The Structure Factor The Structure Factor

Suggested Reading
P 303 312 i D G f &M H Pages 303-312 in DeGraef & McHenry
Pages 59-61 in Engler and Randle
1
Structure Factor (F
hkl
)
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

Describes how atomic arrangement (uvw)

1 i=
influences the intensity of the scattered beam.
It tells us which reflections (i e peaks hkl) to It tells us which reflections (i.e., peaks, hkl) to
expect in a diffraction pattern.
2
Structure Factor (F
hkl
)
The amplitude of the resultant wave is given by a
ratio of amplitudes: ratio of amplitudes:
amplitude of the wave scattered by all atoms of a UC
li d f h d b l
hkl
F =
The intensity of the diffracted wave is proportional
amplitude of the wave scattered by one electron
hkl
The intensity of the diffracted wave is proportional
to |F
hkl
|
2
.
3
Some Useful Relations
e
ti
= e
3ti
= e
5ti
= = -1
e
2ti
= e
4ti
= e
6ti
= = +1
e
nti
= (-1)
n
, where n is any integer y g
e
nti
= e
-nti
, where n is any integer
e
ix
+ e
-ix
=2 cos x
Needed for structure factor calculations Needed for structure factor calculations
4
F
hkl
for Simple Cubic
Atom coordinate(s) u,v,w:
0,0,0
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

0,0,0
2 (0 0 0 ) i h k l 2 (0 0 0 ) i h k l
hkl
F fe f
t + +
= =
No matter what atom coordinates or plane indices you substitute into the 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.
5
Thus, all reflections are allowed for simple cubic (primitive) structures.
F
hkl
for Body Centered Cubic
Atom coordinate(s) u,v,w:
0,0,0;
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

0,0,0;
, , .
2
h k l
i
| |
|
2
2 (0)
2 2 2
h k l
i
i
hkl
F fe fe
t
t
| |
+ +
|
\ .
= +

( )
( )
1
i h k l
F f e
hkl
t + +
= +
When h+k+l is even F
hkl
= non-zero reflection.
6
When h+k+l is odd F
hkl
= 0 no reflection.
F
hkl
for Face Centered Cubic
Atom coordinate(s) u,v,w:
0,0,0;
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

0,0,0;
,,0;
,0,;
0,,.
( )
2 2 2
2 0
2 2 2 2 2 2
h k h l k l
i i i
i
f f f f
t t t
t
| | | | | |
+ + +
| | |
\ . \ . \ .
( ) 2 0
2 2 2 2 2 2
i
hkl
F fe fe fe fe
t
\ . \ . \ .
= + + +

7
( ) ( ) ( )
( )
1
i h k i h l i k l
hkl
F f e e e
t t t + + +
= + + +
F
hkl
for Face Centered Cubic
( ) ( ) ( )
( )
1
i h k i h l i k l
hkl
F f e e e
t t t + + +
= + + +
Substitute in a few values of hkl and you will find
the following: the following:
When h,k,l are unmixed (i.e. all even or all odd), then
F
hkl
= 4f. [NOTE: zero is considered even]
F 0 f i d i di (i bi ti f dd F
hkl
= 0 for mixed indices (i.e., a combination of odd
and even).
8
F
hkl
for NaCl Structure
Atom coordinate(s) u,v,w:
Na at 0,0,0 +FC transl.;
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

Na at 0,0,0 FC transl.;
0,0,0;
,,0;
0
This means these
coordinates
,0,;
0,,.
coordinates
(u,v,w)
Cl at ,, + FC transl.
,,; ,,
1 1 0 0
The re-assignment of coordinates is
1,1,; 0,0,
1,,1; 0,,0
,1,1. ,0,0
g
based upon the equipoint concept in
the international tables for
crystallography
9
Substitute these u,v,w values into F
hkl
equation.
F
hkl
for NaCl Structure contd
For Na:
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

( )
2 (0) ( ) ( ) ( ) i i h k i h l i k l
f e e e e
t t t t + + +
+ + + =
( )
( )
( ) ( ) ( ) ( )
( ) ( ) ( )
1
Na
i h k i h l i k l
Na
f e e e e
f e e e
t t t + + +
+ + + =
+ + +
For Cl:
( )
( )
2 ( ) 2 ( ) 2 ( )
( )
2 2 2
l k h
i h k i h l i k l
i h k l
Cl
f e e e e
t t t
t
+ + + + + +
+ +
+ + + =
( )
( )
( ) ( ) ( ) ( )
( ) ( ) ( )
2 2 2 2
( )
2 2 i h k l i i i h k h l k l
Cl
i h k l i i i
Cl
f e e e e
f e e e e
t t t t
t t t t
+ + + + + + + +
+ +
+ + + ~
+ + +
l k h
l k h
These terms are all positive and even.
Whether the exponent is odd or
10
Whether the exponent is odd or
even depends solely on the remaining
h, k, and l in each exponent.
F
hkl
for NaCl Structure contd
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

