Electron Trap States Research Articles

As‐Doped Polycrystalline CdSeTe: Localized Defects, Carrier Mobility and Lifetimes, and Impact on High‐Efficiency Solar Cells

AbstractThe efficiency potential for single‐junction photovoltaics (PV) is described by the detailed balance model, which requires the elimination of nonradiative recombination and perfect minority carrier collection. Improvements in GaAs, Si, and perovskite PV follow this model. It might be more complex for CdTe, a leading thin‐film PV technology. While lifetime, passivation, and doping goals for 25% efficient CdTe solar cells are largely reached, voltage is ≈20% below the detailed balance limit. Why is that? In Se‐alloyed CdSexTe1‐x (Se is required for >20% efficiency) additional losses can occur due to electrostatic and bandgap fluctuations and due to electronic trap states. To understand mechanisms limiting CdSeTe solar cell performance and to suggest improvements, carrier dynamics, and transport in CdSexTe1‐x with variation in Se composition and as doping is analyzed. It is shown that trapping, likely due to anion‐site defects and their complexes, is correlated with low charge carrier mobility of 0.1–0.6 cm2 (Vs)−1. Even with 1000 ns charge carrier lifetimes, carrier diffusion length is less than the absorber thickness, reducing efficiency to ≈23%. Device simulations are used to analyze the performance of CdSexTe1‐x solar cells; thermodynamic models are not sufficient for absorbers with electronic disorder and trapping.

Reduction of recombination at the interface of perovskite and electron transport layer with graded pt quantum dot doping in ambient air-processed perovskite solar cell

The study of charge transfer in thin film solar cells made of several layers is of high importance since they may lose their energy via the recombination process at the interfaces, specifically at the interface of the electron transport layer (ETL) and perovskite. Titanium dioxide (TiO2) is mostly used as an ETL in perovskite solar cells due to its many advantages. However, TiO2 has some disadvantages, such as low electron mobility compared to the perovskite layer and electron trap states on its top at the interface. These effects cause the accumulation of carriers at the ETL/perovskite interface then the non-radiative recombination will be enhanced, which is considered as one of the significant losses in the Perovskite Solar Cells (PSCs). In this work, a new technique is taken for more optimal ETL doping. We fabricated the ETL layers with graded doping of platinum quantum dots (Pt QDs), in which Pt QDs concentration is high at the ETL/Perovskite interface and zero at the FTO/ETL interface. This strategy not only suppresses the recombination at the ETL/perovskite interface and subsequently enhances the device efficiency from 12.92 to 14.36% but also improves the stability of the PSCs.

Antithermal-Quenching All-Inorganic Perovskite Crystals with Green Ultralong Persistent Luminescence for Advanced Anticounterfeiting Applications.

Long persistent luminescence (PersL) materials have revolutionized many fields of optoelectronics and photonics due to their applications in anticounterfeiting, information encryption, and in vivo bioimaging. Here, we reported a novel PersL crystal prepared by the heterovalent doping of Sb3+ into perovskite tetragonal phase RbCdCl3, comparing with the pristine non-perovskite orthorhombic phase analogue without PersL property. Surprisingly, under the UV light irradiation, the title crystals concurrently exhibit green ultralong PersL (>2400 s), high photoluminescence quantum yield (49.1%), and antithermal quenching in the range from 148 to 328 K. It was revealed by experimental results and theoretical analyses that green ultralong PersL and antithermal quenching of perovskite-phase RbCdCl3/Sb3+ crystals originate from the electron transition between the 5s2 level of the dopant Sb3+ and the electronic defect-induced trap states. Enlightened by the excellent optical properties, the tetragonal perovskite-phase RbCdCl3/Sb3+ PersL materials show promising application prospects in anticounterfeiting and encryption of information.

Identifying Rare Events in Quantum Molecular Dynamics of Nanomaterials with Outlier Detection Indices.

Nanoscale and condensed matter systems evolve on multiple length- and time-scales, and rare events such as local phase transformation, ion segregation, defect migration, interface reconstruction, and grain boundary sliding can have a profound influence on material properties. We demonstrate how outlier detection indices can be used to identify rare events in machine-learning based, high-dimensional molecular dynamics (MD) simulations. Designed to order data-points from typical to untypical, the indices enable one to capture atomic events that are hard to detect otherwise. We demonstrate the approach with a nanosecond MD simulation of a grain boundary in a metal halide perovskite that is extensively studied for solar energy and optoelectronic applications. The method captures the initial grain boundary sliding and a spontaneous fluctuation half a nanosecond later, both events giving rise to persistent deep electronic trap states that impact charge carrier lifetime and transport and material performance. The approach offers a generalizable and simple method for identifying outlier events in complex condensed matter, molecular, and nanoscale systems.

