Experimental Determination

of Crystal Structure
Branislav K. Nikolić
Department of Physics and Astronomy, University of Delaware, U.S.A.

PHYS 624: Introduction to Solid State Physics

http://www.physics.udel.edu/~bnikolic/teaching/phys624/phys624.html

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Principles of Diffraction

How do we learn about crystalline structures?

Answer:

Diffraction: Send a beam of particles (of de Broglie wavelength λ=h p

or radiation with a wavelength λ≈a comparable to characteristic
length scale of the lattice (a≈ twice the atomic or molecular radii
of the constituents).

EXPERIMENT: Identify Bragg peaks which originate from a

coherent addition of scattering events in multiple planes
within the bulk of the solid.

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PHYS 624: Experimental Determination of Crystal Structures
Principles of Diffraction in Pictures

Figure 1: Scattering of waves or particles with wavelength of roughly the same

size as the lattice repeat distance allows us to learn about the lattice structure.
Coherent addition of two particles or waves requires that 2d sinθ = λ (the Bragg
condition), and yields a scattering maximum on a distant screen.
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PHYS 624: Experimental Determination of Crystal Structures
Available Particles for
Diffraction Experiments

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PHYS 624: Experimental Determination of Crystal Structures
Bad Particles for Diffraction

Not all particles with de Broglie wavelength λ≈a will work for this
application → For example, most charged particles cannot probe the
bulk properties of the crystal, since they lose energy to the scatterer
very quickly:
dE 4π nq e  mγ v 3 2 2
 q2
≈− ln  ∼ 2
 qeω 0
2
dx mv  v

For non-relativistic electron scattering into a solid with a≈ 2Å
h
a = λ = =12.3⋅10−8cm/ E ⇒E = 50eV
p

The distance at which initial energy is lost is:
δ E = E, n = 1023 cm-3 ⇒ δ x = 100Å

NOTE: Low energy electron diffraction can be used to study the
surface of extremely clean samples.
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PHYS 624: Experimental Determination of Crystal Structures
Electron Probe Sees only Surface

Figure 2: An electron about to

scatter from a typical material.
However, at the surface of the
CONCLUSION:
material, oxidation and surface
reconstruction distort the lattice.
If the electron scatters from this
region, we cannot learn about the
structure of the bulk.

CONCLUSION: Use neutral particles or electromagnetic radiation

which scatter only from nuclei NEUTRONS or X-rays.
→

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PHYS 624: Experimental Determination of Crystal Structures
Neutron Scattering Experiments
Neutrons scatter almost completely isotropic: Elastic scattering gives
precise information about the static lattice structure while Inellastic
scattering allows one to study lattice vibrations.

Antiferromagnet
Spin-Spin
Interactions

Like NaCl
MnO

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PHYS 624: Experimental Determination of Crystal Structures
Sources of Photons (EM Radiation)

Interaction of X-rays with condensed matter: charged particle (electron

density) vibrates at the frequency of the incoming radiation.
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PHYS 624: Experimental Determination of Crystal Structures
Classical Theory of Diffraction

Three basic assumptions:

1. The operator which describes the coupling of the target to the

scattered "object" (in this case the operator is the density)
commutes with the Hamiltonian → realm of classical physics.

2. Huygens principle: Every radiated point of the target will serve

as a secondary source spherical waves of the same frequency
as the source and the amplitude of the diffracted wave is the
sum of the wavelengths considering their amplitudes and relative
phases.

3. Resulting spherical waves are not scattered again. For example,

in the fully quantum theory for neutron scattering this will
correspond to approximating the scattering rate by Fermi golden
rule, i.e., the so-called first-order Born approximation.

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PHYS 624: Experimental Determination of Crystal Structures
Setup of Scattering Experiment

i (k0 ( R+r )−ω0t )

R ≫ r ⇒ AP = A0e (incident wave)
e ik ( R ′ − r )
Hygens: AB ( R′) ∝ ∫ dr AP ρ (r )
R′ − r
i ( k 0 R + kR ′ −ω0t ) ei −(k −k 0 )r
AB ( R′) ∝ A0 e ∫ d r ρ (r ) R ′ − r
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PHYS 624: Experimental Determination of Crystal Structures
The Role of Fourier Transforms in
Diffraction Pattern Analysis
•At very large R′, i.e., in the so-called radiation or far zone:
A0ei (k0R +kR′−ω0t )
AB ( R′) ∝ ∫ drρ (r ) e − i ( k −k 0 ) r

R′
I B ∝ AB
2
•In terms of the scattered intensity
A0 2

∫ d r ρ (r )e
− i (k −k 0 )r
IB ∝
R ′2
A0 2 A0
∫ d r ρ (r )e ρ (K )
− iK r
I B (K ) ∝ =
2

R ′2 R′ 2

Fourier transform of the density of scatterers

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PHYS 624: Experimental Determination of Crystal Structures
Phase Information is Lost!

