High Charge Transport Research Articles

High‐Efficiency Deep‐Blue Solution‐Processed Organic Light‐Emitting Diodes Using Carbazole Dendrons Modified Hybridized Local and Charge‐Transfer Emitters

In the pursuit of efficient and cost‐effective organic light‐emitting diodes (OLEDs), the development of solution‐processed hybridized local and charge transfer (HLCT) emitters presents a promising approach. HLCT materials uniquely integrate the advantages of both singlet and triplet excitons, surpassing the traditional spin statistical limit of 25% while offering high photoluminescence efficiency and balanced charge transport properties. Herein, we report the synthesis and characterization of two new deep blue, solution‐processable HLCT fluorophores, G1FTPI and G2FTPI. These compounds incorporate fluorenyl carbazole dendron units into the HLCT luminogenic triphenylamine‐phenanthroimidazole (TPI) molecule. Their HLCT and photoluminescence (PL) properties were experimentally and theoretically investigated using solvation effects and density functional theory (DFT) calculations. The molecules exhibit deep blue emission with a high solid‐state fluorescence quantum yield, good solution‐processed film‐forming quality, and high hole mobility values of 2.18 – 2.61 × 10‐6 cm2 V‐1s‐1. Both compounds were successfully employed as non‐doped emissive layers in solution‐processed OLEDs, demonstrating excellent electroluminescent (EL) performance. Notably, the G2FTPI‐based device emitted a deep blue light at 432 nm with CIE coordinates of (0.158, 0.098) and achieved a a maximum current efficiency (CEmax) of 3.13 cd A‐1 and a maximum external quantum efficiency (EQEmax) of 5.30%.

Stoichiometric effect on the defect states and optical properties of LiInSe2 single crystals

LiInSe2 crystals are promising semiconductor materials for neutron detectors due to the large neutron capture cross-sectional area of the specific isotopes (6Li) and high charge transport properties. However, the optoelectronic performance fails to reach the expected level due to the difficulty of controlling the crystal defects. Herein, we modulate the stoichiometric ratio to control the type of defects in single LiInSe2 crystals grown by the vertical Bridgman method. The UV‒vis–NIR transmission results indicate that the band gap of the yellow colored Li1.01In1Se2 sample is close to ~ 2.83 eV at room temperature, and this value is consistent with the theoretical band gap of LiInSe2 (~ 2.86 eV). Photoluminescence (PL) spectroscopy was used to analyze the defect concentration. The results indicate that the defect types in the yellow Li1.01In1Se2 single crystal are VSe+ and LiIn2−; these result from the introduction of excess Li and the suppression of the adverse defects in InLi2+ and VLi−. These results demonstrate a feasible route for obtaining high-quality yellow 6LiInSe2 crystals and promote the application of 6LiInSe2 neutron detectors.

Ideal quadratic nodal point in half-Heusler semimetal LaPtBi

The research focus on topological states in electronic systems has recently expanded from traditional linear dispersions to encompass higher-order dispersions. These higher-order dispersions exhibit unique physical properties, including high topological charge, exotic magnetoresponse, and novel transport behaviors. In this study, we employ first-principles calculations to propose the half-Heusler material LaPtBi as an ideal quadratic nodal point semimetal. Our comprehensive analysis of the band structure reveals an ideal nodal point located precisely at the Fermi level, exhibiting quadratic dispersion in all directions. This finding is supported by symmetry analysis and effective model arguments. Moreover, when the spin-orbit coupling effect is considered, the nodal point transitions from triple to quadruple degeneracy, while maintaining its quadratic dispersion. The material also features multiple prominent arc surface states originating from the nodal point, which are distinctly separated from the bulk bands. This separation facilitates experimental verification. Overall, LaPtBi, with its quadratic nodal point and advantageous properties, serves as an ideal platform for further research. The study of this material is expected to enhance our understanding of higher-order topological states in electronic systems, potentially driving future advancements in the field.

