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X-Ray Diffraction

(XRD)

Debjani Banerjee
Department of Chemical Engineering
IIT Kanpur
X-ray Generation & typical spectrum
Conventional X-ray Source & Synchrotron:
Interaction of X-rays with matter
Incident X-rays

SPECIMEN Absorption (Heat)

Fluorescent X-rays
Electrons

Scattered X-rays
Compton recoil Photoelectrons

Coherent Incoherent (Compton modified)


From bound charges From loosely bound charges

Transmitted beam

The coherently scattered X-rays are the ones that are important from
XRD perspective.
Scale of Structure Organization
Diffraction Basics
 For electromagnetic radiation to be diffracted the spacing in the grating
should be of the same order as the wavelength
 In crystals the typical interatomic spacing ~ 2-3 Å so the suitable radiation is
X-rays
 Hence, X-rays can be used for the study of crystal structures
 Neutrons and Electrons are also used for diffraction studies from materials.
 Neutron diffraction is especially useful for studying the magnetic ordering
in materials

X-rays
Beam of electrons Target

A accelerating charge radiates electromagnetic radiation


Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission
spectrum as in the figure below (schematic)

Intense peak, nearly X-ray sources with different  for


K monochromatic doing XRD studies

Target  Of K
White K Metal radiation (Å)
Intensity

radiation Mo 0.71
Cu 1.54
Characteristic radiation →
due to energy transitions Co 1.79
in the atom
Fe 1.94
Cr 2.29

0.2 0.6 1.0 1.4


Wavelength ()

The high intensity nearly monochromatic K x-rays can be used as a radiation source for
X-ray diffraction (XRD) studies  a monochromator can be used to further decrease the
spread of wavelengths in the X-ray
XRD  the first step
 A beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal.
 The electrons oscillate under the influence of the incoming X-Rays and become secondary
sources of EM radiation.
 The secondary radiation is in all directions.
 The waves emitted by the electrons have the same frequency as the incoming X-rays 
coherent.
 The emission can undergo constructive or destructive interference.

Secondary
Incoming X-rays emission

Oscillating charge re-radiates  In phase with


the incoming x-rays

Schematics

Sets nucleus into oscillation


Sets Electron cloud into oscillation
Small effect  neglected
Crystalline materials are characterized by the orderly
periodic arrangements of atoms.
The (200) planes The (220) planes
of atoms in NaCl of atoms in NaCl

• The unit cell is the basic repeating unit that defines a crystal.
• Parallel planes of atoms intersecting the unit cell are used to
define directions and distances in the crystal.
– These crystallographic planes are identified by Miller
indices.
The atoms in a crystal are a periodic array of coherent
scatterers and thus can diffract light.
• Diffraction occurs when each object in a periodic array scatters
radiation coherently, producing concerted constructive interference at
specific angles.
• The electrons in an atom coherently scatter light.
– The electrons interact with the oscillating electric field of the light
wave.
• Atoms in a crystal form a periodic array of coherent scatterers.
– The wavelength of X rays are similar to the distance between
atoms.
– Diffraction from different planes of atoms produces a diffraction
pattern, which contains information about the atomic
arrangement within the crystal
• X Rays are also reflected, scattered incoherently, absorbed, refracted,
and transmitted when they interact with matter.
2012 was the 100th Anniversary of X-Ray Diffraction

•X-rays were discovered by WC Rontgen in 1895


•In 1912, PP Ewald developed a formula to describe the passage of light
waves through an ordered array of scattering atoms, based on the
hypothesis that crystals were composed of a space-lattice-like
construction of particles.
•Maxwell von Laue realized that X-rays might be the correct wavelength
to diffract from the proposed space lattice.
•In June 1912, von Laue published the first diffraction pattern in
Proceedings of the Royal Bavarian Academy of Science.
The Laue diffraction pattern

