Charge Transport Channels Research Articles

Asymmetric CuS1N4 as Axial Polarization Site Trigger Rapid Charge Transport Channels for Boosting Photosynthesis of Ammonia

AbstractEffective photogenerated charge transfer and utilization have been regarded as a critical factor for achieving highly efficient photosynthesis of ammonia. However, the lacks necessary driving force in many catalysts limit the directly charge transfer. In this work, Cu porphyrin‐based monoatomic layer (PML‐Cu) is modified on face‐centered cubic structured defective CdIn2S4 via solvothermal reaction, with a strong coupled interfacial Cu─S bond is constructed. Owing to the formation of axial CuS1N4 polarization site, the local interfacial asymmetric configuration can be created between CdIn2S4 and PML‐Cu to form a strong potential difference, inducing the rapid charge transport from CdIn2S4 to PML‐Cu via Cu─S bond. Meantime, the electron‐enriched CuS1N4 site is beneficial to the stabilization of *NHOH intermediate state, and then lowering the *NHO→*NHOH rate‐limiting step energy barrier. Benefiting from these features, the PML‐Cu/CdIn2S4 exhibit good NH3 generation rate of 1979.0 µmol g−1 h−1, with apparent quantum efficiency of 8.56% at 380 nm and 7.40% at 450 nm, respectively. This work provides an accessible pathway for designing interfacial asymmetric configuration with strong coupling to boost photocatalysis.

Molecular Design and Alignment for Ambipolar SCLC Mobility in Self-Assembled Columnar Discogens.

The future of next-generation electronics relies on low-cost organic semiconductors that are tailored to simultaneously provide all requisite optoelectronic properties, focusing greatly on ambipolar charge-transport and solution processability. In this regard, room-temperature discotic liquid crystals (DLCs) are potential candidates, where quasi-1D self-assembly affords a charge-transport channel along their columnar axis. This work shows a molecular design strategy by utilizing anthraquinone as the primary motif, surrounded by ester functionalized tri-alkoxy phenyl units to develop room-temperature DLCs (1.1-1.3). Here, the polar ester functionality stabilizes the columnar mesophase over a wide range through the involvement of dipole-dipole interaction along with the π-π stacking. Throughout the entire mesophase transition, reported compounds 1.1-1.3 exhibit a highly ordered 2D columnar oblique (Colob) self-assembly. Space charge limited current (SCLC) experiments reveal balanced ambipolar charge transport, with the maximum hole and electron mobilities of 5.04 and 4.93 cm2 V-1 s-1, respectively. From the conoscopic results, their propensity to align in a highly homeotropic fashion is demonstrated. It is further justified by the azimuthal plot corresponding to the (11) peak of grazing incidence small angle X-ray scattering (GISAXS), denoting the crucial role of the design and alignment for efficient movement of charge carriers in the material.

Topological Defect-Regulated Porous Carbon Nanoribbon for High-Performance Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) using carbonaceous anode materials have attracted a great deal of research interest. However, the large atomic size of potassium ions inevitably leads to huge volume expansion and the collapse of anodes during intercalation, which greatly hinders rate performance and cycling life. In this work, carbon nanotube-derived porous N-doped carbon nanoribbon (CNR) bundles are designed as an anode for PIBs. These CNR materials are in rich defects which provide fast channels for charge transport and abundant active sites for potassium ion storage. The CNR materials exhibit a maximum capacity of 441.4mAhg-1 at a current density of 0.2Ag-1 after 200 cycles as well as a highly reversible capacity of 263.6mAhg-1 at a current density of 5.0Ag-1 even after 1000 cycles. This work provides guidance for the structure design of nanoribbon materials for high-performance PIBs.

