Electron emission from deep states in the intrinsic layer of a‐Si:H p‐i‐n structures was investigated by post‐transit time‐of‐flight photocurrents in space‐charge‐limited current mode. The emission timetEfrom the deep levels is thermally activated for temperatures above 250 K. The frequency pre‐factor &ngr;0(attempt‐to‐escape frequency) varies between 1011Hz and 1013Hz, with the corresponding activation energiesEain the range of 0.42 to 0.52 eV for our samples. A Meyer–Neldel relation between &ngr;0andEais observed. Below 250 K,tEbecomes less temperature sensitive. The density of states in the upper part of the gap is evaluated from the current in the post‐extraction regime. At low temperature, the resolved distribution of gap states becomes inconsistent with higher‐temperature data, similar to what is observed by standard post‐transit photocurrent analysis. Possible mechanisms for the observed behavior of both thetEand the density of states are discussed: re‐trapping, hopping‐assisted release from deep states, the shift of transport energy with temperature and the energy dependence of the attempt‐to‐escape frequency. The shift of transport energy with temperature can partially explain the temperature dependence of the measured &ngr;0and the density of states. ©1995 American Institute of Physics.