PQI members Hrvoje Petek, Jin Zhao and their colleagues investigated a less known fact about the microscopic details of how the combined optical, electronic and chemical properties of metal/semiconductor interfaces define the coupling of light into the electronic reagents on their recent paper published in Nature Photonics. In this study, they investigated the coherence and hot electron dynamics in a prototypical Ag nanocluster/TiO2 heterojunction via ultrafast two-photon photoemission (2PP) spectroscopy, scanning tunneling microscopy (STM) and density functional theory (DFT). The silver nanoclustors used in this study were grown via e-beam evaporation of Ag on top of TiO2 surface.They have shown that the plasmon excitation, dephasing and hot electron processes that are related to plasmonically enhanced photocatalysis involve complex physical and chemical interactions, with strong interfacial character involving the chemical and plasmonic coupling of Ag nanoclusters and the TiO2 substrate that cannot be predicted by the properties of the component materials, but rather require an understanding of their interactions. They found that the dephasing of the perpendicular and parallel plasmons by the dielectric screening response of the TiO2 substrate generates hot electrons with anisotropic and non-thermal distributions.
The interface between nano-sized precious metal clusters such as Silver (Ag) and a semiconductor such as graphite (Gr) is called a heterojunction (Ag/Gr). Heterojunctions have great promise in enhance solar energy conversion due to their unique and enhanced optical, electronic, and chemical properties. When excited with laser pulses, electrons in the system acquire a mean energy higher than its thermal equilibrium value and are referred to as "hot electrons". In fact, graphitic materials are model systems for the study of hot electron dynamics. An ineffective screening within the layers of graphite allows the hot electrons to reach temperatures comparable to that in the solar photosphere!
In a study supported by the Center for Chemistry at the Space-Time Limit recently published in the Journal of the American Chemical Society, Hrvoje Petek and his group modified the Gr surface with Ag nanoclusters (NC)s to investigate how the excitation of the plasmonic resonance of the Ag/Gr heterojunction affects the generation, spatial distributions, and relaxation processes of hot electrons. Plasmonic resonance is a prominent feature of precious-metal nanoparticles; it is a sharp and intense absorption band in the visible range that arise from a collective resonant oscillation of the free electrons of the conduction band of the metal called plasmon.