Charge Carrier Transport Research Articles

Unprecedented Photocatalytic Hydrogen Peroxide Production via Covalent Triazine Frameworks Constructed from Fused Building Blocks

AbstractCovalent organic frameworks (COFs) have garnered attention for their potential in photocatalytic hydrogen peroxide (H2O2) production. However, their photocatalytic efficiency is impeded by insufficient exciton dissociation and charge carrier transport. Constructing COFs with superior planarity is an effective way to enhance the π‐conjugation degree and facilitate electron‐hole separation. Nonetheless, the conventional linear linkers of COFs inevitably introduce torsional strain that disrupts coplanarity. Herein, we address this issue by introducing inherently coplanar triazine rings as linkers and fused building blocks as monomers to create covalent triazine frameworks (CTFs) with superior coplanarity. Both experimental and theoretical calculations confirm that CTFs constructed from fused building blocks significantly enhance the electron‐hole separation efficiency and improve the photocatalytic performance, compared to the CTFs constructed with non‐fused building blocks. The frontier molecular orbitals and electrostatic potentials (ESP) revealed that the oxygen reduction reaction (ORR) is preferentially facilitated by the triazine rings, with the water oxidation reaction (WOR) likely occurring at the thiophene‐containing moiety. Remarkably, CTF‐BTT achieved an exceptional H2O2 production rate of 74956 μmol g−1 h−1 when employing 10 % benzyl alcohol (V/V) as a sacrificial agent in an O2‐saturated atmosphere, surpassing existing photocatalysts by nearly an order of magnitude. Our findings provide valuable insights for designing highly coplanar polymer‐based photocatalysts that enhance the solar‐to‐chemical energy conversion process.

Unprecedented Photocatalytic Hydrogen Peroxide Production via Covalent Triazine Frameworks Constructed from Fused Building Blocks.

Covalent organic frameworks (COFs) have garnered attention for their potential in photocatalytic hydrogen peroxide (H2O2) production. However, their photocatalytic efficiency is impeded by insufficient exciton dissociation and charge carrier transport. Constructing COFs with superior planarity is an effective way to enhance the π-conjugation degree and facilitate electron-hole separation. Nonetheless, the conventional linear linkers of COFs inevitably introduce torsional strain that disrupts coplanarity. Herein, we address this issue by introducing inherently coplanar triazine rings as linkers and fused building blocks as monomers to create covalent triazine frameworks (CTFs) with superior coplanarity. Both experimental and theoretical calculations confirm that CTFs constructed from fused building blocks significantly enhance the electron-hole separation efficiency and improve the photocatalytic performance, compared to the CTFs constructed with non-fused building blocks. The frontier molecular orbitals and electrostatic potentials (ESP) revealed that the oxygen reduction reaction (ORR) is preferentially facilitated by the triazine rings, with the water oxidation reaction (WOR) likely occurring at the thiophene-containing moiety. Remarkably, CTF-BTT achieved an exceptional H2O2 production rate of 74956 μmol g-1 h-1 when employing 10 % benzyl alcohol (V/V) as a sacrificial agent in an O2-saturated atmosphere, surpassing existing photocatalysts by nearly an order of magnitude. Our findings provide valuable insights for designing highly coplanar polymer-based photocatalysts that enhance the solar-to-chemical energy conversion process.

Modulation of the Microstructure and Enhancement of the Photocatalytic Performance of g-C3N4 by Thermal Exfoliation

