High performance n-type single crystalline transistors of naphthalene bis(dicarboximide) and their anisotropic transport in crystals

High-performance n-type organic single crystal transistors of a naphthalene diimide are demonstrated. The accomplished transistors exhibit electron mobility as high as 0.7 cm(2) V(-1) s(-1). The anisotropic charge transport in the elongated hexagonal crystals of the naphthalene diimide is also explored. The transport anisotropy along different directions is at least 1.6 (mobility ratio).     

High electron mobility in ladder polymer field-effect transistors

Field-effect mobility of electrons as high as 0.1 cm2/(V s) is observed in n-channel thin film transistors fabricated from a solution spin-coated conjugated ladder polymer, poly(benzobisimidazobenzophenanthroline) (BBL), under ambient air conditions. This is the highest electron mobility observed to date in a conjugated polymer semiconductor. Comparative studies of n-channel thin film transistors made from a structurally similar nonladder conjugated polymer BBB gave an electron mobility of 10-6 cm2/(V s). These results demonstrate that electron transport can be as facile as hole transport in conjugated polymer semiconductors and that ladder architecture of a conjugated polymer can substantially enhance charge carrier mobility.     

Charge carrier transport in high purity perylene single crystal studied by time-of-flight measurements and through field effect transistor characteristics

Electronic transport has been studied by measuring the characteristics of field effect transistors using high purity perylene and the results have been compared with those from time-of-flight measurements. The purity of the material has been monitored by carrier trapping time and delayed fluorescence lifetime. Three types of field effect transistors have been studied: (1) thin film transistor, (2) transistor prepared by placing a single crystal flake on a substrate and (3) transistor fabricated on a single crystal by depositing electrodes and insulating layer onto it. Compared to thin film transistors prepared by evaporating perylene onto a SiO₂/Si substrate, higher mobility values were obtained with transistors using single crystals, but the electrical characteristics of the transistors were far from ideal: large threshold gate voltage observed in the second class of FETs indicated that a high density of traps are present at the interface between the organics and the insulator. A transistor of the third class showed that it functioned indeed as a FET with a reasonably high mobility, but the operation was not stable enough to allow reliable measurements. Much remains to be improved in the design and construction of a perylene FET before the potentiality of the material is fully developed. Also, it remains to be explored to what extent the bulk purity and the molecular order at the organics/insulator interface influence the transport of the charge carriers in an organic FET.     

基于蒽衍生高迁移率发光材料的研究进展

高迁移率发光有机半导体材料是实现有机发光场效应晶体管(OLETs)的重要材料, 但其设计合成面临巨大挑战. 本文综合评述了近年来高迁移率发光材料, 特别是基于蒽的高迁移率发光材料的研究进展, 重点介绍了目前报道的20余种基于蒽的高迁移率发光有机半导体材料, 包括分子的设计策略、 相关的光电性能及其在OLETs器件方面的应用研究, 以便为进一步的相关研究提供有意义的指导和借鉴. 本文还对该领域未来发展的挑战、 发展方向及机遇进行了简单评述.     

高迁移率有机薄膜晶体管材料进展

对近几年来高迁移率有机薄膜晶体管材料研究的主要发展作了简要介绍和评述,讨论了高迁移率有机半导体材料存在的问题和发展方向．     

Novel highly stable semiconductors based on phenanthrene for organic field-effect transistors

Two novel phenanthrene-based conjugated oligomers were synthesized and used as p-channel semiconductors in field-effect transistors; they exhibit high mobility and excellent stability during long-time ambient storage and under UV irradiation.     

Rubrenes: planar and twisted

Surprisingly, despite its very high mobility in a single crystal, rubrene shows very low mobility in vacuum-sublimed or solution-processed organic thin-film transistors. We synthesized several rubrene analogues with electron-withdrawing and electron-donating substituents and found that most of the substituted rubrenes are not planar in the solid state. Moreover, we conclude (based on experimental and calculated data) that even parent rubrene is not planar in solution and in thin films. This discovery explains why high mobility is reported in rubrene single crystals, but rubrene shows very low field-effect mobility in thin films. The substituted rubrenes obtained in this work have significantly better solubility than parent rubrene and some even form films and not crystals after evaporation of the solvent. Thus, substituted rubrenes are promising materials for organic light-emitting diode (OLED) applications.     

有机薄膜晶体管半导体材料的研究进展

有机薄膜晶体管(organic thin-film transistors,OTFTs)具有工艺简单、成本低及柔性良好等优点,在有源显示、传感及逻辑电路等领域有着十分重要的应用前景.实用性有机薄膜晶体管应具备高迁移率、高开关比、低阈值电压及良好的稳定性等性能.有机半导体材料是有机薄膜晶体管的主要组成部分,对器件的性能有着重要影响.介绍了有机薄膜晶体管的基本结构和运行模式,按照p型、n型及双极性分类总结了有机薄膜晶体管半导体材料的研究进展情况,最后对有机半导体材料的前景进行了展望.     

