Robert Laskowski

Oxide heterostructures for efficient solar cells.

We propose an unexplored class of absorbing materials for high-efficiency solar cells: heterostructures of transition-metal oxides. In particular, LaVO(3) grown on SrTiO(3) has a direct band gap ∼1.1  eV in the optimal range as well as an internal potential gradient, which can greatly help to separate the photogenerated electron-hole pairs. Furthermore, oxide heterostructures afford the flexibility to combine LaVO(3) with other materials such as LaFeO(3) in order to achieve even higher efficiencies with band-gap graded solar cells. We use density-functional theory to demonstrate these features.

DFT Study of the Role of Al3+ in the Fast Ion-Conductor Li7–3xAl3+xLa3Zr2O12 Garnet

We investigate theoretically the site occupancy of Al3+ in the fast-ion-conducting cubic-garnet Li7–3xAl3+xLa3Zr2O12 (Ia-3d) using density functional theory. By comparing calculated and measured 27Al NMR chemical shifts an analysis shows that Al3+ prefers the tetrahedrally coordinated 24d site and a distorted 4-fold coordinated 96h site. The site energies for Al3+ ions, which are slightly displaced from the exact crystallographic sites (i.e., 24d and 96h), are similar leading to a distribution of slightly different local oxygen coordination environments. Thus, broad 27Al NMR resonances result reflecting the distribution of different isotropic chemical shifts and quadrupole coupling constants. From an energetic point of view, there is evidence that Al3+ could also occupy the 48g site with its almost regular octahedral coordination sphere. Although this has been reported by neutron powder diffraction, the NMR chemical shift calculated for such an Al3+ site has not been observed experimentally.

NMR Shielding in Metals Using the Augmented Plane Wave Method

We present calculations of solid state NMR magnetic shielding in metals, which includes both the orbital and the complete spin response of the system in a consistent way. The latter contains an induced spin-polarization of the core states and needs an all-electron self-consistent treatment. In particular, for transition metals, the spin hyperfine field originates not only from the polarization of the valence s-electrons, but the induced magnetic moment of the d-electrons polarizes the core s-states in opposite direction. The method is based on DFT and the augmented plane wave approach as implemented in the WIEN2k code. A comparison between calculated and measured NMR shifts indicates that first-principle calculations can obtain converged results and are more reliable than initially concluded based on previous publications. Nevertheless large k-meshes (up to 2 000 000 k-points in the full Brillouin-zone) and some Fermi-broadening are necessary. Our results show that, in general, both spin and orbital components of the NMR shielding must be evaluated in order to reproduce experimental shifts, because the orbital part cancels the shift of the usually highly ionic reference compound only for simple sp-elements but not for transition metals. This development paves the way for routine NMR calculations of metallic systems.