有机发光二极管中三重态激子的单重态转换

在OLED的研究中如何充分利用三重态激子以提高器件的电-光转换效率一直是人们关注的问题,近年来出现的经热激活逆向上转换过程获得延迟荧光的办法,使OLED的研究出现了一派崭新的前景。本文综合前人的工作对有关这一领域的研究基础,如：电子跃迁、激发态的分裂、单重态/三重态的交换能量、载流子的重合和激子的形成,以及在纯有机化合物与有机-过渡金属配合物中的电荷转移（CT）问题等,进行了较详细的讨论。     

蓝光热激子材料的研究进展

热激子荧光材料由于交错的能级排列,激子在电致发光过程中可由高位三重态通过反向系间窜跃转换到单重态,从而最大限度利用三重态激子,实现理论100%的最大内量子效率,这不仅突破了传统荧光材料和三重态-三重态上转换发光材料在激子利用上的限制,而且克服了热活化延迟荧光(TADF)材料在高电流密度下效率滚降严重的问题,因而在电致发光上显现出独特的优势.蓝光长期以来是有机光电全彩显示的短板.蓝光显示上,磷光材料和TADF材料的色纯度和稳定性往往不尽如人意,而热激子材料可实现更高品质的蓝光发射,即使在深蓝领域也能表现出不俗的器件性能.系统地综述了蓝光热激子材料的发光机理、设计准则以及近年来具有代表性的研究成果,并对其发展趋势进行展望.     

钙钛矿太阳能电池中小分子空穴传输材料的研究进展

有机-无机钙钛矿太阳能电池(PSCs)从2009年低于5%的能量转换效率到现在经过认证的超过22%的效率,成为科研热点和最有希望商业化的新型太阳能电池。在高性能的PSCs中,空穴传输材料是关键的一环,起到从钙钛矿活性层材料到对电极有效抽取和传输空穴的作用。本文在现有研究成果的基础上,对有机分子空穴传输材料在PSC中的应用进行总结,并强调分子材料结构对PSC器件性能(效率和稳定性)的影响。     

挥发固体添加剂调控有机太阳能电池性能的研究进展

本体异质结(BHJ)有机太阳能电池(OSC)因具有可溶液制备、绿色无毒及可柔性化等特点而被视为具有广阔应用前景的太阳能电池技术之一.活性层内部的纳米形貌是决定器件性能和工作稳定性的关键因素之一.基于此,研究者先后开发了热退火、溶剂退火和溶剂添加剂等形貌优化方法.然而,上述处理方式不能与大面积印刷工艺兼容,而且不利于器件内部形貌和性能的稳定性,因此寻找简单高效的形貌调控手段是OSC研究的热点.近年来,挥发固体添加剂因其独特的分子特性,能够与给受体分子间形成较强的相互作用力,被认为是提升OSC能量转换效率(PCE)和稳定性的发展方向.本文系统总结了非卤素及卤素型挥发固体添加剂调控OSC形貌和光伏性能的研究现状,深入讨论了挥发固体添加剂优化活性层形貌的不同机理,包括分子间吸附能、给体与受体的相互作用、晶体成核和生长等;分析了挥发固体添加剂策略所面临的挑战和未来的发展趋势.     

不饱和卡宾的单重态与三重态

对X2C=C:和X2C=C=C:(X=H,Li,F)进行了量子化学计算和研究,得到了不饱和卡宾单重态(^1A1)和三重态(^3B1)的几何构型及其相对稳定性随取代基X电负性变化的一般规律,结果表明,不饱和卡宾的基态都是单重态,第一激发态与基态的能量差ΔE(^1A1 - ^3B1)随X的电负性大小而变化,其值一般在60kcal.mol^-^1以内,累积烯基的大小对ΔE(^IA1-^3B1)的影响相对较小,^IA1和^3B1的平衡几何构型并不相同。     

