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.

Switching of electrochemical selectivity due to plasmonic field-induced dissociation.

Electrochemical reactivity is known to be dictated by the structure and composition of the electrocatalyst-electrolyte interface. Here, we show that optically generated electric fields at this interface can influence electrochemical reactivity insofar as to completely switch reaction selectivity. We study an electrocatalyst composed of gold-copper alloy nanoparticles known to be active toward the reduction of CO2 to CO. However, under the action of highly localized electric fields generated by plasmonic excitation of the gold-copper alloy nanoparticles, water splitting becomes favored at the expense of CO2 reduction. Real-time time-dependent density functional tight binding calculations indicate that optically generated electric fields promote transient-hole-transfer-driven dissociation of the O─H bond of water preferentially over transient-electron-driven dissociation of the C─O bond of CO2. These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.

Hot Electron Cooling in n-Doped Colloidal Nanoplatelets Following Near-Infrared Intersubband Excitation.

Intersubband transition was recently discovered in colloidal nanoplatelets, but the associated intersubband carrier relaxation dynamics remains poorly understood. In particular, it is crucial to selectively excite the intersubband transition and to follow the hot electron dynamics in the absence of valence-band holes. This is achieved herein by exciting the predoped electrons in CdSe/ZnS nanoplatelets using near-infrared femtosecond pulses and monitoring nonequilibrium electron dynamics using broad-band visible pulses. We find that the n = 2 electrons relax to the n = 1 subband and establish a Fermi-Dirac distribution within 200 fs, and finally reach an equilibrium with the lattice within a few ps. The cooling dynamics depend mainly on the excitation fluence but weakly on the doping density and the lattice temperature. These characteristics are well captured by our numerical simulation that explicitly accounts for the state occupation effect and optical phonon scattering.

Direct Hot-Electron Transfer at the Au Nanoparticle/Monolayer Transition-Metal Dichalcogenide Interface Observed with Ultrahigh Spatiotemporal Resolution.

Plasmon-induced hot-electron transfer at the metallic nanoparticle/semiconductor interface is the basis of plasmon-enhanced photocatalysis and energy harvesting. However, limited by the nanoscale size of hot spots and femtosecond time scale of hot-electron transfer, direct observation is still challenging. Herein, by using spatiotemporal-resolved photoemission electron microscopy with a two-color pump-probe beamline, we directly observed such a process with a concise system, the Au nanoparticle/monolayer transition-metal dichalcogenide (TMD) interface. The ultrafast hot-electron transfer from Au nanoparticles to monolayer TMDs and the plasmon-enhanced transfer process were directly measured and verified through an in situ comparison with the Au film/TMD interface and free TMDs. The lifetime at the Au nanoparticle/MoSe2 interface decreased from 410 to 42 fs, while the photoemission intensities exhibited a 27-fold increase compared to free MoSe2. We also measured the evolution of hot electrons in the energy distributions, indicating the hot-electron injection and decay happened in an ultrafast time scale of ∼50 fs without observable electron cooling.

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.

Metal-Semiconductor Heterojunction with Ohmic Contact Realizes Efficient Infrared-Light-Driven Photocatalysis.

Efficient utilization of solar energy for photocatalytic applications, particularly in the infrared spectrum, is crucial for addressing environmental challenges and energy scarcity. Herein we present a general strategy for constructing efficient infrared-driven photocatalysts in a metal/semiconductor heterojunction with Ohmic contact, where metals with low work function as the infrared-light absorber and semiconductors with electron storage ability can overcome the unfavorable electron flowback. Taking the NixB/MO2 (M = Ce, Ti, Sn, Ge, Zr, etc.) heterojunction as an example, both experimental and theoretical investigations reveal that the formation of an Ohmic contact facilitates the transfer of hot electrons from NixB to MO2, which are stored by the ion redox pairs for the variable valence character of M. As expected, the heterojunction exhibits remarkable photocatalytic activity under infrared light (λ ≥ 800 nm), as evidenced by the efficient photofixation of CO2 to high-value-added cyclic carbonates. This study offers a general platform for designing infrared-light-driven photocatalysts.

