Energy Bands, Intrinsic and Extrinsic Semiconductors
Quick answer Classifies solids as conductors, insulators and semiconductors using energy-band theory, then explains how doping creates n-type and p-type semiconductors.
When a very large number of atoms come together to form a solid, the sharply defined energy levels of an isolated atom split and merge into continuous energy bands. The highest band that is normally filled with electrons is the valence band; the next higher band, where electrons can move freely and carry current, is the conduction band. Between them lies the forbidden energy gap, Eg, a range of electron energies that cannot exist in the crystal.
Solids are classified by the size of this gap. In metals the valence and conduction bands overlap (or the conduction band is partly filled), so electrons conduct freely even at low temperature. In insulators, Eg is large (typically above 3 eV; diamond has Eg ≈ 5.4 eV), so essentially no electron is thermally excited across it at room temperature. Semiconductors have a small gap (silicon ≈ 1.1 eV, germanium ≈ 0.7 eV) — small enough that some electrons gain enough thermal energy at room temperature to jump into the conduction band, leaving behind vacant bonds called holes in the valence band. A hole behaves as a mobile, effectively positive charge carrier.
In a chemically pure crystal, called an intrinsic semiconductor, every thermally excited electron leaves exactly one hole behind, so the electron concentration ne equals the hole concentration nh, both equal to the intrinsic concentration ni. Conductivity of an intrinsic semiconductor is low and rises rapidly with temperature, unlike a metal whose resistance rises with temperature.
Useful semiconductor behaviour comes from doping — deliberately adding a controlled trace of impurity atoms. Adding a pentavalent impurity (phosphorus, arsenic, antimony) to silicon or germanium gives an n-type semiconductor: four of the five valence electrons of each impurity atom form covalent bonds with neighbouring Si/Ge atoms, and the fifth electron is very loosely bound, occupying a donor energy level just below the conduction band. This electron is easily donated to the conduction band, so electrons become the majority carriers and holes the minority carriers. Adding a trivalent impurity (boron, aluminium, indium) instead creates a p-type semiconductor: the impurity atom can complete only three covalent bonds, leaving one bond incomplete, which readily accepts an electron from a neighbouring atom. This creates an acceptor energy level just above the valence band and generates a mobile hole, so holes become the majority carriers and electrons the minority carriers. In both cases the crystal remains electrically neutral overall — the extra carriers are mobile, but the impurity ions left behind are fixed in the lattice.
Even in a doped (extrinsic) semiconductor, the product of electron and hole concentrations remains fixed at a given temperature: nenh = ni2, known as the law of mass action.
Worked Example: Silicon is doped with a donor concentration Nd = 1×1020 m-3, with ni = 1.5×1016 m-3 at 300 K. Since Nd ≫ ni, almost every donor atom is ionised, so ne ≈ Nd = 1×1020 m-3. Using the law of mass action, the hole concentration is nh = ni2/ne = (1.5×1016)2 / (1×1020) = 2.25×1012 m-3. Electrons outnumber holes by nearly eight orders of magnitude, confirming this is a strongly n-type sample.
- Solids are classified by the forbidden energy gap Eg between the valence and conduction bands: metals (no gap/overlap), semiconductors (small Eg ~1 eV), insulators (large Eg > 3 eV)
- Intrinsic (pure) semiconductor: thermally generated electron-hole pairs give ne = nh = ni, and conductivity rises with temperature
- Doping with a pentavalent impurity (P, As, Sb) gives an n-type semiconductor with electrons as majority carriers
- Doping with a trivalent impurity (B, Al, In) gives a p-type semiconductor with holes as majority carriers
- The law of mass action, nenh = ni^2, holds for both intrinsic and doped semiconductors at a given temperature
- The semiconductor crystal remains overall electrically neutral even though majority and minority carrier concentrations differ hugely
