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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 polarizer 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, we demonstrate highly efficient inherent linearly polarized light-emitting diodes (LP-LEDs) 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 light-emitting diodes 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, we demonstrate for the first time an inter-chip polarized optical communication system consisting of organic SCs. 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. This article is protected by copyright. All rights reserved.

Organic field-effect transistors with parallel transmission and learning functions are of interest in the development of brain-inspired neuromorphic computing. However, the poor performance and high power consumption are the two main issues limiting their practical applications. Herein, we demonstrate an ultralow-power vertical transistor based on MXene and organic single crystal. The transistor exhibits a high J

Bendable organic single crystals are promising candidates for flexible electronics owing to their superior charge-transport properties. However, large-area high-quality organic single crystals are rarely available on the polymer substrates generally used in flexible electronics. Here, a surface-assisted assembly strategy based on a polymer modification, poly(amic acid) (PAA), is developed to grow large-area organic singe crystals on polymer substrates using a simple drop-casting method. The unique surface properties of PAA that enable molecular solution superwetting and promote molecular ordered assembly produce an extraordinary self-driven "meniscus-guided coating" behavior, enabling the fabrication of millimeter-sized, highly aligned organic single crystals for a variety of organic semiconductors. Organic field-effect transistors based on a mode molecule of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene demonstrate the highest (average) mobility of 18.6 cm

Anomalous negative phototransistors in which the channel current decreases under light illumination hold potential to generate novel and multifunctional optoelectronic applications. Although a variety of design strategies have been developed to construct such devices, NPTs still suffer from far lower device performance compared to well-developed positive phototransistors (PPTs). In this work, a novel 1D/2D molecular crystal p-n heterojunction, in which p-type 1D molecular crystal (1DMC) arrays are embedded into n-type 2D molecular crystals (2DMCs), is developed to produce ultrasensitive NPTs. The p-type 1DMC arrays act as light-absorbing layers to induce p-doping of n-type 2DMCs through charge transfer under illumination, resulting in ineffective gate control and significant negative photoresponses. As a result, the NPTs show remarkable performances in photoresponsivity (P) (1.9 × 10

Covalent organic frameworks (COFs), an emerging class of organic crystalline polymers with highly oriented structures and permanent porosity, can adopt 2D or 3D architectures depending on the different topological diagrams of the monomers. Notably, 2D COFs have particularly gained much attention due to the extraordinary merits of their extended in-plane π-conjugation and topologically ordered columnar π-arrays. These properties together with high crystallinity, large surface area, and tunable porosity distinguish 2D COFs as an ideal candidate for the fabrication of functional materials. Herein, this review surveys the recent research advances in 2D COFs with special emphasis on the preparation of 2D COF powders, single crystals, and thin films, as well as their advanced optical, electrical, and magnetic functionalities. Some challenging issues and potential research outlook for 2D COFs are also provided for promoting their development in terms of structure, synthesis, and functionalities.

Organic single crystalline semiconductors are highly desired for fabrication of integrated electronic circuits, yet the uniform growth and efficient patterning of them is a huge challenge. Here, a general solution procedure named soft-template-assisted-assembly method (STAA method) is developed to prepare centimeter-scale monolayer molecular crystal (MMC) arrays with precise regulation over their size and location via capillary confinement crystallization process. It is remarkable that the field-effect mobility of the array is highly uniform, with variation less than 4.4%, which demonstrates the most uniform organic single crystal arrays ever reported so far. Simulations based on fluid dynamics were carried out to understand the function mechanism of this method. Thanks to the ultrasmooth crystalline orientation surface of MMCs, high-quality p-n heterojunction arrays can be prepared by weak epitaxy growth of n-type material atop the MMC. The p-n heterojunction FETs show ambipolar characteristics and the corresponding inverters constructed by these heterojunctions exhibit a competitive gain of 155. This work provides a general strategy to realize the preparation and application of logic complementary circuits based on patterned organic single crystals. This article is protected by copyright. All rights reserved.

Constructing multicolor photoluminescent materials with tunable properties is an attractive research objective on account of their abundant applications in materials science and biomedical engineering. By comparison with covalent synthesis, supramolecular chemistry has provided a more competitive and promising strategy for the production of organic materials and the regulation of their photophysical properties. By taking advantage of dynamic and reversible noncovalent bonding interactions, supramolecular strategies can, not only simplify the design and fabrication of organic materials, but can also endow them with dynamic reversibility and stimuli responsiveness, making it much easier to adjust the superstructures and properties of the materials. Occasionally, it is possible to introduce emergent properties into these materials, which are absent in their precursor compounds, broadening their potential applications. In an attempt to highlight the state-of-the-art noncovalent strategies available for the construction of smart luminescent materials, an overview of color-tunable materials is presented in this Review, with the emphasis being placed on the examples drawn from host-guest complexes, supramolecular assemblies and crystalline materials. The noncovalent synthesis of room-temperature phosphorescent materials and the modulation of their luminescent properties are also described. Finally, future directions and scientific challenges in the emergent field of color-tunable supramolecular emissive materials are discussed.

