High-temperature gallium sesquisulfides and a fragment of the T-x diagram of the Ga – S system with these phases
Abstract
It is known that phases with disordered stoichiometric vacancies are promising candidates for new materials with outstanding thermoelectric, radiation-resistant, catalytic, and other properties, which can be explained by a large concentration of the so-called stoichiometric vacancies, caused by the fact that their stoichiometry does not correspond to the structural type. It is interesting to search for such compounds in AIII – BVI semiconductor systems, whose sesquichalcogenides (Me2Ch3, Me = Ga, In; Ch = S, Se, Te) are known to have both sphalerite and wurtzite structures and the share of stoichiometric vacancies in the cationic sublattice of about 1/3. The purpose of our study was to determine or confirm the high-temperature structures of gallium sesquisulfides and determine the stability regions corresponding to the phases with these structures
on refined T-x diagrams in the high temperature region (T = 878 oC).
Various methods of structure and thermal analysis allowed us to prove that at temperatures above 878 °С, close to the stoichiometry of Ga2S3, gallium sesquisulfide has four modifications similar in terms of structure, which are connected with each other and other phases of the Ga – S system by enantiotropic transitions. The study confirmed that g-Ga2+dS3 with a sphalerite-like cubic structure is formed over a narrow temperature range (878 – 922 °С). The composition of the phase was specified (59.3 mol %). The study demonstrated that at temperatures above 912 °С and a slight excess of gallium (up to ~1 mol %) as compared to the stoichiometry of Ga2S3 two modifications are formed: a defected wurtzite-like structure
(b-Ga2S3, P63mc) and its derivative phase, who structure has a lower symmetry (a-Ga2S3, P61) and reaches the stage of congruent melting (1109 ± 2 °С). The study also accounts for the existence of a distectoid transformation a-Ga2S3 ↔ b-Ga2S3 (~1040 °C). The fourth modification with a monoclinic structure (a¢-Ga2S3, Сс) is stable over a temperature range from room temperature to ~1006 °С. Its composition satisfies the formula of Ga2S3. The article presents a corresponding T-x diagram of the Ga – S system with the areas of existence of the said phases
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