含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

胺烷基侧链取代三苯胺类红光聚合物的合成及性能研究

通过Suzuki偶合反应合成了一系列胺烷基侧链取代的基于三苯胺和芴的共轭聚合物聚[4-(N,N-二甲基胺丙氧基)苯-4,4′-二苯胺-9,9-二辛基芴-4,7-二噻吩-2-基-2,1,3-苯并噻二唑](PFTD), 并对其化学结构和光电性能进行了表征. 末端胺基的存在提高了此类聚合物作为发光层应用于聚合物电致发光器件的性能(采用高功函数的金属铝作为阴极时). 结构为ITO/PVK/PFTD-5(DBT摩尔分数为5%时的聚合物)/Al的器件最大电致发射峰位于647 nm, 最大外量子效率达到了1.24%.     

新型以咔唑为主链的能量转移型发光聚合物

用Suzuki偶合反应合成了一系列以咔唑为主链，与不同的芳香环和杂环化合物 共聚的新型电致发光无规共聚物．这些共聚物溶于普通的有机溶剂，发较强的荧光 ．咔唑链段为共聚物提供了很好的空穴传输和空穴注入性能．与咔唑共聚的窄能隙 单体，如蒽(ANT)、噻吩(Th)、2，1，3-苯并噻二唑(BTDZ)、2，1，3—苯并硒二唑 (BseDZ)和4，7—二噻吩—2，1，3—苯并噻二唑(DBT)在聚合物中含量小于50％时 成为陷阱中心．还观察到极为有效的分子内能量转移．由于共聚单体的能隙不同， 这些电致发光共聚物的发光范围可覆盖整个可见光谱区．研究结果表明，用咔唑作 为宽带主体，与少量低带隙单体共聚，有可能成为一种合成同时兼有优异空穴注入 特性，又能广泛调节发光颜色的新的发光聚合物体系．     

含胺烷基侧链的共轭磷光聚芴的合成、表征及其光电性能研究

通过Suzuki聚合反应合成了一种新型的含磷光单元的主链型聚芴类聚合物, 对其进行了表征分析, 并且研究了其在薄膜状态下的光学性质. 在以这种聚合物作为电致发光器件的发光层时, 用高功函数金属铝(Al)作为器件阴极时可以获得和用低功函数金属钡(Ba)作为阴极时相当的器件性能.     

以碱金属盐为阴极界面层的有机光电器件的制备及性能

以碱金属盐Li F,Na F,Cs F和Cs2CO3作为阴极界面材料,制备了高效率有机小分子电致发光二极管(SMOLEDs)、聚合物电致发光二极管(PLEDs)及聚合物太阳能电池(PSCs).在SMOLEDs和PLEDs中,Cs F作为阴极界面层的器件流明效率和功率效率最高.在以聚对苯乙烯撑(P-PPV)为发光层的PLEDs中,Cs F作为阴极界面层的器件最大流明效率可达17.85 cd/A,比Li F作为阴极界面层的器件流明效率提高近300%.在以聚(3-己基噻吩)(P3HT)∶[6,6]-苯基-C61-丁酸甲酯(PC61BM)为活性层的PSCs中,当Li F为阴极界面层时,器件功率转换效率(PCE)可达4.12%.而以Na F,Cs2CO3和Cs F为阴极界面层时,PCE分别为3.72%,3.55%和3.2%.这是因为从上述碱金属盐中分解出来的碱金属原子扩散进入器件的有机层并对有机层进行了n型掺杂,影响了器件的电流密度和效率.     

含噻吩单元的硅芴共聚物的合成及其蓝色电致发光性能

将少量(摩尔分数为1%—3％)含噻吩的窄带隙单体和宽带隙硅芴单体进行共聚, 合成了聚{9,9-二己基-3,6-硅芴-co-[2,5-二(2-甲基苯撑-4-基)-噻吩]}和聚{9,9-二己基-3,6-硅芴-co-[2,5-二(2-苯撑-4-基)-噻吩]}两类硅芴共聚物, 通过紫外-可见吸收光谱、光致发光光谱, 并制作聚合物发光二极管器件测试电致发光光谱等手段, 系统表征了两类硅芴共聚物材料的性能. 实验结果表明, 噻吩的加入形成了新的蓝色发光中心, 并且实现了从硅芴链段到含噻吩发光中心的有效能量转移. 通过增加发光中心结构的空间位阻来减小其共轭程度, 可以使聚合物的PL和EL光谱发生较大蓝移. 最终得到了效率为0.46%和色坐标(CIE)为(0.19, 0.16)的蓝光LED器件.     

