~100 nm. Extreme UV
lithography with wavelengths in the range of 11–13 nm has also been explored
for fabricating features with even smaller dimensions and is a strong candidate for
achieving dimensions of 70 nm and below [7].
11.1.4 Phase-Shifting Photolithography
In this method, a transparent mask induces abrupt changes of the phase of the light
used for exposure, and cause optical attenuation at desired locations. These phase
masks, also known as phase shifters, have produced futures of ~100 nm in photore-
sist. Figure 11.2 schematically illustrates the principles of phase-shifting lithography.
A clear film, i.e. a phase shifter or a phase mask, whose thickness is λ/2 (n − 1) is
placed on a photoresist with conformal contact, the phase angle of the exposure light
passing through the film shifts by the amount of π to the incident light arriving at
the surface of the photoresist. Here λ is the wavelength of the exposure light and n
is the index of refraction of the phase mask. Because the light phase angle between
the phase shifter and the photoresist is inverted, the electric field at the phase shifter
edge is 0. So the intensity of the exposure light at the surface of the photoresist would
Fig. 11.2 Schematic illustrating the principles of phase shifting lithography, which utilizes the
optical phase, changes at the phase shifter edge
be zero. An image having zero intensity can be formed about the edge of the phase
shifter. Phase masks can be used in both projection and contact-mode photolitho-
graphic techniques. For a phase-shifting contact-mode photolithography, there are
two possible approaches to increase the resolution: (i) reducing the wavelength of
the source of exposure light and (ii) increasing the index of refraction of the pho-
toresist. The achievable photolithographic resolution is roughly of ~λ/4n, where A is
the wavelength of the exposure light and n is the refractive index of the photoresist.
Although contact-mode photolithography with a phase-shifting mask has a higher
resolution, conformal contact between the phase-shifting mask and the photoresist
on wafer is difficult to achieve, due to the presence of dust, non-uniformities in
the thickness of the photoresist, and bowing of the mask or the substrate. However,
by introducing elastomeric phase-shifting masks, conformal contact can be rela-
tively easily achieved and feature lines as narrow as 50 nm have been generated.
The resolution achieved corresponds approximately to λ/5. An improved approach
to conformal near field photolithography is to use masks constructed from “soft”
organic elastomeric polymer [8]. Figure 11.3 shows a pattern created using such a
contact-mode phase-shifting photolithographic process.
11.1.5 Electron Beam Lithography
A finely focused beam of electrons can be deflected accurately and precisely over
a surface. When the surface is coated with a radiation sensitive polymeric material,
the electron beam can be used to write patterns of very high resolution. The first
experimental electron beam writing systems were designed to take advantage of the
high resolution capabilities in the late sixties. Electron beams can be focused to
Fig. 11.3 Parallel lines formed in photoresist using near field contact-mode photolithography have
widths on the order of 100 nm and are −300 nm in height as imaged by a AFM and b SEM.
Reprinted with permission from © Journal of Nanomaterials, Article. No. 936876, p. 7 (2015)
a few nanometers in diameter and rapidly deflected either electromagnetically or

electrostatically. Electrons possess both particle and wave properties; however, their
wavelength is on the order of a few tenths of angstrom, and therefore their resolution
is not limited by diffraction considerations. Resolution of electron beam lithography
is, however, limited by forward scattering of the electrons in the resist layer and back
scattering from the underlying substrate. Nevertheless, electron beam lithography is
the most powerful tool for the fabrication of feathers as small as 3–5 nm. When an
electron beam enters a polymer film or any solid material, it loses energy via elastic
and inelastic collisions known collectively as electron scattering [9]. Elastic collisions
result only in a change of direction of the electrons, whereas inelastic collisions lead
to energy loss. These scattering processes lead to a broadening of the beam, i.e.
the electrons spread out as they penetrate the solid producing a transverse or lateral
electron flux normal to the incident beam direction, and cause exposure of the resist
at points remote from the point of initial electron incidence, which in turn results in
developed resist images wider than expected. The magnitude of electron scattering
depends on the atomic number and density of both the resist and substrate as well
as the velocity of the electrons or the accelerating voltage. Exposure of the resist by
the forward and backscattered electrons depends on the beam energy, film thickness
and substrate atomic number. As the beam energy increases, the energy loss per unit
path length and scattering cross-sections decreases. Thus the lateral transport of the
forward scattered electrons and the energy dissipated per electron decrease while the
lateral extent of the backscattered electrons increases due to the increased electron
range. As the resist film thickness increases, the cumulative effect of the small angle
collisions by the forward scattered electrons increases. Thus the area exposed by the
scattered electrons at the resist substrate interface is larger in thick films than in thin
films. Proper exposure requires that the electron range in the polymer film be greater
than the film thickness in order to ensure exposure of the resist at the interface. As
the substrate atomic number increases, the electron reflection coefficient increases
which in turn increases the backscattered contribution. Electron beam systems can
be conveniently considered in two broad categories: those using scanned, focused
electron beams which expose the wafer in serial fashion, and those projecting an
entire pattern simultaneously onto a wafer. Scanning beam systems can be further
divided into Gaussian or round beam systems and shaped beam systems. All scanning
beam systems have four typical subsystems: (i) electron source (gun), (ii) electron
column (beam forming system), (iii) mechanical stage and (iv) control computer
which is used to control the various machine subsystems and transfer pattern data to
the beam deflection systems [10].
11.1.6 X-Ray Lithography
X-rays with wavelengths in the range of 0.04–0.5 nm represent another alterna-

tive radiation source with potential for high-resolution pattern replication into poly-
meric resist materials. X-ray lithography was first demonstrated that to obtain high-
resolution patterns using X-ray proximity printing by Spears and Smith. The essential
ingredients in X-ray lithography include:
(1) A mask consisting of a pattern made with an X-ray absorbing material on a thin
X-ray transparent membrane,
(2) An X-ray source of sufficient brightness in the wavelength range of interest to
expose the resist through the mask, and
(3) An X-ray sensitive resist material.
There are two X-ray radiation sources: (i) electron impact and (ii) synchrotron
sources. Conventional electron impact sources produce a broad spectrum of X-rays,
centered about a characteristic line of the material, which are generated by bombard-
ment of a suitable target material by a high energy electron beam. The synchrotron
or storage ring produces a broad spectrum of radiation stemming from energy loss
of electrons in motion at relativistic energies. This radiation is characterized by an
intense, continuous spectral distribution from the infrared to the long wavelength
X-ray region. It is highly collimated and confined near the orbital plane of the cir-
culating electrons, thereby requiring spreading in the vertical direction of moving
the mask and wafer combination with constant speed through the fan of synchrotron
radiation. Synchrotrons offer the advantage of high power output. Absorption of an
X-ray photon results in the formation of a photoelectron which undergoes elastic
and inelastic collisions within the absorbing material producing secondary electrons
which are responsible for the chemical reactions in the resist film. The range of the
primary photoelectrons is on the order of 100–200 nm [11].
11.1.7 Focused Ion Beam (FIB) Lithography
The focused ion beam has been rapidly developed into a very attractive tool in lithog-
raphy, etching, deposition, and doping. Since scattering of ions in the MeV range is
several orders of magnitude less than that for electrons, ion beam lithography has
long been recognized to offer improved resolution. The commonly used FIBS are
Ga and Au–Si–Be alloys LMI sources due to their long lifetime and high stabil-
ity. FIB lithography is capable of producing electronic devices with submicrometer
dimension. The advantages of FIB lithography include its high resist exposure sen-
sitivity, which is two or more orders of magnitude higher than that of electron beam
lithography, and its negligible ion scattering in the resist and low back scattering
from the substrate. However, FIB lithography suffers from some drawbacks such as
lower throughput and extensive substrate damage. Therefore, FIB lithography is more
likely to find applications in fabricating devices where substrate damage is not criti-
cal. FIB etching includes physical sputtering etching and chemical assisted etching.
Physical sputtering etching is straightforward and is to use the highly energetic ion
beams to bombard the area to be etched and to erode material from the sample. The
advantages of this process are simple, capable of self-alignment, and applicable to
any sample material [12]. Chemical etching is based on chemical reactions between
the substrate surface and gas molecules adsorbed on the substrate. Chemical etching
offers several advantages: an increased etching rate, the absence of redeposition and
little residual damage. Particularly, the chemical assisted etching rate ranges 10–
100 folds for various combinations of materials and etchant gases, and the absence
of redeposition permits very high aspect ratios. FIB can also be used for deposit-
ing. Similar to etching, there are direct deposition and chemical assisted deposition.
Direct deposition uses low energy ions, whereas chemical assisted deposition relies
on chemical reactions between the substrate surface and molecules adsorbed on the
substrate. FIB lithography offers several advantages for the fabrication and process-
ing of magnetic nanostructures in comparison with electron beam lithography. Ions
are substantially heavier than electrons, and thus the FIB is much less influenced
by magnetic properties of the material. Another advantage is its ability of achieving
direct etching and/or deposition without using extra patterning steps [13].
11.1.8 Neutral Atomic Beam Lithography
In neutral atomic beams, no space charge effects make the beam divergent; there-
fore, high kinetic particle energies are not required. Diffraction is no severe limit
for the resolution because the de Broglie wavelength of thermal atoms is less than 1
angstrom. These atomic beam techniques rely either on direct patterning using light
forces on atoms that stick on the surface, or on patterning of a special resist. Interac-
tion between neutral atoms and laser light has been explored for various applications,
such as reduction of the kinetic-energy spread into the nanokelvin regime, trapping
atoms in small regions of space or manipulation of atomic trajectories for focusing

and imaging [14]. Basic principle of atomic beam lithography with light forces can
be understood in a classical model as follows. The induced electric dipole moment
of an atom in an electromagnetic wave can be resonantly enhanced by tuning the
oscillation frequency of the light ωL close to an atomic dipole transition with fre-
quency ωA Depending on the sign of the detuning δ = ωL − ωA the dipole moment
is in phase (δ < 0) or out of phase (δ > 0). In an intensity gradient, this induced dipole
feels a force towards the local minimum (δ < 0) or maximum (δ > 0) of the spatial
light intensity distribution.
Therefore, a standing light wave acts as a periodic conservative potential for the
motion of the atoms and forms the analogue of an array of cylindrical lenses [15]. If
a substrate is positioned at the focal plane of this lens array, a periodic structure is
written onto the surface. Figure 11.4 schematically illustrates the basic principles of
neutral atom lithography with light forces and Fig. 11.5 shows the resulting chromium
nanowires of 64 nm on silicon substrate grown by neutral atomic beam deposition
with laser forces.
Fig. 11.4 Schematic illustrating the basic principles of neutral atom lithography with light forces.
Reprinted with permission from © Proceedings of the National Academy of Sciences, 99, 6509–
6513 (2002)
Fig. 11.5 SEM image showing chromium nanowires of 64 nm on silicon substrate grown by neutral
atomic beam deposition with laser forces. Reprinted with permission from © Proceedings of the
National Academy of Sciences, 99, 6509–6513 (2002)
11.2 Nanolithography
SPM-based nanolithography has been exploited for local oxidation and passivation,
localized chemical vapor deposition, electrodeposition, mechanical contact of the
tip with the surface, and deformation of the surface by electrical pulses. There are
direct anodic oxidation of the sample surface and exposure of electron resist. Patterns
with a minimal size of 10–20 nm105 or to 1 nm in UHV have been demonstrated.
Nanometer holes can be formed using low energy electrons from a STM tip when a
pulsed electric voltage is applied at the presence of sufficient gas molecules between
the substrate and the tip. For example, holes of 7 nm deep and 6 nm wide on HOPG
substrate were formed in nitrogen at a pressure of 25 bar by applying a −7 V pulse to
the tip for 130 ms with the distance between the tip and the substrate being 0.6–1 nm.
A possible mechanism is that the electric field induces the ionization of gas molecules
near the STM tip, and accelerates the ions towards the substrate. Ions bombard the
substrate and consequently nanometer-sized holes are created. A certain electric field
is required to generate field emitted electrons. The diameter of electron beam ejected
from a STM tip is dependent on the applied bias voltage and the diameter of the
tip. At low bias (<12 V), the diameter of the ejected electron beam remains almost
constant; however, the beam diameter changes significantly with bias voltage and the
diameter of the tip. Nanostructures can be created using field evaporation by applying
11.2 Nanolithography 139
bias pulses to the STM tip-sample tunneling junction. For example, nano-dots, lines,
and corrals of gold on a clean stepped Si (111) surface were fabricated by applying a
series of bias pulses <10 V and ~30 ps to a STM gold tip at UHV a base pressure of
~10−10 mbar. Nano-dots with diameter as small as a few nanometers can be realized.
By decreasing the distance between adjacent nano-dots, it was possible to create
continuous nano-lines of a few nanometer wide and over a few hundred nanometer
long. A nano-corral of about 40 nm in diameter formed by many Au nano-dots for a
few nanometers in diameter each was also created on the silicon (111) surface [16].
11.2.1 AFM Based Nanolithography
Direct contacting, writing, or scratching is referred to as a mechanical action of the

AFM tip that is used as a sharply pointed tool in order to produce fine grooves on
sample surfaces. Although direct scratching creates grooves with high precision, low
quality results are often obtained due to tip wear during the process. An alternative
approach is to combine scratching on a soft resist polymer layer, such as PMMA or
polycarbonate, as a mask for the etching process and subsequent etching to transfer
the pattern to the sample surface. This method ensures reduced tip damage, but
also precludes an accurate alignment to the structures underneath. A two-layer mask
has been investigated as a further improvement [17]. For example, a mask coating
consisting of a thin layer of polycarbonate of 50–100 m and a film of easy-to-deform
and fusible metal such as indium or tin was used to create 50 nm wide structures.
Figure 11.6 is the typical layout of the sample and the process steps with AFM
lithography.
11.2.2 Soft Lithography
Soft lithography is a set of non-photolithographic techniques for microfabrication

that are based on the printing of SAMs and molding of liquid precursors. Soft lithog-
raphy techniques include contact printing, micromolding in capillaries, microtransfer
molding and replica molding. Soft lithography has been developed as an alternative
to photolithography and a replication technology for both micro- and nanofabrication
[18].
11.2.3 Microcontact Printing
Microcontact printing is a technique that uses an elastomeric stamp with relief on

its surface to generate patterned SAMs on the surface of both planar and curved
substrate. The procedure of microcontact printing is experimentally simple and
inherently parallel.
Fig. 11.6 Layout of the sample and the process steps: a sample multilayer structure, b thin mask
patterning by AFM lithography, c polymer removal in plasma oxygen, d titanium stripe etch-
ing, and e resulting electrodes after sacrificial layers removal. Reprinted with permission from ©
Nanotechnology, 10, 458–463 (1999)
The elastomeric stamp is fabricated by casting and polymerizing PDMS monomer

in a master mold, which can be prepared by photolithography or other relevant tech-
niques. The stamp with a desired pattern is brought in contact with ink, a solution to
form a SAM on the surface of the stamp. The inked stamp then contacts a substrate and
transfers the SAM onto the substrate surface with patterned structure. A very impor-
tant advantage that the microcontact printing offers over other patterning techniques
is the capability to fabricate a patterned structure on a curved surface. The success of
microcontact printing relies (i) on the conformal contact between the stamp and the
surface of the substrate, (ii) on the rapid formation of highly ordered monolayers as a
result of self-assembly, and (iii) on the autophobicity of the SAM, which effectively
blocks the reactive spreading of the ink across the surface. Microcontact printing has
been used with a number of systems including SAMs of alkanethiolate on gold, silver
and copper, and SAMs of alkylsiloxanes on HO-terminated surfaces. Microcontact
printing can routinely form patterns of alkanethiolate SAMs on gold and silver with
in-pane dimensions at the scale of ~500 nm. But smaller futures, such trenches in
gold as ~35 nm wide and separated by ~350 nm can be fabricated with a combination
Fig. 11.7 Schematic showing the principal procedures of a typical microcontact printing: a printing
on a planar substrate with a planar PDMS stamp, b printing on a planar substrate with a rolling
stamp, and c printing on a curved substrate with a planar stamp. Reprinted with permission from
© Angew Chem Int Ed Engl, 37, 550–575 (2016)
of microcontact printing of alkanethiolate SAMs and wet etching. Figure 11.7 is the
schematic showing of the principal procedures of a typical microcontact printing:
(a) printing on a planar substrate with a planar PDMS stamp, (b) printing on a planar
substrate with a rolling stamp, and (c) printing on a curved substrate with a planar
stamp [19].
11.2.4 Molding
A number of molding techniques have been developed for the fabrication of

