The first part of my PhD work is about the lattice vibrations in silicon nanowires. First-principles calculations based on the linear response are performed to investigate the quantum confinement effect in lattice vibrations of silicon nanowires (SiNW). The radial breathing modes (RBM) are found in our calculations, which have a different size-dependent frequency shift compared with the optical modes. They are well explained by the elastic model. Finally, the relative activity of the Raman scattering in the smallest SiNW is calculated. The RBM can be clearly identified in the Raman spectrum, which can be used to estimate the size of nanowires in experiment. In the second part of my PhD work, we focus on the electron-hole pair (exciton) in semiconductor nanowires and its influence on the optical absorption spectra. First-principles calculations are performed for a hydrogen-passivated silicon nanowire with a diameter of 1.2 nm. Using plane wave and pseudopotentials, the quasiparticle states are calculated within the so-called GW approximation, and the electron-hole interaction is evaluated with the Bethe-Salpeter Equation (BSE). The enhanced excitonic effect is found in the absorption spectrum. The third part of my work is about the electronic structure in Si/Ge core-shell nanowires. The electronic band structure is studied with first-principles methods. Individual conduction and valence bands are found in the core part and the shell part, respectively. The band offsets are determined, which give rise to the spatial separation of electron and hole charge carriers in different regions of the nanowires. This allows for a novel-doping scheme that supplies the carriers into a separate region in order to avoid the scattering problem. This is the key factor to create high-speed devices. With the confinement effect, our results show important correction in the band offset compared with the bulk heterostructure. Finally, an optimum doping strategy is proposed based on our band-offset data.

Dye-sensitized solar cells (DSSCs) have attained considerable attention during the last decade because of the potential of becoming a low cost alternative to silicon based solar cells. Electron transport is one of the prominent processes in the cell and it is further a complex process because the transport medium is a mesoporous film. The gaps in the pores are completely filled by an electrolyte with high ionic strength, resulting in electron-ion interactions. Therefore, the electron transport in these so called state-of-the-art systems has a practical limit because of the low electron diffusion coefficient (Dn) in this mesoporous film photoanode. This work focuses on the influence of the advanced core-shell nanoarchitecture geometry on electron transport and also on the influence of electron-ion interactions. In order to achieve the proposed goals, DSSCs based on ordered, highly aligned, 3D radial core-shell Au-TiO2 hybrid nanowire arrays were fabricated, using three different approaches. J-V, IPCE, and EIS characteristics were studied. The efficiency, light scattering and charge transport properties of the core-shell nanowire based devices were compared to TiO2 nanotube as well as TiO2 mesoporous film based DSSCs. The Au nanowires inside the crystalline TiO2 anatase nanoshell provided a direct conduction path from the TiO2 shell to the TCO substrate and improved transport of electrons between the TiO2 and the TCO. The optical effects were studied by IPCE measurement which demonstrated that Au-TiO2 nanowires showed an improved light harvesting efficiency, including at longer wavelengths where the sensitizer has weak absorption. The metal nanostructures could enhance the absorption in DSSCs by either scattering light enabling a longer optical path-length, localized surface plasmon resonance (LSPR) or by near-field coupling between the surface plasmon polariton (SPP) and the dye excited state. Rapid, radial electron collection is of practical significance because it should allow alternate redox shuttles that show relatively fast electron-interception dynamics to be utilized without significant sacrifice of photocurrent. A combination of improved electron transport and enhanced light harvesting capability make Au-TiO2 core-shell nanowire arrays a promising photoanode nanoarchitecture for improving photovoltaic efficiency while minimizing costs by allowing thinner devices that use less material in their construction.