EXPERIMENTAL MODULE 1

Crystal Structure Determination.

I: Cubic Structures

OBJECTIVE OF THE EXPERIMENT

To index the x-ray diffraction pattern, identify the Bravais lattice, and
calculate the lattice parameters of some common materials with a cubic
structure.

MATERIALS REQUIRED

Fine powders (-325 mesh, <45/lm in size) of chromium (Cr), copper

(Cu), iron (Fe), nickel (Ni), silicon (Si), and titanium nitride (TiN).

BACKGROUND AND THEORY

A knowledge of crystal structure is a prerequisite to understand

phenomena such as plastic deformation, alloy formation, and phase
transformations. Recall that the size and shape of the unit cell determine
the angular positions of the diffraction peaks, and the arrangement of the
atoms within the unit cell determines the relative intensities of the peaks.
Thus, it is possible to calculate the size and shape of the unit cell from the
angular positions of the peaks and the atom positions in the unit cell
(though not in any direct manner) from the intensities of the diffraction
peaks.
Complete determination of an unknown crystal structure consists of
three steps:

97
98 II • Experimental Modules

1. Calculation of the size and shape of the unit cell from the angular
positions of the diffraction peaks
2. Computation of the number of atoms per unit cell from the size
and shape of the unit cell, the chemical composition of the sped-
men, and its measured density
3. Deduction of the atom positions within the unit cell from the
relative intensities of the diffraction peaks
In this experimental module, we only do step 1 (assuming that the
shape is cubic).

Indexing the Pattern

"Indexing the pattern" involves assigning the correct Miller indices to
each peak in the diffraction pattern. These peaks are also referred to a~
reflections, and as in Part I, we use both terms interchangeably. It is
important to remember that correct indexing is done only when all the
peaks in the diffraction pattern are accounted for and no peaks expected
for the structure are missing from the diffraction pattern.
A typical example of indexing diffraction patterns obtained from
materials with a cubic structure is presented here. The procedure is the
same for a metal, a semiconductor, or a ceramic.
The interplanar spadng d, the distance between adjacent planes in the
set (hkl) of a material with a cubic structure and lattice parameter a, may
be obtained from the equation

(l.l)
d2 a2
Combining Bragg's law (A. = 2d sin 8) with Eq. (1.1) yields
1 h 2 + 12 + f 4 sin2 e (1.2)

Rearranging gives

sin 2e (:2)
= (h 2 + 12 + f) (1.3)

Realizing that 1..2 /4a 2 is a constant for anyone pattern, we note that
sin 2 8 is proportional to h2 + ~ + P; i.e., as 8 increases, planes with higher
Miller indices will diffract. Writing Eq. (1.3) for two different planes and
dividing, we get
 7 • Crystal Structure Determination. I 99

(1.4)
-------
sirr 9 2 h~ + IS + l~

In the cubic system, the first reflection in the diffraction pattern is due
to diffraction from planes with the Miller indices (100) for primitive
cubic, (110) for body-centered cubic, and (Ill) for face-centered cubic
lattices (planes with the highest planar density in each case), so
h 2 + J<2 + [2 = I, 2, or 3, respectively. Since the ratio of sin 2 e values scales
with the ratio of h2 + k2 + [2 values for different planes, and since h, k,
and [ are always integers, the h 2 + J<2 + [2 values can be obtained by
dividing the sin 2 e values of different reflections with the minimum one
(Le., sin 2 e of the first reflection) and multiplying the ratios thus obtained
by an appropriate integer. Therefore, the sin 2 e values calculated for all
peaks in the diffraction pattern are divided by the smallest value (first
reflection). These ratios, when multiplied by 2 or 3, yield integers (if they
are not already integers). These subsequent integers represent the
h2 + k2 + [2 values; therefore, the hk[ values can be easily identified from
the quadratic forms listed in Appendix 2. You may also index the
diffraction pattern using the ratio of 1/ d 2 values instead of the sin 2 e
values. Since e is a directly measurable quantity we have chosen to use
the sin2 e values.

