有机发光晶体管的关键材料和器件研究※

有机发光晶体管(organic light-emitting transistor, OLET)是一种变革性的小型化有机光电器件, 其在同一器件中集成了场效应晶体管和发光二极管的两种器件功能, 在材料的基础物性研究、新型柔性显示/照明、有机电泵浦激光以及片上集成光电子器件等方面都具有着重要的研究意义. OLET独特的器件结构及工作模式使其对核心的关键材料和器件制备提出了新的要求, 而高性能OLET器件的构筑需要从材料和器件两个方面同时进行优化与改善. 近五年作者课题组和合作者在全面调研和分析OLET领域整体研究背景和存在基本科学问题基础上, 聚焦于高迁移率发光有机半导体关键材料的开发和高效OLET器件(线光源和面光源发光模式)的构筑两个方面开展了初步的探索性研究, 发展了系列特别是基于蒽和芴的高迁移率发光/激光有机半导体材料, 构筑了高性能的单组分有机单晶OLET器件和新型平面OLET面光源发射显示器件, 为进一步推动OLET及其相关领域发展奠定了重要的材料和器件研究基础.     

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．     

有机半导体材料中的电荷转移

在介绍有机半导体材料电荷转移基本理论的基础上,对利用电荷转移研究有机半导体材料的导电、光电导和发光过程的现状进行评述,认为电荷转移是有机半导体材料研究的关键问题,开展其研究不仅有助于弄清一些新现象、新效应的物理起因,还可望找到预测有机半导体材料相关性能的有效手段.     

前言

有机材料通常被认为是绝缘体,但是自从20世纪50年代发现有机色素的半导体特性以来,有机半导体材料的相关研究逐渐兴起.1963年,纽约大学的Pope等利用蒽单晶制备了单层有机电致发光器件,但是起亮电压高,器件性能很差;1970年,美国IBM公司首先将有机光导材料（聚乙烯咔唑/三硝基芴酮）用于复印机的感光鼓,实现了有机半导体材料最早的应用;1987年,     

高分子发光材料研究进展

高分子发光材料具有可溶液加工的特点,适于制备低成本、大面积发光器件,在平板显示和固体照明领域具有潜在的应用前景.近年来,高分子发光材料在发光机制、材料体系和器件性能等方面均取得了重要进展,各项性能得到了大幅度提升.本文从材料和器件角度,围绕高分子荧光材料、高分子磷光材料和高分子热活化延迟荧光材料的分子设计策略,总结和评述了高分子荧光材料的颜色调控和效率提升途径,高分子磷光材料的磷光掺杂剂、高分子主体、拓扑结构等因素对发光性能的影响规律,以及高分子热活化延迟荧光材料的设计原理和典型材料体系.同时,分析了高分子发光材料未来发展面临的机遇和挑战.     

蒽类衍生物的电荷传输性质

以具有较高迁移率的对称取代类蒽的衍生物{2,6-二[2-(4-戊基苯基)乙烯基]蒽,DPPVAnt;2,6-二-噻吩蒽,DTAnt;2,6-二[2-己基噻吩]蒽,DHTAnt}为研究对象,采用密度泛函理论的B3LYP方法,在6-31G(d)的基组水平上研究了三种蒽类衍生物的分子结构、电子结构、重组能和电荷传输积分,采用Einstein关系式计算了室温下的载流子迁移率,并与蒽的相关计算结果进行了比较.DPPVAnt是较好的空穴传输材料,其空穴迁移率为0.49cm2·V-1·s-1;DHTAnt有利于电子传输,其电子迁移率为0.12cm2·V-1·s-1;而DTAnt是一种较好的双极性材料,其空穴迁移率和电子迁移率分别为0.069和0.060cm2·V-1·s-1.计算得到的迁移率与实验结果处于同一数量级.三种蒽类衍生物的电子重组能与蒽的相近,而空穴重组能均大于蒽的空穴重组能,大小顺序为蒽DPPVAntDTAntDHTAnt.这与计算的迁移率结果不一致,说明分子的堆积结构决定材料的电荷传输性质.     

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.     