Synergistic potentiation between P3HT and PTAA enables blade-coated carbon-electrode perovskite solar cells with >21% outdoor and >35% indoor efficiencies

P3HT is a promising hole-transport layer (HTL) for efficient and stable carbon electrode-based perovskite solar cells (C-PSCs). However, the reported low efficiencies of P3HT C-PSCs, resulting from the unmatched band alignment and electronically poor contact between perovskite and P3HT, is an obstacle. In this work, we propose a binary HTL system that incorporates PTAA into P3HT to address this issue, thereby achieving efficiencies of 21.3 % (0.04 cm2) and 18.8 % (1.0 cm2) under AM 1.5G illumination, and 35.2 % under indoor illumination of 1000 lx, all of which are the highest reported values for low-temperature printable C-PSCs. Experimental and theoretical results revealed that the performance improvements mainly stem from the following collaborative effects between P3HT and PTAA: 1) the introduction of PTAA increases more face-on orientations of P3HT as well as enhanced π–π stacking, forming more effective charge transport channels as molecular bridges; 2) the hole extraction barrier from perovskite to P3HT is reduced by 0.07 eV through incorporating PTAA; 3) triarylamine PTAA and other more face-on configurations can provide additional and stronger passivation sites, intensifying the defect passivation effects. Finally, unencapsulated P3HT-PTAA C-PSCs maintain ≈91 % of initial performance after maximum power point tracking for over 900 h.

Synthesis of Ni(OH)2‐g‐C3N4/C Composite by Biological Template for Asymmetric Supercapacitor

Nickel hydroxide (Ni(OH)2) is recognized as a promising material for electrodes in supercapacitors owing to its exceptional theoretical specific capacitance. However, Ni(OH)2 has several drawbacks, including a short cycle life, susceptibility to volume expansion, and poor electrical conductivity. In this work, Ni(OH)2 nanosheets anchored on layered g‐C3N4/C (Ni(OH)2–g–C3N4/C) are designed by biological template induction and a hydrothermal method. Ni(OH)2–g–C3N4/C has unique petal‐like structures, which can provide a vertical charge transport channel to increase reaction potential of the material during the charge–discharge process. The introduction of biomass carbon can solve the problem of the bulk phase accumulation of g‐C3N4 and can also improve the overall conductivity of the composite. Compared to Ni(OH)2 (522 F g−1), g‐C3N4/C (76.2 F g−1), and g‐C3N4 (16 F g−1), the Ni(OH)2–g–C3N4/C‐0.75 (NGC‐0.75) composite exhibits the highest specific capacitance of 1034 F g−1 at 1 A g−1. Furthermore, after 5000 cycles at 5 A g−1, the capacitance of the material is maintained at 85.97%. Meanwhile, the asymmetric supercapacitor based on the NGC‐0.75 shows a high energy density of 18.29 Wh kg−1 at the power density of 400.02 W kg−1 with excellent cyclic stability of 127.45% over 10 000 cycles.

Non-metallic plasmonic effect and step-like charge transport channel synergistically accelerate surface reaction kinetics and charge separation of TiN/CdS-sensitized ZnO photoanode for efficient photoelectrochemical hydrogen evolution

This work demonstrates the first application to employ TiN/CdS to sensitize ZnO nanotube arrays (NTAs) photoanode for drastically enhanced solar-driven hydrogen evolution through a photoelectrochemical (PEC) cell. The CdS/TiN-sensitized ZnO NTAs photoanode shows drastically boosted PEC water splitting capability for producing hydrogen with a production rate of 168 μmol cm−2 h−1, 1.5- and 18.4-folds that of CdS-sensitized and unsensitized ZnO NTAs photoanodes, respectively. UV–vis absorption spectra demonstrate a significant enhancement in light harvesting efficiency of ZnO with the incorporation of CdS and TiN nanoparticles (NPs). Electrochemical measurement results indicate that TiN NPs accelerates the water oxidation surface reaction kinetics of the photoanode and provides abundant electrochemical active sites. Photoluminescence spectra indicate efficient charge carrier separation in CdS/TiN-sensitized ZnO NTAs and the role as the hot electron provider of TiN NPs. This study provides a new nonmetal plasmonic photoelectrode for efficiently converting solar energy into the clean energy and chemical fuels.

