Deciphering the Space Charge Effect of the CoNiLDH/FeOOH n-n Heterojunction for Efficient Electrocatalytic Oxygen Evolution.

Space charge transfer is an effective strategy to regulate the electron density of narrow bandgap semiconductors for enhancing electrocatalytic activity. Herein, the CoNiLDH/FeOOH n-n heterojunction hollow nanocages structure is constructed. The hollow structure provides abundant catalytic active sites and enhances mass transfer. The space charge region in the n-n heterojunction significantly promotes the adsorption of OH- and electron transfer; and the built-in electric field accelerates the electron transport, optimizes the electronic structure during the catalytic reaction process, and ensures the stability of surface charged active center sites in the heterojunction. Thus, CoNiLDH/FeOOH delivers an excellent oxygen evolution reaction (OER) overpotential of 250 mV to achieve a current density of 10 mA cm-2 with a small Tafel slope of 60 mV dec-1 , and superior electrocatalytic durability for 210 h at a high current density. Density functional theory calculations further verify that the space charge effect and built-in electric field in the n-n heterojunction of CoNiLDH/FeOOH can improve the electron transfer and lower the adsorption energy of OH- and the reaction energy barrier of the rate-determining step. This work provides a new fundamental understanding of the space charge effect of semiconductor heterojunction during the electrocatalytic process for developing more efficient OER electrocatalysts.

An Angular Radial Extended Interaction Amplifier at the W Band.

In this paper, an angular radial extended interaction amplifier (AREIA) that consists of a pair of angular extended interaction cavities is proposed. Both the convergence angle cavity and the divergence angle cavity, which are designed for the converging beam and diverging beam, respectively, are investigated to present the potential of the proposed AREIA. They are proposed and explored to improve the beam-wave interaction capability of W-band extended interaction klystrons (EIKs). Compared to conventional radial cavities, the angular cavities have greatly decreased the ohmic loss area and increased the characteristic impedance. Compared to the sheet beam (0°) cavity, it has been found that the convergence angle cavity has a higher effective impedance and the diverging beam has a weaker space-charge effect under the same ideal electron beam area; the advantages become more obvious as the propagation distance increases. Particle-in-cell (PIC) results have shown that the diverging beam (8°) EIA performs better at an output power of 94 GHz under the condition of lossless, while the converging beam (-2°) EIA has a higher output power of 6.24 kW under the conditions of ohmic loss, an input power of 0.5 W, and an ideal electron beam of 20.5 kV and 1.5 A. When the loss increases and the beam current decreases, the output power of the -2° EIA can be improved by nearly 30% compared to the 0° EIA, and the -2° EIA has a greatly improved beam-wave interaction capacity than conventional EIAs under those conditions. In addition, an angular radial electron gun is designed.

High Thickness Tolerance in All-Polymer-Based Organic Photovoltaics Enables Efficient and Stable In-Door Operation.

Organic photovoltaics (OPVs) have great potential to drive low-power consumption electronic devices under indoor light due to their highly tunable optoelectronic properties. Thick devices (>300 nm photo-active junctions) are desirable to maximize photocurrent and to manufacture large-scale modules via solution-processing. However, thick devices usually suffer from severe charge recombination, deteriorating device performances. Herein, the study demonstrates excellent thickness tolerance of all-polymer-based PVs for efficient and stable indoor applications. Under indoor light, device performance is less dependent on photoactive layer thickness, exhibiting the best maximum power output in thick devices (34.7 µW cm-2 in 320-475 nm devices). Thick devices also exhibit much better photostability compared with thin devices. Such high thickness tolerance of all-polymer-based PV devices under indoor operation is attributed to strongly suppressed space-charge effects, leading to reduced bimolecular recombination losses in thick devices. The unbalanced charge carrier mobilities are identified as the main cause for significant space-charge effects, which is confirmed by drift-diffusion simulations. This work suggests that all-polymer-based PVs, even with unbalanced mobilities, are highly desirable for thick, efficient, and stable devices for indoor applications.

Heterointerfaces: Unlocking Superior Capacity and Rapid Mass Transfer Dynamics in Energy Storage Electrodes.

