Magnetic and electronic properties of CaFeO₂Cl

Abstract

CaFeO2Cl is a unique exception in the family of the iron oxyhalides. Its crystal structure is not related to the Ruddlesden-Popper phases as known for the other members, but contains layers of edge-sharing FeO2/2O3/3 pyramids without Fe–Cl contacts. The iron atoms form a distorted honeycomb substructure. Magnetization measurements on single crystals show an unexpected weak anisotropy and indicate antiferromagnetic ordering of the iron magnetic moments already at room temperature. 57Fe Mössbauer spectra confirm the trivalent oxidation state of iron and the presence of magnetic order. DFT calculations using the LDA + U approach support a Mott-insulating antiferromagnetic ground state and indicate a Néel-type ordered antiferromagnetic state in the honeycomb layer. The band gap from optical measurements is 1.3 eV and agrees with the red-brown colour as well as with the theoretical calculations.