•Von Laue’s diffraction pattern supported


two important hypotheses

–X-rays were wavelike in nature and


therefore were electromagnetic radiation
–The space lattice of crystals

•Bragg consequently used X-ray


diffraction to solve the first crystal
structure, which was the structure of The second diffraction pattern
NaCl published in June 1913. published was of ZnS. Because
•Single crystals produce “spot” patterns this is a higher symmetry
similar to that shown to the right. material, the pattern was less
•However, powder diffraction patterns complicated and easier to analyze
look quite different.
An X-ray powder diffraction pattern is a plot of the intensity
of X-rays scattered at different angles by a sample
• The detector moves in a circle
around the sample
–The detector position is recorded as
the angle 2theta (2θ)
–The detector records the number of
X-rays observed at each angle 2θ
–The X-ray intensity is usually
recorded as “counts” or as “counts per
second”
• Many powder diffractometers use
the Bragg-Brentano parafocusing
geometry
–To keep the X-ray beam properly
focused, the incident angle omega
changes in conjunction with 2theta
–This can be accomplished by rotating
the sample or by rotating the X-ray
tube.
X-rays scatter from atoms in a material and therefore contain
information about the atomic arrangement

•The three X-ray scattering patterns above were produced by three chemically
identical forms SiO2
•Crystalline materials like quartz and Cristobalite produce X-ray diffraction patterns
–Quartz and Cristobalite have two different crystal structures
–The Si and O atoms are arranged differently, but both have long-range atomic order
–The difference in their crystal structure is reflected in their different diffraction
patterns
•The amorphous glass does not have long-range atomic order and therefore produces
only broad scattering features
Diffraction occurs when light is scattered by a periodic array
with long-range order, producing constructive interference
at specific angles
•The electrons in each atom coherently scatter light.
–We can regard each atom as a coherent point scatterer
–The strength with which an atom scatters light is proportional to the number of
electrons around the atom.

•The atoms in a crystal are arranged in a periodic array with long-range order and
thus can produce diffraction.

•The wavelength of X rays are similar to the distance between atoms in a crystal.
Therefore, we use X-ray scattering to study atomic structure.

•The scattering of X-rays from atoms produces a diffraction pattern, which


contains information about the atomic arrangement within the crystal

•Amorphous materials like glass do not have a periodic array with long-range
order, so they do not produce a diffraction pattern. Their X-ray scattering pattern
features broad, poorly defined amorphous ‘humps’.
Crystalline materials are characterized by the long-range orderly
periodic arrangements of atoms.
•The unit cell is the basic repeating unit that defines the crystal
structure.
–The unit cell contains the symmetry elements required to uniquely define the
crystal structure.
–The unit cell might contain more than one molecule:
•for example, the quartz unit cell contains 3 complete molecules of SiO2.
–The crystal system describes the shape of the unit cell
–The lattice parameters describe the size of the unit cell

•Theunit cell repeats in all dimensions to fill space and produce the
macroscopic grains or crystals of the material
The diffraction pattern is a product of the unique crystal structure of a
material

• The crystal structure describes the atomic arrangement of a material.


• The crystal structure determines the position and intensity of the
diffraction peaks in an X-ray scattering pattern.
–Interatomic distances determine the positions of the diffraction peaks.
–The atom types and positions determine the diffraction peak intensities.
• Diffraction
peak widths and shapes are mostly a function of instrument
and microstructural parameters.
Diffraction pattern calculations treat a crystal as a collection
of planes of atoms

•Each diffraction peak is attributed to the scattering from a specific set


of parallel planes of atoms.
•Miller indices (hkl) are used to identify the different planes of atoms
•Observed diffraction peaks can be related to planes of atoms to assist
in analyzing the atomic structure and microstructure of a sample
A Brief Introduction to Miller Indices
•The Miller indices (hkl) define the reciprocal
axial intercepts of a plane of atoms with the
unit cell
–The (hkl) plane of atoms intercepts the unit cell at a/ℎ,
𝑏/𝑘, and 𝑐/𝑙
–The (220) plane drawn to the right intercepts the unit
cell at ½a, ½b, and does not intercept the c-axis.
•When a plane is parallel to an axis, it is
assumed to intercept at ∞; therefore its
reciprocal is 0
•The vector dhkl is drawn from the origin of the
unit cell to intersect the crystallographic plane
(hkl) at a 90° angle.
–The direction of dhkl is the crystallographic
direction.
–The crystallographic direction is expressed using []
brackets, such as [220]
The diffraction peak position is a product of interplanar
spacing, as calculated by Bragg’s law