This work explores the impact of reaction temperature during thermal exfoliation treatment of bulk-g-C3N4 in the air atmosphere on the structure and performance of the resulting CN photocatalyst. The analysis conducted using XRD, FT-IR, XPS, SEM, and elements mapping tests, illustrated an increase in nitrogen-vacancy and oxygen content on the surface of the CN photocatalyst, resulting in a porous and sparse structure, changes in crystal size, and improved visible light absorption performance. The photocatalytic reduction experiments of hexavalent chromium (Cr(VI)) showed that the CN-540 showed the highest reduction rate of 96.9%, with a reaction rate constant 6.21 times that of bulk-g-C3N4. After 100 min of illumination, the photocatalytic degradation rates of CN-540 for TC-HCl and RhB were 66.7% and 60.6%, respectively. The TOC test results indicated mineralization rates of 51.5% for TC-HCl and 46.6% for RhB. Room temperature fluorescence spectroscopy (PL), transient photocurrent response (TPC), and electrochemical impedance spectroscopy (EIS) measurements confirmed the excellent photogenerated charge carrier separation and transport efficiency of CN-540. The photocatalytic mechanism for reducing Cr(VI) by CN-540 was elucidated based on the active species •OH and •O2– and Mott-Schottky (M-S) tests. This study provides experimental data for optimizing the photocatalytic performance of g-C3N4 and paves a new way for developing efficient photocatalysts. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Carbazole and Triazine-Based D-A Covalent Organic Framework for Visible Light-Mediated Photocatalytic C-H Activation of Imidazopyridine and Indole.

Two-dimensional donor-acceptor covalent organic frameworks (COFs) show considerable promise for metal-free and heterogeneous photocatalysis due to their efficient charge carrier separation and exciton transport upon photoexcitation. To date, numerous photocatalysts have been developed. However, they encounter several challenges, such as inadequate sunlight harvesting ability, poor photostability, and nonreusability. Fortunately, the emergence of COFs presents a promising solution to these problems. Herein, we report an imine-linked CzTA-TAPT COF featuring carbazole as the electron donor and triazine as the electron acceptor. Compared to the previously reported C2-linker-derived CzDA-TAPT COF, this C3-linked COF exhibits good charge separation and charge carrier transport. As a consequence, it demonstrates excellent photocatalytic applicability in the C-3 thiocyanation of imidazo[1,2-a]pyridine and indole under ambient conditions under visible light. Moreover, its broad substrate compatibility and high recyclability provide a green and sustainable approach for the thiocyanation of imidazopyridine and indole. To the best of our knowledge, this is the first heterogeneous catalyst demonstrated for the thiocyanation of imidazo[1,2-a]pyridine. These findings will inspire further research in the development of high-performance D-A COFs as photocatalysts for organic transformations.

Enhanced photocatalytic performance of magnetically reclaimable N-doped g-C3N4/Fe3O4 nanocomposites for efficient tetracycline degradation

The growing environmental challenge posed by the persistence of tetracycline (TC) antibiotics in natural waters is of increasing concern. To address this, there is an imperative need for advanced methods to mitigate TC residues. Herein, we demonstrate the preparation of nitrogen-doped graphitic carbon nitride integrated with magnetic Fe3O4 (N-g-CN/Fe3O4) composites, showcasing narrow band gaps optimized for TC degradation. These advanced materials, conceived through a thermal poly-condensation approach, utilize citric acid and melamine as precursors for nitrogen and g-CN, respectively. These composites exhibit a face-centered cubic architecture, with particle dimensions between 8 to 12 nm and encompassing both meso and microporous structure. The results of the Brunauer–Emmett–Teller analysis indicated specific surface areas of 6.73 m²/g for g-CN, 69.80 m²/g for N-g-CN, 62.55 m²/g for Fe3O4, and 148.32 m²/g for N-g-CN/Fe3O4. These values demonstrate an increase in surface area upon the incorporation of heteroatom of nitrogen and Fe3O4, into the g-CN matrix, thus influence the photocatalytic performance. Under solar light exposure, the synthesized photocatalysts demonstrated photocatalytic activity with a degradation efficiency of 94.16 % within 120 min. Specifically, the N-g-CN/Fe3O4 (22.5 %) composites exhibited remarkable photocatalytic efficiency due to the narrow band gap energy between N-g-CN and Fe3O4, enhanced light absorption in the visible range, and effective charge carrier separation and transportation to the pollutants. N-g-CN/Fe3O4 (22.5 %) composites demonstrated good recyclability (five cycles), magnetic sustainability, and stability for the degradation of TC and emerging pollutants from wastewater using photocatalysts. Similarly, FGCN composites exhibited good recyclability (five cycles), magnetic retrievability, and stability for degrading organic and emerging pollutants from wastewater through photocatalysis. This efficiency can be attributed to the harmonious combination of nitrogen doping, refined surface area, and the natural heterojunction between N-g-CN and Fe3O4.

