Chapter One Crystal Structure

Drusy Quartz in Geode Tabular Orthoclase Feldspar Encrusting Smithsonite

Peruvian Pyrite
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[Link]
Snow crystals

the Beltsville Agricultural Research Center

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Solid : Crystal vs. Amorphous (glassy)

Ordered array of atoms Disordered arrangement

Competition between attractive (binding) force and repulsive force.

Regular array lowers system energy.

Complicated ! -- difficult to predict the structure of materials

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☺ Importance : structure plays a major role in
determining physical properties of solids

☺ Determination : X-ray and neutron scattering are key tools

for determining crystal structures. (bulk)
Also microscopic techniques such as SEM, TEM,
STM, AFM… (surface)

☺ Deviations : There is no perfect crystal.

Many key properties depend on deviation more.
Defects – imperfection in crystal
Phonons – lattice vibrations

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 Calcite(CaCO3) crystal is made from
spherical particles.
Christiaan Huygen, Leiden 1690

A crystal is made from spherical particles.

Robert Hooke, London 1745

depicted by René Haüy,

Paris, 1822
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 Crystal
periodic array of atoms : point lattice + basis

Point lattice – mathematical points in space

r
r ′ = r + u1 a 1 + u 2 a 2 + u 3 a 3
u1 , u 2 , u 3 ∈ integer r
a2
r
a1 , a 2 , a 3 = lattice vectors a1
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 Primitive lattice cell
• A cell will fill all space by the repetition of suitable crystal
translation operations. ---- A minimum volume cell.
⊗.One lattice point per primitive cell.
⊗.The basis associated w/. a primitive cell -- a primitive basis
⊗.Not unique.
2 Dimensions
r r
Acell = a1 × a 2
r r
= a1 a 2 sinφ
r
Same for all primitive cells a2
r
a1
Uniform mass density

Wigner-Seitz Primitive cell -- lattice point is at its center

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the highest symmetry cell possible
Wigner-Seitz Primitive cell in 2D (or 3D)

⊗ Draw lines to connect a given lattice point to all nearby lattice points.
⊗. Draw bisecting lines (or planes) to the previous lines.
⊗. The smallest area (or volume) enclosed.

2 D Oblique Lattice

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Fundamental types of Bravais lattices
Based on symmetries :

1) Translational – same if translate by a vector Auguste Bravais

T = u1 a 1 + u 2 a 2 + u 3 a 3
2) Rotational – same if lattice is rotated by an angle about a point
2-fold by 180o 4-fold by 90o
3-fold by 120o 6-fold by 60o

3) Mirror symmetry – same if reflected about a plane

4) Inversion symmetry – same if reflected through a point (equivalent

to rotation 180o and mirror rotational axis r -r

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Five Bravais lattices in two dimensions

Square lattice a1=a2, φ=90o Symmetry

Unit cell element
r
a2 φ
r
a1

Rectangular lattice a1 a2, φ=90o

Symmetry
Unit cell element

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Oblique lattice a1 a2, φ 60o,90o
Symmetry
Unit cell element

Centered Rectangular lattice a1= 2a2cosφ

Symmetry
r Unit cell element
a2
φ
r
a1

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Hexagonal lattice a1=a2, φ=60o

Symmetry
element

Unit cell twofold axis (dia)

threefold axis (triad)
fourfold axis (tetrad)
sixfold axis (hexad)
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mirror line
A Bravais lattice is a lattice in which
every lattice point has exactly the same environment.

How about a honeycomb lattice ?

A honeycomb crystal = A hexagonal lattice + two-pint basis 13

 The seven crystal systems divided into fourteen Bravais lattices
System Number of lattices Unit cell Characteristic
characteristics symmetry elements
Triclinic a1 a2 a3 None
1: Simple
α β γ
Monoclinic 2: a1 a2 a3 One 2-fold
α = β = 90o γ rotation axis
Simple, Base-Centered

Orthorhombic 4: BCC, FCC a1 a2 a3 Three mutually

α = β = γ = 90o orthogonal 2-fold
Simple, Base-Centered
rotation axes
Tetragonal 2: Simple, BCC a1 = a2 a3 One 4-fold
α = β = γ = 90o rotation axis
Cubic 3: Simple, BCC, FCC a1 = a2 = a3 Four 3-fold
α = β = γ = 90o rotation axes
Trigonal 1: Simple a1 = a2 = a3 One 3-fold
α = β = γ<120o 90o rotation axis
Hexagonal 1: Simple a1 = a2 a3
One 3-fold14
α = β = 90o, γ =120o
rotation axis
TRICLINIC (α≠β≠γ) a1 a2 a3

