Chapter 17

RADIATION METHODS AND USES

IN NANOTECHNOLOGY
Dagmara Chmielewska
Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warszawa,
Poland

1. INTRODUCTION

Nanotechnology is a fast growing area in science and engineering. This multi-

disciplinary area has emerged from the convergence of electronics, physics,
chemistry, biology, medicine and materials science to generate new functional
materials of nanoscale dimensions. Figure 1 illustrates this convergence.

Fig.1. The convergence of the disciplines and multisector applications [1].

Nanotechnology is focused on the design, development, characterization

and uses of materials which have at least one dimension that is less than 100
nm. One unique aspect of nanotechnology is that it offers a large increase in
396 Applications of ionizing radiation in materials processing

surface area for many nanomaterials, which generates new possibilities in sur-
face-based technologies, such as catalysis and antibacterial applications. The
physicochemical properties and functions of nanomaterials may differ signifi-
cantly from those of the same material in bulk.
The use of radiation techniques in nanotechnology has been known for
many years. X-ray, electron beam and ion beam lithography are good examples
of such uses. By using electron beams, ion beams or X-rays, structures as small
as 10 nm have been made. Ion track membranes with track diameters ranging
from 10 to 100 nm are used directly or as templates for the electrodeposition
of nanowires of metal, of semiconductors and of magnetic materials. Progress
in X-ray, focused ion beam (FIB) and electron beam nanolithography, and in
three-dimensional (3D) fabrication has been noted in recent years. Heavy ion
beams can be used for the fabrication of nanopores which serve as templates
for making nanowires. The use of radiation processing has proved to be an
essential technique for the fabrication of nanostructures with high resolution
since radiation beams can be focused down to a few nanometers or less. Four
groups of nanoscale products are fabricated by radiation techniques: nanopar-
ticles, nanogels, nanotubes and nanocomposites [1].

2. FUNDAMENTALS

The prefix “nano-” is derived from the Greek word “νᾶνος“ meaning “dwarf”.
One nanometer (nm) is a unit of length in the metric system equal to one bil-
lionth of a meter or about the width of 6 carbon atoms or 10 water molecules.
A human hair is approximately 80 000 nm wide and a red blood cell is ap-
proximately 7000 nm wide. Atoms are smaller than 1 nm, whereas many mol-
ecules including those of some proteins range between 1 nm and larger [2].
The concept of the nanotechnology was introduced in a presentation en-
titled “There’s plenty of room at the bottom” at the Annual Meeting of the
American Physical Society on 29 December 1959 by Nobel laureate Richard
P. Feynman. Feynman described a process for manipulating and controlling
matter on a miniature scale, creating nanomaterials atom by atom or molecule
by molecule. The term “nanotechnology” was first used in 1974 by Norio
Taniguchi, a professor at the Tokyo Science University, and was defined as
follows: “Nano-technology mainly consists of the processing of separation,
consolidation, and deformation of materials by one atom or one molecule.” [3].
Two complementary approaches to nanomaterial fabrication are used
(Fig.2):
• The “top-down” approach – where fabrication starts from the bulk material
and reduces it down to the nanoscale.
Chapter 17 397

• The “bottom-up” approach – where fabrication starts from the atomic or

molecular level and by building atoms or molecules together complex nano-
structures are created.
The term “nanomaterials” describes, in principle, materials that have at
least one dimension in the range between 1 and 100 nm.

Fig.2. Scheme of the two approaches used in the fabrication of nanomaterials:

“top-down” and “bottom-up” [4].

