Photoconductivity of the Single Crystals Pb4Ga4GeS12 and Pb4Ga4GeSe12

Abstract

Quaternary semiconductor materials of the Pb4Ga4GeS(Se)12 composition have attracted the attention of researchers due to their possible use as active elements of optoelectronics and nonlinear optics. The Pb4Ga4GeS(Se)12 phases belong to the solid solution ranges of the Pb3Ga2GeS(Se)8 compounds which form in the quasi-ternary systems PbS(Se)−Ga2S(Se)3−GeS(Se)2 at the cross of the PbGa2S(Se)4−Pb2GeS(Se)4 and PbS(Se)−PbGa2GeS(Se)6 sections. The quaternary sulfide melts congruently at 943 K. The crystallization of the Pb4Ga4GeSe12 phase is associated with the ternary peritectic process Lp + PbSe ↔ PbGa2S4 + Pb3Ga2GeSe8 at 868 K. For the single crystal studies, Pb4Ga4GeS(Se)12 were pre-synthesized by co-melting high-purity elements. The X-ray diffraction results confirm that these compounds possess non-centrosymmetric crystal structure (tetragonal symmetry, space group P–421c). The crystals were grown by the vertical Bridgman method in a two-zone furnace. The starting composition was stoichiometric for Pb4Ga4GeS12, and the solution-melt method was used for the selenide Pb4Ga4GeSe12. The obtained value of the bandgap energy for the Pb4Ga4GeS12 and Pb4Ga4GeSe12 crystals is 1.86 and 2.28 eV, respectively. Experimental measurements of the spectral distribution of photoconductivity for the Pb4Ga4GeS12 and Pb4Ga4GeSe12 crystals exhibit the presence of two spectral maxima. The first lies in the region of 570 (2.17 eV) and 680 nm (1.82 eV), respectively, and matches the optical bandgap estimates well. The locations of the admixture maxima at about 1030 (1.20 eV) and 1340 nm (0.92 eV), respectively, agree satisfactorily with the calculated energy positions of the defects vs. and VSe.

Keywords

• quaternary chalcogenides
• phase equilibria
• single crystals
• photoconductivity