Covalent Bond Torsion-Enabled Unique Crystal-Phase Transformation of an Organic Semiconductor for Multicolor Light-Emitting Transistors.

High-mobility and color-tunable highly emissive organic semiconductors (OSCs) are highly promising for various optoelectronic device applications and novel structure-property relationship investigations. However, such OSCs have never been reported because of the great trade-off between mobility, emission color, and emission efficiency. Here, we report a novel strategy of molecular conformation-induced unique crystalline polymorphism to realize the high mobility and color-tunable high emission in a novel OSC, 2,7-di(anthracen-2-yl) naphthalene (2,7-DAN). Interestingly, 2,7-DAN has unique crystalline polymorphism, which has an almost identical packing motif but slightly different molecular conformation enabled by the small bond rotation angle variation between anthracene and naphthalene units. More remarkably, the subtle covalent bond rotation angle change leads to a big change in color emission (from blue to green) but does not significantly modify the mobility and emission efficiency. The carrier mobility of 2,7-DAN crystals can reach up to a reliable 17 cm2 V-1 s-1, which is rare for the reported high-mobility OSCs. Based on the unique phenomenon, high-performance light-emitting transistors with blue to green emission are simultaneously demonstrated in an OSC crystal. These results open a new way for designing emerging multifunctional organic semiconductors toward next-generation advanced molecular (atomic)-scale optoelectronics devices.

Rational Design of Fluorinated 2D Polymer Film Based on Donor-Accepter Architecture toward Multilevel Memory Device for Neuromorphic Computing.

Fluorine-containing 2D polymer (F-2DP) film is a desired system to regulate the charge transport in organic electronics but rather rarely reports due to the limited fluorine-containing building blocks and difficulties in synthesis. Herein, a novel polar molecule with antiparallel columnar stacking is synthesized and further embedded into an F-2DP system to control over the crystallinity of F-2DP film through self-complementary π-electronic forces. The donor-accepter-accepter'-donor' (D-A-A'-D') structure regulates the charge transportation efficiently, inducing multilevel memory behavior through stepwise charge capture and transfer processes. Thus, the device exhibits ternary memory behavior with low threshold voltage (Vth1 of 1.1 V, Vth2 of 2.0 V), clearly distinguishable resistance states (1:102:104) and ternary yield (83%). Furthermore, the stepwise formation of the charge complex endows the device with a wider range to regulate the conductive state, which allows its application in brain-inspired neuromorphic computing. Modified National Institute of Standards and Technology recognition can reach an accuracy of 86%, showing great potential in neuromorphic computing applications in the post-Moore era.

Highly-Polarized Solar-Blind Ultraviolet Organic Photodetectors.

Developing high-performance polarization-sensitive ultraviolet photodetectors is crucial for their application in military remote sensing, detection, bio-inspired navigation, and machine vision. However, the significant absorption in the visible light range severely limits the application of polarization-sensitive ultraviolet photodetectors, such as high-quality anti-interference imaging. Here, based on a wide-bandgap organic semiconductor single crystal (trans-1,2-bis(5-phenyldithieno[2,3-b:3',2'-d]thiophen-2-yl)ethene, BPTTE), high-performance polarization-sensitive solar-blind ultraviolet photodetectors with a dichroic ratio close to 4.26 are demonstrated. The strong anisotropy of 2D grown BPTTE single crystals in molecular vibration and optical absorption is characterized by various techniques. Under voltage modulation, stable and efficient detection of polarized light is demonstrated, attributed to the intrinsic anisotropy of transition dipole moment in the bc crystal plane, rather than other factors. Finally, high-contrast polarimetric imaging and anti-interference imaging are successfully demonstrated based on BPTTE single crystal photodetectors, highlighting the potential of organic semiconductors for polarization-sensitive solar-blind ultraviolet photodetectors.

Universal Design and Efficient Synthesis for High Ambipolar Mobility Emissive Conjugated Polymers.

High ambipolar mobility emissive conjugated polymers (HAME-CPs) are perfect candidates for organic optoelectronic devices, such as polymer light emitting transistors. However, due to intrinsic trade-off relationship between high ambipolar mobility and strong solid-state luminescence, the development of HAME-CPs suffers from high structural and synthetic complexity. Herein, a universal design principle and simple synthetic approach for HAME-CPs are developed. A series of simple non-fused polymers composed of charge transfer units, π bridges and emissive units are synthesized via a two-step microwave assisted C-H arylation and direct arylation polymerization protocol with high total yields up to 61 %. The synthetic protocol is verified valid among 7 monomers and 8 polymers. Most importantly, all 8 conjugated polymers have strong solid-state emission with high photoluminescence quantum yields up to 24 %. Furthermore, 4 polymers exhibit high ambipolar field effect mobility up to 10-2 cm2 V-1 s-1, and can be used in multifunctional optoelectronic devices. This work opens a new avenue for developing HAME-CPs by efficient synthesis and rational design.

