PTh / ZnO复合纳米粉的固相合成及其光谱特性

0引言导电聚合物/无机物纳米复合材料具有纳米材料和导电聚合物的共同特性,因此在电催化、二次充电电池材料、超级电容器材料等方面具有良好的应用前景[1]。聚噻吩(PTh)以及取代聚噻吩是导电聚合物领域中较早发现的具有环境稳定性和可加工性的材料之一。近年来,有关聚噻吩/无机物纳米复合材料的制备及其光电性能的研究倍受关注,Gebeyehu等[2]用PTh敏化纳米晶TiO2光伏电池,发现其光伏效率明显优于固态光伏电池;Jayant等[3]研究了PTh中的羧基基团的影响以及在纳米晶TiO2     

TiO2纳米微粒对聚苯胺性能的影响

纳米微粒具有量子尺寸效应, 其光、电、声及磁等方面的性能与常规材料有显著的不同, 其中以TiO2纳米微粒的电荷载体、光电活性中心、光学微腔和光电特性等特征[1,2]尤为引人注目. 导电聚合物的纳米复合材料是纳米材料的研究热点之一, 在导电材料、电流体和高密度信息存储材料等方面具有良好的应用前景[3]. 在导电聚合物中, 聚苯胺(PANI)因其具有较高的电导率, 原料便宜, 稳定性好而成为目前最有希望获得实际应用的导电聚合物[4～6]. 将纳米微粒和PANI制成复合材料, 其光电性能等与PANI相比均有所改变. 目前已相继有PANI-ZrO2, PANI-MnO2, PANI-SiO2纳米复合材料的报道[7,8], 而有关PANI-TiO2研究工作尚少见报道. 本文制备了PANI-TiO2纳米复合材料, 通过红外光谱、紫外可见光谱及透射电镜等探讨了复合材料的微结构及性能.     

导电聚合物超级电容器电极材料*

导电聚合物（聚苯胺,聚吡咯,聚噻吩）作为超级电容器电极材料的研究引起了人们广泛的兴趣,该类材料制备的超级电容器具有成本低、容量高、充放电时间短、环境友好和安全性高等优点。本文综述了近年来基于导电聚合物及其与无机材料（碳材料/金属氧化物材料）复合所得电极材料在超级电容器中的应用进展,指出具有纳米结构导电聚合物材料及导电聚合物与无机纳米材料的复合是超级电容器电极材料研究的重要发展方向。     

聚噻吩的光电化学研究

导电聚合物是由一些具有共轭π键的聚合物经化学或电化学掺杂后形成的导电率可从绝缘体延伸到导体范围的一类高分子材料。其中噻吩及其衍生物具有导电率高、环境稳定性好、成膜性好、禁带宽度小等特点,是用做光伏电池的理想材料。相继报道的有聚3-甲噻吩[1]、聚3-己基噻吩[2],聚(3-十一烷基-2,2’-并噻吩)[3]等。对于聚噻吩的光电化学性质的研究,在国际上很少见报道,国内尚未见报道,本文对聚噻吩(PTh)的光电化学性质进行了研究。1实验部分1.1仪器与试剂光电化学实验采用带石英窗口的三电极电解池,工作电极为ITO/PTh膜电极,参比电极为饱和…     

导电聚合物热电材料研究进展

随着煤、石油、天然气等不可再生化石燃料的减少和世界能源需求的不断增加,近年来导电聚合物热电材料的研究逐渐引起人们的关注。本文介绍了近年来导电聚合物热电材料的研究进展,简要分析聚合物热电材料目前存在的主要问题,并提出提高聚合物热电材料性能的初步策略。     

H_2、O_2和CO在PPRUC络合物上吸附的DV-X_α研究

中图分类号Ｏ６４１４文献标识码Ａ导电聚合物是现代科学技术理论发展中一个相当活跃的研究领域．近年来，新的导电高分子材料不断涌现，正日益朝着具有弹性、塑性、导电性、导热性、导磁性、抗蚀性、质量轻及易加工等方向发展．在众多的导电聚合物家族中，掺杂聚吡咯因...     

