The Brillouin Zone

-/a /a
1D Reciprocal lattice

k
-6/a -4/a -2/a 0 2/a 4/a

• Is defined as the Wigner-Seitz primitive cell in

the reciprocal lattice (smallest unique set of
distance/area/volume in reciprocal space)
• Its construction exhibits all the wavevectors k
which can be Bragg-reflected by the crystal
• Also critical for understanding energy diagrams
Group: Determine the shape of the BZ
of the FCC Lattice

How many sides will

it have and along
what directions?

SC BCC FCC
FCC Primitive and
# of nearest Unit
Conventional neighbors
Cells 6 8 12
Nearest-neighbor distance a ½ a 3 a/2
# of second neighbors 12 6 6
Second neighbor distance a2 a a
 WS zone and BZ
Lattice Real Space Lattice K-space

bcc WS cell Bcc BZ (fcc lattice in K-space)

fcc WS cell fcc BZ (bcc lattice in K-space)

The WS cell of bcc lattice in real space transforms to a Brillouin zone

in a fcc lattice in reciprocal space while the WS cell of a fcc lattice
transforms to a Brillouin zone of a bcc lattice in reciprocal space.
 Brillouin Symbol Description

Zone of Γ Center of the Brillouin zone

Simple Cubic
Silicon M Center of an edge
R Corner point
X Center of a face
FCC
Middle of an edge joining
K
two hexagonal faces
L Center of a hexagonal face C6
Middle of an edge joining a
U
hexagonal and a square face
W Corner point
Points of symmetry on the BZ are X Center of a square face C4
important (e.g. determining BCC
bandstructure).
H Corner point joining 4 edges
Electrons in semiconductors are
N Center of a face
perturbed by the potential of the
P Corner point joining 3 edges
crystal, which varies across unit cell.
 Usually, it is sufficient to know the
Nomenclature
energy En(k) curves - the dispersion
relations - along the major directions.

Directions are chosen that lead aong

special symmetry points. These
points are labeled according to the
following rules:
Direction along BZ

Energy or Frequency
• Points (and lines) inside the Brillouin zone are denoted with Greek letters.
• Points on the surface of the Brillouin zone with Roman letters.
• The center of the Wigner-Seitz cell is always denoted by a G
 XRD allows Crystal Structure Determination
POSITION OF LATTICE TYPE
PEAKS

WIDTH OF PERFECTION OF
PEAK LATTICE

INTENSITY OF POSITION OF
PEAKS ATOMS IN BASIS
What do we need to know in order to define the crystal structure?
- The lattice parameters and the lattice type
(this defines the positions of diffraction spots)
- The atom type at each point PbS

(these define the intensity of diffraction spots)

Conclusion: If we measure positions and intensities of many spots,
then we should be able to determine the crystal structure.
 To get a diffraction peak, K has to be a
reciprocal lattice vector, but even if K is,
 f(r)e-irK might still be zero!
Structure Factor Shkl gives intensity of peaks
The scattered x-ray amplitude is proportional to:

A fe
all atoms
i
 i ( ri K )
  f e
lattice basis
i
 i ( ri K hkl )


k'
Structure factor S hkl

K
2

ko Can break this sum into a sum over all lattices
and a sum over all of the atoms within the basis.
 
S hkl   f i e  i ( ri  K hkl )
r○ K
i

r = n1 a1 + n2 a2 + n3 a3 (real space)

K  hb1  kb2  lb3

Different h,k,l

bi a j  2ij

Cubic form: S hkl

Works for any conventional cubic cell

Where xi, yi and zi are the lattice positions of the atoms in the basis.
h, k and l are the miller indices of different planes in the crystal.
 Group: Simple Cubic Lattice
S hkl

Simplify the structure factor for the simple cubic

lattice for a one atom basis. Just let f be a constant.

F   fi exp2ihxi kyi  lzi 

S hkl
i

One atom basis : r  0,0,0 

S hklF  fexp2i0  h  0 k  0  l
   
 f exp 2i 0
 fexp0
f
Where xi, yi and zi are the lattice positions of the atoms in the basis.
 How Do We Determine The Lattice Constant?

