Harvesting non-equilibrium "hot" carriers from photo-excited metal nanoparticles has enabled plasmon-driven photochemical transformations and tunable photodetection with resonant nanoantennas 1-13. Despite numerous studies on the ultrafast dynamics of hot electrons 14-26 , to date, the temporal evolution of hot holes in metal-semiconductor heterostructures remains unknown. An improved understanding of the carrier dynamics in hot-hole-driven systems is needed to help expand the scope of hot-carrier optoelectronics beyond hot-electron-based devices. Here, using ultrafast transient absorption spectroscopy, we show that plasmon-induced hot-hole injection from gold (Au) nanoparticles into the valence band of p-type gallium nitride (p-GaN) occurs within 200 fs, placing hot-hole transfer on a similar timescale as hot-electron transfer 22,25. We further observed that the removal of hot holes from below the Au Fermi level exerts a discernible influence on the thermalization of hot electrons above it, reducing the peak electronic temperature and decreasing the electron-phonon coupling time relative to Au samples without a pathway for hot-hole collection. First principles calculations 27-29 corroborate these experimental observations, suggesting that hot-hole injection modifies the relaxation dynamics of hot electrons in Au nanoparticles through ultrafast modulation of the d-band electronic structure. Taken together, these ultrafast studies substantially advance our understanding of the temporal evolution of hot holes in metal-semiconductor heterostructures and suggest new strategies for manipulating and controlling the energy distributions of hot carriers on ultrafast timescales.

Plasmonic materials have optical cross sections that exceed by 10-fold their geometric sizes, making them uniquely suitable to convert light into electrical charges. Harvesting plasmon-generated hot carriers is of interest for the broad fields of photovoltaics and photocatalysis; however, their direct utilization is limited by their ultrafast thermalization in metals. To prolong the lifetime of hot carriers, one can place acceptor materials, such as semiconductors, in direct contact with the plasmonic system. Herein, we report the effect of operating temperature on hot electron generation and transfer to a suitable semiconductor. We found that an increase in the operation temperature improves hot electron harvesting in a plasmonic semiconductor hybrid system, contrasting what is observed on photodriven processes in nonplasmonic systems. The effect appears to be related to an enhancement in hot carrier generation due to phonon coupling. This discovery provides a new strategy for optimization of photodriven energy production and chemical synthesis.

We have successfully investigated the simultaneous injection of hot electrons and holes upon excitation of gold localized surface plasmon resonance (LSPR). The studies were performed on all-solid-state plasmonic system composed of titanium dioxide (TiO 2 )/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) p−n junctions with gold nanoparticles (Au NPs). The study revealed that both charge carriers are transferred within 200 fs to the respective charge acceptors, exhibiting a free carrier transport behavior. We also confirmed that the transfer of charge carriers are accompanied by change in the initial relaxation dynamics of Au NPs.

The efficient conversion of light energy into chemical energy is key for sustainable human development. Several photocatalytic systems based on photovoltaic electrolysis have been used to produce hydrogen via water reduction. However, in such devices, light harvesting and proton reduction are carried separately, showing quantum efficiency of about 10–12%. Here, we report a nano-hybrid photocatalytic assembly that enables concomitant reductive hydrogen production and pollutant oxidation with solar-to-fuel efficiencies up to 20%. The modular architecture of this plasmonic material allows the fine-tuning of its photocatalytic properties by simple manipulation of a reduced number of basic components.

The recent discovery that metal nanoparticles can generate hot carriers upon light excitation is seen as a breakthrough in the fields of plasmonics and photonics. However, the high expectations for a plasmonic revolution in applications have been dampened by the ultrafast energy dissipation of surface plasmon polariton modes. While research aimed at suppressing loss mechanisms is still pursued, another research direction has emerged where charges are harnessed before they relax. Despite the effort, efficiencies of devices based on hot carriers harnessed from plasmonics are typically very low (a few percent), which is somehow paradoxical since efficiencies for electron injection efficiency have been reported to be in the range from 25% to 40% and hole injection up to 85%. This indicates that the low device performance relates to the undesirable charge back-transfer process, which happens in the picosecond time scale. In this context, we performed a comparative ultrafast spectroscopy investigation with gold nanoparticles in direct contact with different metal oxides, namely, TiO2, ZnO, SnO2, and Al:ZnO. Electron dynamics revealed the decisive role of metal/semiconductor interfaces and semiconductor electronic structure in electron injection efficiency and recombination, with significant implications to the fields of photocatalysis and photovoltaics.