Hole Accumulation Research Articles

Surface-selective growth of noble-metal-free nanodumbbells photocatalyst with spatially separated redox sites using in-situ ion exchange for simultaneous microplastics upcycling and H2 evolution

Solar-driven photocatalytic upcycling of harmful microplastics (MPs) coupled with H2 production is a promising avenue to alleviate global environmental and energy issues. However, developing stable and cost-effective photocatalysts with efficient carrier separation remains a considerable challenge. Herein, based on surface-selective growth followed by in-situ ion exchange method, MoS2 and Cu2S are selectively grown on the tips and sidewalls of CdS nanorods to construct precious-metal-free ternary MoS2-CdS/Cu2S heterojunction nanodumbbells, featuring orderly and spatially separated redox sites. In the nanoarchitecture, site-specific MoS2 and Cu2S serve as electron and hole collectors, respectively, to decouple the collection direction of photogenerated carriers, achieving the spatial separation of redox half-reaction and strong photostability of nanodumbbells. Additionally, the heterojunctions (Schottky junction of MoS2-CdS and p-n junction of CdS/Cu2S) allow the charge to quickly flow in selective directions, resulting in an efficient separation rate of photogenerated excitons. With the joint action of spatially separated redox sites and ternary heterojunction, MoS2-CdS/Cu2S achieves an effective conversion of MPs into acetic acid (acetic acid concentration of 2870.0 µg·L-1 within 20 h) along with H2 evolution (305.0 µmol·g-1 within 4 h) without any sacrificial reagents.

Spatiotemporal evolution of ultrafast photocarrier dynamics across WS2-ReS2 lateral interface.

2D lateral heterostructures possess atomically sharp lateral interfaces, while understanding of their ultrafast photocarrier dynamics from a spatiotemporal viewpoint is rather elusive. In this study, we have investigated the spatiotemporal evolution of photocarrier dynamics across the 1D lateral interface of a WS2-ReS2 2D lateral heterostructure utilizing femtosecond laser pump-probe. The nontrivial band offset across the 1D lateral interface markedly mediates the spatiotemporal photocarrier transfer and transport processes. Subsequently, a hole accumulation region on the WS2 side and an electron accumulation region (1DEG) on the ReS2 side have been spatially identified by correlating ultrafast photocarrier signals. The measured width of the unilateral depletion region is 1360 ± 160nm. Our work has provided substantial insights into mediated photocarrier dynamics in the 2D lateral heterostructure, which will benefit explorations in 2D interfacial physics and 2D lateral optoelectronic devices.

Boosting acetone response of p-type Co3O4 sensor via Sn and Ni co-doping for diabetes diagnosis

The hole accumulation layer (HAL) configuration of p-type oxides (including Co3O4) in ambient air causes intrinsically low gas response and hinders their promising applications in exhaled gas analysis. Herein, Sn and Ni co-doping has been proposed to trigger the response of chemiresistive Co3O4 sensor toward acetone (biomarker of diabetes). Via incorporating 1 at% Sn and 0.5 at% Ni doping (Co2.95Sn0.03Ni0.02O4), the response to 100 ppm acetone has been boosted ∼2 orders (from 1.24 to 125.6) at 70 °C, the limit of detection (LoD) has been reduced ∼4 times (from 47.9 to 12.4 ppb), the optimal operation temperature has been decreased from 130 °C to ∼70 °C. Various characterizations suggest that co-doping induced abundant surface asymmetric oxygen vacancy defects (Co-□-Ni, Sn-□-Ni), which facilitate the catalytic oxidation of acetone molecules at relatively low operation temperature. In addition to excellent reproducibility and long-term stability, Co2.95Sn0.03Ni0.02O4 sensor could also operate under highly humid air background and reliably detect acetone concentration in exhaled breath at 150 °C, opening the opportunity for the practical application of p-type oxide sensors for diabetes diagnosis.

Effects of Ti3C2Tx MXene Addition to a Co Complex/Ionic Liquid-Based Electrolyte on the Photovoltaic Performance of Solar Cells.