Identification of the Bravais Lattice

The Bravais lattice can be identified by noting the systematic presence
(or absence) of reflections in the diffraction pattern (refer to Sec. 2.8 in
Part I for more details). Table 1.1 summarizes the selection rules (or
extinction conditions as they are also known) for cubic lattices. According
to these selection rules, the h 2 + J<2 + [2 values for the different cubic
lattices follow the sequence
Primitive I, 2, 3,4, 5, 6, 8, 9, 10, 11, 12, 13, 14, 16, ...
Body-centered 2,4, 6, 8, 10, 12, 14, 16, ...
Face-centered 3,4, 8, II, 12, 16, 19,20, 24, 27, 32, ...

TABLE 7.7. Selection Rules for the Presence or Absence of Reflections

Bravais Lattice Reflections Present for Reflections Absent for

Primitive all none

Body-centered h+k+leven h+k+lodd
Face-centered h. k. and I unmixed (all even or all odd) h. k. and I mixed
100 /I • Experimental Modules

The diamond cubic structure (adopted by diamond and the elemental semiconduc-
tors silicon and germanium) can be considered as two interpenetrating face-cen-
tered cubic lattices (see Sec. 2.4.2 in Part I). Thus, in a diamond cubic structure only
reflections with h, k, and I even or odd (unmixed) are possibly present. However,
due to destructive interference from some of the atoms in certain planes, some
additional reflections will be absent (even if h, k, and I are odd or even). (We went
through the structure factor calculation for the diamond cubic structure in Sec. 2.8
in Part 1.) Thus, the h 2 + k 2 + [2 sequence for the diamond cubic structure is

3, 8, 11, 16, 19, 24, 27, 32, ...

The Bravais lattice and the crystal structure can be thus unambiguously
identified from the sequence of h 2 + ~ + [2 values in the diffraction
pattern.

e values
If the diffraction pattern contains only six peaks and if the ratio of the sin 2
is 1, 2, 3, 4, 5, and 6 for these reflections, then the Bravais lattice may be either
primitive cubic or body-centered cubic; it is not possible to unambiguously distin-
guish the two. But remember that the simple cubic structure is not very common
and, therefore, in such a situation, you will probably be right if you had indexed
the pattern as belonging to a material with the bcc structure. However, if the
structure is actually simple cubic and the pattern is wrongly indexed as bcc, the first
reflection will be indexed as 110 instead of 100, and consequently the lattice
parameter of the unit cell will be ..f2 times larger than the actual value. This
confusion can be avoided if the x-ray diffraction pattern has at least seven peaks.
In that case, the seventh peak has Miller indices 321 (h 2 + ~ + [2 = 14 = 7 x 2) for
the body-centered cubic lattice and 220 (h 2 + ~ + P = 8) for the primitive cubic
lattice. Note that 7 cannot be expressed as the sum of three squares, and therefore
the seventh peak in the diffraction pattern from a primitive cubic lattice will be
much more separated from the sixth peak than the earlier sets (as illustrated in Fig.
55 in Part I). A large number of peaks in the diffraction pattern can be obtained if
the pattern is recorded with a radiation with a short wavelength. For example, use
Mo Ka instead of eu Ka.
 • Crystal Structure Determination. I 101

Calculation of the Lattice Parameter

The lattice parameter a can be calculated from

sin2 8 = ( ~) (h 2 + J(2 + p) (1.3)

Rearranging gives
(1.5)

or
(1.6)

WORKED EXAMPLE
Let's now do an example of indexing the x-ray diffraction pattern of
a material with a cubic structure. The x-ray diffraction pattern of alumi-
num recorded with eu KCl radiation is presented in Fig. 1.1. Nine peaks
exist in the diffraction pattern, and the 28 values for these peaks are listed
in Table 1.2. (Even though the Cl! and ~ components are resolved for
reflections with 28 > about 80 0 , we have listed only the 28 values
corresponding to the Cl! component). The sin2 8 values have been calcu-
lated, and following the described procedure we have completely indexed
the diffraction pattern and determined the lattice parameter of aluminum.
Note that only reflections with unmixed hkl values (all odd or all even)
are present; and therefore, it can be concluded that the Bravais lattice is

TABLE 1.2. Details of Indexing the X-Ray Diffraction Pattern of Aluminum

Material: Aluminum Radiation: eu Ka AKa! =0.154056 nm
sin 29 . 29
SIn x3
Peak # 29 (0) sin 2 9 sin2 9mln ~
Sln mln h 2 +k2 +r hkl a(nm)

