The Structure Factor

Suggested Reading
Pages 303
P
303-312
312 iin D
DeGraef
G f&M
McHenry
H
Pages 59-61 in Engler and Randle

Structure Factor (Fhkl)

N

Fhkl fi e

2 i ( hui kv j lwi )

i 1
i

Describes how atomic arrangement (uvw)

influences the intensity of the scattered beam.
It tells us which reflections (i
(i.e.,
e peaks
peaks, hkl) to
expect in a diffraction pattern.

Structure Factor (Fhkl)

The amplitude of the resultant wave is given by a
ratio of amplitudes:
Fhkl

amplitude of the wave scattered by all atoms of a UC

amplitude
li d off the
h wave scatteredd by
b one electron
l

The intensity of the diffracted wave is proportional

to |Fhkl|2.

Some Useful Relations

ei = e3i = e5i = = -1
e2i = e4i = e6i = = +1
g
eni = (-1)n, where n is anyy integer
eni = e-ni, where n is any integer
eix + e-ix =2 cos x
Needed for structure factor calculations

Fhkl for Simple Cubic

N

Atom coordinate(s) u,v,w:

Fhkl fi e

2 i ( hui kv j lwi )

i 1

0,0,0

Fhkl fe2 i (0h0k 0l ) f

No matter what atom coordinates or plane indices you substitute into the
structure factor equation for simple cubic crystals, the solution is always
non-zero.
Thus, all reflections are allowed for simple cubic (primitive) structures.
5

Fhkl for Body Centered Cubic

N

Atom coordinate(s) u,v,w:

Fhkl fi e

2 i ( hui kv j lwi )

i 1

0,0,0;
, , .

Fhkl fe 2 i (0) fe

h k l
2 i
2 2 2

i h k l

F
f 1 e
hkl

When h+k+l is even Fhkl = non-zero reflection.

When h+k+l is odd Fhkl = 0 no reflection.
6

Fhkl for Face Centered Cubic

N

Fhkl fi e

Atom coordinate(s) u,v,w:

2 i ( hui kv j lwi )

i 1

0,0,0;
,,0;
,0,;
0,,.

Fhkl ffe

2 i 0

fe
f

h k
2 i
2 2

fe
f

h l
2 i
2 2

fe
f

k l
2 i
2 2

Fhkl f 1 e i h k e i hl e i k l

Fhkl for Face Centered Cubic

i h k

Fhkl f 1 e

i h l

i k l

Substitute in a few values of hkl and you will find

the following:
When h,k,l are unmixed (i.e. all even or all odd), then
Fhkl = 4f. [NOTE: zero is considered even]
Fhkl = 0 ffor mixed
i d iindices
di
(i
(i.e., a combination
bi ti off odd
dd
and even).

Fhkl for NaCl Structure

N

Atom coordinate(s) u,v,w:

Fhkl fi e

2 i ( hui kv j lwi )

i 1

Na at 0,0,0 + FC transl.;

0,0,0;
,,0;
0
,0,;
0,,.

This means these

coordinates
(u,v,w)

Cl at ,, + FC transl.

,,;
11
1,1,;
1,,1;
,1,1.

,,
00
0,0,
0,,0
,0,0

The re-assignment
g
of coordinates is
based upon the equipoint concept in
the international tables for
crystallography

Substitute these u,v,w values into Fhkl equation.

Fhkl for NaCl Structure contd

N

Fhkl fi e

For Na:

2 i ( hui kv j lwi )

i 1

f Na e 2 i ((0)) e i ( h k ) e i ( h l ) e i ( k l )
f Na 1 e i ( h k ) e i ( h l ) e i ( k l )

For Cl:

i ( h k l )

fCl e

2 i ( h k l )
2

2 i ( h k l )
2

2 i ( h k l )
2

fCl e i ( h k l ) e i ( 2 h 2 k l ) e i ( 2 h k 2l ) e i ( h 2 k 2l )
fCl e i ( h k l ) e i ( l ) e i ( k ) e i ( h)

These terms are all positive and even.