A great variety of nanostructures have been classified in different ways in

the literature. Figure 3 shows the most relevant types of nanostructures in
nanotechnology, classified according to four nonexclusive criteria [4].
Nanoparticles can be classified as natural, anthropogenic (incidental), or
engineered in origin [5]. Taking into account the chemical composition, the
dimensions of nanostructures and their distribution within a matrix, they can
be homo- or heterogeneous. The chemical composition of nanostructures can
be classified as inorganic (noble metal nanoparticles, quantum dots, etc.), or-
ganic (fullerenes, carbon nanotubes, dendrimers, etc.) or hybrid (gold nanopar-
ticles modified with calixarenes, carbon nanotubes functionalized with ferro-
398 Applications of ionizing radiation in materials processing

cene, etc.) [5]. The last classification of nanomaterials is based on the dimensions
of the nanostructures and on two different approaches for terms used in nano-
metrology.

Fig.3. Classification of nanostructures according to the different criteria [4].

The Royal Society of Chemistry and the Royal Academy of Engineering

classified nanostructures according to the number of dimensions in the nano-
scale [6]. According to this classification three types of nanostructures can be
distinguished:
• nanoscale in one dimension, such as surfaces, thin films and layers;
• nanoscale in two dimensions, such as tubes and wires;
• nanoscale in three dimensions, which includes nanoparticles and quantum
dots, fullerenes, and dendrimers.
Classification of nanoscale at a zero dimension can also be added, such as
materials composed by dispersed nanoparticles [4].
Other classification of nanostructured materials is based on the number of
dimensions that are above the nanoscale [7]:
• 0-D nanostructures, such as nanoparticles, quantum dots and nanodots.
• 1-D nanostructures, such as nanowires and nanorods.
• 2-D nanostructures, such as coatings and surface layers. This category in-
cludes coatings made of nanocrystalline metals or nanocomposites.
• 3-D nanostructures, which include bulk materials.
Chapter 17 399

The focus below is only on engineered nanostructures, which can be ob-

tained with the use of radiation processing.

3. IONIZING RADIATION IN NANOTECHNOLOGY

Radiation-based methods play an important role in the development and

modification of nanostructures.
Ion beams are used to fabricate track-etched membranes for ultrafiltration,
membranes with electrical and magnetic properties and with potential uses as
chemical detectors and biosensors [8]. The junctions between carbon nanotubes
can be made by electron beam irradiation at elevated temperatures. Electronic
devices require molecular connections between individual nanotubes. Microgels
and nanogels produced by radiation techniques are well suited for biomedical
applications since they are free of monomers, initiators and any other additives.
Thus, they can be used as carriers for enzymes or antibodies used in diagnostics,
as drug carriers for therapeutic purposes (controlled drug delivery) and pos-
sibly for artificial biological fluids and synthetic vectors for drug delivery.
Ionizing radiation is widely used in industry for the crosslinking of polymers
and polymer blends. This technology can be extended to the crosslinking of
nanopolymers and nanocomposites. Potential applications involve the irradia-
tion of various types of polymers (natural rubber, polyolefins, polyimides,
polystyrene, etc.) containing nanosized clays, silica or metal nanoparticles.
Radiation is an important tool in nanotechnology which has already been
used (electron beam and X-ray lithography, track-etched membranes) and as
results of recent studies indicate will to grow [1].

3.1. RADIATION IN THE PRODUCTION OF NANOMATERIALS

3.1.1. Nanogels
There are at least two definitions of polymeric nanogels and microgels.
The first is derived from the definition of polymer gels. A polymer gel is a
two-phase system consisting of a stable three-dimensional network of linked
polymer chains and of molecules of a solvent filling the pores of this network.
The second definition states that a nanogel or a microgel is an internally cross-
linked macromolecule. This approach is based on the fact that, in principle, all
the chain segments of a nanogel or microgel are linked together and are thus
part of one macromolecule. This also reflects the fact that such gels can be
made either by intramolecular crosslinking of single linear macromolecules
or in a single polymerization event (e.g. initiated by one radical) that in the
400 Applications of ionizing radiation in materials processing

Fig.4. Formation of a nanogel from a single macromolecule by intramolecular recom-

bination of polymer radicals.

absence of crosslinking would lead to the formation of a single linear polymer

chain (Fig.4).

