Solid State Physics — Notes

Solid State Physics

Comprehensive Notes
Crystal Structure • Defects • Band Theory

1. Crystalline vs Amorphous Solids

1.1 Crystalline Solids
Crystalline solids have atoms arranged in a highly ordered, repeating 3D pattern called
a crystal lattice. This long-range order extends throughout the entire solid, giving it a
predictable and periodic geometry.
Key properties:
• Sharp, definite melting point — all bonds break simultaneously due to the uniform
structure
• Anisotropic — physical properties (hardness, refractive index, electrical
conductivity) differ depending on direction
• Flat cleavage planes result from regular atomic planes
• Can exist as single crystal (one continuous lattice) or polycrystalline (many grains
of random orientations)
• Examples: NaCl (table salt), diamond, quartz, metals like iron and copper

1.2 Amorphous Solids

Amorphous solids lack long-range atomic order. The atoms are arranged randomly —
essentially a frozen liquid. They possess only short-range order (nearby atoms are
regular), but no periodic repetition over long distances.
Key properties:
• No sharp melting point — they soften gradually over a range of temperatures (the
glass transition temperature, Tg)
• Isotropic — properties are identical in all directions due to random structure
• No defined cleavage — fracture is conchoidal (curved, shell-like)
• Metastable — can slowly crystallise over time
• Examples: glass, rubber, plastics, amorphous silicon

1.3 Comparison Table

Property Crystalline Amorphous
Atomic order Long-range periodic Short-range only

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Property Crystalline Amorphous

Melting point Sharp and definite Gradual (glass transition)
Isotropy Anisotropic Isotropic
Cleavage Defined planes Conchoidal fracture
Stability Thermodynamically stable Metastable
Examples NaCl, diamond, metals Glass, rubber, plastics

2. Unit Cell and Crystal Lattice

2.1 Crystal Lattice
A crystal lattice is the infinite, regular arrangement of points in 3D space, where each
point represents the identical environment of a single atom or group of atoms. The
lattice is an abstract mathematical framework; the actual crystal structure is obtained by
placing a basis (an atom or group of atoms) at each lattice point.
Crystal Structure = Lattice + Basis

2.2 Unit Cell

The unit cell is the smallest repeating unit of the lattice that, when stacked in all three
dimensions, reproduces the entire crystal. It is described by six lattice parameters:
• Three edge lengths: a, b, c
• Three interaxial angles: α (between b and c), β (between a and c), γ (between a
and b)

Coordination number is the number of nearest-neighbour atoms around any given atom.
Higher coordination generally indicates more efficient packing and greater structural
stability.

2.3 The Seven Crystal Systems

Based on the lattice parameters, all crystals are classified into 7 crystal systems, which
give rise to 14 Bravais lattices (primitive, body-centred, face-centred, and base-centred
variants):
Crystal System Edge Lengths Angles Example
Cubic a=b=c α = β = γ = 90° NaCl, diamond
Tetragonal a=b≠c α = β = γ = 90° TiO₂ (rutile)

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Crystal System Edge Lengths Angles Example

Orthorhombic a≠b≠c α = β = γ = 90° BaSO₄
Hexagonal a=b≠c α = β = 90°, γ = 120° Graphite, Zn
Monoclinic a≠b≠c α = γ = 90°, β ≠ 90° Gypsum
Triclinic a≠b≠c α ≠ β ≠ γ ≠ 90° CuSO₄·5H₂O
Rhombohedral a=b=c α = β = γ ≠ 90° Calcite, quartz

3. SC, BCC, and FCC Structures

The three most important cubic crystal structures differ in where atoms are located
within the unit cell, leading to different packing efficiencies and physical properties. The
Atomic Packing Factor (APF) is the fraction of the unit cell volume actually occupied by
atoms.
APF = (n × (4/3)πr³) / a³
where n = effective atoms per cell, r = atomic radius, a = lattice parameter.

