Hot Electrons Research Articles

Interface Engineering for Efficient Photocarrier Generation and Transfer in Strongly Coupled Metallic/Semiconducting 1T'/2H MoS2 Heterobilayers.

Developing alternative two-dimensional (2D) metallic/semiconducting (M/S) van der Waals heterostructures (vdWHs) along with an understanding of interfacial photocarrier behavior is crucial for designing high-performance optoelectronic devices. Here, we comprehensively explored the photophysical model of photocarrier generation and interfacial transfer in as-grown 2D 1T'/2H MoS2 vdWHs using various spectroscopic characterizations. We demonstrated the transitions of activated photocarrier transfer trajectories by tuning the pump photon energies across the 2H MoS2 bandgap. The importance of confined bilayer transfer systems and strong interlayer coupling at vdW interfaces for transfer efficiency was elucidated. Additionally, the fluorophlogopite substrate was found to be an external method for regulating photocarrier generation in individual 2H layers through the p-doping effect at the substrate-2H layer interfaces, and this influence was alleviated after introducing the 2H-1T' vdW interface. Particularly, 1T' MoS2 as a broadband hot carrier absorber enabled the ultrafast (∼133 fs) injection and extraction of energetic hot carriers into the 2H layer via a photothermionic emission mechanism, achieving a high efficiency of ∼41% under 900 nm photoexcitation at room temperature. Our work offers fundamental insights into the complex interfacial carrier photophysics in 2D M/S vdWHs, providing a way of constructing advanced multifunctional devices by using these emerging materials as active components and interface engineering.

Polypyrrole-bismuth tungstate/polypyrrole core-shell for optoelectronic devices exhibiting Schottky photodiode behavior.

A polypyrrole-bismuth tungstate (Ppy-Bi2WO6) core-shell nanocomposite (n-type material) has been developed on a layered Ppy (p-type) base as an efficient light-capturing material exhibiting photodiode behavior. This device demonstrates promising sensitivity for light sensing and captures across a broad spectral range, from near IR to UV. The Bi2WO6/Ppy nanocomposite boasts an optimal bandgap of 2.0eV, compared to 3.4eV for Ppy and 2.5eV for Bi2WO6. The crystalline size of the core-shell composite is approximately 21nm, emphasizing its photon absorption capabilities. The composite particles, around 100nm in length, feature a highly porous morphology that effectively traps incident photons. The performance of this optoelectronic device is evaluated using current density (J) measurements under light (Jph) and dark (Jo) conditions. In darkness, the n-p type semiconductor exhibits limited current with a Jo of -0.22mA cm-2 at 2.0V. When exposed to white light, the Ppy- Bi2WO6/Ppy device generates hot electrons, achieving a Jph value of 1.1mA/cm-2 at 2.0V. It shows a superior responsivity (R) of 6.6mA/W at 340nm, gradually decreasing to 6.3mA/W at 440nm and 4.2mA/W at 540nm, indicating high sensitivity across the UV-Vis spectrum. At 730nm, the R-value is 2.6mA/W, highlighting its sensitivity in the near IR region. Additionally, at 340nm, the device achieves a detectivity (D) value of 0.15 × 10¹⁰ Jones, which decreases with longer wavelengths to 0.14 × 10¹⁰ Jones at 440nm, 0.9 × 10⁹ Jones at 540nm, and 0.63 × 10⁹ Jones at 730nm. With its great stability, low cost, easy fabrication, and potential for mass production, this optoelectronic light sensor and photodiode device holds significant promise for industrial applications as a highly effective optoelectronic device.

Hot carrier transfer from plasmon decay in Ag20at H-Si(111) surface: real-time TDDFT simulation in Wannier gauge.

