Photocatalytic doping of organic semiconductors.

Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1-3 and ultimately enhances device performance4-7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8-10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm-1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices.

Transition metal-catalysed molecular n-doping of organic semiconductors.

Chemical doping is a key process for investigating charge transport in organic semiconductors and improving certain (opto)electronic devices1-9. N(electron)-doping is fundamentally more challenging than p(hole)-doping and typically achieves a very low doping efficiency (η) of less than 10%1,10. An efficient molecular n-dopant should simultaneously exhibit a high reducing power and air stability for broad applicability1,5,6,9,11, which is very challenging. Here we show a general concept of catalysed n-doping of organic semiconductors using air-stable precursor-type molecular dopants. Incorporation of a transition metal (for example, Pt, Au, Pd) as vapour-deposited nanoparticles or solution-processable organometallic complexes (for example, Pd2(dba)3) catalyses the reaction, as assessed by experimental and theoretical evidence, enabling greatly increased η in a much shorter doping time and high electrical conductivities (above 100 S cm-1; ref. 12). This methodology has technological implications for realizing improved semiconductor devices and offers a broad exploration space of ternary systems comprising catalysts, molecular dopants and semiconductors, thus opening new opportunities in n-doping research and applications12, 13.

Selective Cleavage of α-Olefins to Produce Acetylene and Hydrogen.

Acetylene production from mixed α-olefins emerges as a potentially green and energy-efficient approach with significant scientific value in the selective cleavage of C-C bonds. On the Pd(100) surface, it is experimentally revealed that C2 to C4 α-olefins undergo selective thermal cleavage to form surface acetylene and hydrogen. The high selectivity toward acetylene is attributed to the 4-fold hollow sites which are adept at severing the terminal double bonds in α-olefins to produce acetylene. A challenge arises, however, because acetylene tends to stay at the Pd(100) surface. By using the surface alloying methodology with alien Au, the surface Pd d-band center has been successfully shifted away from the Fermi level to release surface-generated acetylene from α-olefins as a gaseous product. Our study actually provides a technological strategy to economically produce acetylene and hydrogen from α-olefins.

Cyano-Functionalized Pyrazine: A Structurally Simple and Easily Accessible Electron-Deficient Building Block for n-Type Organic Thermoelectric Polymers.

Developing low-cost and high-performance n-type polymer semiconductors is essential to accelerate the application of organic thermoelectrics (OTEs). To achieve this objective, it is critical to design strong electron-deficient building blocks with simple structure and easy synthesis, which are essential for the development of n-type polymer semiconductors. Herein, we synthesized two cyano-functionalized highly electron-deficient building blocks, namely 3,6-dibromopyrazine-2-carbonitrile (CNPz) and 3,6-Dibromopyrazine-2,5-dicarbonitrile (DCNPz), which feature simple structures and facile synthesis. CNPz and DCNPz can be obtained via only one-step reaction and three-step reactions from cheap raw materials, respectively. Based on CNPz and DCNPz, two acceptor-acceptor (A-A) polymers, P(DPP-CNPz) and P(DPP-DCNPz) are successfully developed, featuring deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels, which are beneficial to n-type organic thin-film transistors (OTFTs) and OTEs performance. An optimal unipolar electron mobility of 0.85 and 1.85 cm2 V-1 s-1 is obtained for P(DPP-CNPz) and P(DPP-DCNPz), respectively. When doped with N-DMBI, P(DPP-CNPz) and P(DPP-DCNPz) show high n-type electrical conductivities/power factors of 25.3 S cm-1 /41.4 µW m-1 K-2 , and 33.9 S cm-1 /30.4 µW m-1 K-2 , respectively. Hence, the cyano-functionalized pyrazine CNPz and DCNPz represent a new class of structurally simple, low-cost and readily accessible electron-deficient building block for constructing n-type polymer semiconductors.

Atomic Level-Macroscopic Structure-Activity of Inhomogeneous Localized Aggregates Enabled Ultra-Low Temperature Hybrid Aqueous Batteries.

