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.

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.

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.

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.

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.

Non-Equal Ratio Cocrystal Engineering to Improve Charge Transport Characteristics of Organic Semiconductors: A Case Study on Indolo[2,3-a]carbazole.

Rare studies of cocrystal engineering have focused on improving carrier mobility of organic semiconductors mainly because of the generation of ambipolarity, the alteration of the charge carrier polarity or the reduction of electronic couplings. Herein, we utilize indolo[2,3-a]carbazole (IC) as the model compound and 2,6-diphenylanthraquinone (DPAO) and 9-fluorenone (FO) as the coformers to construct IC2-DPAO and IC-FO cocrystals with 2 : 1 or 1 : 1 ratios, respectively, through hydrogen bonds and donor-acceptor interactions. Interestingly, the more appropriate packing structure, possessing not only enhanced electronic couplings but also increased intermolecular distances, is achieved in IC2-DPAO, which shows an improved carrier mobility of 0.11 cm2  V-1 s-1 by four orders of magnitude relative to the IC crystal. These results suggest that non-equal ratio cocrystal engineering opens up the possibility to develop organic semiconductors with enhanced charge transport behaviors.

Regulating Crystal Packing by Terminal tert-Butylation for Enhanced Solid-State Emission and Efficacious Charge Transport in an Anthracene-Based Molecular Crystal.

Organic semiconductors with combinative high carrier mobility and efficient solid-state emission are full of challenges but urgently pursued for developing new emerging optoelectronics. Herein, by delicately regulating the crystal packing of an anthracene-based molecular crystal via terminal tert-butylation, we developed a superior high mobility emissive molecule, 2,6-di(6-tert-butylnaphthyl)anthracene (TBU-DNA). The unique "slipped herringbone" packing motif of TBU-DNA enables its appropriate exciton-exciton coupling and electron-phonon coupling, thus resulting in remarkably high solid-state emission (photoluminescence quantum yield, ΦF ≈74.9 %) and efficacious charge transport (carrier mobility, µ=5.0 cm2 V-1 s-1 ). Furthermore, OLETs based on TBU-DNA show an external quantum efficiency (EQE) of 1.8 %, which is among the highest EQE values for single component OLETs reported till now. This work presents a crystal engineering strategy via exquisite molecular design to realize high mobility emissive organic semiconductors.

Integrating Unexpected High Charge-Carrier Mobility and Low-Threshold Lasing Action in an Organic Semiconductor.

Integrating high charge-carrier mobility and low-threshold lasing action in an organic semiconductor is crucial for the realization of an electrically pumped laser, but remains a great challenge. Herein, we present an organic semiconductor, named as 2,7-di(2-naphthyl)-9H-fluorene (LD-2), which shows an unexpected high charge-carrier mobility of 2.7 cm2  V-1 s-1 and low-threshold lasing characteristic of 9.43 µJ cm-2 and 9.93 µJ cm-2 and high-quality factor (Q) of 2131 and 1684 at emission peaks of 420 and 443 nm, respectively. Detailed theoretical calculations and photophysical data analysis demonstrate that a large intermolecular transfer integral of 10.36-45.16 meV together with a fast radiative transition rate of 8.0×108  s-1 are responsible for the achievement of the superior integrated optoelectronic properties in the LD-2 crystal. These optoelectronic performances of LD-2 are among the highest reported low-threshold lasing organic semiconductors with efficient charge transport, suggesting its promise for research of electrically pumped organic lasers (EPOLs).

Creating Organic Functional Materials beyond Chemical Bond Synthesis by Organic Cocrystal Engineering.

Organic cocrystal engineering refers to two or more organic molecules stoichiometrically combined and held together by noncovalent intermolecular interactions, which differs from standard chemical synthesis involving covalent bond breakage and formation. Organic cocrystals have unique properties and offer a new strategy for creating enhanced organics. First, however, some key questions need to be addressed: How do diverse monomers affect the intermolecular interaction kinetics during cocrystallization? How do the intermolecular forces in cocrystals affect cocrystal functions? In this Perspective, the definition and advantages of organic cocrystal engineering, specifically in the construction of a reliable intermolecular interaction-stacking structure-performance relationship, are outlined. Additionally, recent developments in the field and the questions above are discussed. Finally, a brief conclusion and some hints on likely future developments are provided.