基于分子内非共价相互作用构建非富勒烯受体材料的研究进展*

非富勒烯稠环电子受体因具有易调控的分子结构、宽且强的光谱吸收及较高的光电转换效率吸引了科研人员的广泛的研究兴趣。非富勒烯稠环电子受体分子的中心给电子单元一般为较大的共轭稠环平面结构,这类稠环结构通常是经过多步反应得到,包括合成成本高、难度大且产率低的关环反应过程。研究人员在分子中引入带有O、F、N、Se等杂原子单元, 利用分子内非共价键相互作用来锁定分子骨架得到类似稠环结构的非共价稠环电子受体材料,减少合成过程中关环反应的使用,使得合成更容易,成本更低;利用分子内的非共价相互作用可以增强分子平面性,拓展吸收光谱,降低材料的制备成本。综述了近年来利用分子内非共价键相互作用合成非富勒烯受体材料及其在有机太阳能电池中应用的研究进展, 并展望了其发展趋势和应用前景。     

龙脑烯醛同单重态氧反应的立体选择性

用竹红菌甲素匹配高压钠灯光敏氧化龙脑烯醛,高产率并有立体选择性地获得反应主产物,α-(2,2-二甲基-3-亚甲基-4-羟基-1-环戊烷基)乙醛。反应具有协同的“ene”反应特性。反应的立体选择性被龙脑烯醛的分子构象,取代基的空间位阻效应和烯丙基氢的轴向定位所控制。羰基同环戊烯基的相互隐蔽的分子构象对反应的立体选择性起关键作用。     

有机光伏研究进展

以有机半导体材料为活性层的有机太阳能电池,可通过印刷制备大面积柔性器件,具有成本低、多彩、半透明等特点,是一种极具发展前景的光伏技术.研究者们多年来致力于设计高性能光伏材料,优化器件界面,改善活性层微观形貌,开发新型器件结构,探究器件工作机理等,目前实验室制备的小面积有机太阳能电池的能量转换效率已经超过18%.另外,面向有机光伏产业化,在制备大面积柔性器件、降低器件成本、提高器件寿命以及探究光伏建筑一体化和室内光伏等潜在应用方面的研究也取得了重要进展,在国际上处于领跑地位.中国科学家在有机光伏领域做出了诸多开创性和引领性的工作.本文首先对有机太阳能电池的背景进行简单介绍,接着按照分子工程、器件工程、器件物理和应用探索四个方面综述有机光伏领域的重要研究进展,最后对有机光伏所面临的机遇与挑战进行展望.     

分子堆叠和器件性能:基于苯并二噻吩及其衍生物的高效小分子给体研究进展（英文）

有机全小分子太阳能电池由于具备结构精确和批次差异小的特点,有广阔的应用前景,近年来该领域的发展备受关注.本文回顾了基于苯并二噻吩(BDT)及其衍生物的小分子给体的发展.基于分子结构、堆叠特性和器件性能之间的关系,分析了小分子BDT系列的成功案例,旨在阐明分子结构、分子聚集和器件性能之间的联系,为未来高效分子的设计提供参考.     

大面积有机太阳能电池的研究进展

近年来,有机太阳能电池发展十分迅速,小面积器件的光电转化率已经突破19%,然而大面积器件的研究远远滞后.深入研究有机光伏大面积器件中的关键基础问题、开发大面积印刷制备方法,对推动有机太阳能电池的工业化应用具有重要意义,是未来有机太阳能电池的发展的热点和难点方向.相较于小面积器件,大面积器件对活性层材料的膜厚容忍度、透明电极的电阻、器件的加工方式等都有较高的要求,如何制备高效、稳定的刚性/柔性大面积器件仍是一个挑战.本综述着眼于刚性基底与柔性基底大面积器件中使用的材料、器件的涂布工艺、阳极/阴极传输层及电极材料的开发等方面,系统总结了近年来领域内的代表成果,并对未来高性能大面积有机太阳能器件的发展进行了展望.     

