Pressure stabilized Se–Se dimer formation in PbSe 2

Abstract

The preparation of PbSe 2 through the reaction of PbSe with excess Se at 4.5 GPa and 650 °C is reported. The crystal structure, determined from X-ray powder diffraction data (CuAl 2 structure type, I4/mcm (#140), a = 6.42695(11) Å, c = 7.70254(13) Å, Z = 4), consists of layers of [Se 2] 2- dimers with Pb 2+ in square antiprismatic coordination with Se. This is a rare crystal structure for divalent metal chalcogenides, previously only identified for SrS 2 and BaTe 2. Undoped PbSe 2 as well as Bi 3+- and Ag +-doped samples (10% Pb substitution) show semi-metallic resistivity down to 0.4 K. Magnetic susceptibility measurement of PbSe 2 shows no magnetic ordering above 1.8 K. The Seebeck coefficients show nearly linear behavior from 35 to 400 K and the largest numerical values are found in the case of undoped PbSe 2, + 99 μVK −1, and Bi 3+-doped PbSe 2, - 146 μVK −1, at the highest temperature measured, 400 K.