38.52 0.1088 1.000 3.000 3 111 0.40448

2 44.76 0.1450 1.333 3.999 4 200 0.40457
3 65.14 0.2898 2.664 7.992 8 220 0.40471
4 78.26 0.3983 3.661 10.983 11 311 0.40480
5" 82.47 0.4345 3.994 11.982 12 222 0.40480
6" 99.11 0.5792 5.324 15.972 16 400 0.40485
7" 112.03 0.6876 6.320 18.960 19 331 0.40491
8" 116.60 0.7238 6.653 19.958 20 420 0.40491
9" 137.47 0.8684 7.982 23.945 24 422 0.40494

"The a, and lIz peaks have been resolved for these refiections. But, since we do not need a very high
accuracy, we have taken the 29 values of the a, component only.
102 /I • Experimental Modules

n.,

en
Q.
U

'I 'I 'I 'I 'I 'I 'I 'I

j
'I 'I
1.
'I' 'I' 'I'
i1
' I' 'I' 'I' 'I'
1
'I '

26 40 60 80 100 120

2 Theta
FIG. 1. 1. X-ray diffraction pattern of aluminum.

face-centered cubic, The lattice parameter is calculated as 0,4049 nm,

Thus, aluminum has an fcc structure with lattice parameter a = 0.4049
nm.
From Table 1.2 you can see that the lattice parameter increases with
increasing 29 values, Since the systematic error in sin 2 9 decreases as 9
increases, you should select the value of a for the highest-angle peak in
the diffraction pattern as the most accurate. (See Experimental Module 3
for predse lattice parameter measurements.)

ANALYT/CAL METHOD
An analytical approach can also be used to index diffraction patterns
from materials with a cubic structure. Look again at Eq. (1.3) :

sin2 e = (far) (h 2 + J!- + p) (1.3)

 1 • Crystal Structure Determination. I 103

Since}..2 / 4a 2 is constant for any pattern, which we call A, we can write

(1.7)

In a cubic system, the possible h2 + k2 + [2 values are 1, 2, 3, 4, 5, 6, 8, ...

(even though all may not be present in every type of cubic lattice). The
observed sin2 e values for all peaks in the diffraction pattern are therefore
divided by the integers 2, 3,4, 5, 6, ... to obtain a common quotient,
which is the value of A, corresponding to h2 + ~ + [2 = 1. We can then
calculate the lattice parameter from the value of A by using the relation-
ship
A (1.8)
or a=--
2-i4"
Dividing the sin2 e values of the different reflections by A gives the
h2 + k2 + [2 values, from which the hk[ values of each reflection can be
obtained by using the listing in Appendix 2.
The aluminum x-ray diffraction pattern indexed earlier is now in-
dexed with the analytical approach, and the results are presented in Table
1.3.

Worked Example
The lowest common sin 2 e value in Table 1.3 is 0.0363 (indicated in
bold). Note that 0.1086 also appears as a common sin 2 evalue in some of
the columns, but this is approximately 3 x 0.0363. Therefore, you must
look for the smallest value of sin 2 e among the values. However, realize

TABLE 1.3. Calculation of the Common Quotient

Material: Aluminum Radiation: eu Ka AK<Xl = 0.154056 nm

sin2 e sin2 e sin2 e sin2 e sin2 e sin2 e

Peak # 29 (0) sin2 9 -2- -3- -4- -5- -6- -8-

38.52 0.1088 0.0544 0.0363 0.0272 0.0218 0.0181 0.0136

2 44.76 0.1450 0.0725 0.0483 0.0363 0.0290 0.0242 0.0181
3 65.14 0.2898 0.1449 0.0966 0.0725 0.0580 0.0483 0.0362
4 78.26 0.3983 0.1992 0.1328 0.0996 0.0797 0.0664 0.0498
5 82.47 0.4345 0.2173 0.1448 0.1086 0.0869 0.0724 0.0543
6 99.11 0.5792 0.2896 0.1931 0.1448 0.1158 0.0965 0.0724
7 112.03 0.6876 0.3438 0.2292 0.1719 0.1375 0.1146 0.0860
8 116.60 0.7238 0.3619 0.2413 0.1810 0.1448 0.1206 0.0905
9 137.47 0.8684 0.4342 0.2895 0.2171 0.1737 0.1447 0.1086
104 1/ • Experimental Modules