A Domino Protocol toward High-performance Unsymmetrical Dibenzo[d,d']thieno[2,3-b;4,5-b']dithiophenes Semiconductors.

Unsymmetric organic semiconductors have many advantages such as good solubility, rich intermolecular interactions for potential various optoelectronic applications. However, their synthesis is more challenging due to intricate structures thus normally suffering tedious synthesis. Herein, we report a trisulfur radical anion (S3⋅-) triggered domino thienannulation strategy for the synthesis of dibenzo[d,d']thieno[2,3-b;4,5-b']dithiophenes (DBTDTs) using readily available 1-halo-2-ethynylbenzenes as starting materials. This domino protocol features no metal catalyst and the formation of six C-S and one C-C bonds in a one-pot reaction. Mechanistic study revealed a unique domino radical anion pathway. Single crystal structure analysis of unsymmetric DBTDT shows that its unique unsymmetric structure endows rich and multiple weak S⋅⋅⋅S interactions between molecules, which enables the large intermolecular transfer integrals of 86 meV and efficient charge transport performance with a carrier mobility of 1.52 cm2 V-1 s-1. This study provides a facile and highly efficient synthetic strategy for more high-performance unsymmetric organic semiconductors.

High-Performance Organic Narrow Dual-Band Circular Polarized Light Detection for Encrypted Communications and Color Imaging.

Conventional circularly polarized light (CPL) detectors necessitate several optical elements, posing difficulties in achieving miniature and integrated devices. Recently developed organic CPL detectors require no additional optical elements but usually suffer from low detectivity or low asymmetry factor (g-factor). Here, an organic CPL detector with excellent detectivity and a high g-factor is fabricated. By employing an inverted quasi-planar heterojunction (IPHJ) structure and incorporating an additional liquid crystal film, a CPL detector with an outstanding g-factor of 1.62 is developed. Unfavorable charge injection is effectively suppressed by the IPHJ structure, which reduces the dark current of the organic photodetector. Consequently, a left CPL detectivity of 6.16 × 1014 Jones at 640 nm is realized, surpassing all of the latest photodiode-type CPL detectors. Adopting a liquid crystal film with adjustable wavelengths of selectively reflected light, the hybrid device achieves narrow dual-band CPL detection, varying from 530 to 640 nm, with a half-maximum full width below 90 nm. Notably, the device achieves excellent stability of 260 000 on/off cycles without attenuation. To the best of the authors' knowledge, all these features have rarely been reported in previous work. The CPL detector arrays are also demonstrated for encrypted communications and color imaging.

High Mobility Emissive Excimer Organic Semiconductor Towards Color-Tunable Light-Emitting Transistors.

Organic light-emitting transistors (OLETs) are highly integrated and minimized optoelectronic devices with significant potential superiority in smart displays and optical communications. To realize these various applications, it is urgently needed for color-tunable emission in OLETs, but remains a great challenge as a result of the difficulty for designing organic semiconductors simultaneously integrating high carrier mobility, strong solid-state emission, and the ability for potential tunable colors. Herein, a high mobility emissive excimer organic semiconductor, 2,7-di(2-anthryl)-9H-fluorene (2,7-DAF) was reasonably designed by introducing a rotatable carbon-carbon single bond connecting two anthracene groups at the 2,7-sites of fluorene, and the small torsion angles simultaneously guarantee effective conjugation and suppress fluorescence quenching. Indeed, the unique stable dimer arrangement and herringbone packing mode of 2,7-DAF single crystal enables its superior integrated optoelectronic properties with high carrier mobility of 2.16 cm2 ⋅ V-1 ⋅ s-1 , and strong excimer emission with absolute photoluminescence quantum yield (PLQY) of 47.4 %. Furthermore, the voltage-dependent electrically induced color-tunable emission from orange to blue was also demonstrated for an individual 2,7-DAF single crystal based OLETs for the first time. This work opens the door for a new class of high mobility emissive excimer organic semiconductors, and provides a good platform for the study of color-tunable OLETs.

Unraveling the crucial role of trace oxygen in organic semiconductors.

