硼氮杂稠环化合物的合成与电子学应用

有机半导体材料的开发为有机电子学的发展提供了材料基础。杂原子的引入进一步丰富了材料的种类和数量。作为CC单元的等电子体,BN单元对有机半导体材料的性能调节受到了科学家们的关注。本文主要介绍了有机共轭体系中BN单键的构筑方法,以及这类硼氮杂稠环分子在有机电子学领域的应用。     

高性能的n-型和双极性有机小分子场效应晶体管材料

作为有机场效应晶体管的关键组成部分,有机半导体材料直接决定了器件的性能和稳定性。相比于p-型有机半导体材料,n-型和双极性有机半导体材料在迁移率和稳定性等方面则显著滞后。因此,n-型和双极性小分子有机半导体材料的设计与合成已成为高性能OFETs的学术研究的焦点。这篇综述重点突出了近十年报道的具有较好性能的n-型和双极性小分子有机半导体材料,并且对其结构和性能的关系进行了归纳,旨在对设计合成高性能、空气稳定的n-型和双极性有机小分子半导体材料提供一些指导帮助。     

苯丙炔酸和苯丙烯酸酯苯并菲盘状液晶电荷传输的理论研究

电荷传输是有机材料的重要性质之一．根据电子转移的半经典模型对含苯丙炔酸和苯丙烯酸酯支链的苯并菲盘状液晶化合物分子的电荷传输性质进行理论研究．研究结果表明,所计算的三个苯并菲衍生物分子均具有高的电荷传输性能．标题化合物分子的负电荷传输速率均比苯并菲大,含苯丙烯酸酯链的苯并菲分子比含苯丙炔酸酯链的苯并菲分子具有较大的空穴传输速率及较小的负电荷传输速率．对于含苯丙烯酸酯链的苯并菲分子,链烷氧基越长,正电荷传输速率越大,负电荷传输速率越小．     

苯并菲类液晶高分子合成及应用

苯并菲液晶材料能够自组装成柱状相,被广泛应用在光电材料方面、功能分子膜、信息储存等方面。苯并菲衍生物合成方法简单,并且具有非常良好的光电性质,引起了研究者的广泛关注。苯并菲液晶高分子可以分为不同的类型,其合成方法也不相同。本文在简单介绍苯并菲液晶高分子合成方法的同时,对苯并菲液晶高分子的应用也做简要的概括。     

酰胺与酰亚胺类n型有机半导体材料的研究进展

有机半导体材料具有来源丰富、化学结构可裁剪、柔韧性较高、器件制备温度低和塑料衬底兼容性好等优点, 极大地拓展了电子器件的功能与应用. 然而, 电子传输型(n型)有机半导体在分子多样性、载流子迁移率和空气稳定性方面远远落后于空穴传输型(p型)半导体, 从而阻碍了双极晶体管、p-n结和有机互补电路的发展. 酰胺或酰亚胺功能化能显著提高有机材料的电子亲和势, 是构建高性能n型有机半导体的重要策略. 本综述总结了近年来萘二酰亚胺类、苝二酰亚胺类、吡咯并吡咯二酮类、异靛蓝类和其他酰胺/酰亚胺类小分子和聚合物n型有机半导体材料的研究进展, 从分子设计角度出发, 深入讨论了分子结构如何改变分子前线轨道能级、分子间相互作用力、聚集态结构、器件稳定性和电学性能, 最后对其未来的发展方向和面临的挑战进行了展望.     

苯并菲类液晶高分子合成及应用北大核心CSCD

苯并菲液晶材料能够自组装成柱状相,被广泛应用在光电材料方面、功能分子膜、信息储存等方面。苯并菲衍生物合成方法简单,并且具有非常良好的光电性质,引起了研究者的广泛关注。苯并菲液晶高分子可以分为不同的类型,其合成方法也不相同。本文在简单介绍苯并菲液晶高分子合成方法的同时,对苯并菲液晶高分子的应用也做简要的概括。     

基于有机纳米纤维薄膜的荧光化学传感

薄膜荧光化学传感提供了一种固相、便携、易操作的气相分子检测技术,在环境、安全、生物医学、健康监测等领域具有重要的应用价值和发展前景.基于本课题组在超分子自组装构建n-型有机半导体苝二酰亚胺衍生物(PTCDI)一维纳米纤维及其荧光薄膜检测胺类等气相分子领域研究,结合其他课题组工作,本文阐述了该类纳米纤维多孔薄膜在结构调控,荧光传感应用性能、机制和意义方面的研究进展.同时,也介绍了本课题组在p型有机半导体咔唑角亚乙炔四环(ACTC)和咔唑三聚体等在本领域的进展,最后对未来挑战和发展方向进行了展望.     