Plasmon decay is believed to play an essential role in inducing hot carrier transfer at the interfaces between plasmonic nanoparticles and semiconductor surfaces. In this work, we employ real-time time-dependent density functional theory (RT-TDDFT) simulation in the Wannier gauge to gain quantum-mechanical insights into the nonlinear dynamics of the plasmon decay in the Ag20nanoparticle at a semiconductor surface. The first-principles simulations show that the plasmon decay is more than two times faster when the Ag20nanoparticle is adsorbed on a hydrogen-terminated Si(111) surface, taking place within 100 femtoseconds of the plasmon excitation. Hot carrier transfer across the interface is observed as the plasmon decay takes place, and nearly 30% of holes are generated deep in the valence band of the semiconductor surface. The use of Wannier gauge in RT-TDDFT simulation is particularly convenient for gaining quantum-mechanical insights into non-equilibrium electron dynamics in complex heterogeneous systems.

Hot carrier solar cells by adiabatic cooling

Hot carrier solar cell is proposed where charge carriers are cooled adiabatically in the charge transport layers adjoining the absorber. The device resembles an ideal thermoelectric converter where thermopower and therefore also carrier entropy are maintained constant during cooling from the temperature attained in the absorber to the temperature at contacts.

Ultrafast dynamics of two-dimensional electron gas at Al2O3/SrTiO3 interface studied by surface terahertz spectroscopy.

Two-dimensional electron gas (2DEG) confined at the interface of SrTiO3-based heterostructure exhibits intriguing electronic and optoelectronic properties. In this work, we study the ultrafast dynamics of 2DEG at the Al2O3/SrTiO3 interface using surface-specific terahertz difference-frequency spectroscopy. Through proper polarization selection, we have resolved simultaneously the evolution of 2DEG confined in the quantum well and the surface potential after optical pump with different photon energies. The hot electrons excited from 2DEG with pump photon energy below the band gap relax to the ground state through two processes, a fast interfacial process associated with electron-electron and electron-phonon scattering on the order of tens of picoseconds and a slow surface-to-bulk transport on the order of hundreds of picoseconds. When the pump photon energy exceeds the bandgap, electrons are directly injected from the valence band to 2DEG at the interface and relax via electron-hole recombination in 3ps. The recorded dynamic change of interfacial potential provides the key information to identify the drift and diffusion of photocarriers at the interface. Our results broaden the horizon of investigation on the comprehension of complex oxide interfaces and their photonics capabilities.

Generation of 10 kT axial magnetic fields using multiple conventional laser beams: A sensitivity study for kJ PW-class laser facilities

Strong multi-kilotesla magnetic fields have various applications in high-energy density science and laboratory astrophysics, but they are not readily available. In our previous work [Y. Shi et al., Phys. Rev. Lett. 130, 155101 (2023)], we developed a novel approach for generating such fields using multiple conventional laser beams with a twist in the pointing direction. This method is particularly well-suited for multi-kilojoule petawatt-class laser systems like SG-II UP, which are designed with multiple linearly polarized beamlets. Utilizing three-dimensional kinetic particle-in-cell simulations, we examine critical factors for a proof-of-principle experiment, such as laser polarization, relative pulse delay, phase offset, pointing stability, and target configuration, and their impact on magnetic field generation. Our general conclusion is that the approach is very robust and can be realized under a wide range of laser parameters and plasma conditions. We also provide an in-depth analysis of the axial magnetic field configuration, azimuthal electron current, and electron and ion orbital angular momentum densities. Supported by a simple model, our analysis shows that the axial magnetic field decays owing to the expansion of hot electrons.

Core–Shell–Satellite Au@CeO2–Pd Plasmonical Photocatalysts for Suzuki–Miyaura Coupling Reaction