• Bragg’s law relates the diffraction angle, 2θ, to dhkl


– In most diffractometers, the X-ray wavelength λ is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific
angle 2θ.
• dhkl is a geometric function of the size and shape of the unit cell
– dhkl is the vector drawn from the origin to the plane (hkl) at a 90° angle.
– dhkl, the vector magnitude, is the distance between parallel planes of atoms in
the family (hkl)
– Therefore, we often consider that the position of the diffraction peaks are
determined by the distance between parallel planes of atoms.
The diffraction peak intensity is determined by the
arrangement of atoms in the entire crystal

• The structure factor Fhkl sums the result of scattering from all of the atoms in
the unit cell to form a diffraction peak from the (hkl) planes of atoms.
• The amplitude of scattered light is determined by:
– where the atoms are on the atomic planes
• this is expressed by the fractional coordinates xj yj zj
– what atoms are on the atomic planes
• the scattering factor fj quantifies the efficiency of X-ray
scattering at any angle by the group of electrons in each atom
– The scattering factor is equal to the number of electrons
around the atom at 0° θ, the drops off as θ increases
• Nj is the fraction of every equivalent position that is occupied
by atom j
Bragg’s law provides a simplistic model to understand what conditions
are required for diffraction.

• For parallel
planes of atoms, with a space dhkl between the planes,
constructive interference only occurs when Bragg’s law is satisfied.

– In our diffractometers, the X-ray wavelength λ is fixed.


– A family of planes produces a diffraction peak only at a specific angle 2θ.

• Additionally, the plane normal [hkl] must be parallel to the


diffraction vector s
– Plane normal [hkl]: the direction perpendicular to a plane of atoms
– Diffraction vector s: the vector that bisects the angle between the incident
and diffracted beam
Many powder diffractometers use the Bragg-Brentano
parafocusing geometry.
A single crystal specimen in a Bragg-Brentano diffractometer
would produce only one family of peaks in the diffraction pattern.
A polycrystalline sample should contain thousands of crystallites.
Therefore, all possible diffraction peaks should be observed.

•For every set of planes, there will be a small percentage of crystallites that are
properly oriented to diffract (the plane perpendicular bisects the incident and
diffracted beams).
•Basic assumptions of powder diffraction are that for every set of planes there is an
equal number of crystallites that will diffract and that there is a statistically relevant
number of crystallites, not just one or two.
Powder diffraction is more aptly named polycrystalline
diffraction
• Samples canbe powder, sintered pellets, coatings on substrates,
engine blocks...

• The ideal “powder” sample contains tens of thousands of randomly


oriented crystallites
– Every diffraction peak is the product of X-rays scattering from an equal number
of crystallites
– Only a small fraction of the crystallites in the specimen actually contribute to
the measured diffraction pattern

• XRPD is a somewhat inefficient measurement technique

• Irradiating a larger volume of material can help ensure that a


statistically relevant number of grains contribute to the diffraction
pattern
–Small sample quantities pose a problem because the sample size limits the
number of crystallites that can contribute to the measurement
X-rays are scattered in a sphere around the sample
• Each diffraction peak is actually a Debye diffraction cone produced by the
tens of thousands of randomly oriented crystallites in an ideal sample.
–A cone along the sphere corresponds to a single Bragg angle 2theta
• The linear diffraction pattern is formed as the detector scans along an arc
that intersects each Debye cone at a single point
• Only a small fraction of scattered X-rays are observed by the detector.
X-Ray Powder Diffraction (XRPD) is a somewhat
inefficient measurement technique

• Only asmall fraction of crystallites in the sample actually contribute to


the observed diffraction pattern

–Other crystallites are not oriented properly to produce diffraction


from any planes of atoms
–You can increase the number of crystallites that contribute to the
measured pattern by spinning the sample

• Only a small fraction of the scattered X-rays are observed by the


detector

–A point detector scanning in an arc around the sample only observes


one point on each Debye diffraction cone
–You can increase the amount of scattered X-rays observed by using a
large area (2D) detector
Diffraction patterns are collected as absolute intensity vs 2θ,
but are best reported as relative intensity vs dhkl.

