InP quantum dots (QDs) are promising building blocks for use in solar technologies because of their low intrinsic toxicity, narrow bandgap, large absorption coefficient, and low-cost solution synthesis. However, the high surface trap density of InP QDs reduces their energy conversion efficiency and degrades their long-term stability. Encapsulating InP QDs into a wider bandgap shell is desirable to eliminate surface traps and improve optoelectronic properties. Here, we report the synthesis of "giant" InP/ZnSe core/shell QDs with tunable ZnSe shell thickness to investigate the effect of the shell thickness on the optoelectronic properties and the photoelectrochemical (PEC) performance for hydrogen generation. The optical results demonstrate that ZnSe shell growth (0.9-2.8 nm) facilitates the delocalization of electrons and holes into the shell region. The ZnSe shell simultaneously acts as a passivation layer to protect the surface of InP QDs and as a spatial tunneling barrier to extract photoexcited electrons and holes. Thus, engineering the ZnSe shell thickness is crucial for the photoexcited electrons and hole transfer dynamics to tune the optoelectronic properties of "giant" InP/ZnSe core/shell QDs. We obtained an outstanding photocurrent density of 6.2 mA cm-1 for an optimal ZnSe shell thickness of 1.6 nm, which is 288% higher than the values achieved from bare InP QD-based PEC cells. Understanding the effect of shell thickness on surface passivation and carrier dynamics offers fundamental insights into the suitable design and realization of eco-friendly InP-based "giant" core/shell QDs toward improving device performance.
Keywords: InP/ZnSe quantum dots; charge transfer dynamics; heavy-metal free; photoelectrochemical hydrogen generation; shell thickness.