3.1.2. Metal nanoparticles

Noble metal nanoparticles have attracted interest because of their potential
use in areas such as catalysis, nanoelectronics, sensors, health care and medicine
[9-12].
During the electron beam or gamma-ray irradiation of liquids, most of the
energy is absorbed by the water, so water radiolysis takes place, which results
in the formation of reactive species such as the oxidizing hydroxyl radical (OH)
and very powerful reducing radicals as the hydrated electron (e–aq) and hydro-
gen atom (H) [13]. Metal ions in solution are first reduced by these reducing
agents to lower valence ions and then into metal atoms. Different parameters,
as the initial concentration of metal cations in the solution, the irradiation dose,
the dose rate, and the pH, can significantly influence the size of silver nanopar-
ticles [14]. Making metal nanoparticles in an aqueous solution is difficult,
because of a tendency for the particles to aggregate. The growth of metal nano-
particles must be controlled by the use of stabilizing (capping) agents, for
example polymers with a high affinity for metal atoms, or the use of a solid
support for nanoparticle binding. Different metal nanoparticles, Co, Zn, Pd
[15], Cu, Hg [16], Ni [17], Ag [18], Au [19], Pt [20] and others [13], can be
made with the use of ionizing radiation. Bi- and multimetallic nanoparticles
can be also obtained in this way [13].
Metal clusters are generated by radiation-induced reduction either of ion
precursors in solution or of ions impregnated in a solid support. The first step
is the radiolysis of water which yields reactive free radicals, such as hydrated
electrons, hydroxyl radicals and hydrogen atoms, and the molecular products
H2O2 and H2, according to the stoichiometry [21] included in reaction (1):
H2O 0.28 e–aq, 0.062 H, 0.28 OH, 0.047 H2, 0.073 H2O2, 0.28 H3O+ (1)
The solvated electron (e–aq) and hydrogen atom are strong reducing agents
(with standard reduction potentials E0(H2O/e–aq) = –2.87 VNHE and E0(H+/H)
= –2.31VNHE, respectively [21]), so can easily reduce metal ions down to the
zero-valence state:
Chapter 17 401

M+ + e–aq → M0 (2)
M + H → M 0 + H +
+
(3)
where M+ is the symbol for monovalent metal ions and M0 is the symbol for
zero-valent metal.
In the water radiolysis process, OH radicals that are able to oxidize ions
or atoms to a higher oxidation state are also generated. To prevent this reaction,
a scavenger for OH radicals, such as a secondary alcohol or formate anion, is
added to the solution. As the scavenger of OH radicals is added, substances
whose oxidation by OH generate radicals that exhibit a strong reducing
power, such as the radicals of secondary alcohols or of the formate anions [13]:
(CH3)2CHOH + OH → (CH3)2COH + H2O (4)
HCOO– + OH → COO– + H2O (5)
The (CH3)2COH and COO– radicals are strong reducing agents too, with
standard reduction potentials E0[(CH3)2CO/(CH3)2COH] = –1.8 VNHE and
E0[CO2/COO–] = –1.9 VNHE, respectively [13].

Fig.5. Scheme of metal ion reduction in solution with application of ionizing radia-
tion [13].
402 Applications of ionizing radiation in materials processing

In the next step, the generated radicals are able to reduce metal ions:
M+ + (CH3)2COH → M0 + (CH3)2CO + H+ (6)
–
M + COO → M + CO2
+ 0
(7)
Metal atoms are formed with a homogeneous distribution throughout the
solution. The binding energy between two transition metal atoms is stronger
than the atom–solvent or atom–ligand bond energy. As a result, these atoms
tend to dimerize when they encounter or associate with an excess of ions [13]:
M0 + M0 → M2 (8)
M0 + M+ → M2+ (9)
By a continuation of this process, these species progressively coalesce into
clusters following homogeneous kinetics [13]:
Mm+xx+ + Mn+yy+ → Mp+zz+ (10)
where m, n and p represent the nuclearites (i.e. the number of reduced atoms),
and x, y and z are the numbers of associated ions, as illustrated in Fig.5. The
redox potential of the clusters increases progressively with the nuclearity.
When a high dose rate is used, all of the reducing radicals are produced in
a short time, which results in the coalescence of the atoms that were separately
formed (Fig.6A). At a low dose rate, atoms dimerization and the coalescence
A

