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XRD ANALYSIS

AIM :

To determine (h,k,l) values and lattice parameter for different samples by

analyzing XRD data.
THEORY :

The d spacing equations for different crystal structures are

Cubic

1 h2 + k 2 + l 2
=
d2
a2

Hexagonal
Tetragonal
Orthorhombic

Rhombohedral

Monoclinic
Triclinic

2
2
2
2
2
1 ( h + k + l ) sin + 2 ( hk + kl + hl ) ( cos cos )
=
d2
a 2 ( 1 3cos 2 + 2 cos3 )

1
1
=
2
d
sin 2

h 2 k 2 sin 2 l 2 2 hl cos
+ 2
2+

b2
c
ac
a

1
1
= 2 ( S11h 2 + S22 k 2 + S33l 2 + 2S12 hk + 2S 23kl + 2S13hl )
2
d
V

In the equation for triclinic crystals

V - volume of unitcell
2 2
2
S11 - b c sin ,

2 2 2
S22 - a c sin ,
2 2
2
S33 - a b sin ,

S12 -

abc 2 ( cos cos cos ) ,

2
S23 - a bc ( cos cos cos ) ,
2
S13 - ab c ( cos cos cos )

PROCEDURE :
INDEXING A DIFFRACTION PATTERN FROM CUBIC MATERIALS :

The data is given in the form of intensity of diffracterd rays versus 2 (angle of diffraction) plot as shown.

METHOD 1
The graph is in the form of several peaks of different intensities. The values
of 2 corresponding to maximum intensity positions are tabulated. From this can

be calculated. Knowing the values of , corresponding Sin and Sin 2 values are
found out. Calculate Sin2 / Sin2min and multiply by the appropriate integers. This
gives the simplest set of values which does not include forbidden numbers. If it
contains forbidden numbers (7,15,23,28,31) repeat the procedure by multiplying
the Sin2 / Sin2min values by 2,3,4, until set of ratios which does not include
forbidden numbers are obtained. If the values so obtained are decimal numbers,
then round off it to integer values and this gives (h2+k2+l2 ). The (h,k,l) values are
calculated from the values of (h2+k2+l2 ).
Each of 4 common cubic lattice types is recognizable by a characteristic
sequence of diffraction lines and those in turn are described by their sequential
(h2+k2+l2 ). The (h2+k2+l2 ) values are given below.
For simple cubic : 1,2,3,4,5,6,8,9,10,11
For body centered : 2,4,6,8,10,12,14,16
For face centered : 3,4,8,11,12,
For diamond cubic : 3,8,11,16,
The obtained values of (h2+k2+l2 ) are compaired with the above standard
values and from this; we can interpret the lattice type which the specimen belongs
to.
The basic principle behind the analysis of crystal structure is the Braggs law
For cubic crystals, interplanar spacing is given as
1 h2 + k 2 + l 2
=
d2
a2

(1)

= 2d sin

2 = 4d 2 sin 2
1 4sin 2
=
d2
2

Compairing eqn (1) and (2)

1 h2 + k 2 + l 2
4sin 2
=
2
d2
a2
=

2 2
2
2
2
sin = 2 ( h + k + l )
2
4a
Or
where and a are constants and hence 4a is a
2

constant
2
2
2
2
Or sin is proportional to ( h + k + l ) or planes with higher miller indices diffract
at higher values of .

sin 2

sin 2
sin 2 min

sin 2
2
sin 2 min

sin 2
3
sin 2 min

h2 + k 2 + l 2

METHOD 2
2 2
2
2
2
sin = 2 ( h + k + l )
2
4a
We have
and 4a = constant for all planes.
2

2
sin 2 = K ( h 2 + k 2 + l 2 )
2
4a
Let K =
then
2
2
2
For any cubic system , h + k + l = 1,2,3,4,5,6,8,9,10,11,12,

a (A)

If we determine sin2 for each peak and and divide the values by the integers
2,3,4,5,6,8,9,10,11, we can obtain a commom quotient, which is the value of K.

1)

2)

Determine sin2.

3)

Calculate the ratio sin2/(integers) .

4)

Identify the lowest common quotient from (3) and identify the integers to
which it corresponds. The common quotient be K.

5)

Divide sin2 by K for each peak. This will give you a list of integers
corresponding to h2+k2+l2.

6)

Select the appropriate pattern of h2+k2+l2 values and identify the Bravais
lattice.

7)

WORKED EXAMPLE:

The 2 - intensity values of Cu is given. The XRD pattern is plotted.

