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X-ray Diffraction: Principles and Practice
Ashish Garg and Nilesh GuraoDepartment of Materials Science and
EngineeringIndian Institute of Technology Kanpur
Layout of the Lecture
Materials Characterization Importance of X-ray Diffraction
Basics Diffraction X-ray Diffraction Crystal Structure and X-ray Diffraction
Different Methods Phase Analysis Texture Analysis Stress Analysis Particles Size Analysis ………..
Summary
Materials Characterization
Essentially to evaluate the structure and properties
Structural Characterization Diffraction
X-ray and Electron Diffraction Microscopy Spectroscopy
Property Evaluation Mechanical Electrical Anything else
Time Line 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
Electromagnetic Spectrum
Generation of X-rays
Commercial X-ray Tube
X-ray Spectrum from an Iron target
Short Wavelength Limit
Continuous spectrum
Characteristic X-ray Moseley’s Law
)( ZCn
kK VVBiI )(
mCS AiZVI
12400(nm)SWL V
λSWL
Use of Filter
Ni filter for Cu Target
Crystal Systems and Bravais Lattices
Structure of Common Materials
Metals Copper: FCC -Iron: BCC Zinc: HCP Silver: FCC Aluminium: FCC
Ceramics SiC: Diamond Cubic Al2O3: Hexagonal MgO: NaCl type
Diffraction A diffracted beam may be defined as a beam
composed of a large number of scattered rays mutually reinforcing each other
ScatteringInteraction with a single particle
DiffractionInteraction with a crystal
Scattering Modes 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
d
Diffraction of light through an aperture
-15 -10 -5 0 5 10 150
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Intensity
an
λsinθ
Minima Maxima
n = 0, 1,.. an2
12sin
n = 1, 2,..
-15 -10 -5 0 5 10 150
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Intensity
d sinθ = mλ, m = 1,2,3…..
d sinθ = (m+½)λ, m = 1,2,3…..
Constructive Interference
Destructive Interference
Young’s Double slit experiment
InterferencePhase Difference = 0˚
Phase Difference = 180˚
Phase Difference = 90˚
Interference and Diffraction
Bragg’s Law
n=2d.sinn: Order of
reflectiond: Plane spacing = : Bragg Angle
Path difference must be integral multiples of the wavelengthin=out
in out
2
2 2 2
a
h k l
Braggs Law
sin2nd
2
1sin d
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
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
λ=2d’ sin
*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 vectorsUsed 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.
Real space Reciprocal space
Crystal Lattice Reciprocal Lattice
Crystal structure Diffraction pattern
Unit cell content Structure factor
x
y
y’x’
y’x’
Reciprocal space
Reciprocal lattice of FCC is BCC and vice versa
)(*
)(*
)(*
cbabac
cbaacb
cbacba
a
b
c
100
001
010
Ewald sphere
2
hkl2
hkld1
Limiting sphere
Ewald sphere
1
hklk
k'
Ewald sphere
J. Krawit, Introduction to Diffraction in Materials Science and Engineering, Wiley New York 2001
Two Circle Diffractometer For polycrystalline Materials
Four Circle Diffractometer
For single crystals
2 Circle diffratometer 2 and 3 and 4 circle diffractometer 2θ, ω, φ, χ 6 circle diffractometer θ, φ, χ and δ, γ, µ
www.serc.carleton.edu/Hong et al., Nuclear Instruments and Methods in Physics Research A 572 (2007) 942
NaCl crystals in a tube facing X-ray beam
Powder Diffractometer
Calculated Patterns for a Cubic Crystal
(100
)
(110
)
(200
)(1
11)
(210
)(2
11)
(220
)(3
30)(2
21)
(310
)(3
11)
(222
)(3
20)
(321
)
(400
)(4
10)
Structure Factor
2 ( )
1
n n n
Ni hu kv lw
hkl nF f e − h,k,l : indices of the diffraction plane under consideration − u,v,w : co-ordinates of the atoms in the lattice− N : number of atoms − fn : scattering factor of a particular type of atom
Bravais Lattice
Reflections possibly present
Reflections necessarily absent
Simple All NoneBody Centered
(h+k+l): Even (h+k+l): Odd
Face Centered
h, k, and l unmixed i.e. all odd or all even
h, k, and l: mixed
Intensity of the diffracted beam |F|2
Systematic Absences
Simple Cubic
(100), (110), (111), (200), (210), (211), (220), (300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..
