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# Determination of Crystal Structure

## Unit cell line positions

Atom position line intensity (known chemistry)

## Three steps to determine an unknown structure:

(1) Angular position of diffracted lines shape and
size of the unit cell.
(2) sizes of unit cell, chemical composition, density
# atoms/unit cell
(3) Relative intensities of the peaks
positions of the atoms within the unit cell
Preliminary treatment of data:
Ensure true random orientation of the particles of the
sample
Remove extraneous lines from
(1) K or other wavelength:

2d hkl sin ;2d hkl sin
sin sin
In the analyzing step, the sin2 is used
2

2
For most
sin sin
2 2

## filament contamination W KL radiation

Diffraction by other substance
Calibration curve using known crystal
Effect of sample height displacement

2 scos
R
R
s: sample height displacement
s

Length of
a larger error for low angle
scos
peaks for the most accurate
unit cell parameters it is
generally better to use the high
angle peaks for this calculation.
Example for sample height displacement
Assume a crystal; cubic structure; a = 0.6 nm.
Consider the error that can be introduced if the sample
was displaced by 100 microns (0.1 mm) for (100) and
(400) diffraction peaks? Assume = 0.154 nm and R =
225 mm.
2d100 ( 0.6) sin 0.154 7.37
2d 400 ( 0.15) sin 0.154 30.87

## The displacement cause these peaks to shift by

2 2 0.1 cos 7.37 / 225 8.81 104 0.051 0.025

4
0.022

## (100): = 7.395o 2d100 sin 7.395 0.154 a 0.5982

(400): = 30.892o 2d 400 sin 30.892 0.154 a 0.5999
Pattern Indexing

## Simplest example: indexing cubic pattern

a
2d hkl sin d hkl
h2 k 2 l 2
a sin 2 2 Constant for a
2 sin 2 2 given crystal
h k l
2 2 2 h k l 2 2
4a

Define s h2 k 2 l 2
Values for h2 + k2 + l2 for cubic system
SC BCC FCC Diamond S
100 X X X 1
110 X X 2
111 X 3
200 X 4
210 X X X 5
211 X X 6
220 8
221 X X X 9
300 X X X 9
310 X X 10
311 X 11
222 X 12
320 X X X 13
SC: 1, 2, 3, 4, 5, 6, 8, FCC: 3, 4, 8, 11, 12, 16, 19, 20,
BCC: 2, 4, 6, 8, 10, 12, 14, .. Diamond: 3, 8, 11, 16, 19,
SC: 1, 2, 3, 4, 5, 6, 8, s is doubled in BCC,
BCC: 2, 4, 6, 8, 10, 12, 14, .. No s = 7 in SC
Indexing Tetragonal system
1 h2 k 2 l 2
2
2
2 sin / 2d hkl
d hkl a c
2
2
h 2
k 2
l 2

sin
2
2

2
A( h 2
k 2
) Cl 2

hkl
2 d 4 a c
A 2 / 4a 2 ; C 2 / 4c 2

## Possible values for h2 + k2: 1, 2, 4, 5, 8, 9, 10,

sin 2 A( h 2 k 2 ) Cl 2
Possible values for l2 are 1, 4, 9, 16,
Indexing Hexagonal system
1 4 h 2 hk k 2 l 2
2
2
2
d hkl 3 a c

2 h 2 hk k 2 2 l 2
sin 2 A( h 2
hk k 2
) Cl 2

3 a2 4 c 2

A 2 / 3a 2 ; C 2 / 4c 2

## Possible values for h2 + hk + k2 are 1, 3, 4, 7, 9, 12,

The rest of lines are sin 2 A(h 2 hk k 2 ) Cl 2
Possible values for l2 are 1, 4, 9, 16,
Example:
sin2 sin2/3 sin2/4 sin2/7
1 0.097 0.032 0.024 0.014
2 0.112 0.037 0.028 0.016 100
3 0.136 0.045 0.034 0.019
4 0.209 0.070 0.052 0.030
5 0.332 0.111 0.083 0.047 110
6 0.390 0.130 0.098 0.056
7 0.434 0.145 0.109 0.062
8 0.472 0.157 0.118 0.067
9 0.547 0.182 0.137 0.078
10 0.668 0.223 0.167 0.095
11 0.722 0.241 0.180 0.103

