X-ray Diffraction

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

NanoLab/NSF NUE/Bumm

X-ray Diffraction
Bragg¶s Law Lattice Constants Laue Conditions - 2 Scan Scherrer¶s Formula Data Analysis Examples

NanoLab/NSF NUE/Bumm

Bragg¶s 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 condition¶s
The diffraction condition can be written in vector form 2k·G + G2 = 0 k - is the incident wave vector k¶ - is the reflected wave vector G - is a reciprocal lattice vector such that where G = ¨k = k - k¶ the diffraction condition is met

NanoLab/NSF NUE/Bumm

Lattice Constants
The distance between planes of atoms is d(hkl) = 2 / |G| hkl) |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) hkl) (h Or a = d * (h2 + k2 + l2)(1/2) a is the spacing between nearest neighbors
NanoLab/NSF NUE/Bumm

Laue Conditions
a1·¨k = 2 1 a2·¨k = 2 a3·¨k = 2 3
2

Each of the above describes a cone in reciprocal space about the lattice vectors a1, a2, and a3.  the i are integers When a reciprocal lattice point intersects this cone the diffraction condition is met, this is generally called the Ewald sphere.
NanoLab/NSF NUE/Bumm

Summary of Bragg & Laue
When a diffraction condition is met there can be a reflected X-ray X

Extra atoms in the basis can suppress reflections

nP d! 2 sin U

Three variables , , and d  is known  is measured in the experiment (2 )  d is calculated

a ! d h k l

2

2

2

From the planes (hkl) (hkl) 
NanoLab/NSF NUE/Bumm

a is calculated

- 2 Scan
The - 2 scan maintains these angles with the sample, detector and X-ray source XNormal to surface

Only planes of atoms that share this normal will be seen in the
NanoLab/NSF NUE/Bumm

- 2 Scan

- 2 Scan
The incident X-rays may reflect in many directions Xbut 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.
NanoLab/NSF NUE/Bumm

- 2 Scan

NanoLab/NSF NUE/Bumm

Smaller Crystals Produce Broader XRD Peaks

Scherrer¶s Formula
K P t! B  cosUB
t = thickness of crystallite K = constant dependent on crystallite shape (0.89) P = x-ray wavelength B = FWHM (full width at half max) or integral breadth UB = Bragg Angle

Scherrer¶s Formula
What is B? B = (2 High) ± (2 Low) B is the difference in angles at half max
Peak 2 low 2 high

Noise

When to Use Scherrer¶s Formula 


Crystallite size <1000 Å 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 20%-

Sherrer¶s Formula References Corman, D. Scherrer¶s 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 Scherrer¶s 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!

Scherrer¶s Example
Au Foil
10000 9000 8000 7000 6000 Counts 5000 4000 3000 2000 1000 0 2 The a
      £         ¢

98 25 400
¡  

95

95 5

96

96 5

97

97 5

98

98 5

99

99 5

100

100 5

101

101 5

102

Scherrer¶s Example
0.89  P t! B  cos U B
t = 0.89* / (B Cos (B
= 0.89*1.54 0.89*1.54 / ( 0.00174 * Cos (98.25/ 2 ) )
B)

= 1.54

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