X-Ray Diffraction

Analysis

Dr. Majid Khan

Instrument Settings
• Source
– Cu Kα
• Slits
• Angle Range
– Increment
– Rate (deg/min)
• Detector

Bruker D8 Focus
Geometry and Configuration
 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

Incident Beam Part Diffracted Beam Part

Sample Diffracted Beam

Optics
Source Incident Beam Detector
Optics
 Measurements

Detector
Motorized
X-ray Source Slits
tube
Φ

w q 2q

• Measurements:
– The incident angle w is always ½ of the detector angle 2q .
– The x-ray source is fixed, the sample rotates at q °/min and the detector
rotates at 2q °/min.
• Angles
– The incident angle (ω) is between the X-ray source and the sample.
– The diffracted angle (2q) is between the incident beam and the detector.
– In plane rotation angle (Φ)
 Bragg’s law and Peak Positions.

l  2d hkl sin q

• For parallel planes of atoms, with a space dhkl between the planes,
constructive interference only occurs when Bragg’s law is satisfied.
– First, the plane normal must be parallel to the diffraction vector
• Plane normal: the direction perpendicular to a plane of atoms
• Diffraction vector: the vector that bisects the angle between the incident and diffracted
beam
– X-ray wavelengths l are:
• Cu Kα1=1.540598 Å and Cu Kα2=1.544426 Å
• Or Cu Kα(avg)=1.54278 Å
– dhkl is dependent on the lattice parameter (atomic/ionic radii) and the crystal
structure
Diffraction
 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
 Information in a Diffraction Pattern

• Phase Identification
• Crystal Size
• Crystal Quality
• Texture (to some extent)
• Crystal Structure
Sample Preparation

Crystal Orientation Matters

 Orientations Matter in Single Crystals
(a big piece of rock salt)

200

220

111 222
311

2q

At 27.42 °2q, Bragg’s law The (200) planes would diffract at 31.82 The (222) planes are parallel to the (111)
fulfilled for the (111) planes, °2q; however, they are not properly planes.
producing a diffraction peak. aligned to produce a diffraction peak
 For phase identification you want a random powder
(polycrystalline) sample

200

220

111 222
311

2q 2q 2q

• When thousands of crystallites are sampled, for every set of planes, there will be a small
percentage of crystallites that are properly oriented to diffract
• All possible diffraction peaks should be exhibited
• Their intensities should match the powder diffraction file
Sample Preparation

Inducing Texture In A Powder

Sample
 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
• 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
• 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
 Texture in Samples
• Common Occurrences • How to Prevent
– Plastically deformed metals – Grind samples into fine
(cold rolled) powders
– Powders with particle – Unfortunately you can’t or
shapes related to their don’t want to do this to
crystal structure many samples.
• Particular planes form the faces
• Elongated in particular
directions (Plates, needles,
acicular,cubes, etc.)
Phase Identification
One of the most important uses of
XRD
Phase Identification
Indexing and lattice constants determination
 Indexing
FCC; wavelength=1.54056Å
Simple
BCCCubic
SS1 (mm) q() q() sin2q h22+k
sin
2 2
q +l hsin
2q/
22+k 22 2+k2sin
22+lh +l2 22q/ Lattice
h22+k22+l22Parameter, a (Å)
1
(mm)
38 19.0 0.11 21 0.11
0.055
38 19.0 0.11 3 0.037 4.023
45 22.5 0.15 42 0.75
0.038
45 22.5 0.15 4 0.038 3.978
66 33.0 0.30 63 0.10
0.050
66 33.0 0.30 8 0.038 3.978
78 39.0 0.40 84 0.10
0.050
78 39.0 0.40 11 0.036 4.039 Not
NotSimple
BCC
83 41.5 0.45 5
10 0.09
0.045
Cubic
83 41.5 0.45 12 0.038 3.978
97 49.5 0.58 6
12 0.097
0.048
97 49.5 0.58 16 0.036 4.046
113 56.5 0.70 8
14 0.0925
0.050
113 56.5 0.70 19 0.037 4.023
118 59.0 0.73 9
16 0.081
0.046
118 59.0 0.73 20 0.037 4.023
139 69.5 0.88 10
18 0.088
0.049
139 69.5 0.88 24 0.037 4.023
168 84.9 0.99 11
20 0.09
0.050
168 84.9 0.99 27 0.037 4.023
Not Constant
Constant; so it is FCC
 For cubic structures it is often possible to
distinguish crystal structures by considering
the periodicity of the observed reflections.

