Organic Semiconductors Research Articles

Aerosol Doping System for Microscale Seamless p-n Patterning of Carbon Nanotube Films.

Carbon nanotube (CNT) films are extensively researched as a promising material for wearable thermoelectric generators (TEGs) owing to their good flexibility and high thermoelectric conversion ability. Miniaturizing a pair of p- and n-type thermocouples and increasing the number of repeating elements can effectively increase the power of TEGs. However, conventional p-n patterning methods, such as dipping and printing, have a coarse resolution at the submillimeter level, thereby limiting the miniaturization rate. This study developed an aerosol doping system as a fine n-doping method. A dopant aerosol with a <3 μm diameter was formed through ultrasonic nebulization and air separation, while n-doping was achieved by exposing the CNT film to the dopant aerosol. Microscale p-n patterning of 1 μm was achieved through exposure using small-sized aerosols at an exceptionally slow rate of 3 Å/min. This resolution is 100 times higher than those of conventional p-n patterning methods. The developed aerosol doping system for CNTs can also be used on organic semiconductor materials, such as PEDOT/PSS and perovskite materials. Therefore, it has the potential to significantly impact the realization of Internet of Things (IoT) terminals, such as flexible TEGs, transistors, and solar cells.

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.

A Conjugated Carboranyl Main Chain Polymer with Aggregation-Induced Emission in the Near-Infrared.

Materials exhibiting aggregation-induced emission (AIE) are both highly emissive in the solid state and prompt a strongly red-shifted emission and should therefore pose as good candidates toward emerging near-infrared (NIR) applications of organic semiconductors (OSCs). Despite this, very few AIE materials have been reported with significant emissivity past 700 nm. In this work, we elucidate the potential of ortho-carborane as an AIE-active component in the design of NIR-emitting OSCs. By incorporating ortho-carborane in the backbone of a conjugated polymer, a remarkable solid-state photoluminescence quantum yield of 13.4% is achieved, with a photoluminescence maximum of 734 nm. In contrast, the corresponding para and meta isomers exhibited aggregation-caused quenching. The materials are demonstrated for electronic applications through the fabrication of nondoped polymer light-emitting diodes. Devices employing the ortho isomer achieved nearly pure NIR emission, with 86% of emission at wavelengths longer than 700 nm and an electroluminescence maximum at 761 nm, producing a significant light output of 1.37 W sr-1 m-2.

Tuning Structure and Properties of a Ferromagnetic Organic Semiconductor via a Magnetic Field-Modified Reduction Process

The development of novel synthesis and assembly strategies is critical to achieving a ferromagnetic organic semiconductor with high Curie temperature. In this study, we report a high magnetic field (HMF)-modified solvothermal approach for the reduction in neutral perylene diimide (PDI) into the dianion species to prepare the PDI magnets comprising radical anions after subsequent oxidation processes. The PDI materials, assembled from the dianion solution by an HMF-modified reduction, exhibit a smaller crystallite size and an enlarged distance of the π-π stacking in the PDI aggregates. Furthermore, the PDI magnets obtained from the process under a 9T field reveal weakened ferromagnetism and the rapid degradation of electrical conductivity compared to those prepared without a magnetic field. Based on spectral and structural characterizations, such performance deterioration originates from the enhanced instability of the radical anions exposed to air, as well as the decreased crystallinity for the radical PDIs synthesized from the HMF-modified reduction process. This work demonstrates that magnetic fields offer an effective way in the material synthesis process to manipulate the structure and magnetic properties of the radical-based organic magnets.