## Lets say A = 0.112

sin2 sin2-A sin2-3A 0.097 belongs to Cl2.
1 0.097 002 What is the l?
2 0.112 0 100 There are two lines
101 between 100 and 110.
3 0.136 0.024
Probably, 10l1 and
4 0.209 0.097 102
10l2
5 0.332 0.220 110 ,103 0.024 and 0.097
6 0.390 0.278 0.054 004 are different ls.
7 0.434 0.322 0.098 112 0.097/0.024 ~ 4
8 0.472 0.360 0.136 0.220/0.024 ~ 9
0.390/0.024 ~ 16
9 0.547 0.435 0.211
C = 0.02441
10 0.668 0.556 0.332
11 0.722 0.610 0.386
12 0.806 0.694 0.470
13 0.879 0.767 0.543
Indexing orthorhombic system:
2 h 2
k 2
l 2

sin 2 2 2 Ah 2 Bk 2 Cl 2
2

4 a b c

More difficult!
Consider any two lines having indices hk0 and hkl
Cl2 put it back get A and B.
guess right (consistent)
not right, try another guesses C

## Even more complex, 6 variables must have enough

diffraction lines for the computer to indexing.
Effect of Cell distortion on the powder Pattern
Autoindexing

http://www.ccp14.ac.uk/solution/indexing/index.html
Determination of the number of atoms in a unit cell
Indexing the power pattern
shape and size of unit cell (volume)
number of atoms in that unit cell.

## VC: unit cell volume; : density

VC N 0 N0: Avogodros number;
n M: molecular weight;
M
n: number of molecules in a unit cell

in 3
g V in g/cm3
nM VC (1083 cm 3 ) ( 3 ) N 0 (6.022 1023 ) C
cm 1.66054
Determination of Atom positions

## Relative intensities determine atomic positions

(a trial and error process)

1 cos2 2 N
I F p 2 ; F f n exp2i ( hun kvn lwn )
2

sin cos n 1

## (un vn wn): position of nth atom in a unit cell.

Trial and error: known composition, known number of
molecules, known structure eliminate some trial
structure.

## Space groups and Patterson Function

(selection of trial structures)
Example: CdTe
Chemical analysis which revealed:
49.8 atomic percent as Cd (46.6 weight percent)
50.2 atomic percent as Te (53.4 weight percent)

46.6 53.4
Cd : Te :
112.4 127.6
1 : 1.0009 49.8 : 50.2
* Make powder
diffraction and list
sin2: index the
pattern! Assume it is
cubic
SC BCC FCC Diamond
sin2
s s s s close
0.0462 1 0.0462 2 0.0231 3 0.0154 3 0.0154
0.1194 2 0.0597 4 0.02985 4 0.02985 8 0.01493
Very 0.1615 3 0.05383 6 0.02692 8 0.02019 11 0.01468
weak 0.179 4 0.04475 8 0.02237 11 0.01627 16 0.01119
0.234 5 0.0468 10 0.0234 12 0.0195 19 0.01232
0.275 6 0.04583 12 0.02292 16 0.01719 24 0.01146
0.346 8 0.04325 14 0.02471 18 0.01922 27 0.01281
0.391 9 0.04344 16 0.02444 20 0.01955 32 0.01222
0.461 10 0.0461 18 0.02561 24 0.01921 35 0.01317
0.504 11 0.04582 20 0.0252 27 0.01867 40 0.0126
0.575 12 0.04792 22 0.02614 32 0.01797 43 0.01337
0.616 13 0.04738 24 0.02567 35 0.0176 49 0.01257
0.688 14 0.04914 26 0.02646 36 0.01911 51 0.01349
0.729 16 0.04556 30 0.0243 40 0.01822 56 0.01302
0.799 17 0.047 32 0.02497 43 0.01858 59 0.01354
sin 2 sin 2 sin 2 sin 2
s s s s
Diamond structure and Zinc blend structure:
forbidden peaks! Which one has more peaks?
removing line 4 first

