Plasmon-Induced Hot Carriers: An Atomistic Perspective of the First Tens of Femtoseconds

Abstract

For more than a decade the harvesting of the plasmon-induced hot carrier (HC) has promised a clean and efficient way to harness light irradiation. Here, we expose the difficulties that arise to describe the full process of plasmon-induced HC and its injection into the environment. Then, we share the perspective that we have built during the last years employing an atomistic and real-time approach of the ultrafast events that take place in the generation and direct injection of HC and their photocatalytic effect. Finally, we provide a nonexhaustive enumeration of the “lines to follow” that evidence that the plasmon-induced HC field will remain hot for many years to come.

Photodissociation of H2 on Ag and Au Nanoparticles: Effect of Size and Plasmon versus Interband Transitions on Threshold Intensities for Dissociation

“…The plasmon peak for the Au 489 H 2 system arises at around 2.3 eV, which is similar to the plasmon in larger gold NPs with a roughly spherical shape. , Here, the plasmon peak is more pronounced and is distinct from the high-energy interband transitions. This also agrees with the previous study by Berdakin and co-workers where plasmon peaks start to appear distinct from interband transitions for icosahedral Au NPs involving more than 300 atoms. We note that the broad oscillating structures in the Au NP spectra in Figure at energies above 2.3 eV were also observed by Schatz and co-workers , for tetrahedral Au NPs using the TDDFT calculations.…”

Computational Analyses of Plasmonics of a Silver Nanoparticle in a Vacuum and in a Water Solution by Classical Electronic and Molecular Dynamics Simulations

“…Density functional theory (DFT), which describes the electronic structure based on first-principles from the atomic level, and its extension in time domain, namely, time-dependent density functional theory (TDDFT), − are capable of providing accurate and detailed insights into optical properties, light–electron interactions, − and plasmon-induced charge transfer, , quantum mechanically. Recent developments in this direction have enabled calculations of the larger sizes of metal NPs over a thousand atoms system using efficient methods − and massive pallarelization . The first-principles methods, however, would be difficult to apply to a condensed or mesoscale system and a longer time scale due to the high computational cost.…”

Schottky barrier effect on plasmon-induced charge transfer

“…Nowadays, plasmon-induced direct charge transfer at the interface has been established as a dominant mechanism, in which hot carriers are injected directly from the metallic nanostructure to a semiconductor via plasmon decay. [20][21][22][23][24][25][26][27][28][29][30][31][32] The direct charge transfer is induced by the coupling of electronic states at the interface. It occurs within a few tens of femtoseconds, and thus avoids hot carrier dissipation in the metallic nanostructure, which rationalizes the high charge transfer efficiencies observed in experiments.…”

“…However, previous theoretical studies on the plasmon-induced charge transfer have only considered pristine semiconductors. [26][27][28][29][37][38][39] The direct charge transfer at the Schottky junction with band bending has not been discussed yet.…”