How the secrets behind photocurrents are revealed in Ag-TiO2 heterostructures-based plasmonic photoelectrochemical systems: A collaborative approach of EC-SERS and photoelectrochemical methods.

Plasmon-mediated chemical reactions (PMCR) have garnered growing interest as a promising concept for photocatalysis. However, in electrochemical systems at solid-liquid interfaces, the photo-induced charge transfer on the surface of metal-semiconductor heterostructures involves complex processes and mechanisms, which are still poorly understood. We explore the plasmon-mediated carrier transfer mechanism and the synergistic effect of light and electric fields on Ag-TiO2 heterostructures, through a combination of electrochemical surface-enhanced Raman spectroscopy and photoelectrochemical methods, with para-aminothiophenol (PATP) serving as a probe molecule. The results show that photocurrent responses are dependent on not only excitation wavelengths and applied potentials, but also the irreversibility of redox. The relationship between photocurrent responses and the chemical transformation between PATP and 4,4'-dimercaptoazobenzene is established, reflecting the photo-induced charge transfer of the heterostructures. The collaboration of spectroscopic and photoelectrochemical methods provide valuable insights into the chemical transformation and kinetic information of adsorbed molecules on the heterostructure during PMCR, offering opportunities for modulating of photocatalytic activities of hot carriers.

Quantifying Ultrafast Energy Transfer from Plasmonic Hot Carriers for Pulsed Photocatalysis on Nanostructures.

Photocatalysis with plasmonic nanostructures has lately emerged as a transformative paradigm to drive and alter chemical reactions using light. At the surface of metallic nanoparticles, photoexcitation results in strong near fields, short-lived high-energy "hot" carriers, and light-induced heating, thus creating a local environment where reactions can occur with enhanced efficiencies. In this context, it is critical to understand how to manipulate the nonequilibrium processes triggered by light, as their ultrafast (femto- to picoseconds) relaxation dynamics compete with the process of energy transfer toward the reactants. Accurate predictions of the plasmon photocatalytic activity can lead to optimized nanophotonic architectures with enhanced selectivity and rates, operating beyond the intrinsic limitations of the steady state. Here, we report on an original modeling approach to quantify, with space, time, and energy resolution, the ultrafast energy exchange from plasmonic hot carriers (HCs) to molecular systems adsorbed on the metal nanoparticle surface while consistently accounting for photothermal bond activation. Our analysis, illustrated for a few typical cases, reveals that the most energetic nonequilibrium carriers (i.e., with energies well far from the Fermi level) may introduce a wavelength-dependence of the reaction rates, and it elucidates on the role of the carriers closer to the Fermi energy and the photothermally heated lattice, suggesting ways to enhance and optimize each contribution. We show that the overall reaction rates can benefit strongly from using pulsed illumination with the optimal pulse width determined by the properties of the system. Taken together, these results contribute to the rational design of nanoreactors for pulsed catalysis, which calls for predictive modeling of the ultrafast HC-hot adsorbate energy transfer.

Mass Transport Limitations in Plasmonic Photocatalysis.

The interpretation of mechanisms governing hot carrier reactivity on metallic nanostructures is critical, yet elusive, for advancing plasmonic photocatalysis. In this work, we explored the influence of the diffusion of molecules on the hot carrier extraction rate at the solid-liquid interface, which is of fundamental interest for increasing the efficiency of photodevices. Through a spatially defined scanning photoelectrochemical microscopy investigation, we identified a diffusion-controlled regime hindering the plasmon-driven photochemical activity of metallic nanostructures. Using low-power monochromatic illumination (<2 W cm-2), we unveiled the hidden influence of mass transport on the quantum efficiency of plasmonic photocatalysts. The availability of molecules at the solid-liquid interface directly limits the extraction of hot holes, according to their nature and energy, at the reactive spots in Au nanoislands on an ultrathin TiO2 substrate. An intriguing question arises: does the mass transport enhancement caused by thermal effects unlock the reactivity of nonthermal carriers under steady state?