ABSTRACTIntegration of localized surface plasmon resonance (LSPR) metallic nanocrystals into photocatalysis is an intriguing approach for light‐driven organic transformations. However, uncertain direction of hot carriers is a grand challenge, which fails to take full advantage of the LSPR excitation. In this work, core–shell gold@ceria nanosphere–supported segregated palladium species (Au@CeO2–Pd) have developed to steer the light absorption capability and charge carrier migration. Under simulated solar light irradiation, the core–shell–satellite Au@CeO2–Pd exhibited efficient light harvesting and colossal activity in the Suzuki coupling reaction. The plasmon‐induced hot electrons overpassed the Schottky barrier at the Au@CeO2 interfaces and migrated from Au core to CeO2 shell accordingly. Subsequently, the photogenerated electrons and hot electrons migrated from Au@CeO2 core–shells to Pd, which acted as an electron acceptor. Detailed photocatalytic mechanism studies revealed that both photoexcited electrons and holes were the main active species involved in the photocatalytic Suzuki coupling reaction process. In particular, the diphenyl yield over Au@CeO2–Pd catalyst was ~1.7 times higher than that of core–shell–satellite Au@SiO2–Pd, where a 19‐nm‐thick SiO2 shell was introduced to prevent the migration of hot electrons. This distinctly certified that the hot electrons transfer in the core–shell–satellite Au@CeO2–Pd under illumination played an important role to drive Suzuki reaction. Overall, this design of core–shell–satellite Au@CeO2–Pd plasmonic photocatalyst has the potential in the field of photo‐driven organic transformations.

Constructing an Active Sulfur-Vacancy-Rich Surface for Selective *CH3-CH3 Coupling in CO2-to-C2H6 Conversion With 92% Selectivity.

To achieve high selectivity in photocatalytic CO2 reduction to C2+ products, increasing the number of CO2 adsorption sites and lowering the energy barriers for key intermediates are critical. A ZnIn2S4 (ZIS)/MoO3-x (Z-M) photocatalyst is presented, in which plasmonic MoO3-x generates hot electrons, creating a multielectron environment in ZIS that facilitates efficient C─C coupling reactions. Density functional theory (DFT) calculations reveal that MoO3-x reduces the formation energy of sulfur vacancies (SV) in ZIS, thereby enhancing CO2 adsorption and activation. The SV-rich surface lowers the energy barrier for forming HCOO* to -0.33 eV whereas the energy barrier for forming *COOH is 0.77 eV. Successive hydrogenation of HCOO* leads to *CH2, which converts to *CH3 with an energy barrier of -0.63 eV. The energy barrier for *CH3-CH3 coupling is 0.54 eV, which is lower than the 0.73 eV for *CH2-CH2 coupling to form *C2H4. Thus, Z-M preferentially produces C2H6 over C2H4. Under visible light, Z-M achieves a CO2-to-C2H6 conversion rate of 467.3 µmol g-1 h-1 with 92.0% selectivity. This work highlights the dual role of plasmonic photocatalysts in enhancing CO2 adsorption and improving C2+ production in CO2 reduction.

Electronic Coupling Between Perovskite Nanocrystal and Fullerene Modulates Hot Carrier Capture

AbstractThe efficient harnessing of hot carriers holds transformative potential for next‐generation optoelectronic devices. Halide perovskites, with their remarkably long carrier lifetimes exceeding 10 picoseconds, stand at the forefront of this research frontier. Yet, a fundamental paradox persists: why does efficient hot carrier capture remain elusive despite these extended lifetimes? Here, this conundrum is unraveled by constructing a donor–acceptor model system: perovskite nanocrystal and fullerene hybrids. It is demonstrated that the challenge lies not only in the carrier lifetime itself but in the nature of the coupling between donor and acceptor components. Remarkably, it is discovered that the formation of ground‐state complexes, with effective coupling across a wide energy range, not only overcomes the initially forbidden hot carrier capture within these hybrids but also dramatically enhances it, achieving a ≈76% hot carrier capture efficiency. This finding shifts the paradigm of hot carrier capture from extending carrier lifetimes to engineering donor–acceptor coupling, illuminating a path toward practical hot carrier applications.

Ultrafast terahertz conductivity in epitaxial graphene nanoribbons: an interplay between photoexcited and secondary hot carriers

Abstract Optical pump-terahertz probe spectroscopy has been used to investigate ultrafast photo-induced charge carrier transport in 3.4 µm wide graphene ribbons upon scaling the optical pump intensity. For low pump fluences, the deposited pump energy is rapidly redistributed through carrier-carrier scattering, producing secondary hot carriers: the picosecond THz photoconductivity then acquires a negative sign and scales linearly with an increasing pump fluence. At higher fluences, there are not enough equilibrium carriers able to accept the deposited energy, directly generated (excess) carriers start to contribute significantly to the photoconductivity with a positive sign leading to its saturation behavior. This leads to a non-monotonic variation of the carrier mobility and plasmonic resonance frequency as a function of the pump fluence and, at high fluences, to a balance between a decreasing carrier scattering time and an increasing Drude weight. In addition, a weak carrier localization observed for the polarization parallel to the ribbons at low pump fluences is progressively lifted upon increasing the pump fluence as a result of the rise of initial carrier temperature.

