Basic Structure Characterization

Nilesh Prakash Gurao

Associate Professor
Department of Materials Science and Engineering
Indian Institute of Technology Kanpur
Co-ordinates: FB-408, 6688, npgurao@iitk.ac.in
 We have studied crystal structure and microstructure

 Characterization is important to study structure

 Different techniques

 Input signal, output, noise, amplification

 Resolution, accuracy, precision

 Signal to noise ratio is the most important parameter

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Resolution-Accuracy-Precision-Sensitivity

High precision-High accuracy Low precision-High accuracy

High precision-Low accuracy Low precision-Low accuracy

https://phidgets.wordpress.com/2014/05/20/accuracy-precision-and-resolution-theyre-not-the-same/
 Accuracy is a measure of “trueness”, while precision is a measure of variability

 One way that the resolution and precision are always related is that resolution determines the
upper limit of precision. The precision in data cannot exceed resolution

 Resolution is the smallest unit of measurement that can be indicated by an instrument

 Sensitivity is the smallest amount of difference in quantity that will change an instrument's reading

 A measuring tape for example will have a resolution, but not sensitivity. An analytical balance will
have both issues. An oscilloscope will have sensitivity but may not have resolution issues, depending
on several variables

 Fidelity, reliability and error are also important

 Systematic and Random errors

Probes

 Visible light, electrons, X-rays

 Wave particle duality

 Basic physics

 Velocity of light 3 ×108 m/s

 Quantized photon
Interaction of EMR with matter

 Transmission

 Reflection

 Scattering

 Diffraction

 X-rays are EMR that interact with electrons

 Scattering of X-rays by electrons in a material

History

• 1665: Diffraction effects observed by Italian mathematician

Francesco Maria Grimaldi
• 1868: X-rays Discovered by German Scientist Röntgen
• 1912: Discovery of X-ray Diffraction by Crystals: von Laue
• 1912: Bragg’s Discovery

λSWL
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Generation of X-rays

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• Random arrangement of atoms in space gives rise to scattering in
all directions: weak effect and intensities add

• By atoms arranged periodically in space

• In a few specific directions satisfying Bragg’s law: strong intensities of the
scattered beam :Diffraction
• No scattering along directions not satisfying Bragg’s law

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“Elements of X-ray Diffraction”,
B.D. Cullity & Stock

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Scattering of X-rays by an unit cell

 Braggs equation
in out
n=2d.sin
n: Order of reflection
2
d: Plane spacing
a
=
h2  k 2  l 2

: Bragg Angle

Path difference must be integral multiples of the wavelength

in=out
 n 1
d sin   d
2 sin  2


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Geometry of Bragg’s law

The incident beam, the normal to the reflection plane, and the diffracted beam
are always co-planar.

The angle between the diffracted beam and the transmitted beam is always 2
(usually measured).

Sin  cannot be more than unity; this requires

nλ < 2d, for n=1, λ < 2d

λ should be less than twice the d spacing we want to study

Order of reflection

Rewrite Bragg’s law λ=2 sin d/n

A reflection of any order as a first order reflection from planes, real or

fictitious, spaced at a distance 1/n of the previous spacing

Set d’ = d/n

λ=2d’ sin
An nth order reflection from (hkl) planes of spacing d may be considered
as a first order reflection from the (nh nk nl) plane of spacing d’ = d/n

*The term reflection is only notional due to symmetry between incoming and
outgoing beam w.r.t. plane normal, otherwise we are only talking of diffraction.
Reciprocal lattice vectors

 Used to describe Fourier analysis of electron concentration of the diffracted

pattern

 Every crystal has associated with it a crystal lattice and a reciprocal lattice

 A diffraction pattern of a crystal is the map of reciprocal lattice of the crystal.