The utilization of hybrid aqueous electrolytes has significantly broadened the electrochemical and temperature ranges of aqueous batteries, such as aqueous zinc and lithium-ion batteries, but the design principles for extreme operating conditions remain poorly understood. Here, we systematically unveil the ternary interaction involving salt-water-organic co-solvents and its intricate impacts on both the atomic-level and macroscopic structural features of the hybrid electrolytes. This highlights a distinct category of micelle-like structure electrolytes featuring organic-enriched phases and nanosized aqueous electrolyte aggregates, enabled by appropriate low donor number co-solvents and amphiphilic anions. Remarkably, the electrolyte enables exceptional high solubility, accommodating up to 29.8 m zinc triflate within aqueous micelles. This configuration maintains an intra-micellar salt-in-water setup, allowing for a broad electrochemical window (up to 3.86 V), low viscosity, and state-of-the-art ultralow-temperature zinc ion conductivity (1.58 mS cm-1 at -80°C). Building upon the unique nature of the inhomogeneous localized aggregates, this micelle-like electrolyte facilitates dendrite-free Zn plating/stripping, even at -80°C. The assembled Zn||PANI battery showcases an impressive capacity of 71.8 mAh g-1 and an extended lifespan of over 3000 cycles at -80°C. This study opens up a promising approach in electrolyte design that transcends conventional local atomic solvation structures, broadening the water-in-salt electrolyte concept.

Synergistic Contribution of Oligo(ethylene glycol) and Fluorine Substitution of Conjugated Polymer Photocatalysts toward Solar Driven Sacrificial Hydrogen Evolution.

To separately explore the importance of hydrophilicity and backbone planarity of polymer photocatalyst, a series of benzothiadiazole-based donor-acceptor alternating copolymers incorporating alkoxy, linear oligo(ethylene glycol) (OEG) side chain, and backbone fluorine substituents is presented. The OEG side chains in the polymer backbone increase the surface energy of the polymer nanoparticles, thereby improving the interaction with water and facilitating electron transfer to water. Moreover, the OEG-attached copolymers exhibit enhanced intermolecular packing compared to polymers with alkoxy side chains, which is possibly attributed to the self-assembly properties of the side chains. Fluorine substituents on the polymer backbone produce highly ordered lamellar stacks with distinct π-π stacking features; subsequently, the long-lived polarons toward hydrogen evolution are observed by transient absorption spectroscopy. In addition, a new nanoparticle synthesis strategy using a methanol/water mixed solvent is first adopted, thereby avoiding the screening effect of surfactants between the nanoparticles and water. Finally, hydrogen evolution rate of 26 000 µmol g-1  h-1 is obtained for the copolymer incorporated with both OEG side chains and fluorine substituents under visible-light irradiation (λ > 420 nm). This study demonstrates how the glycol side chain strategy can be further optimized for polymer photocatalysts by controlling the backbone planarity.

Deciphering the Effects of Molecular Dipole Moments on the Photovoltaic Performance of Organic Solar Cells.

The dielectronic constant of organic semiconductor materials is directly related to its molecule dipole moment, which can be used to guide the design of high-performance organic photovoltaic materials. Herein, two isomeric small molecule acceptors, ANDT-2F and CNDT-2F, are designed and synthesized by using the electron localization effect of alkoxy in different positions of naphthalene. It is found that the axisymmetric ANDT-2F exhibits a larger dipole moment, which can improve exciton dissociation and charge generation efficiencies due to the strong intramolecular charge transfer effect, resulting in the higher photovoltaic performance of devices. Moreover, PBDB-T:ANDT-2F blend film exhibits larger and more balanced hole and electron mobility as well as nanoscale phase separation due to the favorable miscibility. As a result, the optimized device based on axisymmetric ANDT-2F shows a JSC of 21.30 mA cm-2 , an FF of 66.21%, and a power conversion energy of 12.13%, higher than that of centrosymmetric CNDT-2F-based device. This work provides important implications for designing and synthesizing efficient organic photovoltaic materials by tuning their dipole moment.

