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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 .1895 .Discovery of X-rays Wilhelm Konrad Röntgen (1845-1923) Paolo Fornasini Univ. Trento Würzburg (Germany) November 8.

Electromagnetic waves Paolo Fornasini Univ. Trento Speed (in vacuum): c ≈ 3×10 8 m/s λ c Electric field Magnetic field € € € Wavelength λ 1 Å = 10-10 m 1 nm = 10-9 m € Frequency ν = c/λ ω = 2 πν Photon energy € E = hν = hω € € .

Trento r k 2π k= λ € Plane wave λ € € .Wave-vector Paolo Fornasini Univ.

Trento r r € r E r k € r r 2π k= λ € r r r r r E(r ) = E 0 cos k ⋅ r ( ) rr ik ⋅r r r r = E 0 € for k ⋅ r = 2nπ Complex notation € € Re e { } .Plane wave Paolo Fornasini Univ.

Electromagnetic spectrum E (eV) Photon energy Wavelength 10-12 Paolo Fornasini Univ.01÷10 Å ν ≈ 1017 ÷10 20 Hz E ≈ 0. Trento ν (Hz) 102 ELF Radio waves λ (m) 106 E = hν = hc / λ Frequency 10-8 106 102 Micro waves IR 10-6 UV 10-4 1010 10-2 X-rays 1 1014 λ ≈ 0.4 ÷ 400 keV 108 1022 104 1018 X γ 10-10 10-14 .

Trento E EA Fluorescence hν F Photo-electric absorption hν € Incoming beam (monochromatic) € € hν Elastic scattering Beam attenuation € hν ' Inelastic scattering Scattering € .Interaction of x-rays with matter Auger electrons Photo-electrons Paolo Fornasini Univ.

R. 10-8 10-6 1 µm I.4 λ[Å] Imaging Scattering Spectroscopy λ = 2dsin θ Intensity Bragg angle Absorption Energy .X-RAYS and X-ray techniques X-rays 10-12 10-10 1Å U. 10-4 10-2 Paolo Fornasini Univ.V. Trento λ (m) E[keV] = 12.

 Crystals .

Crystals Macroscopic regularities (e. Trento Classification of crystals Quartz crystal (SiO2) Regular packing of microscopic structural units R.J. Haüy (1743-1822) .g. constancy of angles) Paolo Fornasini Univ.

Atoms and crystals HYPOTHESIS: Structural units = atoms Paolo Fornasini Univ.6 x 1021 atoms 0.85 x 10-24 g Cubic structure 1 cm3 m = 2.12 x 10-24 g Cl 58. Trento Example: NaCl Atomic masses: Na 38.28 nm = 2.8 Å CONCLUSION: Inter-atomic distances Atomic dimensions ≈ X-ray wavelengths .165 g N = 44.

Trento Munich. Friedrich & P.X-ray diffraction from crystals Paolo Fornasini Univ. 1912: • Max von Laue • W.Knipping .

1912/13 Paolo Fornasini Univ.Crystallography Cambridge. Trento William Henry Bragg (1862-1942) William Lawrence Bragg (1890-1971) Bragg spectrometer .

Trento 1-D 1-D Molecule 2-D 2-D 3-D 3-D Protein .Crystal structure Bravais lattice + Basis Atom Paolo Fornasini Univ.

Bravais lattice + basis Paolo Fornasini Univ. Trento 1-D 2-D 3-D .

 Crystal lattices .

Trento 2-D r R For every lattice point r b r r r R = n1a + n2b r € a Arbitrary origin € integers primitive vectors € .Translation vectors (2D) Paolo Fornasini Univ.

b .Primitive vectors (2D) Paolo Fornasini Univ. Trento 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 2-D pairs are primitive € r b r € a r R r R € r R € € r r r R ≠ n1a + n2b . Trento Not all r r a.Non-primitive vectors (2D) Paolo Fornasini Univ.

b . c r a € .Primitive vectors (3D) Paolo Fornasini Univ. Trento r r r r R = n1a + n2b + n3c 3-D € r c r b € € r r r Different choices of primitive vectors a .

Trento 2-D r b r a Different choices of primitive unit cells € Primitive cell = 1 lattice point .Primitive unit cells (2D) Paolo Fornasini Univ.

Trento 2-D r b r a € More than 1 lattice point per unit cell .Conventional unit cells (2D) Paolo Fornasini Univ.

Non-Bravais lattices Atoms Paolo Fornasini Univ. Trento 2-D r r r R ≠ n1a + n2b Un-equivalent sites € .

