Crystalography

Basic crystallography
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

Wilhelm Konrad Rntgen (1845-1923)
Paolo Fornasini Univ. Trento
Wrzburg (Germany) November 8,1895
Electromagnetic waves
Speed (in vacuum):
c 310 8 m/s
Electric field Magnetic field
Wavelength
1 = 10-10 m 1 nm = 10-9 m
Frequency
= c/
= 2
Photon energy
E = h = h
Wave-vector
r k
2 k=
Plane wave
Plane wave
r r
r E
r k
r r
2 k=
r r r r r E(r ) = E 0 cos k r
( )
rr ik r
r r r = E 0 for k r = 2n
Complex notation
Re e
{ }
Electromagnetic spectrum
E (eV)
Photon energy Wavelength 10-12
(Hz)
102 ELF Radio waves
(m)
106
E = h = hc /
Frequency
10-8
106
102 Micro waves IR 10-6 UV
10-4
1010
10-2
X-rays
1
1014
0.0110 1017 10 20 Hz
E 0.4 400 keV
108 1022 104 1018
10-10
10-14
Interaction of x-rays with matter

Auger electrons Photo-electrons
EA
Fluorescence
h F
Photo-electric absorption
Incoming beam (monochromatic)
h
Elastic scattering
Beam attenuation
h '
Inelastic scattering
Scattering
X-RAYS and X-ray techniques

X-rays
10-12 10-10 1 U.V. 10-8 10-6 1 m I.R. 10-4 10-2
(m)
E[keV] =
12.4 []
Imaging
Scattering
Spectroscopy
= 2dsin
Intensity
Bragg angle
Absorption
Energy
Crystals
Crystals
Macroscopic regularities
(e.g. constancy of angles)
Classification of crystals
Quartz crystal (SiO2)
Regular packing of microscopic structural units

R.J. Hay (1743-1822)
Atoms and crystals

HYPOTHESIS: Structural units = atoms
Example: NaCl
Atomic masses:
Na 38.12 x 10-24 g Cl 58.85 x 10-24 g
Cubic structure 1 cm3 m = 2.165 g N = 44.6 x 1021 atoms
0.28 nm = 2.8
CONCLUSION:
Inter-atomic distances Atomic dimensions
X-ray wavelengths
X-ray diffraction from crystals
Munich, 1912: Max von Laue W. Friedrich & P.Knipping
Crystallography
Cambridge, 1912/13
William Henry Bragg (1862-1942)
William Lawrence Bragg (1890-1971)
Bragg spectrometer
Crystal structure
Bravais lattice + Basis
Atom
1-D 1-D
Molecule 2-D 2-D
3-D 3-D
Protein
Bravais lattice + basis
1-D
2-D 3-D
Crystal lattices
Translation vectors (2D)
2-D
r R
For every lattice point
r b
r r r R = n1a + n2b
r a
Arbitrary origin
integers
primitive vectors
Primitive vectors (2D)
r r r R = n1a + n2b
r R
2-D
r b
r a
r R
r R
Different choices of primitive vectors
r r a, b
Non-primitive vectors (2D)
Not all
r r a, b
2-D
pairs are primitive
r b
r a
r R
r R
r R
r r r R n1a + n2b
Primitive vectors (3D)
r r r r R = n1a + n2b + n3c
3-D
r c
r b
r r r Different choices of primitive vectors a , b , c
r a
Primitive unit cells (2D)
2-D
r b
r a
Different choices of primitive unit cells
Primitive cell = 1 lattice point
Conventional unit cells (2D)
2-D
r b
r a
More than 1 lattice point per unit cell
Non-Bravais lattices
Atoms
2-D
r r r R n1a + n2b
Un-equivalent sites
Bravais lattices
Bravais lattice
Basis
Classification of cells
2-D 3-D
r b
r c
r a
a b c
latin greek
r b
r a
Surface Bravais lattice
2-D
Non-primitive unit cell
3-D Bravais lattices

3-D
4 unit cells 7 crystal systems +

P = primitive I = body centered F = face centered C = side centered
14 Bravais lattices
Coordinates
(3, 2)
Lattice points: integer coordinates
1
1 1
Inside cell: fractional coordinates
r r r R = n1a + n2b
2 4 1 4 3 4
1
3 1 , 4 2
1 1 , 4 4
Some relevant crystal structures
Simple cubic lattice

84-Po
a=3.35
Bravais lattice
a
lattice parameter
Primitive unit cell (1 lattice point per cell)

Coordination number = 6
Body centered cubic lattice (bcc)