Inverted device architecture for high efficiency single-layer organic light-emitting diodes with imbalanced charge transport

Many wide-gap organic semiconductors exhibit imbalanced electron and hole transport, therefore efficient organic light-emitting diodes require a multilayer architecture of electron- and hole-transport materials to confine charge recombination to the emissive layer. Here, we show that even for emitters with imbalanced charge transport, it is possible to obtain highly efficient single-layer organic light emitting diodes (OLEDs), without the need for additional charge-transport and blocking layers. For hole-dominated emitters, an inverted single-layer device architecture with ohmic bottom-electron and top-hole contacts moves the emission zone away from the metal top electrode, thereby more than doubling the optical outcoupling efficiency. Finally, a blue-emitting inverted single-layer OLED based on thermally activated delayed fluorescence is achieved, exhibiting a high external quantum efficiency of 19% with little roll-off at high brightness, demonstrating that balanced charge transport is not a prerequisite for highly efficient single-layer OLEDs.

Dopant-induced Morphology of Organic Semiconductors Resulting in High Doping Performance.

Doping plays a crucial role in modulating and enhancing the performance of organic semiconductor (OSC) devices. In this study, the critical role of dopants is underscored in shaping the morphology and structure of OSC films, which in turn profoundly influences their properties. Two dopants, trityl tetrakis(pentafluorophenyl) (TrTPFB) and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (DMA-TPFB), are examined for their doping effects on poly(3-hexylthiophene) (P3HT) and PBBT-2T host OSCs. It is found that although TrTPFB exhibits higher doping efficiency, OSCs doped with DMA-TPFB achieve comparable or even enhanced electrical conductivity. Indeed, the electrical conductivity of DMA-TPFB-doped P3HT reaches over 67 S cm-1, which is a record-high value for mixed-solution-doped P3HT. This can be attributed to DMA-TPFB inducing a higher degree of crystallinity and reduced structural disorder. Moreover, the beneficial impact of DMA-TPFB on the OSC films' morphology and structure results in superior thermoelectric performance in the doped OSCs. These findings highlight the significance of dopant-induced morphological and structural considerations in enhancing the film characteristics of OSCs, opening up a new avenue for optimization of dopant performance.

Conjugated Polymer/Recombinant Escherichia coli Biohybrid Systems for Photobiocatalytic Hydrogen Production.

Biohybrid photocatalysts are composite materials that combine the efficient light-absorbing properties of synthetic materials with the highly evolved metabolic pathways and self-repair mechanisms of biological systems. Here, we show the potential of conjugated polymers as photosensitizers in biohybrid systems by combining a series of polymer nanoparticles with engineered Escherichia coli cells. Under simulated solar light irradiation, the biohybrid system consisting of fluorene/dibenzo [b,d]thiophene sulfone copolymer (LP41) and recombinant E. coli (i.e., a LP41/HydA BL21 biohybrid) shows a sacrificial hydrogen evolution rate of 3.442 mmol g-1 h-1 (normalized to polymer amount). It is over 30 times higher than the polymer photocatalyst alone (0.105 mmol g-1 h-1), while no detectable hydrogen was generated from the E. coli cells alone, demonstrating the strong synergy between the polymer nanoparticles and bacterial cells. The differences in the physical interactions between synthetic materials and microorganisms, as well as redox energy level alignment, elucidate the trends in photochemical activity. Our results suggest that organic semiconductors may offer advantages, such as solution processability, low toxicity, and more tunable surface interactions with the biological components over inorganic materials.

Constructing an Asymmetric Covalent Triazine Framework to Boost the Efficiency and Selectivity of Visible-Light-Driven CO2 Photoreduction.

The photocatalytic reduction of CO2 represents an environmentally friendly and sustainable approach for generating valuable chemicals. In this study, a thiophene-modified highly conjugated asymmetric covalent triazine framework (As-CTF-S) is developed for this purpose. Significantly, single-component intramolecular energy transfer can enhance the photogenerated charge separation, leading to the efficient conversion of CO2 to CO during photocatalysis. As a result, without the need for additional photosensitizers or organic sacrificial agents, As-CTF-S demonstrates the highest photocatalytic ability of 353.2µmolg-1 and achieves a selectivity of ≈99.95% within a 4h period under visible light irradiation. This study provides molecular insights into the rational control of charge transfer pathways for high-efficiency CO2 photoreduction using single-component organic semiconductor catalysts.

