Structure Factor

Textbook’s convention:

(Note: form factor are tabulated as functions of s=g/2)

Atomic coordinates: d m = xm a1 + ym a 2 + zm a3 = ( xm , ym , zm )

(expressed as fractions of basis vectors)

RLV: g = hb1 + kb 2 + lb3

Notice that: g ⋅ d m = hxm + kym + lzm

A general result: Fhkl = ∑

m atoms
fme
2 πi ( hxm + hym + lzm )
 Example:
Simple cubic (sc) with two-atom basis
The basis vectors are:

The “basis” sometimes refers to all the atoms in the unit cell.

First atom: d1 = (0, 0, 0 )

Second atom: fB d 2 = (x, y, z )

2 πi (hx+ky+lz ) 2 πi (hx+ky+lz )
Fhkl = fA ei 0 + fB e = fA + fB e

This is the structure factor for any integers (hkl).

 Example:
Body-centered cubic (bcc) structure

The bcc structure can be generated using a sc lattice

with a two-atom basis.

First atom: f d1 = (0, 0, 0 )

Second atom: f d 2 = (0.5, 0.5, 0.5 )

Structure Factors: Fhkl = f ⋅ 1 + e πi( h + k +l ) 

πi (h+k+l )
1, h + k + l = even
e = allowed reflections:
−1, h + k + l = odd {110}
{200}
2 f , h + k + l = even {202}
So, Fhkl =  {222}
0, h + k + l = odd
{400}
systematic absences ...
 Example:
Face-Centered Cubic (fcc) Structure
The fcc structure can be generated from a sc lattice
with a four-atom basis.
First atom: f d1 = (0, 0, 0 )
Second atom: f d 2 = (0, 0.5, 0.5 )
Third atom: f d 3 = (0.5, 0, 0.5 )
Fourth atom: f d 4 = (0.5, 0.5, 0 )

πi ( k + l )
Structure Factors: Fhkl = f ⋅ 1 + e + e ( ) + e ( ) 
πi h + l πi h + k

allowed reflections:
{200}
{111}
4 f , h, k,l all even or all odd
So, Fhkl =  {220}
0, h, k,l mixed even/odd {311}
{400}
...
 Crystal Potential and Structure Factors
Crystal Potential: Φ (r ) = ∑ Φ g e−2 πig⋅r
g

Fourier Components: Φ g =φ ( g ) X g

Crystal Function: Xg = 1 v (when g is an RLV)

Unit-Cell Potential: φ (g ) = ∑ φ m e 2 πig⋅d m

m atoms

2πme
Atomic Form Factors: =fm φm
h2

Structure Factors: Fg = ∑
m atoms
f m e 2 πig⋅dm

2me Fg
Structure Function: U= Φ=
πv
g 2 g
h

The Fourier components of the crystal potential are normalized by the unit-cell volume.
 Diamond structure
Two identical, interpenetraing fcc lattices offset by ¼[111]
First lattice: d1 = 0 = 0 ⋅ a1 + 0 ⋅ a 2 + 0 ⋅ a3 = ( 0, 0, 0 )

Fhk1 = f ⋅ 1 + e πi( k + ) + e πi( h + ) + e πi( h + k ) 

( )  

Second lattice: d 2 = a ( xˆ + yˆ + zˆ ) 4 = ( a1 + a 2 + a3 ) 4= (1 4,1 4,1 4 )

Fhk2 = f ⋅ 1 + e πi( k +  ) + e πi( h +  ) + e πi( h + k )  ⋅ e πi( h + k +  ) 2
( )

Structure Factors: 4 or 0 2, 1±i or 0

Fhkl = Fhkl1 + Fhkl2 = f ⋅ 1 + e πi( k +l ) + e πi( h +l ) + e πi( h + k )  ⋅ 1 + e πi( h + k +l ) 2 

( ) ( )

8 f ,          h + k +  =4N

for hkl all even/all odd: Fhk = 4 (1 ± i ) f , h + k + = 2 N + 1
0,           h + k + = 4 N + 2


As for fcc, allowed reflections have h,k,l all even or all odd.
However, some of these reflections are kinematically forbidden.
 Zincblende Structure
Two distinct, interpenetraing fcc lattices offset by ¼[111]