Sub-bandgap Photocurrent Spectra of p-i-n Perovskite Solar Cells with n-Doped Fullerene Electron Transport Layers and Bias Illumination.

In p-i-n perovskite solar cells optical excitation of defect states at the interface between the perovskite and fullerene electron transport layer (ETL) creates a photocurrent responsible for a distinct sub-bandgap external quantum efficiency (EQE). The precise nature of these signals and their impact on cell performance are largely unknown. Here, the effect of n-doping the fullerene on the EQE spectra is studied. The n-doped fullerene is either deposited from solution or by coevaporation. The latter method is used to create undoped-doped fullerene bilayers and investigate the effect of the proximity of the doped region on the EQE spectra. The intensity of the sub-bandgap EQE increases when the ETL is n-doped and also when the device is biased with green light. Using these results, the sub-bandgap EQE signal is attributed to originate from electron trap states in the perovskite with an energy below the conduction band that are filled by excitation with low-energy photons. The trapped electrons give rise to photocurrent when they are collected at a nearby electrode. The enhanced sub-bandgap EQE observed when the ETL is n-doped or bias light is applied, is related to a higher probability to extract trapped electrons under these conditions.

Optoelectronic Synapse Behaviors in Tb3+ and Al3+ Co-Doped CaSnO3 with Long-Persistent Luminescence.

Neuromorphic computation draws inspiration from the remarkable features of the human brain including low energy consumption, parallelism, adaptivity, cognitive functions, and learning ability. These qualities hold the promise of unlocking groundbreaking computational techniques that surpass the limitations of traditional computing systems. This paper reports a remarkable photo-synaptic behavior in the field of rare earth ion-doped luminescent oxides by using long-persistent luminescence (LPL). This system utilizes electron trap states to regulate the synaptic behavior, operating through a fundamentally different mechanism from that of electronic-based synaptic devices. To realize this strategy, Tb3+ doped CaSnO3, which shows a significant LPL property under UV-light excitation, is prepared. The luminescent system shows key neuromorphic characteristics such as paired-pulse facilitation, pulse-number/timing dependent potentiation, and pulse-number/timing dependent short- to long-term plasticity transition, which are required for realizing synaptic devices. This feature expands the way for advanced neuromorphic technologies employing light stimuli.

Enhanced photocatalytic aerobic oxidative desulfurization of diesel over FeMo6Ox nanoclusters decorated on CuS nanosheets

Photocatalytic aerobic oxidative desulfurization (PAODS) presents a promising and carbon-neutral avenue for desulfurizing petroleum products. However, existing photocatalysts encounter limitations in activating oxygen and show sluggish kinetics in sulfide-to-sulfone conversion, hampering widespread implementation. Herein, we present a FeMo6Ox nanocluster-modified CuS photocatalyst for PAODS reaction using air as an oxygen source. Through experimental characterization and density functional theory (DFT) calculations, we elucidate that the incorporation of FeMo6Ox nanoclusters can modulate the CuS electron density, which results in the generation of electron trap states and facilitates the separation of electron-hole pairs. We show that the variation of water content in air alters the generation efficiency of different reactive oxygen species (ROS), highlighting the potential to optimize moisture levels for achieving the highest catalytic efficiency. The optimized catalytic system exhibits a record specific activity of 10.42 mmol g−1 h−1, and more importantly, achieves deep desulfurization of authentic diesel, showcasing its appealing application prospects.

Electronic relaxation in PLD TiO2 films processed with femtosecond UV-laser

Modifications of shallow electron trap states near conduction band was analyzed after surface structuring of TiO2 thin films prepared via pulsed laser deposition method. Laser-induced periodic surface structures (LIPSS) were produced on the large-area films after irradiation with femtosecond KrF laser (λ = 248 nm). While spatial period of LIPSS Λ ≈ 190 ± 10 nm was not affected by laser fluence, coherence was increased with an increase of laser dose. Time-resolved microwave conductivity measurements accompanied by theoretical modelling revealed energetic positions of shallow electron trap states, connected to LIPSS. A possibility to alter the trap states energy via surface structuring of the material was shown.

Understanding the Activation Mechanism of RhCrOx Cocatalysts for Hydrogen Evolution with Nanoparticulate Electrodes.