Decoupling Plasmonic Hot Carrier from Thermal Catalysis via Electrode Engineering.

Increased attention has been directed toward generating nonequilibrium hot carriers resulting from the decay of collective electronic oscillations on metal known as surface plasmons. Despite numerous experimental endeavors, demonstrating hot carrier-mediated photocatalysis without a heating contribution has proven challenging, particularly for single electron transfer reactions where the thermal contribution is generally detrimental. An innovative engineering solution is proposed to enable single electron transfer reactions with plasmonics. It consists of a photoelectrode designed as an energy filter and photocatalysis performed with light function modulation instead of continuously. The photoelectrode, consisting of FTO/TiO2 amorphous (10 nm)/Au nanoparticles, with TiO2 acting as a step-shape energy filter to enhance hot electron extraction and charge-separated state lifetime. The extracted hot electrons were directed toward the counter electrode, while the hot holes performed a single electron transfer oxidation reaction. Light modulation prevented local heat accumulation, effectively decoupling hot carrier catalysis from the thermal contribution.

Efficient Charge Transport in Inverted Perovskite Solar Cells via 2D/3D Ferroelectric Heterojunction.

While the 2D/3D heterojunction is an effective method to improve the power conversion efficiency (PCE) of perovskite solar cells (PSCs), carriers are often confined in the quantum wells (QWs) due to the unique structure of 2D perovskite, which makes the charge transport along the out-of-plane direction difficult. Here, a 2D/3D ferroelectric heterojunction formed by 4,4-difluoropiperidine hydrochloride (2FPD) in inverted PSCs is reported. The enriched 2D perovskite (2FPD)2PbI4 layer with n = 1 on the perovskite surface exhibits ferroelectric response and has oriented dipoles along the out-of-plane direction. The ferroelectricity of the oriented dipole layer facilitates the enhancement of the built-in electric field (1.06 V) and the delay of the cooling process of hot carriers, reflected in the high carrier temperature (above 1400 K) and the prolonged photobleach recovery time (139.85 fs, measured at bandgap), improving the out-of-plane conductivity. In addition, the alignment of energy levels is optimized and exciton binding energy (32.8 meV) is reduced by changing the dielectric environment of the surface. Finally, the 2FPD-treated PSCs achieve a PCE of 24.82% (certified: 24.38%) with the synergistic effect of ferroelectricity and defect passivation, while maintaining over 90% of their initial efficiency after 1000 h of maximum power point tracking.

Optoelectronic tuning of plasmon resonances via optically modulated hot electrons.

Fast optical modulation of nanoplasmonics is fundamental for on-chip integration of all-optical devices. Although various strategies have been proposed for dynamic modulation of surface plasmons, critical issues of device compatibility and extremely low efficiency in the visible spectrum hamper the application of optoplasmonic nanochips. Here we establish an optoplasmonic system based on Au@Cu2-xS hybrid core-shell nanoparticles. The optical excitation of hot electrons and their charge transfer to the semiconductor coating (Cu2-xS) lead to lowered electron density of Au, which results in the red shift of the localized surface plasmon resonance. The hot electrons can also transport through the Cu2-xS layer to the metal substrate, which increases the conductance of the nanogap. As such, the coupled gap plasmon blue-shifts with a magnitude of up to ∼15 nm, depending on the excitation power and the thickness of the coatings, which agrees with numerical simulations. All of this optoelectronic tuning process is highly reversible, controllable and fast with a modulated laser beam, which is highly compatible and sufficiently useful for on-chip integration of nanophotonic devices.

Determining Quasi-Equilibrium Electron and Hole Distributions of Plasmonic Photocatalysts Using Photomodulated X-ray Absorption Spectroscopy.

