Hot Electron Generation Research Articles

Ni/n-Si Schottky junction: Self-biased infrared photodetection via hot carrier photoemission

Internal photoemission-based hot electron generation at metal-semiconductor junctions holds significant potential for silicon-based sub-bandgap NIR photodetectors. In this work, we designed a simple nickel-silicon Schottky junction using the pulsed laser deposition technique and performed both experimental and theoretical analyses. To reduce the complexity of fabrication and lower costs, we used a planar nickel thin film on top of n-type silicon. The thickness of the nickel thin film was optimized to improve absorption and hot electron generation near the Ni/Si interface. We measured and calculated reflectance using the transfer matrix approach to quantify the effect of thickness on EQE. We also calculated the thickness-dependent absorption profile to estimate hot electron production near the junction. The current-voltage characterization of Ni/n-Si Schottky photodetector was investigated under the dark conditions as well under 1200 nm and 1300 nm light illumination. Under self-bias conditions, a photodiode with a 12 nm Ni thickness exhibits responsivity of 0.124 mA/W and 0.069 mA/W under illumination from 1200 nm and 1300 nm LED light, respectively. Furthermore, we used a comprehensive theoretical model to quantify the planar Ni/Si hot carrier generation and emission efficiency. and experimentally validated the calculated EQEs with the fabricated device. We believe the proposed complementary metal-oxide-semiconductor-compatible and simply structured Ni/Si Schottky photodetector will have potential applications in the silicon-based optoelectronics market.

Chiral Symmetry Breaking in Colloidal Metal Nanoparticle Solutions by Circularly Polarized Light.

Shape symmetry breaking in the formation of inorganic nanostructures is of significant current interest. It was typically achieved through the growth of colloidal nanoparticles with adsorbed chiral molecules. Photochemical processes induced through asymmetric plasmon excitation by circularly polarized light in surface immobilized nanostructures also led to symmetry breaking. Here, we show that chiral symmetry breaking can be achieved by randomly rotating gold@silver core-shell nanobars in colloidal solution using circularly polarized illumination, where orientational averaging does not eliminate the symmetry breaking of an asymmetric plasmon-induced galvanic replacement reaction. Different morphological effects that are produced by circularly vs linearly polarized light illumination demonstrate the intricate effect of light polarization on the localized plasmonic-induced photochemical response. The essential features of this symmetry breaking, such as illumination wavelength dependence, were reproduced by simulations of circularly polarized light-excited-plasmon-induced hot-electron generation as the source for asymmetric metal deposition. The symmetry breaking becomes smaller in more symmetric geometrical shapes, such as triangular nanoprisms and nanocubes, and down to zero in spherical ones. The degree of symmetry breaking rises when the nanobars are immobilized on a substrate and illuminated from a single direction.

Flexible transparent conductors with a percolated Ag nanostructure and its application as efficient self-bias plasmonic photodetector

A percolated silver (Ag) nanostructured-based transparent conductor has been deposited by physical vapor deposition (PVD) technique where lateral growth of Ag has been enhanced by a pre-deposited Ag-TiO2 thin film. This Ag-TiO2 film has embedded Ag nanoparticles (NPs) within TiO2 thin film which is grown in a low temperature (100 °C) solution processed technique. This process includes Li4Ti5O12 (LTO) thin film deposition by a sol–gel method followed by ion-exchange (Li+ → Ag+) process to yield an Ag-TiO2 thin film. The percolated Ag network has appeared as soon film mass-thickness reaches close to 10 nm, resulting in an abrupt drop of electrical resistivity of the film. This percolated Ag nanostructured thin film (10 nm Ag/Ag-TiO2/plastic) has resistivity of ∼50 Ω/□ and an average visual transmittance of >70 % up to 450 nm. In higher wavelength range, transparency gradually reduces, and it reaches to ∼50 % at 600 nm which is mostly due to the plasmon absorption of this film. By utilizing its combined optical transparency and surface plasmon absorption, this film has been used to develop plasmonic hot electron photodetectors where Ag-thin film works as transparent electrode as well as plasmon induced photo-excited hot electron generation. Device has been fabricated on a heavily doped n type Si (n++-Si) with a metal–semiconductor-metal (M−S−M) device geometry. External quantum efficiency (EQE) data reveal that photocurrent of this device is mostly generated in the plasmonic absorption region with a peak detectivity of 2.84 × 1012 Jones at 510 nm under −3V external bias. Besides, the device shows fast response with a response time of ∼25 ms.

