Single plasmon hot carrier generation in metallic nanoparticles

Abstract

Hot carriers produced from the decay of localized surface plasmons in metallic nanoparticles are intensely studied because of their optoelectronic, photovoltaic and photocatalytic applications. From a classical perspective, plasmons are coherent oscillations of the electrons in the nanoparticle, but their quantized nature comes to the fore in the novel field of quantum plasmonics. In this work, we introduce a quantum-mechanical material-specific approach for describing the decay of single quantized plasmons into hot electrons and holes.We find that hot carrier generation rates differ significantly from semiclassical predictions.We also investigate the decay of excitations without plasmonic character and show that their hot carrier rates are comparable to those from the decay of plasmonic excitations for small nanoparticles. Our study provides a rigorous and general foundation for further development of plasmonic hot carrier studies in the plasmonic regime required for the design of ultrasmall devices. arXiv:1904.03697v1 [cond-mat.mes-hall]

Generation of plasmonic hot carriers from d-bands in metallic nanoparticles

“…This is a consequence of the large matrix elements for transitions between states that are close to the Fermi energy, see Eq. (19), which is also consistent with the trends observed in time-dependent DFT calculations [34]. Similarly to the d-to-sp case, the curves exhibit a peak when the photon energy is sufficiently large to excite a localized surface plasmon, see inset of Fig.…”

In Situ Visualization of Localized Surface Plasmon Resonance‐Driven Hot Hole Flux

“…[ 1,3,4,6,12–27 ] To promote the generation of hot carriers with applications in photovoltaics, photodetection, and photoelectrochemical devices, pioneering studies demonstrated the key role that localized surface plasmon resonance (LSPR) plays in hot‐electron‐based energy conversion. [ 6,9,12,28–32 ] It has been established that the LSPR‐driven hot carriers expand the boundary of performance of efficient near‐infrared (NIR) detection of silicon‐based photodiodes, [ 21 ] improve photoconversion efficiency, [ 20,33,34 ] and enhance selectivity for CO production over hydrogen evolution. [ 14 ]…”

Dielectric Engineering of Hot-Carrier Generation by Quantized Plasmons in Embedded Silver Nanoparticles

“…We have studied hot-carrier properties of embedded spherical silver nanoparticles consisting of between 68 and 254 atoms corresponding to diameters between 1.08 and 2.10 nm. To calculate hot-carrier distributions in these systems, we extended the approach developed in ref ( 22 ) for alkali metal nanoparticles. Following this approach, the decay of the localized surface plasmon (LSP) into a single electron-pair is considered.…”

“… 26 The TDDFT calculations were carefully converged with respect to the number of empty states. Note that our framework includes a quantized treatment of the plasmon, relevant to describe quantum effects present in small nanoparticles and/or when a low density of plasmons are excited as introduced in ref ( 22 ).…”

“…In this paper, we present a quantum-mechanical approach for calculating the effect of a dielectric environment on hot-carrier properties in embedded silver nanoparticles. In particular, we combine a recently developed method for describing hot-carrier generation by quantized plasmons 22 with a screened interaction between conduction electrons that takes the dielectric response of the environment and also of the polarizable d-band electrons into account. We present results for four different host materials (silicon dioxide, titanium dioxide, silicon nitride, and gallium phosphide) and compare them to results obtained for nanoparticles in air.…”