Plasmon-induced long-lived hot electrons in degenerately doped molybdenum oxides for visible-light-driven photochemical reactions

Plasmon-induced hot electrons offer unique advantages in solar-light-driven chemical reactions. Noble metal nanostructures have been the most studied plasmonic materials, but the hot electron lifetime is extremely short. Here, we have discovered extraordinarily long-lived hot electrons in degenerately doped molybdenum oxides with surface plasmon resonance in the visible and near-infrared region. Their lifetime is nanosecond-scale, which is enhanced by 4 orders of magnitude compared to their noble metal counterparts. Such a property is ascribed to the quasi-metallic feature of molybdenum oxides driven by hydrogen dopant-induced bandgap trap states, in which the electron–phonon scattering is dominant over the ultrafast electron–electron scattering in the decay dynamics of hot electrons. The plasmonic dye oxidation and hydrogen evolution are explored without the coupling of semiconductors, providing a viable way towards expanding the candidates for direct plasmonic photocatalysis.     

Plasmonic photoanodes for solar water splitting with visible light

We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO(2), forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.     

Probing hot electron flow generated on Pt nanoparticles with Au/TiO2 Schottky diodes during catalytic CO oxidation

Hot electron flow generated on colloid platinum nanoparticles during exothermic catalytic carbon monoxide oxidation was directly detected with Au/TiO2 diodes. Although Au/TiO2 diodes are not catalytically active, platinum nanoparticles on Au/TiO2 exhibit both chemicurrent and catalytic turnover rate. Hot electrons are generated on the surface of the metal nanoparticles and go over the Schottky energy barrier between Au and TiO2. The continuous Au layer ensures that the metal nanoparticles are electrically connected to the device. The overall thickness of the metal assembly (nanoparticles and Au thin film) is comparable to the mean free path of hot electrons, resulting in ballistic transport through the metal. The chemicurrent and chemical reactivity of nanoparticles with citrate, hexadecylamine, hexadecylthiol, and TTAB (tetradecyltrimethylammonium bromide) capping agents were measured during catalytic CO oxidation at pressures of 100 Torr O2 and 40 Torr CO at 373-513 K. We found that chemicurrent yield varies with each capping agent but always decreases with increasing temperature. We suggest that this inverse temperature dependence is associated with the influence of charging effects due to the organic capping layer during hot electron transport through the metal-oxide interface.     

Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis

Surface plasmon resonance of coinage metal nanoparticles is extensively exploited to promote catalytic reactions via harvesting solar energy. Previous efforts on elucidating the mechanisms of enhanced catalysis are devoted to hot electron‐induced photothermal conversion and direct charge transfer to the adsorbed reactants. However, little attention is paid to roles of hot holes that are generated concomitantly with hot electrons. In this work, 13 nm spherical Au nanoparticles with small absorption cross‐section are employed to catalyze a well‐studied glucose oxidation reaction. Density functional theory calculation and X‐ray absorption spectrum analysis reveal that hot holes energetically favor transferring catalytic intermediates to product molecules and then desorbing from the surface of plasmonic catalysts, resulting in the recovery of their catalytic activities. The studies shed new light on the use of the synergy of hot holes and hot electrons for plasmon‐promoted catalysis.     

Ultrafast heating and thermomechanical coupling induced by femstosecond lasers

This work focuses on the ultrafast thermomechanical waves generated by the hot electrons excited by ultrafast, ultra-intense lasers. The dominating effects during the short-time transient, including ultrafast thermalization and relaxation between electrons and phonons, result in thermomechanical coupling that cannot be described by Fourier’s law alone. The various thermomechanical properties are grouped to characterize the ultrafast heating and deformation. A finite-difference differential formulation is used as a general tool to tackle the new set of coupled equations that are formulated to describe the severe impingement of a hot-electron blast in the presence of nonequilibrium heating, rapid expansion/contraction of the metal lattices, phonon relaxation, and thermomechanical coupling.     