Self-Driven Graphene Photodetector Arrays Enabled by Plasmon-Induced Asymmetric Electric Field.

Gap surface plasmon (GSP) modes enhance graphene photodetectors (GPDs)' performance by confining the incident light within nanogaps, giving rise to strong light absorption. Here, we propose an asymmetric plasmonic nanostructure array on planar graphene comprising stripe- and triangle-shaped sharp tip arrays. Upon light excitation, the noncentrosymmetric metallic nanostructures show strong light-matter interactions with localized field close to the surface of tips, causing an asymmetric electric field. These features can accelerate the hot electron generation in graphene, forming a directional diffusion current. Accordingly, the artificial GPDs exhibit a wavelength-dependence behavior covering the wavelength range from 0.8 to 1.6 μm, with three photoresponse maxima corresponding to the nanostructures' resonances. Additionally, the polarization-dependent GPDs can realize a responsivity of ∼25 mA/W and a noise equivalent power of ∼0.44 nW/Hz1/2 at zero bias when excited at the resonance of 1.4 μm. Overall, our study offers a new strategy for preparing compact and multifrequency infrared GPDs.

Anomalous hot electron generation from two-plasmon decay instability driven by broadband laser pulses with intensity modulations

We investigate the hot electrons generated from two-plasmon decay (TPD) instability driven by laser pulses with intensity modulated by a frequency Δω m using theoretical and numerical approaches. Our primary focus lies on scenarios where Δω m is on the same order of the TPD growth rate γ 0 ( Δωm∼γ0 ), corresponding to moderate laser frequency bandwidths for TPD mitigation. With Δω m conveniently modeled by a basic two-color scheme of the laser wave fields in fully-kinetic particle-in-cell simulations, we demonstrate that the energies of TPD modes and hot electrons exhibit intermittent evolution at the frequency Δω m , particularly when Δωm∼γ0 . With the dynamic TPD behavior, the overall ratio of hot electron energy to the incident laser energy, fhot , changes significantly with Δω m . While fhot drops notably with increasing Δω m at large Δω m limit as expected, it goes anomalously beyond the hot electron energy ratio for a single-frequency incident laser pulse with the same average intensity when Δω m falls below a specific threshold frequency Δω c . This anomaly arises from the pronounced sensitivity of fhot to variations in laser intensity. We find this threshold frequency Δω c primarily depends on γ 0 and the collisional damping rate of plasma waves, with relatively lower sensitivity to the density scale length. We develop a scaling model characterizing the relation of Δω c and laser plasma conditions, enabling the potential extention of our findings to more complex and realistic scenarios.

Boosting external quantum efficiency of a WSe2 photodetector across visible and NIR spectra through harnessing plasmonic hot electrons

The layered two-dimensional material tungsten diselenide ( WSe2 ) has triggered tremendous interests in the field of optoelectronic devices due to its exceptional carrier transport property. Nevertheless, the limited absorption of WSe2 in the near infrared (NIR) band poses a challenge for the application of WSe2 photodetectors in night vision, telecommunication, etc. Herein, the enhanced performance of the WSe2 photodetector is demonstrated through the incorporation of titanium nitride nanoparticles (TiN NPs), complemented by an atomically-thick Al2O3 layer that aids in suppressing the dark current. It is demonstrated that TiN NPs can dramatically enhance the absorption of light in the proposed WSe2 photodetector in the NIR regime. This enhancement boosts photocurrent responses through the generation of plasmonic hot electrons, leading to external quantum efficiency (EQE) enhancement factors of 379.66% at 850 nm and 178.47% at 1550 nm. This work presents, for the first time, to our knowledge, that the WSe2 photodetector is capable of detecting broadband light spanning from ultraviolet to the telecommunication range, all achieved without the reliance on additional semiconductor materials. This achievement opens avenues for the advancement of cost-effective NIR photodetectors.