Most photocatalytic and photovoltaic devices operate under broadband, constant illumination. Electron and hole dynamics in these devices, however, are usually measured by using ultrafast pulsed lasers in a narrow wavelength range. In this work, we use excited-state X-ray theory originally developed for transient X-ray experiments to study steady-state photomodulated X-ray spectra. We use this method to attempt to extract electron and hole distributions from spectra collected at a nontime-resolved synchrotron beamline. A set of plasmonic metal core-shell nanoparticles is designed as the control experiment because they can systematically isolate photothermal, hot electron, and thermalized electron-hole pairs in a TiO2 shell. Steady-state changes in the Ti L2,3 edge are measured with and without continuous-wave illumination of the nanoparticle's localized surface plasmon resonance. The results suggest that within error the quasi-equilibrium carrier distribution can be determined even from relatively noisy data with mixed excited-state phenomena. Just as importantly, the theoretical analysis of noisy data is used to provide guidelines for the beamline development of photomodulated steady-state spectroscopy.

Understanding the Behaviors of Plasmon-Induced Hot Carriers and Their Applications in Photocatalysis.

Photocatalysis driven by plasmon-induced hot carriers has been gaining increasing attention. Recent studies have demonstrated that plasmon-induced hot carriers can directly participate in photocatalytic reactions, leading to great enhancement in solar energy conversion efficiency, by improving the catalytic activity or changing selectivity. Nevertheless, the utilization efficiency of hot carriers remains unsatisfactory. Therefore, how to correctly understand the generation and transfer process of hot carriers, as well as accurately differentiate between the possible mechanisms, have become a key point of attention. In this review, we overview the fundamental processes and mechanisms underlying hot carrier generation and transport, followed by highlighting the importance of hot carrier monitoring methods and related photocatalytic reactions. Furthermore, possible strategies for the further characterization of plasmon-induced hot carriers and boosting their utilization efficiency have been proposed. We hope that a comprehensive understanding of the fundamental behaviors of hot carriers can aid in designing more efficient photocatalysts for plasmon-induced photocatalytic reactions.

Hot-Carrier Damage in N-Channel EDMOS Used in Single Photon Avalanche Diode Cell through Quasi-Static Modeling.

A single photon avalanche diode (SPAD) cell using N-channel extended-drain metal oxide semiconductor (N-EDMOS) is tested for its hot-carrier damage (HCD) resistance. The stressing gate-voltage (VGS) dependence is compared to hot-hole (HH) injection, positive bias temperature (PBT) instability and off-mode (VGS = 0). The goal was to check an accurate device lifetime extraction using accelerated DC to AC stressing by applying the quasi-static (QS) lifetime technique. N-EDMOS device is devoted to 3D bonding with CMOS imagers obtained by an optimized process with an effective gate-length Leff = 0.25 µm and a SiO2 gate-oxide thickness Tox = 5 nm. The operating frequency is 10 MHz at maximum supply voltage VDDmax = 5.5 V. TCAD simulations are used to determine the real voltage and timing configurations for the device in a mixed structure of the SPAD cell. AC device lifetime is obtained using worst-case DC accelerating degradation, which is transferred by QS technique to the AC waveforms applied to N-EDMOS device. This allows us to accurately obtain the AC device lifetime as a function of the delay and load for a fixed pulse shape. It shows the predominance of the high energy hot-carriers involved in the first substrate current peak during transients.

Long-Range Hot-Carrier Transport in Topologically Connected HgTe Quantum Dots.

