Effect of a Sulfur Precursor on the Hydrothermal Synthesis of Cu2MnSnS4

Edyta Waluś; Maciej Manecki; Grzegorz Cios; Tomasz Tokarski

doi:10.3390/ma14133457

Effect of a Sulfur Precursor on the Hydrothermal Synthesis of Cu₂MnSnS₄

Materials (Basel). 2021 Jun 22;14(13):3457. doi: 10.3390/ma14133457.

Authors

Edyta Waluś¹, Maciej Manecki^{1

2}, Grzegorz Cios³, Tomasz Tokarski³

Affiliations

¹ Department of Mineralogy, Petrography, and Geochemistry, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków, Poland.
² Department of Earth Sciences, Uppsala University, Villavägen 16, SE-752 36 Uppsala, Sweden.
³ Academic Centre for Materials and Nanotechnology, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków, Poland.

Abstract

Cu₂MnSnS₄ (CMTS) is acknowledged as an alternative to traditional semiconductors. The structure and microstructure of synthetic CMTS depend on, among other things, the types of sulfur sources used. Traditionally obtained CMTS mostly has a tetragonal structure. In this study, the effect of using thiourea (Tu) or Na₂S as a sulfur source on the product structure was compared using hydrothermal synthesis at 190 °C for 7 days (ethylene glycol with water in the presence of poly(vinylpyrollidone) was used as a solvent). When Tu was used, CMTS precipitated in the form of concentric microspheres, 1-1.5 µm in size, consisting of hexagonal (in the cores) and tetragonal (the rims) forms. Most probably, the rapidly formed hexagonal nucleus was later surrounded by a slower-forming rim with a tetragonal structure. In contrast, when Na₂S was used as a precursor, microspheres were not formed and a fine crystalline material with a homogeneous tetragonal structure was obtained. This allowed for the choice of micromorphology and product structure during synthesis.

Keywords: CMTS; Na2S; hexagonal; microspheres; tetragonal; thiourea.

Grants and funding

DI2016 - 004946/Ministerstwo Nauki i Szkolnictwa Wyższego, Poland