聚苯乙烯负载多吡啶铂(Ⅱ)炔基络合物的合成

通过自由基共聚成功地将具有高磷光发光效率的-苯基-2,2’-二联吡啶(C^N^N)Pt(Ⅱ)苯乙炔络合物共价键合在聚苯乙烯高分子骨架上,得到了发射磷光的聚合物.实验表明,发光聚合物基本保持了多吡啶铂络合物单体的光谱性质.具有与小分子相当的光致发光效率.     

含1,1-二（4-（N,N-二甲基胺基）苯基）-2,3,4,5-四苯基噻咯的聚合物在三种阴极结构中的电致发光性能

设计合成了一种1,1-位为二（4-（N,N-二甲基胺基）苯基的新型噻咯单体,并与2,7-芴单体聚合得到六苯基噻咯单体投料量为1%、10%、20%的三种共聚物PF-N-HPS1～20.研究了这些共聚物的紫外吸收光谱、电化学性质、光致发光光谱和电致发光性能.PF-N-HPS的HOMO能级为5.25～5.58eV,呈现绿光发射.以PF-N-HPS为发光层,制作了三种聚合物发光二极管（器件结构A：ITO/PEDOT/PF-N-HPS/Al;器件结构B：ITO/PEDOT/PF-N-HPS/Ba/Al;器件结构C：ITO/PEDOT/PF-N-HPS/TPBI/Ba/Al）.其中器件结构A的电致发光效率仅为0.1～0.33cd/A,说明PF-N-HPS中的4-（N,N-二甲基胺基）苯基结构不能使单独的Al阴极实现良好的电子注入.采用了低功函金属Ba阴极的器件结构B能改善电子的注入,使电致发光效率提高到0.85～1.44cd/A.器件结构C采用TPBI（HOMO：6.2eV）作为电子传输和空穴阻挡层,促进了电子和空穴的有效复合,进一步提高了电致发光效率（4.56～7.96cd/A）,其中TPBI层将噻咯聚合物与金属阴极隔离可能减少发光层在阴极界面处的激子猝灭也起到了一定的作用,器件结构C较器件结构B还获得了更好的绿光光谱.     

含硅宽禁带聚合物的合成及其光电性能研究

采用Suzuki聚合方法合成了以菲并咪唑为侧链的4种含硅宽禁带发光聚合物,并研究了这4种聚合物的光物理、电化学性质与电致发光性能.结果表明四苯基硅基团的引入能够得到宽的带隙,侧基上菲并咪唑的引入可以实现深蓝光发射.其中,基于聚合物P1的电致发光器件最大外量子效率为0.65%,最大发光效率为0.33 cd A~(-1),色坐标为(0.163,0.099).     

一种含三苯胺链段的PPV类交替共聚物的合成、表征及性能

合成了三苯胺二醛和1-甲氧基-4-辛氧基-2,5-二甲苯双(三苯基氯化)两种单体,通过Wittig反应制得了共轭聚合物,对共轭聚合物进行了表征和性能测试.这类共轭聚合物的氯仿溶液和膜在紫外光激发下能发出强的蓝绿光,与小分子三苯胺衍生物(TPD)相比,具有相对较高的热稳定性和良好的成膜性.电化学分析表明聚合物具有很好的空穴传输能力.同时对共轭聚合物的光致发光和电致发光性能进行了研究,结果表明,此聚合物与同类聚对亚苯基亚乙烯基(PPV)型聚合物相比具有较低的驱动电压和较高的发光亮度,是一种潜在的有机高分子电致发光材料.     