Plasmonic Metal Mediated Charge Transfer in Stacked Core–Shell Semiconductor Heterojunction for Significantly Enhanced CO2 Photoreduction

Construction of core–shell semiconductor heterojunctions and plasmonic metal/semiconductor heterostructures represents two promising routes to improved light harvesting and promoted charge separation, but their photocatalytic activities are respectively limited by sluggish consumption of charge carriers confined in the cores, and contradictory migration directions of plasmon-induced hot electrons and semiconductor-generated electrons. Herein, a semiconductor/metal/semiconductor stacked core–shell design is demonstrated to overcome these limitations and significantly boost the photoactivity in CO₂ reduction. In this smart design, sandwiched Au serves as a “stone”, which “kills two birds” by inducing localized surface plasmon resonance for hot electron generation and mediating unidirectional transmission of conduction band electrons and hot electrons from TiO₂ core to MoS₂ shell. Meanwhile, upward band bending of TiO₂ drives core-to-shell migration of holes through TiO₂–MoS₂ interface. The co-existence of TiO₂ → Au → MoS₂ electron flow and TiO₂ → MoS₂ hole flow contributes to spatial charge separation on different locations of MoS₂ outer layer for overall redox reactions. Additionally, reduction potential of photoelectrons participating in the CO₂ reduction is elaborately adjusted by tuning the thickness of MoS₂ shell, and thus the product selectivity is delicately regulated. This work provides fresh hints for rationally controlling the charge transfer pathways toward high-efficiency CO₂ photoreduction.     

Surface plasmon-driven hot electron flow probed with metal-semiconductor nanodiodes

A continuous flow of hot electrons that are not at thermal equilibrium with the surrounding metal atoms is generated by the absorption of photons. Here we show that hot electron flow generated on a gold thin film by photon absorption (or internal photoemission) is amplified by localized surface plasmon resonance. This was achieved by direct measurement of photocurrent on a chemically modified gold thin film of metal-semiconductor (TiO(2)) Schottky diodes. The short-circuit photocurrent obtained with low-energy photons is consistent with Fowler's law, confirming the presence of hot electron flows. The morphology of the metal thin film was modified to a connected gold island structure after heating such that it exhibits surface plasmon. Photocurrent and optical measurements on the connected island structures revealed the presence of a localized surface plasmon at 550 ± 20 nm. The results indicate an intrinsic correlation between the hot electron flow generated by internal photoemission and localized surface plasmon resonance.     

The radiation-induced galvanic effect at a metal–dielectric interface

The effect observed upon interaction between the electromagnetic radiation with quantum energy of 25–1000 eV and a dielectric with metal coating is investigated. The radiation source was a megampere Z-pinch. Measurements performed on optical glass samples showed that radiation with a power of ~10⁶ W/cm² in the electric circuit switching on the metalized dielectric induces the current. It is shown that the observed galvanic effect originates from the generation of hot electrons in the dielectric.     

Ultrathin tunnel insulator films on silicon for electrochemiluminescence studies

Thin insulating films on conductive substrates have been used for tunnel emission of hot electrons into aqueous solution. The hydrated electrons thus formed induce electrochemiluminescence (ECL) in various luminophores, e.g. rare-earth metal chelates, which can be detected in sub-nanomolar concentrations. The luminophores can be used as labels for antibodies, enabling simple and highly sensitive immunoassays. This paper compares thermal silicon dioxide, low pressure chemical vapor deposited silicon nitride, plasma enhanced chemical vapor deposited silicon dioxide and nitride, atomic layer deposited alumina, and liquid phase deposited silicon dioxide for electrodes in ECL applications.     