Ionic Dopant-Free Polymer Alloy Hole Transport Materials for High-Performance Perovskite Solar Cells.

The dominated hole transport material (HTM) used in state-of-the-art perovskite solar cells (PSCs) is Spiro-OMeTAD, which needs to be doped to improve its conductivity and mobility. The inevitable instability induced by deliquescent dopants and the necessary oxidation process in air hinders the commercialization of this technology. Here, an alloy strategy using two conjugated polymers with highly similar structures but different crystallinities for dopant-free HTM and high-performance PSCs has been demonstrated. We found that the polymeric packing and crystallinity of a polymer alloy could be regulated finely by blending the polymer PM6 and our developed polymer PMSe, which exhibits a shorter π-π stacking distance due to the improved planarity of the polymer backbone with strong C═O···Se noncovalent interactions. The structure-property relationship of the polymer alloy is investigated by theoretical and experimental analyses. The optimized PSCs using the polymer alloy HTM without any ionic dopants feature an excellent power conversion efficiency of 24.53% and a high open circuit voltage (VOC) of 1.19 V with much improved stability. This efficiency is much higher than that of the control device using doped Spiro-OMeTAD HTM (PCE = 22.54%). Our work provides a very effective strategy to design and construct dopant-free hole transport materials for highly efficient perovskite solar cells and other applications.

Side-Chain Substituents on Benzotriazole-Based Polymer Acceptors Affecting the Performance of All-Polymer Solar Cells.

Recently, the strategy of polymerized small-molecule acceptors (PSMAs) has attracted extensive attention for applications in all-polymer solar cells (all-PSCs). Although side-chain engineering is considered as a simple and effective strategy for manipulating polymer properties, the corresponding effect on photovoltaic performance of PSMAs in all-PSCs has not been systemically investigated. Herein, a series of PSMAs based on the benzotriazole (BTz)-core fused SMAs with different N-alkyl chains including branched 2-butyloctyl, linear n-octyl, and methyl on the BTz unit, namely PZT-C12, PZT-C8, and PZT-C1, respectively, is presented. Comparative studies show that the size of alkyl chains has a significant impact on the solid-state behavior of PZT polymers, which in turn affects their light absorption and charge transporting capacities, and subsequently the all-PSC performances. When combining with the polymer donor PBDB-T, PZT-C1 affords a champion power conversion efficiency of 14.9%, compared to 13.1% of PZT-C12, and 13.8% of PZT-C8 in the resultant all-PSCs, mainly benefiting from its better crystallinity and the more favorable blend morphology. This work emphasizes the importance of optimizing side-chain substituents on PSMAs for improving the device efficiency of all-PSCs.

Thiazole Imide-Based All-Acceptor Homopolymer with Branched Ethylene Glycol Side Chains for Organic Thermoelectrics.

n-Type semiconducting polymers with high thermoelectric performance remain challenging due to the scarcity of molecular design strategy, limiting their applications in organic thermoelectric (OTE) devices. Herein, we provide a new approach to enhance the OTE performance of n-doped polymers by introducing acceptor-acceptor (A-A) type backbone bearing branched ethylene glycol (EG) side chains. When doped with 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), the A-A homopolymer PDTzTI-TEG exhibits n-type electrical conductivity (σ) up to 34 S cm-1 and power factor value of 15.7 µW m-1 K-2 . The OTE performance of PDTzTI-TEG is far greater than that of homopolymer PBTI-TEG (σ=0.27 S cm-1 ), indicating that introducing electron-deficient thiazole units in the backbone further improves the n-doping efficiency. These results demonstrate that developing A-A type polymers with EG side chains is an effective strategy to enhance n-type OTE performance.

Tailoring Phase Alignment and Interfaces via Polyelectrolyte Anchoring Enables Large-Area 2D Perovskite Solar Cells.

