Efficient Carrier Transport Research Articles

Impurity-healing interface engineering for efficient perovskite submodules.

One issue that always strands the scaling-up development of perovskite photovoltaics is the significant efficiency drop when enlarging the device area, which is caused by the inhomogeneous distribution of defected sites1-3. In the narrow band gap formamidinium lead iodide (FAPbI3), the native impurities of PbI2 and δ-FAPbI3 non-perovskite could induce unfavored non-radiative recombination, as well as inferior charge transport and extraction 4,5.Here, we develop an impurity-healing interface engineering strategy to well address the issue both in small-area solar cell and large-scale submodule. With the introduction of a functional cation, 2-(1-cyclohexenyl)ethyl ammonium, two-dimensional (2D) perovskite with high mobility is rationally constructed on FAPbI3 to horizontally cover the film surface and vertically penetrate to the grain boundaries of 3D perovskites. Such unique configuration not only comprehensively transforms the PbI2 and δ-FAPbI3 impurities into stable 2D perovskite and realize a uniform defect passivation, but also provides interconnecting channels for efficient carrier transport. As a result, the FAPbI3-based small-area (0.085 cm2) solar cells achieve a champion efficiency over 25.86% with a notably high fill factor (FF) of 86.16%. More encouragingly, the fabricated submodules with the aperture area of 715.1 cm2 obtain a certified record efficiency of 22.46% with a good FF of 81.21%, showcasing the feasibility and effectualness of the impurity-healing interface engineering for scaling-up promotion with well-preserved photovoltaic performance.

Multi-Functional Silole Hole Transport Layer for Efficient and Stable Lead-Tin Perovskite and Tandem Solar Cells.

Despite high theoretical efficiencies and rapid improvements in performance, high-efficiency ≈1.2eV mixed Sn-Pb perovskite solar cells (PSCs) generally rely on poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS) as the hole transport layer (HTL); a material that is considered to be a bottleneck for long-term stability due to its acidity and hygroscopic nature. Seeking to replace PEDOT: PSS with an alternative HTL with improved atmospheric and thermal stability, herein, a silole derivative (Silole-COOH) tuned with optimal electronic properties and efficient carrier transport by incorporating a carboxyl functional group is designed, which results in an optimal band alignment for hole extraction from Sn-Pb perovskites and robust air and thermal stability. Thin films composed of the Silole-COOH exhibit superior conductivity and carrier mobility compared to PEDOT: PSS, in addition to reduced nonradiative quasi-Fermi-level splitting losses at the HTL/perovskite interface and improved quality of Sn-Pb perovskite. Replacement of PEDOT: PSS with Silole-COOH leads to 23.2%-efficient single-junction Sn-Pb PSCs, 25.8%-efficient all-perovskite tandems, and long operating stability in ambient air.

Theoretical study on structural stability and electronic properties of CH3NH3PbI3/ZnO heterojunction

The structural stability and electronic properties of CH3NH3PbI3/ZnO heterojunctions were investigated using first-principles method. Our results show that the interfacial termination of CH3NH3PbI3 influences the orientational order of C–N bonds and structural stability of heterojunction. For the first time, it was confirmed that the ionic polarization of CH3NH3PbI3 material in CH3NH3PbI3/ZnO induced by interfacial electrostatic interaction plays an important role in high efficient separation and transport of photo-generated carriers, which is a new physical mechanism. This study could provide an in-depth understanding of the properties of CH3NH3PbI3/ZnO, and improve the stability and performance of perovskite solar cells.

Modulating Copper Ladder Spacing in Copper Phenylacetylide for Enhanced Photocatalysis via Substituent Control.

Copper phenylacetylide (PACu) is a promising photocatalyst due to its unique copper ladder (CL) electron transport channel, which facilitates efficient charge transfer. However, the structure-activity relationship between the CL spacing and its catalytic performance has yet to be revealed. In this study, we skillfully selected multiple substituents to regulate the CL spacing of the PACu photocatalyst. Our findings indicate that reducing the CL spacing significantly enhances carrier separation and transport efficiency, leading to improved oxygen adsorption and activation. Specifically, PACu-F demonstrated superior photocatalytic activity, achieving a 99% conversion rate in benzylamine oxidation and maintaining an excellent stability over multiple cycles. This study confirms the feasibility of tuning the CL spacing in PACu using donor/acceptor substituents to achieve a high-efficiency photocatalytic performance, offering crucial insights into the rational design of advanced photocatalysts.

