New Metastable Phase of Bismuth (III) Selenide: Crystal Structure and Electrical Properties

Abstract

Using high‐pressure–high‐temperature treatment at P = 4–7.7 GPa; T = 1373–1473 K with subsequent quenching, a new metastable phase of bismuth selenide (m‐Bi2Se3) is synthesized and its crystal structure, electrical resistivity, and annealing at heating are investigated. Using X‐ray powder diffraction, and analogy with high‐pressure structures of the rare‐earth element sesquichalcogenides, the crystal structure of the new metastable phase of m‐Bi2Se3 is determined as an orthorhombic distorted cation‐deficient structure of the Th3P4 type with the Fdd2 space group and Z = 10.66. The unit‐cell dimensions are: a = 13.4660(7) Å, b = 12.7772(7) Å, c = 9.0896(5) Å. The density of m‐Bi2Se3 (7.47 g cm−3) is slightly less than the initial rhombohedral phase of Bi2Se3, but the coordination number (CN) = 8 is higher than CN = 6 of the initial phase. The period of stability under ambient conditions of the new m‐Bi2Se3 phase is only about 2 months. After 300 °C annealing, m‐Bi2Se3 completely returns to the initial layered structure, and differential scanning calorimetry confirms that the reverse transformation as well as the direct transition occur through an amorphous state. The new phase is a narrow bandgap semiconductor with the energy gap of about 80 meV.

Prediction of wide-gap topological insulating phase in metastable BiTeI

“…53) Except for epitaxial films, there are many other techniques to synthesize the desired structures, such as the recently reported synthesis of the metastable phase of bismuth selenide using quenching. 54) Compared to the results of previous studies, 18,20) we believe that growing the P3m1 structure on Bi 2 Te 3 substrates is a better choice than growing on BiTeI (P3m1) substrates. Lattice constants a of the P3m1 structure and P3m1 structure are 4.37278 Å and 4.38868 Å, respectively, while that of Bi 2 Te 3 is 4.386 Å, 55) which is closer to that of the P3m1 structure.…”

High-performance Bi2Se3/MXene/SWCNT heterostructures as binder-free anodes in lithium-ion batteries

“…In addition, it has been shown recently that presented on the surface of MXenes functional groups facilitate formation of Bi 2 Se 3 /Mxene heterostructures due to their active interaction with cations. 37 Bismuth selenide (Bi 2 Se 3 ) has already shown its perspective as an anode material for LIBs due to its high theoretical specific capacity (491 mA h g À1 ), 38 exceptional stability, high electronic conductivity (10 6 S cm À1 ), 39 and high density (7.47 g cm À3 ). 38 The unique five-atomic plane arrangement (perpendicular to the trigonal C-axis) of Bi 2 Se 3 forms a following quintuple layer pattern: Se 1 -Bi-Se 2 -Bi-Se 1 , where the interconnection between these layers is ensured by the van der Waals gaps which are located between Se 1 atoms.…”

A theoretical study of thePnmaandR3̄mphases of Sb2S3, Bi2S3, and Sb2Se3

“…[6][7][8][9][10][11][12] Additionally, Sb 2 Se 3 has recently found a number of other applications including in solid-state batteries, fiber lasers, and photoelectrochemical devices. [13][14][15][16] Since several phases, including the Pnma phase, have been synthesized for Bi 2 Se 3 , which usually crystallizes in the tetradymite-like R% 3m structure, [17][18][19][20] it is natural to wonder whether the R% 3m structure could be adopted by other sesquichalcogenides that generally adopt the U 2 S 3 -type structure, viz. Sb 2 S 3 , Bi 2 S 3 , and in particular Sb 2 Se 3 .…”

“…Since several phases, including the Pnma phase, have been synthesized for Bi 2 Se 3 , which usually crystallizes in the tetradymite-like R 3̄ m structure, 17–20 it is natural to wonder whether the R 3̄ m structure could be adopted by other sesquichalcogenides that generally adopt the U 2 S 3 -type structure, viz. Sb 2 S 3 , Bi 2 S 3 , and in particular Sb 2 Se 3 .…”