24-Cr 26-Fe 42-Mo
a=2.88 a=2.87 a=3.15
Bravais lattice
a
lattice parameter
conventional unit cell (2 lattice points per cell)

Face centered cubic lattice (fcc)

29-Cu 47-Ag 79-Au
a=3.61 a=4.09 a=4.08
Bravais lattice
a
lattice parameter
conventional unit cell (4 lattice points per cell)

Diamond structure
6-C 14-Si 32-Ge Non-Bravais lattice fcc Bravais lattice
a=3.57 a=5.43 a=5.66
2-atom basis
1 1 1 , , 4 4 4
(0, 0, 0)
conventional unit cell (8 atoms per cell)
Zincblende (sphalerite) structure

ZnS GaAs SiC Non-Bravais lattice fcc Bravais lattice
a=5.41 a=5.65 a=4.35
2-atom basis
1 1 1 , , 4 4 4
(0, 0, 0)

Cordination number = 4
Rock-salt (NaCl) structure

NaCl KBr CaO Non-Bravais lattice fcc Bravais lattice
a=5.64 a=6.60 a=4.81
2-atom basis
1 1 1 , , 2 2 2
(0, 0, 0)

Simple hexagonal structure
Top view
a
2 lattice parameters
Hexagonal symmetry
Primitive cell
lattice point per cell) (1
Primitive unit cell
r a2
a1 = a2
r a1
Hexagonal close packed structure

4-Be 12-Mg 48-Cd Non-Bravais lattice
a=2.29 a=3.21 a=2.98
primitive cell
2-atom basis
1 1 1 , , 2 2 2
(0, 0, 0)
8 c= a 3
Conventional unit cell (2 atoms per cell)

Coordination number
diamond cubic
bcc
N=4
N=6
N=8
fcc
hcp
Close packing
N=12
Close-packing of spheres
A A
1st layer
A A A A A A
A A A A A
A A A A A
A A A
2nd layer
B B B B
B B B B
B B B B
B B
A A
A A
3rd layer
A A A A A A
A A A A A
ABA
A A A A A
A C A C A
ABC
C C C C
C C
A A
hcp versus fcc

A
hcp
A A A A A A A A A A A A A A A A A A A A A A A
fcc
C C C C C C C C
Crystal planes
Crystal planes
2-D
Miller indices, 2-D (a)

2-D
r b
r a
(hk) = (21)
(hk) = (11)
Miller indices, 2-D (b)
(hk) = (01)
(hk) = (1 1 )
(hk) = (10)
(hk) = (2 1 )
Miller indices, 3-D

r c
(hkl) = (100)
(hkl) = (111)
r b
r a
3-D
r b
r a r c
(hkl) = (114)
rr cc
(hkl) = (210)
r b
r a
r b
r a
Miller indices, cubic lattices
sc
(100) (110) (111)
bcc
(200) (110)
(222)
fcc
(200)
(220)
(111)
Interplanar distance
dhkl
Cubic lattices
2 dhkl
a2 = 2 2 2 h + k +l
Copper, fcc, a=3.61
d200 =
a = 1.805 2
d220 =
a 2 2
= 1.276
d111 =
a = 2.084 3
Planes and directions
Perpendicular direction
[hkl]
Family of planes
(hkl)
Equivalent planes and directions

Equivalent directions
< 100 >
[100]
(100)
[010]
[001]
(010) (001)
Equivalent planes
{100}
Reciprocal lattice
X-ray diffraction pattern
Direct space
3-dimensional lattice
Reciprocal space
2-dimensional projection
Basic idea
A) Family of planes wave-vector
r K hkl
dh'k'l'
K hkl 2 = dhkl
r K h'k'l'
dhkl
B) Wave-vectors set of points
C) Set of points lattice
Reciprocal quantities
Periodic behaviour
time
= 2 /T
frequency
position
k = 2 /
wave-vector
Harmonics
Periodic behaviour
time
0
20
30
fundamental
2nd harmonic
3rd harmonic
frequency
Periodic behaviour
1-D
Direct space Reciprocal space
2 a = a
*
r a
r* a
r a
r* a
2-D, rectangular lattice (a)

r R
r b
r a
2 2 b a = = a ab 2 2 a b* = = b ab r* r a b r* r b a
*
r* R
r* b
r a*
r r r R = n1a + n2b
r* r* r* R = m1a + m2b
2-D, rectangular lattice (b)

2-D, rectangular lattice (c)

2-D, rectangular lattice (d)

2-D, oblique lattice (a)

r b
r R
r a
2 2 b = a sin ab sin 2 2 a b* = = b sin ab sin r* r a b r* r b a a* =
r* b r* a
2-D, oblique lattice (b)