Therefore F
hkl
:
( )
( )
( ) ( ) ( )
( ) ( ) ( ) ( )
1
i h k i h l i k l
hkl Na
i h k l i i i
Cl
F f e e e
f e e e e
t t t
t t t t
+ + +
+ +
= + + + +
+ + +
l k h
( )
Cl
f e e e e + + +
which can be simplified to
*
:
( )( )
( ) ( ) ( ) ( )
1
i h k l i h k i h l i k l
hkl Na Cl
F f f e e e e
t t t t + + + + +
= + + + +
11
F
hkl
for NaCl Structure
When hkl are even F
hkl
= 4(f
Na
+ f
Cl
)
Primary reflections Primary reflections
When hkl are odd F = 4(f f ) When hkl are odd F
hkl
= 4(f
Na
- f
Cl
)
Superlattice reflections
When hkl are mixed F
hkl
= 0
N fl ti No reflections
12
(200)
100
80
90
NaCl
CuK radiation
(220)
%
)
60
70
I
n
t
e
n
s
i
t
y

(
50
I
30
40
(111)
(222)
(400)
(420)
(422) (600)
(442)
10
20
13
(111)
(311)
(400)
(331)
(333)
(511)
(440)
(531)
20 30 40 50 60 70 80 90 100 110 120
2 ()
0
10
F
hkl
for L1
2
Crystal Structure
Atom coordinate(s) u,v,w:
0,0,0;
A
B
2 ( )
1
i j i
N
i hu kv lw
hkl i
i
F f e
t + +
=
=

0,0,0;
,,0;
,0,;
A
0,,.
( ) ( ) ( )
2 2 2
2 (0)
2 2 2 2 2 2
h k h l k l
i i i
i
t t t
t
+ + +
( ) ( ) ( )
2 (0)
2 2 2 2 2 2
A B B B
i
F f e f e f e f e
hkl
t
= + + +

14
( )
( ) ( ) ( )
A B
i h k i h l i k l
F f f e e e
hkl
t t t + + +
= + + +
F
hkl
for L1
2
Crystal Structure
( )
( ) ( ) ( )
A B
i h k i h l i k l
F f f e e e
hkl
t t t + + +
= + + +
(1 0 0) F
hkl
= f
A
+ f
B
(-1-1+1) = f
A
f
B
(1 1 0) F
hkl
= f
A
+ f
B
(1-1-1) = f
A
f
B
A
B
(1 1 1) F
hkl
= f
A
+ f
B
(1+1+1) = f
A
+3 f
B
(2 0 0) F
hkl
= f
A
+ f
B
(1+1+1) = f
A
+3 f
B
(2 1 0) F
hkl
= f
A
+ f
B
(-1+1-1) = f
A
f
B
(2 1 0) F
hkl
f
A
f
B
( 1 1 1) f
A
f
B
(2 2 0) F
hkl
= f
A
+ f
B
(1+1+1) = f
A
+3 f
B
(2 2 1) F
hkl
= f
A
+ f
B
(1-1-1) = f
A
f
B
(3 0 0) F
hkl
= f
A
+ f
B
(-1-1+1) = f
A
f
B
(3 1 0) F
hkl
= f
A
+ f
B
(1-1-1) = f
A
f
B
(3 1 1) F
hkl
= f
A
+ f
B
(1+1+1) = f
A
+3 f
B
15
(3 1 1) F
hkl
f
A
+ f
B
(1+1+1) f
A
+3 f
B
(2 2 2) F
hkl
= f
A
+ f
B
(1+1+1) = f
A
+3 f
B
Intensity (%)
100
(111)
Example of XRD pattern
from a material with an
L1
2
crystal structure
A
B
80
90
100
A
B
60
70
80
40
50
60
(200)
30
40
(220)
(311)
2 ()
10
20
(100)
(110)
(210)
(211) (221)
(300)
(310)
(222)
(320)
(321)
16
( )
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115
0
( ) ( )
F
hkl
for MoSi
2
Atom positions:
Mo atoms at 0,0,0; ,,
Si t t 0 0 0 0 1/3
c
Si atoms at 0,0,z; 0,0,z; ,,+z; ,,-z; z=1/3
MoSi
2
is actually body centered tetragonal with
a = 3.20 and c = 7.86
z
c
c
a
c
x
y
x y
z
x y
z
b
x
y
z
a
b
a
b
a
b
Viewed down z-axis
17
a a
Viewed down x-axis Viewed down y-axis
F
hkl
for MoSi
2
Substitute in atom positions:
( ) 2
1
t + +
=
=

i j i
N
i hu kv lw
hkl i
i
F f e
Mo atoms at 0,0,0; ,,
Si atoms at 0,0, ; 0,0,z; ,,+z; ,,-z; z=1/3
( ) ( ) ( )
5 | | | | h k l h k l h k l l l
( ) ( ) ( )
( ) ( )
5
2 2 2 2 ( ) 2 ( )
2 (0)
2 2 2 2 2 6 2 2 6 3 3
5
t t t t t
t
| | | |
+ + + + + +
| |
= + + + + +
| |
| |
\ . \ .
| |
h k l h k l h k l l l
i i i i i
i
F f e f e f e f e f e f e
hkl Mo Mo Si Si Si Si
l l l l
h k h k
( )
( ) ( )
5
2 ( ) 2 ( )
3 3 3 3
1
t t t t
t
| |
+ + + +
| | + + |
= + + + + +
|
|
\ .
|
\ .
l l l l
i h k i h k i i
i h k l
F f e f e e e e
Mo Si
Now we can plug in different values for h k l to determine the structure factor.
F h k l 1 0 0 For h k l = 1 0 0
( )
( )
( ) ( )
5( 0) ( 0)
( 0) ( 0)
3 3
3 3
1 0 1 0
2 ( ) 2 ( )
1 0 0
2
1
0
(1 1) (1 1 1 1) 0
t t
t t
t
+ + + +

