Nonequilibrium Carriers Research Articles

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.

The Effect оf Laser Radiation оn Functional Properties of MOS Structures

The electrophysical properties of instrument MOSFET structures (capacitor, field-effect transistor with an isolated gate and an induced channel, CMOS integrated circuit) when exposed to unmodulated laser radiation are studied. Static and dynamic characteristics were measured. The theoretical study was carried out using the developed SPICE models and numerical experiments. An expression is obtained for the volt-ampere characteristic of a field-effect transistor operating in a mode with constant optical illumination. It is shown that the characteristics of the structures are determined by the generation and recombination of nonequilibrium charge carriers, the field effect, the photovoltaic effect in p—n junctions, the photo-Dember effect and tunneling of charge carriers through a gate dielectric. The results of the work are of interest from the point of view of creating high-speed transistors and integrated circuits of a new type.

Excited State Band Mapping and Ultrafast Nonequilibrium Dynamics in Topological Dirac Semimetal 1T-ZrTe2.

We performed time- and polarization-resolved extreme ultraviolet momentum microscopy on the topological Dirac semimetal candidate 1T-ZrTe2. Excited state band mapping uncovers the previously inaccessible linear dispersion of the Dirac cone above the Fermi level. We study the orbital texture of bands using linear dichroism in photoelectron angular distributions. These observations provide hints about the topological character of 1T-ZrTe2. Time-, energy-, and momentum-resolved nonequilibrium carrier dynamics reveal that intra- and interband scattering processes play a major role in the relaxation mechanism, leading to multivalley electron-hole accumulation near the Fermi level. We also show that electrons' inverse lifetime has a linear dependence as a function of their excess energy. Our time- and polarization-resolved XUV photoemission results shed light on the excited state electronic structure of 1T-ZrTe2 and provide valuable insights into the relatively unexplored field of quantum-state-resolved ultrafast dynamics in 3D topological Dirac semimetals.

Broadband nonlinear refraction transients in C-doped GaN based on absorption spectroscopy

Optical nonlinear response and its dynamics of wide-bandgap materials are key to realizing integrated nonlinear photonics and photonic circuit applications. However, those applications are severely limited by the unavailability of both dispersion and dynamics of nonlinear refraction (NLR) via conventional measurements. In this work, the broadband NLR dynamics with extremely high sensitivity (λ/1000) can be obtained from absorption spectroscopy in GaN:C using the refraction-related interference model. Both the absorption and refraction kinetics are found to be significantly modulated by the C-related defects. Especially, we demonstrate that the refractive index change Δn of GaN:C is negative and can be used to realize all-optical switching applications owing to the large NLR and ultrafast switching time. The NLR under different non-equilibrium carrier distributions originates from the capture of electrons by CN+ defect state, while the absorption modulation originates from the excitation of tri-carbon defects. We believe that this work provides a better understanding of the GaN:C nonlinear properties and an effective solution to broadband NLR dynamics of transparent thin films or heterostructure materials.

Advances in the heterostructures for enhanced hydrogen production efficiency: a comprehensive review.

The growing global energy demand and heightened environmental consciousness have contributed to the increasing interest in green energy sources, including hydrogen production. However, the efficacy of this technology is contingent upon the efficient separation of charges, high absorption of sunlight, rapid charge transfer rate, abundant active sites and resistance to photodegradation. The utilization of photocatalytic heterostructures coupling two materials has proved to be effective in tackling the aforementioned challenges and delivering exceptional performance in the production of hydrogen. The present article provides a comprehensive overview of operational principles of photocatalysis and the combination of photocatalytic and piezo-catalytic applications with heterostructures, including the transfer behavior and mechanisms of photoexcited non-equilibrium carriers between the materials. Furthermore, the effects of recent advances and state-of-the-art designs of heterostructures on hydrogen production are discussed, offering practical approaches to form heterostructures for efficient hydrogen production.

