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Harnessing non-equilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field. It promises to enable control of activity and selectivity of photochemical reactions, especially for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot carrier-driven processes in metal/semiconducting heterostructures has remained elusive. In this work, we reveal the complex interdependence between plasmon excitation, hot carrier generation, transport and interfacial collection in plasmonic photocatalytic devices, uniquely determining the charge injection efficiencies at the solid/solid and solid/liquid interfaces. Interestingly, by measuring the internal quantum efficiency of ultrathin (14 to 33 nm) single-crystalline plasmonic gold (Au) nanoantenna arrays on titanium dioxide substrates, we find that the performance of the device is governed by hot hole collection at the metal/electrolyte interface. In particular, by combining a solid- and liquid-state experimental approach with ab initio simulations, we show a more efficient collection of high-energy d-band holes traveling in [111] orientation, resulting in a stronger oxidation reaction at the {111} surfaces of the nanoantenna. These results thus establish new guidelines for the design and optimization of plasmonic photocatalytic systems and optoelectronic devices.

Carrier transport in materials is often diffusive due to momentum-relaxing scattering with phonons and defects. Suppression of momentum-relaxing scattering can lead to the ballistic and hydrodynamic transport regimes, wherein complex non-Ohmic current flow patterns, including current vortices, can emerge. In the ballistic regime addressed here, transverse magnetic focusing is habitually understood in a familiar single-particle picture of carriers injected from a source, following ballistic cyclotron orbits and reaching a detector. We report on a distinctive nonlocal magnetoresistance phenomenon exclusive to fermions, in an enclosed mesoscopic geometry wherein transverse focusing magnetoresistance peaks also occur at values of the cyclotron diameter that are incommensurate with the distance between the source and detector. In low-temperature experiments and simulations using GaAs/AlGaAs heterostructures with high electron mobility, we show that the peaks occur independently of the location of the detector, and only depend on the source-drain separation. We reproduce the experimental findings using simulations of ballistic transport in both semiclassical and quantum-coherent transport models. The periodicity of magnetic field at which the peaks occur is matched to the lithographically defined device scale. It is found that, unlike in transverse magnetic focusing, the magnetoresistance structure cannot be attributed to any set of ordered single-particle trajectories but instead requires accounting for the collective dynamics of the fermion distribution and of all particle trajectories. The magnetoresistance is further associated with current flow vorticity, a collective phenomenon., Comment: 11 figures

Protected surface states arising from non-trivial bandstructure topology in semimetals can potentially enable new device functionalities in compute, memory, interconnect, sensing, and communication. This necessitates a fundamental understanding of surface-state transport in nanoscale topological semimetals. Here, we investigate quantum transport in a prototypical topological semimetal NbAs to evaluate the potential of this class of materials for beyond-Cu interconnects in highly-scaled integrated circuits. Using density functional theory (DFT) coupled with non-equilibrium Green's function (NEGF) calculations, we show that the resistance-area RA product in NbAs films decreases with decreasing thickness at the nanometer scale, in contrast to a nearly constant RA product in ideal Cu films. This anomalous scaling originates from the disproportionately large number of surface conduction states which dominate the ballistic conductance by up to 70% in NbAs thin films. We also show that this favorable RA scaling persists even in the presence of surface defects, in contrast to RA sharply increasing with reducing thickness for films of conventional metals, such as Cu, in the presence of surface defects. These results underscore the promise of topological semimetals like NbAs as future back-end-of-line (BEOL) interconnect metals.

The increasing resistance of Cu interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7-nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries of the interconnects at the nanoscale. Topological semimetals, owing to their topologically protected surface states and suppressed electron backscattering, are promising material candidates to potentially replace current Cu interconnects as low-resistance interconnects. Here, we report the attractive resistivity scaling of topological metal MoP nanowires and show that the resistivity values are comparable to those of Cu interconnects below 500 nm$^2$ cross-section areas. More importantly, we demonstrate that the dimensional scaling of MoP nanowires, in terms of line resistance versus total cross-sectional area, is superior to those of effective Cu and barrier-less Ru interconnects, suggesting MoP is an attractive solution to the current scaling challenge of Cu interconnects., Comment: 4 figures