•The peak position as 2theta depends on instrumental characteristics


such as wavelength.
–The peak position as dhkl is an intrinsic, instrument-independent,
material property.
•Bragg’s Law is used to convert observed 2θ positions to dhkl.

•The absolute intensity, i.e. the number of X rays observed in a given


peak, can vary due to instrumental and experimental parameters.
–The relative intensities of the diffraction peaks should be instrument
independent.
•To calculate relative intensity, divide the absolute intensity of
every peak by the absolute intensity of the most intense peak,
and then convert to a percentage. The most intense peak of a
phase is therefore always called the “100% peak”.
–Peak areas are much more reliable than peak heights as a measure
of intensity.
Powder diffraction data consists of a record of photon intensity
versus detector angle 2θ.
•Diffraction data can be reduced to a list of peak positions and intensities
–Each dhkl corresponds to a family of atomic planes {hkl}
–individual planes cannot be resolved- this is a limitation of powder diffraction versus
single crystal diffraction
You can use XRD to determine
• Phase Composition of a Sample
– Quantitative Phase Analysis: determine the relative amounts of phases in a
mixture by referencing the relative peak intensities

• Unit cell lattice parameters and Bravais lattice symmetry


– Index peak positions
– Lattice parameters can vary as a function of, and therefore give you information
about, alloying, doping, solid solutions, strains, etc.

• Residual Strain (macrostrain)

• Crystal Structure
– By Rietveld refinement of the entire diffraction pattern

• Epitaxy/Texture/Orientation
• Crystallite Size and Microstrain
– Indicated by peak broadening
– Other defects (stacking faults, etc.) can be measured by analysis of peak shapes
and peak width
Phase Identification
• The diffraction pattern for every phase is as unique as your
fingerprint
– Phases with the same chemical composition can have drastically different
diffraction patterns.
– Use the position and relative intensity of a series of peaks to match
experimental data to the reference patterns in the database
The diffraction pattern of a mixture is a simple sum of the scattering
from each component phase
Databases such as the Powder Diffraction File (PDF)
contain dI lists for thousands of crystalline phases.
• The PDF contains over 200,000 diffraction patterns.
• Modern computer programs can help you determine what phases are
present in your sample by quickly comparing your diffraction data to all of
the patterns in the database.
• The PDF card for an entry contains a lot of useful information, including
literature references.
You cannot guess the relative amounts of phases based only
on the relative intensities of the diffraction peaks

•The pattern shown above contains equal amounts of TiO2 and Al2O3
•The TiO2 pattern is more intense because TiO2 diffracts X-rays more
efficiently
With proper calibration, you can calculate the amount of each phase
present in the sample
Unit Cell Lattice Parameter Refinement
• By accurately measuring peak positions over a long range of 2theta,
you can determine the unit cell lattice parameters of the phases in
your sample
– alloying, substitutional doping, temperature and pressure, etc
can create changes in lattice parameters that you may want to
quantify
– use many peaks over a long range of 2theta so that you can
identify and correct for systematic errors such as specimen
displacement and zero shift
– measure peak positions with a peak search algorithm or profile
fitting
• profile fitting is more accurate but more time consuming
– then numerically refine the lattice parameters
Crystallite Size and Microstrain
• Crystallites smaller than ~120nm create broadening of diffraction
peaks
– this peak broadening can be used to quantify the average crystallite size of
nanoparticles using the Scherrer equation
– must know the contribution of peak width from the instrument by using a
calibration curve
• microstrain may also create peak broadening
– analyzing the peak widths over a long range of 2theta using a Williamson-Hull
plot can let you separate microstrain and crystallite size
00-043-1002> Cerianite- - CeO 2

K
B2q  
Intensity (a.u.)