Self‐Confined Construction of Facet Heterojunction with Tunable Band Alignment for Enhanced Photocatalytic CO2 Reduction

AbstractAlthough crystal facet engineering is extensively studied in energy and environmental technologies, the in‐depth understanding of intrinsic mechanisms governing crystal facet heterojunctions in tuning band alignments is still limited. Here, novel Bi5O7NO3 crystals exposing tailor {080} facets are synthesized via NH4+‐assisted self‐confined construction. It has been confirmed that NH4+ ions selectively adsorb on the {141} facets, inversely inducing the growth of desired {080} crystal facets, while the tailored {080} facets facilitate the generation of oxygen vacancies. The controllable concentration of oxygen vacancies, influenced by different exposed facets, can optimize the relative positions of Fermi levels and shift the photoelectron transfer route between the {141} and {080}‐OV facets from type‐II to S‐scheme, thus triggering rapid charge transport channels and effectively suppressing electron‐hole recombination. DFT calculation verifies that the energy barrier for the *COOH formation on Bi5O7NO3‐{080}‐OV is the lowest, thereby promoting the generation of CO. The well‐designed Bi5O7NO3 crystals with the optimal {080}/{141} facet ratio exhibit a 3.8‐fold enhancement in photocatalytic CO2 reduction, compared to traditional Bi5O7NO3 dominated by the {141} facets. This work offers new insights into the regulation of band alignments at heterointerfaces and the design of high‐efficiency photocatalysts.

Photovoltage-Driven Photoconductor Based on Horizontal p-n-p Junction.

The photoconductive gain theory demonstrates that the photoconductive gain is related to the ratio of carrier lifetime to carrier transit time. Theoretically, to achieve higher gain, one can either prolong the carrier lifetime or select materials with high mobility to shorten the transit time. However, the former slows the response speed of the device, while the latter increases the dark current and degrades device sensitivity. To address this challenge, a horizontal p-n-p junction-based photoconductor is proposed in this work. This device utilizes the n-region as the charge transport channel, with the charge transport direction perpendicular to the p-n-p junction. This design offers two advantages: (i) the channel is depleted by the space charge layer generated by the p and n regions, enabling the device to maintain a low dark current. (ii) The photovoltage generated in the p-n junction upon light absorption can compress the space charge layer and expand the conductive path in the n-region, enabling the device to achieve high gain and responsivity without relying on long carrier lifetimes. By adopting this device structure design, a balance between responsivity, dark current, and response speed is achieved, offering a new approach to designing high-performance photodetectors based on both traditional materials and emerging nanomaterials.

Achieving stable organic solar cells with 19.2 % efficiency via fine interpenetrating network with fused-ring aromatic lactone donor

The ternary strategy has enhanced the power conversion efficiency (PCE) of organic solar cells. However, long-term stability remains a challenge due to heat-induced molecular interactions and excessive self-aggregation. The fused-ring aromatic lactone (FAL) unit, with its extended molecular plane and electron-withdrawing ability, acts as an ideal building block in our newly designed donor P35. By introducing P35 into PM6:L8-BO systems, it optimizes film morphology and enhances π-π stacking, facilitating phase separation and balancing charge transport channels. The electron-withdrawing capability of P35 lowers the HOMO levels, thereby decreasing non-radiative recombination. Additionally, the extended molecular plane of P35 provides structural support to prevent the collapse of fiber-like PM6 and crosslinks with PM6 to form a thermodynamically stable interpenetrating network. This effectively limits the formation of isolated SMA islands, thereby minimizing the degeneration of the active layer. Consequently, an optimized PCE of 19.2 % (certified 18.55 %) is achieved in the PM6:P35:L8-BO devices, which still retains 80 % initial PCE under 600 h of AM 1.5 G illumination and 90 % PCE after 950 h storage in darkness. This research emphasizes the importance of electron-withdrawing capabilities and extended molecular planes in achieving long-term stability and high efficiency.