Designing new quantum materials with long-lived electron spin states urgently requires a general theoretical formalism and computational technique to reliably predict intrinsic spin relaxation times. We present a new, accurate and universal first-principles methodology based on Lindbladian dynamics of density matrices to calculate spin-phonon relaxation time ($\tau_s$) of solids with arbitrary spin mixing and crystal symmetry. This method describes contributions of Elliott-Yafet (EY) and D'yakonov-Perel' (DP) mechanisms to spin relaxation for systems with and without inversion symmetry on an equal footing. We show that intrinsic spin and momentum relaxation times both decrease with increasing temperature; however, for the DP mechanism, spin relaxation time varies inversely with extrinsic scattering time. We predict large anisotropy of spin lifetime in transition metal dichalcogenides. The excellent agreement with experiments for a broad range of materials underscores the predictive capability of our method for properties critical to quantum information science., Comment: 12 pages, 7 figures

Harvesting non-equilibrium hot carriers from photo-excited metal nanoparticles has enabled plasmon-driven photochemical transformations and tunable photodetection with resonant nanoantennas. Despite numerous studies on the ultrafast dynamics of hot electrons, 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. 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 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., Comment: 12 pages, 4 figures

The Dirac point and linear band structure in Graphene bestow it with remarkable electronic and optical properties, a subject of intense ongoing research. Explanations of high electronic mobility in graphene, often invoke the masslessness of electrons based on the effective relativistic Dirac-equation behavior, which are inaccessible to most undergraduate students and are not intuitive for non-physics researchers unfamiliar with relativity. Here, we show how to use only basic concepts from semiconductor theory and the linear band structure of graphene to explain its unusual effective mass and mobility, and compare them with conventional metals and semiconductors. We discuss the more intuitive concept of transverse effective mass that emerges naturally from these basic derivations, which approaches zero in the limit of undoped graphene at low temperature and is responsible for its extremely high mobility., Comment: 5 pages, 3 figures

Transition metal dichalcogenides have been the primary materials of interest in the field of valleytronics for their potential in information storage, yet the limiting factor has been achieving long valley decoherence times. We explore the dynamics of four monolayer TMDCs (MoS$_2$, MoSe$_2$, WS$_2$, WSe$_2$) using ab initio calculations to describe electron-electron and electron-phonon interactions. By comparing calculations which both omit and include relativistic effects, we isolate the impact of spin-resolved spin-orbit coupling on transport properties. In our work, we find that spin-orbit coupling increases carrier lifetimes at the valence band edge by an order of magnitude due to spin-valley locking, with a proportional increase in the hole mobility at room temperature. At temperatures of 50~K, we find intervalley scattering times on the order of 100 ps, with a maximum value ~140 ps in WSe$_2$. Finally, we calculate excited-carrier generation profiles which indicate that direct transitions dominate across optical energies, even for WSe$_2$ which has an indirect band gap. Our results highlight the intriguing interplay between spin and valley degrees of freedom critical for valleytronic applications. Further, our work points towards interesting quantum properties on-demand in transition metal dichalcogenides that could be leveraged via driving spin, valley and phonon degrees of freedom., Comment: 6 pages, 5 figures

We report on quantum emission from Pb-related color centers in diamond following ion implantation and high temperature vacuum annealing. First-principles calculations predict a negatively-charged Pb-vacancy center in a split-vacancy configuration, with a zero-phonon transition around 2.3 eV. Cryogenic photoluminescence measurements performed on emitters in nanofabricated pillars reveal several transitions, including a prominent doublet near 520 nm. The splitting of this doublet, 2 THz, exceeds that reported for other group-IV centers. These observations are consistent with the PbV center, which is expected to have the combination of narrow optical transitions and stable spin states, making it a promising system for quantum network nodes.

Harnessing short-lived photoexcited electron-hole pairs in metal nanostructures has the potential to define a new phase of optoelectronics, enabling control of athermal mechanisms for light harvesting, photodetection and photocatalysis. To date, however, the spatiotemporal dynamics and transport of these photoexcited carriers have been only qualitatively characterized. Plasmon excitation has been widely viewed as an efficient mechanism for generating non-thermal hot carriers. Despite numerous experiments, conclusive evidence elucidating and quantifying the full dynamics of hot carrier generation, transport, and injection has not been reported. Here, we combine experimental measurements with coupled first-principles electronic structure theory and Boltzmann transport calculations to provide unprecedented insight into the internal quantum efficiency, and hence internal physics, of hot carriers in photoexcited gold (Au)-gallium nitride (GaN) nanostructures. Our results indicate that photoexcited electrons generated in 20 nm-thick Au nanostructures impinge ballistically on the Au-GaN interface. This discovery suggests that the energy of hot carriers could be harnessed from metal nanostructures without substantial losses via thermalization. Measurements and calculations also reveal the important role of metal band structure in hot carrier generation at energies above the interband threshold of the plasmonic nanoantenna. Taken together, our results advance the understanding of excited carrier dynamics in realistically-scaled metallic nanostructures and lay the foundations for the design of new optoelectronic devices that operate in the ballistic regime., Comment: 9 pages, 4 figures