S hkl  f e  f  I hkl  S hkl  f 2

For the simple cubic lattice i (0) 2
with a one atom basis:

So the x-ray intensity is nonzero for all values of (hkl), subject to the Bragg
condition, which can be expressed   2d hkl sin  .

a
We know for cubic lattices (a=b=c): d hkl 
h 2
 k2  l2 1/ 2

2
Substituting and squaring both sides: sin 2  
4a 2
h 2
 k2  l2 

Thus, if we know the x-ray

wavelength and are given (or can
sin 2 
measure) the angles at which each
diffraction peak occurs, we can
determine a for the lattice! How?
h2  k 2  l 2
Missing Spots in the Diffraction Pattern
In some lattices, the
arrangement and spacing of
planes produces diffractions
from planes that are always
exactly 180º out of phase
causing a phenomenon called
Can you extinction.
For the BCC lattice the (100)
think of an planes are interweaved with
example? an equivalent set at the
halfway position, giving a
reflection exactly out of phase,
which exactly cancel the
signal. =/2
 Extinction in BCC

(-101)

(001)

What about the 101 family of planes?

 Group: The Structure Factor of BCC
What values of hkl do not have diffraction peaks?
Analysis of more than one lattice point per conventional unit cell
E.g: bcc and fcc lattices

S hkl   f i e  iK hkl r

i S hkl

bcc conventional lattice has two

a1  ax  y  z 
1  b1  y  z 
2 
atoms
 per
2 unit cell located
 a at
a 2  12 a x  y  z  b 2  2a x  z 
r1 = (0,0,0) and r2 = (1/2,1/2,1/2)

a3  2 ax  y  z  b3  a x  y 
1 2
 Group: Find the structure factor for BCC.
Under what h,k,l is it non-zero?
S hkl
1 1 1 
 
Two atom basis : r  0,0,0 & r   , , 
2 2 2 
  1 1 1 

  
S hklF  f exp 2i 0  h  0 k  0  l  exp2i  h  k   l
 2 2 2 

  
 f 1 exp i h k  l 
h, k & l are integers, so h k  l  N (where N is an integer)
The exponential can then take one of two values :
  
exp i h k  l  1 if N  even
expih k  l 1 if N  odd
So :
S hkl
F = 2f if N  even
S hkl
F = 0 if N  odd
 Visualizing the structure
factor for BCC
• Allowed low order reflections are: 002 022
– 110, 200, 112, 220, 310, 222,
321, 400, 330, 411, 420 … 112
011
– Draw lowest on this cube -> 202
• Forbidden reflections are: 121
– 100, 111, 210… 101
000
020
– Due to identical plane of atoms 211
halfway between causes
110
destructive interference
• Real bcc lattice has an fcc
200 220
reciprocal lattice (this is a good
trick for remembering the rule)
This kind of argument leads to rules for identifying
the lattice symmetry from "missing" reflections.
 How to determine lattice parameter this time?
For a bcc lattice with a one atom basis, the x-ray intensity is
nonzero for all planes (hkl), subject to the Bragg condition, except
for the planes where h+k+l is odd. Thus, diffraction peaks will be
observed for the following planes:
(100) (110) (111) (200) (210) (211) (220) (221) (300) …

Just as before, if we are given or can

measure the angles at which each sin 2  What if you don’t
diffraction peak occurs, we can
know the h k l values?
graphically determine a for the lattice!
h2  k 2  l 2

A similar analysis can be done for a crystal with the fcc

lattice with a one atom basis. For materials with more
than one of the same atom type per basis in a cubic
lattice, the rules for the structure factor can be modified.
 Allowed Diffraction Peaks
(See a trend?) sin    h 
2
2
2
2
 k2  l2
4a
More lattice points in conventional cell  less peaks

