Analytical Methods for Materials

Lesson 18
The Structure Factor

Suggested Reading
Chapter 3 in Waseda, pp. 100-106

Chapters 3 and 4 in Cullity & Stock

Chapter 2 in Brandon & Kaplan
Pages 303-312 in DeGraef & McHenry
475
 Structure Factor (Fhkl)
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.

476
 Structure Factor (Fhkl)
• The amplitude of the resultant wave is given by the
ratio of amplitudes.

amplitude of the wave scattered by all atoms of a UC

Fhkl 
amplitude of the wave scattered by one electron

• The intensity of the reflected wave is proportional to

|Fhkl|2.

477
 Some Useful Relations

ei = e3i = e5i = … = −1

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

YOU WILL NEED THESE FOR STRUCTURE FACTOR

CALCULATIONS

The quadratic forms of the Miller Indices will also be

needed (Appendix 9 in Cullity).
478
Quadratic Forms of Miller Indices
2 2 2 2 2
h +k +l h k l hkl h +hk+k h k
Simple Face-Centered Body-Centered Diamond
1 1 0 0 100 1 1 0
2 1 1 0 110 110 2
3 1 1 1 111 111 111 3 1 1
4 2 0 0 200 200 200 4 2 0
5 2 1 0 210 5
6 2 1 1 211 211 6
7 - - - --- --- --- --- 7 2 1
8 2 2 0 220 220 220 220 8
9 3 0 0 300, 221 9 3 0
9 2 2 1 9
10 3 1 0 310 310 10
11 3 1 1 311 311 311 11
12 2 2 2 222 222 222 12 2 2
13 3 2 0 320 13 3 1
14 3 2 1 321 321 14
15 - - - --- --- --- --- 15
16 4 0 0 400 400 400 400 16 4 0
17 4 1 0 410, 322 17
17 3 2 2 17
18 4 1 1 411, 330 411, 330 18
18 3 3 0 18
19 3 3 1 331 331 331 19 3 2
20 4 2 0 420 420 420 20
21 4 2 1 421 21 4 1
22 3 3 2 332 332 22
23 - - - --- --- --- --- 23
24 4 2 2 422 422 422 422 24
25 5 0 0 500 25 5 0
25 4 3 0 433 25
(See Appendix 9 in Cullity for a more complete list) 479
 Fhkl for Simple Cubic
N
Fhkl   fi e
• Atom coordinate(s) u,v,w:
2 i ( hui  kv j lwi )

i 1

– 0,0,0

2 i (0  h  0  k  0  l )
F  fe  f
hkl

I  F2  f 2

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. 480
 Fhkl for Simple Cubic
2 i (0  h  0  k  0  l )
F  fe  f
hkl
(1 0 0) S=1 Fhkl = f (1) = f
(1 1 0) S=2 Fhkl = f (1) = f
(1 1 1) S=3 Fhkl = f (1) = f
(2 0 0) S=4 Fhkl = f (1) = f
(2 1 0) S=5 Fhkl = f (1) = f
(2 1 1) S=6 Fhkl = f (1) = f
(2 2 0) S=8 Fhkl = f (1) = f
(2 2 1) S=9 Fhkl = f (1) = f
(3 0 0) S=9 Fhkl = f (1) = f (S = h2+k2+l2)
(3 1 0) S = 10 Fhkl = f (1) = f
(3 1 1) S = 11 Fhkl = f (1) = f
(2 2 2) S = 12 Fhkl = f (1) = f 481
Intensity (%)
1,0,0
100

90

SC
80
CuKα radiation

1,1,0

70

60

50

40

2,1,0

30
1,1,1

2,1,1

20

2,2,1
3,0,0
2,0,0

3,2,1 4,1,0
10 3,1,0
3,1,1 3,2,2
2,2,0 4,1,1
3,2,0 3,3,0

2,2,2
4,0,0
0

482
15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120
 Fhkl for Body Centered Cubic
N
Fhkl   fi e
• Atom coordinate(s) u,v,w:
2 i ( hui  kv j lwi )

i 1

– 0,0,0;
– ½, ½, ½.

F  fe
2 i (0)
 fe
2i hk  l
2 2 2 
hkl


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.

