Hot Electrons Research Articles

Ab initio investigation of hot electron transfer in CO2 plasmonic photocatalysis in the presence of hydroxyl adsorbate.

Photoreduction of carbon dioxide (CO2) on plasmonic structures is of great interest in photocatalysis to aid selectivity. While species commonly found in reaction environments and associated intermediates can steer the reaction down different pathways by altering the potential energy landscape of the system, they are often not addressed when designing efficient plasmonic catalysts. Here, we perform an atomistic study of the effect of the hydroxyl group (OH) on CO2 activation and hot electron generation and transfer using first-principles calculations. We show that the presence of OH is essential in breaking the linear symmetry of CO2, which leads to a charge redistribution and a decrease in the OCO angle to 134°, thereby activating CO2. Analysis of the partial density of states (pDOS) demonstrates that the OH group mediates the orbital hybridization between Au and CO2 resulting in more accessible states, thus facilitating charge transfer. By employing time-dependent density functional theory (TDDFT), we quantify the fraction of hot electrons directly generated into hybridized molecular states at resonance, demonstrating a broader energy distribution and an 11% increase in charge-transfer in the presence of OH groups. We further show that the spectral overlap between excitation energy and plasmon resonance plays a critical role in efficiently modulating electron transfer processes. These findings contribute to the mechanistic understanding of plasmon-mediated reactions and demonstrate the importance of co-adsorbed species in tailoring the electron transfer processes, opening new avenues for enhancing selectivity.

Influence of Hot Carrier Cooling and Band‐Filling Effect on Linewidth of Perovskite Microlasers

AbstractIn semiconductor‐based microlasers, the generated excited carriers can affect both the optical absorption coefficient and refractive index, influencing the lasing behavior and device performance. In this study, the lasing behavior of individual MAPbBr3 microrods pumped by femtosecond laser pulses is investigated using an ultrafast optical Kerr gating technique. By analyzing the spectral and temporal evolution of the lasing behavior, it is found that the band‐filling (BF) effect can cause a significant change in the refractive index of the material, which results in an unfavorable red‐shift and broadening of the resonant modes, deteriorating the laser linewidth and quality factor. The hot carrier cooling process can provide a buffer for alteration of the energy level occupation state, resulting in a small transient refractive index change and slight red‐shift. These results offer insights into the lasing behavior driven by photogenerated carrier dynamics and provide an optimization strategy for semiconductor‐based microlasers.

Regulating the Phase and Optical Properties of Mixed‐Halide Perovskites via Hot‐Electron Engineering

AbstractThe rapid development of mixed‐halide perovskites has established a versatile optoelectronic platform owing to their extraordinary physical properties, but there remain challenges toward achieving highly reliable synthesis and performance, in addition, post‐synthesis approaches for tuning their photoluminescence properties after device fabrication remain limited. In this work, an effective approach is reported to leveraging hot electrons generated from plasmonic nanostructures to regulate the optical properties of perovskites. A plasmonic metasurface composed of Au nanoparticles can effectively tailor both photoluminescence and location‐specific phase segregation of mixed‐halide CsPbI2Br thin films. The ultrafast transient absorption spectroscopy measurements reveal hot electron injection on the timescale of hundreds of femtoseconds. Photocurrent measurements confirm the hot‐electron‐enhanced photon‐carrier conversion, and in addition, gate‐voltage tuning of phase segregation is observed because of correlated carrier injection and halide migration in the perovskite films. Finally, the characteristics of the gate‐modulated light emission are found to conform to a rectified linear unit function, serving as nonlinear electrical‐to‐optical converters in artificial neural networks. Overall, the hot electron engineering approach demonstrated in this work provides effective location‐specific control of the phase and optical properties of halide perovskites, underscoring the potential of plasmonic metasurfaces for advancing perovskite technologies.

Charge fluctuations on the dust grains in the presence of energetic electrons

Abstract Dust charging is an arbitrary process occurring at random times which results in fluctuations of dust charge around its equilibrium value. To have a better insight into the mechanism of charge fluctuations, a numerical simulation of the statistical nature of the dust charging process is investigated. Here, a multicomponent non-Maxwellian hydrogen plasma comprising two electron groups, positive ions, and dust grains is modelled. An increase in the overall negative dust charge number is reported in the presence of non-Maxwellian electrons. Additionally, the study emphasizes the role of electron distribution and hot electron temperature and density on the charge fluctuations of the dust grains.