2 3 4 5 6 8

2 3 4 5 6 7

4 8 11 16 19
/ / / 4 / /
3 3 3 3 3
 Group: Find the structure factor and
extinctions for FCC.
S hkl
1 1  1 1  1 1
 
Four atom basis: r  0,0,0 , r   , ,0 , r   ,0,  & r   0, , 
2 2  2 2  2 2

S hklF  f 1 exp  i h  k   exp  i k  l  exp  i h  l
So:
S hklF=4f if h,k,l all even or odd
S hklF=0 if h,k,l are mixed even or odd
 Group: Find the structure factor for FCC.
1 1  1 1  1 1
 
Four atom basis: r  0,0,0 , r   , ,0 , r   ,0,  & r   0, , 
2 2  2 2  2 2
SFhkl f 1 exp  i h  k   exp  i k  l  exp  i h  l
So:
002 022
S hklF=4f if h,k,l all even or odd
S hklF=0 if h,k,l are mixed even or odd

202

Allowed low order reflections are: 000 111

111, 200, 220, 311, 222, 400, 331, 310 020
Forbidden reflections:
100, 110, 210, 211

200 220
 What did we get for the structure
factor of simple cubic?
How would you expect the intensity of
the peaks to compare?
(arbitrary
Intensity

units)

Why might the intensities not be the same?

 Al
When more than one element Ni
Ni3Al Nickel aluminide structure, what is it?
Simple cubic lattice, with a four atom basis

1 1   1 1  1 1
 
rAl  0,0,0 , rNi   , ,0 , rNi   ,0,  & rNi   0, , 
2 2   2 2  2 2
     
F  fal  fNi(exp  i h  k   exp  i k  l   exp  i h  l  )
So :
F=fAl +3fNi if h,k,l all even or odd
F=fAl -fNi if h,k,l are mixed even or odd

Again, since simple cubic, intensity at all points.

But each point is ‘chemically sensitive’.
S hkl
Common to see an average decrease
in intensity of the diffraction peaks
despite rules for peak intensities

S hkl   f i e  i ( ri  K hkl )

i
 Atomic Form Factor f (key points)
(aka Scattering Factor)
Atoms are of a comparable size to the wavelength of the x-rays and so
the scattering is not point like. There is a small path difference between
waves scattered at either side of the electron cloud

• This effect increases with angle

• For x-rays, scattering strength depends on electron density
• All electrons in atom (Z of them) participate, core e- density ~spherical
40

Mean Atomic Scattering Factors

Also, thermal effects increase Zn
30
the effective size of atom
20

Zr
10 Ca

0
0 0.5 1.0 1.5
-1
[sin()]/ (Å )

Only at 2=0 does f=Z

What Would You Expect for Diamond?
Calculate the structure factor for the
diamond structure. Lattice = FCC.
Primitive Basis = (000), (¼ ¼ ¼)

I expect you to show your

work to calculate the
structure factor. Obviously
you can check your
answers with published
work, but I want to make
sure you can do it.
Structure Factor with Different Atoms
NaCl (rock salt) structure
Na on each fcc site, but with a two atom basis :
1 1 1 
 
rNa  0,0,0 & rCl   , ,  S hkl
2 2 2 
  
F  fNa  fCl exp i h k  l
1 expih k expik  l expih  l

F  4 fNa  fCl  if h,k,l all even
F  4f Na  fCl  if h,k,l all odd
F0 if h, k,l mixed

FCC Reminder:
Structure Factor with Different Atoms
NaCl (rock salt) structure
Na on each fcc site, but with a two atom basis :
1 1 1 
 
rNa  0,0,0 & rCl   , ,  S hkl
2 2 2 
  
F  fNa  fCl exp i h k  l
1 expih k expik  l expih  l

F  4 fNa  fCl  if h,k,l all even
F  4f Na  fCl  if h,k,l all odd
F0 if h, k,l mixed

What would happen if you offset

one of the atoms in the basis?
 Use Bragg’s law and structure factor,
calculate the diffraction angles (2) for
the first three peaks in an aluminum
powder pattern if a = 0.404 nm and the
x-ray source wavelength is .1542 nm.
2
sin   h  k2  l2 
How to start?
2 2
2
4a

