主链含有非共轭结构的聚芴类蓝光聚合物的合成与性能研究

通过Suzuki偶合反应合成出了主链中含有非共轭烷氧基组分(-O-CH2-CH2-CH2-CH2-O-)的聚芴类衍生物聚- 2,7-(9,9-二辛基芴)-co-4,4’-丁氧基二苯(PFP)和聚-2,7-(9,9-二辛基芴)-co-4,4’-丁氧基二苯-co-N-苯基-4,4’-二苯胺(PFTP11)并通过相同的条件合成出主链由芴和三苯胺交替相连的聚合物聚-2,7-(9,9-二辛基芴)-co-N-苯基-4,4’-二苯胺(PFTPA)作为参比材料. 通过1H NMR和FT-IR分析对这些聚合物的化学结构进行了表征. 这三种聚合物在常用的有机溶剂中具有很好的溶解性, 可通过溶液加工的方式制备聚合物薄膜. 这些聚合物均具有较高的热分解温度(＞400 ℃), 聚合物PFP具有较高的玻璃化转变温度(～130 ℃)而PFTP11和PFTPA则未出现明显的玻璃化转变过程. 通过对聚合物的吸收特性进行测试得知它们具有较大的光学带宽(2.89～3.29 eV). 所有聚合物在固体薄膜状态下均发射出蓝色荧光, PFP, PFTP11和PFTPA的最大PL发射分别位于425, 437和440 nm. 通过对其电化学性能进行测试可知由于三苯胺基团的引入聚合物的HOMO能级明显提高, 这意味着聚合物的空穴传输能力得到了有效的改善.     

芴与噻吩发光共聚物的合成及其电致发光性能

采用Suzuki偶合方法合成出了一系列新型的 9,9 二辛基芴 (DOF)和噻吩 (Th)的共聚物 .其中 ,DOF与Th的投料比 (摩尔比 )分别为 95∶5 (PTF5 )、90∶1 0 (PTF1 0 )、85∶1 5 (PTF1 5 )、70∶3 0 (PTF3 0 )、5 0∶5 0 (PTF5 0 ) .所有的聚合物均可溶于常用的有机溶剂 ,如THF,CHCl3等 ,其分子量在 60 0 0～ 5 3 0 0 0之间 .当在聚芴主链中引入噻吩后 ,其发光波长发生了红移 ,最大发光波长由PTF5时的 490nm红移到PTF5 0时的 5 41nm .随着聚芴主链中噻吩含量的增加 ,最大电致发光和光致发光效率都逐渐降低 由这些聚合物所制得的器件 ,最大电致发光效率为PTF5和PTF1 0的 0 45 %.由此表明 ,在聚芴主链中引入少量的低带隙单体噻吩可以调节聚芴的发光颜色及发光效率     

吡啶-芴类电荧光聚合物的光谱特性

用Suzuiki聚合反应将二溴代吡啶 (2 ,5 、2 ,6 、3,5 取代 )与芴共聚 ,合成了不同主链结构的吡啶 芴共聚物 .研究结果表明 ,将吡啶基引人聚芴主链可以调节共聚物的发光颜色 .间位吡啶基引入聚芴主链 ,使聚合物的能级加宽 ,PL、EL光谱发生蓝移 ;对位吡啶基则使光谱红移 .间位吡啶基 (3,5 Py、2 ,6 Py)引入聚芴主链 ,可提高聚合物的色纯度 .共聚物中 3,5 Py含量为 4 0mol%时 ,可得到较纯的蓝光 .     

三苯胺-芴类共聚物的合成及发光性能

在主链上嵌入三苯胺基团来改善聚芴的空穴传输能力、平衡载流子的注入是目前改善聚芴材料发光效率的一种好方法。本文用Suzuki缩聚法合成了芴-三苯胺类共聚物。实验结果表明．在聚芴主链上引入少量的TPA(10％～20％)时．不仅提高了EL效率．而且可以改善光谱的色纯度。TPA含量为20％时,共聚物的EL效率为1．28％。     

9,9-二辛基芴的电化学聚合

在三氟化硼乙醚(BFEE)中, 9,9-二辛基芴可以直接阳极氧化制备高质量聚(9,9-二辛基芴)膜, 其电导率为1×10^－2 S/cm. 9,9-二辛基芴在BFEE中的起始氧化电位为1.25 V vs. SCE, 低于单体在0.1 mol/L Bu₄NBF₄的乙腈溶液体系中的起始氧化电位(1.52 V vs. SCE). BFEE中获得的聚(9,9-二辛基芴)膜具有良好的电化学性质. 聚合物部分溶于氯仿、四氢呋喃、二甲基亚砜等极性溶剂. FTIR和¹H NMR表明聚合反应主要发生在2,7位. 荧光光谱表明聚合物是一种良好的蓝色荧光物质.     

