Professional Documents
Culture Documents
Paolo Fornasini
Department of Physics
University of Trento, Italy
Overview
• X-rays
• Crystals
• Crystal lattices
• Some relevant crystal structures
• Crystal planes
• Reciprocal lattice
• Crystalline and non-crystalline materials
X-rays
1895 - Discovery of X-rays
Paolo
Fornasini
Univ. Trento
Würzburg (Germany)
November 8,1895
Paolo
c ≈ 3×10 8 m/s
λ
Electric field
€
Magnetic field
c
€ €
1 Å = 10-10 m
Wavelength λ 1 nm = 10-9 m
€ Frequency ν = c/λ ω = 2 πν
Photon energy
€ E = hν = hω
€ €
Wave-vector Paolo
Fornasini
Univ. Trento
r
k
2π
k=
€ λ
λ
Plane wave
€
€
Plane wave Paolo
Fornasini
Univ. Trento
r
E
r
r
r
€ k 2π
k=
λ
€ r
r
€ r r r r r r r r
( )
E(r ) = E 0 cos k ⋅ r = E 0 € for k ⋅ r = 2nπ
rr
€
{ }
Re e ik ⋅r Complex
notation
€
Electromagnetic spectrum Paolo
Fornasini
Univ. Trento
Micro
Frequency 1010
10-4 waves 10-2
IR
X-rays 1014
1 10-6
λ ≈ 0.01÷10 Å
UV
Auger
electrons
Photo-electrons Fluorescence
EA Photo-electric
E hν F absorption
hν
€ Beam attenuation
€
Incoming beam €
(monochromatic)
€ Scattering
hν ' hν
Inelastic Elastic
scattering scattering
€
X-RAYS and X-ray techniques
Paolo
Fornasini
Univ. Trento
λ = 2dsin θ
Absorption
Intensity
Macroscopic regularities
(e.g. constancy of angles)
Classification of crystals
Regular packing
of microscopic structural units
R.J. Haüy (1743-1822)
Atoms and crystals
Paolo
Fornasini
Univ. Trento
Cubic structure
1 cm3 m = 2.165 g
N = 44.6 x 1021 atoms
0.28 nm = 2.8 Å
Inter-atomic distances
CONCLUSION: ≈ X-ray wavelengths
Atomic dimensions
X-ray diffraction from crystals
Paolo
Fornasini
Univ. Trento
Munich, 1912:
• Max von Laue
• W. Friedrich & P.Knipping
Crystallography
Paolo
Fornasini
Univ. Trento
Cambridge, 1912/13
Bragg spectrometer
Crystal structure Paolo
Fornasini
Univ. Trento
1-D
1-D Atom
Molecule
2-D
2-D
3-D
3-D Protein
Bravais lattice + basis
Paolo
Fornasini
Univ. Trento
1-D
2-D
3-D
Crystal lattices
Translation vectors (2D)
Paolo
Fornasini
Univ. Trento
2-D
r
R
For every lattice point
r r r
r R = n1a + n2b
b
r €
a
integers primitive
Arbitrary origin € vectors
€
Primitive vectors (2D)
Paolo
Fornasini
Univ. Trento
r r r 2-D
R = n1a + n2b
r r
R r R
R
€
r
b
r € €
a €
€ r r
Different choices of primitive vectors a, b
Non-primitive vectors (2D)
Paolo
Fornasini
Univ. Trento
2-D
r r
Not all a, b pairs are primitive
r r
R r R
R
€
r
b €
r € €
a
r r r
€
R ≠ n1a + n2b
Primitive vectors (3D)
Paolo
Fornasini
Univ. Trento
r r r r 3-D
R = n1a + n2b + n3c
€
r r
c b
r
a
€ € r r r
Different choices of primitive vectors a , b , c