Permitted Reflections
Diffraction Methods
Method Wavelength Angle Specimen
Laue Variable Fixed Single Crystal
Rotating Crystal
Fixed Variable (in part)
Single Crystal
Powder Fixed Variable Powder
Laue Method
• Uses Single crystal• Uses White Radiation• Used for determining crystal orientation and quality
Transmission
Zone axis
crystal
Incident beamFilm
Reflection Zone axis
crystal
Incident beam Film
Rotating Crystal Method
Determination of unknown crystal structures
Powder Method
• Useful for determining lattice parameters with high precision and for identification of phases
Incident Beam Sample
Film
Indexing a powder pattern
1
2
Sθ (for front reflections)or2W
Sθ 1 (for back reflections)2 W
Bragg’s Lawn = 2d sin
For cubic crystals
hkl 2 2 2
2 2
2 2 2 2
adh k l
which gives rise to
sin θh k l 4awhich is a constant
IndexingBCC
S1 (mm) () sin2 h2+k2+l2 sin2/ h2+k2+l2
Not BCC
38 19.0 0.11 2 0.055
45 22.5 0.15 4 0.038
66 33.0 0.30 6 0.050
78 39.0 0.40 8 0.050
83 41.5 0.45 10 0.045
97 49.5 0.58 12 0.048
113 56.5 0.70 14 0.050
118 59.0 0.73 16 0.046
139 69.5 0.88 18 0.049
168 84.9 0.99 20 0.050
Not Constant
Simple CubicS1 (mm) () sin2 h2+k2+l2 sin2/ h2+k2+l2
Not Simple Cubic
38 19.0 0.11 1 0.1145 22.5 0.15 2 0.7566 33.0 0.30 3 0.1078 39.0 0.40 4 0.1083 41.5 0.45 5 0.0997 49.5 0.58 6 0.097113 56.5 0.70 8 0.0925118 59.0 0.73 9 0.081139 69.5 0.88 10 0.088168 84.9 0.99 11 0.09
Not Constant
FCC; wavelength=1.54056ÅS1 (mm)
() sin2 h2+k2+l2
sin2/ h2+k2+l2
Lattice Parameter, a (Å)
38 19.0 0.11 3 0.037 4.02345 22.5 0.15 4 0.038 3.97866 33.0 0.30 8 0.038 3.97878 39.0 0.40 11 0.036 4.03983 41.5 0.45 12 0.038 3.97897 49.5 0.58 16 0.036 4.046113 56.5 0.70 19 0.037 4.023118 59.0 0.73 20 0.037 4.023139 69.5 0.88 24 0.037 4.023168 84.9 0.99 27 0.037 4.023
Constant; so it is FCC
But what is the lattice parameter?
Diffraction from a variety of materials
(From “Elements of X-ray Diffraction”, B.D. Cullity, Addison Wesley)
Reality
0.9cos
B
tB
Crystallite size can be calculated using Scherrer Formula
Instrumental broadening must be subtracted(From “Elements of X-ray Diffraction”, B.D. Cullity, Addison Wesley)
• polarization factor• structure factor (F2)• multiplicity factor• Lorentz factor• absorption factor• temperature factor
For most materials the peaks and their intensity are documented
JCPDS
ICDD
Intensity of diffracted beam
Name and formulaReference code: 00-001-1260
PDF index name: Nickel Empirical formula: NiChemical formula: NiCrystallographic parameters
Crystal system: Cubic Space group: Fm-3m
Space group number: 225a (Å): 3.5175 b (Å): 3.5175 c (Å): 3.5175 Alpha (°): 90.0000 Beta (°): 90.0000 Gamma (°): 90.0000
Measured density (g/cm^3): 8.90 Volume of cell (10^6 pm^3): 43.52
Z: 4.00 RIR: -Status, subfiles and quality
Status: Marked as deleted by ICDDSubfiles: InorganicQuality: Blank (B)
ReferencesPrimary reference: Hanawalt et al., Anal. Chem., 10, 475, (1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res. Council Bull. 107 Unit cell: The Structure of Crystals, 1st Ed.
http://ww1.iucr.org/cww-top/crystal.index.html
Stick pattern from JCPDS
Bulk electrodeposited nanocrystalline nickel
Lattice parameter, phase diagrams
Texture, Strain (micro and residual)
Size, microstructure (twins and dislocations)
Actual Pattern
Powder X-ray diffraction
is essentially a misnomer and should be replaced by
Polycrystalline X-ray diffraction
Information in a Diffraction Pattern
Phase Identification Crystal Size Crystal Quality Texture (to some extent) Crystal Structure
Analysis of Single PhaseIn
tens
ity (a
.u.)