Nanoscale subsurface imaging by non-steady-state electron beam-driven scanning thermoelectric capacitance microscopy

Nanoscale subsurface characterization technologies based on the scanning electron microscope platform offer incomparable advantages of nondestructiveness and penetration depths up to the micrometer scale. However, the electron beam can serve not just as a mechanical/electrical excitation source but also as an excellent nanoscale thermal excitation source, which can facilitate the development of nanoscale subsurface imaging methods based on the Seebeck effect in semiconducting materials. In this work, a subsurface nondestructive imaging technology, scanning thermoelectric capacitance microscopy (STeCM), was developed based on the interaction between a non-steady-state electron beam and semiconducting materials, exploiting the Seebeck effect. In STeCM, a square wave-modulated hot electron beam with huge kinetic energy excites a “thermal wave” in the subsurface local region of the semiconducting sample. The heated local region, acting as a thermoelectric capacitor, undergoes cyclic charging and discharging, leading to the generation of periodic current due to non-equilibrium carrier migration. The second-order harmonic component of this current is demodulated to visualize embedded local thermal/thermoelectric inhomogeneities. Amazingly, for STeCM sample, only a smooth or polished surface is required, eliminating the need for any microfabrication, which will effectively decrease the configuration difficulty in the experiment. STeCM offers an alternative subsurface nondestructive imaging technology for more efficient, simple, and robust characterization.

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.

Energy transfer, conversion and mechanical regulation in graded piezoelectric semiconductor bipolar junction transistor

While the effective regulation of carrier redistribution in piezoelectric semiconductor devices by mechanical loads through piezoelectric polarized electric fields is well-studied, there is a scarcity of reported research on the influence of energy transfer and conversion characteristics in a non-thermal equilibrium state of these devices. This paper establishes a nonlinear multi-field coupling model for piezoelectric semiconductor graded bipolar junction transistor (PS-GBJT) and proposes a corresponding multi-gradient iterative algorithm. We regard the product of current and built-in electric field as the work done by electric field force on carriers. By incorporating the energy absorbed/released during carrier recombination/generation process, we observe that non-equilibrium carriers act as a medium that facilitates energy conversion between these two mechanisms. Additionally, the non-uniformly distributed doping extends the influence of space charge region throughout entire transistor. In terms of external input electrical energy, the emitter, base, and collector regions play roles of input energy, transfer energy, and output energy, respectively. The study concludes by demonstrating the regulation of energy transfer or conversion efficiency in emitter, base, and collector regions through mechanical loads, thereby altering the heating behavior of entire GBJT and reshaping its energy transfer path. This leads to the significant finding that distinct energy transfer paths fundamentally define the various operational states of GBJT. The novel insights gained from this research hold reference value for thermal design and energy management of electronic devices.

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.

A fast-switching low-loss field-stop IGBT with dual control gate of SIPOS material

A fast-switching low-loss field-stop insulated gate bipolar transistor with a dual control gate (DIGBT) of a semi-insulating polycrytalline silicon (SIPOS) material is proposed in this paper. Because the SIPOS has uniform high resistance, it has an approximate linear electric potential distribution. When DIGBT conducts, the higher electric potential on SIPOS causes the P-type drift region (P-drift) to generate an inversion layer of electrons, adjusting the number of carriers and making the generation of non-equilibrium carriers no longer dependent on the doping concentration in P-drift (Nd) but on the electric potential distribution on SIPOS. Therefore, it can solve the contradiction among the breakdown voltage, forward voltage drop [VCE(sat)], turn-off time (toff), and turn-off loss (Eoff) caused by the Nd. Through Technology Computer Aided Design (TCAD) simulation, the VCE(sat) of DIGBT is 30.6% lower than that of SJFS IGBT. Meanwhile, DIGBT reduces the toff by 62.8% while reducing the Eoff by 83.0% compared to SJFS IGBT. In addition, the static latch-up I–V and the forward biased safe operating area of the DIGBT have been significantly improved. This paper adjusts the number of carriers through the characteristics of SIPOS material, enabling the above-mentioned physical phenomena to be applied in insulated gate bipolar transistor power devices and achieving device performance breakthroughs.