Air-Processed Efficient Cesium-Based Two-Dimensional Perovskite Solar Cells Based on Asymmetric Chiral Ammonium Salts.

Cesium-based two-dimensional (2D) perovskites with attractive phase and environmental stability have broad application prospects in single-junction and tandem perovskite solar cells (PSCs). However, the severe nonradiative recombination and significant energy losses due to disordered phase orientations and phase distributions greatly hinder the carrier transport performance of cesium-based 2D PSCs and severely limit their photovoltaic performance. Here, we employ an asymmetric chiral spacer cation source, (R)-α-phenylethylamine acrylate (R-α-PEAAA), to prepare high-quality 2D cesium-based films with uniform phase distribution and high out-of-plane orientation by air processing, resulting in efficient carrier transport. More importantly, the asymmetric chiral spacer R-α-PEA has a stronger dipole moment than its isomer (PEA), which can regulate the dielectric properties of cesium-based 2D perovskites and promote charge dissociation. In addition, the chiral R-α-PEA can optimize the morphology and out-of-plane orientation of perovskite films, reduce trap density and nonradiative recombination loss, and optimize energy level alignment, thus enhancing carrier transport. As a result, cesium-based 2D PSCs (R-α-PEA2Cs4Pb5I16, n = 5) achieved a record power conversion efficiency of 19.71% and the unencapsulated device maintained over 90% efficiency after 1500 h of continuous light exposure and ambient storage (35 ± 5% relative humidity). This study provides an idea for the development of chiral 2D perovskite with efficient charge carrier transport toward efficient and stable cesium-based 2D PSCs.

A flower-like g-C3N4/CDs/Bi2WO6 hierarchical structure for enhanced photocatalytic degradation of tetracycline

Tetracycline (TC), as one of antibiotic emerging pollutants, has posed potential threats to ecological environment and human health because it is hardly biodegradable and prone to be accumulated in water. In this study, g-C3N4/CDs/Bi2WO6 S-scheme heterojunction with flower-like hierarchical structure was synthesized by hydrothermal method. The optimized composite demonstrates significantly enhanced photocatalytic activity with a TC degradation efficiency of 90.1% after 120 min of visible light irradiation and good reusability up to four consecutive cycles. This can be attributed to the improved light capture capability and efficient separation of photo-generated electron-hole pairs in the constructed S-scheme heterojunction. The introduced carbon dots (CDs) can be served as an efficient carrier transport highway, providing a superior photogenerated carrier separation efficiency and an expanded absorption spectrum. As a result, the strongest redox potentials of the CBCN and VBBWO can be retained for participating the photocatalytic reaction. Free radical capture and electron spin resonance experiments indicate that ·O2- and h+ are the principal active species in the g-C3N4/CDs/Bi2WO6 system. This work provides new strategy for the development of advanced materials in the field of photocatalytic treatment of wastewater.

Enhanced visible light responsive piezoelectric photocatalysis based on Bi2S3 coated BaTiO3 nanorods heterostructures

Although the presence of the built-in electric field will solve the problem of carrier complexation in photocatalytic systems to some extent. However, free carriers will quickly shield the stabilized electric field and lose its effect. Therefore, how to introduce the dynamic piezoelectric field into the photocatalytic system has become an imminent problem. Herein, we developed an overcoated, visible light responsive, piezoelectric-assisted photocatalytic system by depositing Bi2S3 photocatalysts with a narrow-band system onto the surface of highly piezo-responsive BaTiO3 nanorods (BTO NRs). The heterojunction structure, bound by Bi-O chemical bonding, enhances carrier transport efficiency under the influence of the piezoelectric field. In the degradation experiments, the first-order rate constant for the degradation of chlortetracycline hydrochloride (CTC) in the BTO NRs/Bi2S3 system with the optimal complex ratio was 0.0276 min−1, which was 3.1 and 7.8 times higher than that of BTO NRs and Bi2S3, respectively. Additionally, we deduced the degradation pathways of CTC through a combination of Density functional theory (DFT) calculations and Liquid Chromatograph Mass Spectrometer (LC-MS), evaluating the toxicity of the intermediates. This complex system, featuring a highly photo-responsive semiconductor as a photo-acceptor deposited on a piezoelectric semiconductor surface providing a dynamic built-in electric field, enhances carrier separation efficiency under optimal light energy utilization conditions. These findings present novel and effective strategies for addressing two primary challenges in photocatalytic systems: low spectral utilization and significant photogenerated carrier complexation.