Fig.6. Nucleation and growth of metal clusters generated by radiolytic radicals at high
dose rate (A), low dose rate (B) and with an electrons donor D (C).
Chapter 17 403

process are faster than the production rate of the reducing radicals (Fig.6B).
When a chemical that can play a role of an electron donor is added, the reduc-
tion potential is not negative enough to directly reduce isolated metal ions to
atoms. In this case, the reduction of ions adsorbed on the nuclei generated by
radiolysis act as seeds. This results in larger clusters being formed (Fig.6C) [22].
Metal atoms created by irradiation tend to coalesce into oligomers and then
continually grow into larger clusters and eventually into precipitates. To prevent
this growth, polymers acting as cluster stabilizers (capping agent) are added.
Functional groups with a high affinity for the metals (e.g. –NH2, –COOH and
–OH) ensure the embedding of the molecule at the cluster surface and the
polymeric chain protects the cluster from coalescing with a next one through
electrostatic repulsion or steric hindrance [22]. Stabilizers should not chemi-
cally reduce metals ions bound on the surfaces of clusters. Different polymers,
such as poly(vinyl alcohol) (PVA), sodium dodecylsulfate (SDS) [23], sodium
polyvinyl sulfate (PVS) [24], polyacrylamide (PAM) or poly(N-methylacryl-
amide) (PNMAM) [20] and poly(ethylene glycol)s [25] have been used as
metal cluster stabilizers. Some ligands (e.g. CN–, EDTA – ethylenediaminetetra-
acetic acid) are also able to stabilize small-sized metal particles, because they
are strongly connected with the cluster and prevent their coalescence by elec-
trostatic repulsion. Another possibility for the limitation of the growth of metal
nanoparticles is to make them in the presence of a solid support such as silica
[14], titanium [26] and alumina. Ionizing radiation is able to penetrate the sup-
port and reduce the atoms of the metals to cations embedded on the surface or
in the pores or in situ everywhere that the ions have diffused.
Bi- and multimetallic nanoparticles, composed of two or more different
metal elements, are of greater importance than monometallic ones due to their
improved catalytic properties in contrast to single-metal catalysts and to the
development of new properties, which may not exist for the monometallic
catalysts [27].
The preparation of bimetallic nanoparticles from metal salts can be di-
vided into two groups: co-reduction and successive reduction of two metal
salts. These processes yield an alloyed or a core-shell structure. Two ionic
precursors of two different metal ions M+ and M’+ can be reduced by radio-
lytic radicals with equal probabilities:
e–aq + M+ → M0 (11)
e–aq + M’+ → M’0 (12)
However a further electron transfer from less noble metal atoms (for example
M’) to more noble metal ions M+ systematically favors the reduction into M [13].
M’ + M+ → (MM’)+ → M + M’+ (13)
(MmMn’) + M → (Mm+1Mn’)
x+ + (x+1)+
→ (Mm+1Mn-1’) + M’
x+ +
(14)
If the ionic precursors are plurivalent, an electron transfer is also possible
between the low valences of both metals. This increases the probability of
segregation [13]. The less noble metal ions act as an electron relay towards the
404 Applications of ionizing radiation in materials processing