N‐Heterocyclic‐Carbene‐Treated Gold Surfaces in Pentacene Organic Field‐Effect Transistors: Improved Stability and Contact at the Interface

N‐Heterocyclic carbenes (NHCs), which react with the surface of Au electrodes, have been successfully applied in pentacene transistors. With the application of NHCs, the charge‐carrier mobility of pentacene transistors increased by five times, while the contact resistance at the pentacene–Au interface was reduced by 85 %. Even after annealing the NHC–Au electrodes at 200 °C for 2 h before pentacene deposition, the charge‐carrier mobility of the pentacene transistors did not decrease. The distinguished performance makes NHCs as excellent alternatives to thiols as metal modifiers for the application in organic field‐effect transistors (OFETs).     

Synergistic Effects of Solvent Vapor Assisted Spin-coating and Thermal Annealing on Enhancing the Carrier Mobility of Poly(3-hexylthiophene) Field-effect Transistors

Poly(3-hexylthiophene)(P3 HT) thin films, obtained by normal spin-coating and solvent vapor assisted spin-coating(SVASP) before and after thermal annealing(TA), and the corresponding devices were prepared to unravel the microstructure-property relationship, which is of great importance for the development of organic electronics. When SVASP-TA films were used as the active layers of the organic field-effect transistors,a hole mobility up to 0.38 cm~2·V~(–1)·s~(–1) was achieved. This mobility was one of the highest values and one order of magnitude higher than that of the normal spin-coating films based transistors. The relationship between the microstructure and the device performance was fully investigated by UV-Vis absorption spectra, grazing incident X-ray diffraction(GIXD), and atomic force microscopy(AFM). The impressive mobility was attributed to the high crystallinity and ordered molecule packing, which stem from the synergistic effects of SVASP and thermal annealing.     

Role of mesoscopic molecular organization in organic-based thin film transistors

Organic-based thin film transistors have been realized from various organic conjugated materials, which can be gathered into two categories, according to the mechanism describing charge transport. In conjugated polymers and amorphous materials, occurrence of a variable range hopping mechanism leads to a direct relationship between doping level, conductivity and carrier mobility, which explains the difficulty for achieving materials possessing, at the same time, a high mobility and a low conductivity. On the other hand, the trap-limited mechanism of charge transport in conjugated oligomers allows a distinct control of carrier mobility and conductivity. Carrier mobility in thin films of conjugated oligomers can be increased by lowering the concentration of grain boundaries, which can be readily achieved by imposing long range structural ordering of oligomer molecules. Thin films of oligomer with a liquid crystal-like structure have thus been realized, using a self-assembly approach, which presents a mobility close to that of a single crystal of this oligomer. On the other hand, conductivity of these oligomers can be decreased by controlling the purity of these materials. High mobility and low conductivity values can thus be achieved with conjugated oligomers, allowing the realization of organic thin-film transistors presenting characteristics close to those of amorphous-silicon based ones.     

Control of polymorphism in solution-processed organic thin film transistors by self-assembled monolayers

Polymorphism of organic semiconductor films is of key importance for the performance of organic thin film transistors(OTFTs).Herein, we demonstrate that the polymorphism of solution-processed organic semiconductors in thin film transistors can be controlled by finely tuning the surface nanostructures of substrates with self-assembled monolayers(SAMs). It is found that the SAMs of 12-cyclohexyldodecylphosphonic acid(CDPA) and 12-phenyldodecylphosphonic acid(Ph DPA) induce different polymorphs in the dip-coated films of 2-dodecyl[1]benzothieno[3,2-b][1]benzothiophene(BTBT-C12). The film of BTBT-C12 on CDPA exhibits field effect mobility as high as 28.1 cm~2 V~(-1) s~(-1) for holes, which is higher than that of BTBT-C12 on Ph DPA by three times. The high mobility of BTBT-C12 on CDPA is attributable to the highly oriented films of BTBT-C12 with a reduced in-plane lattice and high molecular alignment.     

Correlation between crystal structure and mobility in organic field-effect transistors based on single crystals of tetrathiafulvalene derivatives

Recently, it was reported that crystals of the organic material dithiophene-tetrathiafulvalene (DT-TTF) have a high field-effect charge carrier mobility of 1.4 cm(2)/(V x s). These crystals were formed by a simple drop-casting method, making this material interesting to investigate for possible applications in low-cost electronics. Here, organic single-crystal field-effect transistors based on materials related to DT-TTF are presented and a clear correlation between the crystal structure and the electrical characteristics is observed. The observed relationship between the mobilities in the different crystal structures is strongly corroborated by calculations of both the molecular reorganization energies and the maximum intermolecular transfer integrals. The most suitable materials described here exhibit mobilities that are among the highest reported for organic field-effect transistors and that are the highest reported for solution-processed materials.     

