Vanadium doped layered copper-chromium sulfides: The correlation between the magnetic properties and XES data

Abstract

X-ray emission spectroscopy and static magnetochemistry study of CuCr1-xVxS2 (x = 0 ÷ 0.40) was carried out. The atom charge were estimated using the core-level S, V, Cr and Cu(Kα)-lines energy. The additional data on the electron density distribution on the vanadium and copper atoms were studied analyzing the V(Lα) and Cu(Lα,β) spectra fine structure features. The charge distribution in the CuCrS2 matrix was found to be Cu+Cr3+(S2−)2. In the case of low vanadium concentrations x < 0.15 both Cu+Cr3+(S2−)2 and Cu0+δCr(4−δ)+1-xV(4−δ)+x(S2−)2 (δ→0) charge/magnetic configurations were found. The charge distribution for solid solutions doped with concentration x = 0.15 ÷ 0.40 was described as Cu+Cr3+1-xV3+x(S2−)2. The obtained data on the charge/magnetic configurations is in good agreement with the magnetochemical measurements results. The oxidation state changes could be due to the defectness caused by intercalation of the vanadium atoms into the copper sublattice.