Harnessing hot electrons and holes resulting from the decay of localized surface plasmons in nanomaterials has recently led to new devices for photovoltaics, photocatalysis and optoelectronics. Properties of hot carriers are highly tunable and in this work we investigate their dependence on the material, size and environment of spherical metallic nanoparticles. In particular, we carry out theoretical calculations of hot carrier generation rates and energy distributions for six different plasmonic materials (Na, K, Al, Cu, Ag and Au). The plasmon decay into hot electron-hole pairs is described via Fermi's Golden Rule using the quasistatic approximation for optical properties and a spherical well potential for the electronic structure. We present results for nanoparticles with diameters up to 40 nm, which are embedded in different dielectric media. We find that small nanoparticles with diameters of 16 nm or less in media with large dielectric 1 arXiv:1802.05096v1 [cond-mat.mtrl-sci] 14 Feb 2018 constants produce most hot carriers. Among the different materials, Na, K and Au generate most hot carriers. We also investigate hot-carrier induced water splitting and find that simple-metal nanoparticles are useful for initiating the hydrogen evolution reaction, while transition-metal nanoparticles produce dominantly holes for the oxygen evolution reaction. Keywordshot electrons, plasmon decay, nanoparticles, water splitting, nanophotonics Energetic or "hot" electrons and holes produced by the decay of localized surface plasmons (LSP) in metallic nanostructures have recently generated much excitement. They can be harnessed in optoelectronic devices, such as photodetectors, or for solar energy conversion, i.e. in photocatalytic or photovoltaic devices. 1-8 For example, Mukherjee et al. observed that plasmon-induced hot electrons can trigger H 2 dissociation reactions on the surface of gold nanoparticles. 9 An important advantage of nanoplasmonic devices compared to traditional systems is their tunability: their optical and electronic properties depend sensitively on the nanoparticle size and shape, but also on the nanoparticle material and its environment. 10-15To guide experimental progress and identify nano-devices with favorable hot-carrier properties, a detailed theoretical understanding of the physico-chemical processes that govern hot-carrier generation is needed. However, developing such a theory is challenging because of the large size of experimentally relevant nanoparticles. Atomistic ab initio calculations are currently only feasible for metallic clusters and very small nanoparticles. 5,16,17 To model properties of experimentally relevant nanoparticles with radii of 10 nm or more, two different strategies have been employed. In many calculations, simplified models for the electronic structure of the nanoparticle are used, such as jellium models or non-interacting electron models. 18-21 For example, Manjavacas et al. employed a spherical well model to simulate hot-carrier generation in silver nanoparticles with di...

We have studied the thermalization of hot carriers in both pristine and defective titanium nitride (TiN) using a two-temperature model. All parameters of this model, including the electron-phonon coupling parameter, were obtained from first-principles density-functional theory calculations. The virtual crystal approximation was used to describe defective systems. We find that thermalization of hot carriers occurs on much faster time scales than in gold as a consequence of the significantly stronger electronphonon coupling in TiN. Specifically, the largest thermalization times, on the order of 200 femtoseconds, are found in TiN with nitrogen vacancies for electron temperatures around 4000 K. Keywordshot electrons, two temperature model, titanium nitride, electron-phonon interaction, virtualcrystal approximation 1 arXiv:1908.06620v1 [physics.comp-ph]

Computational design can accelerate the discovery of new materials with tailored properties, but applying this approach to plasmonic nanoparticles with diameters larger than a few nanometers is challenging as atomistic first-principles calculations are not feasible for such systems. In this paper, we employ a recently developed material-specific approach that combines effective mass theory for electrons with a quasistatic description of the localized surface plasmon to identify promising bimetallic core-shell nanoparticles for hot-electron photocatalysis. Specifically, we calculate hot-carrier generation rates of 100 different core-shell nanoparticles and find that systems with an alkali-metal core and a transition-metal shell exhibit high figures of merit for water splitting and are stable in aqueous environments. Our analysis reveals that the high efficiency of these systems is related to their electronic structure, which features a two-dimensional electron gas in the shell. Our calculations further demonstrate that hot-carrier properties are highly tunable and depend sensitively on core and shell sizes. The design rules resulting from our work can guide experimental progress towards improved solar energy conversion devices.

Coherent optical manipulation of exciton states provides a fascinating approach for quantum gating and ultrafast switching. However, their coherence time for incumbent semiconductors is highly susceptible to thermal decoherence and inhomogeneous broadening effects. Here, we uncover zero-field exciton quantum beating and anomalous temperature dependence of the exciton spin lifetimes in CsPbBr3 perovskite nanocrystals (NCs) ensembles. The quantum beating between two exciton fine-structure splitting (FSS) levels enables coherent ultrafast optical control of the excitonic degree of freedom. From the anomalous temperature dependence, we identify and fully parametrize all the regimes of exciton spin depolarization, finding that approaching room temperature, it is dominated by a motional narrowing process governed by the exciton multilevel coherence. Importantly, our results present an unambiguous full physical picture of the complex interplay of the underlying spin decoherence mechanisms. These intrinsic exciton FSS states in perovskite NCs present fresh opportunities for spin-based photonic quantum technologies.

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