2(˚) d (Å) (I/I1)*100
27.42 3.25 1031.70 2.82 10045.54 1.99 6053.55 1.71 556.40 1.63 3065.70 1.42 2076.08 1.25 3084.11 1.15 3089.94 1.09 5I1: 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 More Complex Several permutations combinations possible e.g. d1; d2; and d3, the first three strongest
lines show several alternatives Then take any of the two lines together and
match It turns out that 1st and 3rd strongest lies
belong to Cu and then all other peaks for Cu can be separated out
Now separate the remaining lines and normalize the intensities
Look for first three lines and it turns out that the phase is Cu2O
If more phases, more pain to solve
d (Å) I/I1
3.01 52.47 722.13 282.09 1001.80 521.50 201.29 91.28 181.22 41.08 201.04 30.98 50.91 40.83 80.81 10
*
*
*
*
**
*
Pattern for Cud (Å) I/I1
2.088 1001.808 461.278 201.09 171.0436
5
0.9038
3
0.8293
9
0.8083
8
Remaining Linesd
(Å)I/I1
Observed
Normalized
3.01
5 7
2.47
72 100
2.13
28 39
1.50
20 28
1.29
9 13
1.22
4 6
0.98
5 7
Pattern of Cu2O
d (Å) I/I1
3.020 9
2.465 100
2.135 37
1.743 1
1.510 27
1.287 17
1.233 4
1.0674
2
0.9795
4
Broadeing 2 2 tan
dbd
Lattice Strain
Non-uniform Strain
Uniform Strain
No Strain
do
2
2
2
d strain
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
[uvw] i.e. perpendicular to the surface of all grains is parallel to a direction [uvw]
Also, if the direction [u1v1w1] is parallel for all regions, the structure is like a single crystalHowever, the direction [u1v1w1] is not aligned for all regions, the structure is like a mosaic structure, also called as Mosaic Texture
Pole Figures
(100) pole figures for a sheet material(a) Random orientation (b) Preferred orientation
Thin Film Specimen
Smaller volume i.e. less intensity of the scattered beam from the film
Grazing angle Useful only for polycrystalline specimens
Substrate
Film or CoatingB BGrazing angle (very small, ~1-5)
Thin Film XRD Precise lattice constants measurements derived from 2-
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 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
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
(hkl) plane of the substrate
B B
Single Crystal SubstrateSingle Crystal Substrate
B1 B2
B1B2
i.e. No Diffraction from hkl plane
Diffraction from hkl plane occurs
Oriented thin films Bismuth Titanate
thin films on oriented SrTiO3
substrates Only one type of
peaks It apparent that
films are highly oriented
004 00
8
0010
0012 0014
0016
0018
0020 00
2200
24
0026
0028
△△
△
*
2216
△ △
014
4016
/04
16
△00
6 SrTiO3 (100)
SrTiO3 (110)
SrTiO3 (111)
Degree of orientation
Substrate
Film
Side view
[uvw] corresponding to planes parallel to the surface
But what if the planes when looked from top have random orientation?
Top view
Pole Figure
4 Peaks at ~50 Excellent in-
plane orientation
1
1
1
1
2
22
2
1
1
12
2
2
3
3
3
1
2
3
2 sets of peaks at ~ 5, 65 and 85°
Indicating a doublet or opposite twin growth
3 sets of peaks at ~ 35 and 85°
indicating a triplet or triple twin growth
(117) Pole Figures for Bismuth Titanate Films
SrTiO3 (100) SrTiO3 (110) SrTiO3 (111)
Texture Evolution
BNdT/SrTiO3 (111)
3 (100) planes inclined at 54.7° to (110) plane, separated by 120°STO(111)
54.7°
STO(111)
BNdT/SrTiO3 (110)
STO(110)
45
Two (100) planes inclined at 45° to (110) plane in opposite directions
BNdT/SrTiO3 (100)
BNdT [100
]
STO [100]
STO(100)
BNdT(001)
SrTiO3 (100)Film
Rocking Curve An useful method for evaluating the quality of oriented samples such
as epitaxial films is changed by rocking the sample but B is held constant Width of Rocking curve is a direct measure of the range of orientation
present in the irradiated area of the crystal
Inte
nsity
(a
.u.)
()17.5 17.6 17.7 17.8
FWHM = 0.07°
(0010) Rocking curve of (001)-oriented SrBi2Ta2O9 thin film
Inte
nsity
(a
.u.)
()32.4 32.6 32.8 33.0 33.2
(2212) Rocking curve of (116)-oriented SrBi2Ta2O9 thin film
FWHM = 0.171°
B
Normal
Order Disorder Transformation Structure factor is dependent on the
presence of order or disorder within a material
Present in systems such as Cu-Au, Ti-Al, Ni-Fe
Order-disorder transformation at specific compositions upon heating/cooling across a critical temperature
Examples: Cu3Au, Ni3Fe
Order Disorder Transformation Structure factor is dependent on the presence
of order or disorder within a material.