Mixed oxides of Rh-Cr (RhCrOx), containing Rh3+ and Cr3+ cations, are commonly used as cocatalysts for the hydrogen evolution reaction (HER) on particulate photocatalysts. The precise physicochemical mechanisms of the HER at the catalytic sites of these oxides are not well understood. In this study, model cocatalyst electrodes, composed of nanoparticulate RhCrOx, were fabricated to investigate the physicochemical mechanisms of the HER. Electroanalytical and X-ray photoelectron spectroscopic measurements revealed that nanoparticulate RhCrOx produces reduced Rh (Rh0) species by maintaining an electrode potential more negative than 0.03 V versus the reversible hydrogen electrode (VRHE). This results in significant enhancement of the HER activity. The catalytic activity for the HER stems from the reduced Rh species, and the inclusion of Cr3+ (CrOx) aided in the electron transfer process at the solid/liquid interface, resulting in a higher current density during the HER. To achieve a solar-to-hydrogen efficiency of over 3%, the conduction band minimum of the particulate photocatalyst should be positioned more negatively than -0.10 VRHE. Moreover, the formation of electron trap states at potentials more positive than 0.03 VRHE should be avoided. This study highlights the importance of understanding the catalytic sites on metal oxide cocatalysts. Moreover, it offers a design strategy for enhancing the efficiency of photocatalytic water splitting.

Timescale correlation of shallow trap states increases electrochemiluminescence efficiency in carbon nitrides

Highly efficient interconversion of different types of energy plays a crucial role in both science and technology. Among them, electrochemiluminescence, an emission of light excited by electrochemical reactions, has drawn attention as a powerful tool for bioassays. Nonetheless, the large differences in timescale among diverse charge-transfer pathways from picoseconds to seconds significantly limit the electrochemiluminescence efficiency and hamper their broad applications. Here, we report a timescale coordination strategy to improve the electrochemiluminescence efficiency of carbon nitrides by engineering shallow electron trap states via Au-N bond functionalization. Quantitative electrochemiluminescence kinetics measurements and theoretic calculations jointly disclose that Au-N bonds endow shallow electron trap states, which coordinate the timescale of the fast electron transfer in the bulk emitter and the slow redox reaction of co-reagent at diffusion layers. The shallow electron trap states ultimately accelerate the rate and kinetics of emissive electron-hole recombination, setting a new cathodic electrochemiluminescence efficiency record of carbon nitrides, and empowering a visual electrochemiluminescence sensor for nitrite ion, a typical environmental contaminant, with superior detection range and limit.

Accelerating Charge Separation and CO2 Photoreduction in Aqueous Phase under Visible Light with Ru Nanoparticles Loaded on Ga-Doped NiTiO3 in a Batch Photoreactor.

Titanate perovskite (ATiO3) semiconductors show prospects of being active photocatalysts in the conversion of CO2 to chemical fuels such as methanol (CH3OH) in the aqueous phase. Some of the challenges in using ATiO3 are limited light-harvesting capability, rapid bulk charge recombination, and the low density of catalytic sites participating in CO2 reduction. To address these challenges, Ga-doped NiTiO3 (GNTO) photocatalysts in which Ga ions substitute for Ti ions in the crystal lattice to form electron trap states and oxygen vacancies have been synthesized in this work. The synthesized GNTO was then loaded with Ru nanoparticles to accelerate charge separation and enable excellent CO2 photoreduction activity under visible light. CO2 photoreduction was conducted in a batch photoreactor charged with a 0.1 M NaHCO3 aqueous solution at room temperature and a 3.5 bar pressure using a 1.0 wt % Ru-GNTO photocatalyst to yield methanol at a rate of 84.45 μmol g-1 h-1. A small amount of methane was produced as a side product at 21.35 μmol g-1 h-1, which is also a fuel molecule. We attribute this high catalytic activity toward CO2 photoreduction to a synergistic combination of our novel heterostructured 1.0 wt % Ru-GNTO photocatalyst and the implementation of a pressurized photoreactor. This work demonstrates an effective strategy for metal doping with active nanospecies functionality to improve the performance of ATiO3 photocatalysts in valorizing CO2 to solar fuels.

Self-rectifying resistive switching in MAPbI3-based memristor device

A critical stage in developing high-density memristors is addressing the sneak current within the crossbar architecture. One of the effective strategies to endow the memristive cell with the ability to prevent sneak currents when it is in a low resistance state is to give it an inherent diode, known as a self-rectifying memristive cell. This study demonstrates the Schottky diode inside the MAPbI3-based memristive cell, a consequence of its interaction with the tungsten (W) electrode. The performance of memory devices is reliable with low-voltage operation, a resistance window having over ten of magnitude, and the retention time remains over 104 s. Prominently, the self-rectifying behavior is sustainable over 150 cycles and exhibits a rectification ratio of approximately 102 times. Density functional theory calculation reveals the presence of unoccupied gap states on an interfaced MAPbI3 surface, serving as electron trapping states during the charge transport across the W/MAPbI3 Schottky interface. Consequently, the conduction mechanism is primarily governed by an interfacial-controlled model, notably Schottky emission. This improvement promises to eliminate sneak currents in future crossbar array fabrication.

