Illumination creates excess electrons and holes which populate the extended and localized states at the band edges and give rise to photoconductivity. The ability to sustain a large excess mobile carrier concentration is crucial for efficient solar cells and light sensors and depends on the carriers having a long recombination lifetime. The carrier lifetime is a sensitive function of the density and distribution of localized gap states, so that the study of recombination in a-Si: H gives much information about the nature of the gap states as well as about the recombination mechanisms.

The recombination process comprises two sequential steps, as illustrated in Fig. 8.1. An excited electron or hole first loses energy by many transitions within the band, in which the energy decrements are small but frequent. This process is referred to as thermalization. The thermalization rate decreases as an electron moves into the localized band tail states and the density of available states is lower. Eventually the electron completes the recombination by making a transition to a hole with the release of a large energy. Recombination lifetimes are generally much longer than the thermalization times, so that the two processes usually occur on distinctly different time scales.

Recombination is either radiative or non-radiative. The radiative process is accompanied by the emission of a photon, the detection of which is the basis of the luminescence experiment. The radiative transition is the inverse of optical absorption and the two rates are related by detailed balance.