I (K) ∝ ρ (K)
2

ρ (K) = ∫ drρ (r)e−iKr = ρK eiθ K

From a complete experiment, measuring intensity for all scattering angles, one
→

does not have enough information to get density of scatterers by inverting Fourier
transform Instead guess for one of the 14 Bravais lattices and the basis, Fourier
→

transform this, fit parameters to compare to experimental data.

•From the Fourier uncertainty principle ∆ x ∆ k ≈ π : Resolution of

smaller structures requires larger values of K (some combination of
large scattering angles and short wavelenght of the incident light).
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PHYS 624: Experimental Determination of Crystal Structures
Patterson Function

I (K ) ∝ ρ (K ) ∝ ∫ ρ ( r )e
− iK r
′
d r ∫ ρ (r ) e − iK r ′
dr′
2

r → r′ + r

∫ d r ′ ∫ ρ ( r )ρ ( r ′ + r ) d r
iK r ′
I (K ) ∝ e

•The Patterson function is the autocorrelation function of the scattering

density (it has maximum whenever r ′ corresponds to a vector between
two atoms in the structure):
P ( r ′) = ∫ ρ ( r )ρ ( r ′ + r ) d r
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PHYS 624: Experimental Determination of Crystal Structures
Vocabulary: Patterson Function, Structure
Factor, Pair Correlation Function
Patterson:P (r ′) = Nf 2δ 0, r ′ + N ∫ ρ (r )ρ (r ′ + r ) dr , ρ ( r ) = ∑ρ
j ≠i
atom ( r − rj )
N 2
Pair Correlation: f g ( r ′) = ∫ ρ ( r )ρ ( r + r ′) d r
V N
Structure Factor: I(K ) ∝ S(K )=1+ ∫ g ( r )e iK ⋅r dr
V

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PHYS 624: Experimental Determination of Crystal Structures
Scattering From 1D Periodic Structures

Density of periodic crystal:

ρ ( x + ma) = ρ ( x) ⇒ ρ ( x) = ∑ ρn e iGn x

ρ ( x + ma) = ∑ ρn eiG ( x + ma ) = ∑ ρn eiG x eiG ma = ρ ( x)

n n n

n n

2nπ
e iGn ma
= 1 ⇒ Gn =
a
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PHYS 624: Experimental Determination of Crystal Structures
Scattering from 3D Periodic Structures

Generalization to three-dimensional structures:

ρ(r + rn ) = ρ(r), r = n1a1 + n2a2 + n3a3; n1, n2 , n3 ∈ℤ

G ⋅ rn = 2mπ , m ∈ ℤ

G = hg1 + kg2 + lg3 ⇒( hg1 + kg2 + lg3 ) ⋅ n1a1 = 2mπ, m∈ℤ

g1 ⋅ a1 = 2π, g2 ⋅ a1 = g3 ⋅ a1 = 0

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PHYS 624: Experimental Determination of Crystal Structures
Reciprocal Lattice (in Reciprocal Space)

 The orthonormal set (g1, g2 , g3 ) forms the basis of the

reciprocal lattice:
a2 ×a3 a3 ×a1 a1 ×a2
g1 = 2π , g2 = 2π , g3 = 2π
a1 ⋅ (a2 ×a3 ) a1 ⋅ (a2 ×a3 ) a1 ⋅ (a2 ×a3 )
http://www.matter.org.uk/diffraction/geometry/sperposition_of_waves_exercises.htm

(2π )3 (2π )3
ΩBZ =| g1 ⋅ (g2 × g3 ) |= =
| a1 ⋅ (a2 × a3 ) | ΩPUC
 Real-space and reciprocal lattice have the same point
group symmetry (but do not necessarily have the same
Bravais lattice: example FCC and BCC are reciprocal to
each other with point group symmetry Oh).
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PHYS 624: Experimental Determination of Crystal Structures
Scattering intensity for a crystal: Laue
2
A0
ρ (r) = ∑ ρG e iGr
⇒ I B (K ) ∝ 2 ∫ ∑ G
dr ρ e − i ( K −G ) r

G R′ G

− i ( K −G ) r V , G = K
∫e dr = 
0, G ≠ K
V − lattice volume
A0
I B ( K ) ∝ 2 ρ G V 2δ G , K
2