MONOCLINIC (β=γ=90o ≠ α)
a3

β α a2
γ
a1
a3

Simple

a2
a1

Simple Base-centered 15
Orthorhombic (α=β=γ=90o) a1 a2 a3

a3

α
a2
β
γ
a1

Simple Base-centered BCC

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FCC
 Tetragonal (α=β=γ=90o) a1 a

α
β a

γ
a1

Simple BCC

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 Cubic (α=β=γ=90o)

β α
a
γ
a

Simple BCC FCC

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Trigonal Hexagonal
(α=β=γ<120o , 90o ) (α=β=90o, γ=120o)

a a3 a
a
a

a3
a
γ=120o

a
Simple

Simple
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 Characteristics of cubic lattices

Simple Body-centered Face-centered

Lattice points/cell 1 2 4
Number of
nearest neighbors 6 8 12
Nearest- neighbor 3 a
distance a a
2 2
π 3 2
Packing fraction = 0.524 π = 0.680 π = 0.740
6 8 6
Maximum,
same as hexagonal

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Crystal – Periodic arrangement of atoms
Bravais lattice + Basis of atom
(Array of point in space) (Arrangement of atoms within unit cell)

2 Dimensions 5 types
By symmetry
3 Dimensions 14 types

Crystal may have same or less symmetry than original Bravais lattice.

Basis
Symmetry “4mm”

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Introducing new symmetries for basis with multiple atoms :

• Point group symmetries :

combinations of rotation, inversion, reflection that hold
one point fixed and return original structure.
2 Dimensions , 10
3 Dimensions , 32

• Space group symmetries :

point group operations + translations that return original structure.
2 Dimensions , 17
3 Dimensions , 230

There are many possible types by symmetry but most are never observed.
Real crystals form a few types due to energies of crystal formation.

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Directions and planes in crystals
Useful to develop a notation for describing directions and
identifying planes of atoms in crystals

Consider lattice defined by a1 , a 2 , a 3

r
Vector direction r = u1 a1 + u 2 a 2 + u 3 a 3 is described as [u1 u2 u3]
where u1, u2, and u3 are the lowest reduced integers.

Note :
• [8 6 0] same as [4 3 0]
• use ū instead of -u [121]
• [u1 u2 u3] not as the same as Cartesian coordinate direction
except for simple cubic crystal

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Cubic has highest symmetric directions
[001] [111]

[010]
[110]

[100]

By symmetry, [ 1 0 0 ], [ 0 1 0 ], [ 0 0 1 ] are equivalent

[ 1 0 0 ], [ 0 1 0 ], [ 0 0 1 ]
Denote { 1 0 0 } ≡ set of equivalent directions

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Crystal planes – atoms fall on planes labeled by “Miller indices”

Note :
• Find the intercepts on the axes in terms of a1, a2, and a3 h’ k’ l’
1 1 1
• Take reciprocals and make integers ( ) × h' k ' l '
h' k' l '
• Reduce to smallest three integers
• If the plane does not intersect one of the crystal axes, that
intercept is taken to be infinitely far from the origin and the
corresponding index is zero.

(hkl) is called Miller index of the plane

Miller indices
specify a vector normal to the plane, and not a specific plane :
all parallel planes have the same indices
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 Schematic illustrations of lattice planes
Lines in two dimensional crystals

r (01)
a2
r
a1
(25)
(11)

Low index plane : more dense and more widely spaced

High index plane : Less dense and more closely spaced

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Most common crystal structures :
Simple Cubic lattice : Po conventional cell : 1 atom/cube
Body Centered Cubic lattice :

Conventional cell : 2 atoms/ cube

Not a primitive lattice

(1/2,1/2,1/2) 8 nearest neighbors

(0,0,0)
Alkali metals : Li, Na, K, Rb, Cs
Ferromagnetic metals : Cr, Fe
Transition metals : Nb, V, Ta, Mo, W