Thickness Optimization of Front and Recombination ITO in Monolithic Perovskite/Silicon Tandem Solar Cells

Optical losses of perovskite/silicon tandem solar cells can be effectively reduced by optimizing the thin‐film layer thicknesses. Herein, the thicknesses of DC sputtered indium tin oxide (ITO) films, which serve as the front electrode and the recombination layer connecting the subcells, are optimized to reach high transparency and good lateral charge transport simultaneously. Optical simulations of the full perovskite/silicon tandem solar cell stacks are performed to find the optimum recombination and front electrode ITO thicknesses for solar cells as well as modules. Implementation of the optimized 25 nm front electrode ITO thickness in semitransparent single‐junction perovskite solar cells increases the short‐circuit density by 1.5 mA cm−2 compared to the former reference thickness of 75 nm. Combined with an optimized 20 nm recombination ITO layer, high short‐circuit density of 20.3 mA cm−2 is reached in perovskite/silicon tandem solar cell devices, which is the highest reported value for planar front perovskite/silicon tandem solar cells to the best of knowledge. Further interface passivation enables 28.8% power conversion efficiency.

Atmospheric modulation of apparent electrical conductivity in a metal−organic framework

Combining high surface area and efficient charge transport, electrically conductive metal−organic frameworks (MOFs) find wide applications in energy storage, sensing, and electrocatalysis. Reliable characterization of electrical conductivity, the key metric for assessing this class of materials, remains challenging due to its high sensitivity to the atmosphere. Herein, through electrical characterization of an exemplary MOF, Cd2(TTFTB) (TTFTB4− = tetrathiafulvalene tetrabenzoate), under various controlled atmospheres, we show that adsorption of water in humid air or N2 improves the apparent room-temperature electrical conductivity by one to two orders of magnitude compared to the values observed in dry atmospheres. This observation in conjunction with spectroscopic characterization, structural analysis, and band structure calculations indicates significant contribution of water-mediated proton conductivity and/or proton-electron coupling to the apparent electrical conductivity. Thus, controlling and reporting atmospheres in electrical conductivity measurements of MOFs is critical to improve their reproducibility and to gain insights into electrical conduction mechanisms.

High mobility charge transport in a multicarrier altermagnet CrSb

High mobility charge transport in a multicarrier altermagnet CrSb

Helical Ni‐Cluster Organic Framework Constructed from Enantiopure Lactate Derivative: Synthesis, Structure and Properties

AbstractUnder hydrothermal condition, lactate derivative (R)‐4‐(1‐ carboxyethoxy)‐2‐methylbenzoic acid ((R)‐H2cma) as chiral synthon assembled with 4,4′‐di(1H‐imidazol‐1‐yl)‐1,1′‐biphenyl (4,4’‐dib) and Ni(II) ions to obtain complex {[Ni2((R)‐cma)2(4,4’‐dib)2(H2O)] ⋅ 2H2O}n (HU20‐R). In complex HU20‐R, carboxyl group from lactate unit of (R)‐cma2− anion and coordinating H2O molecule adopt a μ2‐coordination mode to obtain dinuclear [Ni2(CO2)2(H2O)]2+ cluster. (R)‐cma2− anions and Ni(II) ions build single left‐handed (R)‐cma‐Ni‐chain, while 4,4’‐dib ligands are bridged by different Ni(II) centers to form double left‐handed 4,4’‐dib‐Ni‐chain. These helical secondary structures are further connected together to result in an 8‐connected 3D framework. PXRD tests indicated that complex HU20‐R has well hydro‐stability. UV‐vis absorption experiment confirmed that HU20‐R is a semi‐conducting material with strong absorption capacity for ultraviolet‐visible (UV‐vis) light. Additionally, electrochemical experiment revealed that HU20‐R has low impedance and high charge transport capacity. Further test results confirm that HU20‐R has noticeable photo‐catalytic effect in photodegradation of Rhodamine B (RhB) and antiferromagnetic property.