noble metal ions. As a result, monometallic clusters, Mn, are formed first and
then, when the M+ ions are spent, M’+ ions are reduced at the surface of the Mn.
The result is a core-shell bimetallic cluster where the more noble metal, M, is
covered by the other metal M’.
Sometimes the inter-metal electron transfer does not occur. Then the initial
reduction reactions are followed by mixed coalescence:
M’ + M → (MM’) (15)
(MM’) + M → (M2M’) (16)
and association of atoms and clusters with ions as in reactions (13) and (14)
[5]:
(MmMn’)x+ + M+ → (Mm+1Mn’)(x+1)+ (17)
(Mm+1Mn’)(x+1)+ + e–aq (or R) → (Mm+1Mn’)x+ (or + R+) (18)
Dose rate is a crucial parameter when deciding on the formation of an al-
loyed cluster or of a core-shell structure since these depend on the kinetic
competition between the inter-metal electron transfer and the coalescence
process during the radiolytic reduction of mixed metal ion solutions.

3.1.3. Carbon nanotubes

A new method using radiation techniques to grow carbon nanotubes was
reported in 1996 by Yamamoto et al. [28]. In this work, carbon nanotubes were
grown using an argon ion beam for the irradiation of an amorphous carbon
target under high vacuum condition (4 × 10–5 Torr) [28]. The incident angle of
the ion beam was normal to the target surface and the ion acceleration energy
was 3 keV. Nanotubes were produced outside the sputtering region on the tar-
get surface after ion irradiation. The tubes had multilayered walls with the
distance between carbon layers of 0.34 nm and tube wall thicknesses ranging
from 10 to 15 sheets [28].
Single-walled nanotubes (SWNTs) have a diameter that is close to 1 nm,
with a tube length that may be many thousands of times longer. The structure
of a SWNT can be conceptualized by taking out the one-atom-thick layer from
a graphite stack and wrapping it into a seamless cylinder. Single-walled carbon
nanotubes have been found to possess the most remarkable electronic and
mechanical properties and are used in various nanoscale devices.
Terrones et al. demonstrated that single-walled carbon nanotubes can be
joined by electron beam irradiation to form molecular junctions [29]. Stable
junctions of various geometries have been made in situ in a high voltage trans-
mission electron microscope (TEM) with the specimen temperatures at 800°C.
After a few minutes of irradiation of two crossing tubes, they consolidate at
the point of contact, which results in the formation of a junction with an X
shape. The ready-formed X junctions can be manipulated in order to create
Y- and T-like molecular connections. The continuous sputtering of carbon atoms
from the nanotube body occurs during irradiation, leading to dimensional
changes and surface reconstructions [30]. The removal of one of the “arms”
Chapter 17 405

of an X junction generates a Y or T junction by using carefully chosen irra-

diation conditions. Exposing carbon nanotubes at high temperatures to an
electron beam induces structural defects, which promote the joining of tubes
via the crosslinking of pendant bonds. Junctions can be made via vacancies
and interstitials, induced by a focused electron beam, to promote the formation
of inter-nanotube links. It may now be possible to construct nanotube networks
by growing crosslinked SWNTs followed by controlled electron beam irra-
diation at high temperatures.

3.1.4. Nanocomposites
Nanocomposite material consists of multiple nanoscale materials or a
nanoscale material incorporated into a bulk material. The fabrication of nano-
composites has some challenges to make sure there is compatibility of the
different material components in order to obtain desirable properties for the
nanocomposite. Virtually all types and classes of nanocomposite materials lead
to new and improved properties when compared to their macrocomposite
counterparts. Nanocomposites can offer new uses in many fields, such as
mechanically reinforced lightweight components, non-linear optics, battery
cathodes and ionics, nanowires, sensors and other systems [1].
On the basis of their matrices, nanocomposites can be classified into three
major categories:
• polymer matrix nanocomposites,
• metal matrix nanocomposites,
• ceramic matrix nanocomposites.
Polymer nanocomposites consist of a polymer or copolymer having nano-
particles or nanofillers dispersed in the polymer matrix. Since many monomers
can polymerize upon exposure to gamma rays, monomer polymerization has
been used to make nanocrystalline materials [31, 32]. A novel strategy is to
synthesize semiconductor/polymer nano-assemblies in a single step at room
temperature by gamma irradiation. In general, a metal ion source, chalcogen
salt and an organic monomer are mixed homogeneously as a deaerated aqueous
solution with an appropriate amount of alcohol, as hydroxyl radical scavenger.
The resulting mixture is then subjected to gamma irradiation (irradiation dose
– 104 Gy) leads to the simultaneous formation of nanocrystalline metal chal-
cogenide particles and the polymerization of the monomers. The metal ion
attached onto the surface or inside the polymer microspheres and the chalcogen
ion, which is released by decomposition of the salt upon gamma irradiation, a
homogeneous dispersion of nanocrystalline metal chalcogenide particles in
microsphere polymer matrixes can be precipitated. Nanocomposites are thus
formed at room temperature and under ambient pressure without the use of
chemical initiators. By appropriate control of the reaction conditions, the
gamma irradiation method may be extended to the preparation of a variety of
spherical assemblies of metals and of semiconductors/polymer nanocomposites
406 Applications of ionizing radiation in materials processing

