BaCu2SiS4: A New Member of the AIIBI2MIVQ4 Chalcogenide Family with a Chiral Crystal Structure

Abstract

AbstractNoncentrosymmetric ternary and quaternary chalcogenides are studied as promising nonlinear optical (NLO) materials in the mid‐infrared region. Here, we report the synthesis of a new material BaCu2SiS4 in the AIIBI2MIVQ4 family (A=divalent metal; B=monovalent metal; M=tetrel, Q=chalcogen), and discuss its crystal structure, thermal stability, optical behavior, and electronic structure. BaCu2SiS4 crystallizes in the noncentrosymmetric chiral space group P3221 with lattice parameters a=6.1440(3) Å, c=15.3542(8) Å, V=501.95(6) Å3, Z=3. The structure features helical channels formed by corner‐sharing [CuS4] and [SiS4] tetrahedral units. Synthesis was carried out in a molten salt flux, as opposed to a traditional solid‐state route from elements, to minimize the formation of a competing ternary phase, Ba2SiS4. BaCu2SiS4 is a semiconductor with an experimentally‐determined direct bandgap of ~2.2 eV. The material exhibits second harmonic generation (SHG) activity, confirming the noncentrosymmetric nature of the structure. Analysis of reported AIIBI2MIVQ4 crystal structures pointed out a correlation among potential structure types and the radii of the constituent elements. Total energy calculations were carried out to explore the relative stability of several reported crystal structures in this family of compounds.