Heterogeneous electrode materials possess abundant heterointerfaces with a localized "space charge effect", which enhances capacity output and accelerates mass/charge transfer dynamics in energy storage devices (ESDs). These promising features open new possibilities for demanding applications such as electric vehicles, grid energy storage, and portable electronics. However, the fundamental principles and working mechanisms that govern heterointerfaces are not yet fully understood, impeding the rational design of electrode materials. In this study, the heterointerface evolution during charging and discharging process as well as the intricate interaction between heterointerfaces and charge/mass transport phenomena, is systematically discussed. Guidelines along with feasible strategies for engineering structural heterointerfaces to address specific challenges encountered in various application scenarios, are also provided. This review offers innovative solutions for the development of heterogeneous electrode materials, enabling more efficient energy storage beyond conventional electrochemistry. Furthermore, it provides fresh insights into the advancement of clean energy conversion and storage technologies. This review contributes to the knowledge and understanding of heterointerfaces, paving the way for the design and optimization of next-generation energy storage materials for a sustainable future.

Modulating space charge of FeP/CoP p-n heterojunction for boosting oxygen evolution reaction.

Surface reconstruction of electrocatalysts is an effective strategy to modulate the space charge distribution to enhance the electrocatalytic activity. The p-n heterostructured FeP/CoP-2D octagonal nanoplates were successfully constructed by cation-exchange method. The space charge effect caused by the p-n heterojunction accelerated the electron transfer, optimized the electronic structure, and improved the activity of the active sites during the oxygen evolution reaction process. As a result, FeP/CoP-2D required only 247 mV overpotential to achieve a current density of 10 mA cm-2 with a Tafel slope as low as 68 mV dec-1. Density-functional theory calculations confirmed that the construction of p-n heterojunctions can enhance the adsorption of *OH in the active centers and optimize the Gibbs free energy of the OER reaction. This study provides an effective and feasible strategy for constructing p-n heterojunctions to modulate the space charge state for optimizing the OER performance of electrocatalysts.

Reduction of recombination effects in large plane parallel beam monitors for FLASH radiotherapy with scanned ion beams.

PURPOSE: Radiotherapy escalating dose rates above 50Gys-1, might offer a great potential in treating tumours while further sparing healthy tissue. However, these ultra-high intensities of FLASH-RT lead to new challenges with regard to dosimetry and beam monitoring. FLASH experiments at HIT (Heidelberg Ion Beam Therapy Center) and at GSI (GSI Helmholtz Centre for Heavy Ion Research) have shown a significant loss of signal in the beam monitoring system due to recombination effects. To enable accurate beam monitoring, this work investigates the recombination loss of different fill gases in the plane parallel ionisation chambers (ICs). METHODS: Therefore, saturation curves at high intensities were measured for the currently used fill gases Ar/CO2 (80/20) and pure He and also for He/CO2 mixtures as alternative fill gases. Furthermore, breakdown voltages and ion mobilities were measured in ICs filled with He/CO2 mixtures. A numerical model for volume recombination in plane parallel ionisation chambers was developed and implemented in Python. This includes a novel simulation method of the space charge effect from the charge carriers in the detector volume and predicts a significant effect on the electric field for high intensity beams. RESULTS: Even at high intensities the He/CO2 mixtures allow operation of the ICs at an electric field strength of 2 kVcm-1 or more which reduces recombination to negligible levels at intensities larger than 3 × 101012C-ions per second. Our measurements show that added fractions of CO2 to He decrease the ion mobility in the fill gas but significantly increase the breakdown voltage in the ICs compared to pure He.

Facilely Achieved Self-Biased Black Silicon Heterojunction Photodiode with Broadband Quantum Efficiency Approaching 100.

Photodiodes are fundamental components in modern optoelectronics. Heterojunction photodiodes, simply configured by two different contact materials, have been a hot research topic for many years. Currently reported self-biased heterojunction photodiodes routinely have external quantum efficiency (EQE) significantly below 100% due to optical and electrical losses. Herein, an approach that virtually overcomes this 100% EQE challenge via low-aspect-ratio nanostructures and drift-dominated photocarrier transport in a heterojunction photodiode is proposed. Broadband near-ideal EQE is achieved in nanocrystal indium tin oxide/black silicon (nc-ITO/b-Si) Schottky photodiodes. The b-Si comprises nanostalagmites which balance the antireflection effect and surface morphology. The built-in electric field is explored to match the optical generation profile, realizing enhanced photocarrier transport over a broadband of photogeneration. The devices exhibit unprecedented EQE among the reported leading-edge heterojunction photodiodes: average EQE surpasses ≈98% for wavelengths of 570-925 nm, while overall EQE is greater than ≈95% from 500 to 960 nm. Further, only elementary fabrication techniques are explored to achieve these excellent device properties. A heart rate sensor driven by nanowatt faint light is demonstrated, indicating the enormous potential of this near-ideal b-Si photodiode for low power consuming applications.