Polymer-Assisted Space-Confined Strategy for the Foot-Scale Synthesis of Flexible Metal-Organic Framework-Based Composite Films.

At the gas-liquid interface, the confined synthesis of metal-organic framework (MOF) films has been extensively developed by spreading an ultrathin oil layer on the aqueous surface as a reactor. However, this interface is susceptible to various disturbances and incapable of synthesizing large-area crystalline MOF films. Herein, we developed a polymer-assisted space-confined strategy to synthesize large-area films by blending poly(methyl methacrylate) (PMMA) into the oil layer, which improved the stability of the gas-liquid interface and the self-shrinkage of the oil layer on the water surface. Meanwhile, the as-synthesized MOFs as a quasi-solid substrate immobilized the edge of the oil layer, which maintained a large spreading area. Thanks to this synergistic effect, we synthesized the freestanding MOF-based film with a foot-level (0.66 ft) lateral dimension, which is the largest size reported so far. Besides, due to the phase separation of the two components, the MOF-PMMA composite film combined the conductivity of MOFs (1.13 S/m) with the flexibility of PMMA and exhibited excellent mechanical properties. More importantly, this strategy could be extended to the preparation of other MOFs, coordination polymers (CPs), and even inorganic material composite films, bringing light to the design and large-scale synthesis of various composite films for practical applications.

Copper Tetracyanoquinodimethane: From Micro/Nanostructures to Applications.

Copper tetracyanoquinodimethane (CuTCNQ) has been investigated around 40 years as a representative bistable material. Meanwhile, micro/nanostructures of CuTCNQ is considered as the prototype of molecular electronics, which have attracted the world's attention and shown great potential applications in nanoelectronics. In this review, methods for synthesis of CuTCNQ micro/nanostructures are first summarized briefly. Then, the strategies for controlling morphologies and sizes of CuTCNQ micro/nanostructures are highlighted. Afterwards, the devices based on these micro/nanostructures are reviewed. Finally, an outlook of future research directions and challenges in this area is presented.

1D Mixed-Stack Cocrystals Based on Perylene Diimide toward Ambipolar Charge Transport.

There is very limited repertoire of organic ambipolar semiconductors to date. Electron donor-acceptor alternative stacking is a unique and important binary motif for 1D mixed-stack cocrystals, opening up possibilities for the development of organic ambipolar semiconductors. Herein, four 1D mixed-stack cocrystals using N,N'-bis(perfluorobutyl)-1,7-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDICNF) as the acceptor and anthracene, pyrene, perylene, and meso-diphenyl tetrathia[22]annulene[2,1,2,1] (DPTTA) as the donors are achieved in a stoichiometric ratio (D:A = 1:1) through solution or vapor processed methods. Their packing structures, energy levels, charge transfer interactions, coassembling behaviors, and molecular orientations are systematically investigated by single-crystal X-ray analysis, absorption spectra, fluorescence quenching, Job's curve plot, and polarized photoluminescence measurements with the help of theoretical calculations. The donor-acceptor alternative stacking direction coincides with the long axis for all the four cocrystals. The field-effect transistors based on Pyrene-PDICNF show the electron mobility up to 0.19 cm2 V-1 s-1 , which is the highest value among perylene diimide-based cocrystals. Moreover, DPTTA-PDICNF cocrystals possess well-balanced electron and hole mobility with 1.7 × 10-2 and 2.0 × 10-2  cm2 V-1 s-1 respectively due to both hole and electron strong superexchange interactions, shedding light on the design of 1D mixed-stack cocrystals with excellent ambipolar transport behaviors.

Molecular Weight Engineering in High-Performance Ambipolar Emissive Mesopolymers.