Effective Lifetime of Nonequilibrium Carriers in Perovskite‐Inspired Cu2AgBiI6

Perovskite‐inspired materials (PIMs) are potential alternatives to lead halide perovskites, as they not only inherit the benign optoelectronic properties but also diminish the stability and toxicity issues of lead halide perovskites. As a newly discovered PIM, Cu2AgBiI6 has exhibited promising potential for photovoltaic applications. However, studies on its fundamental properties related to photovoltaic performance are scarce, particularly from a theoretical perspective. Herein, the effective lifetime of nonequilibrium carriers (photo‐excited charge carriers) is systematically investigated, a critical property affecting the photovoltaic performance of Cu2AgBiI6, based on the nonadiabatic molecular dynamics simulations. It is found that under the standard solar spectrum illumination, the dominant recombination mechanism affecting the effective lifetime can be band‐to‐band nonradiative decay, band‐to‐band radiative decay, or Shockey–Read–Hall defect‐assisted decay. The specific mechanism is highly dependent on the radiative recombination coefficient and the density of defect recombination levels. The effective lifetime can vary from 0.1 ms to 10 ns. When considering different illumination conditions (generation rates), Auger decay can also become the dominant recombination mechanism, with the effective lifetime varying from 0.1 s to 0.1 ns. These findings can be vital for further experimental researches aimed at enhancing the power conversion efficiency of Cu2AgBiI6‐based solar devices.

Effect of Gamma Irradiation on Electrophysical Parameters of Silicon Solar Cells Doped with Nickel

The results of the studies of changes in the electro-physical parameters (Voc – no-load voltage, Isc – short-circuit current density; τ – lifetime of nonequilibrium charge carriers) of photocells made on plates of monocrystalline silicon of the p-type conductivity with the specific resistance ρ 0.5 Ohm cm, doped with nickel, under irradiation with γ-quanta from 60Co source are presented. It is shown that the efficiency of the solar energy conversion in nickel-doped photovoltaic cells remains higher than in standard cells up to irradiation doses of 108 rad. It was established that with increasing diffusion temperature of nickel atoms radiation stability of electrophysical parameters of photovoltaic cells also increases. A decrease in the concentration of recombination-active radiation defects is due to the getterization by nickel atoms of technological (background) impurities and the action of nickel clusters as effluents for radiation-induced vacancies.

The differences between the hydrogenation by means of photon-injection and electron-injection for N-type tunnel oxide passivated contacts solar cells

Tunnel Oxide Passivated Contact (TOPCon) solar cells have received widespread attention in recent years, especially in improving conversion efficiency. This paper investigated the impact of hydrogenation technology using photon-injection (HPI) and electron-injection (HEI) processes on TOPCon solar cells, highlighting the higher improvement effect and broader application scope of HPI compared to HEI. In TOPCon cells, several methods are available to prepare the tunneling oxide layer, such as plasma oxidation (PO) and indirect thermal oxidation (TO). The research results indicated that significant improvement differences could be observed when utilizing the HEI treatment for TOPCon solar cells prepared by PO and TO methods, with values of 0.133%abs. and −0.039%abs., respectively. Meanwhile, HPI treatment induced a more significant efficiency improvement for these two types of cells, and the increase in efficiency is 0.247%abs. and 0.244%abs., respectively. The experimental results demonstrated that the passivation effect for TOPCon solar cells prepared by PO and TO methods remained almost the same under the HPI treatment, and the improvement effect is less dependent on the tunnel oxidation technique used. Thus, the different passivation effects between HPI and HEI were further investigated, and the reason for the difference was attributed to the charge states and concentrations of hydrogen and non-equilibrium carriers during the hydrogenation. The results provided an improved scheme for enhancing the efficiency of TOPCon solar cells, shedding light on the role of HPI and HEI in the passivation process. This work brings further insights to TOPCon solar cells.

