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Free-exciton luminescence spectra and reflection spectra were measured at 2 K as a function of the deviation from stoichiometry in ZnSe. The deviation from stoichiometry is regulated by heat-treating specimens under controlled Zn or Se pressure. With the increase of Se pressure, the emission (E x ) due to the radiative annihilation of excitonic polaritons in the bottleneck region shifts towards higher energy and then disappears, and a new emission peak appears near 2.804 eV. These behaviors are explained by the trapping of excitons by native neutral acceptors, i.e. zinc vacancies ( V Zn ) or complexes containing V Zn . The energies corresponding to the minimum and maximum in the reflection spectra are found to be independent of the deviation from stoichiometry.
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Satoh et al. (1980) studied this question.
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