Syntheses, structural variants and characterization of AInM′S4 (A=alkali metals, Tl; M′ = Ge, Sn) compounds; facile ion-exchange reactions of layered NaInSnS4 and KInSnS4 compounds

Abstract

Ten AInM′S4 (A=alkali metals, Tl; M′= Ge, Sn) compounds with diverse structure types have been synthesized and characterized by single crystal and powder X-ray diffraction and a variety of spectroscopic methods. They are wide band gap semiconductors. KInGeS4(1-β), RbInGeS4(2), CsInGeS4(3-β), TlInGeS4(4-β), RbInSnS4(8-β) and CsInSnS4(9) compounds with three-dimensional BaGa2S4 structure and CsInGeS4(3-α) and TlInGeS4(4-α) compounds with a layered TlInSiS4 structure have tetrahedral [InM′S4]− frameworks. On the other hand, LiInSnS4(5) with spinel structure and NaInSnS4(6), KInSnS4(7), RbInSnS4(8-α) and TlInSnS4(10) compounds with layered structure have octahedral [InM′S4]− frameworks. NaInSnS4(6) and KInSnS4(7) compounds undergo facile topotactic ion-exchange, at room temperature, with various mono-, di- and tri-valent cations in aqueous medium to give rise to metastable layered phases.