Strong Acceptors Based on Derivatives of Benzothiadiazoloimidazole

Despite the rapid progression of organic semiconductors, developing high-air-stability n-type organic semiconductors are still challenging. Herein, novel strong acceptors based on benzothiadiazoloimidazole units are reported. The results reveal that the strong acceptor BTI-NDI-BTI-a has good solubility and high electron affinity (3.94 eV), accompanied by 1D slipped-stacking crystals. Notably, the material presents promising potential for developing into air-stable n-type organic semiconductor materials.

Tailoring Cyano Substitutions on Quinoxaline‐based Small‐Molecule Acceptors Enabling Enhanced Molecular Packing for High‐Performance Organic Solar Cells

AbstractCyanation is a common chemical modification strategy to fine‐tune the energy levels and molecular packing of organic semiconductors, especially materials used in organic solar cells (OSCs). Generally, cyanation is used to modify the end groups of high‐performance small‐molecule acceptors (SMAs). However, the cyanation strategy has not been investigated on the central backbone of SMAs, which could introduce stronger intermolecular interaction and enhance the π–π stacking for rapid charge transport. This paper, for the first time, reports a new cyanation strategy on the central benzo‐quinoxaline core and synthesizes two novel A‐DA'D‐A type SMAs, named BQx‐CN and BQx‐2CN, with mono‐ and di‐cyanide groups, respectively. Through tailoring the number of CN groups, the BQx‐CN‐based OSC exhibits the best device performance of 18.8%, which is significantly higher than the non‐cyano BQx‐based one. The reason for the superior performance of BQx‐CN‐based devices can be attributed to the fine‐tuned energy level, stronger packing, and ideal phase segregation, which lead to superior exciton dissociation, faster charge transport, and suppressed recombination, therefore the highest fill factor (FF) and power conversion efficiencies (PCE). The research demonstrates the effectiveness of the cyanation strategy on the central core of SMAs for enhanced molecular packing and better performance of OSCs.

Organic Synaptic Transistors with Environmentally Friendly Core/Shell Quantum Dots for Wavelength-Selective Memory and Neuromorphic Functions.

Organic transistors based on organic semiconductors together with quantum dots (QDs) are attracting more and more interest because both materials have excellent optoelectronic properties and solution processability. Electronics based on nontoxic QDs are highly desired considering the potential health risks but are limited by elevated surface defects, inadequate stability, and diminished luminescent efficiency. Herein, organic synaptic transistors based on environmentally friendly ZnSe/ZnS core/shell QDs with passivating surface defects are developed, exhibiting optically programmable and electrically erasable characteristics. The synaptic transistors feature linear multibit storage capability and wavelength-selective memory function with a retention time above 6000 s. Various neuromorphic applications, including memory enhancement, optical communication, and memory consolidation behaviors, are simulated. Utilizing an established neuromorphic model, accuracies of 92% and 91% are achieved in pattern recognition and complicated electrocardiogram signal processing, respectively. This research highlights the potential of environmentally friendly QDs in neuromorphic applications and health monitoring.

Predicting fundamental gaps accurately from density functional theory with non-empirical local range separation.

We present an exchange-correlation approximation in which the Coulomb interaction is split into long- and short-range components and the range separation is determined by a non-empirical density functional. The functional respects important constraints, such as the homogeneous and slowly varying density limits, leads to the correct long-range potential, and eliminates one-electron self-interaction. Our approach is designed for spectroscopic purposes and closely approximates the piecewise linearity of the energy as a function of the particle number. The functional's accuracy for predicting the fundamental gap in generalized Kohn-Sham theory is demonstrated for a large number of systems, including organic semiconductors with a notoriously difficult electronic structure.

