Analytical Methods for Materials

Laboratory Module #1
Crystal Structure Determination for Cubic Crystals

Suggested Reading
1. C. Suryanarayana and M.G. Norton, X-ray Diffraction A Practical Approach, (Plenum Press, New
York, 1998), pages 97-152.
2. B.D. Cullity and S.R. Stock, Elements of X-ray Diffraction, 3rd edition, (Prentice Hall, Upper Saddle
River, NJ, 2001), Ch. 10, pages 295-315.

569
 Steps for Crystal Structure
Determination
• Calculate size and shape of unit cell from angular
positions of diffraction peaks

• Calculate the number of atoms per unit cell from

unit cell shape and size, chemical composition,
and measured density.

• Deduce the atom positions within the unit cell

from the relative intensities of the diffraction
peaks.

570
 Indexing

• Assign correct Miller indices to each peak in the

diffraction pattern.

• Only correct when all peaks are accounted for.

• Process is easy for simple structures and very

tedious for more complex crystals.

571
 Generation and Treatment of Data
• Record diffraction pattern over as wide a range
of 2θ as possible.

• Calculate value of sin2θ for each diffraction line.

You can also determine the value of dhkl for each
line. It can also be used to determine crystal
structure.

• We will do this later for unknowns.

572
 Generation and Treatment of Data – cont’d

• Values of sin2θ always contain systematic errors.

These errors can interfere with the determination
of structures, particularly for non-cubic crystals.

• We can remove these errors from the data by

calibrating the diffractometer by mixing a
standard (i.e., a substance of known lattice
parameter) with the unknown.

573
CUBIC CRYSTALS

574
 Recall Bragg’s Law

  2d sin 
Rearrange   4d sin 
2 2 2

 2
sin  
2

4d 2

The only variable

quantity

575
 For cubic crystals

• Obtain interplanar spacing, dhkl, from the plane

spacing equation:

1 2
h k l
2 2
1 h k l 2 2 2
 or 2 
d hkl
2
a 2
d a 2

576
 For cubic crystals
• Substitute plane-spacing equation into Bragg’s
law:

1 h 2  k 2  l 2 4sin 2 
 
d 2
a 2
2
or
 2

2 
sin  
2
h 2
 k 2
 l 2

4a

577
 VERY IMPORTANT
For any single diffraction pattern

  
2
 2   CONSTANT
 4a 
THUS

sin   h  k  l
2 2 2 2

Integer
Related to indices of diffracting planes
as θ increases, planes with higher
order Miller indices will diffract
578
 Methods
• Mathematical

• Analytical

• Both methods are based upon manipulations of

Bragg’s law and the plane-spacing equations.

579
Mathematical Method of Indexing
Cubic crystals

580
 For any two different reflections/planes,
θ1 and θ2

sin 2 1 h12  k12  l12 k1

 2 
sin  2 h2  k2  l2 k2
2 2 2

Both the numerator and denominator are integers that

scale with h k l

581
1. Obtain h2 + k2 + l2 for a given reflection by
dividing the sin2 values for each reflection with
that for the first (i.e., minimum) one

2. Multiply by the appropriate number to obtain an

integer (usually 1, 2 or 3)

3. Subsequent integers represent the quadratic

form of the Miller indices

582
 Identify Bravais Lattices
• Note the sequence of h2 + k2 + l2 values

– Primitive Cubic
1,2,3,4,5,6,8,9,10,11,12,13,14,16…
– Body-centered Cubic
2,4,6,8,10,12,14,16…
– Face-centered Cubic
3,4,8,11,12,16,19,20,24,27,32…
– Diamond cubic
3,8,11,16,19,24,27,32...

583
 Peak location (°2)
Relative Intensity
Intensity (%)

100
(38.43,100.0) CuK radiation
90

80
ALUMINIUM
 =1.540562 Å
70

60

50 (44.67,46.9)

40

30 (65.02,26.4) (78.13,27.9) (116.36,11.9)

20
(111.83,12.2)
10
(82.33,7.8)
(98.93,3.6)

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120

• Identify the peaks.

• Determine sin2.
• Calculate the ratio sin2/sin2min and multiply by the appropriate integers.
• Select the result from (3) that yields h2+k2+l2 as an integer.
• Compare results with the sequences of h2+k2+l2 values to identify the Bravais lattice.
• Calculate lattice parameters. 584
 Step 1
• Identify the peaks and their proper 2 values. Eight peaks for this
pattern. Note: most patterns will contain 1 and 2 peaks at higher
angles. It is common to neglect 2 peaks in this analysis.

sin 2  sin 2  sin 2 

Peak 1 2 2 2 3 2
No. 2 sin2 sin  min sin  min sin  min h2+k2+l2 hkl a (Å)
1 38.43
2 44.67
3 65.02
4 78.13
5 82.33
6 98.93
7 111.83
8 116.36