Or I could work this

backwards! Just angles.
 Extra slides
• There is a lot of useful information on
diffraction. Following are some related slides
that I have used or considered using in the
past.
• A whole course could be taught focusing on
diffraction so I can’t cover everything here.
 The X-ray Shutter is the most important
safety device on a diffractometer
H2O In H2O Out

• X-rays exit the tube through X-ray

transparent Be windows.
XRAYS
Be
window

Cu ANODE
Be
window
Primary
Shutter
e-
• X-Ray safety shutters contain the Secondary
Shutter FILAMENT
XRAYS

beam so that you may work in the

(cathode)
Solenoid metal

diffractometer without being (vacuum) (vacuum)

glass

exposed to the X-rays.

• Being aware of the status of the AC CURRENT

shutters is the most important

factor in working safely with X rays.SAFETY SHUTTERS
 If the wavelength of the incident x-rays and the scattering angle are
known, then one can deduce the distance (already done) between the
planes, dhkl, responsible for each scattering peak. The following twelve
lines were obtained from a crystalline powder, known to belong to a
cubic system. This is a process of trial and error! (Computers are good at this)

Line d(Å) relative intensity

Conditions for Peak 1 3.157 94
SC All points 2 1.931 100
3 1.647 35
BCC Sum = even
4 1.366 12
FCC All Even/odd 5 1.253 10
Diam All Odd or sum4n 6 1.1150 16
7 1.0512 7
NaCl All Even/odd FCC 8 0.9657 5
Ni3Al All Points (SC) 9 0.9233 7
10 0.9105 1
11 0.8634 9
12 0.8330 3
Index the lines in terms of their Miller indices (hkl) and calculate the
lattice constant of the cubic lattice. Establish the type of cubic lattice.
Non-xray Diffraction Methods
(more in later chapters)
• Any particle will scatter and create diffraction
pattern
• Beams are selected by experimentalists depending
on sensitivity
– X-rays not sensitive to low Z elements, but neutrons are
– Electrons sensitive to surface structure if energy is low
– Atoms (e.g., helium) sensitive to surface only
• For inelastic scattering, momentum conservation is
important

X-Ray Neutron Electron

λ = 1A° λ = 1A° λ = 2A°

E ~ 104 eV E ~ 0.08 eV E ~ 150 eV

interact with electron interact with nuclei interact with electron

Penetrating Highly Penetrating Less Penetrating
 Group: Consider Neutron Diffraction
• Qualitatively discuss the atomic scattering
factor (e.g., as a function of scattering angle)
for neutron diffraction (compared to x-ray) by
a crystalline solid.
• For x-rays, we saw that f is related to Z and has
a strong angular component. For neutrons?
• The same equation applies, but since the
neutron scatters off a tiny nucleus, scattering
is more point-like, and f is ~ independent of .
 Systematic Extinction
• Systematic extinction is
a consequence of lattice
Symmetry Extinction Conditions
type
• At right is table of simple none
systematic extinctions for
symmetry elements C hkl; h + k = odd
• Other extinctions can
B hkl; h + l = odd
occur as a consequence
of screw axis and glide A hkl; k + l = odd
plane translations (Dove,
Ch.6 Structure and body hkl; h + k + l = odd
Dynamics)
• Accidental Extinctions All faces hkl; h, k, l mixed even
may occur resulting from and odd
mutual interference of
other scattering vectors
Key: C, B, A = side-centered on c-, b-, a-face; I = body centered; F = face centered (001)
 Symmetry within the Structure Factor
• Structure factors are subject to the same point
symmetry of the crystal.
• For mirror symmetry (y’=-y, x’=x, z’=z):
S hkl
• For 2-fold rotation axis about [001], (y’=-y, x’=-x, z’=z):
S hkl
• Thus, the point group symmetry operations are
reflected in the diffraction pattern.
• Alternative method to figure out the symmetry