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Classical Diffraction PDF
Classical Diffraction PDF
Classical Diffraction PDF
of Crystal Structure
Branislav K. Nikolić
Department of Physics and Astronomy, University of Delaware, U.S.A.
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Principles of Diffraction
How do we learn about crystalline structures?
Answer:
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PHYS 624: Experimental Determination of Crystal Structures
Principles of Diffraction in Pictures
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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
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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)
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PHYS 624: Experimental Determination of Crystal Structures
Setup of Scattering Experiment
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
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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
→
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
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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
2nπ
e iGn ma
= 1 ⇒ Gn =
a
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PHYS 624: Experimental Determination of Crystal Structures
Scattering from 3D Periodic Structures
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PHYS 624: Experimental Determination of Crystal Structures
Reciprocal Lattice (in Reciprocal Space)
(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
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
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
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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
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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:
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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