3.1 Simple Cubic (SC)

In simple cubic, atoms occupy only the 8 corners of the cube. Each corner atom is
shared among 8 adjacent unit cells.
• Effective atoms per unit cell: 8 × (1/8) = 1
• Coordination number: 6 (nearest neighbours along each face)
• Relationship: atoms touch along cube edge, so 2r = a
• APF: 52% (very low packing efficiency)
• Close-packed direction: ⟨100⟩
• Example: Polonium (only metal with SC at room temperature)

3.2 Body-Centred Cubic (BCC)

BCC adds one atom at the exact centre of the cube in addition to the 8 corner atoms.
• Effective atoms per unit cell: 8 × (1/8) + 1 = 2
• Coordination number: 8 (body-centre atom touches all 8 corners)
• Relationship: atoms touch along body diagonal, so 4r = a√3
• APF: 68%
• Close-packed direction: ⟨111⟩
• Examples: Iron (α-Fe below 912°C), Tungsten, Chromium, Molybdenum,
Vanadium

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3.3 Face-Centred Cubic (FCC)

FCC (also called cubic close-packed, CCP) places atoms at all 8 corners plus the
centres of all 6 faces.
• Effective atoms per unit cell: 8 × (1/8) + 6 × (1/2) = 4
• Coordination number: 12 (highest among cubic systems)
• Relationship: atoms touch along face diagonal, so 4r = a√2
• APF: 74% (maximum possible for equal spheres — closest packing)
• Close-packed direction: ⟨110⟩
• Close-packed planes: {111} planes (slip planes in FCC metals)
• Examples: Copper, Aluminium, Gold, Silver, Nickel, Lead, γ-Iron (austenite)

3.4 Summary Comparison Table

Property SC BCC FCC
Atoms per unit cell 1 2 4
Coordination number 6 8 12
APF 52% 68% 74%
Relation r to a 2r = a 4r = a√3 4r = a√2
Close-packed direction ⟨100⟩ ⟨111⟩ ⟨110⟩
Common metals Po Fe, W, Cr, Cu, Al, Au, Ag, Ni
Mo, V

4. Defects in Crystals
Real crystals are never perfect. Defects are deviations from the ideal periodic lattice and
profoundly affect mechanical, electrical, and optical properties. They are classified by
their geometric dimensionality.

4.1 Point Defects (0D)

Point defects are localised disturbances at single lattice sites or between sites.
Vacancy (Schottky Defect in Metals)
A lattice site from which an atom is missing. Vacancies are always present in
thermodynamic equilibrium. Their concentration follows the Arrhenius relation:
n = N · exp(−Eᵥ/kT)

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where n = number of vacancies, N = total atom sites, Eᵥ = vacancy formation energy, k

= Boltzmann constant, T = temperature. Vacancies are the primary mechanism enabling
atomic diffusion in solids.

Interstitial Defect
An extra atom squeezed into the space between regular lattice sites (interstices). In
metals, small atoms like carbon, hydrogen, and nitrogen commonly occupy interstitial
positions. Carbon in iron creates interstitial solid solution, which is the basis of steel.
Self-interstitials (same species) are rare due to large lattice strain.

Substitutional Defect
A host atom replaced by a foreign atom. This is the basis of solid-solution alloying. For
extensive substitutional solid solubility, the Hume-Rothery rules must be satisfied:
• Atomic size difference < 15%
• Similar electronegativity
• Same crystal structure
• Similar valence
Example: zinc substituting copper atoms in brass (Cu-Zn alloy).

Schottky Defect (Ionic Crystals)

A pair of cation and anion vacancies created simultaneously to maintain electrical
charge neutrality. Common in NaCl, KBr, and similar ionic compounds. Schottky defects
increase with temperature and contribute to ionic conductivity.

Frenkel Defect
An atom leaves its lattice site (creating a vacancy) and migrates to a nearby interstitial
position. The total number of atoms is conserved; only the atomic positions change.
Common in ionic crystals where the cation is much smaller than the anion (e.g., AgBr,
ZnS). Frenkel defects are responsible for the photosensitivity of silver halides used in
photographic film.

4.2 Line Defects (1D)

Edge Dislocation
Caused by the insertion of an extra half-plane of atoms into the crystal lattice. The
boundary (bottom edge) of this half-plane defines the dislocation line. The Burgers
vector b, which quantifies the magnitude and direction of the lattice distortion, is
perpendicular to the dislocation line.

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The symbol for an edge dislocation is ⊥ (or ⊤), where the stem points toward the extra
half-plane.

Screw Dislocation
Caused by shear displacement of one part of the crystal relative to another, creating a
helical (screw-like) distortion around the dislocation line. The Burgers vector b is parallel
to the dislocation line. A screw dislocation has no extra half-plane.

