Role of Regeneration of Nanoclusters in Dictating the Power Conversion Efficiency of Metal-Nanocluster-Sensitized Solar Cells.

Metal nanoclusters (NCs) have emerged as feasible alternatives to dyes and quantum dots in light energy conversion applications. Despite the remarkable enhancement in power conversion efficiency (PCE) in recent years and the increase in the number of NCs available as sensitizers, a comprehensive understanding of the various interfacial charge-transfer, transport, and recombination events in NCs is still lacking. This understanding is vital to the establishment of design principles for an efficient photoelectrode that uses NCs. In this work, we carefully design a comparison study of two representative NCs, Au and Ag, based on transient absorption spectroscopy and electrochemical impedance spectroscopy, methods that shed light on the true benefits and limitations of NC sensitizers. Low NC regeneration efficiency is the most critical factor that limits the performance of metal-nanocluster-sensitized solar cells (MCSSCs). The slow regeneration that results from sluggish hole transfer kinetics not only limits photocurrent generation efficiency but also has a profound effect on the stability of MCSSCs. This finding calls for urgent attention to the development of an efficient redox couple that has a great hole-extraction ability and no corrosive nature. This work also reveals different interfacial behaviors of Au and Ag NCs in photoelectrodes, suggesting that utilizing the benefits of both types of NCs simultaneously by cosensitization or using AuAg alloy NCs may be one avenue for further PCE improvement in MCSSCs.