in aqueous systems. Analogously, several kinds of semiconductor/polymer

nanowires have been made in a heterogeneous solution system. In this system,
an organic monomer with polar groups can self-organize into amphiphilic
supramolecules (micelles, microemulsions, vesicles and monolayers on sur-
faces), using the difference in the solubility of different fragments in the
monomer. Under gamma irradiation, such supramolecules can polymerize to
a pre-organized polymer tubule with a hydrophilic core and a hydrophobic
sheath. The polymer tubule acts as both a template and a nanoreactor for the
following growth of inorganic semiconductor nanowires in the hydrophilic
cores from various water soluble systems [33].
Another example of the use of ionizing radiation in making polymer matrix
composites is that of producing silver nanostructures in a cotton matrix using
electron beam irradiation [12]. Ag-cotton nanocomposites exhibit antibacterial
activity against gram-negative and gram-positive bacteria. Cotton samples were
placed in silver nitrate solutions of different concentrations and then exposed
to the electron beam irradiation using a 10 MeV, 8 kW linear accelerator. Water
radiolysis generated very powerful reducing radicals that were able to overcome
of the thermodynamic barrier of reducing the single metal ion while in solution.
In this way, silver nanoparticles were embedded in the cotton fibers, as shown
in Fig.7.

Fig.7. Silver nanoparticles embedded in a cotton matrix.

Among the large number of inorganic layered materials that exhibit inter-
calation capabilities, layered silicates are one of the most typical because of the
versatility of their reactions. In particular, the smectite group of clay minerals,
such as montmorillonite, saponite and hectorite, has been used since they have
excellent intercalation ability. The combination of clay silicate layers and
polymer matrices at the nanoscale level constitutes the basis for preparing an
important class of inorganic-organic nanostructured materials.
Chapter 17 407

Fig.8. The overall process of preparing nanocomposites based on clay and polymer/
monomers.

Clay such as montmorillonite consists of a dioctahedral aluminum sheet

sandwiched between two silica tetrahedral sheets in a layered structure that is
~1 nm thick (Fig.8). Stacking layers lead to a regular Van der Waal’s space
between the layers called the interlayer. Clay has the ability to undergo ex-
tensive interlayer expansion or swelling, exposing a large active surface area,
permitting guest molecules to enter into the interlayer. Interlayer cations such
as Na+, Ca2+, and K+ exist on the internal surfaces but can be exchanged with
alkyl ammonium cations to give surfaces that are less ionic or polar. Such in-
terlayers can be organically modified since they are more easily penetrated by
polymers (either in the molten state or in solution) or by monomers which can
be subsequently crosslinked or polymerized chemically or by using radiation
[34]. In the process of making polymer-clay nanocomposites, it is important to
ensure the compatibility of the entering polymer/monomer (hydrophobic) with
the clay surface interlayer (ionic) by using intermediates, such as exchangeable
organic based cations, intercalation agents or compatibilizers.