microstructures, but are also capable of fabricating nanostructures. These techniques
include micromolding in capillaries, microtransfer molding, and replica molding. An
elastomeric (PDMS) stamp with relief on its surface is central to each of these pro-
cedures. In micromolding in capillaries, a liquid precursor wicks spontaneously by
capillary action into the network of channels formed by conformal contact between
an elastomeric stamp and a substrate. In microtransfer molding, the recessed regions
of an elastomeric mold are filled with a liquid precursor, and the filled mold is brought
into contact with a substrate. After solidifying, the mold is removed, leaving a micro-
or nanostructure on the substrate.
Micromolding in capillaries can only be used to fabricate interconnected struc-
tures, whereas microtransfer molding is capable of generating both isolated and
interconnected structures. In replica molding, micro- or nanostructures are directly
formed by casting and solidifying a liquid precursor against an elastomeric mold.
This method is effective for replicating feature sizes ranging from ~30 nm to several
centimeters and Fig. 11.8 shows AFM images of such prepared structures. Replica
molding also offers a convenient route to fabricating structures with high aspect
ratios. Molding has been used to fabricate microstructures and nanostructures of a
Fig. 11.8 a and b AFM images of chromium nanostructures on a master, and a polyurethane replica
prepared from a PDMS mold cast from this master. c and d AFM images of Gold nanostructures
on another master, and a polyurethane replica produced from a different PDMS mold cast from this
master. Reprinted with permission from © Annu. Rev. Mater. Sci, 28, 153–84 (1998)
wide range of materials, including polymers, inorganic and organic salts, sol-gels,
polymer beads, and precursor polymers to ceramics and carbon [20].
11.2.5 Nanoimprint
Nanoimprint lithography is a conceptually straightforward method in fabrication

of patterned nanostructures. Nanoimprint lithography has demonstrated both high
resolution and high throughput for making nanometer scale structures. Figure 11.9
schematically illustrates the principal steps of a typical nanoimprint process. First
a stamp with the desired features is fabricated, for example by optical or electron
beam lithography followed by dry etching or reactive ion etching. The material to
be printed, typically a thermoplastic polymer, is spun onto a substrate where the
nanostructures are to be fabricated, The second step is to press the stamp on the
polymer layer with the temperature raised above the glass transition point for a
certain period of time to allow the plastic to deform. In the third step, the stamp is
separated from the polymer after cooling. The patterned polymer left on the substrate
is used for further processing, such as dry etching or lift-off, or for use directly as
a device component. Although the process is technically straightforward, there are
several key issues that require special attention to make the process competitive
as a nanofabrication technology as briefly summarized below. The first challenge
for the nanoimprint lithography is the multilevel capability or the ability of exact
Fig. 11.9 Principal steps of a typical nanoimprint process. A stamp with the desired features is
pressed on the polymer layer with the temperature raised above the glass transition point for a
certain period of time to allow the plastic to deform. The stamp is separated from the polymer after
cooling and the patterned polymer left on the substrate are used for further processing, such as
drying etching or lift off, or for use directly as a device component. Reprinted with permission from
© Design of Polymeric Platforms for Selective Biorecognition, 123–155 (2015)
alignment of multilayers. Various approaches have been explored to achieve exact

alignment including use of commercially available stepper and aligner. Stamp size
should be controlled, since large stamp size may introduce potential drawback, such
as the parallelity of the substrate and stamp and thermal gradients in printing. The
flow of the displaced polymer could set a limit to the feature density that imprinting
stamps can achieve. Imprint of 50 nm features separated by 50 nm spaces within
an area of 200 × 200 μm2 has been demonstrated. Sticking is another challenge to
the nanoimprint lithography. Ideally, there should be no sticking at all between the
polymer layers to be imprinted and the stamp. The choice of printing temperature,
the viscoelastic properties of the polymer and the interfacial energy are among the
key factors [21].
11.2.6 Dip-Pen Nanolithography
Dip-pen nanolithography is a direct-write method based upon an AFM and works

under ambient conditions. Chemisorption is acted as a driving force for moving the
molecules from the AFM tip to the substrate via the water filled capillary, when the
tip is scanned across a substrate. Various nanostructures have been demonstrated
and multicomponent nanostructures can readily be created. Figure 11.10 shows an
example by DPN: fifteen nanometer dots spaced ~5 nm apart in the form of an “N”
on an Au (111) substrate [22].
Fig. 11.10 SEM micrograph

showing an example by
dip-pen nanolithography:
fifteen nanometer dots
spaced ~5 nm apart in the
form of an “N” on an Au
(111) substrate. Reprinted
with permission from ©
Imperial College Press,
London (2004)
11.3 Etching 145
11.3 Etching
Etching is an important step in semiconductor device processing. Etching techniques

are normally classified into two categories: wet and dry etching. For wet etch, the
etchant is supplied from the liquid phase and can be carried out simply from a liquid
container such as a beaker. For dry etch, etchant is supplied from the vapor phase.
Common dry etching techniques include reactive ion etching (RIE), inductively cou-
pled plasma (ICP)-RIE, chemical assisted ion beam etching (CAIBE), all of which
require vacuum, plasma generation, ion optics etc. A widely used method is wet
chemical etching. For example, dilute HF is used to etch a SiO2 layer covering sili-
con. The HF reacts with SiO2 and does not affect the photoresist or silicon. That is,
this wet chemical etch is highly selective. However, the rate of etching is the same for
any direction, lateral or vertical, so the etching is isotropic. Using an isotropic etching
technique is acceptable only for relatively large structures. For nanosize structures,
anisotropic etching with faster vertical etching is preferable [23].
Anisotropic etching generally exploits a physical process, or some combination of
both physical and chemical methods. The best-known method of anisotropic etching
is reactive-ion etching. Reactive-ion etching is based on the use of plasma reactions.
This method works as follows. An appropriate etching gas, for example a chloroflu-
orocarbon, fills the chamber with the wafers. The pressure is typically reduced, so
that a radiofrequency (RF) voltage can produce plasma. The wafer we want to etch is
a cathode of this RF discharge, while the walls of the chamber are grounded and act
as an anode. Figure 11.11 illustrates a principal scheme for the ion-etching method.
The electric voltage heats the light electrons and they ionize gaseous molecules,
creating positive ions and molecular fragments (so-called chemical radicals). Being
accelerated in the electric field, the ions bombard the wafer normal to the surface.
This normal incidence of bombarding ions contributes to the etching and makes the
etching highly anisotropic. This process, unfortunately, is not selective. However,
Fig. 11.11 Reactive-ion

etching. Reprinted with
permission from ©
Microelectronics Reliability,
52, 347–351 (2012)
the chemical radicals present in the chamber give rise to chemical etching, which, as
we discussed, is selective. Now we see that the method combines both isotropic and
anisotropic components and can give good results for etching on the nanoscale [24].
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Chapter 12
Nanostructured Materials for Optical
and Electronic Applications
Abstract Nanostructured materials in the area of optical and electronic applications

are advancing more with more device development as solar panels, optoelectronic
switches, batteries and sensors. This chapter particularly focuses on the optoelec-
tronic applications. All electronic tools have one thing in common: an integrated
circuit (IC) acting as their brain. Nano-electromechanical systems have evolved
early years and creating sensors eyes and actuators arms at the same scale as the
accompanying nanoelectronics. Recent developments in synthesis of nanomaterials
with excellent electrical and mechanical properties have extended the boundaries of
NEMS applications to include more advanced devices such as the non-volatile nano-
electro-mechanical memory, where information is transferred and stored through a
series of electrical and mechanical actions at the nanoscale (Venkateswara Rao and
Kumar Yadav in Int J Eng Sci 4:6–9, 2015 [1]).
12.1 Applications of Nanostructured Materials in Solar

Cells
The aim of device modeling is to develop a link between materials properties and the
electrical device characteristics of a nano-structured solar cell. This is in contrast to
materials modeling, where materials parameters like the optical absorption α (λ), the
electrical mobilities μe , μh of electrons and holes, various relevant energy parameters,
etc. are studied and theoretically modeled based on physical and chemical phenomena
and interactions. In device modeling, we suppose that all materials parameters needed
are already known, either from quantitative materials modeling or from experiments.
The optical analysis of the cell already has been resulted in the knowledge of the
optical generation of electron–hole pairs and excitons, both as a function of position
and wavelength [2].

https://doi.org/10.1007/978-3-030-26145-0_12
150 12 Nanostructured Materials for Optical and Electronic Applications
12.1.1 Dye-Sensitized Nanostructured ZnO Electrodes

for Solar Cell Applications
Dye-sensitized nanostructured solar cells (DNSCs) based on nanostructured metal

oxide films have attracted more attention. They offer the prospect of low-cost pho-
tovoltaic energy conversion. Promising solar-to-electrical energy conversion effi-
ciencies of more than 10% has been achieved and good progress has been made
on long-term stability. The working mechanism of dye-sensitized solar cells differs
completely from conventional p–n junction solar cells, but is, after more than 15 years
of research, still not completely resolved. Research has largely focused on nanos-
tructured TiO2 (anatase) as the metal oxide to which the dye is bound. Good results
have been obtained using other n-type metal oxides, such as ZnO, Nb2 O5 and SnO2 .
There will be focus on ZnO as a material for DNSC. ZnO is an attractive material for
nanoscale optoelectronic devices, as it is a wide-band gap semiconductor with good
carrier mobility and can be doped both n and p-type. The electron mobility is much
higher in ZnO than in TiO2 , while the conduction band edge of both materials is
located at approximately the same level. The material properties will be discussed in
more detail in Section. A large range of fabrication procedures is available for ZnO
nanostructures, such as sol–gel processes, chemical bath deposition, electrodeposi-
tion and vapor-phase processes. Different morphologies such as spherical particles,
rods, wires and hollow tubes can be prepared with relative ease.
ZnO shows more flexibility in synthesis and morphology than TiO2 . The chemical
stability of ZnO is, however, less than that of TiO2 , which can lead to problems in
the dye adsorption procedure. The performance of dye-sensitized ZnO solar cells in
terms of solar-to electrical energy conversion efficiencies is so far significantly lower
than that of TiO2 , reaching currently about 4–5%. An analysis of the energetics and
kinetics of ZnO-based DNSCs suggests that this is mainly due to the lesser degree of
optimization in case of ZnO compared to TiO2 -based DNSCs. The main problem in
dye-sensitized ZnO solar cells appears to be the troublesome dye adsorption process
[3] (Fig. 12.1).
12.2 Photoconductive Oxide Nanowires as Nanoscale

Optoelectronic Switches
Among all possible nano-devices, switches are critical for important applications like
memory and logic. Electrical switching on nanometer and molecular level has been
predominantly achieved through proper electrical gating configuration, as exem-
plified by nanotube transistors. It is possible to create highly sensitive electrical
nanowire switches by exploring the photoconductivity of the individual semicon-
ductor nanowires. It shows the conductance of the ZnO nanowire is extremely sensi-
tive to ultraviolet light exposure. The light induced insulator-to-conductor transition
allows us reversibly switching the nanowires from OFF to ON states, an “optical
12.2 Photoconductive Oxide Nanowires as Nanoscale … 151
Fig. 12.1 Schematic illustration of the working principle of the DNSC. Incoming light excites
the sensitizing dye, which induces an electron injection from the dye into the conduction band of
the semiconductor nanoparticle. The electron is transported through the nanoporous structure to
the back contact of the working electrode (WE). The electrons can then be utilized in work in an
external circuit. The circuit is connected to the counter electrode (CE) where the redox system is
effectively reduced with the help of a catalyst (nanoparticulate Pt in the case of I− /I3 − ). The circuit
is closed when the redox system reduces the sensitizing dye. Reprinted with permission from ©
Nanostructured Materials for Solar Energy Conversion, 227–254 (2006)
gating” phenomena as compared to commonly used electrical gating. Four-probe

measurement of individual ZnO nanowires indicates that these nanowires are essen-
tially insulating in dark with a resistivity above 3.5 M cm−1 . When the nanowires
were exposed to UV light with wavelengths below 400 nm, it was found that the
nanowire resistivity instantly decreases by typically 4–6 orders of magnitude. In
addition to the high sensitivity of the nanowire photoconductor, they also exhibit
excellent wavelength selectivity.
The evolution of the photocurrent when a nanowire was exposed first to highly
intense light at 532 nm (Nd:YAG, 2nd harmonics) for 200 s and then to UV light at
365 nm. There is no photoresponse at all to the green light while exposure to less
intense UV-light shows the typical change of conductivity of 4 orders of magnitude.
Measurements of the spectral response show that our ZnO nanowires indeed have a
cut-off wavelength of 385 nm which is expected from the bandgap of ZnO [4].
It has been unambiguously established that oxygen chemisorption plays a pro-
found role in enhancing photosensitivity of bulk or thin film ZnO. It is believed that
a similar photoresponse mechanism could be applied to the nanowire system with
additional consideration of high surface area of the nanowire, which could further
enhance the sensitivity of the device. It was generally believed that the photoresponse
of ZnO consists of two parts: a solid-state process where an electron and a hole are
created (hν → h+ + e− ) and a two-step process involving oxygen species adsorbed
on the surface. In the dark, oxygen molecules adsorb on the oxide surface as a neg-
atively charged ion by capturing free electrons of the n-type oxide semiconductor
(O2 (g) + e− → O2 − (ad)) thereby creating a depletion layer with low conductiv-
ity near the nanowire surface. Upon exposure to UV-light, photogenerated holes
migrate to the surface and discharge the negatively charged adsorbed oxygen ions
(h+ + O2 − (ad) → O2 (g)) through surface electron-hole recombination. Meantime,
photo-generated electrons destruct the depletion layer, as a result, the conductivity of
the nanowire increase significantly. The characteristics of the ZnO photoconducting
nanowires indicates that they could be good candidates for optoelectronic switches,
i.e. the insulating state as “OFF” in the dark and the conducting state as “ON” when
exposed to UV-light [5].
12.3 Energy Storage, Batteries, Fuel Cells
One of the outstanding properties of nanotubes and other kinds of nanoparticles is

their extremely large surface area, which can reach 2800 m2 /g in the case of carbon
nanotubes. This means that ca. 2.5 g of nanotubes possess the same surface area
as a soccer field (ca. 70 × 100 m2 ). This makes nano-structured materials ideal for
applications in chemical processes relying on surface processes, e.g. catalysis, but
also for the storage of energy, especially in the form of hydrogen. In fact, given the
problems with fossil fuels, a new technology emerges to provide power supplies
e.g. for transportation, buildings, and portable electrical devices, which is called
hydrogen economy. It consists of the production of hydrogen from renewable or
fossil energy sources e.g. by electrolysis of water, use it as a transportable energy
carrier, and then convert it at the point of use to electricity e.g. by means of fuel
cells. In each of these steps nanostructured materials, given their high surface to
volume ratio, are envisioned to a play in future a most important role. However,
nanostructured materials will also have a great impact on other technologies for the
production, conversion, storage and application of energy (e.g. batteries, solar cells,
etc.) [6].
The only data storage device was 5 1/4 floppy disk with a capacity of 110 kB,
while the internal memory of his Commodore Pet computer was 32 kB. Today, use
of CDs with a capacity of 700 MB, DVDs with 4 or more GB, and memory sticks
with a capacity of 16 GB. In the case of memories, there are always two aspects
which have to be kept in mind: The data have to be stored in a medium by some
kind of effect, but that also have to be written and read within a reasonable time,
which at least in the case of reading is defined by real time reproduction of music,
films etc. As in the case of semiconductor devices, higher storage densities have been
achieved by reducing the sizes of a bit, and similar to semiconductor devices, the
technologies are currently approaching limits by reaching the nanometer region with
12.3 Energy Storage, Batteries, Fuel Cells 153
Fig. 12.2 a Carbon-carbon bond length in graphene: 0.142 nm; b length of a transistor gate in
the latest CPU technology from Intel: 22 nm; c size of a single bit of information on a DVD disk:
400 nm
the consequences emphasized throughout this contribution. In the case of technique

using ferromagnets as storage medium (such as hard disks), for example, a lower
limit of the size of a bit is given by the superparamagnetic effect. For compact discs
and their successors which rely on optical readout, the wavelength of the lasers used
has been reduced from infrared (CD) over red (DVD) to blue (Blue-ray discs). The
pit size for the latter is 160 × 320 nm2 . However, future improvement will very
probably require completely new approaches. One possibility is the use of optical
near-field techniques for which the Rayleigh criterion is not applicable, or the use
of three dimensional approaches, e.g. holographic techniques. In the former case,
the reading head must be situated a few nanometers only from the storage medium.
A large research effort is presently devoted to the so-called phase change materials,
which exhibit drastic differences of their electrical (resistivity) and optical properties
(refractive index) properties, depending on their structure (crystalline or amorphous).
As a change of the structure can be easily achieved in very short times by heating
with a laser beam either to the crystallization or to the melting temperature, data can
be written optically, while the readout can take place either electrically or optically
[7] (Fig. 12.2).
12.4 Nanostructured Semiconductor Materials

for Optoelectronic Applications
Semiconductor nanostructures allow the control of basic material parameters only