Whether the exponent is odd or
even depends solely on the remaining
h, k, and l in each exponent.
10

Fhkl for NaCl Structure contd

N

Fhkl fi e

Therefore Fhkl:

2 i ( hui kv j lwi )

i 1

Fhkl f Na 1 e i ( h k ) e i ( hl ) e i ( k l )
f Cl e i ( h k l ) e i ( l ) e i ( k ) e i ( h)

which can be simplified to*:

Fhkl f Na f Cl e i ( h k l ) 1 e i ( h k ) e i ( hl ) e i ( k l )

11

Fhkl for NaCl Structure

When hkl are even Fhkl = 4(fNa + fCl)
Primary reflections
When hkl are odd Fhkl = 4(fNa - fCl)
Superlattice reflections
When hkl are mixed Fhkl = 0
N reflections
No
fl ti

12

(200)

100

90

NaCl
CuK radiation

80

Intensity (%)
I

70

(220)

60

50

40

30

20

(420)

(222)

(422)
10

(111)

(400)
(311)

0
20

30

40

50

(333)
(511)

(331)
60

70

(600)
(442)

80

90

(440)
(531)
100

110

2 ()
120

13

Fhkl for L12 Crystal Structure

N

Fhkl fi e

Atom coordinate(s) u,v,w:

F
hkl

0,0,0;
,,0;
,0,;
0,,.

i 1

2 i ( hui kv j lwi )

hk
h l
kl
i
i
i
2

2 i (0)
2 2 f e
2 2 f e
2 2
f Ae
fBe
B
B

F
hkl

i(h k ) i(h l ) i (k l )
f A fB e
e
e

14

Fhkl for L12 Crystal Structure

i (h k ) e i (h l ) e i (k l )

F
f A fB e
hkl
(1 0 0)

Fhkl = fA + fB(-1-1+1) = fA fB

(1 1 0)

Fhkl = fA + fB(1-1-1) = fA fB

(1 1 1)

Fhkl = fA + fB(1+1+1) = fA +3 fB

(2 0 0)

Fhkl = fA + fB(1+1+1) = fA +3 fB

(2 1 0)

Fhkl = fA + fB((-1+1-1)
1 1 1) = fA fB

(2 2 0)

Fhkl = fA + fB(1+1+1) = fA +3 fB

(2 2 1)

Fhkl = fA + fB(1-1-1) = fA fB

(3 0 0)

Fhkl = fA + fB(-1-1+1) = fA fB

(3 1 0)

Fhkl = fA + fB(1-1-1) = fA fB

(3 1 1)

Fhkl = fA + fB(1+1+1) = fA +3 fB

(2 2 2)

Fhkl = fA + fB(1+1+1) = fA +3 fB

15

Example of XRD pattern

from a material with an
L12 crystal structure

Intensity (%)
(111)

100

90
80
70
60
50

(200)

40
30

(311)

(220)
20
10
0
20

(100)

(110)

(300)
(221)

(210) (211)
25

30

35

40

45

50

55

60

65

70

75

80

(222)
((320)) (321)

((310))
85

90

95

100

105

110

2 (())
115
16

Fhkl for MoSi2

Atom positions:

Mo atoms at 0,0,0; ,,
Si atoms
t
att 0,0,z;
00 0
0,0,z;
0
,,+z;

,,-z;
z=1/3
1/3
MoSi2 is actually body centered tetragonal with
z

a = 3.20 and c = 7.86

x
c

c
z

z
x

z
y

y
b

Viewed down z-axis

Viewed down x-axis

Viewed down y-axis

17

Fhkl for MoSi2

N

Fhkl f i e

2 i ( hui kv j lwi )

i 1

Substitute in atom positions:

Mo atoms at 0,0,0; ,,
Si atoms at 0,0, ; 0,0,z; ,,+z; ,,-z; z=1/3

2 i h k l

2 i (0)
2 2 2
F
f e
f e
hkl Mo
Mo

2 i h k 5l
2 i h k l
2 i ( l )
2 i ( l )
2 2 6 f e
2 2 6
3 f e
3 f e
Si e
Si
Si
Si

l
i h k l
2 i ( l ) i h k 5l

i h k l
2 i ( 3 )
3 e
3
3 e
e
F f
1 e
f Si e
Mo

Now we can plug in different values for h k l to determine the structure factor.
For
F hkl=100
5( 0 )
(0)
(0)
(0)
i1 0 3
i10 3
2 i ( 3 )
2 i ( 3 )
i1 0 0

f Si e
e
e
e
Fhkl f Mo 1 e

Fhkl2 0

f Mo ((1 1)) f SSii ((1 1 1 1)) 0

You will soon learn that intensity is proportional to Fhk2 l ; there is NO REFLECTION!