Fig.9. Scheme of the fabrication of TiC-reinforced surface composites [35].

408 Applications of ionizing radiation in materials processing

Metal matrix composites reinforced with titanium carbide (TiC) particulates

can be fabricated by high energy electron beam irradiation (Fig.9) [34].
A mixture of magnesium oxide (MgO) and calcium oxide (CaO) powders
were used as a flux in order to obtain uniform TiC dispersion on a composite
surface. Upon electron beam irradiation of a metal surface on which ceramic
powders were evenly deposited, the metal surface melts, while the ceramic
powders are either partially or completely melted and then precipitated again
during solidification, thereby forming a surface composite [35]. Ferrous com-
posites reinforced with TiC show high strength, high elastic modulus, and im-
proved resistance to wear and oxidation.

3.2. LITHOGRAPHY

Lithography is the transfer of a pattern from a master slide/plate/mask to

another surface. Nanolithography is suitable for use in the nanofabrication of
electrical devices, data storage drives, sensors, drug delivery systems, etc. The
two fundamental characteristics of an imaging system are its resolution (RES)
and its depth of focus (DOF). The equations which define these are known as
the Rayleigh criterion and are usually expressed as:
RES = K1 /NA (19)
DOF = K2 /(NA) 2
(20)
whereis the wavelength of the radiation used to carry out the imaging, and
NA is the numerical aperture of the imaging system (or camera). These equa-
tions show that better resolution can be achieved by reducing  and/or by in-
creasing NA.
Ultraviolet radiation has been used to create patterns in lithography. The
move of semiconductor technology towards the miniaturization of integrated
circuits pointed out the limits of photolithography as technique for the fabrica-
tion of structures with dimensions on the submicron to nanometer scale. Due
to diffraction effects, the resolution of the photolithography process is limited

Fig.10. Optical and radiation sources for nanotechnology [36].

Chapter 17 409

to a few microns. To obtain smaller and more precise chips, it was necessary
to go to radiation-based technology using X-rays, electron beams and ion
beams in order to approach submicron patterning (Fig.10) [36].

Fig.11. Aspect ratio and resolution limit of various lithographic methods [36].

Figure 11 [36] shows the aspect ratios and resolution limits (line width) of
optical and radiation processes. Radiation methods are essential to nanotech-
nology because of their high resolution and high aspect ratios. Especially,
nanofabrication requires electron beam and X-ray processes to attain resolu-
tions lower than 10 nm. X-rays, electron beams, and low energy ion beams,
such as electron beam scanning devices and focused ion beam, are useful in
nanolithography, and in 3D nanofabrication. Heavy ion beam processes can be
used for the fabrication of nanopores and nanowires since they too give high
aspect ratio patterns.

3.2.1. Electron beam lithography

The concept of electron beam lithography (EBL) is to write patterns on
thin films of electron sensitive material using a finely focused (submicrometer
diameter) electron beam. The technology is capable of making very complex
patterns with very high resolution, almost to the atomic level. EBL is a flexible
technique that can work with a variety of materials and an almost infinite num-
ber of patterns, but it has some disadvantages, since it is one or more orders of
magnitude slower than optical lithography.
Electron beam lithography was originally developed using an electron beam
from a scanning or transmission electron microscope (SEM or TEM, respec-
tively) to expose an electron-sensitive resist. A silicon substrate was first oxi-
dized to form a layer of silicon dioxide (SiO2) several nanometers thick, which
was then spin-coated with a uniform layer of polymer (the resist) that was
sensitive to ionizing radiation. The beam was controlled by a computer through
410 Applications of ionizing radiation in materials processing