by changing geometric factors without changing the material composition. To under-
stand the strong impact of geometric factors in the nanometer regime one has to briefly
review the bulk properties of semiconductors. Most of the semiconductors used in
electronics and optoelectronics form diamond, like silicon (Si), or zinc blende lat-
tices, like gallium arsenide (GaAs) or indium phosphide (InP) as shown in Fig. 12.3.
Fig. 12.3 Zinc blende lattice of, e.g., GaAs or InP (left). Electronic band structure formation as a
function of the lattice spacing for a diamond type lattice (right). Reprinted with permission from ©
Nanostructured Materials for Advanced Technological Applications, Springer (2008)
During the formation of a crystal from N isolated atoms, e.g., from a liquid or gas
phase, the atomic spacing decreases and the electronic valence states of each atom
overlap each other forming bands with N states. However, the energetic distances
are too small to be distinguishable. In case of the formation of a periodic lattice the
electronic wave functions can interfere with the periodic potential fluctuation of the
crystal and build a band structure with bands and band gap regions, where no electron
can penetrate into the crystal [8].
Nanostructured materials lead to new directions in the fabrication of complex
shape microparts for microdevices. For instance, it was demonstrated that hot
embossing on UFG AA1050 processed via ECAP shows a good potential for appli-
cation in fabrication of microheat exchangers with geometrical features smaller than
10 μm and high thermal conductivity. Hot embossing on this material provided a
very smooth embossed surface with fully transferred pattern and low failure rate of
the mold, while hot embossing on the coarse-grained AA1050 resulted in a much
rougher surface with shear bands. Figure 12.4 shows microforming process used to
fabricate a microturbine from ECAP-processed UFG pure Al at ambient temperature.
Subsequent examination demonstrated that UFG pure aluminum gives much higher
Fig. 12.4 Microturbine of UFG pure aluminum formed at ambient temperature. Reprinted with
permission from © Advanced Engineering Materials, 17, 1022–1033 (2016)
12.4 Nanostructured Semiconductor Materials … 155
strength and more uniform mechanical properties by comparison with conventional

coarse-grained pure aluminum. Downscaling of the SPD processing techniques along
with combination with another processing method can dramatically ease fabrication
of microparts for microdevices. A nice example was presented in, where a miniatur-
ized ECAP die with a millimeter-scale channel was developed to produce Al wires
with grain size of 1–2 μm in a single ECAP step showing enhanced strength. This
ECAP preprocessing can be combined with a final extrusion step where a desired
axisymmetric profile can be easily imparted to the final product. An example of a
possible product is a long bar with a cogwheel profile that can be chopped easily into
MEMS gears [9].
12.5 Carbon-Based Sensors and Electronics
The semiconductor industry has been able to improve the performance of electronic
systems for more than four decades by downscaling silicon-based devices but this
approach will soon encounter its physical and technical limits. This fact, together
with increasing requirements for performance, functionality, cost, and portability
have been driven the microelectronics industry towards the nano world and the
search for alternative materials to replace silicon. Carbon nanomaterials such as
one-dimensional (1D) carbon nanotubes and two-dimensional (2D) graphene have
emerged as promising options due to their superior electrical properties which allow
for fabrication of faster and more power-efficient electronics. At the same time their
high surface to volume ratio combined with their excellent mechanical properties
has rendered them a robust and highly sensitive building block for nanosensors. In
2004, it was shown for the first time that a single sheet of carbon atoms packed in a
honeycomb crystal lattice can be isolated from graphite and is stable at room tem-
perature. The new nanomaterial, which is called graphene, allows electrons to move
at an extraordinarily high speed. This property, together with its intrinsic nature of
being one-atom-thick, can be exploited to fabricate field-effect transistors that are
faster and smaller [10] (Fig. 12.5).
When a layer of graphene is rolled into a tube, a single-walled carbon nanotube
(SWNT) is formed. Consequently, SWNTs inherit the attractive electronic properties
of graphene but their cylindrical structure makes them a more readily available option
for forming the channel in field-effect transistors. Such transistors possess an elec-
tron mobility superior to their silicon-based counterpart and allow for larger current
densities while dissipating the heat generated from their operation more efficiently.
During the last decade, carbon nanotube-based devices have advanced beyond single
transistors to include more complex systems such as logic gates and radio-frequency
components [11] (Figs. 12.6 and 12.7).
Recent advances in nanofabrication techniques have provided the opportunity to
use single molecules, or a tiny assembly of them, as the main building blocks of an
electronic circuit. This, combined with the developed tools of molecular synthesis
Fig. 12.5 The layer of graphene acts as the conducting channel in a field-effect transistor
Fig. 12.6 The artistic expression of an integrated circuit based on individual carbon nanotubes.
Reprinted with permission from © Cees Dekker, TU Delft/Tremani
to engineer basic properties of molecules, has enabled the realization of novel func-
tionalities beyond the scope of traditional solid state devices. A modern memory
device, in its most common implementation, stores each bit of data by charging up
a tiny capacitor. The continuous downscaling of electronic circuits, in this context,
translates to storing less charge in a smaller capacitor. Ultimately, as memory device
dimensions approach the nanometer range, the capacitor can be replaced by a single
12.5 Carbon-Based Sensors and Electronics 157
Fig. 12.7 The additional gold atom that adsorbs on the surface of a vibrating carbon nanotube
would change its resonance frequency which is further detected. Reprinted with permission from
© Zettl Research Group, Lawrence Berkeley National Laboratory and University of California at
Berkeley
organic molecule such as Ferrocene, whose oxidation state can be altered by mov-
ing an electron into or out of the molecule [12]. In contrast to common transistors,
where the switching action requires thousands of electrons, a single electron tran-
sistor needs only one electron to change from the insulating to the conducting state.
Fig. 12.8 A neutral Ferrocene molecule is attached to a nanoelectrode representing a “0” state. An
electron tunnels to the nanoelectrode by the application of an external electrical field. The positively
charged Ferrocene molecule represents a “1” state
Fig. 12.9 The single

electron transistor in a
surface acoustic wave echo
chamber. Reprinted with
permission from © Philip
Krantz, Chalmers University
of Technology
Such transistors can potentially deliver very high device density and power efficiency
with remarkable operational speed. In order to implement single electron transistors,
extremely small metallic islands with sub-100 nm dimensions have to be fabricated.
These islands, which are referred to as quantum dots, can be fabricated by employing
processes made available by the advances in nanotechnology [13] (Figs. 12.8 and
12.9).
While conventional electronic devices rely on the transport of electrical charge
carriers, the emerging technology of spintronics employs the spin of electrons to
encode and transfer information. Spintronics has the potential to deliver nanoscale
memory and logic devices which process information faster, consume less power,
Fig. 12.10 The close-up

look at a hard disk drive
improved with the Giant
Magneto-Resistance
technology
12.5 Carbon-Based Sensors and Electronics 159
and store more data in less space. The extension of the hard disk capacities to the
gigabyte and the terabyte ranges was the main achievement of spintronics by taking
advantage of Giant Magneto-Resistance (GMR) and Tunnel Magneto-Resistance
(TMR) effects which are effective only at the nano scale [14] (Fig. 12.10).
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technological applications. In: Proceedings of the NATO advanced study institute on nanos-
tructured materials for advanced technological applications, Sozopol. Springer, Netherlands
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grained aluminium. J Micromech Microeng 20:045029–045041
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Chapter 13
for Bioapplications
Abstract Nanostructured materials development has high impact on biological,

biomedical and clinical applications. The nanostructural materials applied for bio-
logical system can be an interface with high biodegradability and minimum toxicity.
That concern must to be resolve with design and synthesis of nanoscale structures.
This chapter describes more on biomedical application and their design techniques.
Recent improvements in nanostructured materials and nanotechnology will have pro-

found impact in many areas such as energy technologies and biomedical applications.
In the biomedical applications, traditional materials science and engineering face new
challenges in the synthesis and microstructure development since the requirements
for general materials must be based on special medical needs. The most fascinating
development in nano-biomedicine is to be found in biomedical diagnosis and treat-
ment, and involves the direct use of nanomaterials within a biological system. The
in vivo imaging by fluorescent nanoparticles such as quantum dots is progressing
rapidly; and cell targeting via surface functionalized nanoparticles is undergoing ani-
mal tests and should be available within a few years. The nanoscaled systems with
surface functionalized groups that is able to conjugate with a variety of biological
molecules including DNA, RNA, and viruses [1].
Adaptation of nanostructured materials into biomedical devices and systems has
been of great interest. Through the modification of existing nanostructured materials
one can control and tailor the properties of such materials in a predictable manner,
and impart them with biological properties and functionalities to better suit their
integration with biomedical systems. These modified nanostructured materials can
bring new and unique capabilities to a variety of biomedical applications ranging
from implant engineering and modulated drug delivery, to clinical biosensors and
diagnostics [2]. Silicon Quantum dots (SiQDs) and Silicon Nanowires (SiNWs) are
attractive low-dimensional silicon nanostructures that have found important appli-
cations in biology, particularly fluorescence bioimaging and ultrasensitive biosens-
ing. SiQDs-based fluorescent biological probes Fluorescent biological probes are
powerful tools for biological and biomedical studies.
A high-performance fluorescent cellular probe should be water-dispersible, highly
fluorescent, anti-photobleaching and biocompatible. Organic dyes and fluorescent

https://doi.org/10.1007/978-3-030-26145-0_13
162 13 Nanostructured Materials for Bioapplications
proteins have been widely used in biological studies. Notwithstanding, these dyes and
proteins usually suffer from severe photobleaching that hampers long-term imaging
in vitro or in vivo. In the past, the semiconductor II–VI QDS have been developed as
high-performance fluorescent biological probes because of advantages such as size-
tunable emission color, strong fluorescence and high resistance to photobleaching.
However, the potential toxicity problem of the II–VI QDs associated with release of
heavy metal ions (e.g. Cd ions) has not yet been fully addressed, which limits their
widespread biological and medical applications. Consequently, novel fluorescent
probes with robust photostability, strong fluorescence and favorable biocompatibility
are still urgently required to satisfy various requirements of biological studies [3].
13.1 Nanostructured Ti and Ti Alloys for Biomedical

Engineering
Pure Ti possesses the highest biocompatibility with living organisms, but it has
limited use in medicine due to its low strength. High-strength nanostructured pure Ti
processed via SPD opens new avenues and concepts in medical device technology.
First, expensive and toxic alloying elements are absent in the material. Thus, the
implants made therefrom have better biocompatibility. Second, implant size can be
noticeably reduced decreasing the level of surgical intervention into human body.
Third, the material demonstrates improvement of biological reaction on its surface.
A new SPD-based technology has been recently developed for the fabrication of
nanostructured Ti for dental implants. The processing route consists of Equal channel
angular extrusion ECAP-C leading to grain refinement and secondary processing
swaging provides shaping and additional strengthening. Long rods having lengths
up to 3 m, diameters of 4–8 mm, and accuracy grade h8 suitable for automation of
implant machining can be produced using this method. Mechanical properties of this
nanostructured Ti are even higher compared to those of conventional high-strength
Ti alloys (such as Ti–6Al–4 V) used in biomedical engineering [4] (Fig. 13.1).
13.2 Nanostructured Materials for Biosensors
Biosensors based on nanostructured metal oxides gained much attention in the field
of health care for the management of various important analytes in a biological sys-
tem. The unique properties of nanostructured metal oxides offer excellent prospects
for interfacing biological recognition events with electronic signal transduction and
for designing a new generation of bioelectronics devices. A large number of nanos-
tructured metal oxides such as cerium oxide (CeO2 ), iron oxide (Fe3 O4 ), magnesium
oxide (MnO2 ), niobium oxide (Nb2 O5 ), nickel oxide (NiO), praseodymium oxide
(Pr2 O6 ), tin oxide (SnO2 ), titanium oxide (TiO2 ), zinc oxide (ZnO) and zirconium
13.2 Nanostructured Materials for Biosensors 163
Fig. 13.1 a Dental implant from nanostructured Ti, b X-ray photographs after surgery and c control
photograph after incorporation of dental implants into human jaw
oxide (ZrO2 ) have been used for their application in electrochemical biosensors [5]
(Figs. 13.2 and 13.3).
13.3 Nanobiotechnology
Nanobiotechnology is one of the most important applications of nanotechnology.

There are several reasons driving this development: (i) many biomolecules and bio-
entities are of nanometer size. Even cells, which are in the micrometer range, consist
of nanosized component. Thus, the nanometer range is best suited to study the inter-
actions between bio-entities and non-biological materials, (ii) Adhesion, growth,
proliferation and viability of cells strongly depend not only on the chemical nature
Fig. 13.2 The various form of nanostructures with typical dimensions. a Nanotube, l: length (greater
than 1000 nm), d: diameter (less than 100 nm); b nanowire, l: length (greater than 1000 nm), d:
diameter (less than 100 nm); c nanobelt, l: length (greater than 1000 nm), w: width (less than
500 nm), c: depth (less than 100 nm); d nanodiskette, t: thickness (less than 100 nm), d: diameter
(generally between 500–1000 nm); e nanoparticles, d: diameter (order of few nanometers)
Fig. 13.3 The true example

of nanotechnology: an array
of individually addressable
vertically-aligned carbon
nanofibers for sensing
applications at the nanoscale.
For comparison, a single
human hair is 1000 times
thicker than any of the
nanofibers in the image.
from © Farzan Alavian
Ghavanini, Chalmers
University of Technology
of the substrate but also on its nanostructure, (iii) Biosensors will play an ever increas-
ing role in modern medicine. For the development of such sensors, an understanding
of the interactions between biomolecules and surfaces on the nanoscale is imperative.
On the other hand, devices such as labs-on-a-chip require the sensors themselves to
be of micro- or even nanometer size, (iv) Nanoparticles and other nanostructured
materials are envisioned to play an important role in drug delivery, i.e. the transport
of drugs and other medical substances to the very place of use in the body, and also
in medical imaging. (v) Nature herself very often uses nanostructured approaches to
realize astonishing material properties. The famous lotus effect is but one example.
The nacre of abalone shells is formed by a laminated structure consisting of layers
of inorganic material (CaCO3 ) of about 0.5 µm thickness which are separated by
very thin organic layers of less than 10 nm. Such a structure is simultaneously hard,
strong, and tough [6].
13.4 Gene Therapy 165
13.4 Gene Therapy
Gene carriers holds excessive potential for the prevention or treatment of certain
diseases and genetic disorders by delivering therapeutic nucleic acids into the defec-
tive cells, thereby adjusting and controlling the corresponding cellular processes and
responses. The delivery of therapeutic nucleic acids into cells is one of the major
hurdles for the successful gene therapy. The therapeutic nucleic acids (pDNA or
siRNA) need to be shuttled and successfully transferred into the defective cells by
gene carriers. One way to deal with this problem is through viral based gene carri-
ers. Although viral gene carriers are efficient, the clinical application based on this
approach is restricted by several safety concerns, including immunogenicity, car-
cinogenicity, immune response, and virus replication. Some of these shortcomings
may be overcome by applying non-viral carriers. Polymeric gene carriers have exhib-
ited some unique advantages, such as safety, physiological stability and suitable for
large-scale production. However, the transfection efficiency of the non-viral carriers
is usually lower than that of the viral carriers. Generally, the complexes that the
non-viral carriers form with nucleic acids for gene therapy can be classified into four
categories: polyplex, lipoplex, micelleplex and others [7].
13.5 Bioimaging
Bioimaging is a dominant technique that can directly observe normal and abnormal
biological processes in individual patients. Many bioimaging modalities have been
developed, tested and utilized in preclinical and clinical applications in the past two
decades. However, the applications of this technique are often hampered by the poor
sensitivity, specificity, and targeting ability of the available and suitable bioimaging
probes. The typical polymeric nanostructured bioimaging probes are nanoassemblies
consisting of a bioimaging core and a polymer coating as shell. The polymer coating
not only protects the loaded probes from the environment, but also improves the
pharmacokinetics and bio-distribution of the probes, thus significantly amplifying
the diagnostic imaging signals. The developed modalities include contrast agents for
magnetic resonance imaging (MRI), X-ray computed tomography (CT), fluorescence
imaging (FI), Single-photo emission computed tomography (SPECT) and positron
emission tomography (PET) [8].
13.6 Tissue Engineering and Regenerative Medicine
Nanotechnology and nanoengineering are effective means in the design, preparation,