Mixed Dislocation
Most real dislocations in metals have both edge and screw components. The Burgers
vector has an angle with the dislocation line other than 0° or 90°.

Significance of Dislocations
Dislocations explain why metals deform plastically at stresses far below their theoretical
strength. Rather than an entire plane of atoms shearing simultaneously, a single
dislocation can glide across a slip plane much more easily. This process is called
dislocation glide or slip. Mechanisms that impede dislocation motion strengthen metals:
• Work hardening (strain hardening) — increasing dislocation density creates
tangles
• Solid solution strengthening — solute atoms create stress fields that pin
dislocations
• Precipitation hardening — fine precipitate particles block dislocation motion
• Grain boundary strengthening — Hall-Petch relation: σy ∝ d⁻½

4.3 Planar Defects (2D)

Grain Boundaries
Interfaces between grains (small crystals) of different crystallographic orientations in a
polycrystalline material. Grain boundaries scatter electrons (increasing electrical
resistivity), impede dislocation glide (increasing strength), and accelerate diffusion. The
Hall-Petch relationship quantifies grain-size strengthening:
σy = σ0 + kᴷ · d⁻½
where σy = yield strength, σ0 = lattice friction stress, kᴷ = Hall-Petch constant, d = mean
grain diameter.

Stacking Faults
Errors in the stacking sequence of close-packed planes. For FCC, the normal sequence
is ...ABCABCABC... A stacking fault might give ...ABCABABC..., which is locally HCP-

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like. Materials with low stacking fault energy (e.g., austenitic stainless steel, Cu) exhibit
wide stacking faults, influencing deformation behaviour.

Twin Boundaries
A mirror-image orientation relationship exists across a twin boundary. Twinning is an
alternative to slip as a deformation mechanism, especially important in HCP metals
(titanium, magnesium) and in FCC metals at low temperatures or high strain rates.

Defect Type Dimensionalit Example Effect on Properties

y
Vacancy 0D (Point) Any metal Enables diffusion, increases
resistivity
Interstitial 0D (Point) C in Fe (steel) Solid solution hardening
Substitutional 0D (Point) Zn in Cu Solid solution hardening
(brass)
Schottky 0D (Point) NaCl Ionic conductivity
Frenkel 0D (Point) AgBr Photoconductivity
Edge dislocation 1D (Line) All metals Plastic deformation
Screw dislocation 1D (Line) All metals Plastic deformation
Grain boundary 2D (Planar) Polycrystals Strengthening, diffusion
Stacking fault 2D (Planar) Cu, Stainless Deformation behaviour
steel
Twin boundary 2D (Planar) Ti, Mg Twinning deformation

5. Band Theory of Solids

Band theory is the quantum mechanical framework that explains the electrical behaviour
of solids — why some conduct electricity, some insulate, and some semiconduct — by
analysing the allowed energy states for electrons in a periodic crystal lattice.

5.1 Formation of Energy Bands

In an isolated atom, electrons occupy discrete energy levels (1s, 2s, 2p, 3s, etc.). When
N atoms come together to form a solid, the Pauli exclusion principle forbids two
electrons from occupying the same quantum state. Each discrete atomic level therefore

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splits into N closely spaced levels, forming a quasi-continuous band of allowed

energies. The resulting band structure consists of:
• Allowed bands — ranges of energy where electron states exist
• Band gaps (forbidden gaps) — energy ranges where no electron states exist

5.2 Key Concepts

Valence Band (VB)
The highest energy band fully (or nearly fully) occupied by electrons at 0 K. Electrons in
the valence band are involved in chemical bonding. A completely filled valence band
contributes no net current flow.

Conduction Band (CB)

The lowest energy band that is unoccupied (or only partially occupied) at 0 K. Electrons
in the conduction band are essentially free to move throughout the solid and carry
electrical current.

Band Gap (Eg)

The energy difference between the top of the valence band (VBM) and the bottom of the
conduction band (CBM). This is the single most important parameter determining a
material's electrical classification. No electron states exist within the band gap.

Fermi Level (Eᶠ)

The electrochemical potential of electrons, defined as the energy at which the
probability of occupation is exactly 50%. Described by the Fermi-Dirac distribution:
f(E) = 1 / [exp((E − Eᶠ)/kT) + 1]
At 0 K, all states below Eᶠ are filled and all states above are empty. At higher
temperatures, thermal smearing occurs around Eᶠ.

