Highly Efficient CIGS Based Devices for Solar Hydrogen Production and Size Dependent Properties of ZnO Quantum Dots

Abstract: Materials and device concepts for renewable solar hydrogen production, and size dependent properties of ZnO quantum dots are the two main themes of this thesis.ZnO particles with diameters less than 10 nm, which are small enough for electronic quantum confinement, were synthesized by hydrolysis in alkaline zinc acetate solutions. Properties investigated include: the band gap - particle size relation, phonon quantum confinement, visible and UV-fluorescence as well as photocatalytic performance. In order to determine the absolute energetic position of the band edges and the position of trap levels involved in the visible fluorescence, methods based on combining linear sweep voltammetry and optical measurements were developed.The large band gap of ZnO prevents absorption of visible light, and in order to construct devices capable of utilizing a larger part of the solar spectrum, other materials were also investigated, like hematite , Fe2O3, and CIGS, CuIn1-xGaxSe2.The optical properties of hematite were investigated as a function of film thickness on films deposited by ALD. For films thinner than 20 nm, a blue shift was observed for both the absorption maximum, the indirect band gap as well as for the direct transitions. The probability for the indirect transition decreased substantially for thinner films due to a suppressed photon/phonon coupling. These effects decrease the visible absorption for films thin enough for effective charge transport in photocatalytic applications.CIGS was demonstrated to be a highly interesting material for solar hydrogen production. CIGS based photocathodes demonstrated high photocurrents for the hydrogen evolution half reaction. The electrode stability was problematic, but was solved by introducing a modular approach based on spatial separation of the basic functionalities in the device. To construct devices capable of driving the full reaction, the possibility to use cells interconnected in series as an alternative to tandem devices were investigated. A stable, monolithic device based on three CIGS cells interconnected in series, reaching beyond 10 % STH-efficiency, was finally demonstrated. With experimental support from the CIGS-devices, the entire process of solar hydrogen production was reviewed with respect to the underlying physical processes, with special focus on the similarities and differences between various device concepts.