Redox mediators comprising I-, Co3+, and Ti3C2Tx MXene were applied to dye-sensitized solar cells (DSCs). In the as-prepared DSCs (I-DSCs), wherein hole conduction occurred via the redox reaction of I-/I3- ions, the power conversion efficiency (PCE) was not altered by the addition of Ti3C2Tx MXene. The I-DSCs were exposed to light to produce Co2+/Co3+-based cells (Co-DSCs), wherein the holes were transferred via the redox reaction of Co2+/Co3+ ions. A PCE of 9.01% was achieved in a Co-DSC with Ti3C2Tx MXene (Ti3C2Tx-Co-DSC), which indicated an improvement from the PCE of a bare Co-DSC without Ti3C2Tx MXene (7.27%). It was also found that the presence of Ti3C2Tx MXene in the redox mediator increased the hole collection, dye regeneration, and electron injection efficiencies of the Ti3C2Tx-Co-DSC, leading to an improvement in both the short-circuit current and the PCE when compared with those of the bare Co-DSC without MXene.

Extraction of gap states in AlSiO/AlN/GaN metal-oxide-semiconductor field-effect transistors using the multi-terminal capacitance–voltage method

Direct extraction of gap states from a metal-oxide-semiconductor field-effect transistor (MOSFET) in which inversion electrons and holes in a p-type body coexist is challenging. We demonstrate gap-state extraction in lateral-type GaN MOSFETs with high channel mobilities using multi-terminal capacitance–voltage (C–V) methods. The gate stack of the MOSFET was composed of AlSiO/AlN/p-type GaN formed on a p+/n+ GaN tunnel junction structure. The substrate electrode was short-circuited to a p-type body layer through the tunnel junction. The MOSFET was equipped with gate, source, drain, body, and substrate electrodes. When the gate was the high side and the other electrodes were the low side in the AC circuit, a V-shaped C–V curve was obtained because of electron inversion and hole accumulation. When the body/substrate electrodes were connected to the ground level (i.e., split C–V method), the inversion electrons between the gate and source/drain electrodes could be evaluated. We proposed a “reverse” split C–V method in which the source/drain electrodes are grounded and the body/substrate electrodes are connected to the low side. This method enabled extraction of gap states near the valence-band maximum of GaN, with exclusion of the overlap capacitance and the capacitance due to inversion electrons. The proposed method demonstrated overall gap states in the GaN MOSFET with a wide bandgap. The results suggest that hole traps with discrete energy levels caused negative bias instability (NBI) in the GaN MOSFET. Furthermore, NBI and discrete gap states were consistently suppressed by Mg doping at >1018 cm−3 into a p-type body.

Photo-assisted electrocatalysis of NiO/CeO2 heterojunction for efficient oxygen evolution reaction

In recent years, photo-assisted electrocatalysis has attracted significant interest in the field of electrolytic hydrogen production. By integrating electrical and optical energy, supplementary energy is harnessed for the electrocatalytic process, which offers an efficient strategy to enhance the performance of oxygen evolution reaction (OER). Herein, the heterojunction NiO/CeO2 composite nanostructures supported by nickel foam (represented as NiO/CeO2@NF) was selected as the photo-assisted electrocatalyst, through the mutual synergy of voltage and light to improve the catalytic activity of OER in electrolytic water. Under light irradiation, the NiO component undergoes photoexcited to produce photogenerated electrons that move towards the CeO2 component, stimulating the generation and accumulation of more holes accelerating the formation of Ni (III) to improve the reaction efficiency with electrons, thereby boosting the enhancement of OER activity. The results demonstrate that the overpotential corresponding to NiO/CeO2@NF in non-irradiation at 10 mA cm−2 current density was 280 mV, and the NiO/CeO2@NF in light irradiation displays robust OER activity, with lower over-potentials 260 mV at 10 mA cm−2, which 20 mV lower than in non-irradiation. Moreover, NiO/CeO2@NF in light irradiation exhibits high catalytic activity and durability for OER in an alkaline electrolyte, delivering 100 mA cm−2 at 320 mV and outperforming RuO2 under high current densities.