€
Primitive unit cells (2D)
Paolo
Fornasini
Univ. Trento
2-D
r
b
r
a
Different choices of primitive unit cells
2-D
r
b
r
a
Atoms 2-D
r r r
R ≠ n1a + n2b
Un-equivalent
sites €
Bravais lattices
Paolo
Fornasini
Univ. Trento
Bravais
lattice
Basis
Classification of cells
2-D 3-D
r r
b c
γ
r r
a α b
€
γ
€ r
β a
a b c
€ latin
€ €
α β γ greek
€
Surface Bravais lattice
Paolo
Fornasini
Univ. Trento
2-D
3-D
4 unit cells
7 14
P = primitive
crystal + = Bravais
I = body centered
systems F = face centered
lattices
C = side centered
Coordinates
Paolo
Fornasini
Univ. Trento
2 (3, 2)
Lattice points:
integer
coordinates
€ r r
r
€ R = n1a + n2b
1
1
2
1 €
4
€
1 3
€
0 4 4 1 2 3
€
Inside cell: fractional coordinates
€ €
1 1 3 1
, ,
4 4
€ 4 2
€ €
€
Some relevant crystal
structures
Simple cubic lattice
Paolo
Fornasini
Univ. Trento
84-Po a=3.35 Å
Bravais lattice
a
lattice parameter
€
Primitive unit cell
(1 lattice point per cell)
Coordination number = 6
Body centered cubic lattice (bcc)
Paolo
Fornasini
Univ. Trento
24-Cr a=2.88 Å
26-Fe a=2.87 Å
42-Mo a=3.15 Å
Bravais lattice
a
lattice parameter
€
conventional unit cell
(2 lattice points per cell)
Coordination number = 8
Face centered cubic lattice (fcc)
Paolo
Fornasini
Univ. Trento
29-Cu a=3.61 Å
47-Ag a=4.09 Å
79-Au a=4.08 Å
Bravais lattice
a
lattice parameter
€
conventional unit cell
(4 lattice points per cell)
Coordination number = 12
Diamond structure
Paolo
Fornasini
Univ. Trento
6-C a=3.57 Å
14-Si a=5.43 Å
32-Ge a=5.66 Å
Non-Bravais lattice
1 1 1
, ,
4 4 4
a (0, 0, 0)
€
€
€
conventional unit cell
(8 atoms per cell)
Coordination number = 4
Zincblende (sphalerite) structure
Paolo
Fornasini
Univ. Trento
ZnS a=5.41 Å
GaAs a=5.65 Å
SiC a=4.35 Å
Non-Bravais lattice
1 1 1
, ,
4 4 4
(0, 0, 0)
a
€
€
NaCl a=5.64 Å
KBr a=6.60 Å
CaO a=4.81 Å
Non-Bravais lattice
1 1 1
, ,
2 2 2
(0, 0, 0)
a
€
€
Cordination number = 6
Simple hexagonal structure
Paolo
Fornasini
Univ. Trento
Top view
r
a2
Primitive unit cell
€(1 lattice point per cell) a1 = a2
r
a1
€
Hexagonal close packed structure
Paolo
Fornasini
Univ. Trento
4-Be a=2.29 Å
12-Mg a=3.21 Å
48-Cd a=2.98 Å
Non-Bravais lattice
€
a €
8
c= a
3
fcc hcp
Close packing
N=12
Close-packing of spheres
Paolo
Fornasini
Univ. Trento
A A A A A
B B B B
A A A A
2nd B B B
1st
A A A A A
layer layer B B B B
A A A A
B B B
A A A A A
A A A A A
A A A A C C C
A A A A A C C
3rd
layer A A A A C C C
A A A A A
ABA ABC
hcp versus fcc
Paolo
Fornasini
Univ. Trento
B
C
A
B
A
hcp fcc
A A A A A
A A A A C C C
A A A A A C C
A A A A C C C
A A A A A
Crystal planes