Thin film organic transistors from air-stable heteroarenes: anthra[1,2-b:4,3-b':5,6-b':8,7-b']tetrathiophene derivatives

A facile synthesis of air-stable anthra[1,2-b:4,3-b':5,6-b':8,7-b']tetrathiophene derivatives 1a and 1b has been developed for applications in organic thin film transistors. Both molecules tend to self-associate through pi-pi stacking in solution and in different films. The hole mobility of 0.012 cm2 V(-1) s(-1) is obtained from 1a due to morphology changes in films from less ordered to highly ordered structures after thermal annealing. Good performance remained persistent over a period of 14 days, indicating the high stability of such transistors.     

Sulfur containing stable unsubstituted heptacene analogs

Heptacene and higher polyacenes have been sought for their high degree of charge carrier mobility in thin film transistors. Such acenes are, however, extremely unstable in ambient conditions. Approaches to obtain stable heptacenes include introduction of suitable substituents, of heteroatoms, or both. Methods to synthesize stable linear and a nonlinear unsubstituted heptacene analogs are discussed. No changes in the UV-visible absorption spectra in solution over time for these materials indicate higher oxidative stability compared to analogous polyacenes.     

New n-type semiconductor material based on styryl fullerene for organic field-effect transistors

Organic field-effect transistors with styryl fullerene as a semi conductor layer applied by centrifugation are considered. Electron mobility in the transistors was 0.067 ± 10% cm² V⁻¹ s⁻¹, whereas the mobility of electrons in these devices after the vacuum deposition of a semiconductor layer was much lower (0.023 ± 10% cm² V⁻¹ s⁻¹).     

An Amorphous n-Type Conjugated Polymer with an Ultra-Rigid Planar Backbone

High charge carrier mobility polymer semiconductors are always semi-crystalline. Amorphous conjugated polymers represent another kind of polymer semiconductors with different charge transporting mechanism. Here we report the first near-amorphous n-type conjugated polymer with decent electron mobility, which features a remarkably rigid, straight and planar polymer backbone. The molecular design strategy is to copolymerize two fused-ring building blocks which are both electron-accepting, centrosymmetrical and planar. The polymer is the alternating copolymer of double B←N bridged bipyridine (BNBP) unit and benzobisthiazole (BBTz) unit. It shows a decent electron mobility of 0.34 cm² V⁻¹ s⁻¹ in organic field-effect transistors. The excellent electron transporting property of the polymer is possibly due to the ultrahigh backbone stiffness, small π-π stacking distance, and high molecular weight.     

High Electron Mobility Hot-Exciton Induced Delayed Fluorescent Organic Semiconductors

The development of high mobility emissive organic semiconductors is of great significance for the fabrication of miniaturized optoelectronic devices, such as organic light emitting transistors. However, great challenge exists in designing key materials, especially those who integrates triplet exciton utilization ability. Herein, dinaphthylanthracene diimides (DNADIs), with 2,6-extended anthracene donor, and 3′- or 4′-substituted naphthalene monoimide acceptors were designed and synthesized. By introducing acceptor-donor-acceptor structure, both materials show high electron mobility. Moreover, by fine-tuning of substitution sites, good integration with high solid state photoluminescence quantum yield of 26 %, high electron mobility of 0.02 cm² V⁻¹ s⁻¹, and the feature of hot-exciton induced delayed fluorescence were obtained in 4′-DNADI. This work opens a new avenue for developing high electron mobility emissive organic semiconductors with efficient utilization of triplet excitons.     

Opening of Band Gap of Graphene with High Electronic Mobility by Codoping BN Pairs

Two-dimensional(2D) materials with a high density and low power consumption have become the most popular candidates for next-generation semiconductor electronic devices. As a prototype 2D material, graphene has attracted much attention owing to its stability and ultrahigh mobility. However, zero band gap of graphene leads to very low on-off ratios and thus limits its applications in electronic devices, such as transistors. Although some new 2D materials and doped graphene have nonzero band gaps, the electronic mobility is sacrificed. In this study, to open the band gap of graphene with high electronic mobility, the structure and property of BN-doped graphene were evaluated using first-principles calculations. The formation energies indicate that the six-membered BN rings doped graphene has the most favorable configuration. The band structures show that the band gaps can be opened by such type of doping. Also, the Dirac-cone-like band dispersion of graphene is mostly inhibited, ensuring high electronic mobility. Therefore, codoping BN into graphene might provide 2D materials with nonzero band gaps and high electronic mobility.     

Solution‐Processable Balanced Ambipolar Field‐Effect Transistors Based on Carbonyl‐Regulated Copolymers

It is very important to develop ambipolar field effect transistors to construct complementary circuits. To obtain balanced hole‐ and electron‐transport properties, one of the key issues is to regulate the energy levels of the frontier orbitals of the semiconductor materials by structural tailoring, so that they match well with the electrode Fermi levels. Five conjugated copolymers were synthesized and exhibited low LUMO energy levels and narrow bandgaps on account of the strong electron‐withdrawing effect of the carbonyl groups. Polymer thin film transistors were prepared by using a solution method and exhibited high and balanced hole and electron mobility of up to 0.46 cm² V^?1 s^?1, which suggested that these copolymers are promising ambipolar semiconductor materials.