导电聚合物-半导体纳米颗粒自组装膜(Ⅱ)——光电化学性质

研究了层层自组装技术制备的导电聚合物SPAn／纳米硫化镉复合膜的电化学和光电化学性质。单层SPAn膜在0.1mol/L的LiClO4/乙腈电解液中有弱的阴极光电流效应，为p型半导体，化学沉淀CdS膜为n型半导体。复合膜PSS／Q－CdS仅有阳极光电流效应，为CdS的n型半导体。自组装复合膜SPAn/Q-CdS有两种不同类型的光电响应，在阴极区（导电聚合物SPAn处于未掺杂状态）具有阴极光电流，在阳极区（SPAn处于导电状态）具有阳极光电流；导电聚合物的电化学状态对复合膜的光电化学性质有决定性作用。     

导电聚合物

导电聚合物是20世纪70年代发展起来的一个研究领域，因其诱人的应用前景受到广泛重视，本文介绍了导电聚合物的发展和发展历史，综述了导电聚合物的结构和掺杂特征，制造方法，电导和电化学特性及其本征态共轭聚合物的光电特性，对导电聚合物当前的研究热点和应用前景进行了讨论。     

共轭聚合物微纳晶的制备与表征及其在场效应晶体管器件中的应用

导电聚合物是20世纪70年代发展起来的一个新兴研究领域,因其在有机光电子学中诱人的应用前景备受关注.但是,目前大部分的聚合物光电器件都是基于薄膜构筑的,大量的缺陷及无规的分子排列不利于我们对材料本征性能的评估及高性能光电器件的构筑.有机单晶具有分子长程有序、低缺陷和无晶界等优点,是用来解决这些问题的最佳选择,但是高质量聚合物单晶的获得一直都是一个挑战性的问题.本文综述了目前有关共轭聚合物微纳晶的制备、表征及其在场效应晶体管器件应用中的研究进展,并对共轭聚合物微纳晶材料与器件的发展前景和面临的一些问题做了简要的讨论.     

导电聚合物单体的光电聚合

苯胺、吡咯和噻吩等是重要的导电聚合物单体.光照可促进低聚物的形成,电化学技术可方便地实现单体的电聚合.目前,有关导电聚合物单体的光电聚合的报导还很少.本文研究征水溶液中、铂金属基底上,苯胺、吡咯和噻吩等单体的光电聚合过程.     

Isomeric Effect on Optoelectronic Properties and Photovoltaic Performance of Anthraquinone-Core Perylene Diimide (PDI) and Helical PDI dimers

Isomerism heavily influences the optoelectronic properties and self-assembly behavior of compounds and subsequently affects their device performance. Herein, two pairs of isomeric perylene diimide (PDI) dimers, PDI and PDI2, were designed and synthesized. The electron-deficient 9,10-anthraquinone group was employed as the bridge, and thus, the resultant dimers exhibited an acceptor–acceptor–acceptor (A-A-A) structure. To determine the isomeric effects on the optoelectronic properties and photovoltaic performance of these dimers, their absorptivity, luminescence, and redox behavior were studied. Bulk heterojunction organic solar cells based on these four dimers were fabricated and measured. The two PDI dimers exhibited clear differences in photovoltaic performance, whereas the two PDI2 analogues showed similar power conversion efficiencies (PCEs). The PCEs of the two PDI2 dimers are much higher than those of the PDI dimers. These results illustrate that the isomeric effect of PDI dimers is much larger than that of PDI2 dimers on the device performance, and proper expansion of conjugation could improve the device performance.     

Amphiphilic perylenetretracarboxyl diimide dimer and its application in field effect transistor

A novel perylene diimide (PDI) derivative with typical amphiphilic character, 2, was designed and prepared. The spectroscopic studies on this compound in solution revealed the face-to-face dimeric configuration and effective pi-pi interaction between the two perylene rings. This amphiphilic PDI derivative was fabricated into highly ordered films by Langmuir-Blodgett (LB) technique and fabricated into an organic field effect transistor (OFET), which shows carrier mobility around 0.05 cm(2) V(-1) s(-1) and current modulation of 10(3). This OFET performance is much better than that of monomeric PDI 1 and can be attributed to the unique face-to-face structure of 2, which promotes the interactions between neighboring PDI ring in LB film as indicated by the pi-A isotherms and UV-vis absorption.     

Perylene-3,4,9,10-tetracarboxylic acid diimides: synthesis, physical properties, and use in organic electronics

Perylene-3,4,9,10-tetracarboxylic acid diimides (perylene diimides, PDIs) have been used as industrial pigments for many years. More recently, new applications for PDI derivatives have emerged in areas including organic photovoltaic devices and field-effect transistors. This Perspective discusses the synthesis and physical properties of PDI derivatives and their applications in organic electronics.     