激子的分裂与高效太阳能电池

能将单重态激子分裂为两个三重态激子的化合物,可作为一种新型的敏化剂,较大程度地提高太阳能电池的光-电转换能力.本文扼要地介绍了激子分裂的基本要点和发展状况,并对研究这一现象的实验方法和分裂机制等进行了讨论.在实验方法部分,叙述了通过稳态与瞬态延迟光谱的测定,可对体系中单重态的分裂和三重态重合,进而对激子的分裂进行研究,此外,还对激子的偶合、能级间的能量关系,以及环境效应等作了介绍.文章还对激子分裂过程的可能机制和如何选择这类敏化剂分子的一些基本准则,给予了讨论和说明.     

Singlet Fission in Carbene‐Derived Diradicaloids

Herein, we present a new class of singlet fission (SF) materials based on diradicaloids of carbene scaffolds, namely cyclic (alkyl)(amino)carbenes (CAACs). Our modular approach allows the tuning of two key SF criteria: the steric factor and the diradical character. In turn, we modified the energy landscapes of excited states in a systematic manner to accommodate the needs for SF. We report the first example of intermolecular SF in solution by dimer self‐assembly at cryogenic temperatures.     

Thermodynamic Control of Intramolecular Singlet Fission and Exciton Transport in Linear Tetracene Oligomers

We newly synthesized a series of homo- and hetero-tetracene (Tc) oligomers to propose a molecular design strategy for the efficient exciton transport in linear oligomers by promoting correlated triplet pair (TT) dissociation and controlling sequential exciton trapping process of individual doubled triplet excitons (T+T) by intramolecular singlet fission. First, entropic gain effects on the number of Tc units are examined by comparing Tc-homo-oligomers [(Tc)_n: n=2, 4, 6]. Then, a comparison of (Tc)_n and Tc-hetero-oligomer [TcF₃-(Tc)₄-TcF₃] reveals the vibronic coupling effect for entropic gain. Observed entropic effects on the T+T formation indicated that the exciton migration is rationalized by number of possible TT states increased both by increasing the number of Tc units and by the vibronic levels at the terminal TcF₃ units. Finally, we successfully observed high-yield exciton trapping process (trapped triplet yield: Φ_TrT=176 %).     

Sub‐Picosecond Singlet Exciton Fission in Cyano‐Substituted Diaryltetracenes

Thin films of 5,11‐dicyano‐6,12‐diphenyltetracene ( TcCN ) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T₁)?E(S₁)=?0.17 eV), where S₁ and T₁ are singlet and triplet excitons, respectively. As a result of tuning the triplet‐state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.     

有机太阳能电池中基于苝二酰亚胺结构小分子受体进展

最近几年,有机太阳能电池中的非富勒烯小分子受体研究引起了人们的兴趣。其中,苝二酰亚胺(PDI)类分子因具有良好的电子传输能力,较强的电子亲和力,稳定的光、热、化学性能以及化学结构的可设计性带来的性能可调控性而得到广泛的关注。本文总结了近三年来在体异质结有机太阳能电池应用方面PDI小分子受体的研究进展,重点关注了PDI分子结构对其性能的影响,希望为以后PDI类受体分子的设计思路起到一定的启发作用。     

Influence of Molecular Stacking Pattern on Excited State Dynamics of Copper Phthalocyanine Films