Probing into the low efficiency of CdS/SnS-based solar cells and remediation through surface treatments

Tin sulfide (SnS) is a highly promising photovoltaic absorption material in thin-film solar cells with abundant reserves, environmental friendliness, low cost and long-term stability. An efficiency of up to 4.8 % has been achieved for SnS absorber/CdS heterojunction solar cells where the CdS buffer layer is usually obtained by chemical bath deposition. However, current CdS/SnS devices often suffer from severe interface recombination loss, which deteriorates device performance. This report focuses on the CdS film surface to identify performance-degrading factors for CdS/SnS-based solar cells. XRD and XPS reveal numerous oxides on freshly fabricated CdS films increasing surface roughness and reducing conductivity. Herein, a method based on ammonium sulfide (AS) chemical treatment is proposed, which can effectively reduce the oxide content on the surface of CdS and optimize the band alignment, leading to the facilitation of charge carrier transport and the suppression of interface recombination. Consequently, the PCE of the FTO/CdS/SnS/Ag device is enhanced about three times (from 0.18 % to 0.47 %) with excellent moisture stability.

Correction to “Relation between Spherulitic Growth, Molecular Organization and Charge Carrier Transport in Meniscus‐Guided Coated Organic Semiconducting Films”

Correction to “Relation between Spherulitic Growth, Molecular Organization and Charge Carrier Transport in Meniscus‐Guided Coated Organic Semiconducting Films”

Pyro-phototronic Effect Enhanced Self-Powered Photoresponse in Lead-Free Hybrid Perovskite.

Pyro-phototronic effect (PPE) can significantly boost the performance of hybrid perovskite (HPs) photodetectors due to the effective modulation of photogenerated charge carrier separations, transportation, and extraction. However, there are few reports on the application of PPE in lead-free HPs. Herein, a polar lead-free HP (1,3-BMACH)BiBr5 [1,3-BMACH = 1,3-bis(aminomethyl)cyclohexane] is synthesized and realized broadband self-powered photoresponse from X-rays to near-infrared (NIR) through the PPE. Particularly, this light-induced PPE in lead-free HPs breaks the limitation of the optical band gap, making them suitable for broadband self-powered photodetection. Under 405 nm illumination, compared with a purely photovoltaic system, Iphoto+pyro is boosted by 3100%, and R and D* are both enhanced by 260% after coupled PPE. It is particularly interesting that an obvious X-ray-induced PPE phenomenon is also observed, which endows (1,3-BMACH)BiBr5 with a high sensitivity of 154 μC Gy-1 cm-2 and a low detection limit of 307 nGy s-1 under the self-powered mode. The implementation of light-induced PPE from X-rays to NIR in lead-free HPs provides a new approach for constructing environmentally friendly, broadband, and self-powered optoelectronic devices in the future.

Regulating Electron-Phonon Coupling by Solid Additive for Efficient Organic Solar Cells.

Strong electron-phonon coupling can hinder exciton transport and induce undesirable non-radiative recombination, resulting in a shortened exciton diffusion distance and constrained exciton dissociation in organic solar cells (OSCs). Therefore, suppressing electron-phonon coupling is crucially important for achieveing high-performance OSCs. Here, we employ the solid additive to regulating electron-phonon coupling in OSCs. The planar configuration of SA1 confers a significant advantage in suppressing lattice vibrations in the active layers, reducing the scattering of excitons by phonons. Consequently, a slow but sustained hole transfer process is identified in the SA1-assisted film, indicating an enhancement in hole transfer efficiency. Prolonged exciton diffusion length and exciton lifetime are achieved in the blend film processed with SA1, attributed to a low non-radiative recombination rate and low energetic disorder for charge carrier transport. As a result, a high efficiency of 20 % was achieved for ternary device with a remarkable short-circuit current. This work highlights the important role of suppressing electron-phonon coupling in improving the photovoltaic performance of OSCs.