Recent development of perylene diimide-based small molecular non-fullerene acceptors in organic solar cells

This review summarizes the recent progress of perylene diimide (PDI) derivatives used as the acceptor materials in non-fullerene organic solar cells. The resulting structure-property correlations and design strategies of this type of acceptors are discussed and commented, which will help to constructing high-performance PDI-based acceptor materials in the future. The problems at present and the effort direction are also pointed out in this review.     

Single-wall carbon nanotube-containing cathode interfacial materials for high performance organic solar cells

Water/alcohol soluble cathode interfacial materials(CIMs)are playing important roles in optoelectronic devices such as organic light emitting diodes,perovskite solar cells and organic solar cells(OSCs).Herein,n-doped solution-processable single-wall carbon nanotubes(SWCNTs)-containing CIMs for OSCs are developed by dispersing SWCNTs to the typical CIMs perylene diimide(PDI)derivatives PDIN and PDINO.The Raman and X-ray photoelectron spectroscopy(XPS)measurement results illustrate the ndoped behavior of SWCNTs by PDIN/PDINO in the blend CIMs.The blended and n-doped SWCNTs can tune the work function and enhance the conductivity of the PDI-derivative/SWCNT(PDI-CNT)composite CIMs,and the composite CIMs can regulate and down-shift the work function of cathode,reduce the charge recombination,improve the charge extraction rate and enhance photovoltaic performance of the OSCs.High power conversion efficiency(PCE)of 17.1%and 17.7%are obtained for the OSCs based on PM6:Y6 and ternary PM6:Y6:PC₇₁ BM respectively with the PDI-CNTcomposites CIMs.These results indicate that the ndoped SWCNT-containing composites,like other n-doped nanomaterials such as zero dimensional fullerenes and two dimensional graphenes,are excellent CIMs for OSCs and could find potential applications in other optoelectronic devices.     

Competition between singlet fission and charge separation in solution-processed blend films of 6,13-bis(triisopropylsilylethynyl)pentacene with sterically-encumbered perylene-3,4:9,10-bis(dicarboximide)s

The photophysics and morphology of thin films of N,N-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-bis(dicarboximide) (1) and the 1,7-diphenyl (2) and 1,7-bis(3,5-di-tert-butylphenyl) (3) derivatives blended with 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) were studied for their potential use as photoactive layers in organic photovoltaic (OPV) devices. Increasing the steric bulk of the 1,7-substituents of the perylene-3,4:9,10-bis(dicarboximide) (PDI) impedes aggregation in the solid state. Film characterization data using both atomic force microscopy and X-ray diffraction showed that decreasing the PDI aggregation by increasing the steric bulk in the order 1 < 2 < 3 correlates with a decrease in the density/size of crystalline TIPS-Pn domains. Transient absorption spectroscopy was performed on ~100 nm solution-processed TIPS-Pn:PDI blend films to characterize the charge separation dynamics. These results showed that selective excitation of the TIPS-Pn results in competition between ultrafast singlet fission ((1*)TIPS-Pn + TIPS-Pn → 2 (3*)TIPS-Pn) and charge transfer from (1*)TIPS-Pn to PDIs 1-3. As the blend films become more homogeneous across the series TIPS-Pn:PDI 1 → 2 → 3, charge separation becomes competitive with singlet fission. Ultrafast charge separation forms the geminate radical ion pair state (1)(TIPS-Pn(+?)-PDI(-?)) that undergoes radical pair intersystem crossing to form (3)(TIPS-Pn(+?)-PDI(-?)), which then undergoes charge recombination to yield either (3*)PDI or (3*)TIPS-Pn. Energy transfer from (3*)PDI to TIPS-Pn also yields (3*)TIPS-Pn. These results show that multiple pathways produce the (3*)TIPS-Pn state, so that OPV design strategies based on this system must utilize this triplet state for charge separation.     

Solution-processed bilayer photovoltaic devices with nematic liquid crystals

The cross-linking of polymerisable liquid crystalline semiconductors is a promising approach to solution-processable, multilayer, organic photovoltaics. Here we demonstrate an organic bilayer photovoltaic with an insoluble electron-donating layer formed by cross-linking a nematic reactive mesogen. We investigate a range of perylene diimide (PDI) materials, some of which are liquid crystalline, as the overlying electron acceptor layer. We find that carrier mobility of the acceptor materials is enhanced by liquid crystallinity and that mobility limits the performance of photovoltaic devices.     