Sensitivity Improvement in Gate Engineered Technique Dielectric Modulated GaN MOSHEMT with InGaN Notch for Label-Free Biosensing

Abstract This paper focuses on the impact of gate-engineered dielectric-modulated GaN MOSHEMT with InGaN notch on sensitivity enhancement for label-free biosensing. The novelty of this study utilizes the charge-plasma effect induced by the dual metal gate (DMG) technology adopted to realize the effect of sensitivity on different biomolecules. Moreover, the presence of an InGaN notch enhances carrier confinement in the 2DEG, subsequently improving the threshold voltage and device sensitivity at the AlGaN/GaN interface. The maximum drain current, IDS of 4.602 A/mm, transconductance, gm of 18 mS/mm, and sensitivity has been improved by around 61% for the Uricase biomolecule by introducing the dual metal gate technology. The work function difference of the two metal gates suppresses the Short Channel Effects (SCEs) and hot carrier effects in DMG MOSHEMT, thereby screening the drain potential variations by the gate near the drain. In addition, increased carrier transport efficiency results from a more consistent electric field along the channel. All the simulations are carried out using the Sentaurus TCAD simulator, and the results imply the feasibility of gate-engineered GaN MOSHEMT for label-free biosensing.

The impact of a dopant atom on the distribution of hot electrons and holes in Au-doped Ag nano-clusters.

The generation of hot carriers (HCs) through the excitation of localized surface plasmon resonance (LSPR) in metal nanostructures is a fascinating phenomenon that fuels both fundamental and applied research. In this study, we employ first principles real-time time-dependent density-functional theory (rt-TDDFT) calculations to elucidate the creation and distribution of HCs within Au-doped Ag nanoclusters: Ag11Cl3P7H21, Ag10AucoreCl3P7H21, and Ag10AusurfCl3P7H21 nanoclusters. Our findings indicate that adjustments in HC distribution are achievable through the Au dopant atom, and precise control of HC distribution is possible by manipulating the location of the Au dopant atom. When employing a Gaussian laser pulse tailored to match the LSPR frequency, a substantial accumulation of HCs in the Ag-P bond is observed. This finding suggests a weakening of the Ag-P bonds and, consequently, the initiation of bond stretching. We propose that these findings open up possibilities for tuning HCs in Au-doped chemically functionalized Ag nanoclusters.

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.

Small amplitude solitary electron acoustic wave for hot electrons taking regularized kappa distribution

AbstractThe properties of small‐amplitude solitary electron acoustic waves in a plasma where the hot electrons take regularized kappa distribution are investigated via the reductive perturbation method. It is found there only exists the sup‐electron‐acoustic rarefactive soliton, the electron acoustic velocity is modified by the regularized kappa distribution. The amplitude and width of the electron acoustic soliton decrease monotonously with the increase of the exponential cutoff parameter of hot electrons. But they vary with respect to the spectral index non‐monotonously. As to the observed parameters in the Earth's inner magnetosphere, the speed, electric field strength, and the width of solitary electron acoustic wave are comparable with the observations.

Electric-Tree Resistant Performance and Thermal Charge-Carrier Dissipation Mechanism of Voltage Stabilizer-Modified EPDM

Abstract In order to improve electric-tree resistant performance and dielectric breakdown strength of ethylene-propylene-diene misch-polymere (EPDM) material used for cable accessory reinforce insulation, the two specific aromatic ketone compounds – vinylphenylacetone (VPE) and 4-propylene oxyxy-2-hydroxydibenzenone (AOHBP) are employed as two paradigms of voltage stabilizer for chemical-graft modifications. Electric-tree resistances and insulation performances of modified EPDM materials and their charge trapping mechanism of thermoelectron inhibitions are studied by the accelerated electric-tree aging experiments, alternating current (AC) dielectric breakdown tests, surface potential trap-level analyses and first-principles calculations. Both the two species of voltage stabilizers are effective for promoting electric-tree inception voltage and dielectric breakdown strength, leading to a high extension of electric-tree morphology and smaller dimension of electric-trees growth, in which AOHBP is more significant. The AOHBP and VPE represent a high electron affinity and a small electronic energy gap, which is competent of assimilating the kinetic energies of hot charge carriers whilst restricting Auger electronic excitation. Especially, the benzene group in voltage stabilizer renders shallow level charge traps with a larger carrier capture cross-section than deep traps and simultaneously possesses high atomic vibration frequencies similar as electronic-transition energies, which results in effective dissipation on the kinetic energies of hot charge carriers.

