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of Crystal Structure

Branislav K. Nikolić

Department of Physics and Astronomy, University of Delaware, U.S.A.

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

1

Principles of Diffraction

How do we learn about crystalline structures?

Answer:

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).

coherent addition of scattering events in multiple planes

within the bulk of the solid.

2

PHYS 624: Experimental Determination of Crystal Structures

Principles of Diffraction in Pictures

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.

3

PHYS 624: Experimental Determination of Crystal Structures

Available Particles for

Diffraction Experiments

4

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.

5

PHYS 624: Experimental Determination of Crystal Structures

Electron Probe Sees only Surface

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.

which scatter only from nuclei NEUTRONS or X-rays.

→

6

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

7

PHYS 624: Experimental Determination of Crystal Structures

Sources of Photons (EM Radiation)

density) vibrates at the frequency of the incoming radiation.

8

PHYS 624: Experimental Determination of Crystal Structures

Classical Theory of Diffraction

Three basic assumptions:

scattered "object" (in this case the operator is the density)

commutes with the Hamiltonian → realm of classical physics.

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.

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.

9

PHYS 624: Experimental Determination of Crystal Structures

Setup of Scattering Experiment

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

10

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

11

PHYS 624: Experimental Determination of Crystal Structures

Phase Information is Lost!

I (K) ∝ ρ (K)

2

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

→

smaller structures requires larger values of K (some combination of

large scattering angles and short wavelenght of the incident light).

12

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

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

13

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

14

PHYS 624: Experimental Determination of Crystal Structures

Scattering From 1D Periodic Structures

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

n n n

n n

2nπ

e iGn ma

= 1 ⇒ Gn =

a

15

PHYS 624: Experimental Determination of Crystal Structures

Scattering from 3D Periodic Structures

G ⋅ rn = 2mπ , m ∈ ℤ

g1 ⋅ a1 = 2π, g2 ⋅ a1 = g3 ⋅ a1 = 0

16

PHYS 624: Experimental Determination of Crystal Structures

Reciprocal Lattice (in Reciprocal Space)

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).

17

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

18

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

19

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).

20

PHYS 624: Experimental Determination of Crystal Structures

Graphical Laue: Ewald sphere

(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

21

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

22

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

23

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

24

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 …

25

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

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.

26

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:

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

27

PHYS 624: Experimental Determination of Crystal Structures

Nearly-free-electron-like?

28

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.

29

PHYS 624: Experimental Determination of Crystal Structures

Crystal Electrons in the BZ-realm

30

PHYS 624: Experimental Determination of Crystal Structures

Scattering From a Lattice with a Basis

form factor f, respectively.

31

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

32

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

the unit cell

33

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:

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.

34

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.

affects dynamics of processes in crystals. Example:

α

ρ(r)ρ(r1) ⇒S(k) = ρ(k)ρ(−k) for molecules

35

PHYS 624: Experimental Determination of Crystal Structures

Experimental Techniques:

Rotating Crystal

36

PHYS 624: Experimental Determination of Crystal Structures

Experimental Techniques:

Powders

37

PHYS 624: Experimental Determination of Crystal Structures

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