Exciton Delocalization and Polarizability in Perylenetetracarboxylic Diimide Probed Using Electroabsorption and Fluorescence Spectroscopies

Perylenetetracarboxylic diimide (PTCDI) is an n-type organic semiconductor molecule that has been widely utilized in numerous applications such as photocatalysis and field-effect transistors. Polarizability and dipole moment, which are inherent properties of molecules, are important parameters that determine their responses to external electric and optical fields, physical properties, and reactivity. These parameters are fundamentally important for the design of innovative materials. In this study, the effects of external electric fields on absorption and fluorescence spectra were investigated to obtain the PTCDI parameters. The PTCDI substituted by an octyl group (N,N′-Dioctyl-3,4,9,10-perylenedicarboximide) dispersed in a polymethyl methacrylate (PMMA) matrix was studied in this work. The features of vibronic progression in the absorption spectrum were analogous to those observed in solution. The red shift of the absorption band caused by the Stark effect was mainly observed in the presence of an external electric field. Changes in parameters such as the dipole moment and polarizability between the ground and the Franck–Condon excited states of the PTCDI monomer were determined. The fluorescence spectrum shows a contribution from a broad fluorescence band at wavelengths longer than the monomer fluorescence band. This broad fluorescence is ascribed to the excimer-like fluorescence of PTCDI. The effects of the electric field on the fluorescence spectrum, known as the Stark fluorescence or electrofluorescence spectrum, were measured. Fluorescence quenching is observed in the presence of an external electric field. The change in the polarizability of the monomer fluorescence band is in good agreement with that of the electroabsorption spectrum. A larger change in the polarizability was observed for the excimer-like fluorescence band than that for the monomer band. This result is consistent with exciton delocalization between PTCDI molecules in the excimer-like state.

High-speed blade-coating using liquid crystalline organic semiconductor Ph-BTBT-10

Abstract We have investigated the fabrication of crystalline thin films of liquid crystalline organic semiconductor (2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene: Ph-BTBT-10) by high-speed blade-coating at 140 mm/s. Quite uniform crystalline Ph-BTBT-10 films were fabricated at the temperature over 50 ℃, which is the temperature of liquid crystal phase, without inhomogeneous recrystallization despite the high-speed blade-coating. The transistors fabricated with the uniform and flat crystalline thin films showed high average mobility of the 26 devices was 4.8 cm2/Vs and the coefficient of variation was only 7.3 %. We concluded that liquid crystalline organic semiconductors are useful materials for high-speed meniscus-guided-coating for practical use.

Bromine‐Enhanced Organic Materials for X‐ray Sensors: Unveiling the Potential of Small Molecules and Polymers through Material Design and Film Fabrication

AbstractOrganic X‐ray sensors are a promising new class of detectors with the potential to revolutionize medical imaging, security screening, and other applications. However, the development of high‐performance organic X‐ray sensors is challenged by low sensitivity. This paper reports on the development of nine X‐ray sensors based on new organic materials. It is demonstrated that the incorporation of bromine atoms into the sidechains of carbazolyl‐containing organic molecules significantly enhances their X‐ray sensitivity. This research suggests that incorporating a variety of high‐atomic‐number chemical elements into well‐established organic semiconductors is a promising strategy for designing efficient X‐ray sensor materials.

Gate-Tunable Positive and Negative Photoconductance in Near-Infrared Organic Heterostructures for In-Sensor Computing.

The rapid growth of sensor data in the artificial intelligence often causes significant reductions in processing speed and power efficiency. Addressing this challenge, in-sensor computing is introduced as an advanced sensor architecture that simultaneously senses, memorizes, and processes images at the sensor level. However, this is rarely reported for organic semiconductors that possess inherent flexibility and tunable bandgap. Herein, an organic heterostructure that exhibits a robust photoresponse to near-infrared (NIR) light is introduced, making it ideal for in-sensor computing applications. This heterostructure, consisting of partially overlapping p-type and n-type organic thin films, is compatible with conventional photolithography techniques, allowing for high integration density of up to 520 devices cm-2 with a 5µm channel length. Importantly, by modulating gate voltage, both positive and negative photoresponses to NIR light (1050nm) are attained, which establishes a linear correlation between responsivity and gate voltage and consequently enables real-time matrix multiplication within the sensor. As a result, this organic heterostructure facilitates efficient and precise NIR in-sensor computing, including image processing and nondestructive reading and classification, achieving a recognition accuracy of 97.06%. This work serves as a foundation for the development of reconfigurable and multifunctional NIR neuromorphic vision systems.