Cubic lattices (a)

r c
r b
r* c
r* b
(111)
r a
r* a
(110) (100)
(100)
(110)
(111)
Cubic lattices (b)

r c
r b
r a
r* c r* b r* a
(200)
(200)
(110)
(222)
Cubic lattices (c)

r c
r b
r* c
r* b r* a
(200)
r a
(200)
(220)
(111)
Primitive vectors: general rule

r c
r a
r a
r b
r c
r b
r r r b c a* = 2 r r r a b c r r r* ca b = 2 r r r a b c r r r ab c * = 2 r r r a b c
r* c r* a r* c
* r a r* b
( (
) )
( )
r* b
r r r a b c
Reciprocal lattice and lattice planes
For any family of lattice planes separated by a distance d there are reciprocal lattice vectors perpendicular to the planes, the shortest of which have a length 2/d.
For any reciprocal lattice vector R*, there is a family of lattice planes normal to R* and separated by a distance d, where 2/d is the length of the shortest reciprocal lattice vector parallel to R*.
Microscopic structure of materials
Macro and micro-crystals
Monocrystalline silicon, 13 cm
Cr, electron microscopy
Grain structure
Effects of temperature
Temperature
Thermal motion
Spread of atomic positions
Crystalline and non-crystalline materials

Crystalline solids
Non-crystalline systems
Long-range order
No long-range order
Cooling rate
Slow cooling Fast cooling
High T: liquid
Low T: solid
Thermodynamic equilibrium
No thermodynamic equilibrium
Radial Distribution Function

average density
RDF = 4 r 2 (r ) = 4 r 2 0 g(r )
PDF = Pair Distribution Function
g(r) 1
Short-range order
Summary
Plane waves and wavevector Crystal structure = Bravais lattice + basis Bravais lattices: primitive vectors, unit cells (primitive and conventional), classifications Crystal structures (sc, bcc, fcc, hcp ...) Crystal planes and Miller indices Reciprocal lattice Crystalline and non-crystalline materials
Dolomite mountains in winter

Crystalography

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Crystalography

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Basic crystallography

1895 - Discovery of X-rays

Paolo Fornasini Univ. Trento

Wrzburg (Germany) November 8,1895

Paolo Fornasini Univ. Trento

Speed (in vacuum):

Electric field Magnetic field

Paolo Fornasini Univ. Trento

Paolo Fornasini Univ. Trento

Paolo Fornasini Univ. Trento

102 Micro waves IR 10-6 UV

Interaction of x-rays with matter

Paolo Fornasini Univ. Trento

Incoming beam (monochromatic)

X-RAYS and X-ray techniques

Paolo Fornasini Univ. Trento

Paolo Fornasini Univ. Trento

Quartz crystal (SiO2)

Regular packing of microscopic structural units

Atoms and crystals

Paolo Fornasini Univ. Trento

Na 38.12 x 10-24 g Cl 58.85 x 10-24 g

Cubic structure 1 cm3 m = 2.165 g N = 44.6 x 1021 atoms

Inter-atomic distances Atomic dimensions

X-ray diffraction from crystals

Paolo Fornasini Univ. Trento

Munich, 1912: Max von Laue W. Friedrich & P.Knipping

Paolo Fornasini Univ. Trento

William Henry Bragg (1862-1942)

William Lawrence Bragg (1890-1971)

Paolo Fornasini Univ. Trento

Molecule 2-D 2-D

Bravais lattice + basis

Paolo Fornasini Univ. Trento

Translation vectors (2D)

Paolo Fornasini Univ. Trento

Primitive vectors (2D)

Paolo Fornasini Univ. Trento

Different choices of primitive vectors

Non-primitive vectors (2D)

Paolo Fornasini Univ. Trento

pairs are primitive

Primitive vectors (3D)

Paolo Fornasini Univ. Trento

r r r r R = n1a + n2b + n3c

r r r Different choices of primitive vectors a , b , c

Primitive unit cells (2D)

Paolo Fornasini Univ. Trento

Primitive cell = 1 lattice point

Conventional unit cells (2D)

Paolo Fornasini Univ. Trento

More than 1 lattice point per unit cell

Paolo Fornasini Univ. Trento

Paolo Fornasini Univ. Trento

Surface Bravais lattice

Paolo Fornasini Univ. Trento

Non-primitive unit cell

3-D Bravais lattices

Paolo Fornasini Univ. Trento

4 unit cells 7 crystal systems +

Paolo Fornasini Univ. Trento

Some relevant crystal structures