Complete Disorder Example: AB with A and B atoms
randomly distributed in the lattice Lattice positions: (000) and (½ ½ ½)Atomic scattering factor
favj= ½ (fA+fB)Structure Factor, F, is given by
F = Σf exp[2i (hu+kv+lw)] = favj [1+e( i (h+k+l))] = 2. favj when h+k+l is even = 0 when h+k+l is odd
The expected pattern is like a BCC crystal
AB
Order Disorder Transformation Complete Order Example: AB with A at (000) and B at (½
½ ½)
Structure Factor, F, is given by
F = fA e[2i (h.0+k.0+l.0)]+ fA e[2i (h. ½+k. ½+l. ½)]
= fA+fB when h+k+l is even = fA-fB when h+k+l is odd
The expected pattern is not like a BCC crystal, rather like a simple cubic crystal where all the reflections are present.
Extra reflections present are called as superlattice reflections
AB
Order-Disorder Transformation
Disordered Cu3Au
Ordered Cu3Au
Instrumentation
Diffractometer
Source
Optics
Detector
Source Incident Beam Optics
Sample Diffracted Beam Optics
Detector
Incident Beam Part Diffracted Beam Part
Geometry and Configuration
Source Incident Beam Optics
Sample Diffracted Beam Optics
Detector
Incident Beam Part Diffracted Beam Part
Theta-Theta Source and detector move θ, sample fixed
Theta-2Theta Sample moves θ and detector 2θ , source fixed
Vertical configuration Horizontal sample
Horizontal configuration Vertical sample
XYZ translation
Z translation sample alignment
Sample exactly on the diffractometer circle
Knife edge or laser
Video microscope with laser
XY movement to choose area of interest
Sample translation
X-ray generation X-ray tube (λ = 0.8-2.3 Ǻ)
Rotating anode (λ = 0.8-2.3 Ǻ)
Liquid metal
Synchrotron (λ ranging from infrared to X-ray)
Electrons
X-raysBe window
Metal anodeW cathode
X-ray tube
Rotating anode
Small angle anode Large angle anode
Small focal spot Large focal spot
Rotating anode of W or Mo for high flux
Microfocus rotating anode 10 times brighter
Liquid anode for high flux 100 times brighter and small beam size
Gallium and Gallium, indium, tin alloys
Synchrotron provides intense beam but access is limited
Brighter than a thousand suns
High brilliance and coherence
X-ray bulb emitting all radiations from IR to X-rays
http://www.coe.berkeley.edu/AST/srms
Synchrotron
Moving charge emits radiation
Electrons at v~c
Bending magnet, wiggler and undulator
Straight section wiggler and undulator
Curved sections Bending magnet
Filter to remove Kβ For eg. Ni filter for Cu Kβ
Reduction in intensity of Kα
Choice of proper thickness
Slits To limit the size of beam (Divergence slits)
To alter beam profile (Soller slit angular divergence ) Narrow slits Lower intensity + Narrow peak
Mirror focusing and remove Kα2
Mono-chromator remove Kα2
Si Graphite
Beam Profile
Detector
Sample
Mirror
Source
Soller slit
Mirror
Detector
Sample
Source
Parallel beam
Para-focusing
Detector
Sample
SourcePoint focus
ComparisonParallel beam Para-focusingX-rays are aligned X-rays are divergingLower intensity for bulk samples
Higher intensity
Higher intensity for small samples
Lower intensity
Instrumental broadening independent of orientation of diffraction vector with specimen normal
Instrumental broadening dependent of orientation of diffraction vector with specimen normal
Suitable for GI-XRD Suitable for Bragg-Brentano
Texture, stress Powder diffraction
Detectors
Single photon detector (Point or 0D) scintillation detector NaI proportional counter, Xenon gas semiconductor
Position sensitive detector (Linear or 1D) gas filled wire detectors, Xenon gas charge coupled devices (CCD)
Area detectors (2D) wire CCD
3D detector
X-ray photon
Photoelectron orElectron-hole pair
Photomultiplier tube oramplifier Electrical signal
Resolution: ability to distinguish between energies
Energy proportionality: ability to produce signal proportioanl to energy of x-ray photon detected
Sensitivity: ability to detect low intensity levels
Speed: to capture dynamic phenomenon
Range: better view of the reciprocal space
Data collection and analysis
Choose 2θ range
Step size and time per step
Hardware: slit size, filter, sample alignment
Fast scan followed with a slower scan
Look for fluorescence
Collected data: Background subtraction, Kα2 stripping
Normalize data for comparison I/Imax
Summary X-ray Diffraction is a very useful to characterize
materials for following information Phase analysis Lattice parameter determination Strain determination Texture and orientation analysis Order-disorder transformation and many more things
Choice of correct type of method is critical for the kind of work one intends to do.
Powerful technique for thin film characterization