Regulating Electron‐Phonon Coupling by Solid Additive for Efficient Organic Solar Cells

AbstractStrong electron‐phonon coupling can hinder exciton transport and induce undesirable non‐radiative recombination, resulting in a shortened exciton diffusion distance and constrained exciton dissociation in organic solar cells (OSCs). Therefore, suppressing electron‐phonon coupling is crucially important for achieveing high‐performance OSCs. Here, we employ the solid additive to regulating electron‐phonon coupling in OSCs. The planar configuration of SA1 confers a significant advantage in suppressing lattice vibrations in the active layers, reducing the scattering of excitons by phonons. Consequently, a slow but sustained hole transfer process is identified in the SA1‐assisted film, indicating an enhancement in hole transfer efficiency. Prolonged exciton diffusion length and exciton lifetime are achieved in the blend film processed with SA1, attributed to a low non‐radiative recombination rate and low energetic disorder for charge carrier transport. As a result, a high efficiency of 20 % was achieved for ternary device with a remarkable short‐circuit current. This work highlights the important role of suppressing electron‐phonon coupling in improving the photovoltaic performance of OSCs.

Enhancement effect of biomass-derived Carbon Quantum Dots (CQDs) on the performance of Dye-Sensitized Solar Cells (DSSCs)

Corn stover, an agricultural waste, was used to prepare nitrogen self-doped carbon quantum dots (CQDs) through a simple hydrothermal method with only water at near room temperature for the first time. The surface, electrochemical, and photovoltaic characteristics of CQDs doped TiO2 in dye-sensitized solar cells (DSSCs) were thoroughly and systematically examined. The average diameter of blue-fluorescence CQDs measured by a high-resolution transmission electron microscope (HR-TEM) was 4.63 ± 0.87 nm, which consisted of polar functional groups. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy of the biomass-derived CQDs, determined by the cyclic voltammetry (CV) test, were, −5.48 eV and −3.89 eV, respectively. The negative shift of flat band potential (Vfb) in CQDs incorporated photoanode implies the fermi level shifted upward. Experimental results revealed that the improved performance of DSSCs was due to charge transport enhancement and separation, which resulted in the improved energy level configuration between TiO2, CQDs, and electrolytes. In this regard, the CQDs serve as a mediator that enables charge carrier transport without hindrance. In this study, CQDs added to TiO2 + N719, increased short circuit current density (JSC) and power conversion efficiency (PCE) value by ∼26.00 % (10.13 to 12.69 mA/cm2) and 27.20 % (4.78 % to 6.08 %), respectively.

Tailoring Hematite Photoanodes for Improved PEC Performance: The Role of Alcohol Species Revealed by SHAP Analysis.

We explore the synergistic effects of TiO2 underlayers and varied alcohol species in the precursor solutions on the photoelectrochemical (PEC) performance of hematite photoanodes. Utilizing a robust machine learning (ML) framework combined with comprehensive analytical data sets, we systematically investigate how these modifications influence key physical and chemical properties, directly impacting the efficiency of water splitting processes. Our approach employs an ML model that integrates SHapley Additive exPlanations (SHAP) to quantitatively assess the impact of each dominant descriptor selected in the analytical data on the PEC performance, and they were combined with the SHAP values' dependence on the experimental operations. Specifically, we focus on the type of alcohol (methanol, ethanol, butanol, and 2-ethyl-1-butanol) used in the precursor solutions as the experimental operation, examining their effects on the dominant descriptors selected in the analytical data. The results from the SHAP analysis reveal that different alcohol species significantly alter the physicochemical properties at the hematite/TiO2 interface and in bulk hematite. These changes are primarily manifested in the modulation of the density of states and resistance to promote the charge carrier transport. For example, ethanol and butanol were found to enhance the electron density of states at the interface, which correlates with higher photocurrent outputs and improved PEC activity. In contrast, methanol showed a less pronounced effect, suggesting a nuanced interaction between the alcohol molecular structure and hematite surface chemistry. These findings not only underscore the importance of tailored precursor solution chemistry for enhancing PEC performance but also highlight the power of ML tools in uncovering the underlying physical and chemical mechanisms that govern the behavior of complex material systems. This study sets a foundational approach where ML can bridge the gap between empirical observations and theoretical understanding, leading to the rational design of energy materials.

Asymmetric Charge Distribution in One-dimensional Metal-Organic Assemblies to Promote Photocatalytic Hydrogen Evolution.