Optoelectronic properties of semiconductors are significantly modified by impurities at trace level. Oxygen, a prevalent impurity in organic semiconductors (OSCs), has long been considered charge-carrier traps, leading to mobility degradation and stability problems. However, this understanding relies on the conventional deoxygenation methods, by which oxygen residues in OSCs are inevitable. It implies that the current understanding is questionable. Here, we develop a non-destructive deoxygenation method (i.e., de-doping) for OSCs by a soft plasma treatment, and thus reveal that trace oxygen significantly pre-empties the donor-like traps in OSCs, which is the origin of p-type characteristics exhibited by the majority of these materials. This insight is completely opposite to the previously reported carrier trapping and can clarify some previously unexplained organic electronics phenomena. Furthermore, the de-doping results in the disappearance of p-type behaviors and significant increase of n-type properties, while re-doping (under light irradiation in O2) can controllably reverse the process. Benefiting from this, the key electronic characteristics (e.g., polarity, conductivity, threshold voltage, and mobility) can be precisely modulated in a nondestructive way, expanding the explorable property space for all known OSC materials.

High-Efficiency Area-Emissive White Organic Light-Emitting Transistor for Full-Color Display.

The construction of high-performance white organic light-emitting transistor (OLET) with uniform area emission is crucial for smart display technologies but remains greatly challenging. Herein, high-efficiency uniform area-emissive OLETs based on a unique lateral-integrated device configuration which incorporates efficient energy transfer of phosphorescent and fluorescent guests, enabling color-tunable and white emission, are demonstrated. Through precisely regulating the energy transfer between host and guests, high external quantum efficiency of 13.9% for white-emission OLETs is achieved due to the improved high exciton utilization and light outcoupling efficiency which is the highest value reported so far for OLETs and prevents exciton-charge annihilation and electrode photon losses. Moreover, good loop stability is also achieved, along with effective gate tunability and ultralow driving voltage of below 5 V. Finally, a 4 × 6 white-emission OLET array for full-color display is demonstrated for the first time, suggesting its great potential applications for advanced display technologies.

Dibenzothiophene Sulfone-Based Ambipolar-Transporting Blue-Emissive Organic Semiconductors Towards Simple-Structured Organic Light-Emitting Transistors.

The development of blue-emissive ambipolar organic semiconductor is an arduous target due to the large energy gap, but is an indispensable part for electroluminescent device, especially for the transformative display technology of simple-structured organic light-emitting transistor (SS-OLET). Herein, we designed and synthesized two new dibenzothiophene sulfone-based high mobility blue-emissive organic semiconductors (DNaDBSOs), which demonstrate superior optical property with solid-state photoluminescent quantum yield of 46-67 % and typical ambipolar-transporting properties in SS-OLETs with symmetric gold electrodes. Comprehensive experimental and theoretical characterizations reveal the natural of ambipolar property for such blue-emissive DNaDBSOs-based materials is ascribed to a synergistic effect on lowering LUMO level and reduced electron injection barrier induced by the interfacial dipoles effect on gold electrodes due to the incorporation of appropriate DBSO unit. Finally, efficient electroluminescence properties with high-quality blue emission (CIE (0.179, 0.119)) and a narrow full-width at half-maximum of 48 nm are achieved for DNaDBSO-based SS-OLET, showing good spatial control of the recombination zone in conducting channel. This work provides a new avenue for designing ambipolar emissive organic semiconductors by incorporating the synergistic effect of energy level regulation and molecular-metal interaction, which would advance the development of superior optoelectronic materials and their high-density integrated optoelectronic devices and circuits.

Organic Polarized Light-Emitting Transistors.

Electrically driven polarized light-emitting sources are central to various applications including quantum computers, optical communication, and 3D displays, but serious challenges remain due to the inevitable incorporation of complex optical elements in conventional devices. Here, organic polarized light-emitting transistors (OPLETs), a kind of novel device that integrates the functions of organic field-effect transistors, organic light-emitting diodes, and polarizers into one unique device, are demonstrated with a degree of polarization (DOP) as high as 0.97, which is comparable to completely linearly polarized light (DOP = 1). Under the modulation of gate voltage, robust and efficient polarization emission is proven, ascribed to the intrinsic in-plane anisotropy of the molecular transition dipole moment in organic semiconductors and the open-ended feature of OPLETs instead of other factors. As a result, high-contrast optical imaging and anti-counterfeiting security are successfully demonstrated based on OPLETs, establishing a new direction for photonic and electronic integration toward on-chip miniaturized optoelectronic applications.