Modifying Surface Termination by Bidentate Chelating Strategy Enables 13.77% Efficient Kesterite Solar Cells.

Surfaces display discontinuities in the kesterite-based polycrystalline films can produce large defect densities, including strained and dangling bonds. These physical defects tend to introduce electronic defects and surface states, which can greatly promote nonradiative recombination of electron-hole pairs and damage device performance. Here, an effective chelation strategy is reported to suppress these harmful physical defects related to unterminated Cu, Zn, and Sn sites by modifying the surface of Cu2ZnSn(S,Se)4 (CZTSSe) films with sodium diethyldithiocarbamate (NaDDTC). The conjoint theoretical calculations and experimental results reveal that the NaDDTC molecules can be coordinate to surface metal sites of CZTSSe films via robust bidentate chelating interactions, effectively reducing surface undercoordinated defects and passivating the electron trap states. Consequently, the solar cell efficiency of the NaDDTC-treated device is increased to as high as 13.77% under 100mW cm-2 illumination, with significant improvement in fill factor and open-circuit voltage. This surface chelation strategy provides strong surface termination and defect passivation for further development and application of kesterite-based photovoltaics.

Infrared Irradiation‐Lattice Vibration Coupling‐Initiated N→Π* Electronic Transition in Carbon Nitride Nanosheets for Increased Photocatalysis

AbstractEnabling n→π* electronic transition in graphitic carbon nitride (g‐CN) can significantly enhance its photocatalytic performance by extending visible light absorption. However, achieving this transition remains a grand challenge due to the selection rule that restricts it to planar tri‐s‐triazine units of g‐CN. Here, an effective strategy to induce the n→π* transition in g‐CN nanosheets by coupling infrared irradiation with lattice vibrations is presented. Theoretical simulations reveal two prominent vibration modes perpendicular to tri‐s‐triazine units at 219 and 737 cm−1 can promote the corrugation of tri‐s‐triazine units and facilitate the n→π* electronic transition when coupled with infrared irradiation. Additionally, these vibrational modes enable the efficient exfoliation of bulk g‐CN into 2D nanosheets by overcoming the interplanar binding energy. Through femtosecond transient absorption spectra (fs‐TAS), the n→π* transition prolongs the lifetime of photocatalytically active shallow electron trapping states and charge separation states in g‐CN is demonstrated. Accordingly, the activated n→π* electronic transition and prolonged lifetime of photocatalytically active charges lead to an H2 generation rate of 2485 µmol h−1 gcat−1, ≈40 times higher than that of the bulk counterpart. This work highlights the effectiveness of coupling lattice vibrations with infrared irradiation to drive the n→π* transition for enhanced visible‐light photocatalysis.

Synergizing between interband and intraband defect states in prolonging the charge carrier lifetime of InSe/SiH heterojunctions.

Experiments have demonstrated that defect states can regulate the charge carrier dynamics in heterojunctions. However, the underlying mechanism still remains under debate. Using nonadiabatic molecular dynamics, we have investigated the influence of inter and intraband defect states on charge relaxation in InSe/SiH heterojunctions. The simulations revealed that inter and intraband defect states have a weak effect on electron transfer, whereas they exert a strong influence on hole transfer and electron-hole recombination. Compared to the pristine system, the selenium vacancy creates two interband shallow electron trapping states and one intraband hole trapping state. The interband electron trapping states can capture photo-generated electrons, while the intraband hole trapping state accelerates hole transfer. The synergy between inter and intraband defect states suppresses the charge recombination by a factor of 8.3. This simulation rationalizes the influence mechanism of inter and intraband defect states on charge carrier dynamics, suggesting a valuable principle for enhancing the performance of heterojunction photocatalysts.

Improvement in hot carrier dynamics of all-inorganic halide perovskite CsPbI3 on doping Cu

Hot carrier extraction is crucial for efficient solar energy harvesting, and lead halide perovskite nanocrystals (NCs) are potential candidates for photovoltaic and light-emitting applications. Therefore, swift extraction of hot carriers is an immediate requirement to improve the energy conversion efficiency, which need longer thermalization time. To address this issue, we synthesized nominally Cu-doped CsPbI3 NCs with enhanced structural and optical characteristics compared to undoped CsPbI3 NCs. We investigated the hot carrier dynamics in both the NCs at different fluences using ultrafast transient absorption spectroscopy. Interestingly, we observed very fast thermalization at higher fluences that indicated breaking of the phonon bottleneck. On the contrary, doped NCs preserved the effects and decayed over a longer period of time possibly due to increase in size and introduction of shallow trap states of Cu 3d and Cu 4s electrons in the conduction band, as computed using density functional theory. Notably, as the carrier–carrier interaction increased, we observed a dominating bandgap renormalization in the doped system compared to the undoped system. Overall, our studies improve the understanding of Cu doping in enhancing the hot carrier dynamics in perovskites and open possibilities for further investigation in the quantum phenomenon of these materials.