Trap states and carrier diffusion lengths in NiO/β-Ga2O3 heterojunctions

We report the electrical properties, deep trap spectra, and diffusion lengths of non-equilibrium carriers in Ni Schottky diodes and NiO/Ga2O3 heterojunctions (HJs) prepared on the same n−/n+ β-Ga2O3 epi structures. The heterojunctions decrease the reverse current of Ga2O3 high-power rectifiers. In HJs, in contrast to Schottky diodes, the capacitance and AC conductance show a prominent frequency and temperature dependence, suggesting the presence of two temperature activation processes with activation energies of 0.17 and 0.1 eV. The deep trap spectra of the Schottky diodes and HJs differ by the absence in the HJ of deep electron traps E2* with level near Ec − 0.7 eV considered to be an important center of non-radiative recombination. This correlates with the observed increase in the diffusion length of non-equilibrium charge carriers in the HJs to 370 nm compared to 240 nm in the Schottky diodes. The diffusion length of charge carriers in p-NiO was found to be quite short, 30 nm. Possible reasons for the observed differences and possible origin of the minority-trap-like feature commonly reported to be present in the deep level spectra of HJs and also observed in our experiments are discussed.

Modeling of semiconductor heterostructures for energy converters and sensors

A set of modeling programs for constructing a sequence of energy zones of heterojunctions is presented for analyzing the distribution of charge carriers in the heterostructure and internal characteristics, for describing the processes of charge transfer and accumulation. Wolfram Mathematica analytical system and Delphi programming language were used. The main elements of materials are semiconductors, metals of contact structures and injection regions of nonequilibrium carriers. The programs allow determining the structural characteristics of materials, active zones and spatial charge regions, calculating quasi-Fermi levels and built-in potentials, as well as the efficiency of heterostructures in general and for separation-charge collection, charge accumulation, determining the type of metallization of barrier or ohmic contact.

Microscopic nonlinear optical activities and ultrafast carrier dynamics in layered AgInP2S6

Since the emergence of graphene, transition metal dichalcogenides, and black phosphorus, two-dimensional materials have attracted significant attention and have driven the development of fundamental physics and optoelectronic devices. Metal phosphorus trichalcogenides (MPX3), due to their large bandgap of 1.3–3.5 eV, enable the extension of optoelectronic applications to visible and ultraviolet (UV) wavelengths. Micro-Z/I-scan (μ-Z/I-scan) and micro-pump-probe (μ-pump-probe) setups were used to systematically investigate the third-order nonlinear optical properties and ultrafast carrier dynamics of the representative material AgInP2S6. UV-visible absorption spectra and density functional theory (DFT) calculations revealed a quantum confinement effect, in which the bandgap decreased with increasing thickness. The two-photon absorption (TPA) effect is exhibited under the excitation of both 520 and 1040 nm femtosecond pulses, where the TPA coefficient decreases as the AgInP2S6 thickness increases. In contrast, the TPA saturation intensity exhibits the opposite behavior that the TPA saturation is more likely to occur under visible excitation. After the valence band electrons undergo photon transitions to the conduction band, the non-equilibrium carriers relax through non-radiative and defect-assisted recombination. These findings provide a comprehensive understanding of the optical response process of AgInP2S6 and are a valuable reference for the development of optoelectronic devices.

Photo‐Induced Electrical Gating with the Inserting of an Interfacial Carrier Blocking Layer for Organic/Graphene Phototransistors