Enhanced terahertz radiation generated by intense laser interaction with a two-layer thin solid target

A terahertz radiation enhancing scheme, in which a linearly polarized weakly relativistic laser pulse irradiates a target consisting of two parallel thin-solid layers with a certain gap, is proposed and studied by using two-dimensional particle-in-cell simulations. The radiation is known to be produced by laser-produced hot electrons via mechanisms such as coherent transition radiation at the target surfaces. Under optimized conditions, the energy conversion efficiency of terahertz radiation can be as high as 3.3%, which is nearly 1.5 times higher than that obtained with a single-layer target with the same drive laser. This is mainly due to the enhanced hot electron generation with moderate energy via multiple reflections of the laser pulse between the two target layers. The radiation has two peaks close to 30° from the target surface, which are more collimated than that with the single-layer target. The dependence of the terahertz radiation on a variety of target parameters is given, which can control the terahertz spectrum and radiation efficiency and thus provide guidance for experimental investigations. Moreover, both the coherent transition radiation and antenna radiation models are applied to explain the angular distributions of the terahertz emission found in the simulations. Published by the American Physical Society 2024

Toward machine-learning-assisted PW-class high-repetition-rate experiments with solid targets

We present progress in utilizing a machine learning (ML) assisted optimization framework to study the trends in a parameter space defined by spectrally shaped, high-intensity, petawatt-class (8 J, 45 fs) laser pulses interacting with solid targets and give the first simulation-based overview of predicted trends. A neural network (NN) incorporating uncertainty quantification is trained to predict the number of hot electrons generated by the laser–target interaction as a function of pulse shaping parameters. The predictions of this NN serve as the basis function for a Bayesian optimization framework to navigate this space. For post-experimental evaluation, we compare two separate neural network (NN) models. One is based solely on data from experiments, and the other is trained only on ensemble particle-in-cell simulations. Reviewing the predicted and observed trends across the experiment-capable laser parameter search space, we find that both ML models predict a maximal increase in hot electron generation at a level of approximately 12%–18%; however, no statistically significant enhancement was observed in experiments. On direct comparison of the NN models, the average discrepancy is 8.5%, with a maximum of 30%. Since shot-to-shot fluctuations in experiments affect the observations, we evaluate the behavior of our optimization framework by performing virtual experiments that vary the number of repeated observations and the noise levels. Here, we discuss the implications of such a framework for future autonomous exploration platforms in high-repetition-rate experiments.

Stearic acid-coated plasmonic Ag nanoparticles as a dual catalyst for enhanced NiO chemo and photo catalysis

The phenomenon of Localized Surface Plasmon Resonance (LSPR) in plasmonic metal nanoparticles causes a strong absorption of visible light and leads to the generation of hot electrons on the surface and the creation of localized electromagnetic fields near the surface. This characteristic enhances the catalytic performance of a plasmonic metal Ag–NiO nanocomposite (NiO-SNP) when exposed to low-flux visible light irradiation. The NiO-SNP was synthesized using a simple and cost-effective ultrasonication method. Its structural, morphological, and optical properties were analyzed, confirming the formation of nanocomposites. The proximity of stearic acid-coated Ag nanoparticles (SNP) acts as visible light-harvesting antennas, promoting NiO's activity for effectively reducing paracetamol (PM) drugs. The improved catalytic property is attributed to an electron relay effect, while the strong electromagnetic fields generated by irradiated Ag nanoparticles facilitate the concentration of PM molecules at active sites, leading to accelerated reaction rates. NiO-SNP2 demonstrates remarkable PM degradation: 97 % in tap water and 82.6 % in deionized water within 10 min, demonstrating its catalytic effectiveness. The plasmonic SNP mechanism in NiO-SNP1 nanocomposites enhances photocatalytic efficiency by up to 90 %, owing to efficient charge separation and transfer, resulting in a notable 1.5-fold increase in PM degradation. The degradation kinetics follow a pseudo-first-order model, with rate constants (k) ranging from approximately 0.059 to 0.6104 min⁻1, underscoring the crucial role of Ag nanoparticles in enhancing photocatalytic activity and degradation efficiency. Catalysis and visible light photocatalysis are significantly improved with increasing concentrations of NiO and SNP, respectively. This research could inspire a new approach to transforming traditional metal catalysis into plasmonic-metal catalysis.