Distinguishing Inner and Outer-Sphere Hot Electron Transfer in Au/p-GaN Photocathodes.

Exploring nonequilibrium hot carriers from plasmonic metal nanostructures is a dynamic field in optoelectronics, with applications including photochemical reactions for solar fuel generation. The hot carrier injection mechanism and the reaction rate are highly impacted by the metal/molecule interaction. However, determining the primary type of reaction and thus the injection mechanism of hot carriers has remained elusive. In this work, we reveal an electron injection mechanism deviating from a purely outer-sphere process for the reduction of ferricyanide redox molecule in a gold/p-type gallium nitride (Au/p-GaN) photocathode system. Combining our experimental approach with ab initio simulations, we discovered that an efficient inner-sphere transfer of low-energy electrons leads to an enhancement in the photocathode device performance in the interband regime. These findings provide important mechanistic insights, showing our methodology as a powerful tool for analyzing and engineering hot-carrier-driven processes in plasmonic photocatalytic systems and optoelectronic devices.

TiN/TiO2 embedded in ReS2 nanoflowers with wide light absorption and multi-interfacial charge transfer for efficient photocatalytic hydrogen generation

The design of functional materials with efficient light absorption and charge separation is crucial for photocatalytic energy conversion. Herein, a plasmonic TiN/TiO2/ReS2 ternary hybrid is prepared, which exhibits exceptional photocatalytic activity caused by the plasmon-mediated light absorption and multi-interfacial charge separation. The ternary hybrids were synthesized by heating TiN, Re, and S sources at high pressure and temperature. The TiN was partially oxidized to form TiN/TiO2 hybrids, which were then embedded in ReS2 nanoflowers through Ti-S bonds, creating a 3D flower-like structure with multiple interfaces. The plasmon resonance of TiN and the bandgap excitations of ReS2 and TiO2 endow the hybrids with efficient light absorption in UV–VIS-NIR region. Additionally, the novel embedded structure and the multiple interfaces between TiN, TiO2, and ReS2 facilitate the formation of built-in electric fields and multi-channel charge transfer, which efficiently quicken photoinduced carriers’ migration and hot electron injection. Consequently, the TiN/TiO2/ReS2 hybrids demonstrate a high-efficiency photocatalytic hydrogen generation rate, which is 12.1 times that of commercial P25. Notably, the hybrids also exhibit high photocatalytic activity under near-infrared light irradiation. This study offers innovative insights into the design of photocatalysts and suggests that the prepared materials could be utilized in solar-driven energy conversion applications.

Kinetics of optical phonons and DP depolarization of spins in drift transport: Hot carrier spin effect in semiconductors

<p>Spin-<strong>c</strong>onserving transport of carriers is an essential requirement for the practical semiconductor-based spintronic devices. Kinetics of optical phonons and Dyakonov-Perel (DP) depolarization of spins in drift transport in semiconductor gallium arsenide (GaAs) is theoretically investigated<strong>. </strong>We consider electrons in <em>n</em>-type bulk GaAs subjected to a strong electric field, where the electron distribution is assumed to be drifted Maxwellian. The momentum drift of this distribution results in the enhanced drift velocity, and electrons with the corresponding energy emit optical hot phonons in the drifting process. The hot phonons are incorporated via the longitudinal polar optical phonon (POP) mechanism in the momentum relaxation. It is found that a finite phonon lifetime can reduce the momentum relaxation rate, which results in a delay in the runaway to higher fields, where the effect increases with the electron density. The electron spin is found to relax with the DP relaxation frequencies, and the DP spin lifetimes are found to decrease with increasing the drift field. However, a high field completely depolarizes the electron spin due to an increase of the DP spin precession frequency of the hot electrons in the POP scattering process. It is also found that the DP spin precession frequency decreases with decreasing electron temperature or increasing electron density in the moderate range. However, the findings resulting from this investigation demonstrate the hot carrier effect in the spin transport in semiconductors. The results are discussed in comparison with those obtained in earlier experimental and theoretical studies with different approaches.</p>