The ability to detect light in photodetectors is central to practical optoelectronic applications, which has been demonstrated in inorganic semiconductor devices. However, so far, the study of polarization-sensitive organic photodetectors, which have unique applications in flexible and wearable electronics, has not received much attention. Herein, the construction of polarization-sensitive photodetectors based on the single crystals of a superior optoelectronic organic semiconductor, 2,6-diphenyl anthracene (DPA), is demonstrated. The systematic characterization of two-dimensionally grown DPA crystals with various techniques definitely show their strong anisotropy in molecular vibration, optical reflectance and optical absorption. In terms of polarization sensitivity, DPA-crystal based photodetectors exhibit a linear dichroic ratio up to ≈1.9. Theoretical calculations confirm that intrinsic linear dichroism, originated from the anisotropic in-plane crystal structure, is responsible for the polarization sensitivity of DPA crystals. This work opens up a new door for exploiting organic semiconductors for developing highly compact polarization photodetectors and providing new functionalities in novel flexible optical and optoelectronic applications.

Organic semiconductor materials have been widely used in various optoelectronic devices due to their rich optical and/or electrical properties, which are highly related to their excited states. Therefore, how to manage and utilize the excited states in organic semiconductors is essential for the realization of high-performance optoelectronic devices. Triplet-triplet annihilation (TTA) upconversion is a unique process of converting two non-emissive triplet excitons to one singlet exciton with higher energy. Efficient optical-to-electrical devices can be realized by harvesting sub-bandgap photons through TTA-based upconversion. In electrical-to-optical devices, triplets generated after the combination of electrons and holes also can be efficiently utilized via TTA, which resulted in a high internal conversion efficiency of 62.5%. Currently, many interesting explorations and significant advances have been demonstrated in these fields. In this review, a comprehensive summary of these intriguing advances on developing efficient TTA upconversion materials and their application in optoelectronic devices is systematically given along with some discussions. Finally, the key challenges and perspectives of TTA upconversion systems for further improvement for optoelectronic devices and other related research directions are provided. This review hopes to provide valuable guidelines for future related research and advancement in organic optoelectronics.

2D triangular β-Cu2 S nanosheets with large size and high quality are synthesized by a novel method of super-cooling chemical-vapor-deposition. The phase transition of this 2D material from β-Cu2 S to γ-Cu2 S occurs at 258 K (-15 °C), and such transition temperature is 120 K lower than that of its bulk counterpart (about 378 K).

Nanogap electrodes arrays are fabricated by combining atomic layer deposition, adhesive tape, and chemical etching. A unipolar nonvolatile resistive-switching behavior is identified in the nanogap electrodes, showing stable, robust performance and the multibit storage ability, demonstrating great potential in ultrahigh-density storage. The formation and dissolution of Si conductive filaments and migration of Au atoms is the mechanism behind the resistive switching.

The switching riddle of AgTCNQ is shown to be caused by the solid electrolyte mechanism. Both factors of bulk phase change and contact issue play key roles in the efficient work of the devices. An effective strategy is developed to locate the formation/disruption of Ag conductive filaments using the planar asymmetric configuration of Au/AgTCNQ/AlOx /Al. These novel electrochemical metallization memories demonstrate many promising properties.

Solution-processed n-channel organic thin-film transistors (OTFTs) that exhibit a field-effect mobility as high as 11 cm(2) V(-1) s(-1) at room temperature and a band-like temperature dependence of electron mobility are reported. By comparison of solution-processed OTFTs with vacuum-deposited OTFTs of the same organic semiconductor, it is found that grain boundaries are a key factor inhibiting band-like charge transport.

An ultimate goal of organic electronics is to fabricate large-area electronic devices and circuits on flexible and stretchable substrates. To achieve this target, understanding and/or tuning of the processes that determine charge transport is therefore of paramount importance for the development of high-performance devices, e.g., organic field-effect transistors (OFETs). Significant progress in this field is summarized here, with particular focus on the new insights of charge transport under certain strain effects in flexible and stretchable OFETs.