R′
This is called Laue condition for scattering. The fact that this
2
is proportional to V rather than V indicates that the
diffraction spots, in this approximation, are infinitely bright
(for a sample in thermodynamic limit) → when real
broadening is taken into account, I B ( K ) ∝ V
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PHYS 624: Experimental Determination of Crystal Structures
Freidel Rule

I hkl ∝ ρ hkl
2

ρ (r ) ∈ ℝ ⇔ ρ G = ρ *
−G

I − h − k − l ≡ I hkl = I hkl
•For every spot at k′ − k0 = G , there will be one at k − k0 = G.
Thus, for example, if we scatter from a crystal with a 3-fold
symmetry axis, we will get a 6-fold scattering pattern.
•The scattering pattern always has an inversion center
even if none is present in the target! G → −G

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PHYS 624: Experimental Determination of Crystal Structures
Graphical Laue

If, and only if the three vectors involved form a closed triangle, is
the Laue condition met. If the Laue condition is not met, the
incoming wave just moves through the lattice and emerges on
the other side of the crystal (neglecting absorption).
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PHYS 624: Experimental Determination of Crystal Structures
Graphical Laue: Ewald sphere

Use powder X-ray Diffraction

(powdered sample corresponds to
⇒ averaging over all orientations of the
reciprocal lattice – will observe all
peaks that lie within the radius 2 k0 of
the origin of reciprocal lattice.

Figure 1: The Ewald Construction to determine if the conditions are correct for obtaining a Bragg peak:
Select a point in k-space as the origin. Draw the incident wavevector k0 to the origin. From the base of k ,
0
spin (remember, that for elastic scattering k = k ) in all possible directions to form a sphere. At each
k
point where this sphere intersects a lattice point in k-space, there will be a Bragg peak with G = k − k0. In
0

the example above we find 8 Bragg peaks. If however, we change k by a small amount, then we have none!.
0

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PHYS 624: Experimental Determination of Crystal Structures
Miller Indices

1 1 1
: : = h : k : l ⇒ (hkl), − h ≡ h
u v w
g1 : g2 : g3 = h : k : l → Miller indices ⇔G
G⋅ rn = 2π m ⇔ q = (n1 − pg3 )a1 + (n2 − pg3 )a2 +[n3 + p(g1 + g2 )]a3, G⋅ q = 2π m
2π m
dm = Conventions: hkl, [ hkl ] ,(hkl ),{hkl}, hkl
G
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PHYS 624: Experimental Determination of Crystal Structures
Bragg vs. Laue =
Reciprocal vs. Real Space Analysis

K = K = k − k 0 = G h kl
4π 2π
K = 2 k 0 s in θ = s in θ = ⇒ λ = 2 d h k l s in θ
λ d h kl
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PHYS 624: Experimental Determination of Crystal Structures
Brillouin Zone Interpretation of
Bragg and Laue Diffraction Conditions
We want to know which particular
wave vectors out of many (an infinite
set, in fact) meet the diffraction
(Bragg & Laue) condition for a given
crystal lattice plane.
If we construct Wigner-Seitz cells
in the reciprocal lattice, all wave
vectors ending on the Wigner-Seitz
cell walls will meet the Bragg
condition for the set of lattice
planes represented by the cell wall.

 G hkl 
G hkl  +k = 0
 2 
( ) ( 0 ) ( hkl ) hkl + 2Ghkl ⋅k
= = + = +
2 2 2 2 2
k k G k G k
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PHYS 624: Experimental Determination of Crystal Structures
3D Brillouin Zones
•Constructing Brillouin zones is a good
example for the evolution of complex
systems from the repeated application of
simple rules to simple starting conditions -
any 12-year old can do it in two dimensions,
but in 3D, … Ph.D. thesis in 1965 …

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PHYS 624: Experimental Determination of Crystal Structures
Reciprocal vs. k-vectors
(2π ) 3
| d k |=3

N Ω PUC
BvK: Ψnk (r) = Ψnk (r + N ja j )
 ±2π nx ±2π ny ±2π nz 
k = , ,  , Lx = N1a
 L Ly Lz 
 x
U(r) =U(r + R) ⇒U(r) = ∑U(r)eiG⋅r
G

Arbitrary wave vector k can be written as a sum of some reciprocal

lattice vector G plus a suitable wave vector k´; i.e. we can always write k
= G + k´ and k´ can always be confined to the first Brillouin zone, i.e.
the elementary cell of the reciprocal lattice.
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PHYS 624: Experimental Determination of Crystal Structures
Fourier Analysis in
Solid State Physics of Crystals
Periodic Function, with the same periodicty as the
lattice, expanded in Fourier series:

U(r) =U(r + R) ⇒U(r) = ∑U(r)eiG⋅r

G
Arbitrary wave function expanded in plane waves:

Ψ(r) = ∑Ckeik⋅r
k
Bloch wavefunctions (eigenstates of crystal
Hamiltonian) expansion: uk (r) = uk (r + R)
Ψk (r) = ∑Ck−Gei(k−G)⋅r = ∑Ck−Ge−iG⋅reik⋅r = Ψk+G (r)
G G
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PHYS 624: Experimental Determination of Crystal Structures
Nearly-free-electron-like?