Fabrication of thin film solar cell based on CoO-CoS/P2-Amino-1-mercaptobenzene/polypyrrole with additional promising sensitivities to photons in a broad optical region

The production of a thin-film solar cell device, employing CoO-CoS/P2-Amino-1-mercaptobenzene/polypyrrole (CoO-CoS-P2AMB/Ppy), showcases enhanced sensitivity across a broad optical spectrum. This achievement is realized through a one-pot polymerization process involving 2-Amino-1-mercaptobenzene, Co(NO3)2, and K2S2O8. Notably, the polymerization reaction incorporates the inclusion of a Ppy seeding layer into the solution. To comprehensively characterize the synthesized materials, an array of analytical tools is employed. Subsequently, the CoO-CoS-P2AMB/Ppy device undergoes rigorous testing under diverse light conditions, including darkness, white light, and monochromatic light. These conditions aim to assess the device’s responsiveness to photons of varying energies, where the resulting current density (Jph) serves as an indicator of generated hot electrons and the overall efficiency of the fabricated device. At a potential of 2.0 V, the measured values for Jph and dark current (Jo) stand at 0.11 and 0.04 mA.cm−2, respectively. The solar cell characteristics are further evaluated through measured values for JSC (−0.01 μA.cm−2) and VOC (0.038 V), reflecting the device’s performance under solar testing conditions. In addition to its solar cell attributes, the device exhibits light-sensing behavior, quantified through calculated photoresponsivity (R) and detectivity (D) values. These values, obtained under various monochromatic lights, amount to 0.49 mA.W−1 and 1.1 × 108 Jones, respectively. The exceptional performance of the CoO-CoS-P2AMB/Ppy thin-film solar cell device, coupled with its light-sensing capabilities, positions the device as a promising candidate for commercial applications. Its potential extends to the fabrication of cost-effective thin-film sensing devices, presenting opportunities for widespread utilization in various industries.

Hot carrier photocurrent induced by 0.92 eV photon energy radiation in a Si solar cell

Absorption of the below-bandgap solar radiation and direct pre-thermalizational impact of a hot carrier (HC) on the operation of a single-junction solar cell are ignored by the Shockley-Queisser theory. The detrimental effect of the HC is generally accepted only via the thermalization-caused heating of the lattice. Here, the authors demonstrate experimental evidence of the HC photocurrent induced by the below-bandgap 0.92 eV photon energy radiation in an industrial silicon solar cell. The carriers are heated both through direct free-carrier absorption and by residual photon energy remaining after the electron-hole pair generation. The polarity of the HC photocurrent opposes that of the conventional generation photocurrent, indicating that the total current across the p-n junction is contingent upon the interplay between these two currents. A model of current-voltage characteristics analysis allowing us to obtain a reasonable value of the HC temperature was also proposed. This work is remarkable in two ways: first, it contributes to an understanding of HC phenomena in photovoltaic devices, and second, it prompts discussion of the HC photocurrent as a new intrinsic loss mechanism in solar cells.

Engineering Metal Halide Perovskite Nanocrystals with BODIPY Dyes for Photosensitization and Photocatalytic Applications.