Constructing high efficient carrier channels in double ternary compounds MoSSe/CdSSe heterojunction for photoelectrochemistry and electrocatalytic hydrogen production

Here is a demonstration of constructing MoSSe/CdSSe heterojunction catalyst from bimetallic selenium sulfides. CdSSe has a high conduction band position of −0.65 eV, resulting in a strong reduction potential of photogenerated electrons. However, the high resistance of CdSSe affects the transport of charge carriers. In addition, experiments have confirmed that the presence of S and Se in MoSSe and CdSSe enhances their chemical activity and facilitates bonding. A better connection can be formed between MoSSe and CdSSe, resulting in high carrier transport efficiency. In the X-ray photoelectron spectroscopy results, the Mo and Se signals showed a large shift nearly 1 eV which confirms the strong binding between MoSSe and CdSSe. In the photoelectrochemical tests, the MoSSe/CdSSe heterojunction demonstrated a photocurrent density of 3.097 mA/cm2 at 0 V (RHE) which is 2.7 and 2.9 times that of MoSSe (1.227 mA/cm2) and CdSSe (1.127 mA/cm2) respectively with a low resistance of 161 Ω. Moreover, the MoSSe/CdSSe also has good electrocatalytic hydrogen evolution performance with an overvoltage of 180 mV and Tafel slope of 69 mV/dec. Fluorescence and photocurrent response tests confirmed its higher carrier separation efficiency. This work demonstrates the application of ternary metal selenium sulfide heterojunctions in catalytic energy materials.

Synergistically flexible-robust effects mediate the dynamic reconfiguration of perylene diimide polymer to enhance piezo-photocatalytic nitrate reduction

Identifying the spatial dynamic reconstruction of π-conjugated polymers for efficient carrier transport and controlling the intermediate process of the reaction are urgent and formidable challenges. In this study, a fresh perspective has emerged proposing to synergistically enhance the adaptability and resilience of dynamic torsion patterns in π-conjugated polymers to mediate charge separation and molecular activation. Excitingly, the highest flexible-robust structure and polarity of naphthalene-linked perylene diimide polymer (N-PDA) demonstrates a highest nitrate reduction rate of 5.36 mmol g−1 h−1 under light irradiation and ultrasonic condition, which is 7.5 times that of H-PDA. Theoretical calculations and experimental observations indicate that the strongest flexible-robust structure of N-PDA enhances the inclination of the rigid plane and atomic bond length, resulting in an accelerated uneven distribution of charges, molecular polarity, and electronic coupling to facilitate charge separation dynamics. Moreover, it exposes active sites that promote the adsorption and activation of NO3- ions while simultaneously regulating intermediate hydrogenation processes. Our study offers innovative prospects for enhancing catalytic efficiency through the implementation of spatial steric configuration of π-conjugated polymers.

Biomass Derived Self-Doped Carbon Nanosheets Enable Robust Hole Transport Layers with Ion Buffer for Perovskite Solar Cells.