Crystal planes Paolo
Fornasini
Univ. Trento
2-D
Miller indices, 2-D (a)
Paolo
Fornasini
Univ. Trento
2-D
r
b
r
a
€
€
€ €
r (hkl) = (100)
c (hkl) = (111)
€ r € r
b b
r r
a a
3-D
r € rr€ (hkl) = (210)
c (hkl) = (114) cc
€ €
r
€ b € r
€€ b
r r
a a
€
€
Miller indices, cubic lattices
Paolo
Fornasini
Univ. Trento
sc
€ € €
bcc
€ € €
fcc
2 a2
dhkl = 2 2 2
h + k +l
a a a
d200 = = 1.805 Å d220 = = 1.276 Å d111 = = 2.084 Å
2 2 2 3
Planes and directions
Perpendicular direction
[hkl]
Family of planes
(hkl)
€
Equivalent planes and directions
[010] [001]
€
[100]
€ €
€ € €
Equivalent planes {100}
Reciprocal lattice
X-ray diffraction pattern
Paolo
Fornasini
Univ. Trento
Direct space
3-dimensional lattice
Reciprocal space
2-dimensional projection
Basic idea
Paolo
Fornasini
Univ. Trento
r
K hkl dh'k'l' r
2π
K h'k'l'
K hkl =
dhkl
dhkl
€
€ €
€
B) Wave-vectors → set of points
Periodic behaviour
T ω = 2 π /T
time frequency
€
λ k = 2π / λ
€position wave-vector
Harmonics
Paolo
Fornasini
Univ. Trento
Periodic behaviour
T ω0 fundamental
€
3ω0 3rd harmonic
time€
€
frequency
Periodic behaviour
1-D
Paolo
Fornasini
Univ. Trento
* 2π
a =
a
r r*
a a
€
€ r r*
a € a
2-D, rectangular lattice (a)
Paolo
Fornasini
Univ. Trento
* 2 π 2 πb
a = =
a ab
r 2 π 2 πa
R b* = = r*
b ab
r R
r* r
b r a ⊥b r*
a r* r b
€ b ⊥a
€
€ ar *
€
€ €
r r r € r* r* r*
R = n1a + n2b € R = m1a + m2b
2-D, rectangular lattice (b)
Paolo
Fornasini
Univ. Trento
2π 2 πb
a* = =
a sin θ ab sin θ
2π 2 πa
r b* = =
r b sin θ ab sin θ
R
b r* r r*
a ⊥b
r r* r b
a b ⊥a
€ r*
€ a
€
€
€ €
€
2-D, oblique lattice (b)
Paolo
Fornasini
Univ. Trento
(111)
r r*
c c
r r* €
b b
(110)
r € r* (100)
a a
€ €
€
€
€ €
(100) (110) (111)
Cubic lattices (b)
Paolo
Fornasini
Univ. Trento
r r*
c c
r
b r*
b
r r*
a € a
(200)
€
€ €
€ €
(200) (110) (222)
Cubic lattices (c)
Paolo
Fornasini
Univ. Trento
r r*
c c
r r*
b b
€ r r* (200)
a € a
€ € €
€ €
(200) (220) (111)
Primitive vectors: general rule
Paolo
Fornasini
Univ. Trento
r r*
c r r c
r b ×c
a* = 2π r r r
r
( )
a⋅ b ×c r* r*
r r* r r
c×a
a b
a b b = 2π r r r r*
€ r ( €)
a⋅ b ×c c
r r
c r a×b
c * = 2π r r r
r r (€ )
a⋅ b ×c
€r * r*
a€ b a b
€
€ r r r
€
(
a⋅ b ×c )
€ € €
Reciprocal lattice and lattice planes
Paolo
Fornasini
Univ. Trento
Grain structure
Effects of temperature
Paolo
Fornasini
Univ. Trento
Temperature
High T:
liquid
Low T:
solid
Thermodynamic No thermodynamic
equilibrium equilibrium
Radial Distribution Function
Paolo
Fornasini
Univ. Trento
average density
RDF = 4 πr 2 ρ (r ) = 4 πr 2 ρ 0 g(r )
g(r)
0
Short-range order r
Summary