The sensitization of surface-anchored organic dyes on semiconductor nanocrystals through energy transfer mechanisms has received increasing attention owing to their potential applications in photodynamic therapy, photocatalysis, and photon upconversion. Here, we investigate the sensitization mechanisms through visible-light excitation of two nanohybrids based on CsPbBr3 perovskite nanocrystals (NC) functionalized with borondipyrromethene (BODIPY) dyes, specifically 8-(4-carboxyphenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) and 8-(4-carboxyphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (I2-BDP), named as NC@BDP and NC@I2-BDP, respectively. The ability of I2-BDP dyes to extract hot hole carriers from the perovskite nanocrystals is comprehensively investigated by combining steady-state and time-resolved fluorescence as well as femtosecond transient absorption spectroscopy with spectroelectrochemistry and quantum chemical theoretical calculations, which together provide a complete overview of the phenomena that take place in the nanohybrid. Förster resonance energy transfer (FRET) dominates (82%) the photosensitization of the singlet excited state of BDP in the NC@BDP nanohybrid with a rate constant of 3.8 ± 0.2 × 1010 s-1, while charge transfer (64%) mediated by an ultrafast charge transfer rate constant of 1.00 ± 0.08 × 1012 s-1 from hot states and hole transfer from the band edge is found to be mainly responsible for the photosensitization of the triplet excited state of I2-BDP in the NC@I2-BDP nanohybrid. These findings suggest that the NC@I2-BDP nanohybrid is a unique energy transfer photocatalyst for oxidizing α-terpinene to ascaridole through singlet oxygen formation.

Simultaneous and observations of the ultraluminous source NGC 4190 ULX-1

We present an X-ray analysis of three different XMM-Newton observations together with simultaneous and observations of the ultraluminous X-ray source NGC 4190 ULX-1. Our goal is to constrain the structure of the accretion disk and the geometrical properties of the source. We performed temporal and spectral analyses in the 0.4--30 keV energy range in which the source is significantly detected in dedicated XMM-Newton and NuSTAR observations. The temporal analysis shows no flaring activity in the light curves. No pulsation is detected throughout. The source exhibits a typical ULX spectrum, which can be fitted with two thermal blackbody components plus a Comptonization tail at high energies. The luminosity-temperature ($L-T$) relation of each thermal spectral component is consistent with the $L $ relation expected from an advection-dominated supercritical disk. We interpret these results as a super-Eddington accreting black hole seen almost face-on. A dense wind ejected from the disk obscures the central source, and a hot electron plasma is evacuated through the funnel formed above the hole. Geometric beaming is responsible for the ULX soft emission, whereas the hard tail is the result of the Comptonization of soft photons by the electrons ejected through the funnel.

Three-Dimensionally Nanometallic Superstructure Synthesized via a Single-Particle Soft-Enveloping Strategy.

Three-dimensionally (3D) integrated metallic nanomaterials composed of two or more different types of nanostructures make up a class of advanced materials due to the multidimensional and synergistic effects between different components. However, designing and synthesizing intricate, well-defined metallic 3D nanomaterials remain great challenges. Here, a novel single-particle soft-enveloping strategy using a core-shell Au NP@mSiO2 particle as a template was proposed to synthesize 3D nanomaterials, namely, a Au nanoparticle@center-radial nanorod-Au-Pt nanoparticle (Au NP@NR-NP-Pt NP) superstructure. Taking advantage of the excellent plasmonic properties of Au NP@NR-NP by the synergistic plasmonic coupling of the outer Au NPs and inner Au nanorods, we can enhance the catalytic performance for 4-nitrophenol hydrogenation using Au NP@NR-NP-Pt NP as a photocatalyst with plasmon-excited hot electrons from Au NP@NR-NP under light irradiation, which is 2.76 times higher than in the dark. This process opens a door for the design of a new generation of 3D metallic nanomaterials for different fields.

Construction of piezoelectric photocatalyst Au/BiVO4 for efficient degradation of tetracycline and studied at single-particle level

Piezopotential-assisted catalysis has been proven to be a low-cost and high-efficiency environmental purification process. Herein, Au/bismuth vanadate (BiVO4) piezoelectric photocatalysts are prepared by modifying highly dispersed Au nanoparticles (AuNPs) on piezoelectric BiVO4 microcrystal by a deposition-precipitation approach. Under visible light irradiation and assisted ultrasound excitation, the removal rate of tetracycline was 95% within 60 min, demonstrating the optimum photocatalytic performance over 3Au/BiVO4. The significantly enhanced photocatalytic performance is due to the synergistic coupling of plasmonic and piezotronic effect based on facet engineering. Single-particle spectroscopy technology can provide photoluminescence (PL) lifetime and PL spectra information in the micro-/nano regions, thereby exploring the charge transfer behavior of heterostructures. Single-particle PL images revealed a significant attenuation of PL emission and shortened PL lifetime of 3Au/BiVO4, compared with BiVO4, indicating that high-density dispersed AuNPs promote charge transfer. In situ monitoring of individual BiVO4 and 3Au/BiVO4 particles before and after polarization treatment confirms that the piezoelectric field of the BiVO4 decahedron further promotes separation of photogenerated carriers induced by plasmonic effect. Driven by the piezoelectric potential induced by ultrasonic vibration near the heterostructures, high-energy hot electrons excited on plasmonic AuNPs can be effectively extracted to BiVO4. This work provides new choices for designing high-performance pollutant treatment catalysts.