Trento Bravais lattice Basis .Bravais lattices Paolo Fornasini Univ.

Classification of cells 2-D 3-D r b r c γ r a € a € b c latin greek € r α b γ β α β γ r a € € € .

Trento 2-D Non-primitive unit cell .Surface Bravais lattice Paolo Fornasini Univ.

3-D Bravais lattices 3-D Paolo Fornasini Univ. Trento 4 unit cells 7 crystal systems + P = primitive I = body centered F = face centered C = side centered = 14 Bravais lattices .

Trento 2 € (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 € € 0 € 1  3 1  .  4 4 € € .  4 2 2 3 € € € 1 1  .Coordinates Paolo Fornasini Univ.

 Some relevant crystal structures .

35 Å Bravais lattice a lattice parameter € Primitive unit cell (1 lattice point per cell) Coordination number = 6 . Trento a=3.Simple cubic lattice 84-Po Paolo Fornasini Univ.

Trento a=2.15 Å Bravais lattice a lattice parameter € conventional unit cell (2 lattice points per cell) Coordination number = 8 .87 Å a=3.Body centered cubic lattice (bcc) 24-Cr 26-Fe 42-Mo Paolo Fornasini Univ.88 Å a=2.

08 Å Bravais lattice a lattice parameter € conventional unit cell (4 lattice points per cell) Coordination number = 12 .09 Å a=4.61 Å a=4. Trento a=3.Face centered cubic lattice (fcc) 29-Cu 47-Ag 79-Au Paolo Fornasini Univ.

57 Å a=5. 0. Trento a=3.43 Å a=5.Diamond structure 6-C 14-Si 32-Ge Non-Bravais lattice fcc Bravais lattice Paolo Fornasini Univ.  4 4 4 a € (0. 0) € € conventional unit cell (8 atoms per cell) Coordination number = 4 .66 Å + 2-atom basis 1 1 1  . .

.  4 4 4 a € (0.65 Å a=4.Zincblende (sphalerite) structure ZnS GaAs SiC Non-Bravais lattice fcc Bravais lattice Paolo Fornasini Univ.35 Å + 2-atom basis 1 1 1  . 0. Trento a=5. 0) € € conventional unit cell (8 atoms per cell) Cordination number = 4 .41 Å a=5.

Rock-salt (NaCl) structure
NaCl KBr CaO Non-Bravais lattice fcc Bravais lattice

Paolo Fornasini Univ. Trento

a=5.64 Å a=6.60 Å a=4.81 Å

+

2-atom basis

1 1 1  , ,  2 2 2

a

(0, 0, 0)

conventional unit cell (8 atoms per cell)
Cordination number = 6

Simple hexagonal structure

Paolo Fornasini Univ. Trento

Top view

c

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

Paolo Fornasini Univ. Trento

a=2.29 Å a=3.21 Å a=2.98 Å

c

primitive cell

+

2-atom basis
1 1 1  , ,  2 2 2

(0, 0, 0)

8 c= a 3

a

Conventional unit cell (2 atoms per cell)
Cordination number = 12

Coordination number diamond cubic Paolo Fornasini Univ. Trento bcc N=4 N=6 N=8 fcc hcp Close packing N=12 .

Trento 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 .Close-packing of spheres A A 1st layer Paolo Fornasini Univ.

Trento B C A A B 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 .hcp versus fcc A Paolo Fornasini Univ.

 Crystal planes .

Trento .Crystal planes 2-D Paolo Fornasini Univ.

Trento r b r a € € (hk) = (21) (hk) = (11) . 2-D (a) 2-D Paolo Fornasini Univ.Miller indices.

Miller indices. 2-D (b) Paolo Fornasini Univ. Trento (hk) = (01) (hk) = (1 1 ) € € (hk) = (10) (hk) = (2 1 ) .

Miller indices. 3-D r c € (hkl) = (100) Paolo Fornasini Univ. Trento (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 € .

cubic lattices Paolo Fornasini Univ.Miller indices. Trento sc (100) (110) (111) € € € bcc (200) (110) (222) fcc € € € (200) (220) (111) .

Interplanar distance Paolo Fornasini Univ.276 Å d111 = a = 2.084 Å 3 . Trento dhkl Cubic lattices 2 dhkl a2 = 2 2 2 h + k +l Copper.805 Å 2 d220 = a 2 2 = 1. a=3. fcc.61 Å € d200 = a = 1.