Note that the common quotient of 0.0363 appears only in the columns of
(sin2 8)/3, (sin2 9)/4, and (sin2 9)/8 in Table 1.3. This suggests that the sequence of
h2 + If- + 12 values will be in the ratio 3, 4, 8, ... From the sequence of h2 + If- + 12
values mentioned for different types of cubic lattices, it is clear that the Bravais lattice
of aluminum is face-centered cubic, which will also be proved when we divide the
sin2 8 values by A. The other Bravais lattices can also be identified in a similar way.

that this value (0.0363) does not (and will not) necessarily appear in each
column of the table.
We can now assume that 0.0363 represents the A value in Eq. (1.7)
for h2 + If- + z:z = 1. Since Eq. (1.7) suggests that division of the sin2 8
values by A yields the h 2 + J<2 + z:z values from which the hkl values can
be obtained (see Appendix 2), the calculations can be tabulated as shown
in Table 1.4.
Notice from Table 1.4 that the Miller indices of the reflections again
are unmixed (all odd or all even), so the Bravais lattice is face-centered
cubic. The lattice parameter is calculated from Eq. (1.8). Since A = 0.0363
and a = 'A/2..[A, for aluminum
0.154056
a= = 0.4049 nm
2"0.0363
As you would expect, the results obtained by this analytical method are
the same as those obtained by the earlier method.

TABLE 1.4. Indexing the Diffraction Pattern of Aluminum

Using the Analytical Approach
Material: Aluminum Radiation: Cu Ka A= 0.0363

5in2 a
Peak # sin2 a -::4 h2+!? +1- hkl

0.1088 2.997 3 III

2 0.1450 3.995 4 200
3 0.2898 7.983 8 220
4 0.3983 10.972 II 3II
5 0.4345 11.970 12 222
6 0.5792 15.956 16 400
7 0.6876 18.942 19 331
8 0.7238 19.939 20 420
9 0.8684 23.923 24 422
 7 • Crystal Structure Determination. I 705

In Table 1.4 notice that the value of (sin2 a)/A deviates more from the expected
value at higher diffraction angles than at lower angles. This is so because a small
error in the measurement of a at low angles leads to a large error in the value of
sin a (also in sin2 a). Since the sin2 a value increases with increasing a, a small error
in the lowest value of sin2 a gets multiplied several times at higher angles because
we are dividing all the sin2 a values by the smallest sin2 a value.

EXPERIMENTAL PROCEDURE
Take fine powders (-325 mesh, < 45 J.l.m in size) of chromium (Cr),
copper (Cu), iron (Fe), nickel (Ni), silicon (Si), and titanium nitride (TiN).
Load each powder separately into the x-ray holder and record the x-ray
diffraction patterns, using Cu Ka radiation in the 2a angular range of 25°
to 140°. Using the cursor, locate the maxima of all the peaks in each
diffraction pattern and list the 2a values in increasing order. If the a 1 and
a 2 peaks are resolved, you are advised to take the 2a value of the a 1 peak,
even though for greater accuracy you could use both peaks and use the
respective wavelengths to calculate the lattice parameters. (In case an
x-ray diffractometer is not available, or if you are not able to record the
diffraction pattern for some reason, the x-ray diffraction patterns for Cr,
Cu, Fe, Ni, Si, and TiN are provided in Figs. 1.2 through 1.7, and the 2a
values of all the reflections are listed in the work tables prOvided for each
different material.) Using the worked example for aluminum, index all
the diffraction patterns (find the Miller indices of the planes giving rise to
the diffraction peaks). From the systematic absence (or presence) of
reflections in each pattern and from Table 1.1, identify the Bravais lattice.
Calculate the lattice parameter in each case and tabulate your calculations
in the work tables provided.
Note 1: Indexed diffraction patterns (2a, hkl, and intensity values) and
the lattice parameters of all standard substances can be found in the
Powder Diffraction Files (PDF) published by the JCPDS-International
Centre for Diffraction Data (see Sec. 3.4 in Part I for more information
about the PDF). These files are available with most computers associated
with modern x-ray diffractometers. The "card" numbers for the materials
referred to in this book are listed in Appendix 9.
Note 2: Even though diffraction patterns (from different types of cubic
structures) have been provided in this module, you may index all of them
or only some of them, depending on the time available.
When you finish these calculations, complete Table 1.17.
106 II • Experimental Modules