Real-Time Ab Initio Investigation on Hot Electron Relaxation Dynamics in Silicon.

The relaxation of hot electrons in semiconductors is pivotal for both energy harvesting processes and optoelectronics. Utilizing a self-developed non-adiabatic molecular dynamics simulation approach in the momentum space (NAMD_k), we have examined the dynamics of hot electrons in silicon. Whether excited from the Γ or L point, the relaxation dynamics exhibit two distinct stages. Initially, within 100 fs, electrons scatter with phonons throughout the Brillouin zone. Subsequently, over a few picoseconds, they further relax toward the conduction band minimum as a whole. This picture of hot electron relaxation is highly consistent with the quasi-equilibrium hot electron ensemble (HEE) concept. Throughout the hot electron relaxation process, energy transfer to phonons is efficient, leading to time-dependent phonon excitation, which is thoroughly analyzed. This investigation provides a novel perspective on hot electron relaxation in silicon, which holds substantive implications for the realm of photovoltaic and optoelectronic device applications.

Photoexcited Hot Electron Catalysis in Plasmon-Resonant Grating Structures with Platinum, Nickel, and Ruthenium Coatings.

We report the electrochemical potential dependence of photocatalysis produced by hot electrons in plasmon-resonant grating structures. Here, corrugated metal surfaces with a period of 520 nm are illuminated with 785 nm wavelength laser light swept as a function of incident angle. At incident angles corresponding to plasmon-resonant excitation, we observe sharp peaks in the electrochemical photocurrent and dips in the photoreflectance consistent with the conditions under which there is wavevector matching between the incident light and the spacing between the lines in the grating. In addition to the bare plasmonic metal surface (i.e., Au), which is catalytically inert, we have measured grating structures with a thin layer of Pt, Ru, and Ni catalyst coatings. For the bare Au grating, we observe that the plasmon-resonant photocurrent remains relatively featureless over the applied potential range from -0.8 to +1.2 V vs NHE. For the Pt-coated grating, we observe a sharp peak around -0.3 V vs NHE, three times larger than the bare Au grating, and near complete suppression of the oxidation half-reaction, reflecting the reducing nature of Pt as a good hydrogen evolution reaction catalyst. The photocurrent associated with the Pt-coated grating is less noisy and produces higher photocurrents than the bare Au grating due to the faster kinetics (i.e., charge transfer) associated with the Pt-coated surface. The plasmon-resonant grating structures enable us to compare plasmon-resonant excitation with that of bulk metal interband absorption simply by rotating the polarization of the light while leaving all other parameters of the experiment fixed (i.e., wavelength, potential, electrochemical solution, sample surface, etc.). A 64X plasmon-resonant enhancement (i.e., p-to-s polarized photocurrent ratio) is observed for the Pt-coated grating compared to 28X for the bare grating. The nickel-coated grating shows an increase in the hot-electron photocurrent enhancement in both oxidation and reduction half-reactions. Similarly, Ru-coated gratings show an increase in hot-electron photocurrents in the oxidation half-reaction compared to the bare Au grating. Plasmon-resonant enhancement factors of 36X and 15X are observed in the p-to-s polarized photocurrent ratio for the Ni and Ru gratings, respectively.

H-Glass Supported Hybrid Gold Nano-Islands for Visible-Light-Driven Hydrogen Evolution.

