Crystal Diffraction

Laue 1912

1914 Nobel prize

Max von Laue

(1879-1960)

Lattice spacing
typically
o o
10
10 m  1
 1A
Today X-ray diffraction supplemented by electron and neutron diffration

Energies X-ray, electrons and neutrons wave-particle

hc hc
E  h  
 E
X-ray: o
  1A E 12 k eV
o
  1A me  9.1 10-31 kg
h h h
Electrons: p  k   
 p 2mE E 150 eV
o
  1A mn  1.6749 10-27 kg
h h
Neutrons:   E 0.08 eV
p 2mE
 Typical Laue X-ray diffraction pattern

symmetry of the pattern symmetry of the crystal

Laue X-ray diffraction

YAlO3
c-axis normal to picture

Complementarity of the three types of radiation

X-ray diffraction Electron diffraction Neutron diffraction

•Photon energies 10keV-100keV •Charged particle •Interaction with nuclei

large penetration depth “strong” interaction Improved efficiency
with matter for light atoms
3D crystal structure Inelastic scattering:
low penetration depth phonons
•scattering by electron density •Magnetic moment interacts
best results for Study of: surfaces with moment of electrons
atoms with high Z thin films Magnetic scattering:
Structure, magnons
 Bragg Diffraction Law
Law describing the minimum condition for diffraction
Applicable for photons, electrons and neutrons

Bragg’s law
Condition for efficient specular reflection 2d sin   n  2d hkl sin   
n: integer
(click for java applet)
Spacing dhkl between successive (hkl) planes

a
In cubic systems: dhkl 
h2  k 2  l2

Top view
y

a
d110 a
2
2 d110  a 2
d110 
2

dhkl for non cubic lattice later in the framework

x
of the reciprocal lattice
 •structure factor
Bragg’s law necessary condition Intensity of particular
(hkl) reflection
•atomic form factor

General theory of Diffraction

P
R’-r
r

R’ B
R

X-ray source
 Plane wave incoming at P AP  A0 ei k 0 ( R  r ) it

P
R’-r
k0 r k

R’ B
R

X-ray source Scattered wave contribution from P

incoming at B
i k ( R  r )
AB  AP  (r ) e
i k 0 ( R  r ) it i k ( R  r )
AB  A0 e  (r ) e Electron density at P
i ( k 0 R  k R t )
 A0 e  (r ) e i ( k k 0 ) r
Total scattering from the entire volume:
A    (r ) e i ( k  k 0 ) r d 3 r
Diffraction experiment measures the intensity I of the scattered waves

2 i( k k 0 )r 2
I(  )  A   (r ) e d r 3

i  r 2
  (r ) e 3
d r
where   k  k 0 is the scattering vector

Diffracted intensity is the square of the Fourier transform of the electron density

In crystals (r ) is periodic 1D example ( x )  ( x  na), n  0,  1, ,  2,  3,...

2
i nx
( x )   n e a

n
 Fourier series expansion
2π periodic function decomposed into cos kx and sin kx

a0 
f(x)    ak cos kx  bk sin kx
2 k 1 a 
or 2
0
for k  0 

 
f(x)  c e
k 
k
ikx
where 1
c k   (ak  ibk ) for k  0 

2 
1 
(a
 2 k  ib k ) for k  0 
 


1
 
2 
f(x)eikx dx
 1dimensional case 3dimensional case
2
( x )   n e
i
a
nx
(r )   G ei G r
G
n
2
i n ( x  ma ) translational invariance of (r )
( x  ma )   n e a

n with respect to lattice vector

r n  n1 a1  n 2 a 2  n3 a3
2 2
i nx i n ma
  n e a
e a
(r  r n )  (r )
n
with
i
2
n ma G  r n  2m
e a
 ei 2 n m
 cos 2mn   i sin( 2mn)  1
Reciprocal lattice vectors
2
i nx
( x  ma )   n e a
 ( x )
n
Remember:

Diffracted intensity is the square of the Fourier transform of the electron density

i  r 2
I(  )   (r ) e d r 3

(r )   G ei G r periodic electron density

G

2
i ( G   )r
I(  )   G  e 3
d r
G

1 i( G  )r 3 2 2
with (G   )   e d r I(   G)  G V
VV
(click for information about -functions)
 2 2
I(   G)  G V

Scattering condition G is nothing but Bragg´s law !