The diffusion of iodine species and lead leakage during device degradation represent the main obstacles restricting the commercial application of perovskite solar cells (PSCs). Cobalt loaded ultrathin carbon nanosheets (Co(III)-CNS) derived from biomass are prepared as ion buffer material to construct robust hole transport layers (HTLs). The carbon nanosheets containing trivalent cobalt ions can facilitate the oxidation of the hole transport material while preserving the structural integrity and electrical properties of HTLs under thermal stress, thereby ensuring efficient carrier transport. The two-dimensional ultrathin graphitized lamellar structure of Co(III)-CNS is conducive to alleviate the corrosive effects of the outward diffusion of iodine species on HTLs and silver electrodes, while avoiding irreversible degradation of PSCs. With the improvement of HTL composition and the related interfaces, Co(III)-CNS doped devices can maintain intact device structure under thermal stress and remain above 80% of the original power conversion efficiency (PCE) after thermal aging at 85 oC for 720 h. Notably, the chemical interactions between heteroatoms of self-doped carbon nanosheets and the mobile lead ions can effectively alleviate lead leakage and avoid the potential impacts of device degradation on ecosystem. Ultimately, the Co(III)-CNS doped PSCs with enhanced thermal stability exhibit a champion PCE of 22.32%.

Manipulating Photoconduction in Supramolecular Networks for Solar-Driven Nitrate Conversion to Ammonia and Oxygen.

For photoelectrodes to be used in practical catalytic applications, challenges exist in achieving the efficient production and transport of photogenerated charge-separated states. Analogous concepts in traditional inorganic photoelectrodes can be applied to their organic-polymer counterparts with improved charge-separation efficiencies. In this work, we develop photoconductive organic networks to form a high-performance photoelectrode for NO3- reduction to NH3. In the integrated network, interfaces between the organic electron-donating photoconductor and electron-accepting catalyst can generate charge carriers efficiently upon illumination, leading to enhanced charge separation for photoelectrocatalysis. The photoelectrode network is capable of converting NO3- to NH3 at an external quantum efficiency of 13%. By coupling with a BiVO4 photoanode in tandem, the system reduces NO3- to NH3 and oxidizes H2O to O2 simultaneously at Faradaic efficiencies of 95-98% with sustained photocurrents and production yields. Investigation of the photoconductive network by steady-state/time-resolved spectroscopies reveals the efficient generation and transport of free charge carriers in the photoelectrode, providing a basis for high photoelectrocatalytic performances.

A preliminary investigation into the potential of Ge-enhanced Cu2SnS3 (CTS) thin-film applications for water-splitting photoelectrodes

This study explores the potential of Ge-enhanced Cu2SnS3 (CTS) thin-films as photoelectrode materials for water splitting grown through a simple sulfurization process. The addition of Ge to CTS enabled tuning the bandgap and improved the photocurrent density. Films sulfurized at 520 °C exhibit enhanced grain size and reduced grain boundaries, which contribute to increased carrier transport efficiency. By optimizing Ge content and sulfurization conditions, the Cu2(Sn1−x ,Ge x )S3 films demonstrate promising capabilities for efficient green hydrogen production. This work lays the groundwork for developing advanced photoelectrodes and highlights the need for further refinement to maximize performance for practical applications.

Plasmonic‐Promoted Interatomic Hot Carriers Regulation Enhanced Electrocatalytic Nitrogen Reduction Reaction

Utilizing hot carriers for efficient plasmonic‐mediated chemical reactions (PMCRs) to convert solar energy into secondary energy is one of the most feasible solutions to the global environmental and energy crisis. Finding a plasmonic heterogeneous nanostructure with a more efficient and reasonable hot carrier transport path without affecting the intrinsic plasmonic properties is still a major challenge that urgently needs to be solved in this field. Herein, the mechanism by which plasmonic‐promoted interatomic hot electron redistribution on the surface of Au3Cu alloy nanoparticles promotes the electrocatalytic nitrogen reduction reaction (ENRR) is successfully clarified. The localized surface plasmon resonance (LSPR) effect can boost the transfer of plasmonic hot electrons from Au atoms to Cu atoms, trigger the interatomic electron regulation of Au3Cu alloy nanoparticles, enhance the desorption of ammonia molecules, and increase the ammonia yield by approximately 93.9%. This work provides an important reference for rationally designing and utilizing the LSPR effect to efficiently regulate the distribution and mechanism of plasmonic hot carriers on the surface of heterogeneous alloy nanostructures.

Plasmon-Promoted Interatomic Hot Carriers Regulation Enhanced Electrocatalytic Nitrogen Reduction Reaction.