Sulfur vacancies form charge transport channels on the S-type heterojunction engineered interface to enhance photocatalytic performance

This article presents the synthesis of an S-type heterojunction photocatalyst through a straightforward hydrothermal process, which involves the combination of FeWO4 with Zn0.5Cd0.5S containing sulfur vacancies (Zn0.5Cd0.5Ssv). The study delves into the intrinsic role of sulfur vacancies in enhancing the photocatalytic performance of the S-type heterojunction. The creation of sulfur vacancies effectively controls charge separation and triggers a rapid charge transfer pathway at the heterojunction, improving light absorption and permitting the formation of more photoinduced charges. The material demonstrates an impressive degradation efficiency, capable of breaking down 79.38% of IOH within just 40 minutes. It exhibits robust catalytic activity under both mildly acidic and mildly basic conditions, showing notable resistance to various anions and cations present in water, as well as a significant tolerance to high concentrations of humic acid. Further, trapping experiments reveal that hydroxyl radicals (•OH) and superoxide radicals (•O2⁻) are the predominant reactive species driving the photocatalytic process. This research sheds new light on the modulation of photogenerated charge carrier dynamics at the heterointerface, offering valuable guidance for the development of high-performance S-type photocatalysts.

Photocarrier relay modulating solar CO2-to-syngas conversion

Solar-driven syngas generation by CO2 reduction provides a sustainable strategy to produce renewable fossil fuels. Nevertheless, this promising approach often suffers from tough CO2 activation, sluggish reaction kinetics and complex selectivity. Herein, we exquisitely constructed spatially directional charge transport channel over two-dimensional transition metal chalcogenide (TMC)-based heterostructure via a facile and universal electrostatic self-assembly method. Tailor-made positively charged non-conjugated insulating polymer of poly(diallyl-dimethyl-ammonium chloride) (PDDA) and negatively charged graphene oxide (GO) precursor as building blocks are controllably anchored on the TMC substrate, by which ultrathin PDDA layer is intercalated at the interface of GO and TMC. We ascertain that, in this customized sandwiched heterostructures, PDDA interim layer functions as an electron-relaying mediator, whilst graphene (GR) obtained from in-situ GO reduction during the photocatalytic reaction serves as a terminal electron-trapping reservoir, synergistically facilitating the spatially vectorial charge separation/migration over TMC, thus endowing the TMC/PDDA/GR heterostructures with conspicuously enhanced visible-light-driven photoactivity toward CO2-to-syngas conversion. Our work would inspire judicious ideas for finely modulating charge transfer over polymer-mediated photosystems and benefit our fundamental understanding of solar CO2 conversion.

Band engineering for building cascading charge transport channels in ternary CdS-based nanorod array photoanode toward efficient photoelectrochemical H2 generation

A novel CdS/CdSe/Cu2O nanorod array (NRA) photoelectrode with cascading charge transport channels was designed for the first time to remarkedly boot photoelectrochemical (PEC) hydrogen generation under visible light illumination with zero bias. This ternary photoelectrode was constructed by modifying CdS nanorod arrays with n-type CdSe and p-type Cu2O nanoparticles, successively. In this novel photoanode, CdSe and Cu2O with small band gap not merely highly heighten the visible light absorption capacity of CdS, but more importantly integrate with CdS to build cascading charge transport channels at the CdS/CdSe and CdSe/Cu2O interfaces, dramatically facilitating the separation and transport efficiency for photoexcited electron and hole pairs. The CdS/CdSe/Cu2O NRA photoelectrode gains an obvious hydrogen generation rate of 193.2 μmol·h−1, 8.2 times higher than that of bare CdS NRA photoelectrode. The remarkably enhanced PEC hydrogen production for the CdS/CdSe/Cu2O NRA photoanode can be ascribed to effective solar energy utilization and charge carrier separation.

