Solid-state synthesis, structural variants and transformation of three-dimensional sulfides, AGaSnS4 (A=Na, K, Rb, Cs, Tl) and Na1.263Ga1.263Sn0.737S4

New cubic-AGaSnS4 (A=Na, K, Rb, Cs, Tl) and orthorhombic-NaGaSnS4 compounds were synthesized by solid-state reactions and characterized by X-ray diffraction and diffuse reflectance spectroscopy. Single crystals of orthorhombic-Na1.263Ga1.263Sn0.737S4 were obtained in the crystal growth attempts of sodium compound. All six new compounds have orthorhombic AgGaGeS4 and cubic BaGa2S4 structures, as determined from single crystal X-ray structures of Na1.263Ga1.263Sn0.737S4 and cubic-AGaSnS4 (A=Na, K, Rb). Orthorhombic-NaGaSnS4 and known layered-KGaSnS4 undergo structural transformation to thermodynamically stable cubic form.

Graphical AbstractOrthorhombic-NaGaSnS4 transforms, on quenching or during iodine vapor transport, to thermodynamically stable cubic form of AGaSnS4 (A=Na, K, Rb, Cs, Tl) compounds and decomposes, in molten NaI, to isostructural Na1.263Ga1.263Sn0.737S4.Figure optionsDownload as PowerPoint slide