5.3 Conductors (Metals)

In metals, either the conduction band is only partially filled (e.g., Na, Cu, Al) or the
valence and conduction bands overlap with no gap (e.g., Mg, Zn). The Fermi level lies
inside the conduction band, so a vast number of electrons are immediately available for
conduction with no activation energy required.
• Electrical conductivity: σ ≈ 10⁶–10⁸ S/m (very high)
• Conductivity decreases with temperature — increasing thermal vibration (phonon
scattering) impedes electron flow

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• Examples: Cu (σ ≈ 6 × 10⁷ S/m), Ag, Al, Fe

5.4 Insulators
In insulators, the valence band is completely filled and separated from the empty
conduction band by a large band gap (Eg > 3 eV, often much larger). At room
temperature, thermal energy kT ≈ 0.026 eV is far too small to excite electrons across
the gap. No free carriers exist, so conductivity is negligibly small.
• Band gap examples: Diamond ≈ 5.5 eV; SiO₂ ≈ 9 eV; Al₂O₃ ≈ 8 eV
• Electrical conductivity: σ < 10⁻¹⁰ S/m
• At very high temperatures, breakdown can occur (thermal runaway)

5.5 Semiconductors
Semiconductors have a filled valence band and an empty conduction band separated
by a small band gap (typically 0.1–3 eV). At 0 K they behave as insulators, but at room
temperature thermal excitation promotes some electrons across the gap into the
conduction band, leaving behind positively-charged holes in the valence band. Both
electrons and holes carry current.

Carrier Concentration (Intrinsic)

The intrinsic carrier concentration ni for both electrons and holes follows:
ni = √(Nc·Nv) · exp(−Eg/2kT)
where Nc and Nv are the effective density of states in the conduction and valence
bands respectively. This shows the strong temperature dependence — conductivity
rises exponentially with temperature, opposite to metals.

Important Intrinsic Semiconductors

Material Band Gap (eV) Type Application
Silicon (Si) 1.12 Indirect CMOS, solar cells
Germanium (Ge) 0.67 Indirect Early transistors
Gallium Arsenide 1.43 Direct LEDs, laser diodes, RF
(GaAs)
Indium Phosphide 1.35 Direct High-speed electronics
(InP)
Gallium Nitride 3.4 Direct Blue LEDs, power devices
(GaN)

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Extrinsic (Doped) Semiconductors

Deliberate introduction of impurities (doping) dramatically controls carrier concentration.
This is the foundation of all semiconductor devices.

n-type doping: Adding pentavalent donor atoms (e.g., phosphorus or arsenic in silicon)
introduces energy levels just below the conduction band. At room temperature, these
donors ionise and contribute electrons to the CB, greatly increasing electron
concentration. The Fermi level shifts upward toward the CB. Majority carriers are
electrons.

p-type doping: Adding trivalent acceptor atoms (e.g., boron in silicon) introduces
energy levels just above the valence band. These acceptors capture electrons from the
VB, creating holes. The Fermi level shifts downward toward the VB. Majority carriers are
holes.

Effective Mass
Electrons and holes near band edges behave as if they have a modified effective mass
m* due to their interaction with the periodic crystal potential. Effective mass determines
carrier mobility:
μ = eτ/m*
where μ = mobility, τ = mean scattering time, m* = effective mass. GaAs has m*e ≈
0.067 me (very light), giving extremely high electron mobility (μ ≈ 8500 cm²/Vs vs Si ≈
1400 cm²/Vs), making it ideal for high-frequency and optoelectronic devices.

5.6 Conductor / Semiconductor / Insulator Summary

Material Type Band Gap Eᶠ Position Conductivity Example
(S/m)
Conductor None / Inside CB 10⁶ – 10⁸ Cu, Fe, Al
overlap
Semiconductor 0.1–3 eV In gap 10⁻³ – 10³ Si, Ge, GaAs
(intrinsic) (midpoint)
Insulator > 3 eV In gap < 10⁻¹⁰ SiO₂, diamond
(midpoint)

These five topics form the backbone of solid-state physics and materials science. Crystal
structure governs physical properties; defects explain mechanical behaviour and diffusion; band
theory underlies all of modern electronics.

Solid State Physics