Paper detail

Tetravalent doping of CeO$_2$: The impact of valence electron character on group IV dopant influence

Fluorite CeO$_2$ doped with group IV elements is studied within the DFT and DFT+U framework. Concentration dependent formation energies are calculated for Ce$_{1-x}$Z$_x$O$_2$ (Z= C, Si, Ge, Sn, Pb, Ti, Zr, Hf) with $0\leq x \leq 0.25$ and a roughly decreasing trend with ionic radius is observed. The influence of the valence and near valence electronic configuration is discussed, indicating the importance of filled $d$ and $f$ shells near the Fermi level for all properties investigated. A clearly different behavior of group IVa and IVb dopants is observed: the former are more suitable for surface modifications, the latter are more suitable for bulk modifications.\\ \indent For the entire set of group IV dopants, there exists an inverse relation between the change, due to doping, of the bulk modulus and the thermal expansion coefficients. Hirshfeld-I atomic charges show that charge transfer effects due to doping are limited to the nearest neighbor oxygen atoms.