.7,--------.----------------__________________________ ~

CIJ
D-
U

40 60 80 100 120 140

2 Theta
FIG. 1.2. X-ray diffraction pattern of chromium.

TABLE 1.5. Work Table for Chromium

Material: Chromium Radiation: Cu Ka. AKal =0.154056 nm

sin2 8 sin2 8
Peak # 28 (0) sin2 e x? h 2 + k 2 + z2 hkl a (nm)
sin2 8min sin2 8min

1 44.41

2 64.59

3 81.77

4 98.26

5 115.34

6 135.47
 1 • Crystal Structure Determination. I 107

TABLE 1.6a. Work Thble for Chromium-Analytical Method

Material: Chromium Radiation: Cu Ka. A.Ka.l =0.154056 nm

sin2 9 2
sin 9 sin2 9 sin2 9 2
sin 9 2
sin 9
Peak # 29 (0) sin2 9 - - - - - -
2 3 4 5 6 8

1 44.41

2 64.59

3 81.77

4 98.26

5 115.34

6 135.47

TABLE 1.6b. Work Table for Chromium-Analytical Method

Material: Chromium Radiation: Cu Ka. A=

sin2 6
Peak # sin2 6 ---::r- h 2 + k 2 + P. hkl

6
108 /I • Experimental Modules

253

en
c..
U

'T TT 'T TT IT 'T IT '[

~

'I 'I
J
'I 'I 'I 'I 'I
11
'I 'I 'I 'I
A
40 60 80 100 120 140

2 Theta
FIG. 1.3. X-ray diffraction pattern of copper.

TABLE 1.7. Work Table for Copper

Material: Copper Radiation: Cu Ka A.Ka.l = 0.154056 run

2e (0) sin2 e
sin2 e siJ a x?
Peak # h 2 + k2 + z2 hkl a (run)
sin2 amin siJ amin

1 43.16

2 50.30

3 73.99

4 89.85

5 95.03

6 116.92

7 136.59
 1 • Crystal Structure Determination. I 109

TABLE 7.8a. Work Table for Copper-Analytical Method

Material: Copper Radiation: Cu Kcx A.Kal = 0.154056 run

sin2 e sin2 e sin2 e sin2 e sin2 e sin2 e

Peak # 28 (0) sin2 e -2- -3- -4- -5- -6- -8-

1 43.16

2 50.30

3 73.99

4 89.85

5 ~5.03

6 116.92

7 136.59

TABLE 7.8b. Work Table for Copper-Analytical Method

Material: Copper Radiation: Cu Kcx A=

e sin2 e h 2 + k 2 + P.
Peak # sin2 ---::r- hkl

7
110 /I • Experimental Modules

.4

CIJ
Cl.
U

'I' 'I' 'I 'I 'I 'I 'I

A
'I 'I 'I
A
'I 'I' 'I 'I 'I
A
26 40 60 80 100 120

2 Theta
FIG. 1.4. X-ray diffraction pattern of iron.

TABLE 1.9. Work Table for Iron

Material: Iron Radiation: eu Ka. AKal = 0.154056 run

a sin2 a sin2 a x?
Peak # 26 (0) sin2 h2 + k 2 + z2 hkl a (run)
sin2 amin sin2 amin
1 44.73

2 65.07

3 82.40

4 99.00

5 116.45

6 137.24
 1 • Crystal Structure Determination. I 111

TABLE 1.1 Oa. Work Table for Iron-Analytical Method

Material: Iron Radiation: Cu Ka AKal = 0.154056 nm

sin2 e sin2 e sin2 e sin2 e sin2 e sin2 e

Peak # 28 (0) sin2 e -2- -3- -4- -5- -6- -8-

1 44.73

2 65.07

3 82.40

4 99.00

5 116.45

6 137.24

TABLE 1.1 Ob. Work Table for Iron-Analytical Method

Material: Iron Radiation: Cu Ka A=

sin2 e
Peak # sin2 e -A- h2 + e + z2 hkl