Ruddlesden-Popper phase 2D perovskite solar cells (PSCs) exhibit improved lifetime while still facing challenges such as phase alignment and up-scaling to module-level devices. Herein, polyelectrolytes are explored to tackle this issue. The contact between perovskite and hole-transport layer (HTL) is important for decreasing interfacial non-radiative recombination and scalable fabrication of uniform 2D perovskite films. Through exploring compatible butylamine cations, we first demonstrate poly(3-(4-carboxybutyl)thiophene-2,5-diyl)-butylamine (P3CT-BA) as an efficient HTL for 2D PSCs due to its great hydrophilicity, relatively high hole mobility and uniform surface. More importantly, the tailored P3CT-BA has an anchoring effect and acts as the buried passivator for 2D perovskites. Consequently, a best efficiency approaching 18 % was achieved and we further first report large-area (2×3 cm2 , 5×5 cm2 ) 2D perovskite minimodules with an impressive efficiency of 14.81 % and 11.13 %, respectively.

Intramolecular Chloro-Sulfur Interaction and Asymmetric Side-Chain Isomerization to Balance Crystallinity and Miscibility in All-Small-Molecule Solar Cells.

Intramolecular Cl-S non-covalent interaction is introduced to modify molecular backbone of a benzodithiophene terthiophene rhodamine (BTR) benchmark structure, helping planarize and rigidify the molecular framework for improving charge transport. Theoretical simulations and temperature-variable NMR experiments clearly validate the existence of Cl-S non-covalent interaction in two designed chlorinated donors and explain its important role in enhancing planarity and rigidity of the molecules for enhancing their crystallinity. The asymmetric isomerization of side-chains further optimizes the molecular orientation and surface energy to strike a balance between its crystallinity and miscibility. This carefully manipulated molecular design helps result in increased carrier mobility and suppressed charge recombination to obtain simultaneously enhanced short-circuit current (Jsc ) and fill factor (FF) and a very high efficiency of 15.73 % in binary all-small-molecule organic solar cells.

Intramolecular Noncovalent Interaction-Enabled Dopant-Free Hole-Transporting Materials for High-Performance Inverted Perovskite Solar Cells.

Intramolecular noncovalent interactions (INIs) have served as a powerful strategy for accessing organic semiconductors with enhanced charge transport properties. Herein, we apply the INI strategy for developing dopant-free hole-transporting materials (HTMs) by constructing two small-molecular HTMs featuring an INI-integrated backbone for high-performance perovskite solar cells (PVSCs). Upon incorporating noncovalent S⋅⋅⋅O interaction into their simple-structured backbones, the resulting HTMs, BTORA and BTORCNA, showed self-planarized backbones, tuned energy levels, enhanced thermal properties, appropriate film morphology, and effective defect passivation. More importantly, the high film crystallinity enables the materials with substantial hole mobilities, thus rendering them as promising dopant-free HTMs. Consequently, the BTORCNA-based inverted PVSCs delivered a power conversion efficiency of 21.10 % with encouraging long-term device stability, outperforming the devices based on BTRA without S⋅⋅⋅O interaction (18.40 %). This work offers a practical approach to designing charge transporting layers with high intrinsic mobilities for high-performance PVSCs.

Cyano-Functionalized Bithiophene Imide-Based n-Type Polymer Semiconductors: Synthesis, Structure-Property Correlations, and Thermoelectric Performance.

n-Type polymers with deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels are essential for enabling n-type organic thin-film transistors (OTFTs) with high stability and n-type organic thermoelectrics (OTEs) with high doping efficiency and promising thermoelectric performance. Bithiophene imide (BTI) and its derivatives have been demonstrated as promising acceptor units for constructing high-performance n-type polymers. However, the electron-rich thiophene moiety in BTI leads to elevated LUMOs for the resultant polymers and hence limits their n-type performance and intrinsic stability. Herein, we addressed this issue by introducing strong electron-withdrawing cyano functionality on BTI and its derivatives. We have successfully overcome the synthetic challenges and developed a series of novel acceptor building blocks, CNI, CNTI, and CNDTI, which show substantially higher electron deficiencies than does BTI. On the basis of these novel building blocks, acceptor-acceptor type homopolymers and copolymers were successfully synthesized and featured greatly suppressed LUMOs (-3.64 to -4.11 eV) versus that (-3.48 eV) of the control polymer PBTI. Their deep-positioned LUMOs resulted in improved stability in OTFTs and more efficient n-doping in OTEs for the corresponding polymers with a highest electrical conductivity of 23.3 S cm-1 and a power factor of ∼10 µW m-1 K-2. The conductivity and power factor are among the highest values reported for solution-processed molecularly n-doped polymers. The new CNI, CNTI, and CNDTI offer a remarkable platform for constructing n-type polymers, and this study demonstrates that cyano-functionalization of BTI is a very effective strategy for developing polymers with deep-lying LUMOs for high-performance n-type organic electronic devices.