Flat panel reactors, coated with photocatalytic materials, offer a sustainable approach for the commercial production of hydrogen (H2) with zero carbon footprint. Despite this, achieving high solar-to-hydrogen (STH) conversion efficiency with these reactors is still a significant challenge due to the low utilization efficiency of solar light and rapid charge recombination. Herein, hybrid gold nano-islands (HGNIs) are developed on transparent glass support to improve the STH efficiency. Plasmonic HGNIs are grown on an in-house developed active glass sheet composed of sodium aluminum phosphosilicate oxide glass (H-glass) using the thermal dewetting method at 550°C under an ambient atmosphere. HGNIs with various oxidation states (Au0, Au+, and Au-) and multiple interfaces are obtained due to the diffusion of the elements from the glass structure, which also facilitates the lifetime of the hot electron to be ≈2.94ps. H-glass-supported HGNIs demonstrate significant STH conversion efficiency of 0.6%, without any sacrificial agents, via water dissociation. This study unveils the specific role of H-glass-supported HGNIs in facilitating light-driven chemical conversions, offering new avenues for the development of high-performance photocatalysts in various chemical conversion reactions for large-scale commercial applications.

One-dimensional, multi-fluid model of the plasma wall transition. I. Hot electrons

The plasma-wall transition in a plasma containing singly charged positive ions and two groups of electrons is studied with a one-dimensional steady-state multifluid model, which is presented in some detail. When the temperature and the initial density ratio between the two groups of electrons are varied, a transition between the two types of solutions to the model equations is observed. When the density and temperature of the hot electrons are above certain critical values, a high solution is observed. If the ion mass is decreased, these critical values increase. However, this effect only occurs with artificially small ion masses, which are significantly lower than the proton mass. In the high solution, the potential drop is determined by the hot electrons and is greater in absolute terms than in the low solution, where it is determined by the base electron population. The transition between the low and high solutions is very sharp if a neutrality condition is imposed. However, if the neutrality condition is replaced by the Poisson equation, the transition becomes blurred and the solutions exhibit oscillations. The temperature profiles of the ions are analyzed, and it is confirmed that the ion sound and the ion fluid velocity become equal at the breaking point of the plasma neutrality. It is shown how the ion source term, the initial ion velocity, and the initial electric field are found to be self-consistent. The density profiles of the negatively biased particles resulting from the fluid equations deviate very little those of from the Boltzmann-distributed particles, even if the corresponding source terms are quite large.

Double S-scheme Cu2−xSe/twinned-Cd0.5Zn0.5S homo-heterojunctions with surface plasmon effects for efficient photocatalytic H2 evolution

The enhancement of charge separation and utilization efficiency in both the bulk phase and interface of semiconductor photocatalysts, as well as the expansion of light absorption range, are crucial research topics in the field of photocatalysis. To address this issue, twinned Cd0.5Zn0.5S (T-CZS) homojunctions consisting of wurtzite Cd0.5Zn0.5S (WZ-CZS) and zinc blende Cd0.5Zn0.5S (ZB-CZS) were synthesized via a hydrothermal method to facilitate the bulk-phase charge separation. Meanwhile, Cu2−xSe with localized surface plasmon resonance effect (LSPR) generated by Cu vacancies was also obtained through a hydrothermal process. Due to their opposite electronegativity, a solvent evaporation strategy was employed to combine Cu2−xSe and T-CZS by intermolecular electrostatic. After optimization, the photocatalytic hydrogen (H2) evolution rate of 5 wt% Cu2−xSe/T-CZS reached an impressive value of 60 mmol∙h−1∙g−1, which was 4.6 and 66.6 times higher than that of pure Cu2−xSe and T-CZS, respectively. Furthermore, this composites demonstrated a remarkable rate of 0.46 mmol∙h−1∙g−1 under near-infrared (NIR) wavelength (>800 nm). The enhanced performance observed in Cu2−xSe/T-CZS can be attributed to its unique and efficient double S-scheme charge transfer mechanism which effectively suppresses rapid recombination of electron-hole pairs both within the bulk phase and at the surface interfaces; this conclusion is supported by Density Functional Theory (DFT) calculations as well as electron paramagnetic resonance spectroscopy analysis. Moreover, incorporation of Cu2−xSe enables effective utilization ultraviolet visible-near infrared (UV–Vis-NIR) light by the composites while facilitating injection “hot electrons” into T-CZS for promoting photocatalytic reactions. This study provides a potential strategy for achieving efficient solar energy conversion through synergistic integration of non-stoichiometric plasmonic materials with photocatalysts with twinned-twinned structures.