Tetrachromatic vision-inspired neuromorphic sensors with ultraweak ultraviolet detection.

Sensing and recognizing invisible ultraviolet (UV) light is vital for exploiting advanced artificial visual perception system. However, due to the uncertainty of the natural environment, the UV signal is very hard to be detected and perceived. Here, inspired by the tetrachromatic visual system, we report a controllable UV-ultrasensitive neuromorphic vision sensor (NeuVS) that uses organic phototransistors (OPTs) as the working unit to integrate sensing, memory and processing functions. Benefiting from asymmetric molecular structure and unique UV absorption of the active layer, the as fabricated UV-ultrasensitive NeuVS can detect 370 nm UV-light with the illumination intensity as low as 31 nW cm-2, exhibiting one of the best optical figures of merit in UV-sensitive neuromorphic vision sensors. Furthermore, the NeuVS array exbibits good image sensing and memorization capability due to its ultrasensitive optical detection and large density of charge trapping states. In addition, the wavelength-selective response and multi-level optical memory properties are utilized to construct an artificial neural network for extract and identify the invisible UV information. The NeuVS array can perform static and dynamic image recognition from the original color image by filtering red, green and blue noise, and significantly improve the recognition accuracy from 46 to 90%.

Asymmetric Wettability Mediated Patterning of Single Crystalline Nematic Liquid Crystal and P-N Heterojunction Toward a Broadband Photodetector.

The well aligned and precise patterning of liquid crystals (LCs) are considered as two key challenges for large-scale and high-efficiency integrated optoelectronic devices. However, owing to the uncontrollable liquid flow and dewetting process in the conventional techniques, most of the reported research is mainly focused on simple sematic LCs, which are composed of terthiophenes or benzothieno[3, 2-b][1] benzothiophene backbone; only a few works are carried out on the complicated LCs. Herein, an efficient strategy was introduced to control the liquid flow and alignment of LCs and realized precise and high-quality patterning of A-π-D-π-A BTR, based on the asymmetric wettability interface. Through this strategy, the large-area and well-aligned BTR microwires array was fabricated, which exhibited highly ordered molecular packing and improved charge transport performance. Furthermore, the integration of BTR and PC71BM was achieved to manufacture uniform P-N heterojunction arrays, which still possessed highly ordered alignment of BTR. On the basis of these aligned heterojunction arrays, the high-performance photodetector exhibited an excellent responsivity of 27.56 A W-1 and a specific detectivity of 2.07 × 1012 Jones. This research not only provides an efficient strategy for the fabrication of aligned micropatterns of LCs but also gives a novel insight for the fabrication of high-quality micropatterns of the P-N heterojunction toward integrated optoelectronics.

High-Performance Ambipolar and n-Type Emissive Semiconductors Based on Perfluorophenyl-Substituted Perylene and Anthracene.

Emissive organic semiconductors are highly demanding for organic light-emitting transistors (OLETs) and electrically pumped organic lasers (EPOLs). However, it remains a great challenge to obtain organic semiconductors with high carrier mobility and high photoluminescence quantum yield simultaneously. Here, a new design strategy is reported for highly emissive ambipolar and even n-type semiconductors by introducing perfluorophenyl groups into polycyclic aromatic hydrocarbons such as perylene and anthracene. The results reveal that 3,9-diperfluorophenyl perylene (5FDPP) exhibits the ambipolar semiconducting property with hole and electron mobilities up to 0.12 and 1.89 cm2 V-1 s-1 , and a photoluminescence quantum yield of 55%. One of the crystal forms of 5FDPA exhibits blue emission with an emission quantum yield of 52% and simultaneously shows the n-type semiconducting property with an electron mobility up to 2.65 cm2 V-1 s-1 , which is the highest value among the reported organic emissive n-type semiconductors. Furthermore, crystals of 5FDPP are utilized to fabricate OLETs by using Ag as source-drain electrodes. The electroluminescence is detected in the transporting channels with an external quantum efficiency (EQE) of up to 2.2%, and the current density is up to 145 kA cm-2 , which are among the highest values for single-component OLETs with symmetric electrodes.

Recent advances in n-type and ambipolar organic semiconductors and their multi-functional applications.

