Shift of the photoemission threshold in III–V and II–VI semiconductors

The reasons why the photoemission threshold energy of semiconductors is lower than the ionization energy of constituent atoms have been investigated. It has been indicated that the previously proposed interpretation of this phenomenon based on the inclusion of an additional intra-atomic Coulomb interaction between the valence electrons is insufficient. It has been shown that the calculation of the electronic energy structure of semiconductors, in particular, of the photoemission threshold, requires taking into account a change in the localization region of the valence electrons when a free atom is embedded into a crystal. A way of taking this change into account in the tight-binding theory has been demonstrated. Corrections to the tight-binding Hamiltonian have been found. The photoemission thresholds of III–V and II–VI semiconductors have been calculated with the inclusion of these corrections. Comparison of the results with the experimental data has been performed.