Chapter 2.

Wave Diffraction and the Reciprocal Lattice

Questions: How do we determine crystal structure of solids?

 Contents

1 Bragg law:

2 Scattered wave amplitude: F

3 Reciprocal lattice vectors in momentum space:G

4 Fourier analysis of the basis: structural and atomic factors

5 Brillouin Zone (BZ)

<Introduction>

 Radiation source: x-ray, Neuron, electron source

 Diffraction resolution: type of crystal structure & radiation wavelength
 Measurements: direction and intensity of diffraction patterns
 Resolution: crystal structure & radiation wavelength
 Use comparable wavelength to crystal lattice constant: mutual interaction between atom and wave

X-ray Neutron electron

Wavelength 1å scale
Energy

Properties High energy Low energy probe Strong coupling

probe
Crystal structure/ Magnetic structure Surface structure
Elastic scattering
<X-ray>
 X-rays scatter from the electrons
 Intensity proportional to the electron (charge) density of the atom: n(r)
 Mainly the core electrons around the nucleus
 Elastic scattering: energy conservation before & after scattering

<Neutron>
 Neutrons scatter from the nuclei (and electron magnetic moment)

 In all cases the scattering is periodic - the same in each cell of the crystal
 Diffraction is the constructive interference of the scattering from the very large number
of cells of the crystal: electron=> unit cell=> crystal
X-ray diffraction (XRD) experiment

 Bragg law is valid for wavelength ≤2d

 Typically, d (lattice spacing) ~ a few Å => energy scale : 10-50 KeV

 X-ray tube

-high conductivity
-high melting temperature
Rotate both sample and
detector about axis

 Crystal must be oriented in all directions in 3D space using “Gonier Spectrometer”

 Observe diffraction patterns only at Bragg angles for a fixed wavelength x-ray
Example: experimental results of X-ray diffraction (XRD)

Fe2BiSbO7

Y. Qi et al., Europhys. Lett. 97, 17008 (2012).

Y. Qi et al., Europhys. Lett. 97, 17008 (2012).
1. Bragg law (Bragg condition)

 Assumption:
1) Crystal: planes or sheets
2) Perfect reflectors or specular reflection
3) Multiple reflections between neighbors sheet
 d 4) Constructive IF: path difference

2. Scattered wave amplitude: F

 The Bragg law gives the condition for the constructive interference of waves scattered
from simplified lattice planes.

 Need a deeper analysis to determine the scattering intensity from the basis of atoms,
i.e. from the spatial distribution of electrons within each cell (physical features).

 Use the periodicity of the electron number density n(r) to perform Fourier analysis.

 Define a second lattice associated with the crystal – reciprocal lattice

n(r)=n(r+T)

T=u1a1+u2a2+u3a3 (ui: integer)

Periodicity creates an ideal situation for Fourier analysis.

Reciprocal lattice: G.
Periodic Functions and Fourier Analysis

In time domain,
f(t)
f(t)=sin(Tt)
t

In frequency domain,

f()
Find the periodicity
2/T k

 Any periodic function can be expressed in terms of its periodic Fourier

components (harmonics).
 Example: 1D electron density n(x) with period a in real space
 Example of density n(x) in 1D crystal in Fourier space:

 Easier complex expression:

 Expression for Fourier components or coefficients: Fourier inversion

 Note that n(x) should be real since it’s electron density.


Fourier analysis in 3D

 In 1D case, , p: 0, negative, positive integers

xr
 In 3D case, 2p/a  G

It must be invariant under crystal translation T

We need to find a set of vectors G to satisfy the periodicity

 Fourier analysis: n(r) = ΣG nG exp( i G ⋅ r) where the G’s are vectors, i.e.,

exp(iG ⋅ r) = exp( i (Gx x + Gy y + Gz z) )

 A periodic function satisfies n(r) =n(r + T) where T is any translation

T(n1,n2,…) = n1 a1 + n2 a2 + n3 a3 in 3D)
n(r + T) = ΣG nG exp( i G . r) exp( i G ⋅ T) = n( r )
satisfing exp(i G ⋅ T) = 1 ⇒ G ⋅ T = 2π x integer
3. Reciprocal lattice vectors: G
 The reciprocal lattice is the set of vectors G in Fourier space that satisfy the
requirement for any translation

Lattice vectors: a1, a2, a3 Reciprocal lattice vectors: b1, b2, b3

T=u1a1+u2a2+u3a3 (ui: integer) G=v1b1+v2b2+v3b3 (vi: integer)

 Define:
       
a a a a  a1  a2
b1  2  2 3 ; b2  2  3 1 ; b3  2   
a1  a2  a3 a1  a2  a3 a1  a2  a3
 
bi  a j  2ij , ij=1 (i=j), 0 (i≠j)]
If ai is primitive in real space, bi is primitive in reciprocal space.
 Reciprocal lattice vectors: n(r) invariant under T

 n(r+T)=n(r)

=1

 Why reciprocal lattice vector?