+ + | |
= + + + + +
|
=
\ .
= + + =
i i
i i
i
hkl Mo Si
hkl
Mo Si
F f e f e e e e
F
f f
18
2
( ) ( )
You will soon learn that intensity is proportional to ; there is NOREFLECTION!
Mo S
l
i
hk
F
f f
Nowwe can plug in different values for h k l to determine the structure factor
F
hkl
for MoSi
2
contd
Now we can plug in different values for h k l to determine the structure factor.
For h k l = 0 0 1
( )
( )
( ) ( )
5(1) (1)
1 1
3 3
3 3
0 0 0 0
2 ( ) 2 ( )
0 0 1 0
t t
t t
t
+ + + +

+ + | |
= + + + + +
|
\ .
i i
i i
i
hkl Mo Si
F f e e f e e e e
2
2
3
(1 ) (2 ( ) )
(1 1) ( 1 1) 0
t t
t
= + + +
= + + =

i i
Mo Si
Mo si
f e f COS e
f f
For h k l = 1 1 0
2
0 NOREFLECTION! =
hkl
F
( )
( )
( ) ( )
( )
1 1 0 1 1 0 1 1 0 0 2 (0) 2 (0)
2 (0) (0) 2 2
(1 ) ( )
(2) (4)
t t t t t
t t t
+ + + + + +
= + + + + +
= + + + + +
= +
i i i i i
hkl Mo Si
i i i
Mo Si
Mo si
F f e e f e e e e
f e f e e e e
f f
If you continue for different h k l combinations trends will emerge this will lead you
2
POSITIVE! YOU WILL SEE A REFLECTION

=
hkl
F
19
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
100
(103)
80
90
(110)
MoSi
2
CuK radiation
%
)
60
70
(101)
(110)
I
n
t
e
n
s
i
t
y

(
50
I
30
40
(002)
(213)
10
20
(112)
(200)
(202)
(211)
(116)
(301)
(206)
(303)
20
20 30 40 50 60 70 80 90 100 110 120
2 ()
0
10
(006)
(204)
(222)
(301)
(303)
(312)
(314)
F
hkl
for MoSi
2
contd
2000 J CPDS International Centre for Diffraction Data All rights reserved
21
2000 J CPDS-International Centre for Diffraction Data. All rights reserved
PCPDFWIN v. 2.1
Structure Factor (F
hkl
) for HCP
2 ( )
i j i
N
i hu kv lw
F f
t + +

Describes howatomic arrangement (uvw)

( )
1
i j i
hkl i
i
F f e
=
=

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
structure with atoms located at positions u,v,w.
In HCP crystals (like Ru Zn Ti and Mg) the In HCP crystals (like Ru, Zn, Ti, and Mg) the
lattice point coordinates are:
0 0 0

1 2 1
3 3 2
Therefore, the structure factor becomes:
2
2
h k l
i t
| |
+ +
|

2
3 3 2
1
i
hkl i
F f e
t
| |
+ +
|
\ .

= +
`
)
We simplify this expression by letting: p y p y g
2 1
3 2
h k
g
+
= +
which reduces the structure factor to:
{ }
2
1
ig
hkl i
F f e
t
= +
We can simplify this once more using:
{ }
1
hkl i
F f e +
from which we find:
2
ix ix
2cos
ix ix
e e x + =
2 2 2
2
4 cos
h k l
F f t
+
| |
= +
|
4 cos
3 2
hkl i
F f t = +
|
\ .
Selection rules for HCP
0 when 2 3 and odd h k n l + = =

2
2
2
when 2 3 1 and even
3 when 2 3 1 and odd
i
hkl
f h k n l
F
f h k n l

+ = =

=

+ = =

2
3 when 2 3 1 and odd
4 when 2 3 and even
i
i
f h k n l
f h k n l
+

+ = =

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. ad t e C ca d o u
List of selection rules for different crystals
Crystal Type Bravais Lattice Reflections Present Reflections Absent
Simple Primitive, P Any h,k,l None p , y
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+l=4N then absent
h,k,l mixed and if all even
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=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 If the alloys lack long range order, then you
must average the atomic scattering factor.
f
alloy
=x
A
f
A
+ x
B
f
B
where x
n
is an atomic fraction for the atomic
i constituent
27
Exercises
For CaF
2
calculate the structure factor and
determine the selection rules for allowed determine the selection rules for allowed
reflections.
28