Machine learning driven performance enhancement of perovskite solar cells with CNT as both hole transport layer and back contact

We propose a machine learning-based approach to enhance the performance of perovskite solar cells (PSCs) using carbon nanotubes as both hole transport layer (HTL) and back contact. Carbon-based PSCs offer low fabrication costs, long-term mechanical stability, high charge transport, and broad wavelength transparency. Our study estimates and enhances power conversion efficiency (PCE) of carbon-based PSCs through machine learning. PSC with single-walled carbon nanotube (SWCNT)-based HTL and back contact is investigated in simulations using SCAPS-1D and achieved 14.24% PCE, closely aligning with experimental data. Additionally, we explore the impact of various easily tunable fabrication parameters, such as the band gap and electron affinity of SWCNT in HTL, HTL thickness, active layer thickness, electron transport layer (ETL) thickness, HTL dopant concentration, absorber defect density, and ETL dopant concentration, on PCE. We generate a dataset of 20,480 samples to train classical and neural network-based machine learning models to predict performance parameters of PSCs, including short-circuit current density (JSC), open-circuit voltage (VOC), fill factor (FF), and PCE (η). The current density vs. voltage (J-V) characteristics curve is well-fitted by the predicted JSC, VOC, and FF, as evidenced by an average root mean squared error (RMSE) of 0.03 and a goodness of fit (R2) value of 0.99. The fully connected artificial neural network performs best, with RMSE of 0.05% and R2 of 0.99998 for predicting PCE. Genetic algorithm is used to optimize PCE, yielding a maximum PCE of 20.92%. Furthermore, an analysis of feature dimension and dataset size on prediction performance guides future modeling approaches.

Accomplishing High-Performance Organic Solar Sub-Modules (≈55 cm2) with >16% Efficiency by Controlling the Aggregation of an Engineered Non-Fullerene Acceptor.

The fabrication of environmentally benign, solvent-processed, efficient, organic photovoltaic sub-modules remains challenging due to the rapid aggregation of the current high performance non-fullerene acceptors (NFAs). In this regard, design of new NFAs capable of achieving optimal aggregation in large-area organic photovoltaic modules has not been realized. Here, an NFA named BTA-HD-Rh is synthesized with longer (hexyl-decyl) side chains that exhibit good solubility and optimal aggregation. Interestingly, integrating a minute amount of new NFA (BTA-HD-Rh) into the PM6:L8-BO system enables the improved solubility in halogen-free solvents (o-xylene:carbon disulfide (O-XY:CS2)) with controlled aggregation is found. Then solar sub-modules are fabricated at ambient condition (temperature at 25±3 °C and humidity: 30-45%). Ultimately, the champion 55 cm2 sub-modules achieve exciting efficiency of >16% in O-XY:CS2 solvents, which is the highest PCE reported for sub-modules. Notably, the highest efficiency of BTA-HD-Rh doped PM6:L8-BO is very well correlated with high miscibility with low Flory-Huggins parameter (0.372), well-defined nanoscale morphology, and high charge transport. This study demonstrates that a careful choice of side chain engineering for an NFA offers fascinating features that control the overall aggregation of active layer, which results in superior sub-module performance with environmental-friendly solvents.

A Multi-Interface Structure of Graphdiyne/Cobalt Oxides for Chlorine Production.

A challenge facing the chlor-alkali process is the lack of electrocatalyst with high activity and selectivity for the efficient industrial production of chlorine. Herein the authors report a new electrocatalyst that can generate multi-interface structure by in situ growth of graphdiyne on the surface of cobalt oxides (GDY/Co3O4), which shows great potential in highly selective and efficient chlorine production. This result is due to the strong electron transfer and high density charge transport between GDY and Co3O4 and the interconversion of the mixed valence states of the Co atoms itself. These intrinsic characteristics efficiently enhance the conductivity of the catalyst, facilitate the reaction kinetics, and improve the overall catalytic selectivity and activity. Besides, the protective effect of the formed GDY layer is remarkable endowing the catalyst with excellent stability. The catalyst can selectively produce chlorine in low-concentration of NaCl aqueous solution at room temperature and pressure with the highest Faraday efficiency of 80.67% and an active chlorine yield rate of 184.40mg h-1 cm-2, as well as superior long-term stability.

