Hanoi university of science and

technology
School of materials science

Indexing X-Ray Diffraction Patterns

Report lab 1

Student name: Lưu Hải Đồng

ID: 20216988
MSE 3317 - 747463

LEARNING OBJECTIVES
Upon completion of this module, you will be able to index an X-ray diffraction
pattern, identify the Bravais lattice, and calculate the lattice parameters for
crystalline materials.

BACKGROUND

We need to know about crystal structures because structures largely determine

properties. X-ray diffraction (XRD) is one of several experimental tools that are used
to identify the structures of crystalline solids.
The XRD patterns, the product of an XRD experiment, are somewhat like
fingerprints in that they are unique to the material that is being examined. The
information in an XRD pattern is a direct result of two things:
(1) The size and shape of the unit cells determine the relative positions of the
diffraction peaks.
(2) Atomic positions within the unit cell determine the relative intensities of the
diffraction peaks (remember the structure factor?).
Taking these things into account, we can calculate the size and shape of a unit cell
from the positions of the XRD peaks and we can determine the positions of the
atoms in the unit cell from the intensities of the diffraction peaks.
Full identification of crystal structures is a multi-step process that consists of:
(1) Calculation of the size and shape of the unit cell from the XRD peak positions.
(2) Computation of the number of atoms/unit cell from the size and shape of the
cell, chemical composition, and measured density.
(3) Determination of atom positions from the relative intensities of the XRD peaks
We will only concern ourselves with step (1), calculation of the size and shape of the
unit cell from XRD peak positions. We loosely refer to this as “indexing.” The
laboratory module is broken down into two sections. The first addresses how to
index patterns from cubic materials. The second addresses how to index patterns
from non-cubic materials.

PROCEDURE FOR INDEXING CUBIC XRD PATTERNS

When you index a diffraction pattern, you assign the correct Miller indices to each
peak (reflection) in the diffraction pattern. An XRD pattern is properly indexed when
ALL of the peaks in the diffraction pattern are labeled, and no peaks expected for
the particular structure are missing.
This is an example of a properly indexed diffraction pattern. All peaks are accounted
for. One now needs only to assign the correct Bravais lattice and to calculate lattice
parameters.
How to we correctly index a pattern? The correct procedures follow.

PROCEDURE FOR INDEXING AN XRD PATTERN

The procedures are standard. They work for any crystal structure regardless of
whether the material is a metal, a ceramic, a semiconductor, a zeolite, etc.... There
are two methods of analysis. You will do both. One I will refer to is the mathematical
method. The second is known as the analytical method. The details are covered
below.
Mathematical Method
Interplanar spacings in cubic crystals can be written in terms of lattice parameters
using the plane spacing equation:

You should recall Bragg’s law ( ), which can be re-written either as:
Combining this relationship with the plane spacing equation gives us a new
relationship:

which can be rearranged to:

( )
2
λ
The term in parentheses 2 is constant for any one pattern (because the X-
4a
ray wavelength λ and the lattice parameters a do not change). Thus sin2 θis
proportional to h2 + k 2+l 2 This proportionality shows that planes with higher
Miller indices will diffract at higher values of θ.

( )
2
λ
Since 2 is constant for any pattern, we can write the following
4a
relationship for any
two different planes:

The ratio
of sin2 θ values scales with the ratio of h2 + k 2+l 2 values.
In cubic systems, the first XRD peak in the XRD pattern will be due to
diffraction from planes with the lowest Miller indices, which are the close
packed planes (i.e.: simple cubic, (100), h2 + k 2+l 2 =1; body-centered cubic
2 2 2 2 2 2
(110), h + k +l =2; and face-centered cubic (111) h + k +l =3
Since h, k, and l are always integers, we can obtain h2 + k 2+l 2 values by
dividing the sin2 θ values for the different XRD peaks with the minimum one in
the pattern (i.e., the sin2 θ value from the first XRD peak) and multiplying that
ratio by the proper integer (either 1, 2 or 3). This should yield a list of
integers that represent the various h2 + k 2+l 2 values. You can identify the
correct Bravais lattice by recognizing the sequence of allowed reflections for
cubic lattices (i.e., the sequence of allowed peaks written in terms of the
quadratic form of the Miller indices).

The lattice parameters can be calculated from:

which can be re-written as:

Worked Example

Materials: aluminum Radiation: Cu Kα λ=1.54056( A °)

2 2
2
sin ⁡(θ)
2
sin ⁡(θ) sin ⁡(θ) sin ⁡(θ)
2q ×2 ×3 2 2
h + k +l
2
a(Ao)
sin ⁡(θ)2 min sin ⁡(θ)2 min sin ⁡(θ)2 min
1 38.5 0.109 1 15.9262 3 3 4.044
2
2 44.7 0.145 1.330 2.660 3.990 4 4.046
6
3 65.1 0.289 2.651 5.302 7.953 8 4.047
4
4 78.2 0.389 3.651 7.302 10.953 11 4.0481
6 7
5 82.4 0.434 3.981 7.962 11.943 12 4.0481
7 4
6 99.1 0.579 5.311 10.622 15.933 16 4.0486
1
7 112. 0.688 6.331 12.331 18.933 19 4.049
03
8 116. 0.724 6.642 13.284 19.926 20 4.0488
6
9 137. 0.868 7.963 15.926 23.889 24 4.05
47
 Avg:
4.0477
46

+ Bravais lattice of aluminum is Face-Centered Cubic

+ Average lattice parameter is 4.047746 Ao

XRD pattern of iron

Material: iron Radiation: Cu Kα λ=1.54056( A °)

2
sin ⁡(θ) 2
sin ⁡(θ)
2
sin ⁡(θ) 2 2 2
2q ×2 h + k +l a(Ao)
sin ⁡(θ)2 min sin ⁡(θ)2 min
1 44.73 0.145 1 2 2 2.86075
2 65.07 0.289 1.993 3.986 4 2.86569
3 82.4 0.434 2.993 5.986 6 2.86404
4 99 0.578 3.986 7.972 8 2.86569
5 116.45 0.723 4.986 9.972 10 2.8647
6 137.24 0.867 5.979 11.959 12 2.86569
Avg:
2.86443
+ Bravais lattice of iron is Body-Centered Cubic
+ Average lattice parameter is 2.86443 Ao

XRD pattern of Silicon

Material: silicon Radiation: Cu Kα λ=1.54056( A °)

2 2 2
2 sin ⁡(θ) sin ⁡(θ) sin ⁡(θ) 2 2 2
2q sin ⁡(θ) ×2 ×3 h + k +l a(Ao)
sin ⁡(θ)2 min sin ⁡(θ)2 min sin ⁡(θ)2 min
1 28.4 0.06 1 2 3 3 5.4467
1
2 47.3 0.161 2.683 5.367 8.049 8 5.42976
5
3 56.1 0.221 3.683 7.367 11.049 11 5.43437
2
4 69.1 0.322 5.366 10.733 16.098 16 5.42976
5 76.3 0.382 6.366 12.733 19.098 19 5.43243
5
6 88.0 0.483 8.050 16.100 24.150 24 5.42976
4
7 94.9 0.543 9.050 18.100 27.150 27 5.43164
4
 8 106. 0.644 10.733 21.467 32.199 32 5.42976
75
9 114. 0.704 11.733 23.467 35.199 35 5.43121
11
1 127. 0.805 13.416 26.833 40.248 40 5.42976
0 56
1 136. 0.865 14.416 28.833 43.248 43 5.43094
1 91
Avg:
5.43237

+ Bravais lattice of silicon is Diamond Cubic

+ Average lattice parameter is 5.43237 Ao