烷基链长度对非对称含噻吩五元稠环化合物传输性能的影响北大核心CSCD

含噻吩并苯类分子是一类代表性的高迁移率有机半导体材料,以其为共轭骨架构建的不对称分子在薄膜中倾向于形成双层排列结构,并以二维层状方式生长,有利于实现高迁移率。烷基取代基的长度会对有机半导体材料的堆积形貌产生影响。本文设计合成了不同长度烷基链取代的噻吩并[4,5-b][1]苯并噻吩并[3,2-b][1]苯并噻吩(syn-BTBTT-Cn,n=4,5,6,7,8,10),系统研究了烷基链长度对化合物热稳定性、能级、载流子传输能力、堆积结构和薄膜形貌等方面的影响。结果表明,所有化合物均不具备液晶性,热稳定性良好。在所制备的蒸镀薄膜中所有分子均形成双层堆积结构,共轭核在层内形成鱼骨架堆积,烷基链长度会影响薄膜的有序度和堆积的紧密程度。基于该类材料制备的有机薄膜晶体管(OTFT)器件的迁移率都超过7.0 cm^(2)/(V·s),其中syn-BTBTT-C8分子的迁移率最高可达13.8 cm^(2)/(V·s),平均值为12.5 cm^(2)/(V·s)。     

机械力诱导发光高分子材料

发展具有机械力诱导发光性质的高分子是目前高分子力化学领域的一个新兴前沿课题.这类响应性高分子材料由于能够将机械能转换成灵敏的光信号,是连接微观分子水平研究与宏观材料性能表征的桥梁,因而有望作为高灵敏(在空间和时间2个维度上)应力探针在高分子材料损伤探测与失效机理研究方面发挥重要作用.本文详细介绍了机械力诱导发光高分子的设计与合成策略,以及研究者对发光机理的探索、发光效率的优化、发光过程的应用,揭示这类高分子的发光特点及其作为应力探针的优势,归纳总结已取得的初步进展,并对这类新型响应性高分子材料的发展进行简单的评述和展望.     

联萘基手性发光材料的圆偏振发光

本文综述了近年来基于联萘基结构的圆偏振发光材料的研究工作.从光致发光和电致发光两方面总结了不同体系下联萘基材料的圆偏振发光,为相关领域的研究者提供了设计思路,并对圆偏振发光材料的研究发展方向进行了展望.     

Molecular Materials That Can Both Emit Light and Conduct Charges: Strategies and Perspectives

Molecular materials with concomitant light‐emissive and semiconducting properties have received increasing attention in recent years. Such dual functional materials ensure the development of multifunctional devices (e.g., organic light‐emitting transistors) and the emergence of new technologies. However, owing to the fact that intermolecular interactions and dense packing have opposite effects on photoluminescence and charge‐carrier mobility, it is still rather challenging to rationally design high‐performance molecular materials that exhibit both semiconducting and light‐emissive properties. In fact, only a limited number of such dual functional materials are available, and most of their performances need to be further improved. In this concept article we discuss the design strategies and perspectives of this challenging area with the introduction of representative examples of such dual functional materials reported in recent years.     

高性能双极性聚合物半导体材料与晶体管器件

有机聚合物半导体材料与晶体管器件是融合了化学、材料、半导体以及微电子等学科的前沿交叉研究方向.聚合物半导体材料分子是该领域研究的重要内容,其中双极性聚合物分子半导体材料,兼具了电子和空穴的双重载流子输运能力而受到学术界的广泛关注.本文总结了双极性聚合物半导体材料与器件的研究进展,重点介绍了我们在D-A型双极性聚合物分子半导体材料设计、加工技术与器件制备以及功能应用方面的研究工作,并论述了双极性聚合物分子半导体材料与器件研究过程中存在的科学问题及发展方向.     

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.     

The Prospect of Dimensionality in Porous Semiconductors

With the advent of silicon-based semiconductors, a plethora of previously unknown technologies became possible. The development of lightweight low-dimensional organic semiconductors followed soon after. However, the efficient charge/electron transfers enabled by the non-porous 3D structure of silicon is rather challenging to be realized by their (metal-)organic counterparts. Nevertheless, the demand for lighter, more efficient semiconductors is steadily increasing resulting in a growing interest in (metal-)organic semiconductors. These novel materials are faced with a variety of challenges originating from their chemical design, their packing and crystallinity. Although the effect of molecular design is quite well understood, the influence of dimensionality and the associated change in properties (porosity, packing, conjugation) is still an uncharted area in (metal-)organic semiconductors, yet highly important for their practical utilization. In this Minireview, an overview on the design and synthesis of porous semiconductors, with a particular emphasis on organic semiconductors, is presented and the influence of dimensionality is discussed.     