18

Fhkl for MoSi2 contd

Now we can plug in different values for h k l to determine the structure factor
factor.
For h k l = 0 0 1
i 00 5(1)
i 00 (1)
2 i ( 13 )
2 i ( 13 )
i 0 01

0
3
3
f Si e
e
e
e
Fhkl f Mo e e

f Mo (1 e i ) f Si (2COS ( 23 ) e 2 i )

f Mo (1 1) f si (1 1) 0

Fhkl2 0 NO REFLECTION!

For h k l = 1 1 0

Fhkl f Mo e0 e i110 f Si e 2 i (0) e 2 i (0) e i110 e i110

f Mo (1 e 2 i ) f Si (e(0) e(0) e 2 i e 2 i )
f Mo (2) f si (4)

Fhkl2 POSITIVE! YOU WILL SEE A REFLECTION

If you continue for different h k l combinations

combinations
trends will emerge
emerge this will lead you
to the rules for diffraction
h + k + l = even
19

(103)

100

90

MoSi2

CuK radiation

80
(110)
70

Intensity (%)
I

(101)
60

50

40
(002)

(213)

30
(112)

20

(200)
(116)

(202) (211)
10
0
20

(006)
30

40

50

60

70

(206)
(301)

(204)

(222)

80

90

(303)
(312)
100

110

(314)

2 ()

120

20

Fhkl for MoSi2 contd

2000 JCPDS-International
JCPDS International Centre for Diffraction Data.
Data All rights reserved
PCPDFWIN v. 2.1
21

Structure Factor (Fhkl) for HCP

N

Fhkl fi e

2 i ( hui kv j lwi )

i 1

Describes how atomic arrangement (uvw)

influences the intensity of the scattered beam.
i.e.,
It tells us which reflections (i.e., peaks, hkl) to
expect in a diffraction pattern from a given crystal
structure with atoms located at positions u,v,w.
22

 In HCP crystals (like Ru

Ru, Zn
Zn, Ti
Ti, and Mg) the
lattice point coordinates are:
000
1 2 1

3 3 2

Therefore, the structure factor becomes:

h 2k l
2 i

Fhkl fi 1 e 3 3 2

 We simplify
p y this expression
p
by
y letting:
g
h 2k 1

g
3
2

which reduces the structure factor to:

Fhkl fi 1 e

2 ig

We can simplify this once more using:

from which we find:
eix e ix 2 cos x

h 2k l

F 4 fi cos

2
3
2
hkl

Selection rules for HCP

0
f2
i
2
Fhkl 2
3 fi
4 fi 2

when h 2k
when h 2k
when h 2k
when h 2k

3n and l odd
3n 1 and l even
3n 1 and l odd
3n and l even

For your HW problem, you will need these things to

do the structure factor calculation for Ru.
HINT: It might save you some time if you already
had
ad tthe
e ICDD
C
ca
card
d for
o Ru.
u

List of selection rules for different crystals

Crystal Type

Bravais Lattice

Reflections Present

Reflections Absent

Simple
p

Primitive,, P

Anyy h,k,l

None

Body-centered

Body centered, I

h+k+l = even

h+k+l = odd

Face-centered

Face-centered, F

h,k,l unmixed

h,k,l mixed

NaCl

FCC

h,k,l unmixed

h,k,l mixed

Zincblende

FCC

Same as FCC, but if all even

and h+k+l4N then absent

h,k,l mixed and if all even

and h+k+l4N then absent

Base-centered

Base-centered

h,k both even or both odd

h,k mixed

Hexagonal close-packed

Hexagonal

h+2k=3N with l even

h+2k=3N1 with l odd
h+2k=3N1 with l even

h+2k=3N with l odd

26

What about solid solution alloys?

If the alloys lack long range order, then you
must average the atomic scattering factor.
falloy =xAfA + xBfB
where xn is an atomic fraction for the atomic
constituent
i

27

Exercises
For CaF2 calculate the structure factor and
determine the selection rules for allowed
reflections.

28