characterization and applications of nanoscale devices, which consist of functional
organizations with at least one dimension in the range from several to hundreds
nanometers. Recently, the synergy between nanoscience and tissue engineering has
led to great developments in biomedical research as well as clinical practices, includ-
ing the realms of bone and cartilage regeneration, blood vessel tissue engineering,
wound dressing, and so on [9].
13.7 Bone Implant
The implants and scaffolds for bone repair and regeneration are of considerable inter-
est for biomedical applications of nanostructured materials, as natural bone exhibits
certain hierarchical structures of nanometer dimensions within bone matrices. In
fact, compared to respective micro-sized counterparts most nanoscale bone implant
materials, such as ceramics like alumina, titania, and hydroxyapatite (HA), poly-
mers (PLGA and polyurethane), and metals (Ti, Ti6A14V, and CoCrMo alloy), have
been shown to enhance bone cell responses and functions that include cellular adhe-
sion, proliferation, synthesis of alkaline phosphatase, and calcium deposition. In
spite of the enhancement of cellular responses, poor mechanical properties of the
nano-sized implant materials limit their further applications for bone repair. Poor
mechanical properties restricts clinical use of nano-HA as load-bearing implants,
and limit their applications to small, unloaded and lightly-loaded implants, powders,
coatings, composites, and porous scaffolds for tissue engineering. Furthermore, the
bending modulus of nanophase alumina was 1.8 times greater than that of natural
human femur bone, even though the nanophase ceramic has closer bending proper-
ties to native bone than conventional ceramics. Mismatch in elastic modulus between
alumina and the surrounding bone often causes a stress shield effect in bone tissue,
resulting in bone resorption and loosening of implants. To compensate for these
weak features, modifications of nanostructured bone implant materials are needed
to improve their mechanical properties. Appropriate modifications can also further
reinforce the interface between bone cells and the implant matrix. Different methods
have been proposed to modify existing nanostructured materials for bone implants
[10].
13.8 Modulated Drug Delivery System
In nanoparticle systems, including solid nanoparticles, polymeric nanoparticles, and

polymeric self-assemblies, have attracted increasing attention for use as potential
drug delivery systems. The advantages of using nanoparticle systems for drug deliv-
ery result from their two basic properties. First, nanoparticulate, due to their small
size, can penetrate small capillaries and be taken up by cells, which allows for effi-
cient drug accumulation at target sites in the body. Second, the use of biodegradable
materials for nanoparticulate preparation allows for sustained drug release within
the target over a period of days or even weeks after administration. Furthermore,
13.8 Modulated Drug Delivery System 167
new functions arising from nano-sizing, such as improved solubility, target ability
and adhesion to tissues can be conferred to nano-delivery systems and also provided
the possibility to covert poorly soluble, poorly absorbable, and predisposed biologi-
cally active substances into promising drugs. In spite of these advantages, however,
some technical problems limit clinical applications of these new nanoparticle drug
delivery systems. Some of these limitations include relatively short blood circulation
time, low accessibility to physiological barriers of target sites blood-brain barrier,
lymphatic barrier, etc., and low efficiency of gene transfection. Suitable and effective
modifications of these nanoparticle materials are needed to overcome these technique
obstacles [11].
13.9 DNA Biosensor
Biosensors for DNA are based on the process of hybridization, the matching of one
strand of DNA with its complementary. These biosensors can be used for recognition
and quantization of target DNA in clinical samples. DNA analysis is widely consid-
ered to be the most recent and promising use of biosensors for clinical applications,
especially for genomic sequencing, mutation detection, and pathogen identification
of inherited diseases. Similar to antibody and antigen biosensors, the introduction of
nanostructured materials with appropriate modifications into DNA biosensors greatly
improves properties including sensitivity and broadening of analytes. Bimolecular
grafting, or coupling, is one of the main ways to modify nano-structured materi-
als for DNA biosensors. DNA-functionalized gold nanoparticles have been used in
quartz crystal microbalance (QCM) to enhance DNA sensor sensitivity. In order to
avoid the high negative charge density of DNA, neutral peptide nucleic acid (PNA),
DNA analogues with the entire sugar-phosphate backbone replaced by a polyamide
backbone, have been prepared to modify gold nanocrystals for DNA sensing. The
PNA complexes could offer nanomaterials with two distinct advantages: (1) greater
stability than DNA duplexes and (2) greater mismatch sensitivity. The latter feature
enables PNA-modified nanoparticles to act as highly selective nanoscale sensors.
Furthermore, when coupled with a substantial change in colloidal stability upon
DNA hybridization, PNA-modified nanoparticles can be used to develop novel col-
orimetric DNA assays that detect the presence of single base imperfections within
minutes [12].
13.10 Glucose Biosensor
Blood glucose is a clinically important analyte for diabetic health care. In most
glucose sensors, such as oxygen, hydrogen peroxide, and mediator detectors are
based on electrochemical amperometry and use a glucose oxidase (GOD) as the
recognition element. The main concern when designing enzyme based amperometric
biosensors is how to effectively transfer electrons to the electrodes. Carbon nanotubes

(CNT) have successfully been applied to glucose biosensor platforms to improve the
electronic properties because of their ability to promote electron-transfer reactions
with enzymes. However, to further enhance the function of glucose biosensors and
maintain the biological activity of GOD in the system, modifications of the CNT are
necessary. It was reported that Pt nanoparticles are very effective as matrix of enzyme
sensors because of their biocompatibility, large surface, and good electrocatalytic
activity with hydrogen peroxide. In order to overcome the difficulty of the deposition
of Pt nanoparticles onto CNT, due to the very high hydrophobicity of CNTs, further
surface modifications and sensitization activations of CNT surfaces were needed.
Nafion, a pefluorosulfonated and negatively charged polymer, was found to improve
depositions of Pt nanoparticles on CNTs, due mainly to the charged interactions. In
addition to having a higher sensitivity to glucose than GOD electrode modified with Pt
nanoparticles or CNT alone, Pt nanoparticle-CNT GOD electrodes exhibited other
superior properties, such as excellent electrocatalytic activity, large determination
range, short response time, large current density, and high stability [13].
13.11 Therapies
Multimode imaging is of paramount importance for the identification and diagnosis

of the disease, but the treatment of the disease, especially targeted therapy, is more
important in clinical medicine. Some nanostructures containing UCNPs as thera-
peutic agent could be used for therapy of diseases, especially for tumor therapy.
PTT, PDT and chemotherapy are the most common therapeutic methods based on
upconversion nanostructures [14].
13.11.1 Photodynamic Therapy
Compared to surgery, chemotherapy and radiotherapy, PDT is a noninvasive cancer

treatment. PDT is involved, in which PDT drugs (photosensitizers) are activated by
UV, visible light or NIR to generate cytotoxic reactive oxygen species (ROS) for
killing the target cells. The organic molecules, such as methylene blue (MB), zinc
(II) phthalocyanine (ZnPc), Chlorine6 (Ce6) and so on, and semiconductor nanoma-
terials are the most common photosensitizers for PDT. Because UV and visible light
with low penetration ability limit the development of PDT, utilizing UV and visible
light converted by UCNPs from NIR can overcome the limitation of low penetration
ability. Semiconductor nanomaterials, like ZnO or TiO2 , as photosensitizer, could be
deposited on the surface of UCNPs to construct a core–shell nanostructure for PDT.
The UCNPs@TiO2 nano constructures are used for effective PDT. The absorption
band of TiO2 shell matched well the UV emission from NIR converted by UCNPs.
13.11 Therapies 169
So TiO2 shell can be activated by NIR to generate and release ROS, which could sup-
press tumor growth efficiently. In order to overcome the tumor hypoxia environment
to achieve effective treatment, many ideas have been proposed. An intelligent upcon-
version nano theranostic system (TPZ-UC/PS) has been designed. In this system, PS
could be activated by UV emission from NIR converted by UCNPs to produce ROS,
so that the environment was hypoxia and TPZ was highly cytotoxic under hypoxia.
The synergistic treatment of ROS and TPZ was effective for tumors [15].
13.11.2 Chemotherapy
Although chemotherapy is invasive, it is still an effective method for disease treat-

ment. The chemotherapy based on UCNPs includes two aspects: imaging-guided
chemotherapy and photo trigger-induced chemotherapy.
Imaging-guided chemotherapy could indirectly observe and monitor the extent
of drug release by using the UCL of UCNPs. SiO2 , mesoporous SiO2 or poly-
mer coated UCNPs with porous or hollow structure are good drug and siRNA car-
rier for chemotherapy. Because of the acidic environment of tumor, some cases of
drug release are controlled by pH. For example, Lin’s group reported sub-10 nm
BaGdF5 :Yb/Tm UCNPs as drug carrier. After modified by gelatin, the UCNPs could
be conjugated with DOX via covalent interactions. The drug release of DOX in acidic
environment (tumor) was faster than that in neutral environment (normal tissue), due
to the cleavage of hydrazone bonds between DOX and UCNPs in acidic environment.
The pH trigger-guide drug release combing UCL/MR/CT multimodal imaging has
a great potential for simultaneous diagnosis and therapy of diseases [16].
13.11.3 Photothermal Therapy
PTT is relative noninvasive treatment for cancer diseases, whose core is photother-
mal agent. The photothermal agents could absorb light and then convert it into heat
to cause thermal damage for cancer cells. PTT could be achieved via combining
UCNPs with nanoparticles with photothermal function. Recently, Au and Ag with
surface plasmon resonance absorption are widely used as photothermal agents for
PTT. Therefore, combining Au or Ag nanoparticles with UCNPs is an effective agent
for PTT. For example, the synthesis of a novel class of multifunctional nanoparticles,
UCNPs, Fe3 O4 nanoparticles, and Au nanoparticles via layer-by-layer self-assembly
to be used for multifunctional bioimaging and PTT. Graphene oxide (GO) and Cux S
were also used as photothermal agents for tumor therapy. The synthesis of GO cova-
lently grafted UCNPs and then loading ZnPc on GO, which could act as a theranostic
platform for UCL bioimaging and PTT/PDT of cancer [17].
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529890:2
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laser. Chem A Eur J 18:7082–7090
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Chapter 14
Nanostructured Materials for Photonic
Applications
Abstract The nanostructured materials play a significant role in the technological

progress of photonic and optical applications. More photonic applications are based
on functional nanostructures. The investigation on nonlinear properties are great
importance in the photonic device fabrication. This chapter elaborates the functional
nanomaterials and their properties for photonic applications.
Much of the existing attention in photonics arises due to the applicability of photonics
to current and future information and image processing technologies. The realization
of this advanced technology rests on the development of multifunctional materials
which simultaneously satisfy many functional requirements. Synthesis, processing,
and characterization of nanostructured materials may lead to numerous electronic and
photonic applications. Nanostructured materials include nanowires, nanotubes, quan-
tum dots, nanocrystalline and nanoparticle thin films, self-assembled and deposited
organic nanofilms, etc. The electronic and photonic applications of nanostructured
materials include electronic storage and computing, solar cells, photoluminescence,
waveguide, chemical and biological sensing, and much more [1] (Fig. 14.1).
The excitement in the field of quantum computing was triggered in 1994 by Peter
Shor who showed how a quantum algorithm could exponentially speed up a classical
computation. Such algorithms are implemented in a device that makes direct use of
quantum mechanical phenomena such as entanglement and superposition. Since the
physical laws that govern the behavior of a system at the atomic scale are inherently
quantum mechanical in nature, nanotechnology has emerged as the most appropriate
tool to realize quantum computers [2].
Nanostructures based on organic optical materials, serving as fundamental ele-
ments in modern photonic devices, have attracted a great deal of research interest,
due to the unique advantages of organic compounds, including high reaction activ-
ity, good processability, and high photoluminescence (PL) efficiency. One dimen-
sional (1D) nanostructures have been demonstrated to be effective building blocks
for miniaturized devices, because of the two-dimensional photon confinement. In
addition, crystalline 1D organic nanostructure with the highly ordered stacking of
conjugated molecules offer better stabilities and charge transport properties, which

https://doi.org/10.1007/978-3-030-26145-0_14
172 14 Nanostructured Materials for Photonic Applications
Fig. 14.1 Quantum

computing chip: the two
black squares are the
quantum bits or cubits, the
processing centre; the
meandering line at the Centre
is the quantum bus; and the
lateral meandering lines are
the quantum memory.
from © Erik Lucero
result in better photonic performances of the final devices. Some unique applica-
tions, like tunable color displays, field-effect transistors, chemical sensors, optical
waveguides, and lasers [3].
14.1 Optical Waveguides Based on Small Organic

Molecules
One-dimensional optical waveguides is a key building block to generate and propa-

gate light, have been attracting considerable attention. They can help in the manipula-
tion of light guiding, localization, and enhancement within submicrometer volumes,
and play an essential role in developing micro/nano scale photonic devices. In the past
couple of years, inorganic semiconductor 1D nanomaterials have been successfully
adopted as optical waveguides. In comparison with those of inorganic semiconduc-
tors, micro/nanostructures consisting of organic luminescent molecules with low
molecular weights offer some unique advantages, such as diversity of optoelectronic
properties and easy synthesis either by liquid phase or vapor phase methods. Due to
the weak intermolecular interactions and excellent luminescent properties, organic
micro/nano structures are expected to work as optical waveguides with distinguish-
ing features and can be readily prepared with desired sizes ranging from hundreds
of nanometers to several microns [4].
14.2 Optically Pumped Organic Lasers 173
14.2 Optically Pumped Organic Lasers
Optical waveguides can lead to some properties of laser light, because waveguides
have common laser geometries. 1D waveguiding nanostructures with optically flat
end facets can function as miniature optical cavities, which apply feedback. As the
light passes backwards and forwards, it is amplified by the stimulated emission, and if
the amplification exceeds the losses of the resonator, lasing begins. Nanolasers with
strong polarized output are able to offer great opportunities in future applications
such as nanooptical routing, emission, detection, data storage, sensing and near-
field optics. Inspired by the existing optically and electrically pumped inorganic
semiconductor and polymer nanowire lasers, researchers show increasing interest
in organic-based lasers, for their unique features, such as a high degree of spectral
tunability, large stimulated emission cross-sections, and the potential for simple high-
throughput fabrication. Moreover, the ease of fabrication has made it possible to
produce 1D organic laser with a wide variety of optical microcavities. Therefore, the
fabrication of 1D organic nano laser is of great scientific interest and technological
significance [5].
14.3 3D Photonic Crystals
The three-dimensionally periodic structure has a complete band gap or frequency

range in which light cannot propagate for any direction or polarization. Only very
particular structures have this property. In general, the crystal must be made up of
materials with relatively large difference in refractive index, such as silicon and
air, to create strong enough scattering for a complete gap. In addition, the particular
geometry must be chosen with care. The face-centered cubic (fcc) lattice, for example,
is particularly favorable to the creation of band gaps. Due to its nearly spherical
Brillouin zone, the partial band gaps at the corners of the 3D Brillouin zone tend to
overlap. Two examples of 3D photonic crystals are shown in Fig. 14.2. The woodpile
Fig. 14.2 Examples of 3D photonic crystals: a woodpile structure, b stacked rod and hole layer
structure. Both belong to the fcc class of lattices
structure, shown in Fig. 14.2a, is made up of stacked layers of parallel rods with square
cross-sections. Adjacent layers have perpendicular orientations.
The structure has a large photonic band gap of 17% of the mid-gap frequency for
a silicon structure in air. The structure shown in Fig. 14.2b is made up of alternating
layers of rods and holes. Each layer forms a triangular array. It also has a large
photonic band gap of close to 20% for silicon in air. Because each of the layers
resembles a 2D photonic crystal, the structure facilitates the design of waveguides
and microcavities based on previously existing 2D designs. Because 3Dcrystals allow
complete confinement of light in three dimensions, they may allow the design of
complex, integrated optical circuits with unprecedented control over light flow [6].
14.4 Photonic LEDs
The interesting application of photonic crystals is light-emitting diodes (LEDs).