Molecular design of n-type organic semiconductors for high-performance thin film transistors

This digest aims to provide organic chemists with an overview of recent progress on n-type organic semiconductors for application in organic thin film transistors (OTFTs) with an emphasis on molecular design. Herein, we survey n-type organic semiconductors with field effect mobility of 1 cm²/Vs or higher in OTFTs after a brief introduction to the structure and operation of OTFTs and discussion of two key factors (frontier molecular orbitals and molecular packing) of organic semiconductors. On the basis of this survey, we finally reach conclusions on the current status of n-type organic semiconductors for OTFTs and provide an outlook for molecular design.     

2,6-Bis[2-(4-pentylphenyl)vinyl]anthracene: a stable and high charge mobility organic semiconductor with densely packed crystal structure

The development of new organic semiconductors with improved electrical performance and enhanced environmental stability is the focus of considerable research activity. This paper presents the design, synthesis, optical and electrochemical characterization, crystal packing, modeling and thin film morphology, and organic thin film field effect transistor (OTFT) device data analysis for a novel 2,6-bis[2-(4-pentylphenyl)vinyl]anthracene (DPPVAnt) organic semiconductor. We observed a hole mobility of up to 1.28 cm2/V.s and on/off current ratios greater than 107 for OTFTs fabricated using DPPVAnt as an active semiconductor layer. The mobility value is comparable to that of the current best p-type semiconductor pentacene-based device performance. In addition, we found a very interesting relationship between the charge mobility and molecule crystal packing in addition to the thin film orientation and morphology of the semiconductor as determined from single-crystal molecule packing study, thin film X-ray diffraction, and AFM measurements. The high performance of the semiconductor ranks among the best performing p-type organic semiconductors reported so far and will be a very good candidate for applications in organic electronic devices.     

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.     

Accurate calculation of transport properties for organic molecular semiconductors with spin-component scaled MP2 and modern density functional theory methods

At ambient temperatures, intermolecular hopping of charge carriers dominates the field effect mobility and thus the performance of organic molecular semiconductors for organic-based electronic devices. We have used a wide variety of modern and accurate computational methods to calculate the main parameters associated with charge transport, taking oligoacenes, and its derivatives as the exemplary organic materials. We tackle the problem from a combined inter- and intramolecular approach, in which the parameters are calculated for an isolated single molecule concomitantly with the stability of the dimers found in experimentally determined crystalline structures. Considering that most of the future applications within the field would need a full understanding of the transport mechanism, we assess the reliability of the methods to be employed according to the nature of the problem. Finally, we perform a computationally guided molecular engineering of a new set of materials derived from tetracene (rubrene and highly twisted oligoacenes) which allows to robustly anticipate the reasons for their expected performance in organic-based electronic devices.     

Influence of Intermolecular N?H⋅⋅⋅π Interactions on Molecular Packing and Field‐Effect Performance of Organic Semiconductors

Charge transport in organic semiconductors is strongly dependent on their molecular packing modes in the solid state. Therefore, understanding the relationship between molecular packing and charge transport is imperative, both experimentally and theoretically. However, so far, the fundamental effects of solid‐state packing and molecular interactions (e.g. N? H ??? π) on charge transport need further elucidation. Herein, indolo[3,2‐b]carbazole (ICZ) and a derivative thereof are used as examples to approach this scientific target. An interesting insight obtained thereby is that N? H ??? π interactions among ICZ molecules facilitate charge transport for higher mobility. Subtle changes in the of N? H ??? π interactions can significantly influence both the molecular packing and the charge‐transport properties. Therefore, a method for exploiting intermolecular N? H ??? π interactions would yield novel molecular systems with designable characteristics.     

Recent advances of dithienobenzodithiophene-based organic semiconductors for organic electronics

In recent years, fused aromatic dithienobenzodithiophene(DTBDT)-based functional semiconductors have been potential candidates for organic electronics. Due to the favorable features of excellent planarity, strong crystallinity, high mobility, and so on, DTBDT-based semiconductors have demonstrated remarkable performance in organic electronic devices, such as organic feld-effect transistor(OFET), organic photovoltaic(OPV), organic photodetectors(OPDs). Driven by this success, recent developments in the area of DTBDT-based semiconductors for applications in electronic devices are reviewed, focusing on OFET, OPV, perovskite solar cells(PSCs), and other organic electronic devices with a discussion of the relationship between molecular structure and device performance. Finally, the remaining challenges, and the key research direction in the near future are proposed, which provide a useful guidance for the design of DTBDT-based materials.