Control of morphology in efficient photovoltaic diodes from discotic liquid crystals

We report on the role of morphology in photovoltaic diodes with blend active layers composed of perylene tetracarboxdiimide (EPPTC) and hexabenzocoronene (HBC) derivatives as electron and hole acceptors. Controlled annealing of HBC:EPPTC films while in conformal contact with a flat elastomeric stamp improves photovoltaic response, leading to an external quantum efficiency of 29.5% at 460 nm and an open-circuit voltage of 0.70 V. The improved performance is attributed in part to larger crystalline domains following annealing. The elastomeric stamp restricts the top surface of the thin film during annealing, leading to low surface roughness, while also allowing for greater vertical stratification of the components in the bulk. Blended HBC:EPPTC films also exhibit an unique optical absorption feature near 590 nm, which we attribute to an altered crystalline packing of EPPTC in the presence of HBC. The significance of the local structure at molecular heterojunctions in blended active layer photovoltaic diodes is discussed.     

Tuning the optoelectronic properties of vinylene linked perylenediimide dimer by ring annulation at the inside or outside bay positions for fullerene-free organic solar cells

Among various perylenediimide(PDI)-based small molecular non-fullerene acceptors(NFAs), PDI dimer can effectively avoid the excessive aggregation of single PDI and improve the photovoltaic performance.However, the twist of perylene core in PDI dimer will destroy the effective conjugation. Thus, ring annulation of PDI dimer is a feasible method to balance the film quality and electron transport, but the systematic study has attracted few attentions. Herein, we choose a simple vinylene linked PDI dimer,V-PDI_2, and then conduct further studies on the structure-property-performance relationship of four kinds of derived fused-PDI dimers, namely V-TDI_2, V-FDI_2, V-PDIS_2 and V-PDISe2 respectively. The former two are incorporated thianaphthene and benzofuran at the inside bay positions, and the latter two are fused thiophene and selenophene at the outside bay positions, respectively. Theoretical calculations reveal the inside-and outside-fused structures largely affect the skeleton configuration, the former two tend to be planar structure and the latter two maintain the distorted backbone. The photovoltaic characterizations show that the inside-fused PDI dimers offer high open circuit voltage(V_(OC)), while the outside-fused PDI dimers afford large short-circuit current density(J_(SC)). This variation tendency results from the reasonably tunable energy levels, light absorption, molecular crystallinity and film morphology. As a result,PBDB-T:V-PDISe2 device exhibits the highest power conversion efficiency(PCE) of 6.51%, and PBDB-T:VFDI_2 device realizes the highest V_(OC) of 1.00 V. This contribution indicates that annulation of PDI dimers in outside or inside bay regions is a feasible method to modulate the properties of PDI-based non-fullerene acceptors.     

基于苝二酰亚胺类非富勒烯受体共混体系凝聚态结构调控

非富勒烯太阳能电池具有给受体能级可调、吸收范围宽及可溶液加工等优势,已经成为太阳能电池领域发展趋势。在高性能材料开发及器件结构优化的推动下,能量转换效率已经突破11%。其中,苝二酰亚胺(PDI)类分子价格低廉且具有良好的稳定性及较高的电子迁移率,已经发展成为重要的非富勒烯受体材料。然而,PDI类材料刚性稠环结构使得分子间具有强烈的π-π相互作用(受体-受体分子间及给体-受体分子间),导致共混体系相分离尺寸可控性差,给受体分子间共混程度难于调控,从而发生严重的成对以及非成对电荷复合。本文从分子间作用力入手(溶剂-溶质、给体-受体分子间作用力)详述了非富勒烯共混体系相分离结构、相区尺寸及共混相含量调节的相关原理及方法。研究表明基于PDI共混体系,固-液相分离及分子扩散能力是决定相分离结构的本质因素,通过调控给受体比例及热退火温度实现了孤岛及互穿网络结构的构筑。同时,通过平衡受体分子间π-π作用及给受体间电荷转移,实现了低相容性及高相容性共混体系相区尺寸的可控调节。在此基础上,利用添加剂手段通过调节溶剂与溶质分子间的溶度参数差值,实现了薄膜内共混相的可控调节,并针对具有不同相容性共混体系给出了添加剂的选择原则。