X-Ray Diffraction

➢ It is a scientific method used to determine the arrangement of atoms of a crystalline

solid in three dimensional space.
➢ This technique takes advantage of the interatomic spacing of most crystalline solids by
employing them as a diffraction gradient for X-ray light, which has wavelengths on the
order of 1 angstrom (1Å) . 1Å
0.1 nm
➢ Bragg law: 2𝑑sin𝜃 = 𝑛𝜆 10-10 m
➢ Bragg law can be utilized in 2 ways: 10-8 cm

▪  known, measure , determine 𝑑 ⟹ structure analysis

▪ use crystal with planes of known 𝑑, measure , determine wavelength  of radiation
used  X-Ray spectroscopy

1
 X-Ray Powder Diffraction (XRD)
➢ A rapid analytical technique primarily used for phase identification of a crystalline material and
can provide information on unit cell dimensions.
➢ The analyzed material is finely ground, homogenized, and average bulk composition is
determined.
➢ In powder X-ray diffraction, the diffraction pattern is obtained from a powder of the material,
rather than an individual crystal.
➢ Powder diffraction is often easier and more convenient than single crystal diffraction since it
does not require individual crystals be made.
➢ Powder X-ray diffraction (XRD) also obtains a diffraction pattern for the bulk material of a
crystalline solid, rather than of a single crystal, which doesn't necessarily represent the overall
material. A diffraction pattern plots intensity against the angle of the detector, 2θ.

2
3
 Diffractometer Method

❖ In current conventional XRD, two types of scan available:

➢ Powder scan
Incident angle  is varied and detector position is matched to always keep at 2 angle.
Measures every possible orientation of the unit cell in the sample.
➢ Thin film scan
Incident angle  is fixed and detector position is carried to measure every possible
diffraction angle. Measures the orientation of the unit cell with respect to the holder
(orientation of the film).

4
Strengths
✓ Powerful and rapid (< 20 min) technique for identification of an unknown
mineral
✓ In most cases, it provides an unambiguous mineral determination
✓ Minimal sample preparation is required
✓ XRD units are widely available
✓ Data interpretation is relatively straight forward

Limitations
✓ Homogeneous and single phase material is best for identification of an
unknown
✓ Must have access to a standard reference file of inorganic compounds (d-
spacings, hkls)
✓ Requires tenths of a gram of material which must be ground into a
powder
✓ For mixed materials, detection limit is ~ 2% of sample
✓ For unit cell determinations, indexing of patterns for non-isometric crystal
systems is complicated
✓ Peak overlay may occur and worsens for high angle 'reflections'

5
 ASTM diffraction data card
Material & Formula
ASTM – American Society for Testing Materials
JCPDS No.

Lattice constant, a

Lattice spacing
X-Ray Wavelength, 

Crystal Structure
(hkl)
Lattice constants, a & c

Diffraction intensity

6
7
Gold
FCC
9
10
α-MnO2 nanowires

11
12
13
14
15
5D operando tomographic diffraction imaging of a catalyst bed

16
Sodium (NaCl) Unit Cell

FCC
PDF2 Data: NaCl
NaCl Powder
Curve Fitting – Peak Position, Peak Width and Peak Intensity
d-spacings and Lattice Parameters
✓ Crystal Structure Determination

Silicon (Si) Unit Cell

Diamond
23
 Si in Powder Form
500
Si (111) Si (220)
400

Intensity (cps)
300
Si (311)
200
Amorphous
100

0
10 15 20 25 30 35 40 45 50 55 60
2θ(o)
Scherrer equation:

d = 0.9 / B cos ( B )
where 0.9, , B, B are the Scherrer’s constant, wavelength of Cu-K X-ray source
(=1.5402Å), full width of half-maximum (FWHM) of the diffraction peak and the
peak position at 2B, respectively
 50
45 Silicon
40
35
Intensity (a.u.)

Si 30
25 (311)
Diamond 20 (111)
(220)
15
10
5
0
10 20 30 40 50 60 70 80
2 (Degree)
 Si in Thin Film Form

10
14
9

12 8
7
2 nm
10
6

Intensity
Intensity

8 5
2 nm
18 nm 4
6 3
2
3
1
1 0
20 22 24 26 28 30 32 34 36 38 40 20 22 24 26 28 30 32 34 36 38 40
2 2

Decomposition of the peak at 28 o in the XRD spectrum using Gaussian multi

peaks fitting