See next slide for explanation 483
 Fhkl for Body Centered Cubic
F
hkl 
 f 1 e
 i(h  k  l )

(1 0 0) S=1 Fhkl = f (1−1) = 0
(1 1 0) S=2 Fhkl = f (1+1) = 2f
(1 1 1) S=3 Fhkl = f (1−1) = 0
(2 0 0) S=4 Fhkl = f (1+1) = 4 f
(2 1 0) S=5 Fhkl = f (1−1) = 0
(2 1 1) S=6 Fhkl = f (1+1) = 2f
(2 2 0) S=8 Fhkl = f (1+1) = 2f
(2 2 1) S=9 Fhkl = f (1−1) = 0
(3 0 0) S=9 Fhkl = f (1−1) = 0 (S = h2+k2+l2)
(3 1 0) S = 10 Fhkl = f (1+1) = 2f
(3 1 1) S = 11 Fhkl = f (1−1) = 0
(2 2 2) S = 12 Fhkl = f (1+1) = 2f 484
 Fhkl for Body Centered Cubic
Consider the previous body-centered unit cell containing two atoms of the same
kind located at origin, uvw=000 and uvw=½, ½, ½ basis. (S = h2+k2+l2)

F  fe 2i ( hu  kv  lw )  fe 2i ( 0 )  fe 2i ( h / 2 k / 2 l / 2 )

F  f [1  e i ( h k  l ) ] S= 2 4 6 etc.
F 2f when (h+k+l) is even: (110) (200) (211) etc.
are allowed
Selection
rules for hkl
F2  4 f 2 S= 1 3 5 etc.
reflections F  0 when (h+k+l) is odd: (100) (111) (210) etc.
are not allowed
F2 0

(001) planes are out of phase and cancel whereas (002) planes are allowed.

485
Intensity (%)
1,1,0
100

90

BCC
80
CuKα radiation

70

60

50

40

30

2,1,1
20

2,0,0
3,1,0
10
2,2,0


0 486
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120
 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;
– ½,½,0;
– ½,0,½;
– 0,½,½.

F  fe
2 i (0)
 fe
2i hk

2 2  fe
2 i 
h l

2 2  fe
2 i kl
2 2  
hkl


F
hkl 
 f 1 e
 i (h  k )  i(h  l )  i (k  l )
e e  487
 Fhkl for Face Centered Cubic
F
hkl 
 f 1 e
 i (h  k )  e i (h  l )  e i (k  l )

(1 0 0) S=1 Fhkl = f (1−1−1+1) = 0
(1 1 0) S=2 Fhkl = f (1+1−1−1) = 0
(1 1 1) S=3 Fhkl = f (1+1+1+1) = 4f
(2 0 0) S=4 Fhkl = f (1+1+1+1) = 4 f
(2 1 0) S=5 Fhkl = f (1−1+1−1) = 0
(2 1 1) S=6 Fhkl = f (1+1−1−1) = 0
(2 2 0) S=8 Fhkl = f (1+1+1+1) = 4f
(2 2 1) S=9 Fhkl = f (1+1−1−1) = 0
(3 0 0) S=9 Fhkl = f (1−1−1+1) = 0 (S = h2+k2+l2)
(3 1 0) S = 10 Fhkl = f (1+1−1−1) = 0
(3 1 1) S = 11 Fhkl = f (1+1+1+1) = 4f
(2 2 2) S = 12 Fhkl = f (1+1+1+1) = 4f 488
 Fhkl for Face Centered Cubic
F
hkl 
 f 1 e
 i (h  k )  i (h  l )  i (k  l )
e e 
• Substitute in a few values of hkl and you will find
the following:
Selection rules for hkl reflections

– When h,k,l are unmixed (i.e. all even or all odd), then
Fhkl = 4f. [NOTE: zero is considered even]

– Fhkl = 0 for mixed indices (i.e., a combination of odd

and even).

489
Intensity (%)
1,1,1
100

90

FCC
80
CuKα radiation

70

60

50
2,0,0

40

30
3,1,1
2,2,0

20

3,3,1 4,2,0

10
2,2,2

4,0,0

0

490
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120
 Fhkl for NaCl Structure
N
Fhkl   fi e
• Atom coordinate(s) u,v,w:
2 i ( hui  kv j lwi )

i 1

– Na at 0,0,0 + FC transl.;
• 0,0,0;
• ½,½,0; This means these
coordinates
• 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 of coordinates is
• 1,1,½;  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. 491

 Fhkl for NaCl Structure – cont’d
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:
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.
492
 Fhkl for NaCl Structure – cont’d
N
Fhkl   fi e
• Therefore Fhkl:
2 i ( hui  kv j lwi )

i 1

Fhkl  f Na 1  e i ( h  k )  e i ( h l )  e i ( k l )  
fCl  e i ( h  k l )  e i ( l )  e i ( k )  e i ( h ) 

which can be simplified to*:

Fhkl   f Na  fCl e i ( h  k l ) 1  e i ( h  k )  e i ( h l )  e i ( k l ) 

* See pages 140-142 in Cullity and Stock for a little more detail on this.

