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

1
 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.

2
 Structure Factor (Fhkl)
• The amplitude of the resultant wave is given by a
ratio of amplitudes:

amplitude of the wave scattered by all atoms of a UC

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

• The intensity of the diffracted wave is proportional

to |Fhkl|2.

3
 Some Useful Relations

ei = e3i = e5i = … = -1

e2i = e4i = e6i = … = +1
eni = (-1)n, where n is anyy integer
g
eni = e-ni, where n is any integer
eix + e-ix =2 cos x

Needed for structure factor calculations

4
 Fhkl for Simple Cubic
N
Fhkl   fi e
2 i ( hui  kv j lwi )
• Atom coordinate(s) u,v,w: i 1

– 0,0,0

Fhkl  fe2 i (0h0k 0l )  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
Fhkl   fi e
2 i ( hui  kv j lwi )
• Atom coordinate(s) u,v,w: i 1

– 0,0,0;
– ½, ½, ½.
h k l 
2 i    
Fhkl  fe 2 i (0)  fe  2 2 2


F
hkl 
 f 1 e  i h  k l 

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
2 i ( hui  kv j lwi )
• Atom coordinate(s) u,v,w: i 1

– 0,0,0;
– ½,½,0;
– ½,0,½;
– 0,½,½.

2 i    2 i    2 i   
h k h l k l
2 i  0 
Fhkl  ffe  fe
f 2 2
 fe
f  2 2
 fe
f  2 2



Fhkl  f 1  e i h k   e i hl   e i k l  
7
 Fhkl for Face Centered Cubic

Fhkl  f 1  e  i h  k   i h l 
e  i k l 
e 
• 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).

8
 Fhkl for NaCl Structure
N
Fhkl   fi e
2 i ( hui  kv j lwi )
• Atom coordinate(s) u,v,w: i 1

– Na at 0,0,0 + FC transl.;
• 0,0,0;
• ½,½,0; This means these
coordinates
• ½0½
½,0,½; (u,v,w)
• 0,½,½.

– Cl at ½,½,½ + FC transl.
• ½,½,½;  ½,½,½
The re-assignment
g of coordinates is
• 11½
1,1,½;  00½
0,0,½ based upon the equipoint concept in
• 1,½,1;  0,½,0 the international tables for
crystallography
• ½,1,1.  ½,0,0

• Substitute these u,v,w values into Fhkl equation. 9

 Fhkl for NaCl Structure – cont’d
N
Fhkl   fi e
2 i ( hui  kv j lwi )
• For Na: 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:
fCl e  i ( h  k l )
e
2 i ( h  k  l )
2
e
2 i ( h  k  l )
2
e
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 – cont’d
N
Fhkl   fi e
2 i ( hui  kv j lwi )
• Therefore Fhkl: i 1

Fhkl  f Na 1  e i ( h k )  e i ( hl )  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 ( hl )  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
CuKα radiation
80

70
Intensity (%)

60 (220)

50
I

40

30

(420)
20 (222)
(422) (600)
(442)
10 (111) (400)
(333) (440)
(311) (511)
(331) (531) 2θ (°)
0
20 30 40 50 60 70 80 90 100 110 120 13
 Fhkl for L12 Crystal Structure
N
Fhkl   fi e
2 i ( hui  kv j lwi )
• Atom coordinate(s) u,v,w: i 1

– 0,0,0; A B

– ½,½,0;
– ½,0,½;
– 0,½,½.

F  f Ae
2 i (0)
 fBe
2 ihk

2 2 f e
B
2 i h l

2 2 f e
B
2
 i kl
2 2  
hkl


F
hkl 
 f A  fB e
 i(h  k )  i(h  l )  i (k  l )
e e  14
 Fhkl for L12 Crystal Structure
F
hkl
 f A  fB e   i (h  k )  e i (h  l )  e i (k  l )

(1 0 0) Fhkl = fA + fB(-1-1+1) = fA – fB
A B
(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
Intensity (%) from a material with an
(111)
100 L12 crystal structure
A B
90

80

70

60

50
(200)

40

30
(311)
(220)
20
(100)
(110)
10 (300) (222)
(210) (211) (221)
((310)) ((320)) (321) 2 θ ((°))
0
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115

16
 Fhkl for MoSi2
• Atom positions: c
– Mo atoms at 0,0,0; ½,½,½
– Si atoms
t att 0,0,z;
00 0 0,0,z;
0 ½ ½,½,½+z;
½½ ½
½,½,½-z;
½ ½ z=1/3 1/3
– MoSi2 is actually body centered tetragonal with
a = 3.20 Å and c = 7.86 Å z
y
x

c c c a

z x b
z z y a
x y y x b

Viewed down z-axis

a b b a

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; ½,½,½
• Si atoms at 0,0, ; 0,0,z; ½,½,½+z; ½,½,½-z; z=1/3

F


 f e
2 i (0)
 f e 2 2 2
2 i h  k  l     f2 i ( l )
3  f e
2 i ( l )
3  f e 
2 i h  k  5l
2 2 6  f e  
2 i h  k  l
2 2 6  
hkl  Mo Mo   Si e Si Si Si 
   
   

F f

1 e
 i h  k  l  

  f Si  e
l
 2 i ( 3 )
e

2 i ( l )  i h  k  5l
3 e 
3 e 
i h  k  l
3  
Mo  

 
 
Now we can plug in different values for h k l to determine the structure factor.
• For
F hkl=100
 i1 0 3   i10 3  
   (0) (0) 5( 0 ) (0)
 i1 0 0  2 i ( 3 ) 2 i ( 3 )
Fhkl  f Mo 1  e  f Si  e e e 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 – cont’d
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 00 5(1)
3 
 i 00 (1)
3  
Fhkl  f Mo e  e
0
  i 0 01
 
 f Si  e

2 i ( 13 )
e
2 i ( 13 )
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 i110   f Si e 2 i (0)  e 2 i (0)  e i110   e i110  
 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
CuKα radiation
80

(110)
70
(101)
Intensity (%)

60

50
I

40
(002)
(213)
30

(112) (200)
20
(202) (211) (116) (206)

10 (301) (303)
(006) (314)
(204) (222) (312)
2θ (°)
0
20 30 40 50 60 70 80 90 100 110 120 20
 Fhkl for MoSi2 – cont’d

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:

 2 i     
 h 2k l 
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 2 2
 
 3 2
hkl
 Selection rules for HCP

0 when h  2k  3n and l  odd

f2 when h  2k  3n  1 and l  even
 i
Fhkl   2
2

3 fi when h  2k  3n  1 and l  odd

4 fi 2 when h  2k  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 h,k,l mixed and if all even
and h+k+l4N then absent and h+k+l4N 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=3N with l odd
h+2k=3N1 with l odd
h+2k=3N1 with l even

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