In an isolated single atom, electrons occupy sharp, discrete quantum energy levels governed by the Pauli exclusion principle. However, when N identical atoms assemble closely into a periodic crystal lattice (with interatomic spacing typically 2 - 3 Å), the outer valence electron wavefunctions overlap strongly. Under the influence of the periodic Coulomb potential of neighboring ionic cores, each discrete atomic energy level splits into N closely spaced sub-levels. Because N ≈ 10²⁸ atoms/m³, these sub-levels form a continuous quasi-continuous continuum termed an Energy Band.
The two most critical energy bands governing electrical conduction are:
- Valence Band (VB): The highest occupied energy band formed by the outermost valence electrons. At absolute zero (
0 K), the valence band is completely packed with electrons and cannot contribute to electric conduction under an external electric field. - Conduction Band (CB): The lowest unoccupied or partially filled energy band lying immediately above the valence band. Electrons excited into this band are quasi-free to accelerate in response to an electric field, carrying electrical current.
- Forbidden Energy Gap (E_g): The forbidden energy range separating the top of the valence band (
E_v) and the bottom of the conduction band (E_c). No quantum electron states are allowed within this band gap:E_g = E_c - E_v.
| Material Class | Energy Band Gap (E_g) | Electrical Conductivity (σ) | Representative Materials |
|---|---|---|---|
| Conductors (Metals) | E_g = 0 eV (VB overlaps CB) | 10⁶ - 10⁸ S/m (Huge) | Copper (Cu), Aluminum (Al), Silver (Ag) |
| Semiconductors | 0 < E_g ≤ 3 eV (Moderate) | 10⁻⁶ - 10⁴ S/m (Tunable) | Silicon (1.1 eV), Germanium (0.72 eV), GaAs (1.42 eV) |
| Insulators | E_g > 3 eV (Extremely Wide) | 10⁻¹⁸ - 10⁻¹⁰ S/m (Negligible) | Diamond (5.4 eV), Quartz (SiO₂), Glass, Rubber |
In metals, electrical resistance increases linearly with temperature (α > 0, positive temperature coefficient) due to increased thermal lattice phonon vibrations scattering free electrons. Conversely, in semiconductors, as temperature rises from absolute zero, thermal energy breaks covalent bonds, exciting valence electrons across E_g into the conduction band and creating mobile electron-hole pairs. Consequently, charge carrier concentration increases exponentially:
Thus, semiconductors possess a negative temperature coefficient of resistance (α < 0): their electrical conductivity increases rapidly with increasing temperature.