Progressive Design of Plasmonic Metal–Semiconductor Ensemble toward Regulated Charge Flow and Improved Vis–NIR‐Driven Solar‐to‐Chemical Conversion

Surface plasmon resonance (SPR)‐mediated photocatalysis without the bandgap limitations of traditional semiconductor has aroused significant attention in solar‐to‐chemical energy conversion. However, the photocatalytic efficiency barely initiated by the SPR effects is still challenged by the low concentration and ineffective extraction of energetic hot electrons, slow charge migration rates, random charge diffusion directions, and the lack of highly active sites for redox reactions. Here, the tunable, progressive harvesting of visible‐to‐near infrared light (vis–NIR, λ > 570 nm) by designing plasmonic Au nanorods and metal (Au, Ag, or Pt) nanoparticle codecorated 1D CdS nanowire (1D CdS NW) ensemble is reported. The intimate integration of these metal nanostructures with 1D CdS NWs promotes the extraction and manipulated directional separation and migration of hot charge carriers in a more effective manner. Such cooperative synergy with tunable control of interfacial interaction, morphology optimization, and cocatalyst strategy results in the distinctly boosted performance for vis–NIR‐driven plasmonic photocatalysis. This work highlights the significance of rationally progressive design of plasmonic metal–semiconductor‐based composite system for boosting the regulated directional flow of hot charge carrier and thus the more efficient use of broad‐spectrum solar energy conversion.     

用太阳光发电的一个新观点

当太阳光由玻璃堆变为线偏振光,再通过厚度渐变的1/4波晶片将不同波长太阳光转变为圆偏振光后,在金属细线管中传播时,传播方向的高速旋转磁场绕着被金属细线切割,金属细线中电子因洛伦茨力的作用定向运动,金属线两端产生电势,因此,实现太阳光发电的关键技术是利用纳米技术制作纳米尺寸的金属细线及金属细线管。     

Deposited dielectrics on metal thin films using silicon and glass substrates for hot electron-induced electrochemiluminescence

Electrochemiluminescence by tunnel emission of hot electrons into aqueous solution is a sensitive method for detection of luminophores e.g. rare-earth chelates, which may be used as labels in bioassays. Electrons are injected into solution from an insulating film-coated working electrode, working against a platinum counter electrode. Conductive silicon electrodes with various tunnel dielectric materials e.g. thermal oxide have been used in previous work. In this paper we explore the use of metal thin film electrodes on silicon and glass substrates, using tunneling dielectrics of aluminum oxide and silicon dioxide made by the low-temperature processes of atomic layer deposition or plasma-enhanced chemical vapor deposition.     

The effect of phonon heating on the transverse runaway of hot electrons

A study is made of the influence of phonon heating on the transverse runaway of hot electrons. Under standard conditions, in which the runaway effect is realized, the equilibrium phonon distribution may be disturbed: it is demonstrated that the phonon heating delays the transverse runaway of hot electrons.     

肖特基型光催化剂研究进展

贵金属与半导体复合形成的催化剂具备肖特基结结构,该结构具有整流特性和较低的界面电压,可以调控光生电子的产生和流向,使电子和空穴更有效地分离,提升光催化性能.综述了近年来肖特基半导体光催化剂的研究进展,分析了晶面沉积、形貌结构、表面等离子体效应及共掺杂等因素对该类催化剂性能的影响,从降解污染物、制氢、二氧化碳还原等方面阐述了这类催化剂在环境控制领域的实际应用,并提出了势垒高度、产物控制及催化剂循环利用等潜在的研究方向.肖特基型光催化剂独特的性质将使其成为新的研究热点,得到更深入的研究和应用.     