Magic of Solvents: Effect of Processing Solvents on Hole Transport in Organic Semiconductor Small Molecules

Organic semiconductor small molecules (SMs) attract much attention to the design of various emerging photovoltaic and optoelectronic devices. High charge‐transport characteristics of SMs are important prerequisite for achieving outstanding performance of electronics. Herein, four promising SMs are investigated in terms of modulating charge‐transport properties by solvent engineering. It is shown that the hole mobility of thin films based on push–pull SMs can be effectively enhanced by the replacement of chlorobenzene with environmentally preferable hexane without changing a molecular structure of the compounds. As a result, 2–5 times higher hole mobility is achieved for hexane‐processed films that is attributed to the formation of favorable nanoscale morphology of films. This effortless approach can be applied to other organic semiconductor materials to precisely control the morphology and improve their electrophysical properties.

Superior electron mobility, red electroluminescence with high quantum efficiency from printable room temperature columnar liquid crystalline perylene bisimide

Synthesis of highly fluorescent compounds is currently a critical requirement to facilitate the economical and metal-independent manufacture of organic light-emitting diodes (OLEDs) on a large scale. This study presents a highly soluble, swallow tail based electron deficient perylene bisimide (PBIST) exhibiting room temperature columnar oblique (Colob) liquid crystalline behavior along with a high photoluminescence quantum yield, positioning itself as a promising candidate for efficient OLEDs. Incorporation of swallow tails helped in enhancing the solubility and reduction of the clearing points. This unique tailor-made molecular design with the liquid crystalline phase allowed a demonstration of n-type field effect mobility of 0.008 cm2 V−1s−1 when annealed in the liquid crystalline mesophase range (at 70 °C) which can be exploited in the fabrication of printable electronic devices. Capitalizing on the high charge transport and luminescence attributes of PBIST, a series of devices were fabricated by utilizing PBIST as a single emitter and dispersed at different concentrations of 0.3, 0.5 and 1 wt% in host material CBP. Impressively, doped devices featuring the CBP as a host at a 0.5 wt% PBIST concentration exhibited an external quantum efficiency (EQE) as high as 7 %, accompanied by a luminance of 1787 cd/m2. The high EQE is attributed mainly to the triplet–triplet annihilation (TTA) process. This notable EQE enhancement signifies a substantial stride towards expanding the utility of multifunctional columnar self-assembled materials for the advancement of OLEDs.

Small molecule donor third component incorporating thieno[3,2-b]thiophene unit enables 19.18% efficiency ternary organic solar cells with improved operational stability

The rational design of the third component to enhance the efficiency and stability of organic solar cell (OSC) is a critical and challenge. Herein, a thieno[3,2-b]thiophene (TT) substituted wide-bandgap small molecule donor BTTC, was designed, synthesized and incorporated into the state-of-the-art PM6:L8-BO binary to construct ternary OSC. The rigid side chain and planar molecule skeleton enables strong crystallinity and complementary absorption with binary system. The introduction of BTTC enhanced the molecular packing, fibril-like film and preferred vertical phase separation, yielding balanced and higher charge transport, more efficient exciton dissociation and suppressed charge recombination. Besides, lower energy loss was attained and thus leading to higher open-circuit voltage (VOC). Consequently, the introduction of BTTC achieved the highest efficiency of 18.8% along with extended operational stability. Furthermore, replacing L8-BO to BTP-eC9 further boosted the ternary PCE to 19.18%, standing one of the best charge management in ternary OSC. This work presents efficient rigid side chain substitution strategy to construct the third component of small molecule donor for high performance ternary OSCs with comprehensively improved photovoltaic parameters. This strategy broadens the selection of guest materials toward realizing the actual commercial application of OSCs.

Weak Electrostatic Force on K+ in Gel Polymer Electrolyte Realizes High Ion Transference Number for Quasi Solid-State Potassium Ion Batteries.