Optimizing Energy Levels and Improving Film Compactness in PbS Quantum Dot Solar Cells by Silver Doping.

PbS quantum dot (QD) solar cells harvest near-infrared solar radiation. Their conventional hole transport layer has limited hole collection efficiency due to energy level mismatch and poor film quality. Here, how to resolve these two issues by using Ag-doped PbS QDs are demonstrated. On the one hand, Ag doping relieves the compressive stress during layer deposition and thus improves film compactness and homogeneity to suppress leakage currents. On the other hand, Ag doping increases hole concentration, which aligns energy levels and increases hole mobility to boost hole collection. Increased hole concentration also broadens the depletion region of the active layer, decreasing interface charge accumulation and promoting carrier extraction efficiency. A champion power conversion efficiency of 12.42% is achieved by optimizing the hole transport layer in PbS QD solar cells, compared to 9.38% for control devices. Doping can be combined with compressive strain relief to optimize carrier concentration and energy levels in QDs, and even introduce other novel phenomena such as improved film quality.

Experimental evidences of the direct influence of external magnetic fields on the mechanism of the electrocatalytic oxygen evolution reaction

The use of magnetic fields as external stimuli to improve the kinetics of electrochemical reactions is attracting substantial attention, given their potential to reduce energy losses. Despite recent reports showing a positive effect on catalytic performance upon applying a magnetic field to a working electrode, there are still many uncertainties and a lack of experimental evidence correlating the presence of the magnetic field to the electrocatalytic performance. Here, we present a combination of electrochemical and spectroscopic tools that demonstrate how the presence of an external magnetic field alters the reaction mechanism of the electrocatalytic oxygen evolution reaction (OER), accelerating the overall performance of a Ni4FeOx electrode. Complementary experimental evidence has been gathered supporting the participation of this microscopic magnetic field effect. Electrochemical impedance spectroscopy (EIS) points to a speed-up of the intrinsic reaction kinetics, independent of other indirect effects. In the same direction, the spectro-electrochemical fingerprint of the intermediate species that appear during the electrocatalytic cycle, as detected under operando conditions, indicates a change in the order of the reaction as a function of hole accumulation. All these experimental data confirm the direct influence of an external magnetic field on the reaction mechanism at the origin of the magnetically enhanced electrocatalytic OER.

On electron and hole accumulation in a core-shell nanowire: Study by a Monte Carlo simulation

A Monte-Carlo simulation is used to study carrier accumulation inside a Ge–Si core-shell nanowire inside an n-doped Si substrate in the electron beam induced current technique. An ideal and a like-real nanowires are studied. For the like-real nanowire, imperfections are described by square wave functions representing modulation of Ge and Si radial dimensions. Carriers are created using an electron beam energy of 5 keV in the perpendicular configuration. A part of holes is collected by a nanoscale electrode. Another part is accumulated inside the core. Electrons are accumulated inside the shell since the core-shell is assumed to exhibit type II confinement of band edge alignment. The results show that the hole collection efficiency increases, at the expense of carrier trapping in the nanowire, with the distance depth between the nanowire and the nanocontact until a threshold distance of ∼50 nm from which the induced current reaches a saturation. While the accumulation of both holes and electrons inside the nanowire continues to decline. The only difference between an ideal and a like-real nanowire is underlined by more electrons inside the ideal than the like-real one. The accumulated hole number is weak and shows no difference between the two nanowires.

Stable and efficient pure blue quantum-dot LEDs enabled by inserting an anti-oxidation layer

The efficiency and stability of red and green quantum-dot light-emitting diodes have already met the requirements for commercialization in displays. However, the poor stability of the blue ones, particularly pure blue color, is hindering the commercialization of full-color quantum-dot light-emitting diode technology. Severe hole accumulation at the blue quantum-dot/hole-transport layer interface makes the hole-transport layer prone to oxidation, limiting the device operational lifetime. Here, we propose inserting an anti-oxidation layer (poly(p-phenylene benzobisoxazole)) between this interface to take in some holes from the hole-transport layer, which mitigates the oxidation-induced device degradation, enabling a T50 (time for the luminance decreasing by 50%) of more than 41,000 h with an initial brightness of 100 cd m−2 in pure blue devices. Meanwhile, the inserted transition layer facilitates hole injection and helps reduce electron leakage, leading to a peak external quantum efficiency of 23%.