Balancing the elementary steps via photo-assisted thermal catalysis for boosting propane dehydrogenation

Balancing kinetics behavior is a significant priority in chemical reactions especially involving two or more elementary steps. Propane dehydrogenation (PDH), usually involves a slower 2nd C-H activation step at a low temperature, resulting in heat waste for overcoming a higher energy barrier of the 2nd dehydrogenation. Herein, we develop one Photo-assisted Thermal PDH process (PTPDH) based on PtZn clusters encapsulated in porous MFI zeolite, which effectively balances the kinetic elementary steps via exciting the ground state electrons of the active sites to the positively charged -C3H7 fragments, achieving a 23.4 % growth ratio (from 39.6 to 51.3·10−8 mol·g−1·s−1) with the assistance of ∼5 suns light intensity at 400 °C. The comparison between the temperature-dependent and light intensity-dependent kinetic parameters confirmed that the non-thermal effect instead of the photo-to-thermal effect dominates the PTPDH process. Furthermore, the Lewis acidity-activity correlation experiments, in-situ radiation mass spectrometry and the H2 co-feeds experiment indicate that the hot electrons instead of the holes play a more significant role in propylene production. Last, the in-situ Drifts-MS technique and DFT calculations demonstrate light radiation conduce to the electron transition from metal to the unpopulated electronic states of -C3H7 fragments, while not conducing to the adsorbed C3H8 molecule, thus selectively promoting the 2nd dehydrogenation process and achieving a balanced chemical kinetic condition. Our findings demonstrate that Photo-assisted Thermal PDH is a promising method for balancing the 1st and 2nd dehydrogenation processes.

Au/Ag@ZnS yolk-shell photocatalysts enhanced with noble metals and hyaluronic acid for efficient hydrogen production in rheumatoid arthritis therapy

Rheumatoid arthritis, characterized by the abnormal proliferation of synovial cells and extensive macrophage infiltration, is a chronic inflammatory disease. Molecular hydrogen, known for its antioxidant properties, has shown promise in eliminating reactive oxygen species. However, the low solubility and bioavailability of hydrogen limit the effectiveness of this therapy. To overcome these issues, we developed a novel yolk-shell heterostructure, H-AAZS (Au/Ag@ZnS modified hyaluronic acid), utilizing a hydrothermal cation exchange process. Through ion doping, semiconductor hybridization, and Schottky barriers in H-AAZS, photocatalysis for hydrogen generation has been successfully implemented using 660 nm laser irradiation. Additionally, the H-AAZS demonstrate the capacity for mild photothermal therapy, inducing apoptosis in synovial cells with Au's hot electrons with 660 nm laser irradiation. This strategy not only improves the abnormal proliferation of synovial cells but also avoids the exacerbation of inflammation caused by thermal stimulation. Both in vitro and in vivo experiments validate the synergistic effects of hydrogen production mediated anti-inflammatory responses, macrophage polarization and photothermal therapy. Therefore, this work represents a significant advancement as it ingeniously harnesses photocatalysis to modulate the synovial microenvironment while mitigating the side effects associated with photothermal therapy. This nanocrystal provides new and valuable insights into the potential treatment of Rheumatoid arthritis.

Electron Energization by Ion Density Enhancement in the Martian Magnetotail—MAVEN Observations

It has been long observed at Mars that electron fluxes are enhanced during the tail current sheet crossings, of which the cause is not well understood. We use a novel approach to reveal one of the electron energization mechanisms with observations from the Mars Atmospheric and Volatile EvolutioN (MAVEN) mission. We find the field-aligned potential, derived from comparing electron distribution functions, to be approximately linearly correlated with the logarithmic values of the local total ion density. This is the expected behavior of an ambipolar electrostatic potential. The large amplitude of potential (tens to hundreds of V) is a result of both a significant density gradient (1 order of magnitude) and the high electron temperature (tens of eV) in the tail. Such a mechanism is not limited to ion density enhancements at current sheet crossings but can be present anywhere that large ion density gradients and hot electrons are present.

