X-ray Diffraction (XRD)

X-ray Diffraction: Applications

• Lattice Constants
• Crystal Size (Scherrer’s Formula)
• Crystal Quality
 Crystal (Size)
• Bulk Crystal
• Micro Crystal
• Nano Crystal
 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
[FCC –Cubic]

• 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.
 X-Ray Powder Diffraction (XRPD) uses information about
the position, intensity, width, and shape of diffraction peaks
in a pattern from a polycrystalline sample.

The x-axis, 2theta, corresponds to the angular position of the detector

that rotates around the sample.
 Principle of XRD: Bragg’s Law
nλ = 2 d sin θ
• Constructive interference only occurs for certain θ’s
correlating to a (hkl) plane, specifically when the path
difference is equal to n wavelengths.
 Bragg’s law is a simplistic model to understand
what conditions are required for diffraction.

l = 2d hkl sin q q q

dhkl dhkl
• 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 l is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific angle q.
– Additionally, 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
• The space between diffracting planes of atoms determines peak positions.
• The peak intensity is determined by what atoms are in the diffracting plane.
 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
 Our powder diffractometers typically use the
Bragg-Brentano geometry.

Detector
X-ray
tube

w q 2q

• The incident angle, w, is defined between the X-ray source and the sample.
• The diffracted angle, 2q, is defined between the incident beam and the
detector angle.
• The incident angle w is always ½ of the detector angle 2q .
• In a q:2q instrument (e.g. Rigaku RU300), the tube is fixed, the sample
rotates at q °/min and the detector rotates at 2q °/min.
• In a q:q instrument (e.g. PANalytical X’Pert Pro), the sample is fixed and the
tube rotates at a rate -q °/min and the detector rotates at a rate of q °/min.
q:2qScan
OR
q:q Scan
Scan OR
q:2q Scan
Most of our powder diffractometers use the Bragg-
Brentano parafocusing geometry.
• A point detector and sample are
moved so that the detector is
always at 2q and the sample
surface is always at q to the
incident X-ray beam.
• In the parafocusing arrangement,
the incident- and diffracted-beam
slits move on a circle that is
centered on the sample. Divergent
X rays from the source hit the
sample at different points on its
surface. During the diffraction
process the X rays are refocused F: the X-ray source
at the detector slit. DS: the incident-beam divergence-limiting slit
SS: the Soller slit assembly
• This arrangement provides the S: the sample
best combination of intensity, peak RS: the diffracted-beam receiving slit
shape, and angular resolution for C: the monochromator crystal
AS: the anti-scatter slit
the widest number of samples.
 θ - 2θ Scan
The incident X-rays may reflect in many directions
but will only be measured at one location so we
will require that:

Angle of incidence (θi) = Angle of reflection (θr)

This is done by moving the detector twice as fast

in θ as the source. So, only where θi = θr is the
intensity of the reflect wave (counts of photons)
measured.
q:q Scan
 A single crystal specimen in a Bragg-Brentano
diffractometer would produce only one family of peaks in
the diffraction pattern.

2q

At 20.6 °2q, Bragg’s law
fulfilled for the (100) planes,
producing a diffraction peak.
The (110) planes would diffract at 29.3
°2q; however, they are not properly
aligned to produce a diffraction peak
(the perpendicular to those planes does
not bisect the incident and diffracted
beams). Only background is observed.
The (200) planes are parallel to the (100)
planes. Therefore, they also diffract for this
crystal. Since d200 is ½ d100, they appear at
42 °2q.
 A polycrystalline sample should contain thousands of
crystallites. Therefore, all possible diffraction peaks should
be observed.

2q 2q 2q

• 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.
 θ - 2θ Scan
The θ - 2θ scan maintains these angles with the
sample, detector and X-ray source
Normal to surface

Only planes of atoms that share this normal will be seen in the θ - 2θ Scan
 XRD: Lattice Constant
• When a diffraction
condition is met there can nl
be a reflected X-ray d=
– Extra atoms in the basis can 2 sin q
suppress reflections
• Three variables λ, θ, and d
– λ is known
– θ is measured in the
experiment (2θ)
– d is calculated
For cubic
• From the planes (hkl)
– a is calculated a = d h +k +l
2 2 2
 XRD: Crystal Systems
Crystal System Rotational symmetry Cell dimension constraints

• Triclinic 1-fold none

• Monoclinic 2-fold α=γ=90 degrees
• Orthorhombic three perpendicular 2-folds α=β=γ=90 degrees
• Tetragonal 4-fold a=b, α=β=γ=90 degrees
• Trigonal 3-fold a=b, α=β=γ=120 degrees
• Hexagonal 6-fold a=b, α=β=γ=120 degrees
• Cubic 3 and 2-folds a=b=c, α=β=γ=90 degrees
θ - 2θ Scan
 Methods used to Define Peak Width
• Full Width at Half Maximum
(FWHM)
– the width of the diffraction peak, FWHM

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

• Integral Breadth
– the total area under the peak
divided by the peak height 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
2q (deg.)
– the width of a rectangle having
the same area and the same
height as the peak
Intensity (a.u.)
– requires very careful evaluation
of the tails of the peak and the
background
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
2q (deg.)
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
 Scherrer’s Formula

K *l
t=
B * cos q B

t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
l = x-ray wavelength
B = FWHM (full width at half max) or integral breadth
qB = Bragg Angle
 Data Analysis

• Plot the data (2θ vs. Counts)

• Determine the Bragg Angles for the peaks
• Calculate d and a for each peak
• Apply Scherrer’s Formula to the peaks
 Scherrer’s Example
Au Foil

10000

9000

8000

98.25 (400)
7000

6000
Counts

5000

4000

3000

2000

1000

0
95 95.5 96 96.5 97 97.5 98 98.5 99 99.5 100 100.5 101 101.5 102
2 Theta
 Scherrer’s Example
0.89 * l
t=
B * cos q B
t = 0.89*λ / (B Cos θB) λ = 1.54 Ǻ
= 0.89*1.54 Ǻ / ( 0.00174 * Cos (98.25/ 2 ) )
= 1200 Ǻ

B = (98.3 - 98.2)*π/180 = 0.00174

 Example:

5000

4000 39.2
2 2 0

3000
Intensity (count)

23.83
1 1 1
2000
71.34
4 2 2
62.4
1000 46.5 3 3 1 76.4
3 1 1 5 1 1

20 30 40 50 60 70 80
2 Theta
Peak No. 2Ɵ hkl h2+k2+l2 ‘a’ A.U. Mean ‘a’ A.U.

1 111 3
23.86 6.470993

2 220 8
39.42 6.470207

3 311 11
46.5 6.512322 6.483075

4 331 19
62.5 6.482062

5 422 24
71.3 6.479792
Bragg Example
Diffraction patterns are best reported using dhkl and relative
intensity rather than 2q and absolute intensity.
• The peak position as 2q 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 2q 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.
 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 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
 X-ray Diffraction
• Bragg’s Law
• Lattice Constants
• Laue Conditions
• θ - 2θ Scan
• Scherrer’s Formula
• Data Analysis Examples