Utilizing hot carriers for efficient plasmon-mediated chemical reactions (PMCRs) to convert solar energy into secondary energy is one of the most feasible solutions to the global environmental and energy crisis. Finding a plasmonic heterogeneous nanostructure with a more efficient and reasonable hot carrier transport path without affecting the intrinsic plasmonic properties is still a major challenge that urgently needs to be solved in this field. Herein, the mechanism by which plasmon-promoted interatomic hot electron redistribution on the surface of Au3Cu alloy nanoparticles promotes the electrocatalytic nitrogen reduction reaction (ENRR) is successfully clarified. The localized surface plasmon resonance (LSPR) effect can boost the transfer of plasmon hot electrons from Au atoms to Cu atoms, trigger the interatomic electron regulation of Au3Cu alloy nanoparticles, enhance the desorption of ammonia molecules, and increase the ammonia yield by approximately 93.9 %. This work provides an important reference for rationally designing and utilizing the LSPR effect to efficiently regulate the distribution and mechanism of plasmon hot carriers on the surface of heterogeneous alloy nanostructures.

Achieving 11.23 % efficiency in CZTSSe solar cells via defect control and interface contact optimization

The high open-circuit voltage deficit (VOC, def) caused by structural imperfections in the absorber layer and charge loss during carrier transport is a critical barrier affecting the performance of Cu2ZnSn(S,Se)4 (CZTSSe) devices. In this work, Ag was added to the DMF-based Cu+-Sn4+ system, which significantly improved the crystal morphology and electrical properties of the absorber layer. Additionally, optimizing the selenization process not only reduced surface roughness and eliminated voids at the bottom of the absorber layer but also resulted in the formation of a MoSe2 back interface layer with a more suitable thickness. These measures collectively enhanced the overall quality of the absorber layer, reducing the formation of deep-level defect clusters and effectively boosting carrier transport efficiency. Consequently, the concentration of bulk and interfacial defects decreased, and the impact of potential barriers on carrier movement was minimized. With these comprehensive improvements, the power conversion efficiency of CZTSSe solar cells increased from 8.48 % to 11.23 %. Our research demonstrates that optimizing the structure of the absorber layer can effectively enhance the performance of CZTSSe solar cells, providing valuable insights for the fabrication of high-efficiency devices in the future.

Modulating Surface-Adsorbed Oxygen Species of Bismuth Silicate by a Solid Solution Strategy for Efficient Adsorption and Photocatalytic Activity.

Bismuth silicate photocatalysts suffer from insufficient photocatalytic activity due to an insufficient number of surface active sites and low carrier separation and transport efficiency, which can be solved by defect modulation. Herein, Bi12SiO20/Bi2O2SiO3-BiOClxBr1-x (BSOCB) photocatalysts with a high concentration of surface-adsorbed oxygen species (SAOS) are synthesized by introducing a BiOClxBr1-x solid solution to modify nonhomogeneous BSO via an ion exchange strategy. The introduction of a solid solution enables the generation of dispersed nanoflowers and the regulation of SAOS due to the fact that anion-cation copolymerization guides the crystal growth, and the defects generated by the lattice distortion modulate the concentration of SAOS on the catalysts during the solid solution process. The obtained typical BSOCB photocatalyst possesses both high adsorption and photocatalytic properties, and the results show that it not only can almost completely degrade the traditional pollutant RhB within 20 min but also strongly degrades antibiotics, such as CIP (light for 150 min, 96%), NFX (light for 150 min, 87%), and TC (light for 150 min, 77%). This work provides a new approach for obtaining bismuth-based photocatalysts with controllable morphology and a large number of surface active sites and provides a theoretical and experimental basis for expanding the application scenarios of photocatalysts.

Unveiling the Influence of Linkers on Conformations of Oligomeric Acceptors for High-Performance Polymer Solar Cells.

