Rational design of new inorganic compounds with the ZrSiCuAs structure type using 2D building blocks

Abstract

We have used the concept of 2D building blocks and optimization methods to design (i.e., predict) the composition and the structure of four hypothetical compounds: BaFZnP, BaFZnSb, BaFMnP and SrFZnP. With a high temperature ceramic method and/or a metathesis reaction we have then succeeded to synthesize these compounds. The structure refinement from X-ray powder diffraction patterns have confirmed the structure predictions and showed their good accuracy. The structure of the four compounds (ZrSiCuAs type) results from the alternated stacking of fluorite [AeF] (Ae = Sr, Ba) and anti-fluorite [MPn] (M = Zn, Mn; Pn = P, Sb) 2D building blocks. As shown by band structure calculations these 2D blocks behave as a charge reservoir [AeF]+ and a charge acceptor [MPn]−. The charge transfer between these blocks insures the cohesion of the structure.