• BCC lattice + single atom basis

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• SC lattice + basis of 2 atoms at (0,0,0) and (1/2,1/2,1/2)
Body Centered Cubic lattice

z
a
a1 = (x̂ + ŷ − ẑ)
2
a
a2 a 2 = (− x̂ + ŷ + ẑ)
a3 2
a
a1 y a 3 = (x̂ − ŷ + ẑ)
x 2

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Body-centered Cubic lattice

Primitive cell :
Rhombohedron
w/.
3
1. edge a
2
2. the angle between
two adjacent edges is
109o28’

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 Face Centered Cubic lattice :

Conventional cell : 4 atoms/ cube

Not a primitive lattice

(1/2,0,1/2) 12 nearest neighbors

(0,1/2,1/2)

(0,0,0) Noble metals : Cu, Ag, Au

Transition metals : Ni, Pd, Pt,
(1/2,1/2,0)
Inert gas solids : Ne, Ar, Kr, Xe

• FCC lattice + single atom basis

• SC lattice + basis of 4 atoms at (0,0,0), (1/2,1/2,0) (1/2,0,1/2), and (0,1/2,1/2)

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 Face Centered Cubic lattice
z
a
a1 = (x̂ + ŷ)
2
a
a3 a 2 = (ŷ + ẑ)
a2
2
a
a1 a 3 = (x̂ + ẑ)
y
2
x

The angle between two adjacent edges :

Rhombohedral Primitive cell 60o
2
Edge a
2 32
 Hexagonal Close-Packed lattice

a1 = a 2 , with an included angle 120o

c = 1.633 a1
a1, a2, and c do not construct a primitive lattice
c a1, a2, and a3 construct a primitive lattice
a1 = a 2 = a 3
a3
12 nearest neighbors
a2 Transition metals : Sc, Y, Ti, Zr, Co…
a1
IIA metals : Be, Mg

Basal Plane
Hexgonal lattice + basis of 2 atoms at (0,0,0) and (2/3,1/3,1/2)

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 HCP lattice ABABAB…

x
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FCC lattice ABCABCABC…
Diamond structure : two FCC displaced from each other by ¼
of a body diagonal
FCC lattice + basis of 2 atoms at (0,0,0) and (1/4,1/4,1/4)
0 1/2 0

3/4 1/4

1/2 0 1/2

1/4 3/4

0 1/2 0

Tetrahedral bonding : 4 nearest neighbors

12 next nearest neighbors

The maximum packing fraction = 0.34

Si, Ge, Sn, C, ZnS, GaAs, … 35
 Some atoms form multiple stable structures:
for example, C diamond or graphite (hexagonal)

An STM image of a graphite surface

clearly shows the interconnected
6-membered rings of graphite
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graphite diamond

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Many crystals undergo structural changes with T, P:
for example,

δ-ferrite α-ferrite
BCC FCC BCC Liquid
Fe Temperature
910oC 1400oC 2100oC

HCP FCC Liquid

Na Temperature
36K 371K

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Compounds

NaCl structures NaCl, NaF, KCl, AgCl, MgO, MnO, …

• FCC lattice + basis of two atoms

• Cl (0,0,0), Na (1/2,1/2,1/2)
SC w/. alternating atoms

CsCl structures CsCl, BeCu, ZnCu(brass), AlNi, AgMg, …

• SC lattice + basis of two atoms

• Cs (0,0,0), Cl (1/2,1/2,1/2)
BCC w/. alternating atoms
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ZnS structures ZnS, CuF, CuCl, … compounds

Znicblende CdS Photoconductor

GaAs, GaP, InSb, … III-V semiconducting compounds

• FCC lattice + basis of two atoms

• Zn (0,0,0), S (1/4,1/4,1/4)
• Ga(0,0,0), As(1/4,1/4,1/4)
diamond w/. alternating atoms

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 High Tc superconductors

a b

Pr Pr
Pr
O(4)

Cu(2) Cu(2) Cu(2)

O(2) O(2)
O(2)

O(1) O(1) O(1)

Ba/Pr Ba/Pr Ba/Pr

Cu(1) Cu(1) Cu(1)

O(5)
O(3)
O(3) O(3)

Orthorhombic Tetragonal Orthorhombic

O(I) (Pmmm) T (P4/mmm) O(II) (Cmmm)

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C-60
“Bucky balls”
BuckminsterFullurene

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