The reciprocal lattice

G  r n  2m r n  n1 a1  n2 a 2  n3 a3

G  h g1  k g2  l g3 decomposition into so far unknown basis vectors

with h, k, l integers
The basis vectors g1, g2 , g3 of the reciprocal lattice are determined by:

 a 2  a3
g1  a  2
1
a1  (a 2  a 3 )

 a3  a1
g2  a 2  2
a1  (a 2  a3 )
 a1  a 2
g3  a3  2
a1  (a 2  a3 )

These gi fulfill the condition gi  a j  2ij

G  r n  2m holds, where G  h g1  k g2  l g3

Examples for reciprocal lattices

3 dimensions
2 dimensions
 Important properties of the reciprocal lattice vectors Ghkl  h g1  k g2  l g3

Ghkl lies perpendicular to the lattice plane with Miller indices (hkl)

simple example for the (111) plane in the cubic structure

a1  a 2  (a,a,0)
and span the (111) lattice plane
a3  a 2  (0,a, a)
a3  (0,0, a) a3  a 2  (0,a, a) vector (a1  a 2 )  (a3  a 2 ) (111) plane
(a1  a 2 )  (a 3  a 2 ) 
0
a1  (a,0,0) (a1  a3 )  (a 2  a3 )  (a1  a 2 )  (a 2  a 2 )
a 2  (0, a,0)
 (a3  a1 )  (a 2  a3 )  (a1  a 2 )

a1  a 2  (a,0,0)  ( 0, a,0)  (a,a,0)

 g1  g2  g3  G111
Distance dhkl between lattice planes (hkl) related to Ghkl according to

2
Ghkl 
dhkl gi  a j  2ij

d111 a1 G111 2
a
 cos (a1, G111 )  
a G111
a1 G111
d111
2
d111 
G111
G111
 Equivalence between the scattering condition   Ghkl

and Bragg´s law 2dhkl sin   

k   -k0

k0 Ө
k
Ө
lattice plane (hkl)
Elastic scattering: k=k0

  k   k  2  k 2  2kk 0 cos ( 2)  k 0

2
 k 21  cos 2

4 2
 
 k 2 cos   sin   cos   sin 
2 2 2 2
  2k sin  

sin   G hkl 
dhkl 2dhkl sin   

1 cos 2
Geometrical interpretation of the scattering condition   Ghkl

Ewald construction

reciprocal lattice

k
2Ө
G
k0
(000)
 (click for animation)

Crystal in random orientation not necessarily reflection rotation of the crystal

polychromatic radiation
Rotating crystal arrangement

determine unknown structure

Powder method / Debye Scherrer

incoming monochromatic beam

Precise measurement of
lattice constants
Laue method

transmission

Polychromatic X-rays

reflection

Orientation of crystal with known structure

 The structure factor

2
I(   Ghkl )  G hkl
V2

Controls the actual intensity of the (hkl)-reflex

Scattering condition ( Bragg’s law )

necessary condition

Remember: (r )   G e hkl

i Ghkl r
because crystal periodic (r  r n )  (r )
Ghkl

1
Fourier-coefficients hkl  cell(r ) e d r
i G r 3 hkl

Vc
 Majority of the electrons are centered in a small region around the atoms
core electrons

Scattering from valence electrons can be neglected

Atom in n-th unit cell is located at position r

1 1
hkl  cell(r ) e d r  e   (r ) e d r 

i G r 3
hkl i Ghkl r  i G r  3
hkl

Vc Vc 

r  r   r
atomic scattering factor fα

Fhkl   f e  i Ghkl r 
Structure factor

atomic scattering factor f     (r ) e  i G r d3 r  hkl

Spherically symmetric

f     (r ) e r  sin dr dd

 i Ghklr  cos  2

where  G , r’

     (r ) e  i Ghklr  cos 
r 2 dr d(cos )d
sin Gr  2
 4   (r ) r  dr  
Gr 
G  2k 0 sin 
 atomic scattering factor

sin  4r (sin ) /  ) ) 2

f  4    (r ) r  dr 
 4r (sin ) /  )
Maximum at Ө=0 (forward scattering)

f (  0)  4  (r ) r dr 
  2
Z number of electrons/atom

(Click for calculations of

atomic scattering factors)
 Structure factor of a lattice with basis

Structure factor of the bcc lattice: Conventional cell contains two atoms at

r2=(1/2,1/2,1/2)
r1=(0,0,0)

Both atoms have the same atomic scattering factor f1 = f2 = f

2
Reciprocal unit cell: cube with cell side of 2π/a Ghkl  (h, k, l)
a

Fhkl   f e  i Ghkl r 
 f 1  e  i ( h k l )


 0 for h  k  l odd

Fhkl  f 1  e i( hk l )  
2f for h  k  l even

ei (hk l )  cos( (h  k  l ))  i sin( (h  k  l ))

We observe e.g. diffraction peaks from (110), (200), (211) planes

but no peaks from (100), (111), (2,1,0) planes
 If f1 = f2 like CsI peaks like (100), (111), (2,1,0) appear

Similar situation in the case of fcc KCl/KBr: f(K+)=f(Cl-) = f(Br-)

KCl: Non-zero if all KBr: all fcc-peaks

indices even present

•Shape and dimension of the unit cell can be deduced from Bragg peaks

•Content of the unit cell (basis) determined from intensities of reflections