Abstract
A new metastable Bi3S4 single crystal has been obtained on the initial Bi: S = 2 : 3 mixture at a pressure of 8.0–8.5 GPa with slow cooling from 1300 to 800 °C at a rate of ∼3 °C/min followed by quenching. The crystal has a triclinic structure formed by Bi-centered S-polyhedrons and chain-like clusters of Bi atoms. The relationship between the triclinic model based on single-crystal X-ray diffraction data and the orthorhombic model previously proposed for high-pressure Bi–S and Bi–Se phases with a similar structural motif based on X-ray powder diffraction data is discussed. The new Bi3S4 phase is a narrow-gap (band gap of 0.234 eV) intrinsic n-type semiconductor with a shallow impurity level. Metastable Bi3S4 recovers the structure of bismuthinite Bi2S3 after annealing at 200 °C.
Published Version
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