a2
d hkl 
h2  k 2  l 2
ICCD: JCPDS Files
 Many factors may contribute to
the observed peak profile
• Instrumental Peak Profile
– Slits
– Detector arm length
• Crystallite Size
• Microstrain
– Non-uniform Lattice Distortions (aka non-uniform strain)
– Faulting
– Dislocations
– Antiphase Domain Boundaries
– Grain Surface Relaxation
• Solid Solution Inhomogeneity
• Temperature Factors

• The peak profile is a convolution of the profiles from all of

these contributions
 Crystallite Size Broadening
0.94l
B2q  
Size cosq
• Peak Width B(2q) varies inversely with crystallite size
• The constant of proportionality, K (the Scherrer constant) depends
on the how the width is determined, the shape of the crystal, and
the size distribution
– The most common values for K are 0.94 (for FWHM of spherical
crystals with cubic symmetry), 0.89 (for integral breadth of spherical
crystals with cubic symmetry, and 1 (because 0.94 and 0.89 both
round up to 1).
– K actually varies from 0.62 to 2.08

• Remember:
– Instrument contributions must be subtracted
Strain Effects
Peak Shifts
and
Peak Broadening
 Methods used to Define Peak Width
• Full Width at Half Maximum
(FWHM) FWHM
– the width of the diffraction

Intensity (a.u.)
peak, in radians, at a height
half-way between background
and the peak maximum

• Integral Breadth 46.7 46.8 46.9 47.0 47.1 47.2 47.3 47.4 47.5 47.6 47.7 47.8 47.9

– the total area under the peak 2q (deg.)

divided by the peak height

– the width of a rectangle
Intensity (a.u.)
having the same area and the
same height as the peak
– requires very careful
evaluation of the tails of the 46.7 46.8 46.9 47.0 47.1 47.2 47.3 47.4 47.5 47.6 47.7 47.8 47.9

peak and the background 2q (deg.)

 Williamson-Hull Plot
K l
FWHM  cosq    Strain  4  sinq 
Size

y-intercept slope
(FWHMobs-FWHMinst)
cos(q )

Grain size broadening

4 x sin(q) K≈0.94
Gausian Peak Shape Assumed
 Which of these diffraction patterns comes
from a nanocrystalline material?

Intensity (a.u.) Hint: Why are the

intensities different?

66 67 68 69 70 71 72 73 74

2q (deg.)
• These diffraction patterns were produced from the exact same
sample
• The apparent peak broadening is due solely to the
instrumentation
– 0.0015° slits vs. 1° slits
 Remember, Crystallite Size is
Different than Particle Size
• A particle may be made up of several different
crystallites
• Crystallite size often matches grain size, but there are
exceptions
 Crystallite Shape
• Though the shape of crystallites is usually irregular, we can often
approximate them as:
– sphere, cube, tetrahedra, or octahedra
– parallelepipeds such as needles or plates
– prisms or cylinders
• Most applications of Scherrer analysis assume spherical crystallite
shapes
• If we know the average crystallite shape from another analysis, we
can select the proper value for the Scherrer constant K

• Anistropic peak shapes can be identified by anistropic peak

broadening
– if the dimensions of a crystallite are 2x * 2y * 200z, then (h00) and (0k0)
peaks will be more broadened than (00l) peaks.
Crystal Structure
vs.
Chemistry
 Two Perovskite Samples
• What are the differences?
Assume that they are both
– Peak intensity random powder samples
– d-spacing
• Peak intensities can be strongly affected by changes in electron density due
to the substitution of atoms with large differences in Z, like Ca for Sr.

SrTiO3 and
CaTiO3

200 210 211

2θ (Deg.)
 Two samples of Yttria stabilized Zirconia
Why might the two patterns differ?
• Substitutional Doping can change bond distances, reflected by a change in
unit cell lattice parameters
• The change in peak intensity due to substitution of atoms with similar Z is
much more subtle and may be insignificant

10% Y in ZrO2
50% Y in ZrO2
Intensity(Counts)

R(Y3+) = 0.104Å
R(Zr4+) = 0.079Å

45 50 55 60 65
2θ (Deg)
 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
Assignment # 1
Peak Intensities