0.0462 3 0.0154
0.1194 8 0.01493
0.1615 11 0.01468
0.234 16 0.01463
0.275 19 0.01447
0.346 24 0.01442
0.391 27 0.01448 very
0.461 32 0.01441
0.504 35 0.0144 close
0.575 40 0.01437
2
0.616 43 0.01433
2
0.01413
0.688 49 0.01404 4a
0.729 51 0.01429 1.542
0.799 56 0.01427 a 6.486 A
0.84 59 0.01424 2 0.01413
Alternative:
Assume the first line is from s = 1, s = 2 and s = 3,
sin 2 2 sin 2 3 sin 2
sin 2
0.0462 0.0462 0.0462
0.0462 1.000 1 2.000 2 3.000 3 3
0.1198 2.593 2 5.189 4 7.779 4 8
0.1615 3.496 3 6.991 6 10.487 8 11
0.179 3.874 4 7.749 8 11.623 11 16
0.234 5.065 5 10.130 10 15.195 12 19
0.275 5.952 6 11.905 12 17.857 16 24
0.346 7.489 8 14.978 14 22.468 18 27
0.391 8.463 9 16.926 16 25.390 20 32
0.461 9.978 10 19.957 18 29.935 24 35
0.504 10.909 11 21.818 20 32.727 27 40
0.575 12.446 12 24.892 22 37.338 32 43
0.616 13.333 13 26.667 24 40.000 35 49
0.688 14.892 14 29.784 26 44.675 36 51
0.729 15.779 16 31.558 30 47.338 40 56
0.799 17.294 17 34.589 32 51.883 43 59
Larger error smaller , use the first three lines to
fit a more correct A.
0.01444, Use this number
to divide sin2 ! sin 2
sin 2 / 0.01444 0.01428
0.0462 3.199 3 3.235
0.1198 8.296 8 8.389
0.1615 11.184 11 11.310
0.179 12.396 16 12.535
0.234 16.205 19 16.387
0.275 19.044 24 19.258
0.346 23.961 27 24.230
0.391 27.078 32 27.381
0.461 31.925 35 . 32.283
0.504 34.903 40 35.294
.
0.575 39.820 43 40.266
42.659 49 . 43.137
Larger 0.616
Deviation0.688 47.645 51 48.179
0.729 50.485 56 51.050 New A is 0.01428
0.799 55.332 59 55.952
0.1790/0.01413 = 12.66; 222 s = 12
(forbidden diffraction lines for diamond structure,
OK for zinc-blend structure!)
* = 5.82 g/cm3 then
VC (6.486)3 5.82
nM 953.67
1.66054 1.66054
M for CdTe is 112.4+127.6 = 240 n = 3.97 ~ 4
There are 4 Cd and 4 Te atoms in a unit cell.

## * FCC based structure with 4 molecules in a unit cell

NaCl and ZnS;
CdTe: NaCl or ZnS
NaCl Cd at 000 & Te at + fcc translations
1 1
2i ( h k l 0 )
1 1
2i ( h k 0 l ) 2i ( h 0 k l )
1 1
Fhkl 1 e 2 2 e 2 2
e 2 2

2i ( h k l )
1 1 1
FCC FFCC
Cd
f f Te e 2 2 2

when h, k, l all even Fhkl 16( f Cd fTe )2 2

2 2
when h, k, l all odd Fhkl 16( f Cd f Te )
ZnS Cd at 000 & Te at + fcc translations
2i ( h k l )
1 1 1
Fhkl FFCC f Cd fTee 4 4 4 Unmixed hkl only

2 2 2
when h + k + l is odd Fhkl 16( f Cd f Te )

when h + k + l

2 2
= odd multiple of 2 Fhkl 16( f Cd f Te )

2 2
= even multiple of 2 Fhkl 16( f Cd f Te )
sin
0.0 0.2 0.4 0.6 0.8 1.0 1.2

Cd 48 37.7 27.5 21.8 17.6 14.3 12.0
Te 52 41.3 30.3 24.0 19.5 16.0 13.3
fCd + fTe = 100 and |fCd fTe| = 4 at sin / = 0 to
fCd + fTe = 30.3 and |fCd fTe| = 1.7 at sin / ~ 1.0
sin
0.0 0.2 0.4 0.6 0.8 1.0 1.2

RCd Te 625 482 426 415 381 318 379
fCd fTe 2 R
Several hundreds
fCd fTe 2 Cd Te

## NaCl Cd at 000 & Te at + fcc translations

h, k, l all even: strong diffracted lines
h, k, l all odd: week diffracted lines
ZnS fit better!
Order-Disorder Determination
Substitutional solid solution A, B elements
AB atoms arrangement

order disorder
temperature
low TC high

## Example Cu-Au system (AuCu3), TC = 390 oC

Cu
Au
Cu-Au average

disordered ordered
Complete Disordered structure:

## the probability of each site being

disordered
occupied: Au, Cu
simple FCC with fav f av ( f Au 3 f Cu ) / 4

1 1
2i ( h k l 0 )
1 1
2i ( h k 0 l ) 2i ( h 0 k l )
1 1
Fhkl f av 1 e 2 2 e 2 2
e 2 2

## For mixed h, k, l Fhkl = 0

For unmixed h, k, l Fhkl = (fAu + 3fCu)
Complete Ordered structure:
1 Au atom, at 000,
three Cu atoms at 0, 0 , 0 . ordered
2i ( h 0 k 0 l 0 )
1 1
2i ( h k l 0 )
1 1
2i ( h k 0 l ) 2i ( h 0 k l )
1 1
Fhkl f Au e f Cu e 2 2 f Cu e 2 2
f Cu e 2 2