Oxygen Vacancies Trigger Rapid Charge Transport Channels at the Engineered Interface of S-Scheme Heterojunction for Boosting Photocatalytic Performance.

Although oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in-depth understanding of Ovs in S-scheme heterojunction photocatalysts are still limited. Herein, a novel S-scheme photocatalyst made from WO3-Ov/In2S3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S-scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs-TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S-scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO3-Ov and In2S3 (by 35.5 and 3.9 times, respectively), as well as WO3/In2S3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also helps design highly efficient S-scheme photocatalysts.

Oxygen Vacancies Trigger Rapid Charge Transport Channels at the Engineered Interface of S‐Scheme Heterojunction for Boosting Photocatalytic Performance

AbstractAlthough oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in‐depth understanding of Ovs in S‐scheme heterojunction photocatalysts are still limited. Herein, a novel S‐scheme photocatalyst made from WO3‐Ov/In2S3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S‐scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs‐TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S‐scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO3‐Ov and In2S3 (by 35.5 and 3.9 times, respectively), as well as WO3/In2S3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also helps design highly efficient S‐scheme photocatalysts.

Improve the efficiency of organic solar cells by creating a favorable charge transport channel with a halogen-free additive

In optimizing the mixed film morphology of organic solar cells (OSCs), conventional additives such as 1,8-diiodooctane (DIO) has an important role to play. Anyway, the toxicity inhibits their further development. Here, a new non-toxic, halogen-free additive called Methyl Benzoate (MBZ) has been added into the classic OSCs (PTB7-Th: PC71BM). A series of characterizations demonstrate that the MBZ additive effectively matches well with the active layer material and enhances the formation of network interpenetrating structures. This enhances charge transport and inhibits the recombination of excitons. Power conversion efficiency (PCE) of 8.76 % and fill factor (FF) of 70.9 % are achieved by the device with the MBZ additive. This research paves the way for future large-scale industrial deployment about organic solar cells (OSCs) by presenting a method for replacing conventional additives with halogen-free alternatives.

양자점 디스플레이 분야에서의 원자층증착법 응용

Atomic layer deposition (ALD) is gaining traction in the semiconductor industry due to its ability to meet the demands of high aspect ratios and densities. This is attributed to its excellent step coverage and uniformity, which are based on the self-limiting deposition process. Its applications have expanded to include various components such as memory device capacitors, gate oxides, metal barriers, and charge transport channels. Moreover, ALD is being explored for diverse purposes not only within the semiconductor field but also in displays and optoelectronics. This review aims to explore the versatility of ALD deposition methods, widely utilized in the semiconductor industry, and their potential applications in the display and optoelectronics sectors. Additionally, we present future prospects for ALD applications in display based on current approaches.

Bifunctional nitrogen-doped carbon quantum dot-modified graphitic carbon nitride/cadmium sulfide nanomaterials for antibiotic selective detection and photocatalytic degradation

In this paper, an S-type NCN/CdS heterojunction was formed by anchoring cadmium sulfide on nitrogen-doped carbon quantum dot-modified g-C3N4 (abbreviated as NCN) via hydrothermal and calcination methods. The bifunctional properties of NCN/CdS for the detection and degradation of antibiotics [tetracycline (TC) and chlortetracycline (CTC)] were demonstrated. The S-type heterojunction has a strong redox capacity and effectively separates photogenerated e−-h+ pairs, which improves photocatalytic performance. NCDs is located between cadmium sulfide and g-C3N4, which forms a charge-transport channel that accelerates the carrier transport between the interfaces of the S-type heterojunction. Good photocatalytic performance (TC: 98.0 % for 45 min; CTC: 100 % for 70 min) and excellent cycling stability were obtained. This study provides a new strategy for designing efficient, stable and bifunctional materials for environmental pollution treatment.