Mesopolymers with high solubility, free of structural defects, and negligible batch-to-batch variation open a new avenue for organic optoelectronics. Organic light emitting transistors that combine the functions of organic light-emitting diodes and organic field-effect transistors. However, charge transport ability and light emitting strength are contradictory within one conjugated polymer. Herein, three low-molecular-weight mesopolymers with thienopyrroledione-benzothiadiazole repeating units (meso-TBTF) were obtained. The mesopolymers show strong solid-state emission and high ambipolar carrier mobility. The molecular weights of meso-TBTF can be tuned by polymerization temperature. The mesopolymers have photoluminescence quantum yields (PLQY) of about 50 % in solution and 10 % in solid state. Polymer light emitting diodes of this material are fabricated to explore its potential use in optoelectronic devices.

Cocrystal Engineering: Toward Solution-Processed Near-Infrared 2D Organic Cocrystals for Broadband Photodetection.

Large-area 2D cocrystals with strong near-infrared (NIR) absorption have been designed and prepared. Driven by the intermolecular charge-transfer (CT) interactions, zinc tetraphenylporphyrin (donor) and C60 (acceptor) self-assemble into a NIR cocrystal with absorption wavelength up to 1080 nm. By tailoring the growth solvents and processes, the cocrystal morphologies can be tuned from 1D nanowires, 2D nanosheets to large-area 2D cocrystal films with length reaching several millimeters. Owing to the highly ordered donor-acceptor arrangement, the CT absorption in the 2D cocrystals is enhanced and is comparable to singlet absorption. The uniform 2D cocrystals, with enhanced CT absorption in the NIR region, displays a high responsivity of 2424 mA W-1 to NIR light and a fast response time of 0.6 s. The excellent device performance is attributed to the generation of long-lived free charge carriers as revealed by transient absorption spectroscopy and optimization of device configuration.

High Mobility Organic Lasing Semiconductor with Crystallization-Enhanced Emission for Light-Emitting Transistors.

The development of high mobility organic laser semiconductors with strong emission is of great scientific and technical importance, but challenging. Herein, we present a high mobility organic laser semiconductor, 2,7-diphenyl-9H-fluorene (LD-1) showing unique crystallization-enhanced emission guided by elaborately modulating its crystal growth process. The obtained one-dimensional nanowires of LD-1 show outstanding integrated properties including: high absolute photoluminescence quantum yield (PLQY) approaching 80 %, high charge carrier mobility of 0.08 cm2 V-1 s-1 , Fabry-Perot lasing characters with a low threshold of 86 µJ cm-2 and a high-quality factor of ≈2400. Furthermore, electrically induced emission was obtained from an individual LD-1 crystal nanowire-based light-emitting transistor due to the recombination of holes and electrons simultaneously injected into the nanowire, which provides a good platform for the study of electrically pumped organic lasers and other related ultrasmall integrated electrical-driven photonic devices.

Cocrystallization Tailoring Multiple Radiative Decay Pathways for Amplified Spontaneous Emission.

Amplified spontaneous emission (ASE) is intrinsically associated with lasing applications. Inefficient photon energy transfer to ASE is a long-standing issue for organic semiconductors that consist of multiple competing radiative decay pathways, far from being rationally regulated from the perspective of molecular arrangements. Herein, we achieve controllable molecular packing motifs by halogen-bonded cocrystallization, leading to ten times increased radiative decay rate, four times larger ASE radiative decay selectivity and thus remarkable ASE threshold decrease from 223 to 22 µJ cm-2 , albeit with a low photoluminescence quantum yield. We have made an in-depth investigation on the relationship among molecular arrangements, vibration modes, radiative decay profiles and ASE properties. The results suggest that cocrystallization presents a powerful approach to tailor the radiative decay pathways, which is fundamentally important to the development of organic ASE and lasing materials.

Systematic Modulation of Charge Transport in Molecular Devices through Facile Control of Molecule-Electrode Coupling Using a Double Self-Assembled Monolayer Nanowire Junction.