Newly designed asymmetric diketopyrrolopyrrole conjugated polymers with two different aromatic substituents possess a hole mobility of 12.5 cm(2) V(-1) s(-1) in field-effect transistors and a power conversion efficiency of 6.5% in polymer solar cells, when solution processed from a nonchlorinated toluene/diphenyl ether mixed solvent.

Polymer nanowires based on two diketopyrrolopyrrole conjugated polymers with similar chemical structures are shown to have distinct "edge-on" and "face-on" configurations in addition to high well-balanced hole and electron mobilities of 5.47 and 5.33 cm(2) V(-1) s(-1) in field-effect transistors.

One-dimensional (1D) solid-state supramolecular structures based on porphyrin chromophores arouse numerous expectations from the interdisciplinary scientific communities of supramolecular chemistry and advanced soft materials science. This stems from the intrinsic assembly capability of porphyrins to form various well-defined 1D assemblies, which have broad opportunities in the fields of advanced soft matter. A brief review on 1D porphyrin micro-/nanoassemblies constructed via surfactant-assisted self-assembly is presented here, in terms of addressing new ideas recently developed for controlled assembly, hierarchical organization, and new-type functional surfactants etc. The functionalization of the as-assembled 1D structures with regard to supramolecular photocatalysis, non-linear optics, nanoelectronic gas sensors, photoelectrochemical solar cells, etc. is highlighted.

The multishelled (Co2/3Mn1/3)(Co5/6Mn1/6)2O4 hollow microspheres with controllable shell numbers up to septuple shells are synthesized using developed sequential templating method. Exhilaratingly, the septuple-shelled complex metal oxide hollow microsphere is synthesized for the first time by doping Mn into Co3O4, leading to the change of crystalline rate of precursor. Used as electrode materials for alkaline rechargeable battery, it shows a remarkable reversible capacity (236.39 mAh g−1 at a current density of 1 A g−1 by three-electrode system and 106.85 mAh g−1 at 0.5 A g−1 in alkaline battery) and excellent cycling performance due to its unique structure.

By incorporating crystalline photosensitive nanowires (NWs), an amorphous InZnO (a-IZO) thin film is designed to be sensitive to the primary colors of light via a facile sol-gel approach. The mobility is also improved. The composite devices leverage the advantages of the transparency of a-IZO with the photosensitivity of CdS NWs.

Hierarchical graphene architectures (HGAs) that grow by stacking of layers are produced on a liquid copper surface using chemical vapor deposition. The stacking mode--for example hexagonal-hexagonal-hexagonal or hexagonal-snowflake-dendritic--can be simply controlled. Measurements of the electrical properties of HGAs indicate that hierarchical stacking of graphene may be a simple and effective way of tailoring their properties without degrading them.

Cocrystal engineering with a noncovalent assembly feature by simple constituent units has inspired great interest and has emerged as an efficient and versatile route to construct functional materials, especially for the fabrication of novel and multifunctional materials, due to the collaborative strategy in the distinct constituent units. Meanwhile, the precise crystal architectures of organic cocrystals, with long-range order as well as free defects, offer the opportunity to unveil the structure-property and charge-transfer-property relationships, which are beneficial to provide some general rules in rational design and choice of functional materials. In this regard, an overview of organic cocrystals in terms of assembly, containing the intermolecular interactions and growth methods, two functionality-related factors including packing structure and charge-transfer nature, and those advanced and novel functionalities, is presented. An outlook of future research directions and challenges for organic cocrystal is also provided.

Here, the synthesis of a wafer-scale ultrathin 2D imine polymer (2DP) film with controllable thickness from simple benzene-1,3,5-tricarbaldehyde (BTA) and p-phenylenediamine (PDA) building blocks is reported using a Schiff base polycondensation reaction at the air-water interface. The synthesized freestanding 2DP films are porous, insulating, and more importantly, covalently linked, which is ideally suited for nonvolatile memristors that use a conductive filament mechanism. These devices exhibit excellent switching performance with high reliability and reproducibility, with on/off ratios in the range of 102 to 105 depending on the thickness of the film. In addition, the endurance and data retention capability of 2DP-based nonvolatile resistive memristors are up to 200 cycles and 8 × 104 s under constant voltage stress at 0.1 V. The intrinsic flexibility of the covalent organic polymer enables the fabrication of a flexible memory device on a polyimide film, which exhibits as reliable memory performance as that on the rigid substrate. Moreover, the 2DP-based memory device shows outstanding thermal stability and organic solvent resistance, which are desirable properties for applications in wearable devices.