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 Paolo Fornasini Univ. Trento Direct space 3-dimensional lattice Reciprocal space 2-dimensional projection .

Trento r K hkl dh'k'l' K hkl 2π = dhkl r K h'k'l' dhkl € € € € B) Wave-vectors → set of points C) Set of points → lattice .Basic idea A) Family of planes → wave-vector Paolo Fornasini Univ.

Trento T € time ω = 2 π /T frequency λ €position k = 2π / λ wave-vector .Reciprocal quantities Periodic behaviour Paolo Fornasini Univ.

Trento T € time ω0 2ω0 3ω0 fundamental 2nd harmonic 3rd harmonic € € frequency Periodic behaviour .Harmonics Periodic behaviour Paolo Fornasini Univ.

Trento 2π a = a * r a € r* a € r a € r* a .1-D Direct space Reciprocal space Paolo Fornasini Univ.

Trento r R r b € r a € 2 π 2 πb a = = a ab 2 π 2 πa 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 . rectangular lattice (a) Direct space Reciprocal space Paolo Fornasini Univ.2-D.

2-D. rectangular lattice (b) Direct space Reciprocal space Paolo Fornasini Univ. Trento .

2-D. rectangular lattice (c) Direct space Reciprocal space Paolo Fornasini Univ. Trento .

2-D. rectangular lattice (d) Direct space Reciprocal space Paolo Fornasini Univ. Trento .

oblique lattice (a) Direct space Reciprocal space Paolo Fornasini Univ. Trento r b r R r a € € 2π 2 πb = a sin θ ab sin θ 2π 2 πa b* = = b sin θ ab sin θ r* r a ⊥b r* r b ⊥a a* = r* b r* a € € € € € .2-D.

Trento .2-D. oblique lattice (b) Direct space Reciprocal space Paolo Fornasini Univ.

Trento r c r b r* c r* b € (111) r a € € € € r* a € (110) (100) € (100) (110) € (111) .Cubic lattices (a) Direct space Reciprocal space Paolo Fornasini Univ.

Trento r c r b r a r* c r* b € € r* a € (200) € € (200) € (110) (222) .Cubic lattices (b) Direct space Reciprocal space Paolo Fornasini Univ.

Trento r c r b r* c r* b r* a (200) € € r a € € € € (200) € (220) (111) .Cubic lattices (c) Direct space Reciprocal space Paolo Fornasini Univ.

Trento r c € r a r € a r b r c r b € r r r b ×c a* = 2π r r r a⋅ b ×c r r r* c×a b = 2π r r r a⋅ b ×c € r r r a×b c * = 2π r r r a⋅ b ×c r* c r* a r* c €* r a r* b ( ( ) ) (€ ) € r* b € € r r r a⋅ b ×c ( ) € € .Primitive vectors: general rule Direct space Reciprocal space Paolo Fornasini Univ.

where 2π/d is the length of the shortest reciprocal lattice vector parallel to R*. For any reciprocal lattice vector R*. Trento For any family of lattice planes separated by a distance d there are reciprocal lattice vectors perpendicular to the planes.Reciprocal lattice and lattice planes Paolo Fornasini Univ. the shortest of which have a length 2π/d. there is a family of lattice planes normal to R* and separated by a distance d. .

 Microscopic structure of materials .

Trento Monocrystalline silicon.Macro and micro-crystals Paolo Fornasini Univ. ∅ 13 cm Cr. electron microscopy Grain structure .

Trento Temperature Thermal motion Spread of atomic positions .Effects of temperature Paolo Fornasini Univ.

Trento Non-crystalline systems Long-range order No long-range order .Crystalline and non-crystalline materials Crystalline solids Paolo Fornasini Univ.

Trento High T: liquid Low T: solid Thermodynamic equilibrium No thermodynamic equilibrium .Cooling rate Slow cooling Fast cooling Paolo Fornasini Univ.

Trento RDF = 4 πr 2 ρ (r ) = 4 πr 2 ρ 0 g(r ) € PDF = Pair Distribution Function g(r) 1 Short-range order 0 r .Radial Distribution Function average density Paolo Fornasini Univ.

bcc.) • Crystal planes and Miller indices • Reciprocal lattice • Crystalline and non-crystalline materials ... classifications • Crystal structures (sc. fcc. unit cells (primitive and conventional). Summary • Plane waves and wavevector • Crystal structure = Bravais lattice + basis • Bravais lattices: primitive vectors. hcp .

Dolomite mountains in winter .