X-ray Diffraction

The Basics
Followed by a few examples of
Data Analysis
by
Wesley Tennyson

NanoLab/NSF NUE/Bumm

X-ray Diffraction
Braggs Law
Lattice Constants
Laue Conditions
- 2 Scan
Scherrers Formula
Data Analysis Examples

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Braggs Law
n = 2 d sin
Constructive interference only occurs for certain s
correlating to a (hkl) plane, specifically when the path
difference is equal to n wavelengths.

Bragg conditions
The diffraction condition can be written in vector
form
2kG + G2 = 0
kk G-

is the incident wave vector

is the reflected wave vector
is a reciprocal lattice vector such that where
G = k = k - k
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the diffraction condition is met
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Lattice Constants
The distance between planes of atoms is
d(hkl) = 2 / |G|
Since G can be written as
G = 2/a (h*b1+ k*b2 +l*b3)
Substitute in G
d(hkl) = a / (h2 + k2 + l2)(1/2)
Or
a = d * (h2 + k2 + l2)(1/2)
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a is the spacing between nearest neighbors
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Laue Conditions
a1k = 21
a2k = 22
a3k = 23
Each of the above describes a cone in reciprocal
space about the lattice vectors a1, a2, and a3.
the are integers
i
When a reciprocal lattice point intersects this cone the
diffraction condition is met, this is generally called
the Ewald sphere.
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Summary of Bragg & Laue

When a diffraction
condition is met there can
be a reflected X-ray

Extra atoms in the basis can

suppress reflections

Three variables , , and d

is known
is measured in the
experiment (2)
d is calculated

From the planes (hkl)

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a is
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calculated

n
d
2 sin

a d h k l
2

 - 2 Scan
The - 2 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 - 2 Scan
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 - 2 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 (i) = Angle of reflection (r)
This is done by moving the detector twice as fast
in as the source. So, only where i = r is the
intensity of the reflect wave (counts of photons)
measured.

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 - 2 Scan

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Smaller Crystals Produce Broader XRD Peaks

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

Scherrers Formula
What is B?
B = (2 High) (2 Low)

Peak

2 high

2 low

B is the difference in
angles at half max

Noise

When to Use Scherrers Formula

Crystallite size <1000

Peak broadening by other factors

Causes of broadening
Size
Strain
Instrument

If breadth consistent for each peak then assured

broadening due to crystallite size

K depends on definition of t and B

Within 20%-30% accuracy at best

Sherrers Formula References

Corman, D. Scherrers Formula: Using XRD to Determine Average Diameter of Nanocrystals.

Data Analysis
Plot the data (2 vs. Counts)
Determine the Bragg Angles for the peaks
Calculate

d and a for each peak

Apply Scherrers Formula to the peaks

Bragg Example

Bragg Example
d = / (2 Sin B)
= 1.54
= 1.54 / ( 2 * Sin ( 38.3 / 2 ) )
= 2.35
Simple Right!

Scherrers Example

Scherrers Example
0.89
t
B cos B
t = 0.89* / (B Cos B)

= 1.54

= 0.89*1.54 / ( 0.00174 * Cos (98.25/ 2 ) )

= 1200
B = (98.3 - 98.2)*/180 = 0.00174
Simple Right!