烷基取代聚对亚苯基亚乙烯基衍生物的合成和性质研究

设计了一种合成烷基取代聚对苯撑乙烯 (PPV)衍生物的新方法 ,合成了一种新的烷基取代PPV 聚(2 甲基 5 十二烷基对苯撑乙烯 ) ,并用NMR、IR、GPC、元素分析等方法对化合物进行了表征与鉴定 .同时 ,测试了化合物的热学性质、紫外可见吸收和光致荧光性质 .发现化合物的玻璃化温度和第一分解温度随着共轭程度的增加而升高 ;化合物的THF稀溶液的光致荧光相对量子产率随共轭程度的降低而增加     

噻吩衍生物的合成及其光学性能研究

以3-溴噻吩为原料,通过格氏试剂卤锂交换,在过渡金属催化下双环侨联、烷基取代,合成一种液态状双烷基-二噻吩衍生物材料,正丁基锂与三溴噻吩投料比为2:1时收率最高,达80%以上。通过紫外-可见吸收光谱和荧光光谱对其光线发射、吸收及理论计算做了系统性研究,循环伏安(CV)实验对分子内电荷转移情况进行了测试。结果表明双烷基噻吩衍生物的紫外吸收与3,3-双噻吩相比表现出较宽的光谱吸收范围优势,荧光光学能隙值及量子产率均优于3,3-双噻吩,推测衍生物中噻吩邻位增加的烷基侧链作为有效供电子基团,与主环体的Π电子体系共轭发生了明显的电子离域现象,使得双烷基噻吩衍生物具有较好的紫外-可见吸收和荧光发射响应。双烷基噻吩衍生物在不同非质子溶剂中出现随溶剂极性增大发生的吸收及发射波长红移现象,推测化合物分子与不同极性溶剂产生了相互作用,且在特定光源激发后分子内平面共轭结构产生了不同程度的偶极矩变化。最后利用伏安特性曲线验证了双烷基噻吩衍生物良好的光反应活性和导电优势,为光电材料进一步研究提供了理论基础。     

基于环戊二烯酮结构的新型交替共聚物的合成及性能

以3,4-乙撑二氧噻吩(EDOT)为电子给体单元、烷基链取代的四苯基环戊二烯酮分子为电子受体单元,采用Stille偶联法合成了一种新型的低能带隙交替共聚物(DPPD)。利用核磁共振(NMR)、紫外-可见光谱(UV-Vis)、凝胶渗透色谱(GPC)、循环伏安(CV)、热重分析(TGA)、示差量热分析(DSC)等对共聚物进行了表征。结果表明:共聚物具有良好的溶解性和热稳定性,热分解温度为376.6℃,数均分子量为1.45×104,分子量分布为1.13,光学能带隙约为1.55 eV,500~750 nm有较宽的吸收。以共聚物DPPD和富勒烯C60衍生物[6,6]-苯基-C61丁酸甲酯(PC60BM)制备的本体异质结器件开路电压为0.63 V,短路电流为0.45 mA/cm2,填充因子为0.28,能量转换效率为0.08%。     

基于方酸菁类小分子给体与富勒烯受体材料的有机光伏电池研究进展

方酸菁类小分子材料具有合成路线简单、吸收系数高、能带隙可调、可见-近红外区吸收强烈的性质以及光、热稳定性高的特点,被认为是一类非常有应用前景的有机光伏电池材料.其作为给体材料,结合富勒烯受体材料的有机光伏电池能量转化效率已经超过了8%.综述了近年来基于方酸菁类小分子给体材料和富勒烯受体材料的有机光伏电池的研究进展,系统分析了方酸菁类小分子的分子结构、薄膜形貌和分子聚集等对器件光伏性能的影响.为方酸菁类小分子材料在有机光伏电池方面的应用拓宽了思路,并对以后的研究提出了展望.     

基于蒽/芘分子封端的芴-芳胺衍生物的可溶液加工的蓝光材料的合成与光电性质

合成了两类分别基于芘和蒽封端的芴-芳胺衍生物（FAn,FPy）的新型可溶液加工蓝色发光分子,两种材料均溶于常规的有机溶剂,并且可以旋涂成膜. 通过紫外-可见光谱和荧光光谱对其在溶液中和固态薄膜下的光学性能进行了表征,发现这两类分子在固态下发射峰分别位于449和465 nm,属于蓝色发光材料. 并通过循环伏安法表征了其电化学性能,计算得出FAn和FPy的最高占据分子轨道（HOMO）能级分别为-5.37 和-5.36eV. 结果表明N-己基二苯胺的引入有效阻止了分子在固态下的平面堆积,抑制了长波发射,并且提高了分子HOMO能级,改善了空穴注入能力. 差示扫描量热法（DSC）和热重分析（TGA）测试表明这两类化合物均显示出良好的热稳定性,其中FAn的玻璃化转变温度和热分解温度分别达到了207和439 ℃. 良好的性能使得这两类材料成为一种潜在的可溶液加工的蓝光材料.     