Conventional semiconductor LEDs suffer from poor light extraction efficiencies due
to total internal reflection at the semiconductor–air interface. For a semiconductor
refractive index of n = 3.4 (corresponding to a half-cone angle of sin−1 (1/n) = 17°),
the efficiency is 1/4n2 ~ 2%. Placing the active layer of the LED in a 2D photonic
crystal slab can enhance the extraction efficiency. The photonic crystal should ide-
ally be designed so that the LED emission spectrum falls in a frequency range for
which all modes of the photonic crystal slab radiate to air. For a PC slab of suffi-
ciently large area, close to 100% efficiency is expected theoretically. Experiments
have observed a six-fold enhancement of photoluminescence in a InGaAs/InP double
heterostructure. However, the penetration of air holes into the active layer of a LED
causes additional surface recombination, lowering the internal quantum efficiency.
An alternative scheme places a 2D photonic crystal grating above the active layer of
a LED. If the photonic crystal layer is sufficiently shallow, the enhancement of the
extraction efficiency can be described by the grating diffraction effect. Photonic crys-
tal structures have also been used in vertical cavity surface emitting lasers (VCSELs).
A photonic crystal was incorporated into the top distributed Bragg reflector (DBR),
and an oxide aperture in the bottom DBR was used to restrict lateral current spreading
beyond the area covered by the photonic crystal defect. Single-mode operation was
demonstrated with sub-milliamp threshold current and a milliwatt of output power
[7].
14.5 Photonic Crystal Filters
By combining cavities and waveguides in photonic crystals, it is possible to create

different types of optical filters. Such devices may find application in optical com-
munications, particularly in wavelength division multiplexing (WDM). In WDM
14.5 Photonic Crystal Filters 175
Fig. 14.3 Schematic

diagram of band-rejection
filter
systems, signals are encoded on multiple channels, each of which occupies a sepa-
rate frequency bandwidth. Optical filters that can separate out and redirect particular
channels from the optical data stream are useful for optical processing of the sig-
nal. In comparison to alternate technologies such as micro-ring resonators, photonic
crystal devices are extremely compact in size, allowing denser on-chip integration.
One basic filter design is shown schematically in Fig. 14.3. It consists of a waveguide
side-coupled to a microcavity resonator. For simplicity, we represent the waveguide
with a thick solid line and the microcavity resonator by a solid ellipse [8].
LC displays (LCDs) based on conventional nematic LCs now dominate the global
market of advanced information displays with an annual worth of more than $100
billion, and have drastically revolutionized the way that information is presented.
With LCDs ubiquitous in our daily life, research and applications of LCs are rapidly
venturing into the forefront of the bottom-up nanofabrication of advanced photonic
materials and devices, and promising new techniques have also been developed to
controllably fabricate the liquid-crystalline nanostructures with tailored configura-
tions. Different from the conventional photonic nanostructures fabricated by expen-
sive, time-consuming, environmentally hazardous and scale-prohibitive manufac-
turing procedures of semiconductor based inorganic nanostructures, the unique self-
organization properties inherent in the liquid-crystalline materials make it a quite
advantageous approach toward the green, efficient, and cost-effective production of
large-scale 3D periodic nanostructures. Thanks to the high flexibility of the self-
assembly processes, unique building blocks and novel tuning mechanisms could be
developed depending on the specific applications.
Importantly, being soft makes the liquid-crystalline materials responsive to vari-
ous stimuli such as temperature, light, mechanical force, electric and magnetic field,
and chemical and electrochemical reaction, resulting in tunable photonic band gaps in
the 3D nanostructure. Compared with traditional 3D photonic crystals, the unrivalled
attributes, such as multi stimuli-responsiveness, easy tunability, and real time config-
urability, 3D liquid-crystalline photonic superstructures would undoubtedly provide
tremendous opportunities in the widespread applications of all-optical integrated
circuits and next generation communication systems [9].
14.6 Photonic Crystals: Bright Structural Colour

from Functional Morphology
Butterfly wings, mother-of-pearls and opals are examples of natural photonic struc-
tures displaying structural colour. This arises from interference between light waves
and a periodic or random sub-wavelength medium and determines a range of for-
bidden energies in transmission, known as photonic bandgap. When the structures
are periodic, these materials are called photonic crystals. Mimicking nature photonic
structures with periodicity in one, two and three dimensions were realized. Several
techniques like spin coating, electrochemical etching, and physical vapour deposi-
tion, PVD can be employed to fabricate one-dimensional photonic crystals. Refrac-
tive index contrast is obtained either varying the chemical composition of the layers
or by controlling effective refractive index through the control of layers porosity.
The realization of porous architecture represents a step forward in the exploitation of
photonic crystals as it expands their potential function. Porous photonic crystals pos-
sess two great characteristics: (i) controlled mass transport of fluid analytes through
interconnected porosity, and (ii) optical band structure engineering that enables the
realization of tunable optical devices with potential applications in the fields of
sensing, filtering, ICT (e.g. electro-optical switches), energy (sensitized solar cells),
and photo-catalysis. The fabrication techniques of porous one-dimensional photonic
crystals (p1DPCs) still lag behind the theoretical knowledge, and suffer for several
limitations such as repeatability, scalability, and integrability [10].
The most common top-down fabrication technique for p1DPC is anodic current
modulation during electrochemical etching of conductive wafers (e.g. doped-Si, Al).
Pores size can be periodically changed from nanometers to micrometers obtaining
a multilayer structure. This wet technique is limited to conductive materials and
requires complex and multi-step fabrication achieving low refractive index contrast.
To overcome this criticism a bottom-up assembly methods have been proposed to
demonstrate what previously demonstrated by the theory. A number of different
materials in nanoparticles colloidal dispersions were employed as p1DPC building
blocks. Strong photonic bandgap efficiencies were obtained by using NP’s material
with intrinsically high refractive index and tuning particles size distribution with
thickness of several micrometers (using two different materials) or of few millimeter
(using structures based on opals). Spin coating processes, a cheap and flexible tech-
nique, was the preferred technique for the fabrication of these of devices. p1DPC
was also fabricated from the gas phase via glancing angle deposition, a PVD tech-
nique capable of engineering different films architectures through shadowing of vapor
atoms at highly oblique impact angles. Control over the porosity and thickness of indi-
vidual layers is granted with the possibility to use different materials. The pulsed laser
deposition is proposed as a novel fabrication technique for gas-phase self-assembled
photonic hierarchical nanostructures. As the beetle cuticle, self-assembly of differ-
ent hierarchical porous materials is used to achieve refractive index variations and in
turn the photonic bandgap. Hierarchical one dimensional photonic crystal (h1DPC)
with 75% reflection efficiency in a 0.5 µm thick device and approaching complete
14.6 Photonic Crystals: Bright Structural Colour … 177
reflection in a 1.5 µm thick device was fabricated using a single material (TiO2 ).
Structural density of hierarchical nanostructures can be controlled allowing fabrica-
tion of layers having different optical and morphological properties. When stacked
onto each other they achieve peculiar optical functionalities. The hierarchical pho-
tonic nanostructures respond to fluid infiltration with photonic bandgap red shifting.
PLD allow the realization of patterned photonic devices, on the scale of few µm,
with interesting perspectives in the fields of solar cells, biochemical sensing, photo
electrochemical water splitting, displays and photo-catalysis. The characteristic low
thermal load of PLD process allows using even plastic or biological substrates. PLD
decouples the chemistry from morphological parameters of deposited nanostruc-
tures that are controlled by the background gas pressure. Refractive index contrast
is obtained stacking layers of hierarchical nanostructures grown at pressures [11].
Fig. 14.4 a Patterned photonic crystal, fabricated with thickness gradient of the layers, by using a
mask. Scale bar: 1 cm. b Transmission spectra of the photonic crystal along one of the letter, from
top to bottom; a shift of the photonic band gap spectral position of few hundred of nanometers is
shown. c Pixel structure of hierarchical photonic crystal. d) h1DPC deposited on flexible plastic
substrate. Reprinted with permission from © ACS Nano, 8 (2014)
With PLD is possible to realize patterned porous photonic crystals. In Fig. 14.4a
an example is reported where a h1DPC, placed off-axis with respect to the deposition
source, was physically masked in such a way to obtain a letter pattern with a thickness
gradient giving rise to a PBG red shift (from bottom to top) (Fig. 14.4b). Using the
same approach a pixel structure of h1DPC (pixel size of about 10 × 10 µm) was
realized (Fig. 14.4c). The pixel dimension is matching the requested pixel size in
display technology and it could be appealing for achieving special sensing resolution.
The large oriented and interconnected porosity of h1DPC can be used for measuring
refractive index of fluids, with possible applications in optoelectronic sensors [12].
References
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359:1123–1127
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Chapter 15
for Environmental Remediation
Abstract Currently, more research as concerned on environmental remediation for

improving our daily lives and the environment. The nanoscale materials designed for
environmental application has more concern towards increased surface area, surface
modification, and tunability of size. This review mainly describes recent progress in
the design, fabrication, and modification of nanostructured semiconductor materials
for environmental applications.
Nanostructures have several advantages over their bulk counterparts that could poten-
tially be exploited for environmental remediation. For example, the higher surface
area-to-volume ratio of nanostructures could lead to an enhanced reactivity with envi-
ronmental contaminants that degrade through inner-sphere adsorption mechanisms.
Nanostructured materials feature with controllable size, shape, composition, struc-
ture, and surface, which are difficult or impossible to achieve in their bulk materials.
Such unique features of nanostructured materials can be further tailored and engi-
neered to specifically tackle a particular energy and/or environmental challenge [1].
Also the nanostructured materials provide more flexible space for ease reconstruc-
tion, as their nanosize expands the limits and results in confinement effect, enhanced
mechanical stability, and large surface area, and make them suitable for photocat-
alytic activities. The advancement in synthesis techniques provides the freedom to
alter its physical properties as per the demand [2].
The development of nanostructured materials has opened new paths in differ-
ent scientific fields and is providing new opportunities in environmental science.
Advanced oxidation processes have benefited from the development of nanostruc-
tured semiconductors giving rise to heterogeneous photocatalysis, which can achieve
total mineralization of dissolved organic contaminants in both aqueous media, such as
in air, in less time and without the addition of sacrificial oxidants (H2 O2 , O3 , etc.) [3].
Nanoscale iron particles may offer real advantages over granular iron because they
provide a greater surface area and therefore higher reactivity. Metallic nanoparticles
can be applied through direct injection of the particles to contaminated sediments and
aquifers. Surface modification of metallic nanoparticles gives the added advantage
of protecting the surface from oxidation, thus improving the long-term activity.

https://doi.org/10.1007/978-3-030-26145-0_15
180 15 Nanostructured Materials for Environmental Remediation
The nanostructured materials designed for metal ions trapping and absorbing has
received great research interest and many typical nanostructure systems have been
demonstrated since the end of last century. Basically, the advantages nano could pro-
vide include high surface to bulk ratio associated with high porosity, large metal
ion absorbing capacity, and good regeneration ability. The selection and design
for absorbent materials are required to meet several criteria as follows. First, the
absorbent itself should be non-toxic in nature. Second, the absorbent should have
selectivity and sensitivity as high as possible toward specific type of ion in addition
to the large adsorption capability. Third, the adsorbed ions must be easy to collect off
the surface of absorbent materials so that the absorbents could be used for repeated
times. Many metal oxides are low cost and non-toxic materials and the hierarchical
nature makes them promising for ion removal in the waste water. Typical examples
include magnesium oxide (MgO), aluminum oxide (Al2 O3 ), iron oxide (Fe2 O3 ), tita-
nium oxide (TiO2 ) and so on. Much research progress has been made in the synthesis
of these metal oxides with controlled nanoscale morphology. Hierarchical iron oxide
nanostructures have been extensively studied among all the metal oxide nanostruc-
tures for the heavy metal ion removal. In addition to the large adsorption capacity,
high surface area and low cost, an important advantage over other metal oxides is
the magnetic property which makes it easily recoverable from water after toxic ion
removal. Magnetite (Fe3 O4 ) and magnetite (γ-Fe2 O3 ), which are ferromagnetic and
ferromagnetic in nature, have been proved to act as efficient ion absorbents [4].
15.1 Gas Treatment: Nano-Array Based Catalytic

Converters
The air pollution has become a world-wide crisis resulting from burning of fossil
fuels. A major portion of the air pollutants comes from the automobile exhaust and
power plant. The waste gas usually constitutes nitrogen oxide and sulfur dioxide,
which either triggers photochemical pollution or contributes to acidic rain as well as
hydrocarbon and carbon dioxide, which lead to green-house effect. Specific catalyst
is needed to deal with each pollution gas component. The catalytic techniques are in
the progress for the preparation of nano catalyst toward different gas treatment [5].
15.2 Remediation of Organohalides by Dye Sensitized TiO2
Dye sensitization has been frequently used to extend the photoresponse of TiO2 into
the visible region. Photoexcitation of a sensitizer molecule on the surface of TiO2 can
result in electron injection into TiO2 . This mechanism is illustrated in Fig. 15.1 and
produces a TiO2 (e− )–S* charge separated state that can in principle reduce and/or
oxidize environmental pollutants [6].
15.3 Water Split Application of the Nanostructure Photocatalyst 181
Fig. 15.1 Charge distribution in semiconductor-metal composite system leads to fermi-level

equilibration
15.3 Water Split Application of the Nanostructure

Photocatalyst
Titanium oxide is a most studied photocatalyst as it has low toxicity, high chemical
and biological inertness, and high photocatalytic reactivity. Its limitation is that it is
naturally activated by UV radiations which form a very low percent of solar spectrum.
However, doping with transitional metals such as Pt, V, Cr, or Fe have enabled the
absorption spectrum towards visible. In a similar effort, hierarchal porous structure
(HPT-500) TiO2 was deposited with Pt and Zinc phthalocyanine (PCH-001) to form
a composite. The results showed that Pt-HPT nanocomposite with 0.25 μmol/15 mg
of nanocomposite (HPT-0.25) exhibited maximum H2 evolution. The H2 yield was
found to be 2260 μmol at λ ≥ 450 nm and the turn over number was found to be
18,080. Highest apparent quantum yield (AQY) of 11.97% was achieved at 690 nm
for HPT-0.25. Exfoliation is a technique that can either modify or reduce the size
of the photocatalyst. One major advantage of using exfoliation is that it does not
alter the crystal structure. Due to reduction in size, the migration distance of charge
carriers is reduced and the surface area of the catalyst is increased new ultrasonic
method for rapid and high yield of (TBA/H) Pb2 Nb3 O10 by exfoliation. The obtained
(TBA/H) Pb2 Nb3 O10 was loaded with Pt and used as visible light photocatalyst for
production of hydrogen (λ > 415 nm), thereby making it as a first and foremost
visible light-driven AB2 Nb3 O10 . The perovskite yielded 50 mmol/h and 17 mmol/h
of H2 under full-arc and visible light irradiation, respectively. The study concluded
that, due to smaller migration distance of charge carriers, efficiency of electrons for
hydrogen production improved [7].
15.4 Nanostructure Photocatalyst for Water

and Wastewater Treatment
Nanostructured photocatalytic materials are broadly used in wastewater purification

and for degrading the recalcitrant organics. The most common materials used are
TiO2 , ZnO, WO3 , g-C3 N4 , etc. Photocatalyst have proven to be helpful in degrading
several categories of organic contaminants including POPs and endocrine disrupting

compounds (EDCs). Various parameters that affect the photocatalysis include pH,
availability of solar light, band structure of the photocatalyst, concentration of the
photocatalyst, concentration of pollutant, etc. pH of the reaction mixture exhibits
profound effect on the degradation of pollutants, for instance, in an experiment per-
formed was found that the photocatalyst heterojunction (p-BiOI/p-NiO) was able to
degrade acid orange 7 more effectively at strong acidic condition as compared to
neutral. The acidic condition modified the surface charge of the photocatalyst and
thus enhanced the degradation process. Other important parameters that can affect
the degradation process are photocatalyst dosage and pollutant concentration [8].
Nanostructured membranes (NSM) are used to reject suspended particles, bac-
teria, macromolecules, viruses, colloids, organic compounds, and multivalent ions.
They are mainly utilized for drinking water production for water softening or disin-
fection, and the treatment of landfill leachate and industrial wastewater. The advan-
tages of NSM compared with other treatment methods depend upon the substances
present in the feed water and the water that is subject to cleaning. One advantage
is that different pollutants can be removed in the same filtration step. Depending
on the membrane this removal can be selective towards certain substances or com-
pounds can be only partially removed; for example calcium carbonate in the case
of water softening. It is therefore crucial that the membrane is exactly tailored to
the needs of the treatment plant in order to achieve the maximum removal of the
target compounds. Additional advantages are non-resistant organisms are left, the
use of chemicals is minimal, and the cleaning capacity is not detracted by turbidity,
or economic factors such as costs or energy use.
The development of nanostructured solar energy driven semiconductor photo-
catalyst have received immense attention in the areas of environmental remedia-
tion and energy storage. The numerous organic pollutants are discharged into the
environment by an increasing revolution in industrial and agricultural sectors. The
presence of organic pollutants in the wastewater can change the oxygen levels that
can drastically lead to severe problems in the ecosystem. The photocatalytic degra-
dation is considered to be an effective ways for the removal of organic pollutants
from wastewaters. Therefore, it is necessary to develop highly effective, visible light
active catalytic materials to solve most of the critical problems related to energy and
environment [9].
Detection of toxic gases in the environment is an important and critical aspect
to industry, agriculture and human health. It is essential to develop a reliable
and selective gas sensor for determining toxic gases. Among various gas sensors,
semiconductor-based gas sensors have attracted much attention because of the advan-
tages of convenience, inexpensive, and rapid detection. More recently, MoS2 has been
widely investigated by a number of researchers in gas sensing applications. The gas
molecules can be easily adsorbed on the surface of MoS2 . On the other hand, the
weak interaction allows gas atoms or electrons to infiltrate and transport freely in
MoS2 . Therefore, MoS2 -based nanostructured materials has turned into potential
candidates for the fabrication of high-performance gas sensors, such as NH3 , H2 ,
NO, and many kinds of chemical vapors [10].
15.5 Sensing the Chemical Environment with Semiconductor Nanostructures 183
15.5 Sensing the Chemical Environment

with Semiconductor Nanostructures
The sensors for environmental applications have been continuously developing,