Fundamental Limits of Few-Layer NbSe2 Microbolometers at Terahertz Frequencies.

The rapid development of infrared spectroscopy, observational astronomy, and scanning near-field microscopy has been enabled by the emergence of sensitive mid- and far-infrared photodetectors. Superconducting hot-electron bolometers (HEBs), known for their exceptional signal-to-noise ratio and fast photoresponse, play a crucial role in these applications. While superconducting HEBs are traditionally crafted from sputtered thin films such as NbN, the potential of layered van der Waals (vdW) superconductors is untapped at THz frequencies. Here, we introduce superconducting HEBs made from few-layer NbSe2 microwires. By improving the interface between NbSe2 and metal leads, we overcome impedance mismatch with RF readout, enabling large responsivity THz detection (0.13 to 2.5 THz) with a minimal noise equivalent power of 7 pW/ Hz and nanosecond-range response time. Our work highlights NbSe2 as a promising platform for HEB technology and presents a reliable vdW assembly protocol for custom bolometer production.

Near-Infrared Polarization-Sensitive Detection by All-Si Plasmonic Hot Electron Detectors.

Polarization-sensitive optoelectronic detection has been achieved by an all-Si detector in the NIR range, based on plasmon hot electron generation/internal photoemission effect. An advanced architecture with a specially designed anisotropic metasurface was developed and structurally optimized for maximizing the internal quantum efficiency (IQE). Assisted by finite difference time domain (FDTD) simulations, the well-designed device exhibits a maximum optical absorption of 80% around 1.45 µm, corresponding to an optical discrimination ratio of 120. Optoelectronic measurements show the peak responsivity and detectivity of 51.2 mA/W and 8.05 × 1010 cm Hz1/2/W, respectively, at 1.45 µm. A high polarization photocurrent ratio of 35 nm is also achieved at 1.55 µm. Moreover, the optoelectronic response can be tuned by a back-gate bias. Last but not least, we built up a model for theoretically estimating the IQE, which provides instructive guidance for further enhancing the optoelectronic performance of hot electron detectors.

Circular polarization sensitive opto-neuromorphic operation at plasmonic hot electron transistor using chiral gold nanoparticles.

Opto-neuromorphic operation is critical for biological system to recognize the visual objects and mimicking such operation is important for artificial prosthesis as well as machine vision system for industrial applications. To sophisticatedly mimic biological system, regulation of learning and memorizing efficiency is needed, however engineered synthetic platform has been lack of controllability, which makes huge gap between biological system and synthetic platform. Here we demonstrated controllable learning and memorizing opto-neuromorphic operation at plasmonic hot electron transistor. Especially, circularly polarized light (CPL) sensitive synaptic characteristics and learning experience capability are enabled by incorporating chiral plasmonic nanoparticle. Furthermore, gate voltage gives rise to controllable neuromorphic operation due to hot electron injection and trapping effect, resulting in high remaining synaptic weight of ∼70% at negative gate voltage under CPL excitation. We believe that this discovery makes significant leap toward on-demand in-sensor computing as well as toward bio-realistic device.

Investigating Plasmonic Catalysis Kinetics on Hot-Spot Engineered Nanoantennae.

Strong hot-spots can facilitate photocatalytic reactions potentially providing effective solar-to-chemical energy conversion pathways. Although it is well-known that the local electromagnetic field in plasmonic nanocavities increases as the cavity size reduces, the influence of hot-spots on photocatalytic reactions remains elusive. Herein, we explored hot-spot dependent catalytic behaviors on a highly controlled platform with varying interparticle distances. Plasmon-meditated dehalogenation of 4-iodothiophenol was employed to observe time-resolved catalytic behaviors via in situ surface-enhanced Raman spectroscopy on dimers with 5, 10, 20, and 30 nm interparticle distances. As a result, we show that by reducing the gap from 20 to 10 nm, the reaction rate can be sped up more than 2 times. Further reduction in the interparticle distance did not improve reaction rate significantly although the maximum local-field was ∼2.3-fold stronger. Our combined experimental and theoretical study provides valuable insights in designing novel plasmonic photocatalytic platforms.