Quasi-solid-state potassium-ion batteries (SSPIBs) are of great potential for commercial use due to the abundant reserves and cost-effectiveness of resources, as well as high safety. Gel polymer electrolytes (GPEs) with high ionic conductivity and fast interfacial charge transport are necessary for SSPIBs. Here, the weak electrostatic force between K+ and electronegative functional groups in the ethoxylated trimethylolpropane triacrylate (ETPTA) polymer chains, which can promote fast migration of free K+, is revealed. To further enhance the interfacial reaction kinetics, a multilayered GPE by in situ growth of poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) on ETPTA (PVDF-HFP|ETPTA|PVDF-HFP) is constructed to improve the interface contact and provide sufficient K+ concentration in PVDF-HFP. A high ion transference number (0.92) and a superior ionic conductivity (5.15 × 10-3 S cm-1) are achieved. Consequently, the SSPIBs with both intercalation-type (PB) and conversion-type (PTCDA) cathodes show the best battery performance among all reported SSPIBs of the same cathode. These findings demonstrate that potassium-ion batteries have the potential to surpass Li/Na ion batteries in solid-state systems.

Enhanced Transport Kinetics of Electrochromic Devices by W18O49 NW/Ti3C2Tx Composite Films

AbstractElectrochromic devices can facilitate the realization of a wide set of future applications, ranging from energy‐saving windows to smart wearables and stealth. Historically, tungsten oxides have been the most studied materials for electrochromism, albeit with bottlenecks like limited conductivity, high charge transport barrier, and low ion diffusivity. Here, inspired by the recent MXene materials, the study has engineered an electrochromic composite of MXene nanosheets (Ti3C2Tx) and W18O49 nanowires (NWs). A transparent conductive electrode is fabricated by co‐assembly of Ag and W18O49NWs, followed by depositing W18O49 NW/Ti3C2Tx layers for the fabrication of the electrochromic device. The incorporation of Ti3C2Tx nanosheets enhances the transport of electrons and ions within the electrochromic layer, leading to a significant improvement in the electrochromic performance. Noteworthily, the film structure comprising 15 layers of W18O49 NW/Ti3C2Tx composite reveals enhanced transmittance modulation (61%), rapid response time (4.5 s coloration, 6.5 s bleaching), and high coloration efficiency (139.1 cm2 C−1). Moreover, the electrode also presents a high diffusion coefficient of Li+ and good cycling stability (96.66% after 250 switching cycles). Finally, a large‐scale (15 × 20 cm2) flexible electrochromic device with a solid electrolyte is successfully fabricated and utilized as a smart window and a flexible stealth patch.

Retraction: A novel concept and design for highly efficient photoelectrocatalytic materials with high performance, stability, and charge transport properties: development of an innovative next-generation green technology.

[This retracts the article DOI: 10.1039/D3RA05126A.].

A triazole-based covalent organic framework as a photocatalyst toward visible-light-driven CO2 reduction to CH4.

Solar-light driven reduction of CO2 to CH4 is a complex process involving multiple electron and proton transfer processes with various intermediates. Therefore, achieving high CH4 activity and selectivity remains a significant challenge. Covalent organic frameworks (COFs) represent an emerging class of photoactive semiconductors with molecular level structural tunability, modular band gaps, and high charge carrier generation and transport within the network. Here, we developed a new heterocyclic triazole ring containing COF, TFPB-TRZ, through the condensation reaction between 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 3,5-diamino-1,2,4-triazole (TRZ). The TFPB-TRZ COF with multiple heteroatoms shows suitable visible light absorption, high CO2 uptake capability and an appropriate band diagram for CO2 photoreduction. Photocatalysis results reveal a maximum CO2 to CH4 conversion of 2.34 mmol g-1 with a rate of 128 μmol g-1 h-1 and high selectivity (∼99%) using 1-benzyl-1,4-dihydronicotinamide (BNAH) and triethylamine (TEA) as sacrificial agents. Under similar reaction conditions in the presence of direct sunlight, the TFPB-TRZ COF displays a maximum CH4 yield of 493 μmol g-1 with a rate of 61.62 μmol g-1 h-1, suggesting the robustness and light-harvesting ability of the COF photocatalyst. A femtosecond transient absorption (TA) spectroscopy study shows fast decay of excited state absorption (ESA) in the COF compared to the TFPB building unit due to efficient electron transfer to the catalytic site in the framework. The mechanism of CO2 reduction to CH4 is studied by DFT-based theoretical calculation, which is further supported by an in situ diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) study. The DFT results reveal that the lone pair of electrons on nitrogen heteroatoms present in the triazole ring of the TRZ moiety help in the stabilization of the CO intermediate during CO2 to CH4 conversion. Overall, this work demonstrates the use of a metal-free, recyclable COF-based photocatalytic system for solar energy storage by CO2 reduction.