聚芴基苯并唑类共聚物的合成和光物理性能

通过溶液缩聚法合成了一系列不同组分的无规共聚物--聚对苯撑苯并二噁唑-co-聚(9,9-二辛基芴苯并二噁唑)(PBO-co-PBOF).利用X射线衍射、紫外-可见光吸收光谱、光致荧光光谱研究了不同组分和结构变化对聚合物形态和光物理性能的影响.结果表明:聚合物主链上辛基芴基团的引入使聚合物结构从晶态转变为非晶态.共聚物分...     

绿色单峰发光聚(9,9-二烯丙基芴)的合成及其发光机制

为了得到绿色单峰发光的聚合物材料, 我们设计并合成了9位取代的二烯丙基芴单体, 在NiCl₂的催化下, 合成了可溶的聚芴衍生物, 聚(9,9-二烯丙基芴)(PAF). 较短的烯丙基链既可以增加聚芴的溶解度, 双键的存在又有利于聚芴发生分子间聚集而得到绿光发射的有机电致发光器件(OLED). PAF在溶液和薄膜状态下的荧光峰分别位于403和456 nm的蓝光区域, 而其器件ITO/PEDOT:PSS/PAF/LiF/Al(其中, ITO为氧化铟锡, PEDOT为聚(3,4-乙撑二氧噻吩), PSS为聚苯乙烯磺酸盐)的电致发光峰却红移至绿光区域(532 nm), 得到绿色单峰发光. 紫外吸收光谱、荧光发射光谱、红外光谱以及原子力显微镜(AFM)图像的结果证明, 造成PAF电致发绿光的机制为聚合物分子间聚集.     

一种基于三苯胺类共轭聚合物荧光信号开启的汞离子检测方法

通过Suzuki反应合成出主链中含9,9-二(4-二苯胺基苯基)-3,6-芴的蓝光共轭聚合物—聚[2,7-(9,9-二辛基芴)-co-3,6-(9,9-二三苯胺基芴)] (36PFT).36PFT可特异地与I-相互作用,并淬灭36PFT的荧光.当I-的浓度为0.24 mmol/L时,36PFT的荧光淬灭程度可达95％,...     

芴-苯并噻二唑-苯胺类共聚物的合成与发光性能

用Suzuki缩聚反应分别将窄带隙单元-苯并噻二唑-二苯胺(DPABT)和苯并噻二唑-三苯胺(TPABT)引入聚芴主链,合成了共聚物PF-DPABT和PF-TPABT,并比较了共聚物的发光性能.随着窄带隙单元含量的增加,其特征发射逐渐增强,说明发生了从聚合物主体单元到窄带隙单元有效的能量转移.两种共聚物在低窄带隙单元含量(1mol%)下的电致发光光谱仅出现窄带隙单元的特征发射,PF-DPABT共聚物为650～680nm之间的饱和红光,而PF-TPABT共聚物为590～610nm之间的橙红光,聚芴主体单元的发射被完全淬灭,说明与光致发光过程相比,电致发光过程中的能量转移更完全.基于共聚物PF-DPABT-1及PF-TPABT-5器件的最大外量子效率分别为1.3%和2.0%,器件结构为ITO/PEDOT:PSS/polymer/Ba/Al,是一类有希望的红光材料.     

烷基芴与三苯胺取代-3,6-芴共聚物的合成及其性能

用Suzuki偶联反应制备了一系列新型的9,9-二辛基-2,7-芴(DOF)与9,9-二(4-二苯胺基苯基)-3,6-芴(36FT)的共聚物. 所有的聚合物均可溶于常见的有机溶剂(如THF, CHCl3和甲苯等), 分子量在47000~189000之间. 电化学研究结果表明, 所有聚合物的HOMO能级都高于均聚烷基芴, 并且随着36FT含量的增加, HOMO值逐渐上升. 以该类聚合物为发光层制作了结构为ITO/PEDOT/PVK/polymer/Ba/Al的器件, 获得了稳定的蓝光发射, 其中以36PFT10为发光层的器件获得了0.52%的最大外量子效率.     