L cos q

23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
2q (deg.)
Preferred Orientation (texture)
• Preferred orientation of crystallites can create a
systematic variation in diffraction peak intensities
– can qualitatively analyze using a 1D diffraction pattern
– a pole figure maps the intensity of a single peak as a function
of tilt and rotation of the sample
• this can be used to quantify the texture
10.0 (111) 00-004-0784> Gold - Au

8.0

(311)
Intensity(Counts)

6.0 (200)
(220)
4.0

(222)
2.0

(400)
3
x10
40 50 60 70 80 90 100
Two-Theta (deg)
Non-ideal samples: Texture (i.e. preferred crystallographic
orientation)
•The samples consists of tens of thousands of grains, but the grains are
not randomly oriented
–Some phenomenon during crystallization and growth, processing, or
sample preparation have caused the grains to have preferred
crystallographic direction normal to the surface of the sample
Essential Parts of the Diffractometer

•X-ray Tube: the source of X Rays

•Incident-beam optics: condition the X-ray beam before it hits the


sample

•The goniometer: the platform that holds and moves the sample,
optics, detector, and/or tube

•The sample & sample holder

•Receiving-side optics: condition the X-ray beam after it has


encountered the sample

•Detector: count the number of X Rays scattered by the sample


X-radiation for diffraction measurements is produced
by a sealed tube or rotating anode.
•Sealed X-ray tubes tend to operate at 1.8
to 3 kW.
•Rotating anode X-ray tubes produce much
more flux because they operate at 9 to 18
kW.
–A rotating anode spins the anode at 6000
rpm, helping to distribute heat over a
larger area and therefore allowing the tube
to be run at higher power without melting
the target.
•Both sources generate X rays by striking
the anode target with an electron beam
from a tungsten filament.
–The target must be water cooled.
–The target and filament must be
contained in a vacuum

Be is transparent to x-rays, so it's used in the windows of x-ray tubes, which need to be
strong enough to hold a perfect vacuum, yet thin enough to let the delicate x-rays out.
The wavelength of X rays is determined by the anode of
the X-ray source
•Electrons from the filament strike the target anode, producing characteristic radiation
via the photoelectric effect.
•The anode material determines the wavelengths of characteristic radiation.
•While we would prefer a monochromatic source, the X-ray beam actually consists of
several characteristic wavelengths of X rays.
Spectral Contamination in Diffraction Patterns

•The Kα1 & Kα2 doublet will almost always be present


–Very expensive optics can remove the Kα2 line
–Kα1 & Kα2 overlap heavily at low angles and are
more separated at high angles
•W lines form as the tube ages: the W filament
contaminates the target anode and becomes a new X-
ray source
•W and Kβ lines can be removed with optics
Monochromators remove unwanted wavelengths of
radiation from the incident or diffracted X-ray beam.
•Diffraction from a monochromator crystal can be used to select one
wavelength of radiation and provide energy discrimination.
•Most powder diffractometer monochromators only remove K-beta, W-
contamination, and Brehmstralung radiation
–Only HRXRD monochromators or specialized powder monochromators remove K-
alpha2 radiation as well.
•A monochromator can be mounted between the tube and sample
(incident-beam) or between the sample and detector (diffracted-
beam)
–An incident-beam monochromator only filters out unwanted wavelengths of
radiation from the X-ray source
–A diffracted-beam monochromator will also remove fluoresced photons.
–A monochromator may eliminate 99% of K-beta and similar unwanted wavelengths
of radiation.
–A diffracted-beam monochromator will provide the best signal-to-noise ratio, but
data collection will take a longer time
Beta filters can also be used to reduce the intensity of K-beta and W
wavelength radiation