Au@AgPt core/cage nanoframes as photothermal catalyst for enhanced NIR-induced 4-nitrophenol reduction

The selection and optimization of catalysts have been a subject of considerable research interest in recent decades. Bimetallic and multimetallic nanocatalysts, comprised of plasmonic and catalytic components, have recently emerged as a promising approach to achieving high catalytic performance due to synergistic effects. In this study, an Au@AgPt core/cage nanoframe has been successfully fabricated. It features a controllable hollow silver-platinum alloy nanoframe with an in-built plasmonic gold nanorod, serving as a plasmon-enhanced photothermal catalyst for the reduction of 4-nitrophenol (4-NP). This well-designed trimetallic nanostructure exhibits a unique core-cage nanoframes structure and surface roughness, offering advantages in both composition and structure. The LSPR-excited local heating effect and hot-electron generation, as well as the intrinsic catalytic active sites, work synergistically and are highly beneficial for temperature-sensitive reaction of 4-NP reduction. Experimental results have shown that the optimized nanocatalysts of Au@AgPt-4, featuring an optimal Pt content and robust photothermal performance, display stable photothermal catalytic properties and the best photothermal catalytic performance compared with other nanostructures, completing the reduction reaction within approximately one minute. This study provides a rational design of nanoscale materials with plasma-enhanced properties, which can help to inspire further catalyst design and optimization.

Plasmon-Induced Hot Electrons in Nanostructured Materials: Generation, Collection, and Application to Photochemistry.

Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the plasmon can decay through different channels, including nonradiative Landau damping for the generation of plasmon-induced energetic carriers, the so-called hot electrons and holes. The energetic carriers can be collected by transferring to a functional material situated next to the plasmonic component in a hybrid configuration to facilitate a range of photochemical processes for energy or chemical conversion. This article centers on the recent advancement in generating and utilizing plasmon-induced hot electrons in a rich variety of hybrid nanostructures. After a brief introduction to the fundamentals of hot-electron generation and decay in plasmonic nanocrystals, we extensively discuss how to collect the hot electrons with various types of functional materials. With a focus on plasmonic nanocrystals made of metals, we also briefly examine those based upon heavily doped semiconductors. Finally, we illustrate how site-selected growth can be leveraged for the rational fabrication of different types of hybrid nanostructures, with an emphasis on the parameters that can be experimentally controlled to tailor the properties for various applications.

Enhanced Surface Fields Driven by Fano Resonances in Silver Nanocube Dimers for Efficient Hot Electron Generation

Enhanced Surface Fields Driven by Fano Resonances in Silver Nanocube Dimers for Efficient Hot Electron Generation

Tandem Electric-Fields Prolong Energetic Hot Electrons Lifetime for Ultra-Fast and Stable NO2 Detection.