1,2-硼氮杂芳烃在中国的研究进展

稠环芳烃及其衍生物在有机光电材料领域具有广泛应用,杂原子掺杂可有效调节稠环芳烃的物理化学性质.用等电子体的硼氮单元取代碳碳单元,在保持稠环芳烃芳香性的连续性的同时,可以调节稠环芳烃的电子结构和分子间相互作用,构建具有独特光电性质和生物活性的新型硼氮杂稠环芳烃,既丰富了稠环芳烃的种类,又促进了硼氮杂芳烃在光电材料、催化和生物医药等领域的应用.近年来,中国有机化学及材料化学领域的学者们积极参与并推动了硼氮杂芳烃的快速发展,在硼氮杂芳烃的种类开发和应用拓展方面开展了一系列原创性的工作,取得了瞩目的成绩.本文综述了基于1,2-硼氮杂苯的稠环芳烃(即1,2-硼氮杂芳烃)的合成发展历史和应用研究拓展,最后对硼氮杂芳烃领域的未来发展与应用进行了展望.通过对硼氮芳烃在中国的发展进行系统的梳理和总结,希望能够引起更多科研工作者对硼氮芳烃的兴趣,期待更多的科研工作者能够加入到硼氮杂芳烃的合成拓展与应用探索中.     

盘状液晶材料的研究进展

盘状液晶分子容易形成柱状堆积的超分子组装体, 由于分子在液晶态具有一定的流动性, 使得组装体具有良好的结构缺陷自修复功能. 因此具有特定芳香共轭结构的盘状液晶分子可以呈现较高的导电特性, 能够有效传输电荷, 具有制备光电器件的潜在应用价值. 本文主要介绍以苯环、苯并菲、六苯并蔻、苝和肽菁为中心核的盘状液晶材料, 其分子结构的化学修饰对液晶性能的影响, 液晶材料在有机发光二极管(OLED)、有机场效应晶体管(OFET)和太阳能电池器件中的应用, 以及盘状液晶材料相关的动力学研究进展.     

基于萘二酰亚胺受体单元的n-型聚合物受体材料在光电领域的研究进展

近年来,n-型聚合物受体材料逐步在有机光电器件领域,尤其是全聚物太阳能电池领域,得到了广泛的研究。目前,报道较多的具有高的电荷迁移率和电子亲合性的n-型聚合物主要是基于萘二酰亚胺(NDI)的n-型聚合物受体材料,这类基于NDI的n-型聚合物材料表现出比富勒烯衍生物受体材料更好的热/机械性能及太阳光吸收,同时可以灵活的调节包括光学性能、电子结构、结晶性、溶解性和电荷传输等不同的内在特性从而提高器件的性能。本文根据聚合物结构组成的不同,归纳了近年来基于萘二酰亚胺的D-A聚合物受体材料的研究进展,详细描述了其相对应的给体材料和器件结构及后处理条件对器件性能的影响。同时,总结评述了针对基于萘二酰亚胺的D-A聚合物作为受体材料的全聚物太阳能电池器件工艺条件,最后展望了基于萘二酰亚胺的D-A聚合物应用在全聚物太阳能电池领域的发展前景。     

Temperature Induced Aggregation of Organic Semiconductors

One important feature of organic semiconductors is their solution processability, which allows researchers to tune their aggregation states in solution and solid states and to control the processing conditions to reach desirable electronic and optoelectronic properties. Temperature is one of the most important processing parameters of organic semiconductors and has been studied extensively particularly for those conjugated small- and macro- molecules with strong temperature-dependent aggregation properties. This minireview summarizes the temperature-induced aggregation behaviors of organic semiconductors in solution, during solution casting and upon thermal annealing post-treatment of solid-state thin films. The influences of different aggregation states on the optoelectronic properties, in particular the photovoltaic properties, are discussed. The conclusions in this work will provide a rational guide to precisely control the aggregation states of organic semiconductors to fabricate high-performance optoelectronic devices.     

Imide-Functionalized Polymer Semiconductors

Imide-functionalized π-conjugated polymer semiconductors have received a great deal of interest owing to their unique physicochemical properties and optoelectronic characteristics, including excellent solubility, highly planar backbones, widely tunable band gaps and energy levels of frontier molecular orbitals, and good film morphology. The organic electronics community has witnessed rapid expansion of the materials library and remarkable improvement in device performance recently. This review summarizes the development of imide-functionalized polymer semiconductors as well as their device performance in organic thin-film transistors and polymer solar cells, mainly achieved in the past three years. The materials mainly cover naphthalene diimide, perylene diimide, and bithiophene imide, and other imide-based polymer semiconductors are also discussed. The perspective offers our insights for developing new imide-functionalized building blocks and polymer semiconductors with optimized optoelectronic properties. We hope that this review will generate more research interest in the community to realize further improved device performance by developing new imide-functionalized polymer semiconductors.     