which includes, SnO2 based semiconductor systems that have been used as conducto-
metric gas sensors and a TiO2 electrode for determining the chemical oxygen demand
(COD) of water. Prompted by the discovery of photoluminescence from porous Si
and subsequent observation that many organic and inorganic molecules quench this
emission, has led to their exploitation as chemical sensors. The photoluminescence
in porous Si arises from charge carrier recombination in the quantum confined nano-
sized environments. The feasibility of using porous silicon nanocrystals as sensors
has been demonstrated for detecting nerve gas agents and nitro organics. Using
detection based on electrical conductivity, photoluminescence, or interferometry,
researchers have achieved sensitivity in the range of ppb–ppm levels [11].
15.6 Pollution Control Using Nanostructures
15.6.1 Air Pollution
Air pollution can be remediated using nanotechnology; for example, the use of nano-
catalysts with increased surface area for gaseous reactions. Catalysts work by speed-
ing up chemical reactions that transform harmful vapors from cars and industrial
plants into harmless gases. Catalysts currently in use include a nanofiber catalyst
made of manganese oxide that removes volatile organic compounds from industrial
smokestacks [12]. Another approaches are, using nanostructured membranes that
have small pores to separate methane or carbon dioxide from exhaust. The carbon
nanotubes (CNT) for trapping greenhouse gas emissions caused by coal mining and
power generation. CNT can trap gases up to a hundred times faster than other meth-
ods, allowing integration into large-scale industrial plants and power stations. This
new technology both processes and separates large volumes of gas effectively, unlike
conventional membranes that can only do one or the other effectively.
15.6.2 Water Pollution
The harmful pollutants in water can be converted into harmless chemicals through
chemical reactions. Trichloroethene, a dangerous pollutant commonly found in
industrial wastewater, can be catalyzed and treated by nanoparticles. Researchers
have shown that these materials should be highly suitable as hydrodehalogenation
and reduction catalysts for the remediation of various organic and inorganic ground-
water contaminants [13]. Nanotechnology used for water cleansing process because
inserting nanoparticles into underground water sources is cheaper and more efficient
than pumping water for treatment. The deionization method of using nano-sized fibers
as an electrode is cheaper, and energy efficient. Traditional water filtering systems
use semi-permeable membranes for electrodialysis or reverse osmosis. Decreasing
the pore size of the membrane to the nanometer range would increase the selectiv-
ity of the molecules allowed to pass through. Membranes that can even filter out
viruses are now available. Also widely used in separation, purification, and decon-
tamination processes are ion exchange resins, which are organic polymer substrate
with nano-sized pores on the surface where ions are trapped and exchanged for other
ions.
Ion exchange resins are mostly used for water softening and water purification. In
water, poisonous elements like heavy metals are replaced by sodium or potassium.
However, ion exchange resins are easily damaged or contaminated by iron, organic
matter, bacteria, and chlorine. Recent developments of nano-wires made of potassium
manganese oxide can clean up oil and other organic pollutants while making oil
recovery possible. These nanowires form a mesh that absorbs up to twenty times its
weight in hydrophobic liquids while rejecting water with its water repelling coating.
Since the potassium manganese oxide is very stable even at high temperatures, the
oil can be boiled off the nanowires and both the oil and the nanowires can then be
reused [14].
Designing new catalysts that can efficiently utilize multiple energy sources
can contribute to solving the current challenges of environmental remediation
and increasing energy demands. The fabricated single-crystalline BiFeO3 (BFO)
nanosheets and nanowires that can successfully harness visible light and mechani-
cal vibrations and utilize them for degradation of organic pollutants. Under visible
light both BFO nanostructures displayed a relatively slow reaction rate. However,
under piezocatalysis both nanosheets and nanowires exhibited higher reaction rates
in comparison with photocatalytic degradation. When both solar light and mechan-
ical vibrations were used simultaneously, the reaction rates were elevated even fur-
ther, with the BFO nanowires degrading 97% of Rhodamine B dye within 1 h (k-
value 0.058 min−1 ). The enhanced degradation under mechanical vibrations can be
attributed to the promotion of charge separation caused by the internal piezoelectric
field of BFO. BFO nanowires also exhibited good reusability and versatility toward
degrading four different organic pollutants [15] (Fig. 15.2).
15.7 Field-Effect Transistor (FET) Sensors
FET sensors have been used for detection of heavy metals by utilizing the interaction
between the analyte and semiconductor resistor. FET sensors are capable of real-
time label-free detection of heavy metals. One-dimensional and two-dimensional
semiconducting nanomaterials are especially attractive to the FET sensors because
they have very high surface-to-volume ratio, leading to high sensitivity. A Si nanowire
was used to construct a FET sensor for detection of heavy metals. This FET sensor
15.7 Field-Effect Transistor (FET) Sensors 185
Fig. 15.2 Catalytic degradation schemes of BFO NWs under light and ultrasound. Reprinted with
permission from © Science, 29, 236–246 (2018)
exhibited high sensitivity with a LOD of 10−7 M for Hg2+ and 10−4 M for Cd2+ .
Another example was a selective and sensitive FET sensor constructed with single
walled carbon nanotubes (SWCNTs), which was based on the conductance change
due to the selective redox reaction between SWCNTs and Hg2+ . Reduction from
Hg2+ to Hg0 by the SWCNTs is thermodynamically favorable, while reduction of
other metal ions with SWCNTs is unfavorable due to their negative potentials [16].
Also, Nanostructured porous Si (PSi) has been recognized as a versatile platform
for numerous sensing and biosensing applications, mainly for its tunable optical
properties and large surface area. PSi-based interferometers are highly sensitive to
the presence of chemical or biological molecules within the pores, due to the change
in the average refractive index of the nanostructure. Ultimately, the porous scaffold
offers an unbiased label-free optical detection of a wide variety of biomolecular
interactions, e.g., enzyme-substrate, antibody-antigen4 and DNA fragments, which
are facilitated over a small working area [17].
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by nanostructured porous Si biosensors. Analyst 140:4507–4514
Chapter 16
Miscellaneous Applications
of Nanostructures
Abstract Other than energy, environment, electronic and biomedical applications,

the nanostructured materials used in more advanced and sensitive applications like
cosmetics, food processing, communication and security purpose. This chapter
describes all the applications related to above mentioned sectors.
Nanostructured materials for regenerative medicine also include particles, which can
be used as an important tool for both sensing and actuating tissue morphogenesis. For
example, particles can be used as functional components for biosensors and cell track-
ing devices to characterize nascent tissue morphogenesis in vivo. Nanoparticles can
also serve as critical biomaterials to stimulate in situ tissue morphogenesis by virtue
of such strategies as receptor-ligand interactions, controlled release, and gene deliv-
ery. The use of nanoparticle-based gene delivery vectors study concludes that uptake
of functionalized particles is primarily dependent upon nonspecific interactions with
heparin sulfate in conjunction with integrin binding domains [1].
16.1 Nanostructures in Aerospace Application
The aerospace applications for nanotechnology include high strength, low weight
composites, improved electronics and displays with low power consumption, variety
of physical sensors, multifunctional materials with embedded sensors, large surface
area materials and novel filters and membranes for air purification, nanomaterials
in tires and brakes and numerous others. The opportunities for aerospace industry
are through thermal barrier and wear resistant coatings, sensors that can perform at
high temperature and other physical and chemical sensors, sensors that can perform
safety inspection cost effectively, quickly, and efficiently than the present procedures,
composites, wear resistant tires, improved avionics, satellite, communication and
radar technologies [2].

https://doi.org/10.1007/978-3-030-26145-0_16
188 16 Miscellaneous Applications of Nanostructures
16.2 Nanostructures in RADAR Application
Nanostructured polymer composites have released up new views for multifunc-

tional materials. In particular, carbon nanotubes (CNTs) present potential applica-
tions in order to improve mechanical and electrical performance in composites with
aerospace application. The combination of epoxy resin with multiwalled carbon
nanotubes results in a new functional material with enhanced electromagnetic prop-
erties. The processing of radar absorbing materials based on formulations containing
different quantities of carbon nanotubes in an epoxy resin matrix. The adequate con-
centration of CNTs in the resin matrix was determined and the processed structures
were characterized by scanning electron microscopy, rheology, thermal and reflectiv-
ity in the frequency range of 8.2–12.4 GHz analyses. The microwave attenuation was
up to 99.7%, using only 0.5% (w/w) of CNT, showing that these materials present
advantages in performance associated with low additive concentrations [3]. Radar
Absorbing Materials (RAM) provides energy losses of electromagnetic radiation.
In certain frequency bands, these materials attenuate the incident electromagnetic
wave radiation and dissipate the energy absorbed in the form of heat through internal
mechanisms, magnetic and/or dielectrics. These loss mechanisms can be physical,
chemical or simultaneously both. Increased electromagnetic pollution due to the
presence of microwaves and the use of stealth technology in defense systems and
military platforms have been the major attractions for studies in this area, with invest-
ments in research that already cover the frequency range of 1–40 GHz. Some recent
studies have described radar absorbing structures applied in the frequency range of
10–100 GHz [4].
16.3 Nanostructures in Stealth Application
Block copolymer micelle lithography (BCML) is a potent method for preparing

periodically spaced metallic nanoparticles with sub-100 nm spacing on different sub-
strates. Highly ordered arrays of nanoparticles are fabricated using BCML and used
as etching masks in a reactive ion etching (RIE) process to obtain well-defined arrays
of nanopillars perpendicular to the interface. These nanopillars gradually adjust the
difference in the refractive indices of the substrate material and the surrounding
medium (e.g., vacuum, air, or water). The combination of BCML and RIE is a reflec-
tive method of choice for producing surfaces for antireflection applications in the
ultraviolet (UV) and visible range. Using this physical principle enables increased
light transmittance, reduced reflectance, and low absorption to be obtained within
a range of wavelengths covering several hundred nanometers. The wavelength of
maximal transmittance and minimal reflectance depends on the effective refractive
index and the optical thickness of the layer that is made up of the nanopillar array
[5].
16.3 Nanostructures in Stealth Application 189
One strategy to tune the effective refractive index of this interface layer within
a limited wavelength range is to adjust the spatial spacing and the width of the
nanopillars. The nanostructured stealth surface, with minimal reflectance (<0.02%)
and maximal transmittance (>99.8%) for a wavelength range, covering visible and
near-infrared. Compared to multilayer thin film coatings for near-infrared applica-
tions our antireflective surfaces operate within a much broader wavelength range, are
mechanical stable to resist human touch or contamination, show a 44% higher laser-
induced damage threshold, and are suitable for bended interfaces such as microlenses
as well [6].
16.4 Nanostructured Electrode
Mostly, the lithium–air batteries have been described to have a higher specific capac-
ity than most other batteries systems, but the rate capability, cycle life, and power
performance of lithium–air batteries are still not satisfied for practical applications.
Some of the major obstacles are limiting oxygen solubility and diffusion, accumula-
tion of reaction products, and the lack of effective 3-phase electrochemical interface,
which are directly determined by electrode structure design. A porous electrode
with optimum porosity and effective catalysis site distribution for maximization of
materials utilization is desirable. In addition to optimizing the air electrode composi-
tion which may affect the cathode porosity, more efforts should be devoted towards
designing a novel porous air electrode. The simulated and analyzed several air elec-
trode designs including single pore system, dual pore system in two dimensions, and
dual pore system with multiple time release catalysts.
Some important parameters including the porosity distribution, pore connectivity,
the tortuosity of the pore system, and the catalyst spatial distribution were studied
in detail [7]. The results indicated that the dual pore system offers advantages for
improving oxygen transport into the inner regions of the air electrode. When coupled
with multiple time-release catalysts, the system can substantially extend the dura-
tion at higher powers, and result in maximum utilization of air electrode materials.
Considering the requirement of porous structure and available void volume for dis-
charge products, numerous efforts have been devoted to designing a novel porous air
electrode with maximum void volume. Researchers developed all-carbon–nanofiber
porous electrode with highly efficient utilization of carbon material and void vol-
ume for lithium–air batteries which was found to yield high gravimetric energies
of four times higher than lithium-ion batteries. A similar freestanding carbon nan-
otube/nanofiber mixed buckypaper was also developed and applied in lithium–air
batteries [8] (Fig. 16.1).
The chemical-biochemical functionalization and characterization of devices based
on nanostructured materials i.e. porous silicon (PSi), zinc oxide nanowires (ZnO
NWs) and diatomite for abovementioned applications. A valid chemical functional-
ization strategy is crucial for the realization of devices capable of selective detection
Fig. 16.1 The structure design of an air-breathing lithium–air battery developed by IBM. Reprinted
with permission from © Nano Energy, 2, 443–467 (2013)
due to the combination of specificity of biological recognition probes and the sensi-
tivity of sensor, providing unambiguous identification and accurate quantification. A
common strategy based on the salinization process by aminosilane compound (e.g.
APTES, APDMES) was carried out, resulting a valid preliminary chemical treatment
to passivate and/or functionalize nanostructured surface in order to covalently bind
biological molecules such as single or double stranded DNA, proteins, enzymes,
antibodies, aptamers and so on, acting as bioprobes for biosensor realization. Nanos-
tructured photonic materials are optimal transducers for optical sensing due to their
capacity to convert molecular interactions in light signals without contamination or
deterioration of the samples [9] (Fig. 16.2).
Fig. 16.2 Image of the

porous silicon microarray
integrated with the
microfluidic circuit
16.5 Nanostructures in Antimicrobial Application 191
16.5 Nanostructures in Antimicrobial Application
Nanostructured materials (NSMs) have progressively used as a ancillary for antibi-

otics and additives in various products to impart microbicidal effect. In particular,
use of silver nanoparticles (AgNPs) has gathered enormous researcher’s attention
as potent bactericidal agent due to the inherent antimicrobial property of the silver
metal. Moreover, other nanomaterials carbon nanotubes, fullerenes, graphene, chi-
tosan, etc., have also been studied for their antimicrobial effects in order ensure their
application in widespread domains. Antimicrobial effect of NSMs has been widely
studied by several research groups against a wide range of microorganisms. NSMs
can be regarded as the next generation antibiotics as they possess remarkable potential
to overcome multidrug resistance problems in the pathogenic microbes. Depending
on their ability to provide biostatic and biocidal action against microbial species,
they can also be exploited in healthcare and personal care products, food safety,
crop protection, water treatment, textile industries, etc. Although NSMs have shown
spectacular antimicrobial effect against more than 500 microbial species, however,
accurate mechanism behind their microbicidal activity is not hitherto well-understood
[10] (Fig. 16.3).
Fig. 16.3 The various modes of microbial toxicity caused by nanostructured materials
16.6 Nanostructures in Cosmetic Application
The cosmetics industry uses nanodispersions encapsulation or carrier systems, so

that arbitrators enter into deeper skin layers where they activate skin metabolism
with the aim of improving the skin’s appearance. The functions and benefits of these
encapsulation and carrier systems are, the controlled release and optimization of
the availability of cosmetic agents in certain skin layers, the protection of sensitive
agents, longer shelf life and hence greater product effectiveness, and a reduction in the
amount of agents and additives used in products. They include liposomes, nanoemul-
sions, microemulsions and lipid-nanoparticles which are soluble and biodegradable
[11].
16.6.1 Chitin Nanofibril
A chitin nanofibril is a nanocrystal of a natural polysaccharide obtained from the

crustacean exoskeleton after elimination of the carbonate and protein portions. Hav-
ing a backbone like hyaluronic acid, chitin nanofibril is easily metabolized by the
body’s endogenous enzymes and thus is used in cosmetic dermatology and biotex-
tiles. The crystal average size is 240 × 7 × 5 nm, and its shape is like a thin needle.
It occurs naturally and is considered a safe raw material, it is safe to use and also
it is both bio and eco compatible. As it is easily metabolized by enzymes, it is both
bio- and eco-compatible. As the nanofibril has an average size one-quarter that of a
bacterium, 1 g of the product covers a surface area of 400 m2 . Many studies have
shown that chitin nanofibrils can activate the proliferation of keratinocytes as well
as fibroblasts, regulating not only collagen synthesis but also cytokine secretion and
macrophage activity [12].
16.6.2 Nanoparticles as UV Protective Filters in Sun Screens
The microparticles of titanium dioxide and zinc oxide have been used in cosmetic
products as UV filters. The substances were used as traditional white pigments in the
micrometer sector. The resulting products however were comparatively thick, sticky
pastes which were difficult to administer and were not widely adopted by consumers
as they left a whitish film on the skin. By using nanoparticle-sized titanium dioxide
and zinc oxide the substances are transparent to the human eye, can be applied more
easily on the skin and leave a better skin feeling. In addition, protection against
UV radiation has been radically improved as a result of the smaller sized particles.
The primary size of the nanoparticles used as UV filters is approximately 40 nm.
According to the German Cosmetic, Toiletry, Perfumery and Detergent Association
(IKW) titanium dioxide and zinc oxide are now only to be found in nanoparticle
16.6 Nanostructures in Cosmetic Application 193
form in sunscreens, and products carry a notice advising of the titanium dioxide and
zinc oxide content. Currently only titanium oxide is listed as an authorized sunscreen
filter on the EU Directive on cosmetics list of permitted UV filters [13].
References
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as air electrodes. J Electrochem Soc 157:A953–A956
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Investig Dermatol 3:5–13
13. Greßler S, Gazso A, Simko M (2010) Nanotechnology in cosmetics. Nano Trust dossiers
Chapter 17
Nanostructured Materials Life Time
and Toxicity Analysis
Abstract Now-a-days, the nanostructured materials increased its fabrication skill

and application in important sectors like energy, environment, and medicine. How-
ever, there are some concerns related to its toxicity and life time. This chapter
presents some interesting techniques and analysis to measure life time and toxicity
of nanoscale materials.
The increasing use of nanomaterials in consumer and industrial products has stimu-
lated global concern regarding their fate in biological systems, resulting in a demand
for parallel risk assessment. A number of studies on the effects of nanoparticles
in in vitro and in vivo systems have been published. However, there is still a need
for further studies that conclusively establish their safety/toxicity, due to the many
experimental challenges and issues encountered when assessing the toxicity of nano-
materials. Most of the methods used for toxicity assessment were designed and
standardized with chemical toxicology in mind. However, nanoparticles display sev-
eral unique physicochemical properties that can interfere with or pose challenges
to classical toxicity assays. Recently, some new methods and modified versions of
pre-existing methods have been developed for assessing the toxicity of nanomaterials
[1].
The main focus of current nanomaterial toxicity research is engineered nanoparti-
cles, such as metals, metal oxides, single-walled and multiwalled carbon nanotubes,
C-60, polymeric nanoparticles used as drug carriers, and quantum dots. The increase
in relative surface area that occurs as particle size decreases down to the nanoscale
gives rise to novel and enhanced material properties, but it also renders them more
biologically reactive. Reducing particles to nanosize can also give them access to
distal regions of biological systems that are normally inaccessible to larger particles.
The release of nanoparticles into the environment can occur through many processes,
such as spilling and washing consumer products incorporating nanoparticles; dur-
ing synthesis and production; as an accidental release during transport or use; from
industries that exploit nanotechnology, for example wastewater treatment and drug
delivery [2].

