Crystal Structure

Electrical and Thermal Conductivity

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Quantum Mechanics

Band Theory

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 Theory of Metals
• Quantum theory of metal
• Free electron model
• Conduction in metals

Dielectric
Properties

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3
 Magnetic Properties
Magnetic moment, permeability

Ferromagnetism and magnetic domains

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Superconductivity
• Zero resistance and Meissner effect
• Type I and type II superconductors

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Metamaterial

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Text Book

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 1

General Bonding Principle

• Net force, FN = FA + FR , at equilibrium: 𝐹𝑁 = 𝐹𝐴 + 𝐹𝑅 = 0.
𝑑𝐸(𝑟)
• Potential Energy E(r) is related as 𝐹 𝑁 =
𝑑𝑟

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 Covalently Bonded Solid: Diamond
• Due to the strong Coulombic attraction between the shared electrons and the
positive nuclei, the covalent bond energy is usually the highest for all bond
types, leading to very high melting temperatures and very hard solids: diamond
is one of the hardest known materials.

C-H bond: Methane C-C bond: Diamond

Metallic Bonding
The free electrons inside a metal can drift
under the action of the applied field and give
rise to a current. These free electrons in the
metallic bond are called conduction electrons.

• Metals are good electrical conductors

• Metals are also good thermal
conductors

Silver Copper Aluminum (98.5%)

© McGraw-Hill Education/Mark Dierker © McGraw-Hill Education/Stephen © McGraw-Hill Education/Ken Cavanagh
(mhhe022468.jpg) Frisch (MHED9000878.JPG)
(MHHE005312.JPG)
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 Crystalline Solids
• A crystalline solid is a solid object in which atoms bond with each other in a
regular pattern to form a periodic collection or array of atoms.
• Most important property of a crystal is periodicity leading to long-range order
(location of each atom is well-known by virtue of periodicity).
• Examples of periodic array/crystalline solids: nearly all metals, many ceramics,
semiconductors, various polymers.

Crystalline Solids
• Crystal = Lattice + Basis
• Lattice  an infinite periodic array of geometric points in space (without
atoms)
• Basis  an identical group of atoms
• By putting the basis at each lattice point, we obtain the actual crystal.
• Thus the crystal becomes essentially a periodic repetition of a small volume,
called the unit cell.
• The length of the cubic unit cell is called lattice constant.
• The repetition of the unit cell in 3D will generation the whole crystal.

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 Lattice and Basis

Packing of Solids
• Crystals can be
• Face centered cubic, FCC
• Body centered cubic, BCC
• Hexagonal close packed, HCP

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 BCC

• Atom in the corner and one atom at the center

• In one BCC unit cell, there is one atom in the center, 1/8th atom in 8 corners 
Total of 2 atoms in BCC unit cell
• Coordination number: 8
• Example: Fe, Cr, Mo, W
• Close packed structure with a packing density of 68%
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FCC

• Atoms in the corners and in the centers of the faces

• In one FCC unit cell, 1/8th atom in 8 corners and ½ atom in each of 6-
planes  Total of 4 atoms in FCC unit cell
• Coordination number: 12
• Examples: Ag, Au, Cu, Pt
• Close packed structure with a packing density of 74%.
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 HCP

• On top of layer a, we can place an identical layer b, with the spheres taking
up the voids on layer a. The third layer can be placed on top of b and lined
up with layer a.
• The stacking sequence is abab …
• Number of atoms per unit cell: 6, 2
• Coordination number: 12
• Examples: Many metals  Co, Mg, Ti, Zn 11

Atomic Packing Factor

• Atomic packing factor (APF), packing efficiency or packing fraction is
the fraction of volume in a crystal that is occupied by constituent particles 
a dimensionless quantity and always less than unity.
• APF is determined by assuming that atoms are rigid spheres. Radius of spheres is
taken to be the maximum (atoms do not overlap). For crystals with only one type
of particle, the APF is
𝑁partiCle𝑉partiCle
APF =
𝑉unit Cell

NAPF 𝑁atoms𝑉atoms
: number of particles in the unit cell; Vparticle : volume of each particle;
particle=
and Vunit cell 𝑉
: volume
unit Cell occupied by the unit cell.

