摘要： Thin film silicon based multi-junction solar cells were developed for application in combined photovoltaic electrochemical systems for hydrogen production from water splitting. Going from single, tandem, triple up to quadruple junctions, we cover a range of open circuit voltages from 0.5 V to 2.8 V at photovoltaic cell (PV) efficiencies above 13%. The solar cells were combined with electrochemical (EC) cells in integrated devices from 0.5 cm2 to 64 cm2. Various combinations of catalyst pairs for the oxygen and hydrogen evolution reaction side (OER and HER) were investigated with respect to electrochemical activity, stability, cost and – important for the integrated device – optical quality of the metal catalyst on the HER side as back reflector of the attached solar cell. The combined PV-EC systems were further investigated under varied operation temperatures and illumination conditions for estimation of outdoor performance and annual fuel production yield. For 0.5 cm2 size combined systems a maximum solar-to-hydrogen efficiency ηSTH = 9.5% was achieved under standard test conditions. For device upscaling to 64 cm2 various concepts of contact interconnects for reduced current and fill factor loss when using large size solar cells were investigated. To replace high performance noble metal based catalyst pairs (Pt/RuO2 or Pt/IrOx), more abundant and cheaper NiMo (HER) and NiFeOx (OER) compounds were prepared via electrodeposition. With the NiMo/NiFeOx catalyst pair we obtained ηSTH = 5.1% for a 64 cm2 size solar cell which was even better than the performance of the Pt/IrO2 system (ηSTH = 4.8%). In simulated day-night cycle operation the NiMo/NiFeOx catalyst pair showed excellent stability over several days. The experimental studies were successfully accompanied by simulation of the entire PV-EC device using a series connection model which allowed studies and pre-estimations of device performance by varying individual components such as catalysts, electrolytes, or solar cells. Based on these results we discuss the prospects and challenges of integrated PV-EC devices on large area for hydrogen and solar fuel production in general.