High mobility ambipolar conjugated polymers are seriously absent regardless their great potential for flexible and printed plastic devices and circuits. Here, ambipolar polymers with ultrahigh balanced hole and electron mobility are developed via a two-step CH activation strategy. Diketopyrrolopyrrole-benzothiadiazole-diketopyrrolopyrrole (DBD) and its copolymers with thiophene/selenophene units (short as PDBD-T and PDBD-Se) are used as examples. PDBD-Se exhibits highly efficient ambipolar transport with hole and electron mobility up to 8.90 and 7.71 cm2 V-1 s-1 in flexible organic field-effect transistors, presenting a milestone for ambipolar copolymer screening. Based on this performance metrics and good solubility, PDBD-Se is investigated as inkjet-printable semiconductor ink for organic complementary logic circuits. Under ambient processing, maximum hole and electron mobilities reach 6.70 and 4.30 cm2 V-1 s-1 , respectively. Printed complementary inverter and NAND gates with transition voltages near VDD /2 are fabricated, providing an easy-handling, general material for printed electronics and logic.

Remarkable progress has been made in developing high performance organic field-effect transistors (OFETs) and the mobility of OFETs has been approaching the values of polycrystalline silicon, meeting the requirements of various electronic applications from electronic papers to integrated circuits. In this review, the key points for development of high mobility OFETs are highlighted from aspects of molecular engineering, process engineering and interface engineering. The importance of other factors, such as impurities and testing conditions is also addressed. Finally, the current challenges in this field for practical applications of OFETs are further discussed.

Freestanding, substrate-free organic field-effect transistors and organic circuits with a nominal thickness of 320 nm are demonstrated by using a simple water-floatation method. The devices work well in freestanding status, attached on banknotes, or bent over the blade of a knife. The ultralight devices with extreme bending stability indicate a bright future for organic electronics.

A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules. The electrical switching behavior of a less-studied molecular switch, dihydroazulene/vinylheptafulvene, is described, which is used as a test case.

Single and large-area aligned crystalline microribbons of 6,13-dichloropentacene (DCP) are prepared. The ribbons display excellent charge transport properties with a mobility of up to 9.0 cm(2) V(-1) s(-1) in ambient conditions, one of the highest values reported for organic semiconductors. The slipped π-π stacking with large intermolecular overlap is responsible for the high mobility of DCP ribbons.

Cruciform motifs with two orthogonally oriented π-extended tetrathiafulvalenes and with differently protected thiolate end-groups are synthesized by stepwise coupling reactions. The molecules are subjected to single-molecule conductivity studies in a break-junction and to conducting probe atomic force microscopy studies in a self-assembled monolayer on gold.

Micrometer-sized single-crystal GeSe nanosheets have been synthesized by a solution method. The single GeSe nanosheet exhibits novel anisotropic photoresponse properties in two photodetectors based on individual nanosheet. The on/off switching ratio of the photodetector perpendicular to the nanosheet is 3.5 times higher than that parallel to the nanosheet.

Organic/organic single-crystal coaxial p-n heterojunction nanowire arrays consisting of p-type copper phthalocyanine (CuPc) and n-type 5,10,15,20-tetra(4-pyridyl)-porphyrin (H(2)TPyP) are fabricated through a one-step physical vapor transport (PVT) process. Each single junction wire revealed high photodependent rectifying and sensitive photoresponsive characteristics in devices of light-controlled diodes and photoswitches. The typical photovoltaic device based on a single p-n junction exhibited a high open-circuit voltage (Voc) of 0.64 V.

A novel method using solution-processed ultrathin chemically derived graphene films as soft top contacts for the non-destructive fabrication of molecular junctions is demonstrated. We believe this protocol will greatly enrich the solid-state test beds for molecular electronics due to its low-cost, easy-processing and flexible nature.

2D mica crystals (with thickness < 100 nm) obtained by mechanical exfoliation are incorporated for the first time into the design of organic thin film field-effect transistor arrays and organic single crystal transistors as a gate insulator. The size of mica crystals could be up to the dimensions of an A4 piece of paper. All devices so fabricated exhibited high mobility and low operating voltage, indicating the high quality of the crystals and the great potential of mica crystals as a flexible, low-cost, transparent insulator for organic electronics.

A novel cost-efficient and facile technique, molecular crystal lithography, to fabricate nanogap electrodes efficiently is reported. The gap width of the electrodes can be tuned from ∼9 nm to several micrometers. Organic field-effect transistors based on the nanogap electrodes all exhibit a high performance, indicating the effectiveness and practicability of molecular crystal lithography for mass production of nanogap electrodes.