Catalytic Boosting by Surface-Plasmon-Driven Hot Electrons on Antenna-Reactor Schottky Nanodiodes.

Significant research has focused on enhancing catalytic performance through solar energy conversion, and the design of photocatalysis incorporating surface plasmons is drawing considerable attention as a highly competitive catalyst system. Although the hot electron process is the primary mechanism in plasmonic photocatalysis, the precise function of hot electron transport in catalytic reactions remains unclear due to the absence of direct measurement. Here, we demonstrate the intrinsic relationship between surface-plasmon-driven hot electrons and catalytic activity during hydrogen oxidation, utilizing catalytic Schottky nanodiodes (Pt/Ag/TiO2) for antenna-reactor plasmonic photocatalysis. The simultaneous and independent measurements of hot electron flow and catalytic turnover rate show that the plasmonic effect amplifies the flow of reaction-induced hot electrons (chemicurrent), leading to enhanced catalytic activity. Plasmonic photocatalytic performance can be controlled with light wavelengths, intensity, surface temperature, and structures. These results elucidate the hot electron flow on photocatalysis and offer improved strategies for efficient catalytic devices.

Unveiling Long-Lived Hot-Electron Dynamics via Hyperbolic Meta-antennas.

Conventional plasmonic nanoantennas enable scattering and absorption bands at the same wavelength region, making their utilization to full potential impossible for both features simultaneously. Here, we take advantage of spectrally separated scattering and absorption resonance bands in hyperbolic meta-antennas (HMA) to enhance the hot-electron generation and prolong the relaxation dynamics of hot carriers. First, we show that HMA enables extending plasmon-modulated photoluminescence spectrum toward longer wavelengths due to its particular scattering spectrum, in comparison to the corresponding nanodisk antennas (NDA). Then, we demonstrate that the tunable absorption band of HMA controls and modifies the lifetime of the plasmon-induced hot electrons with enhanced excitation efficiency in the near-infrared region and also broadens the utilization of the visible/NIR spectrum in comparison to NDA. Thus, the rational heterostructures designed by plasmonic and adsorbate/dielectric layers with such dynamics can be a platform for optimization and engineering the utilization of plasmon-induced hot carriers.

How Hot Electron Generation at the Solid-Liquid Interface Is Different from the Solid-Gas Interface.

Excitation of hot electrons by energy dissipation under exothermic chemical reactions on metal catalyst surfaces occurs at both solid-gas and solid-liquid interfaces. Despite extensive studies, a comparative operando study directly comparing electronic excitation by electronically nonadiabatic interactions at solid-gas and solid-liquid interfaces has not been reported. Herein, on the basis of our in situ techniques for monitoring energy dissipation as a chemicurrent using a Pt/n-Si nanodiode sensor, we observed the generation of hot electrons in both gas and liquid phases during H2O2 decomposition. As a result of comparing the current signal and oxygen evolution rate in the two phases, surprisingly, the efficiency of reaction-induced excitation of hot electrons increased by ∼100 times at the solid-liquid interface compared to the solid-gas interface. The boost of hot electron excitation in the liquid phase is due to the presence of an ionic layer lowering the potential barrier at the junction for transferring hot electrons.

Why Does Single-Atom Photocatalysis Work Better Than Conventional Photocatalysis? A Study on Ultrafast Excited Carrier and Structure Dynamics.