Ladder‐Type Heteroarene‐Based Organic Semiconductors

The fusion of heteroaromatic rings into ladder‐type heteroarenes can stabilize frontier molecular orbitals and lead to improved physicochemical properties that are beneficial for applications in various optoelectronic devices. Thus, ladder‐type heteroarenes, which feature highly planar backbones and well‐delocalized π conjugation, have recently emerged as a promising type of organic semiconductor with excellent device performance in organic photovoltaics (OPVs) and organic field‐effect transistors (OFETs). In this Focus Review, we summarize the recent advances in ladder‐type heteroarene‐based organic semiconductors, such as hole‐ and electron‐transporting molecular semiconductors, and fully ladder‐type conjugated polymers towards their applications in OPVs and OFETs. The recent use of ladder‐type small‐molecule acceptor materials has strikingly boosted the power conversion efficiency of fullerene‐free solar cells, and selected examples of the latest developments in ladder‐type fused‐ring electron acceptor materials are also elaborated.     

Discotic liquid crystals: a new generation of organic semiconductors

Discotic (disc-like) molecules typically comprising a rigid aromatic core and flexible peripheral chains have been attracting growing interest because of their fundamental importance as model systems for the study of charge and energy transport and due to the possibilities of their application in organic electronic devices. This critical review covers various aspects of recent research on discotic liquid crystals, in particular, molecular design concepts, supramolecular structure, processing into ordered thin films and fabrication of electronic devices. The chemical structure of the conjugated core of discotic molecules governs, to a large extent, their intramolecular electronic properties. Variation of the peripheral flexible chains and of the aromatic core is decisive for the tuning of self-assembly in solution and in bulk. Supramolecular organization of discotic molecules can be effectively controlled by the choice of the processing methods. In particular, approaches to obtain suitable macroscopic orientations of columnar superstructures on surfaces, that is, planar uniaxial or homeotropic alignment, are discussed together with appropriate processing techniques. Finally, an overview of charge transport in discotic materials and their application in optoelectronic devices is given.     

Recent Advances in Isoindigo‐Inspired Organic Semiconductors

Over the past decade, isoindigo has become a widely used electron‐deficient subunit in donor‐acceptor organic semiconductors, and these isoindigo‐based materials have been widely used in both organic photovoltaic (OPV) devices and organic field effect transistors (OFETs). Shortly after the development of isoindigo‐based semiconductors, researchers began to modify the isoindigo structure in order to change the optoelectronic properties of the resulting materials. This led to the development of many new isoindigo‐inspired compounds; since 2012, the Kelly Research Group has synthesized a number of these isoindigo analogues and produced a variety of new donor‐acceptor semiconductors. In this Personal Account, recent progress in the field is reviewed. We describe how the field has evolved from relatively simple donor‐acceptor small molecules to structurally complex, highly planarized polymer systems. The relevance of these materials in OPV and OFET applications is highlighted, with particular emphasis on structure‐property relationships.     

Anisotropic charge carrier transport of optoelectronic functional selenium-containing organic semiconductor materials

Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials.     

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.     

Photoinduced Charge Separation in Molecular Silicon

Interest in molecular silicon semiconductors arises from the properties shared with bulk silicon like earth abundance and the unique architectures accessible from a structure distinctly different than rigid π‐conjugated organic semiconductors. We report ultrafast spectroscopic evidence for direct, photoinduced charge separation in molecular silicon semiconductors that supports the viability of molecular silicon as donor materials in optoelectronic devices. The materials in this study are σ–π hybrids, in which electron‐deficient aromatic acceptors flank a σ‐conjugated silicon chain. Transient absorption and femtosecond‐stimulated Raman spectroscopy (FSRS) techniques revealed signatures consistent with direct, optical charge transfer from the silane chain to the acceptor; these signatures were only observed by probing excited‐state structure. Our findings suggest new opportunities for controlling charge separation in molecular electronics.     

Molecular design of star-shaped benzotrithiophene materials for organic electronics

Progresses in the design and application of conjugated small molecules, oligomers and polymers have empowered rapid development of organic electronic technology as an alternative to conventional devices. Among the numerous organic electronic materials, benzotrithiophene (BTT)-based oligomers and polymers have recently come in the limelight demonstrating great potential in organic electronics as high performance photovoltaic devices, field-effect transistors, electrochromic materials, high-area capacitors and charge carrier discotic liquid crystals. In this digest, we propose an overview of the organic electronic materials based on BTT isomers, highlighting the structure-performance relationship. The results obtained so far clearly indicate that the BTT isomers are among the most promising building blocks for the development π-extended materials for optoelectronic applications in the near future.