First lattice: d1 = 0 = 0 ⋅ a1 + 0 ⋅ a 2 + 0 ⋅ a3 = ( 0, 0, 0 )

Fhk1 = f A ⋅ 1 + e πi( k + ) + e πi( h + ) + e πi( h + k ) 

( )  

Second lattice: d 2 0.25a ( xˆ + yˆ =

= + zˆ ) 0.25 ( a1 + a 2 +=
a3 ) ( 0.25, 0.25, 0.25 )
Fhk2 = f B ⋅ 1 + e πi( k + ) + e πi( h + ) + e πi( h + k )  ⋅ e πi( h + k + ) 2
( )   

( ) ( )
F=
hkl F 1
hkl + F 2
hkl

4 ( f A + f B ) ,          h + k + l =4 N
So, 
Fhkl= 4 ( f A ± if B ) , h + k + l= 2 N + 1

4 ( f A − f B ) ,       h + k + l= 4 N + 2

Allowed reflections have h,k,l all even or all odd.

 Superlattices
(GaAs)m/(InAs)n FFT diffraction spot

SL spots have fractional Miller indices

Large unit-cell built by ordering of a smaller unit cell

 Atomic ordering in metal alloys
CuAu-I CuPt
Pt

Au

Cu
Cu

(001) superlattice ½(111) superlattice

Specific atomic arrangements in normally random alloys

Atomic ordering in semiconductors

Sublattice ordering
 CuPt-Ordered GaInP2

single-variant

double-variant
Ordering in CuInSe2

CuAu-I (CA) and

Chalcopyrite (CH)
Ordering
 Example: Hexagonal close-packed structure
Basis vectors:
a 3
a1 =
axˆ , a 2 =
− xˆ + ayˆ , c =
czˆ
2 2
c
a is the nearest neighbor distance.

c/2 is the interlayer spacing.

a
The unit-cell volume is: 3 2 a
v= ac
2
Two atoms in the unit cell:
d1 = ( 0, 0, 0 )
First atom: f

1 2 1
Second atom: f d2 =  , , 
3 3 2
 2 πi  + +  
 h 2k  

Structure Factors: F=
hk  f 1 + e  3 3 2  
 
Notice: F00  = 0 for l=odd
 Indexing hexagonal crystals (I)
A direct-lattice vector could be written:
rUVW = U ⋅ a1 + V ⋅ a 2 + W ⋅ a3

There is a third, in-plane, symmetry equivalent vector:

− ( a1 + a 2 )
a12 =
 Indexing hexagonal crystals (II)

We could rewrite a vector as:

ruvtw = u ⋅ a1 + v ⋅ a 2 + t ⋅ a12 + w ⋅ a3 = rUVW
U= u − t
= u ⋅ a1 + v ⋅ a 2 − t ⋅ ( a1 + a 2 ) + w ⋅ a3 V= v − t
ruvtw = ( u − t ) ⋅ a1 + ( v − t ) ⋅ a 2 + w ⋅ a3 W =w

We can pick: t=− (u + v ) u ( 2U − V ) 3

=
=v ( 2V − U ) 3
t= − (U + V ) 3
[100] → 1 [ 2 1 10] w =W
3
[ 010] → 1 [ 12 10] symmetry
3 equivalent
[ 1 10] → 1 [ 1 120]
3
 Comparing close-packed structures: hcp and fcc
hcp
stacking sequence: AB/AB/AB/AB...

d n-n = a (
hcp )
nearest-neighbor distance:

interlayer spacing: d 002 = c 2

fcc stacking sequence: ABC/ABC/ABC...

nearest-neighbor distance: d n-n = a ( fcc ) 2

( fcc ) 2
=
interlayer spacing: d111 a= 3 d n-n
3

"Ideal" hexagonal close-packed

2 8 ( hcp )
c(ideal ) 2=
= d n-n a
3 3
The two structures differ in stacking sequence.
 Example: CdSe on (111) GaAs
HR FFT

111(GaAs)
0002(CdSe)

0001(CdSe)

(0001)||(111)
hexagonal CdSe
cubic

GaAs