Synthesis and optoelectronic properties of amino-functionalized carbazole-based conjugated polymers

A series of alcohol soluble amino-functionalized carbazole-based copolymers were synthesized via Suzuki coupling reaction.The pendent amino groups endow them high solubility in polar solvents,as well as efficient electron injection capability from high work-function metals.The relationships between the photophysical and electrochemical properties and the polymer backbone structure were systematically investigated.These alcohol-soluble carbazole-based copolymers were used as cathode interlayers between the high work-function metal Al cathode and P-PPV emissive layer in polymer light-emitting diodes with device structure of ITO/PEDOT:PSS/P-PPV/interlayer/Al.The resulting devices exhibited improved performance due to the better electron injection/transporting ability of the designed copolymers from Al cathode to the light-emitting layer.     

High-efficiency electrophosphorescent copolymers containing charged iridium complexes in the side chains

A convenient approach to novel charged Ir polymers for optoelectronic devices to achieve red emission was developed. 2-(Pyridin-2-yl)benzimidazole units grafted into the side chains of macroligands (PFCz and PFP) served as ligands for the formation of charged Ir complex pendants with 1-phenylisoquinoline (1-piq). The charged Ir polymers (PFPIrPiq and PFCzIrPiq) showed exclusive Ir(1-piq)(2){N-[2-(pyridin-2-yl)benzimidazole]hexyl}(+)BF(4)(-) (IrPiq) emission, with the peak at 595 nm. The best device performances were obtained from PFCzIrPiq4 with the device configuration of ITO/PEDOT:PSS/PFCzIrPiq4+PBD (30 wt %)/TPBI/Ba/Al (PBD: 5-(4-tert-butylphenyl)-2-(biphenyl-4-yl)-1,3,4-oxadiazole; TPBI: 1,3,5-tris-(2-N-phenylbenzimidazolyl)benzene). A maximum external quantum efficiency (EQE) of 7.3 % and a luminous efficiency (LE) of 6.9 cd A(-1) with a luminance of 138 cd m(-2) were achieved at a current density of 1.9 mA cm(-2). The efficiencies remained as high as EQE=3.4 % and LE=3.3 cd A(-1) with a luminance of 3770 cd m(-2) at a current density of 115 mA cm(-2). The single-layer devices based on charged Ir polymers also showed high efficiency with the high work-function metal Ag as cathode. The maximum external quantum efficiencies of the devices were 0.64 % and 0.66 % for PFPIrPiq2 and PFPIrPiq10, respectively. A possible mechanism of an electrochemical cell associated with its electrochemical redox pathway for single-layer devices has been proposed. The results showed that the charged Ir polymers are promising candidate materials for polymer optoelectronic devices.     

胺基功能化咔唑共轭聚合物的合成及其光电性能研究

发展了新型含有胺基的支化烷基修饰的咔唑单元,并且与芴、咔唑、苯等单元通过Suzuki偶联反应共聚得到不同主链结构的水/醇溶共轭聚合物界面修饰材料,研究了主链结构的变化对材料光物理、电化学性能的影响.所有聚合物均被用作阴极界面材料应用于器件结构为ITO/PEDOT：PSS/P-PPV/界面层/Al的聚合物发光二极管中.在相同器件制备条件下,系统比较了不同主链结构的界面修饰材料在器件中的性能,并研究了性能差异的原因.器件研究结果表明,在高功函数金属Al阴极的聚合物发光二极管中,含胺基功能化咔唑单元的水/醇溶共轭聚合物材料由于界面偶极的形成,均表现出很好的电子注入/传输性能,与之对应的器件性能得到大幅提升.     

Build-up of symmetry breaking using a titanium suboxide in bulk-heterojunction solar cells

The importance of symmetry breaking was investigated in bulk heterojunction solar cells with a conventional device structure. Artificial symmetry breaking was built up by introducing a titanium suboxide. With sufficient symmetry breaking, the influence of the cathode work-function can be diminished, thereby extracting the same level of open circuit voltage regardless of metal work-function.     