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 Real space Reciprocal space

Crystal Lattice Reciprocal Lattice

Crystal structure Diffraction pattern

y’

Unit cell content Structure factor x’

y
y’
x x’

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Reciprocal space

bc Reciprocal lattice of FCC is BCC and

a* 
a  (b  c ) vice versa
ca
b* 
a  (b  c ) 001

a b a
c*  010
a  (b  c ) b

100
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Geometry of diffraction in the reciprocal space
 Condition for diffraction
k – k0 = g
Where k is diffracted beam direction
And k0 is incident beam direction
g is reciprocal lattice vector
g = ha + kb + lc

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 Diffraction occurs in 3D
 Laue conditions


 Diffraction cones
 Smaller the wavelength higher
the size of Ewald sphere
 X-ray, electron and neutron diffraction
 Diffraction very easy in transmission
electron microscope operating a 200 kV than
x-ray diffractometer operating at 40 kV
J. Krawit, Introduction to Diffraction in Materials Science and Engineering, Wiley New York 200
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Scattering of X-rays by an electron

 Thompson effect

 Coherent scattering

 Very small intensity

Scattering of X-rays by an atom

 Directly proportional to number of electrons

 Intensity reduces with angle

Scattering of X-rays by an unit cell

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Structure factor
 Link crystal structure with diffraction pattern
N
 Position and intensity of peaks Fhkl   f n e 2 i ( hun  kvn lwn )
1
 Atomic positions decide presence of hkl peak

 SC: (0, 0, 0), so all peaks possible

 BCC: (0, 0, 0) and (0.5, 0.5, 0.5) so only h+k+l = even peaks
possible

 Remember , where n is an integer

 , if p is odd
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Bravais Lattice Reflections possibly present Reflections necessarily absent

Simple All None

Body Centered (h+k+l): Even (h+k+l): Odd

Face Centered h, k, and l unmixed i.e. all h, k, and l: mixed

odd or all even

Permitted Reflections

Simple Cubic (100), (110), (111), (200), (210), (211),

(220), (300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..

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 From hkl to theta

 We can measure 1/10th of a

nanometer

 In fact we can get a precision

of 1/1000th of a nanometer

 s = 1, 2, 3…6, 8 for SC (no 7)

 s = 2, 4, 6, 8 for BCC

 s = 3, 4, 8, 11, 12, 16….

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 (100)
XRD pattern for Cubic Crystals

(110)

(111)
(200)
(210)
(211)

(220)
(330)(221)
(310)
(311)
(222)
(320)
(321)

(400)
(410)
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Intensity of X-ray pattern
 structure factor (F2)

 polarization factor

 multiplicity factor
Lattice parameter, phase diagrams
 Lorentz factor Texture, Strain (micro and residual)
Size, microstructure (twins and
 absorption factor
dislocations)
 temperature factor

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Seeing is Believing

 A picture is worth a thousand words

 Imaging of microstructure
 Human eye 0.1 mm resolution
Interaction of visible light with matter
Optical microscopes

 Zaccharias Janssen and his father Hans

 Englishman Robert Hooke is credited with the

microscopic milestone of discovering the basic unit of
all life, the cell in the mid 17th century
Resolution
Numerical aperture

The numerical aperture is the collection angle of light that enters the objective
Block diagram of OM

Transmission mode

Reflection mode
Type of image
 Magnesium
 Reflection and transmission mode

 Polarized light microscopy

 Limited resolution
Alpha Ferrite and Pearlite Nano-cellulose
Pearlite
Alpha Ferrite
and Cementite
Scanning Electron Microscope SEM
 Limitation of optical microscope in terms of resolution and depth of field

 Lower wavelength better resolution

 X-rays not possible to focus so electrons

 Electromagnetic lens replace optical lens

 A new class scanning probe microscopes

 SEM operates from to 50 kV

 Modern SEM can go from 100s of volts for non conducting biological samples
Depth of field of optical vs SEM
Electron matter interaction