With the introduction of single atoms in photocatalysis, a small change in the electronic and geometric structure of the substrate can result in higher energy conversion efficiency, whereas the underlying microscopic dynamics are rarely illustrated. Here, employing real-time time-dependent density functional theory, we explore the ultrafast electronic and structural dynamics of single-atom photocatalysts (SAPCs) in water splitting at the microscopic scale. The results demonstrate that a single-atom Pt loaded on graphitic carbon nitride greatly promotes photogenerated carriers compared to traditional photocatalysts, and effectively separates the excited electrons from holes, prolonging the lifetime of the excited carriers. The flexible oxidation state (Pt2+, Pt0, or Pt3+) renders the single atom as an active site to adsorb the reactant and to catalyze the reactions as a charge transfer bridge at different stages during the photoreaction process. Our results offer deep insights into the single-atom photocatalytic reactions and benefit the design of high-efficiency SAPCs.

Enhancing Plasmonic Hot Electron Energy on Ag Surface by Amine Coordination.

Plasmonic catalysis has emerged as a promising approach to solar-chemical energy conversion. Notably, hot carriers play a decisive role in plasmonic catalysis since only when their energy matches with the LUMO or HOMO energy of the reactant molecule, can the reaction be activated. However, the hot carrier energy depends on the intrinsic physicochemical properties of the plasmonic metal substrate and the interaction with incident light. Tuning the hot carrier energy is of great significance for plasmonic catalysis but remains challenging. Here, we demonstrate that the energy of hot electrons can be significantly elevated to an unprecedented level through the coordination of amines on Ag surface. The bonding of amines and Ag reduces the work function of nanoparticles, leading to the increase of hot electron energy by 0.4 eV. This enhancement of energy promotes the cleavage of C-X (X=Cl, F) bonds upon excitation by visible light. This study provides new insights for promoting plasmonic charge transfer and enhancing the photocatalytic performance of plasmon-mediated systems.

Regulating the Scaling Relations in Ammonia Synthesis through a Light-Driven Bendable Seesaw Effect on Tailored Iron Catalyst.

Advancing the energy-intensive Haber-Bosch process faces significant challenges due to the intrinsic constraints of scaling relations in heterogeneous catalysis. Herein, we reported an approach of bending the "seesaw effect" to regulate the scaling relations over a tailored α-Fe metallic material (α-Fe-110s), realizing highly efficient light-driven thermal catalytic ammonia synthesis with a rate of 1260 µmol gcatalyst -1 h-1 without additional heating. Specifically, the thermal catalytic activity of α-Fe-110s was significantly enhanced by the novel stepped {110} surface, exhibiting a 3.8-fold increase compared to the commercial fused-iron catalyst with promoters at 350 °C. The photo-induced hot electron transfer further accelerates the dinitrogen dissociation and hydrogenation simultaneously, effectively overcoming the limitation of scaling relation over identical sites. Consequently, the ammonia production rate of α-Fe-110s was further enhanced by 30 times at the same temperature with irradiation. This work designs an efficient and sustainable system for ammonia synthesis and provides a novel approach for regulating the scaling relations in heterogeneous catalysis.

The Microscopic Mechanisms of Nonlinear Rectification on Si-MOSFETs Terahertz Detector.

Studying the nonlinear photoresponse of different materials, including III-V semiconductors, two-dimensional materials and many others, is attracting burgeoning interest in the terahertz (THz) field. Especially, developing field-effect transistor (FET)-based THz detectors with preferred nonlinear plasma-wave mechanisms in terms of high sensitivity, compactness and low cost is a high priority for advancing performance imaging or communication systems in daily life. However, as THz detectors continue to shrink in size, the impact of the hot-electron effect on device performance is impossible to ignore, and the physical process of THz conversion remains elusive. To reveal the underlying microscopic mechanisms, we have implemented drift-diffusion/hydrodynamic models via a self-consistent finite-element solution to understand the dynamics of carriers at the channel and the device structure dependence. By considering the hot-electron effect and doping dependence in our model, the competitive behavior between the nonlinear rectification and hot electron-induced photothermoelectric effect is clearly presented, and it is found that the optimized source doping concentrations can be utilized to reduce the hot-electron effect on the devices. Our results not only provide guidance for further device optimization but can also be extended to other novel electronic systems for studying THz nonlinear rectification.

Photoemission of the Upconverted Hot Electrons in Mn-Doped CsPbBr3 Nanocrystals.