Realization of an organic semiconductor electroluminescent device with high directionality and color purity

AbstractWe are introducing an innovative organic semiconductor electroluminescent device capable of emitting light with unprecedented characteristics, that is, high directionality with divergence angle of 1.1° and high color purity with the full‐width at half‐maximum of 2.5 nm. This achievement was realized through design techniques aimed at enhancing gain via meticulous recombination zone control and complemented by the reduction of the optical losses. These results demonstrate the simultaneous achievement of a narrow spectrum and high directionality in an organic electroluminescent device.

Design Rules to Optimize the Intermolecular and Long-Range Packing of Organic Semiconductor Crystals

Design Rules to Optimize the Intermolecular and Long-Range Packing of Organic Semiconductor Crystals

Performance Improvement of Formamidinium‐Based Perovskite Photodetector by Solution‐Processed C8‐BTBT Modification

AbstractOrganic–inorganic hybrid perovskite has attracted extensive research due to its excellent optoelectronic properties and is a competitive candidate material for a new generation of photodetectors. However, lateral structure photodetectors based only on perovskite active materials still present moderate performance and poor stability. Herein, lateral structure formamidinium‐based perovskite FA0.9Cs0.1PbI3 photodetectors are reported which are modified by a solution‐processed organic semiconductor 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) layer for improved photosensitive performance and ambient/flexibility stability. High‐mobility organic semiconductor C8‐BTBT serves as an efficient hole transport layer that fills the grain boundaries and gaps of the FA0.9Cs0.1PbI3 film, enabling rapid extraction and transport of the photo‐generated carriers from the perovskite to the electrodes, resulting in enhanced photosensitive performance of the photodetector. Compared with the original device, the C8‐BTBT‐modified photodetector exhibits dramatically improved performance with a best responsivity of 1278 mA W−1, specific detectivity of 1.58 × 1012 Jones, external quantum efficiency of 298%, and fall time of 14.09 ms, which is 10.84 times less than 152.76 ms of the pure perovskite device. Moreover, the C8‐BTBT film acts as a protective layer for the FA0.9Cs0.1PbI3 film because of its good air stability and effective coverage, which significantly improves the ambient stability of the perovskite photodetector compared with the original device, increasing photocurrent retention from 2.5% to 61.5% or 81.5% at different humidity after 6 days. Furthermore, the C8‐BTBT‐modified perovskite photodetector exhibits outstanding flexibility performance, with only a 5% reduction in photocurrent under bending and almost no change after 200 bending cycles, while those of the pristine perovskite device have degraded to ≈80% and ≈75% under the same conditions, respectively. This study provides a facile and effective solution‐processed‐based strategy for constructing high‐performance and stable perovskite photodetectors.

Ring Fusion Elevates the Electronic Mobility of Azabenzannulated Perylene Diimide.

The backwardness of n-type organic semiconductors still exists compared with the p-type counterparts. Thus, the development of high-performance n-type organic semiconductors is of great importance for organic electronic devices and their integrated circuits. In recent years, azabenzannulated perylene diimide (PDI), as one of immense bay-region-annulated PDI derivatives, has drawn considerable attentions. However, the electronic mobilities of azabenzannulated PDI derivatives are barely satisfactory. In this contribution, the peripheral benzene ring in azabenzannulated PDI 2 was fused to the ortho position by intermolecular C-H arylation cyclization. This endows the resultant azabenzannulated PDI 4 a planar configuration as well as electron deficient pentagonal ring. As a result, the electronic mobility of 4 is almost two orders of magnitude higher than that of the nonfused azabenzannulated PDI 2. This work shall pave a new avenue in elevating the performance of azabenzannulated PDI in organic electronics.