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Chalcogenides materials are being considered as some of the most promisingsystems for energy harvesting and energy conversion. Among them, theorthorhombic family of compounds X2Y3 (with X= Bi, Sb and Y= S, Se) hasattracted special attention due to its interesting atomic structure,thermoelectric and optical properties. While Bi2S3 and Sb2Se3 have beingalready applied to solar cells, the new metastable Bi2Se3 is still a challengedue to the lack of data and knowledge on its properties. Here, the vibrationaland structural properties of the orthorhombic metastable phase of Bi2Se3 wereinvestigated by using Raman spectroscopy and ab-initio calculations. We performRaman spectrum measurements along in-situ thermal treatment on samples grown byelectrochemical deposition. We show that by increasing the temperature occursan improved crystallization in the orthorhombic structure, followed by arecrystallization to the usual rhombohedral phase. Our results point out forspecific Raman modes of the orthorhombic phase. First principle computationalresults based on density functional theory support the experimental data anddescribe three singlet Raman active vibrational modes, Ag1, B2g and Ag2.

Vibrational Properties of the Bi2Se3 Orthorhombic Metastable Phase