• For one-component structures, the maximum APF is about 0.74  close-packed

structures. For multiple-component structures, the APF can exceed 0.74.
• APF explains many properties of materials. Metals with a high APF will have a
higher "workability" (malleability or ductility).
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 APF of BCC
𝑁partiCle𝑉partiCle
APF =
𝑉unit Cell

• Simple cubic:

𝑎 = 2𝑟
4
1 ∙ 3 𝜋𝑟3 𝜋
APF = = ≈ 0.5236
(2𝑟)3 6

• Body centered cubic:

4𝑟
𝑎=
3
4
2 ∙ 𝜋𝑟3 𝜋 3
APF = 3 = ≈ 0.6802
4𝑟 3 8
3
13

APF of FCC
𝑁partiCle𝑉partiCle
APF =
𝑉unit Cell

𝑎 = 2 2𝑟

4
4 ∙ 3 𝜋𝑟3 𝜋
APF = = ≈ 0.7405
3 18
2 2𝑟
a
a

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 APF of HCP
𝑁partiCle𝑉partiCle
APF = =?
𝑉unit Cell

𝑉unit Cell =?
3 3 2
𝑉unit Cell = 𝑎𝑐
2

𝑎 =?
c =?

𝑎 = 2𝑟

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APF of HCP
C =?

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 APF of HCP
𝑁partiCle𝑉partiCle
APF =
𝑉unit Cell

𝑉unit Cell =?
3 3 2
𝑉unit Cell = 𝑎𝑐
2

𝑎 = 2𝑟
2
𝑐= ∙ 4𝑟
3

4 4
6 ∙ 𝜋𝑟3 6 ∙ 𝜋𝑟3
APF = 3 = 3
3 3 2 3 3 2
2 𝑎𝑐
2
2 2𝑟 3 ∙ 4𝑟
𝜋
= ≈ 0.7405
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Diamond Cubic Crystal Structure

• Covalently bonded solids have diamond structure due to the directional nature
of the covalent bonds  tetrahedral configuration.
• Examples: Si and Ge
• If we place 2 Si-atoms at each site of an FCC unit cell appropriately, one right
at the lattice point, and the other displaced from it by a/4 along the cube edges,
we can generate the diamond cell  8 atoms per unit cell
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 Zinc-Blende Structure

• In Zinc-Blende structure (e.g. ZnS, GaAs), there are binary compounds involved.
• Thus it looks like a diamond cubic, but Zn and S-atoms alternating positions
• Examples: ZnS, AlAs, GaAs, GaP, GaSb, InAs, InP, InSb, ZnTe.

APF of Diamond Cubic

𝑎
• Neighboring atoms are shifted by 𝑑 = 3
4
𝑑 𝑎
• Radius of atoms 𝑟 = = 3
2 8
3
4 4 3
8 ∙ 3 𝜋𝑟3 8∙ 3𝜋 8 𝑎
AFP = =
𝑎3 𝑎3
3
= 𝜋 ≈ 0.34
16 4

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 Ionic Solid: NaCl

• The crystal structure depends on the relative charge and size per ion.
• Na+ ions are about half of Cl ions, which results 6 nearest neighbors.
• The crystal can be described as two interpenetrating FCC unit cells,
each having oppositely charged ions at the corners and face centers.

Ionic Solid: CsCl

• When the cations and anions have equal charges and are about the same
size, as in the CsCl crystal, the unit cell is called the CsCl structure.
• Each cation is surrounded by eight anions (and vice versa), which are at the
corners of a cube.
• This is not a true BCC unit cell because the atoms at various BCC lattice
points are different. 6

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 Crystal Directions
• Crystal properties – such as elastic modulus, electrical resistivity, magnetic
susceptibility – are different in different directions and planes.
• Therefore, we need to specify directions and planes in a crystal.
• Crystal unit cell geometry  parallelepiped with sides a, b, c and angles , ,  -
known as crystal parameters.
• For BCC and FCC, 𝑎 = 𝑏 = 𝑐, 𝛼 = 𝛽 = 𝛾 = 90°, and cubic symmetry. For HCP,
𝑎 = 𝑏 G 𝑐, 𝛼 = 𝛽 = 90°, and 𝛾 = 120°.