•A material with an absorption


edge between the K-alpha and K-
beta wavelengths can be used as a
beta filter
•This is often the element just
below the target material on the
periodic table
–For example, when using Cu
radiation
•Cu K-alpha = 1.541 Å
•Cu K-beta= 1.387 Å
•The Ni absorption edge= 1.488 Å
–The Ni absorption of Cu
radiation is:
•50% of Cu K-alpha
•99% of Cu K-beta
•Some atoms absorb incident X-rays and fluoresce them as X-rays of a different
wavelength
–The absorption of X-rays decreases the diffracted signal
–The fluoresced X-rays increase the background noise
•The increased background noise from fluoresced X-rays can be removed by using:
–a diffracted-beam monochromator
–an energy sensitive detector
•The diffracted beam signal can only be increased by using a different wavelength of
radiation
•The most problematic materials are those two and three below the target material:
–For Cu, the elements that fluoresce the most are Fe and Co
The X-ray Shutter is the most important safety device
on a diffractometer

•X-raysexit the tube through X-ray


transparent Be windows.

•X-Ray safety shutters contain the


beam so that you may work in the
diffractometer without being exposed
to the X-rays.

•Being aware of the status of the


shutters is the most important factor in
working safely with X rays.
Detectors

•point detectors
–observe one point of space at a time
•slow, but compatible with most/all optics
–scintillation and gas proportional detectors count all photons,
within an energy window, that hit them
–Si(Li) detectors can electronically analyze or filter wavelengths
•position sensitive detectors
–linear PSDs observe all photons scattered along a line from 2 to
10° long
–2D area detectors observe all photons scattered along a conic
section
Preparing a powder specimen

•An ideal powder sample should have many crystallites in random


orientations
–the distribution of orientations should be smooth and equally distributed
amongst all orientations

•Large crystallite sizes and non-random crystallite orientations both lead


to peak intensity variation
–the measured diffraction pattern will not agree with that expected from an ideal
powder
–the measured diffraction pattern will not agree with reference patterns in the
Powder Diffraction File (PDF) database

•If the crystallites in a sample are very large, there will not be a smooth
distribution of crystal orientations. You will not get a powder average
diffraction pattern.
–crystallites should be <10mm in size to get good powder statistics
Grazing Incident Angle Diffraction (GIXD)

• Also called Glancing Angle X-Ray Diffaction

•The incident angle is fixed at a very small angle (<5°) so that X-rays are
focused in only the top-most surface of the sample.

• GIXD can perform many of analyses possible with XRPD with the
added ability to resolve information as a function of depth (depth-
profiling) by collecting successive diffraction patterns with varying
incident angles
–orientation of thin film with respect to substrate
–lattice mismatch between film and substrate
–epitaxy/texture
–macro- and microstrains
–reciprocal space map
Information in a Diffraction Pattern

• Phase Identification
• Crystal Size
• Crystal Quality
• Texture (to some extent)
• Crystal Structure
Analysis of Single Phase
2q(˚) d (Å) (I/I1)*100
27.42 3.25 10
31.70 2.82 100
45.54 1.99 60
53.55 1.71 5
56.40 1.63 30
Intensity (a.u.)

65.70 1.42 20
76.08 1.25 30
84.11 1.15 30
89.94 1.09 5
I1: Intensity of the strongest peak
Procedure
• Note first three strongest peaks at d1, d2, and d3
• In the present case: d1: 2.82; d2: 1.99 and d3: 1.63 Å
• Search JCPDS manual to find the d group belonging to the strongest
line: between 2.84-2.80 Å
• There are 17 substances with approximately similar d2 but only 4 have
d1: 2.82 Å
• Out of these, only NaCl has d3: 1.63 Å
• It is NaCl……………Hurrah

Specimen and Intensities Substance File Number


2.829 1.999 2.26x 1.619 1.519 1.499 3.578 2.668 (ErSe)2Q 19-443
2.82x 1.996 1.632 3.261 1.261 1.151 1.411 0.891 NaCl 5-628
2.824 1.994 1.54x 1.204 1.194 2.443 5.622 4.892 (NH4)2WO2Cl4 22-65
2.82x 1.998 1.263 1.632 1.152 0.941 0.891 1.411 (BePd)2C 18-225
Caution: It could be much more tricky if the sample is oriented or textured or your goniometer is not calibrated
Presence of Multiple phases
d (Å) I/I
• More Complex 1