Plasmonic hot carrier devices extract excited carriers from metal nanostructures before equilibration, and have the potential to surpass semiconductor light absorbers. However their efficiencies have so far remained well below theoretical limits, which necessitates quantitative prediction of carrier transport and energy loss in plasmonic structures to identify and overcome bottlenecks in carrier harvesting. Here, we present a theoretical and computational framework, Non-Equilibrium Scattering in Space and Energy (NESSE), to predict the spatial evolution of carrier energy distributions that combines the best features of phase-space (Boltzmann) and particle-based (Monte Carlo) methods. Within the NESSE framework, we bridge first-principles electronic structure predictions of plasmon decay and carrier collision integrals at the atomic scale, with electromagnetic field simulations at the nano- to mesoscale. Finally, we apply NESSE to predict spatially-resolved energy distributions of photo-excited carriers that impact the surface of experimentally realizable plasmonic nanostructures at length scales ranging from tens to several hundreds of nanometers, enabling first-principles design of hot carrier devices., Comment: 10 pages, 5 figures

High-reflectance in many state-of-the-art optical devices is achieved with noble metals. However, metals are limited by losses, and for certain applications, by their high mass density. Using a combination of ab initio and optical transfer matrix calculations, we evaluate the behavior of graphene-based \AA-scale metamaterials and find that they could act as nearly-perfect reflectors in the mid-long wave infrared (IR) range. The low density of states for electron-phonon scattering and interband excitations leads to unprecedented optical properties for graphene heterostructures, especially alternating atomic layers of graphene and hexagonal boron nitride, at wavelengths greater than $10~\mu$m. At these wavelengths, these materials exhibit reflectivities exceeding 99.7% at a fraction of the weight of noble metals, as well as plasmonic mode confinement and quality factors that are greater by an order of magnitude compared to noble metals. These findings hold promise for ultra-compact optical components and waveguides for mid-IR applications. Moreover, unlike metals, the photonic properties of these heterostructures could be actively tuned via chemical and/or electrostatic doping, providing exciting possibilities for tunable devices.

Ultrafast pump-probe measurements of plasmonic nanostructures probe the non-equilibrium behavior of excited carriers, which involves several competing effects obscured in typical empirical analyses. Here we present pump-probe measurements of plasmonic nanoparticles along with a complete theoretical description based on first-principles calculations of carrier dynamics and optical response, free of any fitting parameters. We account for detailed electronic-structure effects in the density of states, excited carrier distributions, electron-phonon coupling, and dielectric functions which allow us to avoid effective electron temperature approximations. Using this calculation method, we obtain excellent quantitative agreement with spectral and temporal features in transient-absorption measurements. In both our experiments and calculations, we identify the two major contributions of the initial response with distinct signatures: short-lived highly non-thermal excited carriers and longer-lived thermalizing carriers., Comment: Supplementary information available as SI.pdf in source

Nanoscale localization of electromagnetic fields near metallic nanostructures underpins the fundamentals and applications of plasmonics. The unavoidable energy loss from plasmon decay, initially seen as a detriment, has now expanded the scope of plasmonic applications to exploit the generated hot carriers. However, quantitative understanding of the spatial localization of these hot carriers, akin to electromagnetic near-field maps, has been elusive. Here we spatially map hot-electron-driven reduction chemistry with 15 nanometre resolution as a function of time and electromagnetic field polarization for different plasmonic nanostructures. We combine experiments employing a six-electron photo-recycling process that modify the terminal group of a self-assembled monolayer on plasmonic silver nanoantennas, with theoretical predictions from first-principles calculations of non-equilibrium hot-carrier transport in these systems. The resulting localization of reactive regions, determined by hot carrier transport from high-field regions, paves the way for hot-carrier extraction science and nanoscale regio-selective surface chemistry., Comment: 18 pages, 5 figures

We present an accurate equation of state for water based on a simple microscopic Hamiltonian, with only four parameters that are well-constrained by bulk experimental data. With one additional parameter for the range of interaction, this model yields a computationally efficient free-energy functional for inhomogeneous water which captures short-ranged correlations, cavitation energies and, with suitable long-range corrections, the non-linear dielectric response of water, making it an excellent candidate for studies of mesoscale water and for use in ab initio solvation methods., Comment: 6 pages, 5 figures