1) Diffraction pattern of crystal => Map of the reciprocal lattice

2) Microscope image => Map of the lattice in real space
Examples: Real & Reciprocal lattices in 1& 2 D

a2 b2

b2 a2
b1
a1

 b1 perpendicular to a2 , b2 perpendicular to a1
 Crystal lattice Reciprocal lattice

① real space lattice ① momentum space lattice

② 물리량 : [L] ② 물리량 : [L-1]
③ Microscopy pattern ③ diffraction pattern:

<Properties>
 Reciprocal vector is perpendicular to real lattice plane
with index (h k l)
 Distance between two consecutive (h k l):
Diffraction condition in momentum space: I

In and out waves have the form:

For elastic scattering (energy the same for in and out waves)
 Path difference=> phase difference
Scattering wave amplitude: F

F VnG

F 0
Diffraction condition: I

 Scattering amplitude F

when Diffraction condition:1

 The set of reciprocal lattice vectors determines the possible x-ray reflections
Diffraction condition II
k k'
 G
 k=G => k+G=k’ 수직

k
 Bragg condition?

G=hb1+kb2+lb3
 Lattice spacing d(hkl) between parallel
planes that are normal to G
 d(hkl)=2/G
Laue equations

<Laue equations>
k

a1 2v1

 k must lie on a certain cone about the direction a .

 Analogously, it must be on cones for a2 and a13.
 Diffraction occurs when k lies at the intersection of three cones.
Ewald construction

k +G = k '
kout G

90º−
kin θ
2
θ

 A diffracted beam will be formed if the Ewald sphere intersects any other point in
the reciprocal lattice
Fourier analysis of basis

 The intensity of the diffraction at each G is proportional to the square of the scattering
amplitude F

 For crystal of N unit cells

 F  N  n(r ) exp(iG  r )dV  NSG

Structural factor: SG

 integral over a single cell

  
 For basis in a unit cell n(r )   n j (r  rj )
j
r
rj

G=v1b1+v2b2+v3b3

r j= xja 1 + yja 2 +zja 3

Atomic form factor fj

 
SG   f j exp(iG  rj )
j
Example 1: Structure factor for simple cubic lattice

 All the reflections where k=G are allowed for diffraction.

 all reflections of the form (hkl)).
Example 2: Structure factor for BCC lattice

 Basis referred to cubic cell has

identical atoms at (0,0,0) and (½ , ½ , ½ )

=2f v i
even
Example 3: Structure factor for FCC lattice

 Basis referred to cubic cell has identical atoms

at (0,0,0) and (0,½ ,½ ), (½ ,0,½ ), (½ ,½ ,0)

0 if only one of the integers are even or odd

Example 4: Structure factor for CsCl lattice

 Basis: different two atoms at (0,0,0) for atom A and

(1/2,1/2,1/2) for atom B

=even

=odd
Atomic form factor G

     r
f j  cell n j (r ) exp(iG  r )dV G  r  Gr cos
If electron distribution is spherically symmetric about the origin,

If electrons are concentrated at r=0, Gr0 sinGr/Gr  1

f j  4  r n j (r )dr  Z, Z: number of atomic electrons

4. Brillouin Zone; Primitive unit cell of reciprocal lattice
 Brillouin Zone  Wigner-Seitz cell of reciprocal lattice.

 Boundary: Diffraction condition: 2k G  G 2

  1    1 2
k  G    G 
2  2 
Wigner-Seitz cell in reciprocal lattice

 k is on boundary of BZ.
Brillouin zone
 Determine electron and lattice state in a crystal
 BZ boundary: diffraction pattern condition
 Define as a Wigner-seitz primitive cell in a reciprocal lattice
 Primitive cell of the reciprocal lattice: First Brillouin zone

2D
1D

1st Brillouin zone

Only waves whose wavevector k drawn from the origin terminates on a surface of
Brillouin zone can be diffracted by crystal.
First Brillouin zone of simple cubic lattice

In real space In reciprocal space

a 2/a

a 2/a
a 2/a

Primitive vector

The boundaries of the first Brillouin zones are the

planes normal to the six reciprocal lattice vector
±b1, ±b2, ±b3 at their midpoint.
First Brillouin zone of body- and face-centered cubic lattices

First Brillouin zone of bcc lattice First Brillouin zone of fcc lattice