The local charge distribution of photocatalyst is crucial to the catalytic activity due to its influence on the charge separation process. Herein, we report two one-dimensional Ni-based metal-organic assemblies for efficient photocatalytic hydrogen evolution without using noble-metal cocatalysts. By adjusting the aromatic ring in the center of the tricarboxylic ligand, the photocatalytic hydrogen evolution activity was increased from 1715 to 2652 μmol h-1 g-1. The detailed mechanism study shows that the introduced nitrogen atoms in the ligands of the metal-organic coordination assembly could modulate the local charge distribution, and yielding a significant enhancement of the molecular dipole moment which engenders a propulsive force for the effective separation and transport of photoinduced charge carriers. This work provides insights into the local charge distribution via ligand modulation for enhancing the activity of photocatalysts.

Modulation of Charge Transport Layer for Perovskite Light-Emitting Diodes.

Perovskite light-emitting diodes (Pero-LEDs) have garnered significant attention due to their exceptional emission characteristics, including narrow full width at half maximum, high color purity, and tunable emission colors. Recent efficiency and operational stability advancements have positioned Pero-LEDs as a promising next-generation display technology. Extensive research and review articles on the compositional engineering and defect passivation of perovskite layers have substantially contributed to the development of multi-color and high-efficiency Pero-LEDs. However, the crucial aspect of charge transport layer (CTL) modulation in Pero-LEDs remains relatively underexplored. CTL modulation not only impacts the charge carrier transport efficiency and injection balance but also plays a critical role in passivating the perovskite surface, blocking ion migration, enhancing perovskite crystallinity, and improving light extraction efficiency. Therefore, optimizing CTLs is pivotal for further enhancing Pero-LED performance. Herein, this review discusses the roles of CTLs in Pero-LEDs and categorizes both reported and potential CTL materials. Then, various CTL optimization strategies are presented, alongside an analysis of the selection criteria for CTLs in high-performance Pero-LEDs. Finally, a summary and outlook on the potential of CTL modulation to further advance Pero-LED performances are provided.

Enhanced Performance of Close-Spaced Sublimation Processed Antimony Sulfide Solar Cells via Seed-Mediated Growth.

Antimony sulfide (Sb2S3) has attracted much attention due to its great prospect to construct highly efficient, cost-effective, and environment-friendly solar cells. The scalable close-spaced sublimation (CSS) is a well-developed physical deposition method to fabricate thin films for photovoltaics. However, the CSS-processed absorber films typically involve small grain size with high-density grain boundaries (GBs), resulting in severe defects-induced charge-carrier nonradiative recombination and further large open-circuit voltage (VOC) losses. In this work, it is demonstrated that a chemical bath deposited-Sb2S3 seed layer can serve as crystal nuclei and mediate the growth of large-grained, highly compact CSS-processed Sb2S3 films. This seed-mediated Sb2S3 film affords reduced defect density and enhanced charge-carrier transport, which yields an improved power conversion efficiency (PCE) of 4.78% for planar Sb2S3 solar cells. Moreover, the VOC of 0.755V that is obtained is the highest reported thus far for vacuum-based evaporation and sublimation processed Sb2S3 devices. This work demonstrates an effective strategy to deposit high-quality low-defect-density Sb2S3 films via vacuum-based physical methods for optoelectronic applications.

Colossal Dielectric Constant of Nanocrystalline/Amorphous Homo-Composite BaTiO3 Films Deposited via Pulsed Laser Deposition Technique.

We report the pulsed laser deposition (PLD) of nanocrystalline/amorphous homo-composite BaTiO3 (BTO) films exhibiting an unprecedented combination of a colossal dielectric constant (εr) and extremely low dielectric loss (tan δ). By varying the substrate deposition temperature (Td) over a wide range (300-800 °C), we identified Td = 550 °C as the optimal temperature for growing BTO films with an εr as high as ~3060 and a tan δ as low as 0.04 (at 20 kHz). High-resolution transmission electron microscopy revealed that the PLD-BTO films consist of BTO nanocrystals (~20-30 nm size) embedded within an otherwise amorphous BTO matrix. The impressive dielectric behavior is attributed to the combination of highly crystallized small BTO nanograins, which amplify interfacial polarization, and the surrounding amorphous matrix, which effectively isolates the nanograins from charge carrier transport. Our findings could facilitate the development of next-generation integrated dielectric devices.