METHOD 1:
sin 2

sin min

sin 2
sin min

sin

sin 2

34.45

17.225

0.3006

0.2961

0.0877

110

3.677

43.35

21.675

0.3783

0.3693

0.1364

1.5556

3.1113

111

3.611

50.45

25.225

0.4403

0.4262

0.1816

2.0712

4.1424

200

3.614

74.15

37.075

0.6471

0.6029

0.3634

4.1446

8.2892

220

3.613

89.95

44.975

0.785

0.7068

0.4996

5.6969

11.394

11

311

3.613

136.45

68.225

1.1908

0.9286

0.8624

9.8345

19.669

20

420

3.708

h2+k2+l2

(h,k,l)

Compairing with the standard values, the allowed (h,k,l) values are (111), (200),
(220), (311), and (331).
Thus the value of a is 3.6318 A
a = 3.6318 A

METHOD 2:

a(A)

TO FIND THE VALUE OF K

2

34
.45

43
.35

50
.45

74.
15

89

17.2
3

21.6
8

25.2
3

37.0
8

.95

44.9
8

1
136.5

68.2
3

sin sin 2

sin 2
2

sin 2
3

sin 2
4

sin 2
5

sin 2
6

sin 2
8

sin 2
9

sin 2
10

0.3006

0.2
96
1

0.0877

0.0438

0.0292

0.0219

0.0175

0.0146

0.011

0.0097

0.0088

0.3783

0.3
69
3

0.1364

0.0682

0.0455

0.0341

0.0273

0.0227

0.0171

0.0152

0.0136

0.4403

0.4
26
2

0.1816

0.0908

0.0605

0.0454

0.0363

0.0303

0.0227

0.0202

0.0182

0.6471

0.6
02
9

0.3634

0.1817

0.1211

0.0909

0.0727

0.0606

0.0454

0.0404

0.0363

0.785

0.7
06
8

0.4996

0.2498

0.1665

0.1249

0.0999

0.0833

0.0624

0.0555

0.05

1.1908

0.9
28
6

0.8624

0.4312

0.2875

0.2156

0.1725

0.1437

0.1078

0.0958

0.0862

2
2
K = 0.0454. That is 4a = 0.0454

1.5406 A
a = 2 K = 2 0.0454 = 3.6152 A

TO FIND THE (h,k,l) VALUES

2
34.45
43.35
50.45
74.15
89.95
136.4
5

(h,k,l
)

sin

sin2

sin2/K

h2+k2+l2

0.2961

0.0877

1.931496

110

0.3693

0.1364

3.004692

111

0.4262

0.1816

4.000536

200

0.6029

0.3634

8.005288

220

0.7068

0.4996

11.00361

11

311

0.9286

0.8624

18.9953

19

331

Compairing with the standard values, the allowed (h,k,l) values are (111), (200),
(220), (311), and (331).
Thus the value of a is 3.6143 A
a = 3.6143 A

RESULT :
The given sample (Cu) is fcc cubic with lattice constant,
a = 3.6154 A.

Consider HCP plane spacing equation

2 4 2
l2
2
sin = 2 ( h + hk + k ) +
2
( c / a )
4a 3
2

a and c/a are constants for a given diffraction pattern then,

sin 2 = A ( h 2 + hk + k 2 ) + Cl 2
A=

Where

2
3a 2

and

C=

2
4c 2 .

h,k and l are always integers, h2+hk+k2 can only have values like 0,1,3,4,7,9,12,
and l2 can only have values like 0,1,4,9,
We need to calculate sin2 for each peak. Divide each sin2 value by the integers
3,4,7,9,12, and look for the common quotient (ie, sin 2/n value that is equal to
one of the observed sin2 values ).The sin2 values representing this common
quotient refer to hk0 type peaks. Thus this common quotient can be tentatively
assigned as A. Rearrange the terms in the modified euation to obtain C.
This is done as follows:
sin 2 = A ( h 2 + hk + k 2 ) + Cl 2 Cl 2 = sin 2 A ( h 2 + hk + k 2 )

Get the values of C by subtracting from each sin2 the values of nA

(ie, A, 3A, 4A, 7A,). Next look for the remainders that are in the ratio of
1,4,9,16,, which will be peaks of the 00l type, and determine C from these peaks.
The remaining peaks are neither hk0 type nor 00l type. Instead they are hkl type.
They can be indexed from a combination of A and C values.
Thus the steps are
1)

2)

3)

4)

5)

6)

Calculate sin2 - nA where n=1,3,4,7,

7)

Look for the lowest common quotient (LCQ). From this we can identify 00l
type peaks. Recall, that 001 is not allowed for hexagonal systems. The first
00l peak will be 002.
We can calculate C from :
Cl 2 = sin 2 A ( h2 + hk + k 2 )
2

or

C = LCQ/ l2 = sin2/ l2, for 002 planes and

C = sin2/ l2, for 00l planes.