Fluorinated interface engineering targeting high-performance multifunctional composites of BN/aramid nanofibers

Aramid nanofibers (ANFs)-based composites have attracted considerable interest in electronic and electrical engineering due to their exceptional thermal stability, high strength, and superior insulating properties. However, the performance of ANFs-based composites is severely confined by interfacial issues. Accordingly, a novel strategy of fluorinated interface engineering is proposed herein, by which the fillers are grafted by the fluorine-containing functional groups. The introduction of interfacial fluorination yields a dense and compact composite structure which stems from the improved compatibility at the matrix-filler interfaces. The tensile strength and thermal conductivity are increased by 30% and 50%, respectively. Additionally, the band structure variation is observed in the fluorinated BNNs, where the electron trap states are formed at the interface. With the deepened deep trap depth and increased density, the breakdown strength is enhanced by 50%. The breakdown phase field simulations also indicate the high discharge energy consumption by the fluorination effect.

Plasma and Etch Process Modulation of Subgap Trap State Density in a-Ingaznox Thin-Film Transistors

Amorphous oxide semiconductors such as amorphous InGaZnOx (a-IGZO) possess a high concentration of subgap electronic trap states that control the performance of thin-film transistors (TFTs). Using an ultrabroadband spectroscopic method capable of directly resolving the subgap density of states, we report the effects of different etch processing and plasma treatments on the subgap. Back channel etch a-IGZO TFTs are shown to possess an acceptor-like zinc vacancy state centered at ~2.2 eV below the conduction band mobility edge, which is not present in top gate a-IGZO TFTs. We also explore how different active channel compositions and thermal annealing-activated hydrogen incorporation impact the subgap density of states of amorphous oxide semiconductors. Hydrogen is found to behave as a donor in both a-IGZO and a-ITGZO, forming a complex with valence band oxygen states after donating its electron due to its negative-U character in amorphous oxide semiconductors. Figure 1

Interface engineering in ZnO/CdO hybrid nanocomposites to enhanced resistive switching memory for neuromorphic computing

Resistive random-access memory (RRAMs) has attracted significant interest for their potential applications in embedded storage and neuromorphic computing. Materials based on metal chalcogenides have emerged as promising candidates for the fulfilment of these requirements. Due to its ability to manipulate electronic states and control trap states through controlled compositional dynamics, metal chalcogenide RRAM has excellent non-volatile resistive memory properties. In the present we have synthesized ZnO-CdO hybrid nanocomposite by using hydrothermal method as an active layer. The Ag/C15ZO/Pt hybrid nanocomposite structure memristors showed electrical properties similar to biological synapses. The device exhibited remarkably stable resistive switching properties that have a low SET/RESET (0.41/−0.2) voltage, a high RON/OFF ratio of approximately 105, a high retention stability, excellent endurance reliability up to 104 cycles and multilevel device storage performance by controlling the compliance current. Furthermore, they exhibited an impressive performance in terms of emulating biological synaptic functions, which include long-term potentiation (LTP), long-term depression (LTD), and paired-pulse facilitation (PPF), via the continuous modulation of conductance. The hybrid nanocomposite memristors notably achieved an impressive recognition accuracy of up to 92.6 % for handwritten digit recognition under artificial neural network (ANN). This study shows that hybrid-nanocomposite memristor performance could lead to efficient future neuromorphic architectures.

Selective Passivation of Surface toward Bright Yellow Defective Emission of CdS Quantum Dots.

CdE (E = S, Se) quantum dots (QDs) with a broad and large Stokes shift PL emission have emerged as potential materials for white-light LEDs. However, this surface-related emission of nanocrystals is currently limited by low quantum efficiency. Herein, a convenient noninjected one-pot method at a relatively low temperature to prepare CdS QDs was readily achieved. The CdS-368 QD displays intense broad yellow emission in both solution and the solid state at room temperature. The coligation of organic and inorganic ligands passivates the electron trap states at the QD surface and suppresses nonradiative recombination, which is responsible for the high stability of colloids in organic solvents and the distinct fluorescence quantum yield.