Functional coupling hole transport and extraction units over BiVO4 for efficient solar-to-hydrogen conversion

Photoelectrochemical (PEC) water splitting based on BiVO4 nanostructures is largely limited by the fast recombination of charge carriers and the low oxygen evolution reaction (OER) kinetics. To enhance PEC performance of BiVO4, combining hole transport units and hole extraction units is a simple and effective methods. In this work, Co3O4 and NiFe layered double hydroxide (NiFe-LDH) were coupled to promote bulk-phase charge separation and solid–liquid interface transfer, which accelerated OER kinetics on surface of target photoanodes. Moreover, p-n heterojunction between BiVO4 and Co3O4 suppressed charge recombination and promoted charge transfer, resulting in an effectively enhanced photocurrent density and applied bias photon to current efficiency (ABPE). To facilitate involvement of photogenerated holes in OER, BiVO4/Co3O4 electrodes are coated with NiFe-LDH as a hole extraction layer using a straightforward chemical bath deposition (CBD) technique. Successful fabrication of NiFe-LDH with rich oxygen vacancies significantly improves transport of charge carriers and provides many activity sites on the electrode surface. The optimized BiVO4/Co3O4/NiFe-LDH photoanode displayed a photocurrent density of 5.41 mA cm−2 at 1.23 VRHE with an ABPE of 1.08 % at 0.86 VRHE under light. These values are approximately 4.66 and 8.30 times higher than those of BiVO4 photoanodes. This study presents a powerful approach to enhance charge separation and transport in BiVO4-based photoanodes by functionally coupling hole transport and extraction units, thereby enabling efficient solar-to-hydrogen conversion.

27.09%-efficiency silicon heterojunction back contact solar cell and going beyond

Crystalline-silicon heterojunction back contact solar cells represent the forefront of photovoltaic technology, but encounter significant challenges in managing charge carrier recombination and transport to achieve high efficiency. In this study, we produced highly efficient heterojunction back contact solar cells with a certified efficiency of 27.09% using a laser patterning technique. Our findings indicate that recombination losses primarily arise from the hole-selective contact region and polarity boundaries. We propose solutions to these issues and establish a clear relationship between contact resistivity, series resistance, and the design of the rear-side pattern. Furthermore, we demonstrate that the wafer edge becomes the main channel for current density loss caused by carrier recombination once electrical shading around the electron-selective contact region is mitigated. With the advanced nanocrystalline passivating contact, wafer edge passivation technologies and meticulous optimization of front anti-reflection coating and rear reflector, achieving efficiencies as high as 27.7% is feasible.

High-temperature charge carrier transportation behavior of Zn doped perovskite-like La2Ti2O7 ceramics

High-temperature charge carrier transportation behavior of Zn doped perovskite-like La2Ti2O7 ceramics

Polymer Based on Asymmetrically Halogenated Benzotriazole Enables High Performance Organic Solar Cells Prepared in Nonhalogenated Solvent.

Halogenation on the A unit of the D-π-A-type polymer donor has been proven as an effective strategy to improve the performance of organic solar cells (OSCs). Compared with fluorination, chlorination usually increases the open-circuit voltage because of the downward shift of energy levels, but decreases the charge transport ability due to the large steric hindrance of the chlorine atom. We reported herein a method to balance the energy loss and charge transport through asymmetric halogenation on the benzotriazole (BTA) unit of the polymer. The designed PE3-FCl based on the BTA unit containing fluorine and chlorine atoms rendered the highest power conversion efficiency (PCE) of 17.83% when eC9-2Cl-γ and o-xylene were used as the electron acceptor and solvent, respectively. The performance is obviously higher than that of the polymer PE3 containing a difluorinated BTA unit (16.65%) and polymer PE3-2Cl with dichlorinated BTA (14.65%) due to the manipulated morphology by preaggregation, improved and more balanced charge carrier transport, and reduced recombination loss. Notably, this PCE is a breakthrough for the BTA-based polymers processed by nonhalogenated solvent. This work gives deep insight into the asymmetric halogenation of polymer donors for high-performance green solvent-processed OSCs.