Pattern of Cu2O Remaining


3.01 Lines 5
• Several permutations combinations possible 2.47 I/I1 72
d (Å) I/I1 d
• e.g. d1; d2; and d3, the first three strongest lines show(Å) 2.13 28
3.020 9 Observed Normalized
several alternatives 2.09 * 100
• Then take any of the two lines together and match
2.465 100 3.01 5
1.80 *
7
52
• It turns out that 1st and 3rd strongest lies
2.135belong to Cu2.47
37Pattern for Cu
72 1.50 20
100
and then all other peaks for Cu can be1.743 separated out I/I1
1 d (Å) 2.13 28
1.29 9
39
• Now separate the remaining lines and normalize the1.50100 20 1.28 * 28
2.088
18
1.510 27 1.22 4
intensities 1.808 46
1.287 171.278 1.29 9 1.08 * 13
20
• Look for first three lines and it turns out that the 20

phase is Cu2O 1.233 4 1.09 1.22 17 4 1.04 * 36

1.0436 5 0.98 5

 1.0674 2 0.98 5 7
0.91 4
• If more phases, more pain to solve 0.9038 3
0.9795 4 0.8293 9 0.83 * 8
0.8083 8 0.81 * 10
Lattice Strain
do

No Strain
2q

Uniform Strain
q  d  strain 2q

Non-uniform Strain
2q
d
Broadeing b  2q  2 tan q
d
Texture in Materials
• Grains with in a polycrystalline are not
completely randomly distributed
• Clustering of grains about some particular
orientation(s) to a certain degree
• Examples:
– Present in cold-rolled brass or steel sheets
– Cold worked materials tend to exhibit some
texture after recrystallization
• Affects the properties due to anisotropic
nature
Texture
• Fiber Texture
– A particular direction [uvw] for all grains is more or less parallel to the
wire or fiber axis
• e.g. [111] fiber texture in Al cold drawn wire
– Double axis is also possible
• Example: [111] and [100] fiber textures in Cu wire
• Sheet Texture
– Most of the grains are oriented with a certain crystallographic plane
(hkl) roughly parallel to the sheet surface and certain direction [uvw]
parallel to the rolling direction
– Notation: (hkl)[uvw]
Texture in materials


 
 Also, if the direction [u1v1w1] is
parallel for all regions, the

 structure is like a single crystal
However, the direction [u1v1w1]
 is not aligned for all regions, the
 structure is like a mosaic
 structure, also called as Mosaic
 Texture

 [uvw] i.e. perpendicular to the


surface of all grains is parallel to
a direction [uvw]
Pole Figures

(100) pole figures for a sheet material


(a) Random orientation (b) Preferred orientation
Thin Film Specimen

qB qB
Grazing angle (very small, ~1-5)
Film or Coating

Substrate

• Smaller volume i.e. less intensity of the scattered beam


from the film
• Grazing angle
– Useful only for polycrystalline specimens
Thin Film XRD
• Precise lattice constants measurements derived from 2q-q scans, which
provide information about lattice mismatch between the film and the
substrate and therefore is indicative of strain & stress

• Rocking curve measurements made by doing a q scan at a fixed 2 q angle,


the width of which is inversely proportionally to the dislocation density in
the film and is therefore used as a gauge of the quality of the film.

• Superlattice measurements in multilayered heteroepitaxial structures,


which manifest as satellite peaks surrounding the main diffraction peak
from the film. Film thickness and quality can be deduced from the data.