超薄层在白色有机电致发光器件中的应用

以DCJTB为掺杂剂, 以BCP为空穴阻挡层, 研究了两种结构的有机电致发光器件ITO/NPB/BCP/Alq3:DCJTB/Alq3/Al(结构A)和ITO/NPB/BCP/Alq3/Alq3:DCJTB/Alq3/Al(结构B)的电致发光光谱. 实验结果显示, 在结构A器件的电致发光光谱中, 绿光的相对发光强度较弱,增加Alq3层的厚度对绿光的相对发光强度的影响也很小; 而在结构B器件的电致发光光谱中, BCP层与掺杂层(Alq3:DCJTB)之间的Alq3薄层对绿光的相对发光强度影响显著, 用很薄的Alq3层就可以得到强的绿光发射. 进一步改变器件结构, 利用有机超薄层就可以得到稳定的白光器件ITO/NPB(50 nm)/BCP(3 nm)/Alq3(3 nm)/Alq3:DCJTB(1%(w))(5 nm)/Alq3(7 nm)/Al. 随着电压的增加(14-18 V), 该器件的色坐标基本保持在(0.33, 0.37)处不动; 在432 mA·cm-2的电流密度下, 该器件的发光亮度可达11521 cd·m-2.     

带烷氧基的苯基蒎烯吡啶铱配合物在聚合物电致发光器件中的应用研究

采用旋涂法将一组带烷氧基的苯基蒎烯吡啶铱(Ⅲ)配合物(Ir(RO-pppy)₃)磷光材料掺杂到PVK中,制作出了聚合物电致发光器件:ITO/PE-DOT:PSS(40 nm)/PVK_0.7:PBD_0.3:(x%.)Ir-complex(80 nm)/CsF(1.5 nm)/Mg:Ag(200 nm).实验结果表明,带有长烷氧基链配体的铱(Ⅲ)配合物能表现出更好的器件行为,当掺杂浓度为3.2%时,器件的最高发光效率达19.9 cd/A(7.8 lm/W,9.1V),CIE为(0.20,0.56);器件最大亮度为15700 cd/m²(8.4V).通过对这组铱(Ⅲ)配合物的光物理行为及电化学性能的研究,考察了主体材料与配合物之间的能级配置以及能量转移的机理.     

多芳胺取代均三嗪的合成及其光电性能的研究

设计合成了一个新的带有三支链的均三嗪衍生物分子: 2,4,6-三[4-(N,N-二对甲苯基)-苯胺乙基]均三嗪(TBTN); 用1H NMR, 13C NMR, IR, MS (MALDI-TOF)和元素分析确认了化合物的结构. 研究了该化合物的紫外吸收光谱、荧光光谱、电致发光光谱等性能, 用TBTN组装发光器件, 实验结果显示TBTN为发光层时, 该器件能发出稳定白光. 器件结构为ITO/2-TNATA (30 nm)/NPB (20 nm)/TBTN (30 nm)/Alq3 (30 nm)/LiF (0.5 nm)/Al, 在电压为15 V获得最大亮度是1523 cd/m2, 在驱动电压范围内CIE(国际照明委员会)坐标稳定并在白色等能区内.     

A purely organic D-π-A-π-D emitter with thermally activated delayed fluorescence and room temperature phosphorescence for near-white OLED

A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF) and room temperature phosphorescence(RTP) was designed and synthesized by utilizing the benzophenone as an acceptor and the N-phenyl-2-napthylamine as a donor moiety.It exhibits considerable TADF character in doped PMMA film and room temperature phosphorescence with a long lifetime of 74 ms at466 nm in solid state.The devices with the configuration of ITO/Mo_2 O_3(4 nm)/mCP(30 nm)/mCP:x wt%NP2 BP/TmTyPB(60 nm)/LiF(1.5 nm)/AI(100 nm) were prepared by vacuum evaporation to explore their electroluminescent performance.Intere stingly,the non-doped device has obtained near-white emission with a fluorescence emission peak at 475 nm and a phosphore scence emission peak at 563 nm having the CIE coordinate of(0.23,0.32) and the maximum external quantum efficiency of 1.09%.     