https://doi.org/10.1007/978-3-030-26145-0_17
196 17 Nanostructured Materials Life Time and Toxicity Analysis
17.1 Impact of Nanomaterials to Human Health

and Ecosystems
Considering the assessment of nanomaterials life cycle, one of the main concerns
is if they exert any potentially negative impact on human health and ecosystems.
Potential impacts of nanoparticles may be immensely underestimated if genotoxicity
is not considered. For this reason, toxicity, i.e. genotoxicity and ecotoxicity have
been considered. It is shown that the exposure to nanoparticles in plants induces
reduced germination or growth, membrane damage, impaired photosynthesis, slowed
or reduced reproductive development and mortality. The exposure to nanoparticles in
animals induces cytotoxicity by necrosis or apoptosis, tissue or organ-level damage,
growth inhibition, impaired reproduction and/or development and mortality [3].
For humans, molecular changes upon exposure can affect either somatic or germ
cells and subsequent adverse birth outcomes and genetic diseases and carcinogene-
sis. The mitotic spindle aberrations are anticipated in exposed workers to SWCNT.
The observed disruption is common in many solid tumors including the lung can-
cer. Cytotoxic and genotoxic properties of SWCNT have been verified in cells of
the human gastrointestinal tract. Also, oxidative stress responses in the lungs of
mice can be triggered by inhalation of pure CNT. Some recent studies found that
CdSe-core QDs were indeed toxic under certain conditions and this toxicity can be
modeled by processing parameters during synthesis, UV light exposure and surface
coating and that it correlates with the liberation of Cadmium ions. In some studies it
is shown that the penetration of quantum dots through abrasions in the skin is pos-
sible, and also that quantum dots can be transferred through a small food chain. The
minute concentrations of quantum dots could be sufficient to cause long lasting, even
trans generational, effects in exposed cells. Even though quantum dots can partially
degrade in the environment or in biological systems over time, they can eventually
cause small, but cumulative undesirable effects. Regarding nano-TiO2 , there are a
lot of uncertainties and discrepancies in the achieved results. The investigation of
potential genotoxicity of TiO2 nano-particles exposure showed contradictory results.
After 5 days inhalation of mice, no genotoxic effects were observed while, on the
other hand, it is also showed that TiO2 nanoparticles can induce genotoxic affects
both in vivo and in vitro tests. In vivo tests showed that TiO2 nanoparticles can
enter directly into the brain through the olfactory bulb and can be deposited in the
hippocampus region, damaging rat and human glial cells. The investigation of the
potential ecotoxicity impacts on algae, daphnia and fish as a result of direct release
of Ag and TiO2 nano-particles (mainly <200 nm in nominal diameter size) from var-
ious nano-materials products to the freshwater has been analyzed. It was shown that
nanomaterials, constituted from TiO2 had lower ecotoxic impact than those made
from Ag and there was a linear regression between Ag nanomaterials content in the
considered products and the potential ecotoxicity impacts to the freshwater species,
according to the release of total Ag during use (mainly washing). In general, if and
how genotoxicity of nanoparticles can be induced in higher trophic level organisms
through food chain remain undiscovered [4].
17.1 Impact of Nanomaterials to Human Health and Ecosystems 197
The current understanding of Engineered Nanoparticles (ENP) fate and transport

in environmental and biological systems is poor and the current literature relies
exclusively on nominal exposure. The results of potential toxicity, i.e. genotoxicity
of nanoparticles in the living organisms, like for nano-sized TiO2 , are taken from
certain number of studies that deal with the estimation based on the results gathered
from in vitro or in vivo studies where no origin of these particles is taken into account,
i.e. the pathways of these particles from their release till their ingestions by living
beings remain unknown. In other words, the indications of genotoxicity considered
in these studies are not strictly associated with the emissions of nano-TiO2 from the
structures supporting renewable energy provision and storage, such as nanostructured
titania catalyst system and other similar structures, but represents undefined and more
general situation. Due to the lack of exact data about behavior and impact on human
health of these particles, it can only be predicted that they are causing the same effects
on human and animal genome as TiO2 nano particles studied in many articles [5].
17.2 Nanomaterial Toxicity
Humans are exposed to nanoparticles as they are produced by natural processes. Pro-
duction, use, disposal, and waste treatment of products containing nanoproducts are
the prime reasons for the environmental release of nanoparticulates in the original or
modified forms. Foreign substances are generally blocked by human skin, whereas
organs susceptible to foreign substances include the lungs and gastrointestinal tract.
Nanoparticles (NPs) are comparable to viruses in size. For instance, the diameter of
the human immunodeficiency virus (HIV) particle is on the order of 100 nm. NPs
that are inhaled can effortlessly reach the bloodstream and other sites in the human
body including the liver, heart or blood cells. It is significant to mention that the
toxicity of NPs depends on their origin. Many of them seem to be nontoxic and
others have positive health effects. The small size of NPs facilitates translocation of
active chemical species from organismal barriers such as the skin, lung, body tis-
sues and organs. Thus, irreversible oxidative stress, organelle damage, asthma, and
cancer can be caused by NPs depending on their composition. The general acute
toxic effects caused by exposure to NPs and nanostructured materials include reac-
tive oxygen species generation, protein denaturation, mitochondrial disconcertion
and perturbation of phagocytic functions. Uptake by the reticuloendothelial system,
nucleus, neuronal tissue and the generation of neoantigens that causes possible organ
enlargement and dysfunction are common chronic toxic effects of NPs [6].
17.3 A Consideration of All Pertinent Sources

of Nanomaterials
The production of engineered nanomaterials (ENMs) creates an immediate concern;

due to its risk assessment for nanomaterials must take into account with the relative
magnitude of ENMs as sources compared with other sources of materials that may
be identical or similar to ENMs. Nature produces a plethora of nano-scale particles
in processes ranging from forest fires to bacterial metabolism. Human activities
may also produce nano-scale particles by precipitation in waste streams, internal
combustion engines, and other “incidental” sources. In some cases the materials
produced are identical to ENMs as in the case of fullerenes produced in engineered,
natural, or incidental combustion processes [7].
Incidental carbon nanotubes (CNTs) and other fullerene-related nanocrystals have
been reported to originate from propane stoves, wood fires, burning tires and other
sources and fullerene C60 has been found in geologic deposits, candle soot, and
meteorites. TiO2 nanoparticles, similar to ENMs, have been found downstream of
hazard waste sites. An assessment of exposure to nanomaterials must also address
possible releases associated with various stages of fabrication, transport, processing
and disposal; activities that make up what is referred to as the value chain of nanoma-
terial production and use. The nanomaterial value chain involves the production of
basic building blocks of nanomaterials and their incorporation in subsequent stages
into products of increasing complexity [8]. For example, engineered nanomaterials
such as titanium dioxide might be modified with a tailored surface chemistry to yield
suspensions that are then used to create various products ranging from thin films for
self-cleaning windows to catalysts suspensions in water treatment. At each stage in
the value chain, there exists the possibility of nanomaterial release and subsequent
exposure to humans or ecosystems through the production, transport, use and dis-
posal of nanomaterials and nanomaterial-containing products. Important factors to
be identified in evaluating potential nanomaterial exposure at each stage in the value
chain are the format that nanomaterials will be present in as commercial products,
the potential for these materials to be released to the environment, and the transfor-
mations that those materials may undergo that may affect their subsequent potential
for exposure. Indeed, due to modifications along the value chain or environmental
transformations, the potential contact between humans and ecosystems outside of
the work place will most likely involved nanomaterials there bear little resemblance
to the initial material [9] (Fig. 17.1).
An additional set of hazards to be examined is the potential for collateral damage
i.e. environmental impacts that arise from the production and use of nanomaterials
rather than the nanomaterials themselves. In particular, the environmental impacts
associated with upstream energy usage are likely to contribute significantly to the
environmental footprint of nanomaterials production given the high energy inputs
currently employed to create order at the nanoscale. These issues may greatly out-
weigh direct health or environmental impacts associated with an emerging nanoma-
terials industry. The first ever published work on nanomaterial risk assessment dealt
17.3 A Consideration of All Pertinent Sources of Nanomaterials 199
Fig. 17.1 Evaluation of nanomaterial risks to ecosystems and organisms posed by multiple sources
directly with issues of collateral damage. One of the important findings reported
in this work was that methods for manufacturing nanomaterials tend to become
greener with time; substituting, for example, less toxic solvents or implementing
more energy-efficient procedures for fabricating nanomaterials. Subsequent work
by others looking at carbon nanotube production has shown that nanomaterial pro-
duction may involve the production of non-nano wastes that pose significant hazards
[10].
17.4 Nanoparticle Toxicity
When bulk materials are made into nanoparticles, the surface to volume ratio of the
material increases. When this process reaches the nanoscale, the proportion of surface
atoms or molecules in the material increases exponentially and the surface chemistry
also changes, with the material tending to become more chemically reactive. This
is the basis for the production of heterogeneous catalysts in the chemical industry.
Platinum, for example, in the bulk state is particularly chemically unreactive. In the
form of ultrafine particles, however, it can facilitate a number of chemical reactions
[11]. The term nanotoxicology, first used by Donaldson [11] indicates the fact that
such differences require an ad hoc form of toxicology. The essential nature of the
nanotoxicological problem was captured by Myllynen [12] “There are basically two
questions to address: (1) what is the fate of nanoparticles? (i.e. where do they get to)
and (2) if they get to a particular location, does it matter?”.
17.4.1 Mechanisms of Toxicity
A number of mechanisms by which nanoparticles can induce cell damage have been
reported, including, for example:
• oxidative damage through catalysis
• lipid peroxidation
• surfactant properties
• protein misfolding
• direct physical damage
• enzyme poisoning [12].
17.5 Interference of Nanoparticles with in Vitro Toxicity

Assays
In vitro experimentation has always been the first choice for toxicologists, since it
is time- and cost-effective. Although it cannot replace animal experimentation com-
pletely, but it does help to ensure that they are only used when absolutely necessary,
and it sometimes provides mechanistic information on the toxicity of nanoparticles
after in vivo studies. The risk assessment of different aspects of nanotechnology
is still in its early stages. Therefore, most of the studies pertaining to nanoparticle
toxicology that have been carried out so far have been preliminary and confined
to the classical in vitro toxicity test methods established for drugs and chemicals
[13]. However, the methods that are used in traditional toxicology cannot be applied
present nanoparticle toxicology, as nanoparticles display several unique physico-
chemical properties. Due to these properties, nanoparticles interfere with normal test
systems, and this interference has been well documented. Examples of such prop-
erties include: high surface area, leading to increased adsorption capacity; different
optical properties that interfere with fluorescence or visible light absorption detection
systems; increased catalytic activity due to enhanced surface energy; and magnetic
properties that make them redox active and thus interfere with methods based on
redox reactions [14] (Fig. 17.2).
17.6 Nanotoxicology
The distinctive and various physicochemical properties of nanoscale materials rec-

ommend that their toxicological properties may differ from those of the correspond-
ing bulk materials. The potential occupational and public exposure through inhala-
tion, oral ingestion, dermal absorption or by injection of manufactured nanoparticles
(mNPs) with particles size ≤ 100 nm probably will increase in the near future, due
17.6 Nanotoxicology 201
Fig. 17.2 a–d Analyzing

nanoparticle (NP) uptake in
cells by flow cytometry:
a light scattering by a cell
that is not associated with
any nanoparticle;
b nanoparticles adhere to the
cell surface, leading to an
increase in forward scatter
(FSC) and side scatter
(SSC); c nanoparticle
internalization by the cell,
leading to an increase in SSC
alone; d fluorescent
nanoparticle internalization
by the cell, leading to an
increase in SSC and
fluorescence intensity (FL)
to the ability of nanomaterials to improve the quality and performance of many con-
sumer products as well as the development of therapeutic strategies and tests. How-
ever, there is still a lack of information about the impact of mNPs on environment
and on human health, as well as of reliable data on risk assessment [15].
References
1. Dhawan A, Sharma V (2010) Toxicity assessment of nanomaterials: methods and challenges.

Anal Bioanal Chem 398:589–605
2. Kroll A, Pillukat MH, Hahn D et al (2009) Current in vitro methods in nanoparticle risk
assessment: limitations and challenges. Eur J Pharm Biopharm 72:370–377
3. Wang H, Wu F, Meng W et al (2013) Engineered nanoparticles may induce genotoxicity.
Environ Sci Technol 47:13212–13214
4. Winnik FM, Maysinger D (2013) Quantum dot cytotoxicity and ways to reduce it. Acc Chem
Res 46:672–680
5. Chen T, Yan J, Li Y (2014) Genotoxicity of titanium dioxide nanoparticles. J Food Drug Anal
22:95–104
6. Gnach A, Lipinski T, Bednarkiewicz A (2015) Upconverting nanoparticles: assessing the
toxicity. Chem Soc Rev 44:1561–1584
7. Robichaud CO, Uyar AE, Darby MR (2009) Estimates of upper bounds and trends in Nano-TiO2
production as a basis for exposure assessment. Environ Sci Technol 43:4227–4233
8. Becker L, Poreda RJ, Nuth JA (2006) Fullerenes in meteorites and the nature of planetary atmo-
spheres. Natural fullerenes and related structures of elemental carbon. Springer, Netherlands,
pp 95–121
9. Hochella MF, Lower SK, Maurice PA et al (2008) Nanominerals, mineral nanoparticles, and
earth systems. Science 319:1631–1635
10. Plata DL, Gschwend PM, Reddy CM (2008) Industrially synthesized single-walled car-
bon nanotubes: compositional data for users, environmental risk assessments, and source
apportionment. Nanotechnol 19:185706–185719
11. Donaldson K, Stone V, Tran CL (2004) Nanotoxicology. Occup Environ Med 61:727–728
12. Myllynen PK, Loughran MJ, Howard CV et al (2008) Kinetics of gold nanoparticles in the
human placenta. Reprod Toxicol 26:130–137
13. Kahru A, Savolainen K (2010) Potential hazard of nanoparticles: from properties to biological
and environmental effects. Toxicol 269:89–91
14. Doak SH, Griffiths SM, Manshian B et al (2009) Confounding experimental considerations in
nanogenotoxicology. Mutagenesis 24:285–293
15. Bergamaschi E, Bussolati O, Magrini A et al (2006) Nanomaterials and lung toxicity:
interactions with airways cells and relevance for occupational health risk assessment. Int J
Immunopathol Pharmacol 19:3–10
Chapter 18
Nanomaterials Research
and Development
Abstract The specific impact caused by nanoparticles can be assessed by life cycle
assessment analysis. Performing life cycle analysis and potential risk management of
nanoscale materials are increasing to perform better products and further technology
developments. This chapter describes methods for research developed and applied
life cycle assessment (LCA) models to evaluate ENMs and nano-enabled product.
18.1 LCA—Life Cycle Assessment of Nanomaterials
Life cycle assessment (LCA) is based on the conception of life cycle, it is a system-
atic method for assessing the potential environmental impacts of products, services
and processes across their entire life cycles. The LCA methodology, as defined in
ISO 14040, comprises four iterative steps: (i) goal and scope definition, (ii) inven-
tory analysis, (iii) impact assessment, and (iv) interpretation. LCA is accepted as a
powerful tool to identify potential life cycle impacts of nanotechnologies [1].
18.2 The Role of Life Cycle Assessment in the Field

of Nanotechnology
Nanotechnology and the production of nanomaterials and products containing nano-

materials are known as nanoproducts; however, numerous uncertainties exist regard-
ing their possible impact on the environment and human health. Therefore, holistic
and comprehensive assessment tools such as Life Cycle Assessment (LCA) are essen-
tial to analyze, evaluate, understand and manage the environmental and health effects
of nanotechnology. The knowledge of the exposure routes as well as of the potential
environmental impacts of nanoparticles is limited. In addition, potential resource and
environmental advantages of nanomaterials and products using nanomaterials over
conventional products have not been investigated. Therefore, a clear need exists to
establish a full understanding of the environmental benefits and drawbacks of nan-
otechnology and nanomaterials compared with those of conventional technologies

https://doi.org/10.1007/978-3-030-26145-0_18
204 18 Nanomaterials Research and Development
and products over their complete life cycles. LCA is the essential tool to achieve this
[2]. The goal and scope definition of an LCA provides a description of the product
system in terms of the system boundaries and a functional unit, i.e., the reference
unit defining the function of the product system.
The Life Cycle Inventory (LCI) aims at data collection and calculation procedures
in order to quantify from cradle-to-grave the relevant inputs (e.g., material inputs) and
outputs (e.g., emissions to air) of the product system. The purpose of the Life Cycle
Impact Assessment (LCIA) is to aggregate the results from the inventory analysis
and to evaluate the significance of the product’s potential environmental impacts.
This process involves connecting inventory data with specific environmental impact
categories and the respective category indicators, such as global warming potential as
an indicator for climate change. The interpretation considers the findings from both
LCI and LCIA and should provide conclusions and recommendations [3] (Fig. 18.1).
Note that LCA is dissimilar from other techniques, such as environmental perfor-
mance evaluation and risk assessment (RA), as it is a relative and essentially com-
parative approach based on a functional unit, with all inputs and outputs accounted
for in the LCI, and consequently in the LCIA profile, being associated with the
functional unit. LCA is adequate to answer many, but certainly not all, questions
on environmental and human-health impacts of nanotechnology in comparing dif-
ferent products with the same function. However, for assessing social and economic
benefits and/or problems, as would be required in a full sustainability assessment, a
broader assessment framework is required [4].
Fig. 18.1 Stages of life cycle assessment