Semitransparent organic photovoltaics enabled by transparent p-type inorganic semiconductor and near-infrared acceptor

Semitransparent organic photovoltaics (STOPVs) have gained wide attention owing to their promising applications in building-integrated photovoltaics, agrivoltaics, and floating photovoltaics. Organic semiconductors with high charge carrier mobility usually have planar and conjugated structures, thereby showing strong absorption in visible region. In this work, a new concept of incorporating transparent inorganic semiconductors is proposed for high-performance STOPVs. Copper(I) thiocyanate (CuSCN) is a visible-transparent inorganic semiconductor with an ionization potential of 5.45 eV and high hole mobility. The transparency of CuSCN benefits high average visible transmittance (AVT) of STOPVs. The energy levels of CuSCN as donor match those of near-infrared small molecule acceptor BTP-eC9, and the formed heterojunction exhibits an ability of exciton dissociation. High mobility of CuSCN contributes to a more favorable charge transport channel and suppresses charge recombination. The control STOPVs based on PM6/BTP-eC9 exhibit an AVT of 19.0% with a power conversion efficiency (PCE) of 12.7%. Partial replacement of PM6 with CuSCN leads to a 63% increase in transmittance, resulting in a higher AVT of 30.9% and a comparable PCE of 10.8%.

Defect-rich porous graphitic phase carbon nitride layer grafted MXene as desolvation promoter for efficient sulfur conversion in extremely harsh conditions

Lithium-sulfur (Li-S) batteries exhibit superior theoretical capacity and energy density but are still hindered by the sluggish redox conversion kinetic of lithium polysulfides arising from the significant desolvation barrier, especially under high current density or low-temperature environments. Herein, a two-dimensional (2D) porous graphitic phase carbon nitride/MXene (CN-MX) heterostructure with intrinsic defects was designed via electrostatic adherence and in-situ thermal polycondensation. In the design, the defect-rich CN with abundant catalytic activity and porous structure could efficiently facilitate the lithium polysulfides capture, the dissociation of solvated lithium-ion (Li+), and fast Li+ diffusion. Concurrently, 2D MXene nanosheets with high electronic conductivity could act as charge transport channels and provide electrochemical active sites for sulfur redox reactions. The Li-S cells with CN-MX heterostructure modified separator demonstrated uncommon rate performance (945 mAh/g at 4.0 C) and satisfactory areal capacity (5.5 mAh cm−2 at 0.2 C). Most remarkably, even at 0 °C, the assembled Li-S batteries performed favorable cycle stability (91.6% capacity retention after 100 cycles at 0.5 C) and outstanding rate performance (695 mAh/g at 2.0 C), and superior high loading performance (5.1 mAh cm−2 at 0.1 C). This work offers exciting new insights to enable Li-S batteries to operate in extreme environments.

Constructing multiple active sites of Bi2WO6 for efficient photocatalytic NO removal and NO2 inhibition

Insufficient photocatalytic NOx oxidation capacity will lead to excessive toxic by-products (NO2), which still seriously restrict its practical application. Herein, the multiple active sites (Cl, Bi0 and OVs) modified Bi2WO6 has been established by in-situ synthesis method. The synergistic effect of multiple active sites greatly increased the photo-electric properties of the Bi2WO6, resulting in the boosting photocatalytic NOx deep oxidation to nitrate. The visible light driven OVs-Bi@BWO-Cl catalyst exhibited a highest NO conversion efficiency (67.3 %) with extremely low NO2 concentration (17.9 ppb). The synergism of structural regulation from the OVs with Cl-doping and surface plasmon resonance of Bi0 significantly enhanced light absorption and provided a fast charge transport channel, improving the separation efficiency of photo-generated carriers. The in-situ DRIFTS and density functional theory (DFT) results shown that the synergistic effect by multiple active sites could enhance the adsorption and activation of reactants to accelerate the processes of H2O/O2-to-ROS and decrease the energy barrier of NO removal to promote deep oxidation of NO-to-NO3−. This work can provide ideas for the design and preparation of the catalyst for safe photocatalytic environment purification.