非富勒烯聚合物太阳电池研究进展

综述了以p-型共轭聚合物为给体、n-型有机半导体为受体的非富勒烯聚合物太阳电池光伏材料最新研究进展,包括n-型共轭聚合物和可溶液加工小分子n-型有机半导体(n-OS)受体光伏材料,以及与之匹配的p-型共轭聚合物给体光伏材料.介绍的n-型共轭聚合物受体光伏材料包括基于苝酰亚胺(BDI)、萘酰亚胺(NDI)以及新型硼氮键连受体单元的D-A共聚物受体光伏材料,目前基于聚合物给体(J51)和聚合物受体(N2200)的全聚合物太阳电池的能量转换效率最高达到8.26%.n-OS小分子受体光伏材料包括基于BDI和NDI单元的有机分子、基于稠环中心给体单元的A-D-A型窄带隙有机小分子受体材料等.给体光伏材料包括基于齐聚噻吩和苯并二噻吩(BDT)给体单元的D-A共聚物,重点介绍与窄带隙A-D-A结构小分子受体吸收互补的、基于噻吩取代BDT单元的中间带隙二维共轭聚合物给体光伏材料.使用中间带隙的p-型共轭聚合物为给体、窄带隙A-D-A结构有机小分子为受体的非富勒烯聚合物太阳电池能量转换效率已经突破12%,展示了光明的前景.最后对非富勒烯聚合物太阳电池将来的发展进行了展望.     

基于蒽/芘分子封端的芴-芳胺衍生物的可溶液加工的蓝光材料的合成与光电性质（英文）

合成了两类分别基于芘和蒽封端的芴-芳胺衍生物(FAn,FPy)的新型可溶液加工蓝色发光分子,两种材料均溶于常规的有机溶剂,并且可以旋涂成膜.通过紫外-可见光谱和荧光光谱对其在溶液中和固态薄膜下的光学性能进行了表征,发现这两类分子在固态下发射峰分别位于449和465 nm,属于蓝色发光材料.并通过循环伏安法表征了其电化学性能,计算得出FAn和FPy的最高占据分子轨道(HOMO)能级分别为-5.37和-5.36eV.结果表明N-己基二苯胺的引入有效阻止了分子在固态下的平面堆积,抑制了长波发射,并且提高了分子HOMO能级,改善了空穴注入能力.差示扫描量热法(DSC)和热重分析(TGA)测试表明这两类化合物均显示出良好的热稳定性,其中FAn的玻璃化转变温度和热分解温度分别达到了207和439℃.良好的性能使得这两类材料成为一种潜在的可溶液加工的蓝光材料.     

苯基取代聚苯撑乙烯的合成及其电致发光性能

聚苯撑乙烯(PPV)类聚合物是优异的发光材料, 有望作为全色显示中三基色的材料之一得到应用. 我们采用2-溴-1,4-亚二甲苯二乙酯为原料, 合成了商品名为Supper Yellow PPV (SY PPV)的苯基取代PPV. 中间体、单体和聚合物的结构都通过核磁共振、元素分析进行了表征. SY PPV的吸收峰在434 nm, 吸收边在510 nm, 带隙2.44 eV. 光致发光峰值和电致发光峰值分别在516和552 nm. SY PPV的器件性能为: 启动电压为2.4 V, 最大亮度大于49000 cd·m^-2, 最大流明效率为21 cd·A^-1, 显著优于采用老方法合成SY PPV的最大流明效率(16-18 cd·A^-1).     

带不同推电子基团二聚苯撑乙烯的电子结构与发光性能

用Wittig路线合成了一系列带不同推电子取代基的二聚苯撑乙烯,用紫外光谱和循环伏安方法测定其电子结构,并用量子化学计算方法对齐聚物的电子能级进行模拟.讨论了吸收光谱、发射光谱与生色团的电子结构的关系.     