Finding Directions

• A point P on the vector can be expressed by the projections 𝑥0, 𝑦0 and 𝑧0 from
point P onto the 𝑥, 𝑦, and 𝑧 axes.
• 𝑥0, 𝑦0 and 𝑧0 can be expressed in terms of lattice parameters a, b, and c.
1 1
• If 𝑥0, 𝑦0 and 𝑧0 are 𝑎, 𝑏, 𝑐, then P is at 𝑥1, 𝑦1, 𝑧1  ½, 1, ½.
2 2

• These numbers are converted to the smallest integers  𝑢𝑣w = 121 .

• If any integer is a negative number, we use a bar on the top of that integer.
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 Important Directions

• Some directions are equivalent since the coordinate system xyz is arbitrary.
• Directions [100] and [010] are equivalent.

Family of Directions
• A set of directions considered to be equivalent is called a family of
directions.
100 = [100], [010], [001], [1
̅ 00], [01
̅ 0], [001̅ ]

• Family of 111 directions

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 1

Crystal Planes

• We need to describe a particular plane of a crystal  Miller indices.

• Take any plane, note the x, y, z intercepts in terms of lattice parameters a, b, c.
• Invert the numbers – you get the Miller indices  (hkl) = (a1b1c1)
• A bar is used for a negative integer due to a negative intercept.
• [hkl] direction is always perpendicular to the (hkl) plane.

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 Miller Indices

Family of Planes
• Family of planes is represented by curly braces as {100}: (100), (010),
(001), 1̅00, 01̅0, (001̅)

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 Family of Planes
• Family of planes {110}: (110), (101), (011), 1̅10 , 1̅01 , (01̅1),
11̅0, 101̅ , (011̅), 1̅1̅0, 1̅01̅ , (01̅1̅)

Equivalent Planes
• Planes can have the same (hkl) only if they are separated by a
multiple of lattice parameters.

• (010) plane is not identical to the (020) plane, even though they
are geometrically parallel

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 Planar Concentration
• Frequently, we need to know the number of atoms per unit area (planar
concentration) on a given plane (hkl).
• For example, if the surface concentration of atoms is high on one plane,
then that plane may encourage more rapid oxide growth.

Planar Concentration
Among the {100}, {110}, and {111} planes in FCC crystals which one is the
most densely packed?

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 FCC: (100) Plane
Consider the Cu FCC crystal with a = 0.3620 nm

Area, 𝐴 = 𝑎2
1
Number of atoms in 𝐴 = (4 corners) × ( atom) + 1 atom at face center = 2
4
Planar concentration 𝑘100 of (100) is
1
4 +1 2
𝑘 100 = 4
2 = 2 = 15.3 atoms nm2
𝑎 0.3620×10 −9 m

FCC: (110) Plane

Area, 𝐴 = (𝑎)(𝑎 2)
1 1
Number of atoms in 𝐴 = (4 corners) × ( atom) + (2 face diagonals)× ( atom
4 2
at diagonal center) = 2
Planar concentration 𝑘110 of (110) is
2 2
𝑘 110 = = 2
= 10.8 atoms nm2
𝑎2 2 0.3620×10 −9 m
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 FCC: (111) Plane
𝑘(111) =?

𝑎 2

𝑎 2
1 3
Area, 𝐴 = (𝑎 )(𝑎 2)
2 2
1 1
Number of atoms in 𝐴 = (3 corners) × ( atom) + (3 face diagonals)× ( atom
6 2
at diagonal center) = 2
Planar concentration 𝑘111 of (111) is
2 4
𝑘 111 = = 2
= 17.6 atoms nm2
𝑎 2 3/4 3 × 0.3620×10 −9 m 11

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