585
 Step 2
• Determine sin2 for each peak.
– When using Excel, remember you must convert your angles to radians.

sin 2  sin 2  sin 2 

Peak 1 2 2 2 3 2
No. 2 sin2 sin  min sin  min sin  min h2+k2+l2 hkl a (Å)
1 38.43 0.1083
2 44.67 0.1444
3 65.02 0.2888
4 78.13 0.3972
5 82.33 0.4333
6 98.93 0.5776
7 111.83 0.6859
8 116.36 0.7220

586
 Step 3
• Calculate the ratio sin2 / sin2min and multiply by the appropriate
integers.

sin 2  sin 2  sin 2 

Peak 1 2 2 2 3 2
No. 2 sin2 sin  min sin  min sin  min h2+k2+l2 hkl a (Å)
1 38.43 0.1083 1.000 2.000 3.000
2 44.67 0.1444 1.333 2.667 4.000
3 65.02 0.2888 2.667 5.333 8.000
4 78.13 0.3972 3.667 7.333 11.000
5 82.33 0.4333 4.000 8.000 12.000
6 98.93 0.5776 5.333 10.665 15.998
7 111.83 0.6859 6.333 12.665 18.998
8 116.36 0.7220 6.666 13.331 19.997

587
 Step 4
• Select the result from (3) that most closely yields h2+k2+l2 as a
series of integers .

sin 2  sin 2  sin 2 

Peak 1 2 2 2 3 2
No. 2 sin2 sin  min sin  min sin  min h2+k2+l2 hkl a (Å)
1 38.43 0.1083 1.000 2.000 3.000
2 44.67 0.1444 1.333 2.667 4.000
3 65.02 0.2888 2.667 5.333 8.000
4 78.13 0.3972 3.667 7.333 11.000
5 82.33 0.4333 4.000 8.000 12.000
6 98.93 0.5776 5.333 10.665 15.998
7 111.83 0.6859 6.333 12.665 18.998
8 116.36 0.7220 6.666 13.331 19.997

In this case the

best number is 3

588
 Step 5
• Compare results with the sequences of h2+k2+l2 values to identify the
miller indices for the appropriate peaks and the Bravais lattice.

sin 2  sin 2  sin 2 

Peak 1 2 2 2 3 2
No. 2 sin2 sin  min sin  min sin  min h2+k2+l2 hkl a (Å)
1 38.43 0.1083 1.000 2.000 3.000 3 111
2 44.67 0.1444 1.333 2.667 4.000 4 200
3 65.02 0.2888 2.667 5.333 8.000 8 220
4 78.13 0.3972 3.667 7.333 11.000 11 311
5 82.33 0.4333 4.000 8.000 12.000 12 222
6 98.93 0.5776 5.333 10.665 15.998 16 400
7 111.83 0.6859 6.333 12.665 18.998 19 331
8 116.36 0.7220 6.666 13.331 19.997 20 420
Bravais lattice is Face-Centered Cubic

589
 Step 6
• Calculate lattice parameters.
sin 2  sin 2  sin 2 
Peak 1 2 2 2 3 2
No. 2 sin2 sin  min sin  min sin  min h2+k2+l2 hkl a (Å)
1 38.43 0.1083 1.000 2.000 3.000 3 111 4.0538
2 44.67 0.1444 1.333 2.667 4.000 4 200 4.0539
3 65.02 0.2888 2.667 5.333 8.000 8 220 4.0538
4 78.13 0.3972 3.667 7.333 11.000 11 311 4.0538
5 82.33 0.4333 4.000 8.000 12.000 12 222 4.0538
6 98.93 0.5776 5.333 10.665 15.998 16 400 4.0541
7 111.83 0.6859 6.333 12.665 18.998 19 331 4.0540
8 116.36 0.7220 6.666 13.331 19.997 20 420 4.0541
Average lattice parameter is 4.0539 Å
We have completed our task because we have:
• Correctly labeled all peaks,
• Correctly determined the Bravais lattice
• Determined the lattice parameter.

590
Analytical Method of Indexing
Cubic crystals

591
 Recall

  22
sin    2   h  k  l 
2 2 2

 4a 

 
2

 4a 2  = constant
 
For all XRD patterns

592
 Let
  2

 4a 2  = K
 

We can write,

sin   K  h  k  l
2 2 2 2

For any cubic system, the values of
h2+k2+l2 increase as follows:
h2+k2+l2 = 1,2,3,4,5,6,8,9,10,11…

593
E. Koch, in International Tables for Crystallography (2006). Vol. C., Chapter 1.2, pp. 6-9.

594
• Determine sin2 for each peak and divide by the values by
the integers 2,3,4,5,6,8,9,10,11…

• From this we will obtain a common quotient, which equals

the value of K corresponding to h2+k2+l2 = 1

 2  
K   2  or a 
 4a  2 K

• Divide the sin2 values for each peak by K and we will

obtain a list of h2+k2+l2 values.

• For cubic crystals, we can use this sequence to identify the

Bravais lattice and label each XRD peak.
595
 Intensity (%)

100
(38.43,100.0) CuK radiation
90

80
ALUMINIUM
 =1.540562 Å
70

60

50 (44.67,46.9)

40

30 (65.02,26.4) (78.13,27.9) (116.36,11.9)

20
(111.83,12.2)
10
(82.33,7.8)
(98.93,3.6)

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120

• Identify the peaks.