Conformational isomerism of organic photovoltaic materials has a profound impact on their molecular packing and therefore performance of polymer solar cells (PSCs). However, the conformations of oligomeric acceptors (OAs) are mostly predicted by simulations rather than experimental determinations. Herein, the stereochemical S-shaped structure of two dimeric-type acceptor molecules, V-DYIC and V-DYIC-4F, is first confirmed with different end groups (IC for V-DYIC and IC-2F for V-DYIC-4F), incorporating vinylene linkage for connecting the distinct state-of-the-art small molecule acceptor Y-segments. Through the synthetic control of fluorination sites adjacent to the vinyl-linker, S-shaped the conformation by NMR experiments is validated. Compared to the O-shaped dimer, S-shaped conformation results in enhanced lamellar order and reduced nonradiative recombination losses. The optimal acceptor, V-DYIC-4F, achieved a champion efficiency of 18.10% with the lowest energy loss of 0.556eV in its devices paired with PM6 due to their efficient carrier transport, and suppressed recombination compared to other devices, being attributed to the synergistic effect of conformation and end group fluorination. The insights gained in this work contribute valuable knowledge of both synthetic control and structural determination of OAs, providing strategic design guidelines for the future development of dimeric acceptors toward high-efficiency PSCs.

Controlled Crystallization and Enhanced Performance of γ-CsPbI3 Perovskite Through Methylammonium Iodide-Assisted Coevaporation.

Cesium lead triiodide (CsPbI3) perovskites have garnered significant attention owing to their suitable bandgap for tandem silicon substrates and excellent chemical stability. However, γ-CsPbI3 prepared via low-temperature co-evaporation is limited by a narrow black phase processing window and random crystal orientation, hindering its optoelectronic performance and industrial applications. This study introduced trace amounts of methylammonium iodide (MAI) into the co-evaporation system, enhancing the crystallization process, promoting columnar grain growth, and stabilizing the γ-phase perovskite, resulting in films with improved structural integrity and reduced defect density. The optimal Pb/Cs ratio for achieving the best photoelectric performance shifted from 1:1 to 1.1:1 in the presence of MAI. Additionally, the incorporation of MAI allowed for more efficient longitudinal carrier transport, as evidenced by the enhanced photoluminescence (PL) intensity. The bandgap of CsPbI3 remained approximately at 1.7eV before the δ-phase transition, ensuring suitability for photovoltaic applications. Ultimately, a photovoltaic device with 12% efficiency is achieved in the p-i-n structure without additional post-annealing of the CsPbI3 perovskite films, demonstrating the practical benefits of MAI incorporation.

Efficient Microwave Irradiation-Assisted Synthesis of Benzodioxinoquinoxaline and Its Donor-Variegated Derivatives Enabling Long-Lived Emission and Efficient Bipolar Charge Carrier Transport

Efficient Microwave Irradiation-Assisted Synthesis of Benzodioxinoquinoxaline and Its Donor-Variegated Derivatives Enabling Long-Lived Emission and Efficient Bipolar Charge Carrier Transport

Study of mechanical, optoelectronic, and thermoelectric characteristics of Be/Mg ions Based double perovskites A2FeH6 (A= Be, Mg) for hydrogen storage applications

This study addresses the hydrogen storage capabilities and mechanical, optoelectronic, and thermoelectric features of double perovskite hydrides A2FeH6 (A = Be, Mg). The structural aspects suggest the cubic symmetry of studied hydrides. The formation enthalpy value calculation has confirmed the structures' thermal stability. The gravimetric ratios of Be2FeH6 and Mg2FeH6 hydrides are 7.50 wt% and 5.43 wt%, respectively. The desorption temperatures are predicted to be 230.32 K and 208.67 K, respectively. The mechanical and thermophysical characteristics have been elaborated, which demonstrate mechanical stability, higher stiffness, ductile behavior, and higher temperature stability of both materials. The examined electronic properties have revealed band gap values of 2.89 and 3.08 eV, respectively. The optical properties have been assessed to predict the appropriateness of these hydrides for deployment in photovoltaic systems. The thermoelectric characteristics have been evaluated to examine the carrier transport mechanism and efficiency for converting heat into electricity. Finally, the investigated properties and hydrogen storage capacity of these compounds suggest that they are suitable for hydrogen storage and have the potential to play a key role in many energy generation applications.