Aggregation-enhanced emission and efficient electroluminescence of conjugated polymers containing tetraphenylethene units

Tetraphenylethene (TPE) is a popular luminogen characterized by aggregation-induced emission and has been widely used to construct solid-state emissive materials. In this work, two thermally stable polymers (P1 and P2) consisting of TPE conjugated to the 2,7-positions of fluorene and carbazole, respectively, are synthesized and characterized. Both polymers are weakly fluorescent in solutions but show greatly enhanced emission as the aggregate formation, presenting an aggregation-enhanced emission feature. Two kinds of polymer light-emitting diodes are fabricated utilizing P1 and P2 as emitters (EML) (device I: ITO/PEDOT:PSS (45 nm)/PVK:EML (1:1 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag; device II: ITO/PEDOT:PSS (45 nm)/ PVK:OXD-7:EML (3:1:3 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag). The device II of P2 shows the best performances, affording a maximum luminance of 6500 cd/m 2 and a high peak efficiency of 2.11 cd/A.     

Deep‐red light‐emitting phosphorescent dendrimer encapsulated tris‐[2‐benzo[b]thiophen‐2‐yl‐pyridyl] iridium (III) core for light‐emitting device applications

New deep‐red light‐emitting phosphorescent dendrimers with hole‐transporting carbazole dendrons were synthesized by reacting tris(2‐benzo[b]thiophen‐2‐yl‐pyridyl) iridium (III) complex with carbazolyl dendrons by DCC‐catalyzed esterification. The resulting first‐, second‐, and third‐generation dendrimers were found to be highly efficient as solution‐processable emitting materials and for use in host‐free electrophosphorescent light‐emitting diodes. We fabricated a host‐free dendrimer EL device with configuration ITO/PEDOT:PSS (40 nm)/dendrimer (55 nm)/BCP (10 nm)/Alq₃ (40 nm)/LiF (1 nm)/Al (100 nm) and characterized the device performance. The multilayered devices showed luminance of 561 cd/m² at 383.4 mA/cm² (12 V) for 15 , 1302 cd/m² at 321.3 mA/cm² (14 V) for 16 , and 422 cd/m² at 94.4 mA/cm² (18 V) for 17 . The third‐generation dendrimer, 17 (η_ext = 6.12% at 7.5 V), showed the highest external quantum efficiency (EQE) with an increase in the density of the light‐harvesting carbazole dendron. Three dendrimers exhibited considerably pure deep‐red emission with CIE 1931 (Commission International de L'Eclairage) chromaticity coordinates of x = 0.70, y = 0.30. The CIE coordinates remained very stable with the current density. The integration of rigid hole‐transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution‐processable materials for dendrimer light‐emitting diode (DLED) applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7517–7533, 2008     

Synthesis and characterization of blue light-emitting poly(aryl ether)s containing pyrimidine-incorporated oligofluorene pendants with bipolar feature

Novel blue light-emitting poly(aryl ether)s comprising of bipolar oligofluorene pendants as chromophores have been designed and synthesized,in which pyrimidine and arylamine moieties are utilized as the electron acceptor and electron donor,respectively.Through varying π bridge length from monofluorene to bifluorene and end-cappers from hydrogen to carbazole and diphenylamine,the emission color of the resulting polymers covers from deep blue to greenish blue,and their HOMO and LUMO levels can be modulated to facilitate charge injection to improve the device performance.Polymer lightemitting diodes(PLEDs) are fabricated with the device structure of ITO/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid)(PEDOT:PSS)(50 nm)/polymer(80 nm)/Ca(10 nm)/Al(200 nm).Among these polymers,P2Cz5F-Py with bifluorene bridge and carbazole end-capper shows excellent trade-off between the efficiency and emission wavelength,having a peak luminous efficiency as high as 1.26 cd/A and Commission Internationale de L’Eclairage(CIE) coordinates of(0.17,0.17).     

基于蓝黄磷光二元互补色的高效聚合物白光器件

研究了基于互补色的高效聚合物白光器件,双色材料包括蓝绿光材料双(4,6-二氟苯基吡啶-N,C2)吡啶甲酰合铱(Firpic)和黄光材料三[3-(2,6-二甲基苯氧基)-6-(2-噻吩基)-哒嗪]铱(Fs-1),器件结构为ITO/PEDOT(40 nm)/PVK:OXD-7:Firpic:Fs-1(80 nm)/Ba(4 nm)/Al(120 nm).当发光层材料PVK∶OXD-7∶Firpic∶Fs-1质量比为63∶27∶10∶0.25时,用溶液加工方法得到高效白光器件,此时CIE色坐标为(0.30,0.39),最大电流效率为10.8 cd.A-1,亮度可达到4200 cd.m-2.在此基础上,引入水溶性电子注入材料聚[9,9-二(3′-N,N-二甲基胺基丙基-2,7-芴-2,7-交-(9,9-二辛基芴)](PFN)修饰阴极界面,使载流子注入和传输更平衡,当阴极为PFN(20 nm)/Al(120 nm)时,电流效率获得显著改善,达到13.1 cd.A-1,此时电流密度为4.9 mA.cm-2,亮度可达到6096 cd.m-2,白光器件的色坐标为(0.33,0.39),同时发光光谱稳定.另外通过电致发光(EL)、光致发光(PL)光谱及能级结构图分析了载流子俘获和能量转移在发光中的作用.     