18.3 LCA Procedure 205
18.3 LCA Procedure
It consists of four steps: scoping and definition of system boundaries, inventory of

material and energy requirements, environmental impact analysis, and improvement
analysis an iterative procedure that takes place continuously as the LCA is carried
out. LCAs are undertaken for four principal reasons:
(i) to develop information for comparative purposes when choices among designs,
processes, or materials must be made,
(ii) to quantitatively establish the nature of tradeoffs associated with various
choices,
(iii) to examine a single system in order to ascertain those components, parts,
or processes which are the most material or energy intensive and for which
investments of resources or research might be expected to yield the greatest
improvements, and
(iv) to facilitate the communication of risks and benefits to consumers and
stakeholders [5].
LCA impact analysis proceeds by assembling a material inventory of chemical
quantities released to the environment throughout the supply chain. The result is typ-
ically a list of impact categories, such as global warming or human toxicity potential,
that are relevant to the study. Characterization proceeds by converting each chemical
quantity into an equivalent amount of substance that is represent of the impact cate-
gory, such as kg of carbon dioxide (for global warming), or benzene equivalents (for
cancer). In the case of nanomaterials, the use of mass-based equivalencies may be
inappropriate, i.e. nanomaterials may be better characterized in terms of their prin-
cipal functional property, which necessitates an understanding of the form of these
materials in both the product and the environment, and their rate of release [6].
18.4 Life-Cycle Assessment of Engineered Nanomaterials
The progressive diffusion of ENMs in many fields, including nanoremediation, and

the global consensus that their release into the environment will increase, has led not
only to the urge of a sound evaluation of their toxicity effects on human health and
on the environment, but also to the need for the evaluation of their environmental
sustainability [7]. Life-cycle assessment (LCA) is a well-established tool, nowadays
largely used to evaluate the potential environmental impacts of a product system over
its whole life cycle, from the extraction and acquisition of raw materials, to the core
production process, use and end of life treatment, either recovery or final disposal.
The method consists in the compilation and evaluation of the inputs, outputs, and
the potential environmental impacts of a product system throughout its entire life
cycle, from cradle to grave. LCA is considered a holistic method since it provides
the assessment of the potential environmental impacts on several environmental
categories, mainly on global and regional scale, such as global warming potential,
ozone depletion potential, acidification potential, resource depletion etc. Moreover,
LCA permits to define the environmental hotspots of a product system, to analyze
alternative solutions that provide performance improvement and to make comparison
of different scenarios, therefore proving to be a powerful tool for supporting eco-
design and decision-making. LCA is deemed to be the suitable tool to assess the
environmental impacts of emerging technologies such as nanotechnologies and nano-
enabled products, also in comparison to conventional technologies. Although LCA
is strongly recommended as tool to assess the sustainability of ENMs throughout
their life cycle, the scientific community currently agrees on the several information
gaps, which hamper the proper application of LCA in the field. These gaps regard
mainly two broad issues, namely the difficulty of including the whole life cycle of
ENMs and to fully assess their impacts on human toxicity and ecotoxicity.
The first issue stems from the lack, in the life-cycle inventory, of specific features
and properties of the new nanomaterials that differentiate them from the correspond-
ing bulk material and of the quantification of their release into the environment
across their life-cycle [8]. The second issue regards the application of the impact
assessment methods, which currently do not allow consideration of the nano specific
impacts on human health and ecotoxicity. In fact, on one hand the fate of ENMs
in the environment is poorly modeled and quantitatively assessed and on the other
hand, current impact assessment tools (e.g., USEtoxTM) still lack to consider nano
specific properties and thus are not able to provide suitable characterization factors
to include them in the assessment of impacts on health and environment [9].
18.5 LCA of an Emerging Technology
LCA to emerging technologies due to the lack of detailed knowledge regarding the
inputs and output of the system. Nevertheless, there is a general trend to apply LCA
to emerging technologies (e.g., solar, wind, bio-fuels). In the case of CNTs, note
that the application of LCA is a challenging task because many of the technologies
studied are still emerging; introducing a great degree of uncertainty and complexity
into LCA. Obtaining accurate data for emerging technologies can be a challenge
because data based on conceptual designs, and assumption about the scaling up of
laboratory or pilot scale process may not accurately reflect industrial scale opera-
tions. Additionally, early prototypes may undergo several changes during product
development and testing that can alter how a product is manufactured and used. Fur-
thermore, one of the greatest challenges when assessing nanoproducts is the variable
nature of manufacturing processes and how subtle differences in the resulting nano
components can affect the associated nanoproduct [10] (Fig. 18.2).
Increasing research efforts have been made development in the methods to synthe-
size nanomaterials without using raw materials containing scarce natural resources
and hazardous substances, or the production methods that require low energy and
low material consumption. The concept of green nanotechnology applies not only to
18.5 LCA of an Emerging Technology 207
Fig. 18.2 Life cycle of a product system. Reprinted with permission © UNEP (2007)
the manufacturing stage but also to the usage stage, in particular, in environmental
applications. Caution is required so as not to consider the technology as green, only
based on the fact that applications are in the environmental and renewable-energy
sectors. The potential environmental burden of the applications during manufacturing
and disposal stages should be taken into account. Life Cycle Thinking (LCT) helps
in guiding the nanotechnology development towards true eco-friendliness, through
the assessment of the overall risk-benefit balance during the production, usage and
disposal stages of nano-products. Nanotechnology is by nature a multidisciplinary
research field, but the LCT of nanotechnology calls for strong collaborations from the
wider research community beyond physics, chemistry, medicine and biology [11].
18.6 Life Cycle Inventory (LCI)
The inventory analysis comprises the data collection and the calculation procedures
to quantify the inputs energy, raw and ancillary materials, water, etc., and outputs
emissions to soil, emissions to air, water emissions, and waste water and products/sub
products through the system boundaries. Each life stage is analyzed to determine the
relevant inputs and outputs of the system, performing a flow balance. To make the
Fig. 18.3 Life cycle inventory (LCI)
process easier, the system is usually divided in several interconnected subsystems.

Quality data requirements are necessary in order to guarantee their appropriateness
and representativeness in terms of geography, temporality and technology, informa-
tion source and accurateness. Primary data comes from modeling/monitoring pro-
cesses through real measurements. It is recommended to use primary data for core
processes. Secondary data can be used for auxiliary processes; main sources for sec-
ondary data are literature and databases (such as the ELCD, European reference Life
Cycle Database, or commercial databases like Ecoinvent or GABI) [12] (Fig. 18.3).
18.7 Life Cycle Impact Assessment (LCIA)
LCIA is the estimation of indicators of the environmental pressures associated with

the environmental interventions attributable to the life-cycle of a product. In this step,
the LCA the inventory flows are converted into the associated potential environmental
impacts. LCIA stage has four steps:
1. Classification (Mandatory): Assignation of the different material/energy inputs
and outputs inventoried to the relevant impact categories.
2. Characterization (Mandatory): Calculation of the magnitude of the contribu-
tion of each classified input/output to their respective impact categories and
aggregation of the contributions within each category.
3. Normalization (Optional): impact assessment results are multiplied by normal-
ization factors (e.g., European reference values) in order to calculate and compare
the magnitude of their contributions to the impact categories in a dimensional
way.
4. Weighting (Optional): in order to support the interpretation of results, normalized
results are multiplied by a set of weighting factors which reflect the perceived
relative importance of the impact categories considered [13] (Fig. 18.4).
18.7 Life Cycle Impact Assessment (LCIA) 209
Fig. 18.4 Life cycle impact assessment mechanisms and steps [16]
18.8 LCA of Nanomaterials
Life cycle assessment of nano-based technologies are important to detect all poten-
tial environmental burdens, whether positive or negative, of nano-products and to
prevent and treat all potential environmental risks of further technological devel-
opments. So far, a certain number of LCA studies dealing with the use of NM in
sector of renewable energy have been conducted. The most studied nanomaterials in
the aspect of LCA methodology application are carbon nanotubes, i.e. single-walled
carbon nanotubes (SWNT), which are applied in Li-ion batteries, nano photovoltaic,
such as quantum dots and dye-sensitized solar cells, nano-TiO2 which are used in
solar PV cells and for hydrogen generation. Of all environmental impacts occur-
ring from nanomaterials life-cycle toxicity is the one that poses most concern [14].
LCA approach for nanotechnology and nano-products can provide useful informa-
tion about the main environmental impacts and benefits of this emerging technology.
Prospective LCA approaches are needed and experimental data on characteristics
and toxicity of nanoparticles coming from research projects should be included in
LCA methodologies. Adapted exposure and fate modeling are needed in order to
have complete results on the environmental performance of nano-products during all
life cycle stages. LCA information should be used together with other methodologies
such as Risk Assessment (RA) to obtain a deep comprehension on the interactions
of nanomaterials and the environment and the potential damage on environment and
human health in all life cycle stages and exposure levels [15].
References
1. Salieri B, Turner DA, Nowack B et al (2018) Life cycle assessment of manufactured

nanomaterials: where are we? NanoImpact 10:108–120
2. Grieger KD, Laurent A, Miseljic M et al (2012) Analysis of current research addressing com-
plementary use of life-cycle assessment and risk assessment for engineered nanomaterials have
lessons been learned from previous experience with chemicals? J Nanoparticle Res 14:958–980
3. Tsang MP, Sonnemann GW, Bassani DM (2016) A comparative human health, ecotoxicity, and
product environmental assessment on the production of organic and silicon solar cells. Prog
Photovolt: Res Appl 24:645–655
4. Villares M, Isildar A, Mendoza Beltran A et al (2016) Applying an ex-ante life cycle perspective
to metal recovery from e-waste using bioleaching. J Clean Prod 129:315–328
5. Theis TL, Bakshi BR, Durham D et al (2011) A life cycle framework for the investigation of
environmentally benign nanoparticles and products. Phys Status Solidi RRL 5:312–317
6. Auffan M, Rose J, Bottero J et al (2009) Towards a definition of inorganic nanoparticles from
an environmental, health and safety perspective. Nat Nanotechnol 4:634–641
7. Corsi I, Fiorati A, Grassi G et al (2018) Environmentally sustainable and ecosafe
polysaccharide-based materials for water nano-treatment: an eco-design study. Materials
11:1228–1250
8. Gavankar S, Suh S, Keller AF (2012) Life cycle assessment at nanoscale: review and
recommendations. Int J Life Cycle Assess 17:295–303
9. Bauer C, Buchgeister J, Hischier R (2008) Towards a framework for life cycle thinking in the
assessment of nanotechnology. J Clean Prod 16:910–926
10. Lazarevic D, Finnveden G (2013) Life cycle aspects of nanomaterials. US AB, Stockholm
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nol 2:1
12. Seager TP, Linkov I (2009) Uncertainty in life cycle assessment of nanomaterials. Nanomate-
rials: risks and benefits. Springer, Netherlands, pp 423–436
13. Hischier R, Walser T (2012) Life cycle assessment of engineered nanomaterials: state of the
art and strategies to overcome existing gaps. Sci Total Environ 425:271–282
14. Peric M, Hut I, Pelemis S et al (2015) Possible approaches to LCA methodology for
nanomaterials in sustainable energy production. Contemp Mater Renew Energy Sources
2:161–169
15. Hidalgo C, Gonzalez-Galvez D, Janer G et al (2013) Life cycle assessment (LCA) of nanoma-
terials: a comprehensive approach. In: 6th international conference on life cycle management,
Gothenburg
16. Hauschild MZ, Huijbregts MAJ (2015) Introducing life cycle impact assessment. In: Hauschild
M, Huijbregts M (eds) Life cycle impact assessment. LCA compendium—the complete world
of life cycle assessment. Springer, Dordrecht

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Engineering Materials

More information about this series at http://www.springer.com/series/4288

Sabu Thomas Hanna J. Maria

Sabu Thomas Hanna J. Maria

ISSN 1612-1317 ISSN 1868-1212 (electronic)

1 Nanotechnology and Dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.4 Applications of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . 25

6.2 Organic Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . ..... 72

8.4.2 Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

11.2 Nanolithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

14.5 Photonic Crystal Filters . . . . . . . . . .................... 174

18 Nanomaterials Research and Development . . . . . . . . . . . . ....... 203

Abstract The role of nanotechnology towards different field of application

1.1 Fundamentals of Nanomaterials

© Springer Nature Switzerland AG 2020 1

of the low-dimensional structures. The energy spectrum of a quantum well, quantum

1.2 Dimensions of Nanomaterials

Nanolaminated or compositionally modified materials, Grain boundary films, Clay

effect transistors, Surface-engineered materials for increased wear resistance or cor-

1.2.3 Zero Dimensional Confinement

In a zero-dimensional structure, the exciton states are determined by a competition

energy single-particle states. Freeze-out of motion in the confined dimensions also

1.3 Features of Nanoparticles

1.3.1 Activation of Particle Surface

1.3.2 Particle Size

Particle size is tenure to represent the three-dimensional particle in one-dimensional

1.3.3 Particle Shape

The essential properties such as particle diameter, particle shape of nano-size or

1.3.4 Two-Dimensional Particle Projection Image

1.3.5 Three-Dimensional Particle Image

it is difficult to measure the thickness of a particle by the ordinary electron micro-

1.4 Significances of Nanotechnology

1.5 Basic Concept of Nanotechnology

thermal conductivity, increased oscillator strength, blue shifted absorption, increased

2.1 Brief Notes on Nanomaterials

Nanomaterials are keystones of nanoscience and nanotechnology. Nanostructure sci-

© Springer Nature Switzerland AG 2020 11

Fig. 2.1 Naturally occurring and man-made nanoparticles

Fig. 2.2 Incidental and engineered nanoparticle

2.2 Nanomaterial Properties

2.2.1 Structural Properties

2.2.2 Thermal Properties

Fig. 2.4 Schematic diagram

2.2.3 Chemical Properties

The change in structure as a function of particle size is intrinsically linked to the

Fig. 2.5 Schematic diagram

2.2.4 Mechanical Properties

2.2.5 Magnetic Properties

Fig. 2.6 Schematic diagram

only one domain and exhibit a phenomenon known as superparamagnetic. In this

2.2.6 Optical Properties

The nanoclusters has effect of reduced dimensionality on electronic structure has

Fig. 2.7 Size dependence of

properties which may be affected by reduced dimensionality are photocatalysis,

2.2.7 Electronic Properties

2.2.8 Physiochemical Properties of Nanomaterials

2.2.8.1 Melting Point

Fig. 2.9 Relationship

2.2.8.2 Surface Tension