Plasmon induced hot carrier distribution in Ag20 -CO composite.

The interaction between plasmons and the molecules leads to the transfer of plasmon-induced hot carriers, presenting innovative opportunities for controlling chemical reactions on sub-femtosecond timescales. Through real-time time-dependent density functional theory simulations, we have investigated the enhancement of the electric field due to plasmon excitation and the subsequent generation and transfer of plasmon-induced hot carriers in a linear atomic chain of Ag20 and an Ag20 -CO composite system. By applying a Gaussian laser pulse tuned to align with the plasmon frequency, we observe a plasmon-induced transfer of hot electrons from the occupied states of Ag to the unoccupied molecular orbitals of CO. Remarkably, there is a pronounced accumulation of hot electrons and hot holes on the C and O atoms. This phenomenon arises from the electron migration from the inter-nuclear regions of the C-O bond towards the individual C and O atoms. The insights garnered from our study hold the potential to drive advancements in the development of more efficient systems for catalytic processes empowered by plasmonic interactions.

Ultrathin covalent organic framework nanosheets for enhanced photocatalytic water oxidation.

Photocatalytic water oxidation is a key half-reaction for various solar-to-fuel conversion systems but requires simultaneous water affinity and hole accumulation at the photocatalytic site. Here, we present the rational design and synthesis of an ionic-type covalent organic framework (COF) named tetraphenylporphyrin cobalt and cobalt bipyridine complex (CoTPP-CoBpy3) COF, combining cobalt porphyrin and cobalt bipyridine building blocks as a photocatalyst for water oxidation. The good dispersibility of porous large-size (>2 micrometers) COF nanosheets (≈1.45 nanometers) facilitates local water collection; the ultrafast triplet-state charge transfer (1.8 picoseconds) and prolonged charge separation (1.2 nanoseconds) further contribute to the efficient accumulation of holes in the CoTPP moiety, leading to a photocatalytic dioxygen production rate of 7323 micromoles per gram per hour. Moreover, we have identified an end-on superoxide radical (O2·) intermediate at the active site of the CoTPP moiety and proposed an electron-intermediate cascade mechanism that elucidates the synergistic coupling of electron relay (S1-T1-T1') and intermediate evolution during the photocatalytic process.

Boosting carrier separation and transport in CuGaO2 photocathodes by coupled effects of surface polarization and facet-junction

This study investigates the synergistic enhancement of carrier separation and transport in CuGaO2 photocathodes, achieved through the coupled effects of surface polarization and facet-junction engineering. Delafossite CuGaO2 microspheres, which exhibit a flower-like micro-nano hierarchical structure, are synthesized facilely through a one-pot hydrothermal process. These microspheres self-assemble from CuGaO2 nanosheets, driven by electrostatic forces among crystal facets. Morphology and size are systematically modulated by pH values, solvent composition, and reaction temperature. The CuGaO2 nanosheets, serving as fundamental building blocks, manifest notable surface polarization effects that facilitate the efficient transport of photo-generated carriers. The facet-junction formed between intersecting CuGaO2 nanosheets facilitates the collection of photo-generated electrons and holes on both sides of the interface, leading to spatial separation. Consequently, the CuGaO2 microspheres synergistically combine nanoscale surface polarization and microscale facet-junction effects, promoting the effective separation and rapid transport of electron-hole pairs generated under visible-light irradiation. The resulting simple bare photocathode, constructed using CuGaO2 microspheres, demonstrates a photocurrent density of 32 μA/cm2 at zero-bias, with a peak incident photon-to-current efficiency of 12.72 % at a 450 nm wavelength. Further optimization of the CuGaO2 photocathode yields a better photocurrent density of 138 μA/cm2 at 0.33 VRHE. These results underscore the significance of integrating nanoscale surface polarization effects with microscale facet-junction effects to achieve efficient separation and rapid transport of photo-generated carriers in photoelectrochemical cells.