以膦酸酯聚芴作为阴极界面修饰层的高效聚合物红光电致发光器件

以膦酸酯聚芴为阴极界面修饰层, 高功函金属铝为阴极, 制备了一种高效聚合物红光电致发光器件. 通过X射线光电子能谱(XPS)的表征, 分析了经真空蒸镀沉积在膦酸酯聚芴表面的Al原子与下层的膦酸酯聚芴在有机物-金属界面处的作用情况, 结果表明, 在真空蒸镀金属Al的过程中, 在有机物-金属界面处形成了一种氧/铝复合物. 研究了这种氧/铝复合物对器件光电性能的影响, 结果表明, 氧/铝复合物的产生提高了阴极电子的注入, 使器件效率得到了很大提高. 与以Ca/Al为阴极的传统器件相比, 以膦酸酯聚芴/Al为阴极的聚合物电致发光器件的效率提高了75%, 达到7.0 cd/A.     

Conjugated polyelectrolytes and neutral polymers with poly(2,7‐carbazole) backbone: Synthesis,characterization, and photovoltaic application

Poly(2,7‐carbazole) neutral polymers (PC‐N, PC‐NOH, and PC‐P) and polyelectrolytes (PC‐NBr and PC‐SO₃Na) with hydrophilic pendant groups of ammonium, phosphonate, and sulfonate were synthesized as interlayers for cathode modifications in bulk‐heterojunction photovoltaic cells (BHJ PVCs). The absorptions of the polymers were determined by the poly(2,7‐carbazole) backbone, showing absorption peaks at ～390 nm for their solutions and films. Because of large intermolecular interactions, excimer emissions with wavelengths higher than 500 nm were found in the photoluminescence spectra of the films of the polymers, which weakened the light emissions of the polymers. PC‐N, PC‐NBr, PC‐NOH, and PC‐P possessed comparable HOMO levels of ?5.23 eV and LUMO levels of ?2.4 eV, but HOMO and LUMO levels of PC‐SO₃Na were up‐lying to ?4.91 and ?2.12 eV, respectively. PC‐N, PC‐NBr, PC‐NOH, and PC‐P were selected to construct thin interlayers in BHJ PVCs with PFO‐DBT35:PCBM = 1:4 as the active layer. Compared with traditional Al cathode, bilayer cathodes with the interlayers showed improvements of open‐circuit voltages and short‐circuit currents of the PVCs. PC‐NOH was the best for the photovoltaic performances and over 20% increase of power conversion efficiency (PCE) was achieved. The bilayer cathodes would have great potential to further elevate PCE of BHJ PVCs with other active layer materials. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Electroluminescence performances of 1,1-bis(4-(N,N-dimethylamino)phenyl)-2,3,4,5-tetraphenylsilole based polymers in three cathode architectures

A new silole monomer with two 4-(N,N-dimethylamino)phenyl substitutions on silicon atom as designed and synthesized.Three copolymers PF-N-HPS1,PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2,7-fluorene derivatives with the silole monomer at feed ratios of 1%,10%,and 20%.Their UV-vis absorption,electrochemical,photoluminescent,and electroluminescent (EL) properties were investigated.PF-N-HPS possessed HOMO levels of 5.25-5.58 eV,and showed green emissions.Using PF-N-HPS as the emissive layer,three different polymer light-emitting diodes were fabricated as device A with ITO/PEDOT/PF-N-HPS/Al,device B with ITO/PEDOT/PF-N-HPS/Ba/Al,and device C with ITO/PEDOT/PF-N-HPS/TPBI/Ba/Al.For the device A,PF-N-HPS only showed very low EL efficiency of 0.06-0.33 cd/A,indicating that the Al cathode could not inject electron efficiently to the emissive polymers containing the 4-(N,N-dimethylamino)phenyl groups.For the device B,low work function Ba supplied better electron injections,and the EL efficiency could be improved to 0.85-1.44 cd/A.TPBI with a deep HOMO level of 6.2 eV could enhance electron transport and hole blocking.Thus modified recombinations and largely elevated EL efficiency of 4.56-7.96 cd/A were achieved for the device C.The separation of the emissive layer and metal cathode with the TPBI layer may also suppress exciton quenching at the cathode interface.