All-optical method for generating transient microstructured targets in laser ion acceleration

We demonstrate an all-optical method that online produces “microstructured” targets by manipulating a Laguerre-Gaussian (LG) prepulse. Besides the enhancement of the proton number, the cutoff energy is nearly doubled. Such transient “microstructured” targets are characterized using both offline and online approaches. Based on probe experiments and hydrodynamic simulations, we develop a simple model to describe the electron density distribution upon the arrival of the main pulse. Two-dimensional particle-in-cell simulations reveal that the annular plasma acts as an oscillating cavity for hot electrons and results in a cascaded acceleration effect. The combination of low-intensity LG prepulses and ultraintense Gaussian pulses opens another avenue for fine-tuning laser-plasma interactions spatiotemporally in interdisciplinary applications. Published by the American Physical Society 2024

Analysis of degradation mechanism in polycrystalline silicon thin-film transistors under dynamic off-state stress with fast transition time

Abstract This study represents the investigation into the degradation of polycrystalline silicon (poly-Si) thin-film transistors (TFTs) under dynamic off-state stress, with a focus on transition times as rapid as 1 nanosecond (ns). The study found that dynamic off-state stress with larger amplitude leads to more severe device degradation. Unlike previous studies, both the rising time (t r ) and falling time (t f ) of the pulse significantly influence the hot carrier (HC) degradation in the poly-Si TFTs. The on-state current degradation rate (ΔI on ) after 104 s stress dramatically increases from 11.8% to 80.8% when t r decreases from 500 ns to 1 ns. When t f decreases from 500 ns to 1 ns, ΔI on also dramatically increases from 22.9% to 69.2%. Combined with transient simulations, the source of the carrier for HC degradation is clarified and consequently, a non-equilibrium PN junction degradation model modulated by accumulated electrons is developed.

Accurate molecular recognition from the lowest unoccupied molecular orbital

The quantification of the lowest unoccupied molecular orbital level (LUMO) for molecular semiconductors is of great importance, because it determines the charge transport process and hence the performances of diverse electronic devices. Unfortunately, there is always lack of a convenient technique to determine the intrinsic LUMO. This work provides a reliable electrical spectroscopy by employing an easy-operating hot electron transistor, to make an accurate measurement. By taking advantage of a novel method, named the first derivative-assisted linear fitting method, the determination of the intrinsic LUMO becomes more scientific. Here, four kinds of molecular semiconductors are selected as the research objects and the values can be precisely decided even with a quite small difference in LUMO, which demonstrate the universality and the accuracy of our method. As expected, all the measured values are highly repeatable and it further confirms that we have provided a practical technique for the LUMO detection.

Near-Infrared Light-Driven CO2 Reduction on Cup-Stacked Carbon Nanotubes.

Carbon nanotubes feature one-dimensional nature of collective excitations, wherein strong confinement of surface plasmons severely hinders the liberation of hot electrons (HEs), posing grand challenges for their utilization in photochemistry. In this study, we prototypically achieved directed HEs flow and extraction in hybrid plasmonic CNN based on cup-stacked carbon nanotubes (CSCNTs), taking advantage of their privileged edge-plane sites. The localized pz electronic states and accessible intersubband plasmon excitations in the near-infrared (NIR) regime stands in striking contrast to the conventional concentric carbon nanotubes, as evidenced by combined photo-induced force microscopy (PiFM) and transient photocurrent response. The hybrid comprising intimately integrated CSCNTs-C3N4 effectively sustains interfacial electronic states and underlies the energy extraction out of plasmonic components. The CNN demonstrates almost near-unity NIR light-driven CO2 reduction to CO with a rate of 1.35 µmol g-1 h-1. This work sheds light on the exploitation of metal-free carbon-based plasmonic nanostructures for photocatalytic applications.