ZnFe2O4 nanosheets as an electron transport bridge and a hole mediator enhance solar-driven unbiased hydrogen generation of ZnO-based nanorod arrays photoanode

In this study, a novel ternary ZnO-based nanorod arrays (NRAs) photoanode is designed and constructed for the first time for unassisted solar-light-driven water splitting to generate H2 using photoelectrochemical (PEC) cell. The ternary heterojunction photoanode is constructed by modifying ZnO NRAs with ZnFe2O4 nanosheets (NSs) and CdS nanoparticles (NPs), successively. The band alignment study demonstrates that ZnFe2O4 NSs as an interfacial modification layer not only enlarge the contact area with ZnO and CdS respectively to build a stair-step band alignment of conduction band levels for the efficient transport of electrons but also make the valence band of ZnFe2O4 to be as the hole accumulation site in the ternary heterojunction. The electrochemical and photoluminescence measurements demonstrate the efficient separation of the carriers. Consequently, the ternary ZnO-based NRAs photoanode achieves a significant H2 generation rate of 92.9 μmol/h, 6.23 and 2.97 times of ZnO NRAs and ZnO/ZnFe2O4 NRAs/NSs photoanodes, respectively.

Preparation of Surface Dispersed WO3/BiVO4 Heterojunction Arrays and Their Photoelectrochemical Performance for Water Splitting.

In this work, a surface dispersed heterojunction of BiVO4-nanoparticle@WO3-nanoflake was successfully prepared by hydrothermal combined with solvothermal method. We optimized the morphology of the WO3 nanoflakes and BiVO4 nanoparticles by controlling the synthesis conditions to get the uniform BiVO4 loaded on the surface of WO3 arrays. The phase composition and morphology evolution with different reaction precursors were investigated in detail. When used as photoanodes, the WO3/BiVO4 composite exhibits superior activity with photocurrent at 3.53 mA cm-2 for photoelectrochemical (PEC) water oxidation, which is twice that of pure WO3 photoanode. The superior surface dispersion structure of the BiVO4-nanoparticle@WO3-nanoflake heterojunction ensures a large effective heterojunction area and relieves the interfacial hole accumulation at the same time, which contributes to the improved photocurrents together with the stability of the WO3/BiVO4 photoanodes.

Towards a Timepix3 Radiation Monitor for the Accelerator Mixed Radiation Field: Characterisation with Protons and Alphas from 0.6 MeV to 5.6 MeV

A Timepix3 detector with a 300 μm silicon sensor has been studied as a novel radiation monitor for the mixed radiation field at the Large Hadron Collider at CERN. This work describes a test campaign carried out at Centro Nacional de Aceleradores with quasi-mono energetic protons (alphas) from 0.6 (1) to 5 (5.6) MeV, where orthogonal irradiations are used to obtain an energy calibration, and a low-energy angular scan to estimate the front dead layer thickness of the sensor. The detector is operated in hole collection mode and at a partial bias of 250 μm at 50 V, which increases the charge sharing among pixels to mitigate the signal saturation at high energy depositions. The data, supported by FLUKA Monte Carlo simulations of energy losses in the sensor, show that the Timepix3 monitor operates in a linear regime up to energy depositions of around 600 keV per pixel and 2 MeV per cluster. As a result, the detector has been found to be suitable for measuring charged particle fluxes in the LHC mixed radiation field within the linear calibration regime, with the partial exception of inelastic nuclear reaction hits (mostly from neutrons).

Slow hole diffusion limits the efficiency of p-type dye-sensitized solar cells based on the P1 dye.