肖特基型光催化剂研究进展

贵金属与半导体复合形成的催化剂具备肖特基结结构,该结构具有整流特性和较低的界面电压,可以调控光生电子的产生和流向,使电子和空穴更有效地分离,提升光催化性能。综述了近年来肖特基半导体光催化剂的研究进展,分析了晶面沉积、形貌结构、表面等离子体效应及共掺杂等因素对该类催化剂性能的影响,从降解污染物、制氢、二氧化碳还原等方面阐述了这类催化剂在环境控制领域的实际应用,并提出了势垒高度、产物控制及催化剂循环利用等潜在的研究方向。肖特基型光催化剂独特的性质将使其成为新的研究热点,得到更深入的研究和应用。     

Hot-electron relaxation in ZnO films

The energy relaxation of hot electrons in ZnO films was investigated by the electric-field-dependent photoluminescence. From the high-energy tail of photoluminescence, the electron temperature of the hot electrons in ZnO was determined. Longitudinal optical phonon emission alone cannot explain the relationship between the electron temperature and the electron energy loss rate. Instead, it can be explained by a model based on a combination of both the acoustic and longitudinal optical phonon emissions.     

Current transport in monolithic hot-electron structures

Current transport is discussed in the context of shallow structures about 750 Å thick in silicon containing two potential barriers, one for the emission and one for the collection of hot electrons. Measurements indicate that the current gains are higher than those predicted from simplified models using field-free diffusion of hot electrons.     

Integration of Multiple Plasmonic and Co‐Catalyst Nanostructures on TiO2 Nanosheets for Visible‐Near‐Infrared Photocatalytic Hydrogen Evolution

Utilization of visible and near‐infrared light has always been the pursuit of photocatalysis research. In this article, an approach is developed to integrate dual plasmonic nanostructures with TiO₂ semiconductor nanosheets for photocatalytic hydrogen production in visible and near‐infrared spectral regions. Specifically, the Au nanocubes and nanocages used in this work can harvest visible and near‐infrared light, respectively, and generate and inject hot electrons into TiO₂. Meanwhile, Pd nanocubes that can trap the energetic electrons from TiO₂ and efficiently participate in the hydrogen evolution reaction are employed as co‐catalysts for improved catalytic activity. Enabled by this unique integration design, the hydrogen production rate achieved is dramatically higher than those of its counterpart structures. This work represents a step toward the rational design of semiconductor–metal hybrid structures for broad‐spectrum photocatalysis.     

Electron induced dissociation of hydrogen or deuterium–silicon complexes in GaAs; application to the reliability of GaAs based electronic or optoelectronic devices

The results obtained, very recently, in n-type Si-doped GaAs passivated with a hydrogen (H) or deuterium (D) plasma, on the stability of the Si–H or Si–D complexes are summarized. It is shown that a strong dissociation of the Si–H or Si–D complexes, associated with a large isotope effect is observed when hot electrons are produced or externally injected (using an electron-beam) in Si-doped hydrogenated or deuterated GaAs. The application of these results to the reliability of III–V devices is studied. The role of hot electrons is described and the device lifetime improvement, which could be obtained by using suitable thermal annealings, is discussed.     

Effects of porous silicon morphology on ballistic electron emission

Porous silicon ballistic electron emission source with a structure of metal/porous silicon/Si/metal is obtained by anodization, rapid thermal oxidation, and sputtering. The microstructures of porous silicon layers are characterized by means of scanning electron microscope. The results show that disordered pores are formed at anodization current densities of 15 mA/cm2, 30 mA/cm2, and 45 mA/cm2 for 5 min, respectively. However, straight pores are formed at anodization current densities of 60 mA/cm2, and 75 mA/cm2 for 5 min, respectively. The electron emission characteristic of porous silicon ballistic electron emission sources is measured in vacuum. The results show that electrons emitted into the vacuum from the porous silicon samples with disordered pores. Under a bias condition, injected electrons from the substrate are accelerated by the strong electric field on the surfaces of the Si nanocrystallites in disordered pores, and then emitted into the vacuum through Pt film. However, no electron emission is observed in porous silicon samples with straight pores. It attributes to the lack of Si nanocrystallites in straight pores. So there is not accelerating tunnels enough for electrons. According to disordered or straight pores, we can estimate whether PS samples emit electrons or not.