Hot electrons play a crucial role in enhancing the efficiency of photon-to-current conversion or photocatalytic reactions. In semiconductor nanocrystals, energetic hot electrons capable of photoemission can be generated via the upconversion process involving the dopant-originated intermediate state, currently known only in Mn-doped cadmium chalcogenide quantum dots. Here, we report that Mn-doped CsPbBr3 nanocrystals are an excellent platform for generating hot electrons via upconversion that can benefit from various desirable exciton properties and the structural diversity of metal halide perovskites (MHPs). Two-dimensional Mn-doped CsPbBr3 nanoplatelets are particularly advantageous for hot electron upconversion due to the strong exciton-dopant interaction mediating the upconversion process. Furthermore, nanoplatelets reveal evidence for the hot electron upconversion via long-lived dark excitons in addition to bright excitons that may enhance the upconversion efficiency. This study establishes the feasibility of hot electron upconversion in MHP hosts and demonstrates the potential merits of two-dimensional MHP nanocrystals in the upconversion process.

Efficient Hot Electron Capture in CuPc/MoSe2 Heterostructure Assisted by Intersystem Crossing.

Efficient hot electron extraction is a promising approach to develop photovoltaic devices that exceed the Shockley-Queisser limit. However, experimental evidence of hot electron harvesting employing an organic-inorganic interface is still elusive. Here, we reveal the hot electron dynamics at a CuPc/MoSe2 interface using steady-state spectroscopy and transient absorption spectroscopy. A hot electron transfer efficiency of greater than 78% from MoSe2 to CuPc is observed, comparable to that achieved in quantum dot hybrid systems. The mechanism is proposed as follows: the photogenerated hot electrons in MoSe2 transfer to CuPc and form singlet charge transfer states, which subsequently transform into triplet charge transfer states assisted by the rapid intersystem crossing, inhibiting back-donation of electrons and facilitating exciton dissociation into CuPc polarons with a nanosecond lifetime. Our results demonstrate that the intersystem crossing of the hybrid electronic state at organic-inorganic interfaces may serve as a scheme to enable efficient hot electron extraction in photovoltaic devices.

Understanding the Plasmonic Effect of Enhanced Photodegradation with Au Nanoparticle Decorated ZnO Nanosheet Arrays under Visible Light Irradiation.

Plasmonic-enhanced photocatalysis using visible light is considered a promising strategy for pollution photodegradation. However, there is still a lack of comprehensive and quantitative understanding of the underlying mechanisms and interactions involved. In this study, we employed a two-step process to fabricate arrays of ZnO nanosheets decorated with Au nanoparticles (Au-ZnO NS). Various characterization techniques were used to examine the morphological, structural, and chemical properties of the fabricated Au-ZnO NS array. Furthermore, we systematically investigated the photocatalytic degradation of methyl orange under visible light irradiation using Au-ZnO NS arrays prepared with varying numbers of photochemical reduction cycles. The results indicated that as the number of photochemical reduction cycles increased, the photodegradation efficiency initially increased but subsequently decreased. Under visible light irradiation, the Au-ZnO NS array obtained via four cycles of photochemical reduction exhibits the highest photocatalytic degradation rate of methyl orange 0.00926 min-1, which is six times higher than that of the ZnO NS array. To gain a better understanding of the plasmonic effect on photodegradation performance, we utilized electromagnetic simulations to quantitatively investigate the enhancement of electric fields in the Au-ZnO NS array. The simulations clearly presented the nonlinear dependencies of electric field intensity on the distribution of Au nanoparticles and the wavelength of radiation light, leading to a nonlinear enhancement of hot electron injection and eventual plasmonic photodegradation. The simulated model, corresponding to four cycles of photochemical reduction, exhibits the highest electric field intensity at 550 nm, which can be attributed to its strong plasmonic effect. This work provides mechanistic insights into plasmonic photocatalysts for utilizing visible light and represents a promising strategy for the rational design of high-performance visible light photocatalysts.