Lucia Caramella

Electronic structure and phase stability of oxide semiconductors: Performance of dielectric-dependent hybrid functional DFT, benchmarked against GW band structure calculations and experiments

We investigate band gaps, equilibrium structures, and phase stabilities of several bulk polymorphs of wide-gap oxide semiconductors ZnO, TiO2,ZrO2, and WO3. We are particularly concerned with assessing the performance of hybrid functionals built with the fraction of Hartree-Fock exact exchange obtained from the computed electronic dielectric constant of the material. We provide comparison with more standard density-functional theory and GW methods. We finally analyze the chemical reduction of TiO2 into Ti2O3, involving a change in oxide stoichiometry. We show that the dielectric-dependent hybrid functional is generally good at reproducing both ground-state (lattice constants, phase stability sequences, and reaction energies) and excited-state (photoemission gaps) properties within a single, fully ab initio framework.

Hydrostatic strain enhancement in laterally confined SiGe nanostripes

Strain-engineering in SiGe nanostructures is fundamental for the design of optoelectronic devices at the nanoscale. Here we explore a new strategy, where SiGe structures are laterally confined by the Si substrate, to obtain high tensile strain avoiding the use of external stressors, and thus improving the scalability. Spectro-microscopy techniques, finite element method simulations and ab initio calculations are used to investigate the strain state of laterally confined Ge-rich SiGe nano-stripes. Strain information is obtained by tip enhanced Raman spectroscopy with an unprecedented lateral resolution of ~ 30 nm. The nano-stripes exhibit a large tensile hydrostatic strain component, which is maximum at the center of the top free surface, and becomes very small at the edges. The maximum lattice deformation is larger than the typical values of thermally relaxed Ge/Si(001) layers. This strain enhancement originates from a frustrated relaxation in the out-of-plane direction, resulting from the combination of the lateral confinement induced by the substrate side walls and the plastic relaxation of the misfit strain in the (001) plane at the SiGe/Si interface. The effect of this tensile lattice deformation at the stripe surface is probed by work function mapping, performed with a spatial resolution better than 100 nm using X-ray photoelectron emission microscopy. The nano-stripes exhibit a positive work function shift with respect to a bulk SiGe alloy, quantitatively confirmed by electronic structure calculations of tensile strained configurations. The present results have a potential impact on the design of optoelectronic devices at a nanometer length scale.

Oxidation of carbynes: signatures in infrared spectra

We report and solidly interpret the infrared spectrum of both pristine and oxidized carbynes embedded in a pure-carbon matrix. The spectra probe separately the effects of oxidation on sp- and on sp(2)-hybridized carbon, and provide information on the stability of the different structures in an oxidizing atmosphere. The final products are mostly short end-oxidized carbynes anchored with a double bond to sp(2) fragments, plus an oxidized sp(2) amorphous matrix. Our results have important implications for the realization of carbyne-based nano-electronics devices and highlight the active participation of carbynes in astrochemical reactions where they act as carbon source for the promotion of more complex organic species.