Numerical Simulation of Flow Field and Ion Transport for Different Ion Source Sampling Interfaces of a Mass Spectrometer.

Understanding ion transport mechanisms in the flow expansion section of the first vacuum region of a mass spectrometer (MS) with an atmospheric pressure ionization source is essential for optimizing the MS sampling interface design. In this study, numerical simulations of three types of ions in two different MS interface designs have been carried out. In contrast to previously reported numerical studies, nonequilibrium gas dynamics due to rarefied gas effects has been considered in modeling the flow expansion and a realistic space charge effect has been considered in a continuous ion injection mode. Numerical simulations reveal that a flat plate interface has a higher peak buffer gas velocity but a narrower zone of silence compared to the conical interface. Shock wave structures are clearly captured, and the Knudsen number distribution is displayed. Simulation results show that in the axial direction the buffer gas effect is much stronger than the electric force effect in the current configuration. The conical interface leads to both a strong ion acceleration in the zone of silence and a strong ion deceleration downstream. In the radial direction, both the electric force and buffer gas drag force play an important role. The conical interface introduces a relatively stronger ion focusing effect from the radial buffer gas effect and a stronger ion dispersion from the radial electric force than the flat plate interface. The net effect for the current configuration is an increase in ion losses for the conical interface. Nanoelectrospray ionization experiments were carried out to validate the ion transmission efficiency.

Numerical Simulation of Ion Transport in a Nano-Electrospray Ion Source at Atmospheric Pressure.

Understanding ion transport properties from the ion source to the mass spectrometer (MS) is essential for optimizing device performance. Numerical simulation helps in understanding of ion transport properties and, furthermore, facilitates instrument design. In contrast to previously reported numerical studies, ion transport simulations in a continuous injection mode whilst considering realistic space-charge effects have been carried out. The flow field was solved using Reynolds-averaged Navier-Stokes (RANS) equations, and a particle-in-cell (PIC) method was applied to solve a time-dependent electric field with local charge density. A series of ion transport simulations were carried out at different cone gas flow rates, ion source currents, and capillary voltages. A force evaluation analysis reveals that the electric force, the drag force, and the Brownian force are the three dominant forces acting on the ions. Both the experimental and simulation results indicate that cone gas flow rates of ≤250 slph (standard liter per hour) are important for high ion transmission efficiency, as higher cone gas flow rates reduce the ion signal significantly. The simulation results also show that the ion transmission efficiency reduces exponentially with an increased ion source current. Additionally, the ion loss due to space-charge effects has been found to be predominant at a higher ion source current, a lower capillary voltage, and a stronger cone gas counterflow. The interaction of the ion driving force, ion opposing force, and ion dispersion is discussed to illustrate ion transport mechanism in the ion source at atmospheric pressure. Graphical Abstract.

Use of Gradient Dilution to Detect and Correct Matrix Interferences in Inductively Coupled Plasma-Time-of-Flight Mass Spectrometry (ICP-TOFMS).

Our research group earlier used dispersion that occurs during flow injection to detect and reduce matrix interference in inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS). In the absence of a matrix interference, the ratio of signals from any two sample constituents should remain constant, independent of the dilution, over the course of a flow-injection transient. However, when an interferent is present, the signal ratio from different analytes will change with dilution, owing to the difference in severity of the interference on specific analytes. As a result, matrix interference can be recognized (flagged) by monitoring the signal ratios of two analytes over the course of a flow-injection transient; a ratio that changes over time indicates the presence of an interferent. The drawback of this earlier method was that dispersion, and therefore dilution, was somewhat element-specific, causing the ratios to wander even when no interference existed. Here, a gradient HPLC pump is used to overcome this drawback by creating a longer, better-controlled dilution. Under these conditions, variation in dispersion between elements is negligible and difficulties associated with it are reduced or eliminated. Further, when an interference exists, the optimal dilution factor to reduce the interference to an acceptable level can be found from the gradient-dilution curve as the point where the signal ratio between two elements becomes constant.