Effect of nonstoichiometry and doping on the photoconductivity spectra of GeSe layered crystals

The polarization photoconductivity spectra of Bi-doped nonstoichiometric GeSe layered crystals grown by static sublimation were investigated. Two strongly polarized maxima at the photon energies hν_max = 1.35 eV (E ∥ a) and 1.44 eV (E∥ b) due to the V ₁ ^V → V ₁ ^c and Δ ₂ ^v → Δ ₁ ^c optical transitions, respectively, were found in the spectra of nominally undoped GeSe crystals near the intrinsic absorption edge at 293 K. In the low-temperature region, an exciton photoconductivity band peaked at hν_max=1.32 eV, which is due to exciton dissociation at the cation vacancies, was revealed. With an increase in excess Se in crystals, a sharp increase in the intensity of the exciton peak in the photoconductivity spectra was observed. It is shown that doping of GeSe crystals with donor Bi impurity is an effective tool of the control of their electrical and photoelectric properties. Although introduction of Bi into germanium monoselenide does not lead to the conductivity conversion from the p to n type, a sharp increase in the resistivity is observed, the crystals become photosensitive, and a strong impurity band peaked at 1.11 eV arises in the photoconductivity spectra.