High Efficiency (15.8%) All-Polymer Solar Cells Enabled by a Regioregular Narrow Bandgap Polymer Acceptor.

Despite the significant progresses made in all-polymer solar cells (all-PSCs) recently, the relatively low short-circuit current density (Jsc) and large energy loss are still quite difficult to overcome for further development. To address these challenges, we developed a new class of narrow-bandgap polymer acceptors incorporating a benzotriazole (BTz)-core fused-ring segment, named the PZT series. Compared to the commonly used benzothiadiazole (BT)-containing polymer PYT, the less electron-deficient BTz renders PZT derivatives with significantly red-shifted optical absorption and up-shifted energy levels, leading to simultaneously improved Jsc and open-circuit voltage in the resultant all-PSCs. More importantly, a regioregular PZT (PZT-γ) has been developed to achieve higher regiospecificity for avoiding the formation of isomers during polymerization. Benefiting from the more extended absorption, better backbone ordering, and more optimal blend morphology with donor component, PZT-γ-based all-PSCs exhibit a record-high power conversion efficiency of 15.8% with a greatly enhanced Jsc of 24.7 mA/cm2 and a low energy loss of 0.51 eV.

Interfacial Defects Change the Correlation between Photoluminescence, Ideality Factor, and Open-Circuit Voltage in Perovskite Solar Cells.

The ideality factor (nid ) and photoluminescence (PL) analyses assess charge recombination characteristics in perovskite solar cells (PeSCs). However, their correlations with open-circuit voltage (Voc ) are often found to be complicated depending on the recombination types in the devices. Herein, the correlation of nid , PL characteristics and Voc is elucidated depending on the interfacial crystal quality in triple-cation mixed-halide perovskite, Cs0.05 (MA0.17 FA0.83 )0.95 Pb(I0.83 Br0.17 )3 , deposited on different hole transport layers (HTLs). In the devices with low quality interfacial crystals, Voc increases together with nid , which originates from the light intensity-dependence of majority carrier at the interface. Meanwhile, a negative correlation between Voc and nid is observed for devices with high quality interfacial crystals. The authors discuss the cases that PL enhancement by the improvement of overall crystal quality can fail to correlate with a Voc increase if interfacial crystal quality becomes worse. The study highlights that interfacial crystal quality evaluation can help to understand charge recombination via nid and PL measurements, and more importantly provide information of which defect engineering between at the interface and in the bulk would be more effective for device optimization.

Multi-Selenophene-Containing Narrow Bandgap Polymer Acceptors for All-Polymer Solar Cells with over 15 % Efficiency and High Reproducibility.

All-polymer solar cells (all-PSCs) progressed tremendously due to recent advances in polymerized small molecule acceptors (PSMAs), and their power conversion efficiencies (PCEs) have exceeded 15 %. However, the practical applications of all-PSCs are still restricted by a lack of PSMAs with a broad absorption, high electron mobility, low energy loss, and good batch-to-batch reproducibility. A multi-selenophene-containing PSMA, PFY-3Se, was developed based on a selenophene-fused SMA framework and a selenophene π-spacer. Compared to its thiophene analogue PFY-0Se, PFY-3Se shows a ≈30 nm red-shifted absorption, increased electron mobility, and improved intermolecular interaction. In all-PSCs, PFY-3Se achieved an impressive PCE of 15.1 % with both high short-circuit current density of 23.6 mA cm-2 and high fill factor of 0.737, and a low energy loss, which are among the best values in all-PSCs reported to date and much better than PFY-0Se (PCE=13.0 %). Notably, PFY-3Se maintains similarly good batch-to-batch properties for realizing reproducible device performance, which is the first reported and also very rare for the PSMAs. Moreover, the PFY-3Se-based all-PSCs show low dependence of PCE on device area (0.045-1.0 cm2 ) and active layer thickness (110-250 nm), indicating the great potential toward practical applications.

