Valence band structure and charge distribution in the layered lanthanide-doped CuCr0.99Ln0.01S2 (Ln = La, Ce) solid solutions

Abstract The comprehensive study of the electronic density distribution of CuCr 0.99 Ln 0.01 S 2 (Ln = La, Ce) solid solutions was carried out using both X-ray photoelectron and emission spectroscopy. It was found that cationic substitution of chromium with lanthanum or cerium atoms does not significantly affect the atomic charges of the matrix elements (Cu, Cr, S) in the lanthanide-doped solid solutions. The copper atoms in the composition of CuCrS 2 -matrix and the lanthanide-doped solid solutions were found to be in the monovalent state. The chromium and lanthanide atoms were found to be in the trivalent state. This fact indicates the isovalent cationic substitution character. The sulfur atoms were found to be in the divalent state. The near-surface layers contain the additional oxidation forms of sulfur (S 0 , S 4+ , S 6+ ) and copper (Cu 2+ ) atoms. The detailed analysis of the valence band structure using DFT calculations has shown that partial DOS distribution character of the matrix elements is preserved after the cationic substitution. The experimental valence band spectra structure of CuCrS 2 -matrix and CuCr 0.99 Ln 0.01 S 2 is determined by the occupied copper d -states contribution. The contribution of the lanthanide states in the valence band structure is lower in comparison with those for the matrix elements. The major contribution of the lanthanide states was found to be mainly localized near the conduction band bottom.