493
 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

No reflections

494
 (200)
100

90
NaCl
CuKα radiation
80

70
Intensity (%)

60 (220)

50

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 90 100 110 120 495
 Fhkl for L12 Crystal Structure
N
Fhkl   fi e
• Atom coordinate(s) u,v,w:
2 i ( hui  kv j lwi )

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
2 i h l

2 2 f e
2
 i kl
2 2  
hkl B B

F
hkl 
 f A  fB e
 i(h  k )  i(h  l )  i (k  l )
e e  496
 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) = fA − fB
(2 1 1) Fhkl = fA + fB(−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 497
 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

498
 Fhkl for MoSi2
• Atom positions: c
– Mo atoms at 0,0,0; ½,½,½
– Si atoms at 0,0,z; 0,0,z; ½,½,½+z; ½,½,½-z; z=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

499
 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 h k l = 1 0 0
 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 Si (1  1  1  1)  0

You will soon learn that intensity is proportional to Fhk2 l ; there is NO REFLECTION!
500
 Fhkl for MoSi2 – cont’d
Now we can plug in different values for h k l to determine the structure 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… trends will emerge… this will lead you
to the rules for diffraction…
h + k + l = even
501
 (103)
100

90
MoSi2
CuKα radiation
80

(110)
70
(101)
Intensity (%)

60

50

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 90 100 110 120 502
 Fhkl for MoSi2 – cont’d

2000 JCPDS-International Centre for Diffraction Data. All rights reserved

PCPDFWIN v. 2.1

503
 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.
504
• In HCP crystals (like Ru, Zn, 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 this expression by letting:
h  2k l
g 
3 2
which reduces the structure factor to:

Fhkl  fi 1  e 2 ig

• We can simplify this once more using the
following expression:
eix  e  ix  2 cos x

• It is possible for g to be a fraction which keeps

Fhkl complex.
• Since Fhkl represents a wave, we can multiply it
by its complex conjugate.

This gives us the square of absolute value of

wave w/ amplitude F:

F  Fhkl  fi 2 1  e 2 ig 1  e2 ig 

2 2
hkl

 fi 2  2  e 2 ig  e2 ig 
 fi 2  2  2cos(2 g ) 
 fi  2  2  cos ( g )  1 
2 2

 fi 2  4cos 2 ( g ) 
• Now, if we substitute g into the preceding, where
h  2k l
g 
3 2
we get:

 h  2k l 
F  4 fi cos  
2
hkl
2 2
 
 3 2

• Zero is obtained from this equation when:

(h  2k )  multiple of 3
l  odd

• The table on the next page summarizes structure

factor values for HCP crystals.
 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 the ICDD card for Ru.
 Structure Factor (Fhkl) for δ-WC
• Now let’s consider a slightly more complicated
structure.
• Tungsten carbide:
P6m2
– SG: 187 (P6 m2)
– Pearson: hP2
– Atom Coordinates:
Element Wyckoff Symmetry x y z Occ. CN
Symbol
W 1d 6 m2 0 0 0 1 6
C 1a 6 m2 1/ 3 2 / 3 1/ 2 1 6

510
 c
• The crystal structure is drawn
to the right.

b
• This structure is similar to a

HCP, but contains two distinct

equipoints (i.e., C and W).

• Therefore, the structure factor becomes:

 h 2k l 
2 i    
2 i  0 
Fhkl  fW e  fC e  3 3 2

2 ig
 fW  fC e
• As before, we can multiply Fhkl by its complex
conjugate which gives us:
2
F  Fhkl
2
hkl

  fW  fC e2 ig  fW  fC e2 ig 
 fW2  fW fC e2 ig  fW fC e2 ig  fC2  e2 ig e2 ig 
 fW2  fC2  fW fC  e2 ig  e2 ig 
 fW2  fC2  fW fC  2cos(2 g ) 
 fW2  fC2  fW fC 2  2cos 2 ( g )  1
 fW2  fC2  4 fW fC cos 2 ( g )  2 fW fC
  fW  fC   4 fW fC  cos ( g ) 
2 2
 • Now, if we substitute g into the preceding, where
h  2k l
g 
3 2
we will find the selection rules to be:

 fW  fC 
2
when h  2k  3n and l  even

 fW  fC   fW fC when h  2k  3n  1 and l  even
2

Fhkl  
2

 fW  fC 
2
when h  2k  3n and l  odd

 fW  fC   3 fW fC when h  2k  3n and l  odd
2

• I urge you to try it out.

 Selection Rules for Common Crystals
Crystal Type Bravais Lattice Reflections Present for Reflections Absent for
Simple Primitive, P Any 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

514
(From Leng)

515
 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

516