a position generator interface which allowed writing any computer-defined

patterns on the resist. Films with the desired geometry are made by covering
areas where exposure is not wanted with a metallic pattern. Pattern transfer
from the resist to the unpatterned SiO2 film is done by wet or dry etching. Wet
etching uses chemical or electrochemical processes to dissolve and remove the
exposed areas of SiO2. In dry etching, either ion bombardment (sputter etching)
or plasma etching with activate species (ions, atoms, free radicals) is used to
remove the unwanted materials. These dry etching processes can produce
straight and sharp pattern edges with a better resolution. Thus, dry etching is
more useful for patterning ultrafine nanostructures.
Three key parameters of the source are: (i) the virtual source size, (ii) its
brightness (expressed in A·cm–2·sr–1), and (iii) the energy spread of the emitted
electrons (measured in eV). As electrons penetrate the resist, they undergo a
series of low energy elastic collisions, which deflect the electrons slightly. This
results in beam broadening that increases with thickness. This effect is more
significant at low incident energies [37]. Most of the electrons pass entirely
through the resist and penetrate into the depth of the substrate. However part
of those electrons will eventually undergo large angle scattering (backscatter-
ing). At higher energies, backscattered electrons can cause exposure microns
away [38] from where the beam entered. This is related with the so-called
proximity effect [39] where electrons writing a feature at one location increase
the exposure at a nearby feature, causing pattern distortion and overexposure
[40].
Backscattering can be minimized by exposing a thin membrane substrate.
With sufficient exposure, the polymer chains in the resist are either broken
(positive resist) or become crosslinked (negative resist), thus forming a positive
or a negative image of the mask. After irradiation, the resist is developed to
form the desired pattern, which, through an etching process, is then transferred
onto the substrate.
The 3D nanopatterning and nanofabrication, called also stereolithography
(SL), can be conducted by exposing a three-dimensional object to an electron
beam. A special drive is needed to rotate the sample and the use of electron
beam nanolithography, which has resolution 100 times higher than that which
can be obtained using optical or X-ray sources. This results in reasonably fast
3D fabrication and patterning. One key technique is to rotate a 3D sample in
such a way that any of its faces can be exposed to the electron beam. Another
key technique is focusing the beam on a 3D sample. The height (Z coordinate)
and horizontal position (X and Y coordinates) of any point on a sample must
be determined. To measure the height, a confocal laser microscope has been
used. A height map of the sample enables the height of any point on the sample
to be determined, even if the sample is rotated [36].
Chapter 17 411

3.2.2. X-ray and ion beam lithography

X-ray lithography uses X-rays from a synchrotron radiation facility or rays
from a laser-induced plasma. Similar to electron beam lithography, the sample
is covered with a resist layer of high sensitivity to X-rays and then exposed to
the synchrotron X-radiation. Between the radiation source and the sample, at a
few micrometers above the resist layer, a mask, having the same feature sizes
as what will be made, is placed to define the pattern. X-ray masks are usually
made of very thin (about 2 μm) films of silicon carbide, covered by a metal
pattern having the desired geometry that is made of high-Z absorber material
to prevent unwanted X-ray exposure of the sample. After irradiation, the resist
is developed to yield the desired pattern, which, through an etching process, is
then transferred onto the substrate. Both electron beam and X-ray lithography
are capable of patterning down to lines and spaces well under 70 nm.
As with electron beams, ion beams can be used for the direct writing of
nanostructure patterns on a surface being processed. Both electron and ion
beams can be easily focused down to a narrow size, as small as a few nano-
meters, using electromagnetic lenses. Once focused, they can also be scanned
across a surface with great precision. Focused beams can be computer con-
trolled to reproduce a digitally stored image by rastering across the substrate
without the need of resists or masks. This is useful in producing nanostructures
which have high feature fidelity.

4. CONCLUSIONS

The ability to produce materials and structures with very high, nanometric
precision is basic to the development of nanotechnology. Ionizing radiation is
very powerful tool that can be used in this field. Radiation-based techniques
using X-rays, electron beams and ion beams play important role in micropat-
terning. Another use of radiation in nanotechnology is making different nano-
structures and nanocomposites. The use of ionizing radiation in nanotechnol-
ogy has led to the development of new materials and advanced products for
different branches of industry.

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