We report a novel solid-state molecular device structure based on double self-assembled monolayers (D-SAM) incorporated into the suspended nanowire architecture to form a "Au|SAM-1||SAM-2|Au" junction. Using commercially available thiol molecules that are devoid of synthetic difficulty, we constructed a "Au|S-(CH2)6-ferrocene||SAM-2|Au" junction with various lengths and chemical structures of SAM-2 to tune the coupling between the ferrocene conductive molecular orbital and electrode of the junction. Combining low noise and a wide temperature range measurement, we demonstrated systematically modulated conduction depending on the length and chemical nature of SAM-2. Meanwhile, the transport mechanism transition from tunneling to hopping and the intermediate state accompanied by the current fluctuation due to the coexistence of the hopping and tunneling transport channels were observed. Considering the versatility of this solid-state D-SAM in modulating the electrode-molecule interface and electroactive groups, this strategy thus provides a novel facile strategy for tailorable nanoscale charge transport studies and functional molecular devices.

Organic Laser Molecule with High Mobility, High Photoluminescence Quantum Yield, and Deep-Blue Lasing Characteristics.

Here, we design and synthesize an organic laser molecule, 2,7-diphenyl-9H-fluorene (LD-1), which has state-of-the-art integrated optoelectronic properties with a high mobility of 0.25 cm2 V-1 s-1, a high photoluminescence quantum yield of 60.3%, and superior deep-blue laser characteristics (low threshold of Pth = 71 µJ cm-2 and Pth = 53 µJ cm-2 and high quality factor (Q) of ∼3100 and ∼2700 at emission peaks of 390 and 410 nm, respectively). Organic light-emitting transistors based on LD-1 are for the first time demonstrated with obvious electroluminescent emission and gate tunable features. This work opens the door for a new class of organic semiconductor laser molecules and is critical for deep-blue optical and laser applications.

A Highly Sensitive Single Crystal Perovskite-Graphene Hybrid Vertical Photodetector.

Organolead trihalide perovskites have attracted significant attention for optoelectronic applications due to their excellent physical properties in the past decade. Generally, both grain boundaries in perovskite films and the device structure play key roles in determining the device performance, especially for horizontal-structured device. Here, the first optimized vertical-structured photodetector with the perovskite single crystal MAPbBr3 as the light absorber and graphene as the transport layer is shown. The hybrid device combines strong photoabsorption characteristics of perovskite and high carrier mobility of flexible graphene, exhibits excellent photoresponse performance with high photoresponsivity (≈1017.1 A W-1 ) and high photodetectivity (≈2.02 × 1013 Jones) in a low light intensity (0.66 mW cm-2 ) under the actuations of 3 V bias and laser irradiation at 532 nm. In particular, an ultrahigh photoconductive gain of ≈2.37 × 103 is attained because of fast charge transfer in the graphene and large recombination lifetime in the perovskite single crystal. The vertical architecture combining perovskite crystal with highly conductive graphene offers opportunities to fulfill the synergistic effect of perovskite and 2D materials, is thus promising for developing high-performance electronic and optoelectronic devices.

Organic crystalline materials in flexible electronics.

Flexible electronics have attracted considerable attention recently given their potential to revolutionize human lives. High-performance organic crystalline materials (OCMs) are considered strong candidates for next-generation flexible electronics such as displays, image sensors, and artificial skin. They not only have great advantages in terms of flexibility, molecular diversity, low-cost, solution processability, and inherent compatibility with flexible substrates, but also show less grain boundaries with minimal defects, ensuring excellent and uniform electronic characteristics. Meanwhile, OCMs also serve as a powerful tool to probe the intrinsic electronic and mechanical properties of organics and reveal the flexible device physics for further guidance for flexible materials and device design. While the past decades have witnessed huge advances in OCM-based flexible electronics, this review is intended to provide a timely overview of this fascinating field. First, the crystal packing, charge transport, and assembly protocols of OCMs are introduced. State-of-the-art construction strategies for aligned/patterned OCM on/into flexible substrates are then discussed in detail. Following this, advanced OCM-based flexible devices and their potential applications are highlighted. Finally, future directions and opportunities for this field are proposed, in the hope of providing guidance for future research.