8)

Look for values of sin2 that increase by factors of 4,9, (this is because
l= 1,2,3, and l2=1,4,9,Peaks exhibiting these characteristics are 00l
peaks, which can be assigned the indices 004,009,).Also note that the
values of sin2 will be some integral number (A) times the value.

9) Peaks that are neither hk0 nor 00l can be identified using combinations of
our calculated A and C values.
10) Calculate the lattice parameters from the values of A and C.

WORKED EXAMPLE :
Consider the diffraction pattern for Titanium as shown below.

TO FIND THE VALUE OF A

2
35.1

sin

sin 2

sin 2
3

sin 2
4

0.090
9

0.0303

0.0227

0.1081

0.036

0.027

0.1179

0.0393

0.0295

0.3063

40.17

17.55
19.19
5
20.08
5

0.3505

0.3015
0.3287
8
0.3434
1

53

26.5

0.4625

0.4462

0.1991

0.0664

0.0498

62.94

0.5493

0.2725

0.0908

0.0681

0.6165

0.5221
0.5782
1

0.3343

0.1114

0.0836

0.6473

0.603

0.3636

0.1212

0.0909

0.6651

0.6171

0.3808

0.1269

0.0952

77.35

31.47
35.32
5
37.08
5
38.10
5
38.67
5

0.675

0.3905

0.1302

0.0976

82.2

41.1

0.7173

0.4321

0.144

0.108

86.74

43.37

0.7569

0.4716

0.1572

0.1179

92.68

46.34
51.17
5

0.8088

0.6249
0.6573
8
0.6867
1
0.7234
5
0.7790
6

0.5234

0.1745

0.1308

0.6069

0.2023

0.1517

0.9215

0.2115

0.1586

0.6632

0.2211

0.1658

114.22

57.11

0.9968

0.7051

0.235

0.1763

119.28

59.64

1.0409

0.7965
0.8143
7
0.8397
1
0.8628
7

0.6345

109.05

52.8
54.52
5

0.7445

0.2482

0.1861

38.39

70.65
74.17
76.21

102.35
105.6

0.3015 = 1A
0.5221 = 3A
0.603 = 4A
0.7965 = 7A

0.335

0.8932

0.9516

Mean A = 0.0908.

sin 2
7
0.013
0.015
4
0.016
8
0.028
4
0.038
9
0.047
8
0.051
9
0.054
4
0.055
8
0.061
7
0.067
4
0.074
8
0.086
7
0.090
6
0.094
7
0.100
7
0.106
4

sin 2
9
0.0101
0.01201
0.0131
0.02212
0.03028
0.03715
0.0404
0.04231
0.04339
0.04802
0.0524
0.05815
0.06744
0.0705
0.07369
0.07835
0.08273

sin 2
12 h 2 + hk + k 2
0.00
76
0.00
9
0.00
98
0.01
66
0.02
27
0.02
79
0.03
03
0.03
17
0.03
25
0.03
6
0.03
93
0.04
36
0.05
06
0.05
29
0.05
53
0.05
88
0.06
2

hk

10

11

20

21

sin

sin A

0.0909
0.108
1
0.1179
0.1991
0.2725
0.3343
0.3636
0.3808
0.3905
0.4321
0.4716
0.5234
0.6069
0.6345
0.6632
0.7051
0.7445

sin 3A
2

sin 4A
2

sin 7 A
2

0.0001

0.0173
0.0271
0.1083
0.1817
0.2435
0.2728
0.29
0.2997
0.3413
0.3808
0.4326
0.5161
0.5437
0.5724
0.6143
0.6537

C=

LCQ
l2

sin 2 = Cl 2

0.027

0.0001
0.0619
0.0912
0.1084
0.1181
0.1597
0.1992
0.251
0.3345
0.3621
0.3908
0.4327
0.4721

0.0004
0.0176
0.0273
0.0689
0.1084
0.1601
0.2437
0.2712
0.3
0.3419
0.3813

0.0275
0.0695
0.1089

0.027

0.432

TO FIND THE REMAINING PEAKS :

A = 0.0908; C = 0.027
sin 2 = A ( h 2 + hk + k 2 ) + Cl 2

sin 2

( h, k , l )

0.0909
0.1081
0.1179
0.1991
0.2725
0.3343
0.3636
0.3808
0.3905
0.4321
0.4716
0.5234

100
002
101
102
110
103
200
112
201
004
202
104

0.6069
0.6345
0.6632
0.7051
0.7445

A=

203
210
211
114
212

2
2
C
=
3a 2 and
4c 2

a = 2.951 A ; c = 4.686 A ; c/a = 1.588

RESULT :
The given sample (titanium) is Hexagonal structure with lattice parameters,
a = 2.951 A
c = 4.686 A
c/a = 1.588