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Infrared driven hot electron generation and transfer from non-noble metal plasmonic nanocrystals.

ABSTRACT: Non-noble metal plasmonic materials, e.g. doped semiconductor nanocrystals, compared to their noble metal counterparts, have shown unique advantages, including broadly tunable plasmon frequency (from visible to infrared) and rich surface chemistry. However, the fate and harvesting of hot electrons from these non-noble metal plasmons have been much less explored. Here we report plasmon driven hot electron generation and transfer from plasmonic metal oxide nanocrystals to surface adsorbed molecules by ultrafast transient absorption spectroscopy. We show unambiguously that under infrared light excitation, hot electron transfers in ultrafast timescale (<50 fs) with an efficiency of 1.4%. The excitation wavelength and fluence dependent study indicates that hot electron transfers right after Landau damping before electron thermalization. We revealed the efficiency-limiting factors and provided improvement strategies. This study paves the way for designing efficient infrared light absorption and photochemical conversion applications based on non-noble metal plasmonic materials.

SUBMITTER: Zhou D

PROVIDER: S-EPMC7287091 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc3-x N@C80 (x = 0-3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1-T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin-lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

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Infrared driven hot electron generation and transfer from non-noble metal plasmonic nanocrystals.

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