Fhkl f Au f Cu ei ( h k ) ei ( h l ) ei ( k l )
For mixed h, k, l Fhkl = (fAu fCu) Peaks
For unmixed h, k, l Fhkl = (fAu + 3fCu) show up
Define a long range order parameter S:

rA FA
S
1 FA

## rA: fraction of A sites occupied by the right

atoms; FA: fraction of A atoms in the alloy

complete order: rA = 1 S = 1;
complete disorder: rA = FA S = 0

0S1
AuCu3 : order parameter S
Average atomic factor for A-site
rAu S (1 FAu ) FAu 0.75S 0.25
A-site is the 000 equipoint
rAu :fraction of Au atoms in 000 site
the average atomic form factor

## f avA rAu f Au (1 rAu ) f Cu

0.75Sf Au 0.25 f Au 0.75 f Cu 0.75Sf Cu
f avA 0.75S ( f Au f Cu ) 0.25 f Au 0.75 f Cu
= fav
Average atomic factor for B-site
(1 rA): is the fraction of Au occupying the B site
in B site
(1 rA)/3 Au and 1 (1rA)/3 Cu = (2 + rA)/3 Cu

(1 rAu ) f Au ( 2 rAu ) f Cu
f avB
3 3

## f avB 0.25S ( f Cu f Au ) 0.25 f Au 0.75 f Cu

The structure factor is
1 1
2i ( h k l 0 )
1 1
2i ( h k 0 l ) 2i ( h 0 k l )
1 1
Fhkl f avAe 2i ( h 0 k 0l 0 ) f avB e 2 2 e 2 2
e 2 2

## For mixed h, k, l Fhkl f avA f avB

Fhkl 0.75S ( f Au f Cu ) f av 0.25S ( f Cu f Au ) f av S ( f Au f Cu )

## For unmixed h, k, l Fhkl f avA 3 f avB

Fhkl 0.75S ( f Au f Cu ) f av 3 0.25S ( f Cu f Au ) 3 f av 4 f av

## Intensity |F|2 superlattice lines S2

Using different S definition

rB FB
S
1 FB

## What would you get?

Homework!
Intensity weak diffuse background

## If atoms A and B completely random in a solid solution

diffuse scattering

## f decreases as sin/ increases ID as sin/

Weak signal, very difficult to measure
Example Cu-Zn system (CuZn), TC = 460 oC

fZn
fav
fCu

disordered ordered
* Completely random: a BCC structure
1 1 1
2i ( h k l )
2i ( h 0 k 0 l 0 )
Fhkl f av e f av e 2 2 2
f av (1 ei ( h k l ) )
f av 0.5 f Cu 0.5 f Zn

## For h + k + l even Fhkl = fCu + fZn

For h + k + l odd Fhkl = 0

## * Completely order: a CsCl

1 1 1
2i ( h k l )
Fhkl f Cu e 2i ( h 0 k 0l 0 ) f Zn e 2 2 2
f Cu f Zn ei ( h k l )
For h + k + l even Fhkl = fCu + fZn
For h + k + l odd Fhkl = fCu fZn
Define a long range order parameter S:
rA FA
S (practice yourself)
1 FA

## For h + k + l even Fhkl = fCu + fZn

For h + k + l odd Fhkl = S(fCu fZn)
1
Different system

0
T TC
Relative intensity from the superlattice line and
the fundamental line:
* Case AuCu3: ignoring the multiplication factor and
Lorentz-polarization factor, just look at the |F|2.
Intensity (superlattice line) | f Au f Cu |2

Intensity (Fundamental line) | f Au 3 f Cu |2
Assume sin/ = 0 f = z
Intensity (superlattice line) | 79 29 |2
~ 0.09
Intensity (Fundamental line) | 79 3 29 | 2

## Assume sin/ = 0.2

Intensity (superlattice line) | 65 21.6 |2
~ 0.11
Intensity (Fundamental line) | 65 3 21.6 | 2

## About 10%, can be measured without difficulty.

* Case CuZn: the atomic number Z of Cu and Zn is close
atomic form factor is close!!
Intensity (superlattice line) I S | f Cu f Zn |2

Intensity (Fundamental line) I F | f Cu f Zn |2
Assume sin/ = 0 f = z
I S | f Cu f Zn |2 | 29 30 |2
0.0003
I F | f Cu f Zn | | 29 30 |
2 2

## Assume sin/ = 0.2

I S | f Cu f Zn |2 | 21.6 22.4 |2
0.0003
I F | f Cu f Zn |2
| 21.6 22.4 |2

## choose a proper wavelength to resolve the case!

Resonance between the radiation and the
K shell electrons
larger absorption
f

Produce extra
difference in
fCu fZn

## Using Zn K radiation. f for Cu is -3.6 and for Zn is

-2.7
I S | f Cu f Zn |2 | ( 29 3.6) (30 2.7) |2
0.0013
I F | f Cu f Zn | | ( 29 3.6) (30 2.7) |
2 2