Bias‐Free Solar‐to‐Hydrogen Conversion in a BiVO4/PM6:Y6 Compact Tandem with Optically Balanced Light Absorption

Abstract

The high voltage required to overcome the thermodynamic threshold and the complicated kinetics of the water splitting reaction limit the efficiency of single semiconductor‐based photoelectrochemistry. A semiconductor/solar cell tandem structure has been theoretically demonstrated as a viable path to achieve an efficient direct transformation of sunlight into chemical energy. However, compact designs exhibiting the indispensable optimally balanced light absorption have not been demonstrated. In the current work, we design and implement a compact tandem providing the complementary absorption of a highly transparent BiVO4 photoanode and a PM6:Y6 solar cell. Such bandgap combination approaches the optimal to reach the solar‐to‐hydrogen (STH) conversion upper limit for tandem photoelectrochemical cells (PECs). We demonstrate that, by using a photonic multilayer structure to adequately balance sunlight absorption among both tandem materials, a 25% increase in the bias‐free STH conversion can be achieved, setting a clear path to take compact tandem PECs to the theoretical limit performance.