Past exam of the chemistry A course of the University of Cambridge / 2023 / Paper 2 / A10 / b / i / Solution

Arsenic has five valence electrons, whereas silicon has four. A substitutional arsenic atom can therefore supply an extra electron after participating in the silicon bonding network. It acts as a shallow donor impurity, introducing a localized level $E_D$ just below the conduction band. Ionizing that donor costs much less energy than excitation across the full band gap.

At the lowest temperatures, donor electrons remain bound and the valence band is filled. Mobile-carrier populations are negligible: this is dopant freeze-out. Initial heating releases donor electrons into the conduction band, producing a rapid rise in conductivity governed by the shallow-donor energy scale. The positive ionized donor charge compensates the released electronic charge; the bulk need not acquire net charge.

At intermediate temperatures, nearly all donors are ionized but intrinsic electron–hole generation is still small. In an uncompensated sample,where $N_D$ is donor number density. The supply of donor electrons is finite, so further heating cannot keep creating them. This is the extrinsic plateau under the approximation of weakly varying mobility, and its carrier density is much larger than that of the undoped sample at the same temperature. In real material, scattering changes mobility, so donor exhaustion alone predicts a carrier-density plateau rather than guaranteeing perfectly flat conductivity.

At higher temperatures, intrinsic generation becomes comparable to and then exceeds the donor contribution. Once $n_i\gg N_D$, the populations approach $n\simeq p\simeq n_i$, and activation across the main gap causes the steeper rise. The relevant regimes are therefore freeze-out, donor exhaustion, and intrinsic excitation, not three successive types of dopant.