• Determine sin2.
• Calculate the ratio sin2/(integer sequence).
• Identify the lowest common quotient from (3) and identify the integers to which it corresponds. Let the lowest
common quotient be K.
• Divide sin2 by K for each peak. This will give you a list of integers corresponding to the
h2+k2+l2 sequence.
• Select the appropriate pattern of h2+k2+l2 values to ID the Bravais lattice.
• Calculate lattice parameters.
596
 Step 1
• Identify peak locations.

Peak sin 2  sin 2  sin 2  sin 2  sin 2  sin 2 

No. 2 sin 2  2 3 4 5 6 8
1 38.43
2 44.67
3 65.02
4 78.13
5 82.33
6 98.93
7 111.83
8 116.36

597
 Step 2
• Determine sin2 for each peak.

Peak sin 2  sin 2  sin 2  sin 2  sin 2  sin 2 

No. 2 sin 2  2 3 4 5 6 8
1 38.43 0.1083
2 44.67 0.1444
3 65.02 0.2888
4 78.13 0.3972
5 82.33 0.4333
6 98.93 0.5776
7 111.83 0.6859
8 116.36 0.7220

598
 Step 3
The integers represent the quadratic
forms of the Miller indices.

Calculate the ratio sin  /(integers)

2

Peak sin 2  sin 2  sin 2  sin 2  sin 2  sin 2 

No. 2 sin 2  2 3 4 5 6 8
1 38.43 0.1083 0.0542 0.0361 0.0271 0.0217 0.0181 0.0135
2 44.67 0.1444 0.0722 0.0481 0.0361 0.0289 0.0241 0.0181
3 65.02 0.2888 0.1444 0.0963 0.0722 0.0578 0.0481 0.0361
4 78.13 0.3972 0.1986 0.1324 0.0993 0.0794 0.0662 0.0496
5 82.33 0.4333 0.2166 0.1444 0.1083 0.0867 0.0722 0.0542
6 98.93 0.5776 0.2888 0.1925 0.1444 0.1155 0.0963 0.0722
7 111.83 0.6859 0.3430 0.2286 0.1715 0.1372 0.1143 0.0857
8 116.36 0.7220 0.3610 0.2407 0.1805 0.1444 0.1203 0.0903

599
 Step 4

Identify the lowest common quotient from step 3 and

identify the integers to which it corresponds. Let the
lowest common quotient be K.
Peak sin 2  sin 2  sin 2  sin 2  sin 2  sin 2 
No. 2 sin 2  2 3 4 5 6 8
1 38.43 0.1083 0.0542 0.0361 0.0271 0.0217 0.0181 0.0135
2 44.67 0.1444 0.0722 0.0481 0.0361 0.0289 0.0241 0.0181
3 65.02 0.2888 0.1444 0.0963 0.0722 0.0578 0.0481 0.0361
4 78.13 0.3972 0.1986 0.1324 0.0993 0.0794 0.0662 0.0496
5 82.33 0.4333 0.2166 0.1444 0.1083 0.0867 0.0722 0.0542
6 98.93 0.5776 0.2888 0.1925 0.1444 0.1155 0.0963 0.0722
7 111.83 0.6859 0.3430 0.2286 0.1715 0.1372 0.1143 0.0857
8 116.36 0.7220 0.3610 0.2407 0.1805 0.1444 0.1203 0.0903
K = 0.0361

600
 Step 5

Divide sin 2  by K for each peak. This will give you a

list of integers corresponding to h 2  k 2  l 2
(i.e., the hkl values for the diffracting peaks)

Peak sin 2 
No. 2 sin 2  K h2  k 2  l 2 hkl
1 38.43 0.1083 3.000
2 44.67 0.1444 4.000
3 65.02 0.2888 8.001
4 78.13 0.3972 11.001
5 82.33 0.4333 12.002
6 98.93 0.5776 16.000
7 111.83 0.6859 19.001
8 116.36 0.7220 20.000

601
 Steps 6 and 7
Select the appropriate pattern of h 2  k 2  l 2 values.
Use them to identify the Bravais lattice.
Peak sin 2 
No. 2 sin2θ K h2  k 2  l 2 hkl
1 38.43 0.1083 3.000 3 111
2 44.67 0.1444 4.000 4 200
3 65.02 0.2888 8.001 8 220
4 78.13 0.3972 11.001 11 311
5 82.33 0.4333 12.002 12 222
6 98.93 0.5776 16.000 16 400
7 111.83 0.6859 19.001 19 331
8 116.36 0.7220 20.000 20 420
Sequence suggests an fcc Bravais lattice

Calculate lattice parameters as follows.



1.540562 A 
a  = 4.0541 A
2 K 2 0.0361
602
 These methods will work for any cubic
material

It is a very good idea to use both methods, to double-

check your results.

I REQUIRE YOU TO DO BOTH!

603