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PHYS 624: Experimental Determination of Crystal Structures
Crystal Electrons in the BZ-realm

k k0
G
±UG

•All wave vectors that end on a BZ, will fulfill the Bragg condition and thus are diffracted –
states with +
π is Bragg reflected into state with π
− (and vice versa)
a a
•Wave vectors completely in the interior of the 1. BZ, or well in between any two BZs, will
never get diffracted; they move pretty much as if the potential would be constant, i.e. they
behave very close to the solutions of the free electron gas.
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PHYS 624: Experimental Determination of Crystal Structures
Crystal Electrons in the BZ-realm

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PHYS 624: Experimental Determination of Crystal Structures
Scattering From a Lattice with a Basis

Need structure factor S and

form factor f, respectively.

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PHYS 624: Experimental Determination of Crystal Structures
Structure and Form factors
1 1
I hkl ∝ ρhkl , ρhkl = ∫ drρ (r)e −iG hkl r
= ∑ ∫ drρ (r)e−iGhkl r
2

V V cells cell
1
ρhkl = ∑ ∫
V N1 , N2 , N3 cell
drρ (r )e −iG ( rn +rα +r′ )
since r = rn + rα + r′
Structure Factor
1
ρhkl =
Vcell
∑
α
e −iGhkl rα
∫ dr ρα (r )e
′ ′ −iGhkl r′

Atomic
Scattering Form fα = ∫ dr′ρα (r′)e−iGhklr′ ∝ Z ⇒ I ∝ Z 2
Factor
1 Shkl
S= f ⇔ One atom per unit cell ρhkl = ∑e −iGhkl rα
fα =
Vc α Vc
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PHYS 624: Experimental Determination of Crystal Structures
Extinctions
rα = uα a1 + vα a2 + wα a3
f FeX −ray ≈ fCoX −ray
Shkl = ∑ fα exp −2π i ( huα + hvα + wuα ) 
α
f Feneutron ≠ fConeutron
1 1 1
r1 = ( 0,0,0) r2 = ( , , )
2 2 2

0, h + k + l odd
Position of Bragg reflection: Shape
Shkl = f (1+ e−iπ ( h+k +l )
) = 2 f , h + k + l even and dimension of the unit cell

 Intensities of reflections: Content of

the unit cell

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PHYS 624: Experimental Determination of Crystal Structures
Structure Factor Revisted:
Quantum Mechanical Case
Example: Diffraction of electron on crystalline potential λ ∼ a =10 cm⇒E ∼ 0.1eV
−8

e ikr e ik 1r
U (r ) = ∑ U α ( r − rα ) ⇒ e transition from Ψ k =
−
to Ψ k =
α V V
Quantum-Mechanical Probability Amplitude for this transition:

Ak1k = Ψk1 Uˆ Ψk = ∫ dr Ψ*k1 (r)U (r)Ψk (r)

1
Ak1k = ∑ ei (k −k1 )rα ∫ ei (k −k1 )(r −rα )Uα (r − rα )dr = Uα (G)S (G)
V α
1
Uα (G) = ∫ dr eiG (r −rα )Uα (r − rα ) 1
V0 S (G) = ∑ eiGrα
Structure factor is completely determined by geometrical N α
properties of the crystal.
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PHYS 624: Experimental Determination of Crystal Structures
Structure factor: Conclusion

Any matrix element that describes a transition between two
electronic states under the action of crystalline potential will contain a
structure factor.

Crystal potential does not have to be necessarily expressed in terms
of sum of the atomic potentials; furthermore, the transition do not
necessarily involve “external” electrons → everything is valid also for
transition between electronic states of a crystal itself.

Extracting of structure factor reflects how spatial distribution of ions

affects dynamics of processes in crystals. Example:

ρ(r) = ∑ρ(r − rα ) ⇒ ρ(k) = S(k)ρ0 (k) for electrons

α
ρ(r)ρ(r1) ⇒S(k) = ρ(k)ρ(−k) for molecules
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PHYS 624: Experimental Determination of Crystal Structures
Experimental Techniques:
Rotating Crystal

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PHYS 624: Experimental Determination of Crystal Structures
Experimental Techniques:
Powders

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PHYS 624: Experimental Determination of Crystal Structures