Design Considerations of Efficient Photo-Electrosynthetic Cells and its Realization Using Buried Junction Si Thin Film Multi Absorber Cells

Abstract

Abstract As is obvious from previous work on semiconductor photoelectrochemistry, single junction semiconductors do not provide either the required maximum photovoltage or a high photocurrent for solar water splitting, which is required for efficient stand-alone devices. From these experiences we conclude, that multi-junction devices must be developed for bias-free water splitting. In this article we present our design considerations needed for the development of efficient photo-electro-synthetic cells, which have guided us during the DFG priority program 1613. At first, we discuss the fundamental requirements, which must be fulfilled to lead to effective solar water splitting devices. Buried junction and photoelectrochemical arrangements are compared. It will become clear, that the photovoltaic (PV) and electrochemical (EC) components can be optimized separately, but that maximized conversion efficiencies need photovoltages produced in the photovoltaic part of the device, which are adapted to the electrochemical performance of the electrolyzer components without energetic losses in their coupling across the involved interfaces. Therefore, in part 2 we will present the needs to develop appropriate interface engineering layers for proper chemical and electronic surface passivation. In addition, highly efficient electrocatalysts, either for the hydrogen or oxygen evolution reaction (HER, OER), must be adjusted in their energetic coupling to the semiconductor band edges and to the redox potentials in the electrolyte with minimized losses in the chemical potentials. The third part of our paper describes at first the demands and achievements on developing multijunction thin-film silicon solar cells. With different arrangements of silicon stacks a wide range of photovoltages and photocurrents can be provided. These solar cells are applied as photocathodes in integrated directly coupled PV-EC devices. For this purpose thin Pt and Ni catalyst layers are used on top of the solar cells for the HER and a wire connected RuO2 counter electrode is used for the OER. Electrochemical stability has been successfully tested for up to 10,000 s in 0.1 M KOH. Furthermore, we will illustrate our experimental results on interface engineering strategies using TiO2 as buffer layer and Pt nanostructures as HER catalyst. Based on the obtained results the observed improvements, but also the still given limitations, can be related to clearly identified non-idealities in surface engineering either related to recombination losses at the semiconductor surface reducing photocurrents or due to not properly-aligned energy states leading to potential losses across the interfaces.