AbstractAlthough ultrahigh photoconductive gain is achieved in organic semiconductor‐sensitized graphene phototransistors, the response speed is limited by the photo‐induced carrier injection at the organic/graphene interface. In this work, an insulating hexagonal boron nitride layer is inserted between the organic heterostructure and graphene to block the interfacial carrier transport. Above the h‐BN layer, the organic heterostructure is adopted as the light‐absorbing layer, and the photoresponse of graphene is realized through electrical gating of the atop h‐BN dielectric layer, by the accumulated carriers in the organic heterostructure. Under this “photo‐induced electrical gating” mechanism, the recombination of nonequilibrium carriers takes place only within the organic heterostructure. Furthermore, monolayer perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTCDA) is deposited on graphene before transfer of the h‐BN, by which the interfacial encapsulated bubbles are effectively reduced. As a step further, the trap states are pre‐filled with background light illumination, then the carrier recombination follows the band‐to‐band pathway. Finally, the response time of the organic/h‐BN/graphene phototransistor is reduced to 7.15 ms, and a high photoresponsivity is achieved even though the carrier multiplication is sacrificed, which is reconciled by the improvement of the device quantum efficiency.

Evidence of hot carrier extraction in metal halide perovskite solar cells

AbstractThe presence of hot carriers is presented in the operational properties of an (FA,Cs)Pb(I, Br, Cl)3 solar cell at ambient temperatures and under practical solar concentration. Albeit, in a device architecture that is not suitably designed as a functional hot carrier solar cell. At 100 K, clear evidence of hot carriers is observed in both the high energy tail of the photoluminescence spectra and from the appearance of a nonequilibrium photocurrent at higher fluence in light J–V measurements. At room temperature, however, the presence of hot carriers in the emission at elevated laser fluence is shown to compete with a gradual red shift in the PL peak energy as photoinduced halide segregation begins to occur at higher lattice temperature. The effects of thermionic emission of hot carriers and the presence of a nonequilibrium carrier distribution are also shown to be distinct from simple lattice heating. This results in large unsaturated photocurrents at high powers as the Fermi distribution exceeds that of the heterointerface controlling carrier transport and rectification.

CHANGES IN THE ELECTROPHYSICAL AND DETECTOR PROPERTIES OF THE PROMISING DETECTOR MATERIAL Cd1-xMnxTe DEPENDING ON THE CONCENTRATION OF IMPURITIES, DEFECTS AND MANGANESE CONTENT

A model study was carried out about the behavior of the resistivity ρ, the Fermi level F, and the charge collection efficiency η of detectors based on the promising semiconductor material Cd1-xMnxTe, depending on the donor impurity concentration ND for different values of the manganese molar fraction x: 0.035, 0.07, and 0.3 at room temperature. The values of concentrations Ni , activation energies Ei , and the capture cross sections σi of nonequilibrium charge carriers by i-th defects acted as input data for modeling. The regularities of changes in ρ, F, η depending on the content of impurities and cadmium vacancies have been established. Methods of achieving a highresistance state, proper for a material of detector-quality, are considered. A plan for further research issues using experimental published results is defined.

Photoemission Enhancement of Plasmonic Hot Electrons by Au Antenna-Sensitizer Complexes.

The photoemission of surface plasmon decay-produced hot electrons is usually of very low efficiencies, hindering the practical utilization of such nonequilibrium charge carriers in harvesting photons with less energy than the semiconductor band gap for more efficient solar energy collection and photodetection. However, it has been demonstrated that the photoemission efficiency of small metal clusters increases as the particle size decreases. Recent studies have also shown that the photoemission efficiency of surface plasmon-yielded hot carriers can be intrinsically improved through proper material construction. In this paper, we report that the photoemission efficiency of hot electrons on the Au nanodisk-cluster complex/TiO2 interface can be dramatically enhanced under optical nanoantenna-sensitizer design. Such an enhancement is dominantly attributed to three factors. First, the large plasmonic nanodisk antennas provide a significantly enhanced optical near field, which largely increases light absorption in the small Au clusters that are acting as hot electron injection sensitizers. Second, the sub-3 nm size of the Au clusters facilitates the collection of delocalized spreading charges by the semiconductor. Third, the hybrid interface and molecule-like energy level of the Au cluster result in a much longer lifetime of excited electrons. Our results provide a promising approach for the effective harvesting of solar energy with plasmonic antenna-sensitizer complexes.