Cathodoluminesence

EDS/WDS

Imaging

Imaging
Electron matter signal
Interaction volume
Contrast in secondary electron imaging
Electron source
SEM cross section

• Scan coils above objective

• Used to raster image

• Magnification is area of screen by area

scanned
Image formation

• SEM image is 2D intensity map

• Continuous map in analog system

• Discrete map in digital

• Pixel size and scanning rate important

• Signal to Noise ratio

• Fast scan and slow scan; Frame averaging

• Beam drift
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Resolution

• Secondary electron imaging of surface topography: 10 nm

• Backscattered electron imaging of atomic number contrast: 1 μm

• X-ray characterization of elemental chemistry: 2 μm using typical beam voltages

of 20 kV (much better resolution, 100 nm, can be obtained using low voltage
beams)
• Electron diffraction characterization of crystal structure and orientation: 1 μm

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Microanalysis in SEM
Energy and Wavelength Dispersive Spectroscopy
 Energy Dispersive spectroscopy (EDS) records X-rays of all energies simultaneously

 Output is counts versus photon energy

 Wavelength Dispersive spectroscopy (WDS) uses Bragg crystal

 Operates in serial mode

 Spectrometer is tuned to one wavelength at a time

 Use several crystals for different elements

 Better spectral resolution that EDS

Principle of Electron Back Scatter Diffraction

Electron beam incident on sample inclined at 70º

BSE yield increases and path length decreases

Some BSE satisfy Bragg condition

λ = 2d sinθ

 Diffraction occurs from many planes in same unit cell

θB very small, large radius of diffraction cones

 Kikuchi bands

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Intersections of the Kikuchi bands correspond to the
intersection of zone axes in the crystal with the phosphor
screen

w ≈ 2lθ ≈ nlλ/d; Low index plane high d, low w

Diffraction pattern bound to crystal structure of the Kikuchi bands in TEM

sample

Resultant diffraction pattern changes as crystal

orientation changes

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Courtesy Old HKL website
Aged beta titanium alloy

Image quality map Phase map Crystal orientation map

red-alpha green-beta

Gurao, Ali and Suwas, MSEA 2008

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Dual beam Focused Ion Beam (FIB) SEM
• FIB can make ‘cuts’ to remove precisely controlled amounts of material to expose a new surface for
EBSD
• SEM can be used to acquire EBSD data in the normal manner
• Sample is ‘serial sectioned’ using FIB, and EBSD maps obtained after each cut
• Thus many 2D maps are acquired which can be ‘stacked’ and then be recompiled into a 3D view of
the sample interior in a similar manner to tomography in medical imaging

D Raabe, MPIE Dusseldorf

Visualization of grain boundaries

• Determination of precise grain

boundary surface
• Grain boundary engineering in 3D
• Segregation and corrosion related
issues
• Eg. Brittleness in 304L steel due to
phosphorous segregation at ∑9 boundary
D Raabe 2011

S. Mandal et al. Scripta Mater. 81 (2014) 16

Transmission Electron Microscope

• Sampl soul be electron transparent

• Operates at higher voltage than SEM

100 to 1000 kV

• Most between 100 to 300 kV

• Longer in size to focus electron beam

• Analogous to an optical microscope

Imaging Diffraction
 Bright field Dark field Diffraction pattern
Diffraction is very easy as
Ewald sphere radius very
Magnetite
high as voltage is 200-
nanoparticle
1000 kV

Castillo et al. Journal of Nanotechnology 2014

So go for dark field
Bright field Dark field
imaging

Interaction of Defects visible

dislocations with
precipitates in Mg
alloy
Wang et al. Acta Mater. 2020
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High Resolution TEM (HRTEM)

Each diffracted wave presents a different solution to the Schrodinger equation

Manifests periodic potential (strength and spacing) between the
atoms in the sample
Scanning Probe Microscopy: Atomic Force Microscopy
Contact and non-contact mode
Contact and Tapping mode
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