Prolonging energetic hot electrons lifetimes and surface activity in the reactive site can overcome the slow kinetics and unfavorable thermodynamics of photo-activated gas sensors. However, bulk and surface recombination limit the simultaneous optimization of both kinetics and thermodynamics. Here tandem electric fields are deployed at (111)/(100)Au-CeO2 to ensure a sufficient driving force for carrier transfer and elucidate the mechanism of the relationship between charge transport and gas-sensing performance. The asymmetric structure of the (111)/(100)CeO2 facet junction provides interior electric fields, which facilitates electron transfer from the (100)face to the (111)face. This separation of reduction and oxidation reaction sites across different crystal faces helps inhibit surface recombination. The increased electron concentration at the (111)face intensifies the interface electric field, which promotes electron transfer to the Au site. The local electric field generated by the surface plasmon resonance effect promotes the generation of high-energy energy hot-electrons, which maintains charge concentration in the interface field by injecting into (111)/(100)CeO2, thereby provide thermodynamic contributions and inhibit bulk recombination. The tandem electric fields enable the (111)/(100)Au-CeO2 to rapidly detect 5ppm of NO2 at room temperature with stability maintained within 20s.

Electron kinetic effects in back-stimulated Raman scattering bursts driven by broadband laser pulses

We examine electron kinetic effects in broadband-laser-driven back-stimulated Raman scattering (BSRS) bursts using particle-in-cell simulations. These bursts occur during the nonlinear stage, causing reflectivity spikes and generating large numbers of hot electrons. Long-duration simulations are performed to observe burst events, and a simplified model is developed to eliminate the interference of the broadband laser’s random intensity fluctuations. Using the simplified model, we isolate and characterize the spectrum of electron plasma waves. The spectrum changes from a sideband structure to a turbulence-like structure during the burst. A significant asymmetry in the spectrum is observed. This asymmetry is amplified and transferred to electron phase space by high-intensity broadband laser pulses, leading to violent vortex-merging and generation of hot electrons. The proportion of hot electrons increases from 6.76% to 14.7% during a single violent burst event. We demonstrate that kinetic effects profoundly influence the BSRS evolution driven by broadband lasers.

Perovskite quantum laser with enhanced population inversion driven by plasmon-induced hot electron transfer under potential shift polarization conditions

The hot electron transfer resulting in fluorescence enhancement is significantly meaningful for theory and experiment of the study on photoelectric devices. However, the laser emission based on direct hot electron transfer is difficult to realize because of the low transfer efficiency. To achieve a laser with a new-generation mechanism based on hot electron transfer, the photoelectric co-excitation is proposed for improving the efficiency of hot electron transfer. The lasing behavior at 532 nm is realized with a threshold of 5 kw cm−2 and 1 μA, which can be considered as the hot electron transfer resulting in population inversion enhancement. Meanwhile, the lasing output power is 0.3 mW. The hot electrons transfer process was described via the transient absorption spectrum according to the improved ground-state bleaching and excited-state absorption signal in device ON. Through comparison with the optical pump only, the quantum efficiencies of hot electron generation (HEG) and hot electron transfer (HET) were increased ∼31% and 31%, respectively. Most importantly, a triple gain mode coupling device including local surface plasmon, hot electron transfer, and array oscillation was presented. Two modes of population inversion enhancement are proposed. This study can provide theoretical and experimental reference for the research of hot electron lasers and devices.

Phototransformation of achiral metasurfaces into handedness-selectable transient chiral media

Chirality is a geometric property describing the lack of mirror symmetry. This unique feature enables photonic spin-selectivity in light-matter interaction, which is of great significance in stereochemistry, drug development, quantum optics, and optical polarization control. The versatile control of optical geometry renders optical metamaterials as an effective platform for engineered chiral properties at prescribed spectral regimes. Unfortunately, geometry-imposed restrictions only allow one circular polarization state of photons to effectively interact with chiral meta-structures. This limitation motivates the idea of discovering alternative techniques for dynamically reconfiguring the chiroptical responses of metamaterials in a fast and facile manner. Here, we demonstrate an approach that enables optical, sub-picosecond conversion of achiral meta-structures to transient chiral media in the visible regime with desired handedness upon the inhomogeneous generation of plasmonic hot electrons. As a proof of concept, we utilize linearly polarized laser pulse to demonstrate near-complete conversion of spin sensitivity in an achiral meta-platform-a functionality yet achieved in a non-mechanical fashion. Owing to the generation, diffusion, and relaxation dynamics of hot electrons, the demonstrated technique for all-optical creation of chirality is inherently fast, opening new avenues for ultrafast spectro-temporal construction of chiral platforms with on-demand spin-selectivity.