The utilization of hot carriers as a means to surpass the Shockley-Queasier limit represents a promising strategy for advancing highly efficient photovoltaic devices. Quantum dots, owing to their discrete energy states and limited multi-phonon cooling process, are regarded as one of the most promising materials. However, in practical implementations, the presence of numerous defects and discontinuities in colloidal quantum dot (CQD) films significantly curtails the transport distance of hot carriers. In this study, the harnessing of excess energies from hot-carriers is successfully demonstrated and a world-record carrier diffusion length of 15 µm is observed for the first time in colloidal systems, surpassing existing hot-carrier materials by more than tenfold. The observed phenomenon is attributed to the specifically designed honeycomb-like topological structures in a HgTe CQD superlattice, with its long-range periodicity confirmed by High-Resolution Transmission Electron Microscopy(HR-TEM), Selected Area Electron Diffraction(SAED) patterns, and low-angle X-ray diffraction (XRD). In such a superlattice, nonlocal hot carrier transport is supported by three unique physical properties: the wavelength-independent responsivity, linear output characteristics and microsecond fast photoresponse. These findings underscore the potential of HgTe CQD superlattices as a feasible approach for efficient hot carrier collection, thereby paving the way for practical applications in highly sensitive photodetection and solar energy harvesting.

Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis.

Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle's plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.

Nonclassical Mechanism of Metal-Enhanced Photoluminescence of Quantum Dots.

Metal-enhanced photoluminescence is able to provide a robust signal even from a single emitter and is promising in applications in biosensors and optoelectronic devices. However, its realization with semiconductor nanocrystals (e.g., quantum dots, QDs) is not always straightforward due to the hidden and not fully described interactions between plasmonic nanoparticles and an emitter. Here, we demonstrate nonclassical enhancement (i.e., not a conventional electromagnetic mechanism) of the QD photoluminescence at nonplasmonic conditions and correlate it with the charge exchange processes in the system, particularly with high efficiency of the hot-hole generation in gold nanoparticles and the possibility of their transfer to QDs. The hole injection returns a QD from a charged nonemitting state caused by hole trapping by surface and/or interfacial traps into an uncharged emitting state, which leads to an increased photoluminescence intensity. These results open new insights into metal-enhanced photoluminescence, showing the importance of the QD surface states in this process.

Photoinduced Electrogenerated Chemiluminescence Imaging of Plasmonic Photoelectrochemistry at Single Nanocatalysts.

In this study, we proposed a novel imaging technique, photoinduced electrogenerated chemiluminescence microscopy (PECLM), to monitor redox reactions driven by hot carriers on single gold nanoparticles (AuNPs) on TiO2. Under laser irradiation, plasmon-generated hot carriers were separated by an electric field, leaving hot holes on the surface of AuNPs to drive ECL reactions. PECL intensity was highly sensitive to the number of hot carriers. Through quantitative image analysis, we found that PECL density on individual AuNPs decreased significantly with an increase in particle diameter, indicating that particle size has a significant impact on photoelectrochemical conversion efficiency. For the first time, we verified the feasibility of PECLM in mapping the catalytic activity of single photocatalysts. PECLM opens a new prospect for the in situ imaging of photocatalysis in a high-throughput way, which not only facilitates the optimization of plasmonic photocatalysts but also contributes to the dynamic study of photocatalytic processes on micro/nanointerfaces.

Energy Transfer to Molecular Adsorbates by Transient Hot Electron Spillover.

Hot electron (HE) photocatalysis is one of the most intriguing fields of nanoscience, with a clear potential for technological impact. Despite much effort, the mechanisms of HE photocatalysis are not fully understood. Here we investigate a mechanism based on transient electron spillover on a molecule and subsequent energy release into vibrational modes. We use state-of-the-art real-time Time Dependent Density Functional Theory (rt-TDDFT), simulating the dynamics of a HE moving within linear chains of Ag or Au atoms, on which CO, N2, or H2O are adsorbed. We estimate the energy a HE can release into adsorbate vibrational modes and show that certain modes are selectively activated. The energy transfer strongly depends on the adsorbate, the metal, and the HE energy. Considering a cumulative effect from multiple HEs, we estimate this mechanism can transfer tenths of an eV to molecular vibrations and could play an important role in HE photocatalysis.

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.

Confinement and Exciton Binding Energy Effects on Hot Carrier Cooling in Lead Halide Perovskite Nanomaterials.

