Hans Joachim Lewerenz

Efficient Water‐Splitting Device Based on a Bismuth Vanadate Photoanode and Thin‐Film Silicon Solar Cells

A hybrid photovoltaic/photoelectrochemical (PV/PEC) water-splitting device with a benchmark solar-to-hydrogen conversion efficiency of 5.2% under simulated air mass (AM) 1.5 illumination is reported. This cell consists of a gradient-doped tungsten-bismuth vanadate (W:BiVO4 ) photoanode and a thin-film silicon solar cell. The improvement with respect to an earlier cell that also used gradient-doped W:BiVO4 has been achieved by simultaneously introducing a textured substrate to enhance light trapping in the BiVO4 photoanode and further optimization of the W gradient doping profile in the photoanode. Various PV cells have been studied in combination with this BiVO4 photoanode, such as an amorphous silicon (a-Si:H) single junction, an a-Si:H/a-Si:H double junction, and an a-Si:H/nanocrystalline silicon (nc-Si:H) micromorph junction. The highest conversion efficiency, which is also the record efficiency for metal oxide based water-splitting devices, is reached for a tandem system consisting of the optimized W:BiVO4 photoanode and the micromorph (a-Si:H/nc-Si:H) cell. This record efficiency is attributed to the increased performance of the BiVO4 photoanode, which is the limiting factor in this hybrid PEC/PV device, as well as better spectral matching between BiVO4 and the nc-Si:H cell.

Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy

Photoelectrochemical (PEC) cells based on semiconductor/liquid interfaces provide a method of converting solar energy to electricity or fuels. Currently, the understanding of semiconductor/liquid interfaces is inferred from experiments and models. Operando ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) has been used herein to directly characterize the semiconductor/liquid junction at room temperature under real-time electrochemical control. X-ray synchrotron radiation in conjunction with AP-XPS has enabled simultaneous monitoring of the solid surface, the solid/electrolyte interface, and the bulk electrolyte of a PEC cell as a function of the applied potential, U. The observed shifts in binding energy with respect to the applied potential have directly revealed ohmic and rectifying junction behavior on metallized and semiconducting samples, respectively. Additionally, the non-linear response of the core level binding energies to changes in the applied electrode potential has revealed the influence of defect-derived electronic states on the Galvani potential across the complete cell.

Efficiency limits for photoelectrochemical water-splitting

Theoretical limiting efficiencies have a critical role in determining technological viability and expectations for device prototypes, as evidenced by the photovoltaics communitys focus on detailed balance. However, due to their multicomponent nature, photoelectrochemical devices do not have an equivalent analogue to detailed balance, and reported theoretical efficiency limits vary depending on the assumptions made. Here we introduce a unified framework for photoelectrochemical device performance through which all previous limiting efficiencies can be understood and contextualized. Ideal and experimentally realistic limiting efficiencies are presented, and then generalized using five representative parameters—semiconductor absorption fraction, external radiative efficiency, series resistance, shunt resistance and catalytic exchange current density—to account for imperfect light absorption, charge transport and catalysis. Finally, we discuss the origin of deviations between the limits discussed herein and reported water-splitting efficiencies. This analysis provides insight into the primary factors that determine device performance and a powerful handle to improve device efficiency.

Interplay of light transmission and catalytic exchange current in photoelectrochemical systems

We develop an analytic current-voltage expression for a variable junction photoelectrochemical (PEC) cell and use it to investigate and illustrate the influence of the optical and electrical properties of catalysts on the optoelectronic performance of PEC devices. Specifically, the model enables a simple, yet accurate accounting of nanostructured catalyst optical and electrical properties through incorporation of an optical transmission factor and active catalytic area factor. We demonstrate the utility of this model via the output power characteristics of an exemplary dual tandem solar cell with indium gallium phosphide and indium gallium arsenide absorbers with varying rhodium catalyst nanoparticle loading. The approach highlights the importance of considering interactions between independently optimized components for optimal PEC device design.

(Invited) Efficiency Limits for Hydrogen and Formate Production via Fully-Integrated Photoelectrochemical Devices

Limiting efficiencies play a critical role in determining the viability of proposed technologies and, consequently, in motivating and guiding device development. Herein we present an analytic, unified framework for fully-integrated photoelectrochemical device performance and apply it to water-splitting and CO_2 reduction reactions for hydrogen and formate production, respectively. An analytic form for the current-voltage relationship of a photoelectrochemical device is used to calculate limiting efficiencies under specific ideal and realistic conditions for single, dual and triple junction photodiode units. Differences in realistic limiting efficiencies for hydrogen and formate production arise not only from disparate catalyst performance but also from design considerations for liquid vs. gas products and realistic operating pH. The results indicate that dual junction devices are sufficient for water-splitting devices, while triple junction devices are more ideal for CO_2 reduction devices with current high performance components.