Organic semiconductors have received broad attention and research interest due to their unique integration of semiconducting properties with structural tunability, intrinsic flexibiltiy and low cost. In order to meet the requirements of organic electronic devices and their integrated circuits, p-type, n-type and ambipolar organic semiconductors are all necessary. However, due to the limitation in both material synthesis and device fabrication, the development of n-type and ambipolar materials is quite behind that of p-type materials. Recent development in synthetic methods of organic semiconductors greatly enriches the range of n-type and ambipolar materials. Moreover, the newly developed materials with multiple functions also put forward multi-functional device applications, including some emerging research areas. In this review, we give a timely summary on these impressive advances in n-type and ambipolar organic semiconductors with a special focus on their synthesis methods and advanced materials with enhanced properties of charge carrier mobility, integration of high mobility and strong emission and thermoelectric properties. Finally, multi-functional device applications are further demonstrated as an example of these developed n-type and ambipolar materials.

Harvesting Triplet Excitons in High Mobility Emissive Organic Semiconductor for Efficiency Enhancement of Light-Emitting Transistors.

Organic light-emitting transistors (OLETs), a kind of highly integrated and minimized optoelectronic device, demonstrate great potential applications in various fields. The construction of high-performance OLETs requires the integration of high charge carrier mobility, strong emission, and high triplet exciton utilization efficiency in the active layer. However, it remains a significant long-term challenge, especially for single component active layer OLETs. Herein, the successful harvesting of triplet excitons in a high mobility emissive molecule, 2,6-diphenylanthracene (DPA), through the triplet-triplet annihilation process is demonstrated. By incorporating a highly emissive guest into the DPA host system, an obvious increase in photoluminescence efficiency along with exciton utilization efficiency results in an obvious enhancement of external quantum efficiency of 7.2 times for OLETs compared to the non-doped devices. Moreover, well-tunable multi-color electroluminescence, especially white emission with Commission Internationale del'Eclairage  of (0.31, 0.35), from OLETs is also achieved by modulating the doping concentration with a controlled energy transfer process. This work opens a new avenue for integrating strong emission and efficient exciton utilization in high-mobility organic semiconductors for high-performance OLETs and advancing their related functional device applications.

Van der Waals Multilayer Heterojunction for Low-Voltage Organic RGB Area-Emitting Transistor Array.

Organic light-emitting transistors (OLETs) have garnered considerable attention from academy and industry due to their potential applications in next-generation display technologies, multifunctional devices, and organic electrically pumped lasers. However, overcoming the trade-offs among power consumption, external quantum efficiency (EQE), and uniform area emission remains a long-standing issue for OLETs. Herein, a van der Waals multilayer heterojunction methodology is proposed to enhance the layer-to-layer interfacial interaction and contact, resulting in better dipole shielding, carrier transport, exciton recombination, and current density distribution. The prepared multilayer heterojunction OLET (MLH-OLET) array shows uniform and bright RGB area emission and low operating voltage (<30 V among the lowest applied voltage of reported lateral LETs). Additionally, a high brightness under area emission of 1060 cd m-2 , a high EQE value of 0.85%, and a high loop stability (over 380 cycles, outperforming state-of-the-art OLETs) indicate that the proposed multilayer heterojunction is obviously superior to the reported lateral device configuration. The van der Waals multilayer heterojunction developed for the preparation of OLET arrays sufficiently meets the low-voltage, high-performance, and low-cost requirements of future display technologies.

Highly Efficient Inherent Linearly Polarized Electroluminescence from Small-Molecule Organic Single Crystals.

Small-molecule organic single crystals (SCs) with an inherent in-plane anisotropic nature enable direct linearly polarized light emission without the need for spatially separated polarizers and complex optical structures. However, the device performance is severely restricted by the starvation of appropriate SC emitters and the difficulty in the construction of efficient SC electroluminescence (EL) devices, leading to a low external quantum efficiency (EQE) of usually smaller than 1.5%. Here, highly efficient inherent linearly polarized light-emitting diodes (LP-LEDs) are demonstrated by exploiting 2,6-diphenylanthracene (DPA) SCs as intrinsically polarized emitters. The LP-LEDs exhibit a 2.5-fold enhanced maximum EQE of 3.38%, which approaches the theoretical limit for the DPA SC-based EL device and is the highest among organic SC-based LEDs reported thus far. More importantly, a high degree of polarization (DOP) up to 0.74 is achieved for the intrinsically polarized EL emission of the DPA SC-based LP-LEDs. By leveraging the highly efficient LP-LED, an interchip polarized optical communication system consisting of organic SCs is demonstrated for the first time. This work creates a solid foundation for the exploitation of a vast new library of small-molecule organic SCs for LP-LEDs and carries broad implications for polarized optics and relevant optoelectronic devices.