Revisiting properties of CaCoSinO2n+2. Crystal and electronic structure

Abstract

In a public space there are several reports of materials with general stoichiometry CaCoSinO2n+2. Pyroxene CaCoSi2O6 is probably the best-known representative for n = 2 but not much is known about materials with n = 3 and n = 4. In this study, attempts were carried out to synthesize those phantom materials and it was found that they do not exist as a single phase. A quantitative XRD analysis revealed that their chemical composition is correct but the formula should be written as CaCoSi2O6 + (n-2)SiO2. Similar qualitative conclusions were drawn from investigation of magnetic (DC magnetometry) and electronic properties using X-ray Photoelectron Spectroscopy (XPS) and Si K edge X-ray Absorption Spectroscopy (XAS). Additionally, the DFT ab initio calculations were carried out to obtain electronic signature from band structure of CaCoSi2O6. The apparent influence of the excess of SiO2 on magnetic properties of this “series” can be understood in terms of presence and suppression of secondary phases like Ca2CoSi2O7, which form when the starting materials are not homogenized properly. Addition of surplus SiO2 suppresses their formation leaving clear signature from CaCoSi2O6, which also can be synthesized from stoichiometric mixture using proper techniques.