Temperature dependence of the Raman spectrum of orthorhombic Bi2Se3

TL;DR

This study investigates the temperature-dependent Raman spectra of orthorhombic Bi2Se3, combining experimental measurements with ab initio calculations to understand its lattice dynamics, electronic structure, and potential thermoelectric applications.

Contribution

It provides the first detailed analysis of the lattice vibrations and electronic properties of orthorhombic Bi2Se3, including temperature effects and bandgap estimation.

Findings

Optical phonons exhibit anharmonic behavior modeled by two-phonon decay.

Electronic bandgap is at least 0.835 eV and likely indirect.

Ab initio calculations confirm experimental observations and highlight spin-orbit coupling effects.

Abstract

Bismuth selenide, a benchmark topological insulator, grows in a trigonal structure at ambient conditions and exhibits a number of enticing properties related to the formation of Dirac surface states. Besides this polytype, a metastable orthorhombic modification with Pnma space group has been produced by electrodeposition and high-pressure high-temperature synthesis displaying upon Sb doping significant thermoelectric properties in the midtemperature range. However, very little experimental information is available on the fundamental properties of this polytype, such as, e.g., the electronic band gap and the lattice dynamics. We report here the temperature dependence of the Raman spectra of orthorhombic Bi2Se3 between 10 K and 300 K, which displays an anharmonic behavior of the optical phonons that can be modelled with a two-phonon decay channel. In order to analyze the data we performed ab initio calculations of the electronic bandstructure, the phonon frequencies at the center of the Brillouin zone, and the phonon dispersion relations along the main symmetry directions, examining the effect of spin-orbit coupling in both phonon and electronic energies. Lastly, we report here cathodoluminescence experiments at 83 K that set a lower limit to the electronic bandgap at 0.835 eV, pointing to an indirect nature, in agreement with our calculations. These results shed light to essential properties of orthorhombic Bi2Se3 for further understanding of the potential of this semiconductor for thermoelectrics and new applications.