• Glancing incidence x-ray reflectivity measurements, which can determine


the thickness, roughness, and density of the film. This technique does not
require crystalline film and works even with amorphous materials.
Thin Films Specimens

qB1qB2
Diffraction
i.e. from from
No Diffraction hkl plane
hkl
occurs
plane
qB1qB qB2
B

(hkl) plane of the Single Crystal Substrate


substrate

• If the sample and substrate is polycrystalline, then


problems are less
• But if even if one of them is oriented, problems arise
• In such situations substrate alignment is necessary
Oriented thin films SrTiO3 (100)


008

0014
006

0016
0010
0012

0022

0018
004

0028
0026

0024
0020

△ *
• Bismuth Titanate thin △

films on oriented SrTiO3

Log Intensity (a.u.)


substrates 10 20 30 40 50 60 70 80 90


• Only one type of peaks

2216
△ △
• It apparent that films are
SrTiO3 (110)
highly oriented
10 20 30 40 50 60 70 80 90


4016/
0416

014

SrTiO3 (111)
10 20 30 40 50 60 70 80 90
o
2q ( )
Degree of orientation
[uvw] corresponding
to planes parallel to
Film the surface
Substrate
Side view

But what if the planes when looked from top have random orientation?

Top view
Pole Figure
SrTiO3 (100) SrTiO3 (110) SrTiO3 (111)

2 1

1
1 2
2
1 3
2 1
1 2 3
1
2 3 2
2
1 3

 4 Peaks at ~50  2 sets of peaks at ~ 5, 65  3 sets of peaks


 Excellent in-plane and 85° at ~ 35 and 85°
orientation  Indicating a doublet or  indicating a
opposite twin growth triplet or triple
twin growth
(117) Pole Figures for Bismuth Titanate Films
Texture Evolution

3 (100) planes
Film inclined at 54.7°
to (110) plane,
SrTiO3 (100) Two (100) planes
separated by
inclined at 45° to (110)
120°
plane in opposite
directions STO(111)

BNdT(001)
STO [100] 45
54.7°
STO(110)
STO(111)

STO(100)

BNdT/SrTiO3 (100) BNdT/SrTiO3 (110) BNdT/SrTiO3 (111)


Rocking Curve
• An useful method for evaluating the quality of oriented samples such as epitaxial films
•  is changed by rocking the sample but qB is held constant
• Width of Rocking curve is a direct measure of the range of orientation present in the
irradiated area of the crystal

(0010) Rocking curve of (001)-


(2212) SrBi
oriented Rocking
2Ta2Ocurve
9 thin of (116)-
film
oriented SrBi2Ta2O9 thin film
Normal
FWHM = 0.07°

(a.u.)
(a.u.)
FWHM = 0.171°

Intensity
qB 
Intensity

32.432.4 33.0
32.6 32.832.8
17.833.233.2
17.4 17.6 32.6 17.8 18.0
33.0 18.2
17.5 17.6 17.7
 ()  ()
Today X-ray diffraction supplemented by electron and neutron diffraction

Energies X-ray, electrons and neutrons wave-particle

hc hc
E  h  
 E
X-ray: o
  1A E  12 k eV
o
  1A me  9.1 10-31 kg
h h h
Electrons: p k  
 p 2mE E  150 eV
o
  1A mn  1.6749 10-27 kg
h h
Neutrons:   E  0.08 eV
p 2mE
How do we get X-rays?
• The cathode is heated by a heat
source to create an electron beam.
• The beam of electrons is then
accelerated by the high voltage
source, allowing them to collide
with the metal target (usually
Tungsten)
• X-rays are produced when the
electrons are suddenly decelerated
upon collision with the metal target
(Brehmsstrahlung)
• If the bombarding electrons have
sufficient energy, they can knock an
electron out of an inner shell of the
target metal atoms. Then electrons
from higher states drop down to fill
the vacancy, emitting x-ray photons
(characteristic x-rays)
X-ray production Spectrum
• The characteristic x-
rays, shown as two
sharp peaks in the
illustration occur
when vacancies are
produced in the n=1
or K-shell of the
atom
• The x-rays produced
by transitions from
the n=2 to n=1 levels
are called K-alpha x-
rays
• The x-rays produced
in the transition
from n=3  n=1 are
called K-beta x-rays.

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