The relaxation of the above-gap ("hot") carriers in lead halide perovskites (LHPs) is important for applications in photovoltaics and offers insights into carrier-carrier and carrier-phonon interactions. However, the role of quantum confinement in the hot carrier dynamics of nanosystems is still disputed. Here, we devise a single approach, ultrafast pump-push-probe spectroscopy, to study carrier cooling in six different size-controlled LHP nanomaterials. In cuboidal nanocrystals, we observe only a weak size effect on the cooling dynamics. In contrast, two-dimensional systems show suppression of the hot phonon bottleneck effect common in bulk perovskites. The proposed kinetic model describes the intrinsic and density-dependent cooling times accurately in all studied perovskite systems using only carrier-carrier, carrier-phonon, and excitonic coupling constants. This highlights the impact of exciton formation on carrier cooling and promotes dimensional confinement as a tool for engineering carrier-phonon and carrier-carrier interactions in LHP optoelectronic materials.

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.

Competition between Direct Detection Mechanisms in Planar Bow-Tie Microwave Diodes on the Base of InAlAs/InGaAs/InAlAs Heterostructures.

The application of the unique properties of terahertz radiation is increasingly needed in sensors, especially in those operating at room temperature without an external bias voltage. Bow-tie microwave diodes on the base of InGaAs semiconductor structures meet these requirements. These diodes operate on the basis of free-carrier heating in microwave electric fields, which allows for the use of such sensors in millimeter- and submillimeter-wavelength ranges. However, there still exists some uncertainty concerning the origin of the voltage detected across these diodes. This work provides a more detailed analysis of the detection mechanisms in InAlAs/InGaAs selectively doped bow-tie-shaped semiconductor structures. The influence of the InAs inserts in the InGaAs layer is investigated under various illumination and temperature conditions. A study of the voltage-power characteristics, the voltage sensitivity dependence on frequency in the Ka range, temperature dependence of the detected voltage and its relaxation characteristics lead to the conclusion that a photo-gradient electromotive force arises in bow-tie diodes under simultaneous light illumination and microwave radiation.

Optimal Geometry for Plasmonic Hot-Carrier Extraction in Metal-Semiconductor Nanocrystals.

Plasmon-induced energy and charge transfer from metal nanostructures hold great potential for harvesting solar energy. Presently, the efficiencies of charge-carrier extraction are still low due to the competitive ultrafast mechanisms of plasmon relaxation. Using single-particle electron energy loss spectroscopy, we correlate the geometrical and compositional details of individual nanostructures to their carrier extraction efficiencies. By removing ensemble effects, we are able to show a direct structure-function relationship that permits the rational design of the most efficient metal-semiconductor nanostructures for energy harvesting applications. In particular, by developing a hybrid system comprising Au nanorods with epitaxially grown CdSe tips, we are able to control and enhance charge extraction. We show that optimal structures can have efficiencies as high as 45%. The quality of the Au-CdSe interface and the dimensions of the Au rod and CdSe tip are shown to be critical for achieving these high efficiencies of chemical interface damping.

Mechanism for plasmon-generated solvated electrons.

Solvated electrons are powerful reducing agents capable of driving some of the most energetically expensive reduction reactions. Their generation under mild and sustainable conditions remains challenging though. Using near-ultraviolet irradiation under low-intensity one-photon conditions coupled with electrochemical and optical detection, we show that the yield of solvated electrons in water is increased more than 10 times for nanoparticle-decorated electrodes compared to smooth silver electrodes. Based on the simulations of electric fields and hot carrier distributions, we determine that hot electrons generated by plasmons are injected into water to form solvated electrons. Both yield enhancement and hot carrier production spectrally follow the plasmonic near-field. The ability to enhance solvated electron yields in a controlled manner by tailoring nanoparticle plasmons opens up a promising strategy for exploiting solvated electrons in chemical reactions.