Fused Bithiophene Imide Dimer-Based n-Type Polymers for High-Performance Organic Electrochemical Transistors.

The development of n-type organic electrochemical transistors (OECTs) lags far behind their p-type counterparts. In order to address this dilemma, we report here two new fused bithiophene imide dimer (f-BTI2)-based n-type polymers with a branched methyl end-capped glycol side chain, which exhibit good solubility, low-lying LUMO energy levels, favorable polymer chain orientation, and efficient ion transport property, thus yielding a remarkable OECT electron mobility (µe ) of up to ≈10-2  cm2 V-1 s-1 and volumetric capacitance (C*) as high as 443 F cm-3 , simultaneously. As a result, the f-BTI2TEG-FT-based OECTs deliver a record-high maximum geometry-normalized transconductance of 4.60 S cm-1 and a maximum µC* product of 15.2 F cm-1 V-1 s-1 . The µC* figure of merit is more than one order of magnitude higher than that of the state-of-the-art n-type OECTs. The emergence of f-BTI2TEG-FT brings a new paradigm for developing high-performance n-type polymers for low-power OECT applications.

Distannylated Bithiophene Imide: Enabling High-Performance n-Type Polymer Semiconductors with an Acceptor-Acceptor Backbone.

A distannylated electron-deficient bithiophene imide (BTI-Tin) monomer was synthesized and polymerized with imide-functionalized co-units to afford homopolymer PBTI and copolymer P(BTI-BTI2), both featuring an acceptor-acceptor backbone with high molecular weight. Both polymers exhibited excellent unipolar n-type character in transistors with electron mobility up to 2.60 cm2 V-1 s-1 . When applied as acceptor materials in all-polymer solar cells, PBTI and P(BTI-BTI2) achieved high power-conversion efficiency (PCE) of 6.67 % and 8.61 %, respectively. The PCE (6.67 %) of polymer PBTI, synthesized from the distannylated monomer, is much higher than that (0.14 %) of the same polymer PBTI*, synthesized from typical dibrominated monomer. The 8.61 % PCE of copolymer P(BTI-BTI2) is also higher than those (<1 %) of homopolymers synthesized from dibrominated monomers. The results demonstrate the success of BTI-Tin for accessing n-type polymers with greatly improved device performance.

Identification of Varieties of Dried Red Jujubes with Near-Infrared Hyperspectral Imaging.

In order to realize rapid identification of dried red jujubes, this paper proposes a method based on near-infrared hyperspectral imaging technology. The near-infrared hyperspectral images (1 000～1 600 nm) of 240 samples in total from 4 cultivars of dried red jujubes will be acquired. The samples are to be divided into the calibration set and the prediction set in the ratio of 2∶1. 7, 8, 10 effective wavelengths are to be selected by principal component analysis(PCA), x-loading weight(x-LW)and successive projection algorithm(SPA) respectively. The dimensionality of original hyperspectral images will be reduced with PCA, and texture features of the first principal component image are to be extracted with gray-level co-occurrence matrix(GLCM).The partial least squares-discriminant analysis(PLS-DA), back propagation neural network(BPNN)and least square support vector machine(LS-SVM) are to be applied to build identification models with the selected effective wavelengths, texture features and fusion of the former two features. The identification rates of the models based on fusion features will be higher than those of models based on the spectral features or texture features respectively. The BPNN models based on the fusion features will obtain the best results, whose identification rates of prediction set are to be 100%. The results in this paper indicate that the near-infrared hyperspectral imaging technology has great potential to identify the dried red jujubes rapidly.