Influence of molecular structure on the coupling strength to a plasmonic nanoparticle and hot carrier generation.

Strong coupling between metal nanoparticles and molecules mixes their excitations, creating new eigenstates with modified properties such as altered chemical reactivity, different relaxation pathways or modified phase transitions. Here, we explore excited state plasmon-molecule coupling and discuss how strong coupling together with a changed orientation and number of an asymmetric molecule affects the generation of hot carriers in the system. We used a promising plasmonic material, magnesium, for the nanoparticle and coupled it with CPDT molecules, which are used in organic optoelectronic materials for organic electronic applications due to their facile modification, electron-rich structure, low band gap, high electrical conductivity and good charge transport properties. By employing computational quantum electronic tools we demonstrate the existence of a strong coupling mediated charge transfer plasmon whose direction, magnitude, and spectral position can be tuned. We find that the orientation of CPDT changes the nanoparticle-molecule gap for which maximum charge separation occurs, while larger gaps result in trapping hot carriers within the moieties due to weaker interactions. This research highlights the potential for tuning hot carrier generation in strongly coupled plasmon-molecule systems for enhanced energy generation or excited state chemistry.

Porous crystalline conjugated macrocyclic materials and their energy storage applications.

Porous crystalline conjugated macrocyclic materials (CMMs) possess high porosity, tunable structure/function and efficient charge transport ability owing to their planar macrocyclic conjugated π-electron system, which make them promising candidates for applications in energy storage. In this review, we thoroughly summarize the timely development of porous crystalline CMMs in energy storage related fields. Specifically, we summarize and discuss their structures and properties. In addition, their energy storage applications, such as lithium ion batteries, lithium sulfur batteries, sodium ion batteries, potassium ion batteries, Li-CO2 batteries, Li-O2 batteries, Zn-air batteries, supercapacitors and triboelectric nanogenerators, are also discussed. Finally, we present the existing challenges and future prospects. We hope this review will inspire the development of advanced energy storage materials based on porous crystalline CMMs.

A novel concept and design for highly efficient photoelectrocatalytic materials with high performance, stability, and charge transport properties: development of an innovative next-generation green technology.

In semiconductors, generating charges via catalysis is a highly challenging task and characteristic of heterojunction photoanodes. A dithiophene-4,8-dione spin-coated film layer has a positive effect on the holes (positive charge carriers) for a long time in BHJ films in the solid state of materials. The photoexcited holes created in the BHJ film can persist for long periods of time, which is beneficial for catalytic reactions. In this study, a photoanode is electrically coupled to a hydrogen gas-evolving platinum cathode. When the photoanode is electrically coupled to a H2 gas evolving Pt cathode, curiously long-lived hole polaron states are observed on the timescale of seconds under operational conditions. These long-lived holes play a crucial role in enhancing the hydrogen peroxide oxidation performance of the film overlayer spin-coated onto the photoanode. The spin-coated film overlayer on the photoanode achieves the best oxidation performance for hydrogen peroxide of approximately 6.5 mA cm-2 at 1.23 VRHE without the need of a catalyst. This demonstrates the effectiveness of the overlayer in improving the catalytic performance of the photoanode with a better efficiency of 17.5% when using 851 nm excitation. This indicates that a relatively high percentage of incident photons at that specific wavelength is converted into photocurrent by the photoanode. This approach can lead to more efficient oxidation catalysis as demonstrated in the case of hydrogen peroxide oxidation.