Photophysical processes occurring within organic semiconductors is important for designing and fabricating organic solar cells. Copper phthalocyanine (CuPc) is a typical electron acceptor. In this work, the triplet exciton lifetime is prolonged by altering the molecular stacking pattern of the CuPc film. For CuPc thin films, the excited state decays are mainly determined by the triplet-triplet annihilation process. The ultrafast transient absorption measurements indicate that the primary annihilation mechanism is one-dimensional exciton diffusion collision destruction. The decay kinetics show a clearly time-dependent annihilation rate constant with \begin{document}$\gamma$\end{document}\begin{document}$\propto$\end{document}\begin{document}$t^{-1/2}$\end{document}. Annihilation rate constants are determined to be \begin{document}$\gamma_0$\end{document}=(2.87\begin{document}$\pm$\end{document}0.02)\begin{document}$\times$\end{document}10\begin{document}$^{-20}$\end{document} cm\begin{document}$^3$\end{document}\begin{document}$\cdot$\end{document}s\begin{document}$^{-1/2}$\end{document} and (1.42\begin{document}$\pm$\end{document}0.02)\begin{document}$\times$\end{document}10\begin{document}$^{-20}$\end{document} cm\begin{document}$^3$\end{document}\begin{document}$\cdot$\end{document}s\begin{document}$^{-1/2}$\end{document} for upright and lying-down configurations, respectively. Compared to the CuPc thin film with an upright configuration, the thin film with a lying-down configuration shows longer exciton lifetime and higher absorbance, which are beneficial to organic solar cells. The results in this work have important implications on the design and mechanistic understanding of organic optoelectronic devices.     

Chromophore Multiplication To Enable Exciton Delocalization and Triplet Diffusion Following Singlet Fission in Tetrameric Pentacene

A tetrameric pentacene, PT , has been used to explore the effects of exciton delocalization on singlet fission (SF). For the first time, triplet decorrelation through intramolecular triplet diffusion was observed following SF. Transient absorption spectroscopy was used to examine different decorrelation mechanisms (triplet diffusion versus structural changes) for PT and its dimeric equivalent PD on the basis of the rate and activation barrier of the decorrelation step. Charge‐separation experiments using tetracyano‐p‐quinodimethane ( TCNQ ) to quench triplet excitons formed through SF demonstrate that enhanced intersystem crossing, that is, spin catalysis, is a widely underestimated obstacle to quantitative harvesting of the SF products. The importance of spatial separation of the decorrelated triplet states is emphasized, and independent proof that the decorrelated triplet pair state consists of two (T₁) states per molecule is provided.     

Recent Progress on Semi-transparent Perovskite Solar Cell for Building-integrated Photovoltaics

The electricity consumption of buildings is tremendous; moreover, a huge amount of electricity is lost during distribution. Taking away this consumption can significantly reduce energy demand and greenhouse effect gas emission. One of the low-cost and renewable solutions to this issue is to install photovoltaic panels on the buildings themselves, namely, building-integrated photovoltaics(BIPVs). Using this technology, power generation roofs, windows, and facades can harvest solar radiation and convert to electricity for building power consumption. Semi-transparent perovskite solar cells(ST-PSCs) have attracted tremendous attention for the power generation windows, due to the excellent photoelectric properties, versatile fabrication methods, bandgap tunability, and flexibility. Here, an overview is provided on the recent progress of ST-PSCs for BIPV, which mainly focuses on the control of perovskite morphology, optical engineering for an efficient and semi-transparent ST-PSC. We also summarize recent development on various transparent electrodes and present prospects and challenges for the commercialization of ST-PSCs.     

Recent progress of thin-film photovoltaics for indoor application

Indoor photovoltaics have attracted increasing attentions owing to their great potential in supplying energy for low power devices under indoor light in our daily life.The third generation thin-film solar cells,including dye-sensitized solar cells,perovskite solar cells and organic solar cells,have made rapid progress from the aspect of materials design to photovoltaic performance.This review provides an overview on the recent advances in the development of indoor photovoltaic technologies based on the third generation solar cells.The design principles of advanced thin-film indoor photovoltaics were also summarized according to the characteristics of indoor light and the advantages of the third generation solar cells.Finally,after summarizing the current research progress,the perspective on this topic is provided.     

Singlet Fission in Carbene-Derived Diradicaloids

Herein, we present a new class of singlet fission (SF) materials based on diradicaloids of carbene scaffolds, namely cyclic (alkyl)(amino)carbenes (CAACs). Our modular approach allows the tuning of two key SF criteria: the steric factor and the diradical character. In turn, we modified the energy landscapes of excited states in a systematic manner to accommodate the needs for SF. We report the first example of intermolecular SF in solution by dimer self-assembly at cryogenic temperatures.