Bound States in the Continuum for Hot Electron Generation in Integrated-Resonant Metasurfaces

Bound States in the Continuum for Hot Electron Generation in Integrated-Resonant Metasurfaces

Revealing the Loss Mechanism of Chemically-Induced Hot Electron Transport.

Hot electrons are crucial for unraveling the intrinsic relationship between chemical reactions and charge transfer in heterogeneous catalysis. Significant research focused on real-time detection of reaction-driven hot electron flow (chemicurrent) to elucidate the energy conversion mechanisms, but it remains elusive because carrier generation contributes to only part of the entire process. Here, a theoretical model for quantifying the chemicurrent yield is presented by clarifying the contributions of hot carrier losses from the internal emission and multiple reflections. The experimental chemicurrent yield verifies our model with a reliable mean free path of hot electrons, emphasizing the importance of comprehensive consideration of the transport process besides hot electron generation. Moreover, Pt nanoparticles (NPs)-decorated Au/TiO2 is examined, showing the role of NPs-induced carrier losses in the performance of catalytic nanodiodes. These findings are expected to contribute to understanding the hot electron detection efficiency and designing nanodiodes with enhanced hot carrier flow and catalytic activity.

Biosynthesis of Silver Nanoparticles at Various pH values and their Applications in Capturing Irradiation Solar Energy.

Metallic nanoparticles (NPs), in general, are able, due to the high surface area per unit volume, to absorb the maximum incoming light flux through the vicinity of plasmonic structures and then provide local heating. Thus, silver (Ag) NPs has been used to generate heat and increase the temperature of water from solar radiation energy. The optimal plasmonic heating generation can be obtained as soon as the wavelength of the light source is close to the plasmonic resonance wavelength of Ag NPs. Ag NPs have been fabricated through a straightforward, cheap, as well as environmentally friendly approach. In this study, Salix babylonica L., weeping willow leaf extract has been utilized as a reducing, capping, and stabilizing agent, without using any other toxic materials. The importance of this study lies in the generation of hot electrons, which can be obtained by collecting the solar spectrum near the infrared and infrared regions, which cannot be obtained by the conventional photocatalytic devices. Numerous characterization techniques such as; UV-Vis, FT-IR spectroscopy, X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis were used to study the optical, chemical, structural, morphological, properties of the Ag NPs. The impact of pH on the properties of Ag NPs and their performance to generate heat during solar irradiation have been investigated intensively. This study showed that the synthesized Ag NPs with pH value 12 is the optimum condition and can increase the temperature of water dramatically. An evaluation of the current patents displays that the field of green synthesis Ag NPs utilizing plant extracts is a vital field and produces rather stable, safe and effective Ag NPs. The novelty of this patent is that Ag NPs can be synthesized from a one-pot reaction without using any exterior stabilizing and reducing agent, which is not conceivable by means of the existing processes. This study, also, is rare and distinctive, and it demonstrates that even a slight quantity of the Ag NPs is significantly raising the temperature of water effectively.

Tailored mesoscopic plasma accelerates electrons exploiting parametric instability

Laser plasma electron acceleration from the interaction of an intense femtosecond laser pulse with an isolated microparticle surrounded by a low-density gas is studied here. Experiments presented here show that optimized plasma tailoring by introducing a pre-pulse boosts parametric instabilities to produce MeV electron energies and generates electron temperatures as large as 200 keV with the total charge being as high as 350 fC/shot/sr, even at a laser intensity of a few times 1016 Wcm−2. Corroborated by particle-in-cell simulations, these measurements reveal that two plasmon decay in the vicinity of the microparticle is the main contributor to hot electron generation.