Optimization of high-performance blue organic light-emitting diodes containing tetraphenylsilane molecular glass materials

Molecular glass material (4-(5-(4-(diphenylamino)phenyl)-2-oxadiazolyl)phenyl)triphenylsilane (Ph(3)Si(PhTPAOXD)) was used as the blue light-emitting material in the fabrication of high-performance organic light-emitting diodes (OLEDs). In the optimization of performance, five types of OLEDs were constructed from Ph(3)Si(PhTPAOXD): device I, ITO/NPB/Ph(3)Si(PhTPAOXD)/Alq(3)/Mg:Ag, where NPB and Alq(3) are 1,4-bis(1-naphylphenylamino)biphenyl and tris(8-hydroxyquinoline)aluminum, respectively; device II, ITO/NPB/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag, where TPBI is 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene; device III, ITO/Ph(2)Si(Ph(NPA)(2))(2)/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag, where Ph(2)Si(Ph(NPA)(2))(2) is bis(3,5-bis(1-naphylphenylamino)phenyl)-diphenylsilane, a newly synthesized tetraphenylsilane-containing triarylamine as hole-transporting material; device IV, ITO/Ph(2)Si(Ph(NPA)(2))(2)/NPB/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag; device V, ITO/CuPc/NPB /Ph(3)Si(PhTPAOXD)/Alq(3)/LiF/Al, where CuPc is Cu(II) phthalocyanine. Device performances, including blue color purity, electroluminescence (EL) intensity, current density, and efficiency, vary drastically by changing the device thickness (100-600 A of the light-emitting layer) and materials for hole-transporting layer (NPB and/or Ph(2)Si(Ph(NPA)(2))(2)) or electron-transporting material (Alq(3) or TPBI). One of the superior OLEDs is device IV, showing maximum EL near 19 000 cd/m(2) with relatively low current density of 674 mA/cm(2) (or near 3000 cd/m(2) at 100 mA/cm(2)) and high external quantum efficiency of 2.4% (1.1 lm/W or 3.1 cd/A). The device possesses good blue color purity with EL emission maximum (lambda(max)(EL)) at 460 nm, corresponding to (0.16, 0.18) of blue color chromaticity on CIE coordinates. In addition, the device is reasonably stable and sustains heating over 100 degrees C with no loss of luminance on the basis of the annealing data for device V. Formation of the exciplex at the interface of NPB and Ph(3)Si(PhTPAOXD) layers is verified by EL and photoluminescence (PL) spectra studies on the devices with a combination of different charge transporting materials. The EL due to the exciplex (lambda(max)(EL) at 490-510 nm) can be properly avoided by using a 200 A layer of Ph(3)Si(PhTPAOXD) in device I, which limits the charge-recombination zone away from the interface area.     

A pure blue light emitting binaphthyl derivative：Synthesis and properties

A binaphthyl derivative with pyrene on 3 and 3＇ positions was synthesized and characterized via Suzuki coupling reaction. Emission maximum in solution was located at 390 nm with a quantum efficiency of 68% by taking 9,10-diphenyl anthracene as reference,while it is shifted to 450 nm with FWHM of 104 nm resulting from aggregation state in solid film.Glass transition temperature（Tg）and decomposition temperature were measured to be 184 and 447℃,respectively,by DSC and TGA.Unlike its photoluminescence spectrum,electroluminescent spectrum peaked at about 460 nm and shows a FWHM of 69 nm corresponding to a pure blue emission.The turn-on voltage,luminance and efficiency maximum were 5 V,2953 cd/m^2 and 1.37cd/A with CIE color coordinate of（0.16,0.15）,in the device structure of ITO/NPB（40nm）/PY-BN-PY（15nm）/BPhen（40nm）/Mg：Ag.