NiO electrodes are widely applied in p-type dye-sensitized solar cells (DSSCs) and photoelectrochemical cells, but due to excessive charge recombination, the efficiencies of these devices are still too low for commercial applications. To understand which factors induce charge recombination, we studied electrodes with a varying number of NiO layers in benchmark P1 p-DSSCs. We obtained the most efficient DSSCs with four layers of NiO (0.134%), and further insights into this optimum were obtained via dye loading studies and in operando photoelectrochemical immittance spectroscopy. These results revealed that more NiO layers led to an increasing light harvesting efficiency (η LH), but a decreasing hole collection efficiency (η CC), giving rise to the maximum efficiency at four NiO layers. The decreasing η CC with more NiO layers is caused by longer hole collection times, which ultimately limits the overall efficiency. Notably, the recombination rates were independent of the number of NiO layers, and similar to those observed in the more efficient n-type DSSC analogues, but hole collection was an order of magnitude slower. Therefore, with more NiO layers, the beneficial increase in η LH can no longer counteract the decrease in η CC due to slow hole collection, resulting in the overall efficiency of the solar cells to maximize at four NiO layers.

An ultra-sensitive colloidal quantum dot infrared photodiode exceeding 100 000% external quantum efficiency via photomultiplication.

In this study, we present ultrasensitive infrared photodiodes based on PbS colloidal quantum dots (CQDs) using a double photomultiplication strategy that utilizes the accumulation of both electron and hole carriers. While electron accumulation was induced by ZnO trap states that were created by treatment in a humid atmosphere, hole accumulation was achieved using a long-chain ligand that increased the barrier to hole collection. Interestingly, we obtained the highest responsivity in photo-multiplicative devices with the long ligands, which contradicts the conventional belief that shorter ligands are more effective for optoelectronic devices. Using these two charge accumulation effects, we achieved an ultrasensitive detector with a responsivity above 7.84 × 102 A W-1 and an external quantum efficiency above 105% in the infrared region. We believe that the photomultiplication effect has great potential for surveillance systems, bioimaging, remote sensing, and quantum communication.

Carrier modulation of one-dimensional MAPbxSr1-x(IyCl1-y)3 core-shell perovskite nanowires.

Low dimensional hybrid organic-inorganic perovskites (HOIPs) have become one of the most promising materials in solar cells, photodetectors, and lasers due to their low exciton binding energy, high bipolar carrier mobility, and long carrier lifetime. The effective separation and collection of photo-generated electrons and holes have always been crucial for a perovskite as a working medium for optoelectronic devices. However, the surface state of pristine perovskite nanowires causes recombination of electrons and holes at the edge of the energy band, leading to deactivation of charge carriers. In this work, we constructed MAPbxSr1-xI3 core-shell nanowires, which adjust the band gap and control the spatial distribution of charge carriers by changing the Pb composition ratio, achieving spontaneous separation of electron-hole pairs to avoid surface recombination. In addition, MAPbxSr1-x(IyCl1-y)3 core-shell nanowires with different component ratios (x, y) can be constructed by further doping the Cl element, and the spatial distribution of charge carriers in the nanowires can be flexibly manipulated to achieve exchange between type-I and type-II band alignment orders. This study provides a feasible method for enhancing the carrier separation of organic-inorganic hybrid perovskites and improving the performance of optoelectronic devices.

Theoretical estimation of sound absorption characteristics in a collection of rectangular holes: Comparison with experimental results

This study quantifies the sound absorption properties of small rectangular or square pores that are less than a few millimeters per side, based solely on their geometric dimensions. Analytical solutions for the sound absorption coefficient of narrow tubes with rectangular holes have not been obtained. Therefore, alternative methods of predicting the sound absorption coefficient, such as using the circular tube approximation or the two-plane approximation, are possible. In this study, the sound absorption coefficient was estimated by several theoretical models that are considered useful for estimating the sound absorption coefficient in rectangular tubes. The results were then compared with experimental values. For square holes, the accuracy of the sound absorption coefficient increased in the order of the model considering two-sided circumference only, the circular tube model, and Allard's method based on Stinson's. In rectangular holes, Allard's method based on Stinson's showed good agreement with the experimental data across a wide range of aspect ratios. For rectangular holes, the accuracy of Stinson's two-plane approximation was superior to that of the circular tube approximation when the aspect ratio was 4. Furthermore, when the aspect ratio was 8, the accuracy of Stinson's two-plane approximation became comparable to that of Allard's method based on Stinson's.