一种新型低带隙共轭聚合物的合成及其光学性质

在钯催化剂作用下, 通过4,7-二(5-溴-2-噻吩基)[2,1,3]苯并噻二唑与2,5-二乙炔基-3-辛基噻吩的偶联反应, 合成了一种新的共轭高分子聚4,7-二(2-噻吩基)苯并噻二唑-3-辛基噻吩二炔(PTE-DTBT). 通过紫外可见吸收光谱及荧光光谱对其光学性质进行了研究. 紫外-可见吸收谱结果表明, PTE-DTBT的固体膜光学带隙为1.71 eV; 电化学测试其带隙为1.88 eV. TiO₂/PTE-DTBT共混固体膜的荧光发射谱结果表明电子供体PTE-DTBT分子与电子受体TiO₂分子间存在有效的电子转移.     

具有聚集诱导发光效应的咔唑基三苯乙烯衍生物单体及聚合物

合成了一类新的咔唑基三苯乙烯衍生物单体及其聚合物.利用示差扫描量热法(DSC)、热重分析法(TGA)、紫外可见分光光度法和荧光分光光度法等对单体和聚合物的性能进行了初步的表征.实验结果表明,该单体和聚合物具有较高的玻璃化转变温度(Tg),分别为210℃和229℃;单体和聚合物均具有很高的热稳定性,热失重5%的温度分别为466℃和467℃;单体具有明显的聚集诱导发光性能(AIE),而聚合物则具有聚集诱导增强发光性能(AIEE);所合成的单体和聚合物有望在OLED器件以及化学传感器上得到应用.     

Optical properties of ZnO and ZnO:In nanorods assembled by sol-gel method

Self-assembled zinc oxide (ZnO) and indium-doping zinc oxide (ZnO:In) nanorod thin films were synthesized on quartz substrates without catalyst in aqueous solution by sol-gel method. The samples were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM), Raman-scattering spectroscopy, room-temperature photoluminescence (PL) spectra, and temperature-dependent PL spectra measurements. XRD and Raman spectra illustrated that there were no single In2O3 phase in ZnO lattice after indium doping. The PL spectra of ZnO showed a strong UV emission band located at 394 nm and a very weak visible emission associated with deep-level defects. Indium incorporation induced the shift of optical band gap, quenching of the near-band-edge photoluminescence and enhanced LO mode multiphonon resonant Raman scattering in ZnO crystals at different temperatures. Abnormal temperature dependence of UV emission integrated intensity of ZnO and ZnO:In samples is observed. The local state emission peak of ZnO:In samples at 3.37 eV is observed in low-temperature PL spectra. The near-band-edge emission peak at room temperature was a mixture of excitons and impurity-related transitions for both of two samples.     

Competition between the charge transfer state and the singlet states of donor or acceptor limiting the efficiency in polymer:fullerene solar cells

We study the appearance and energy of the charge transfer (CT) state using measurements of electroluminescence (EL) and photoluminescence (PL) in blend films of high-performance polymers with fullerene acceptors. EL spectroscopy provides a direct probe of the energy of the interfacial states without the need to rely on the LUMO and HOMO energies as estimated in pristine materials. For each polymer, we use different fullerenes with varying LUMO levels as electron acceptors, in order to vary the energy of the CT state relative to the blend with [6,6]-phenyl C61-butyric acid methyl ester (PCBM). As the energy of the CT state emission approaches the absorption onset of the blend component with the smaller optical bandgap, E(opt,min) ≡ min{E(opt,donor); E(opt,acceptor)}, we observe a transition in the EL spectrum from CT emission to singlet emission from the component with the smaller bandgap. The appearance of component singlet emission coincides with reduced photocurrent and fill factor. We conclude that the open circuit voltage V(OC) is limited by the smaller bandgap of the two blend components. From the losses of the studied materials, we derive an empirical limit for the open circuit voltage: V(OC) ? E(opt,min)/e - (0.66 ± 0.08)eV.     

Synthesis and photoluminescence stability of non-conjugated polymers based on fluorene and benzoxazole

A kind of non-conjugated blue luminescent polymer based on fluorene and benzoxazole was synthesized via solution condensation polymerization from 2,2-bis(3-amino-4-hydroxyphenyl)-propane and 2,7-dicarboxyl-9,9-dioctyl-fluorene and was characterized with H NMR, FT-IR, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), UV-vis absorption and photoluminescence (PL) spectroscopy. The polymer displayed the maximum photoluminescence emission peak at 415 nm and showed high PL spectroscopic stability. The green-to-blue emission intensity ratio I_Green/I_Blue is only 0.073 even after thermal annealing at 150 °C for 30 h. After being exposed to UV light for 30 min, no bathochromic emission or obvious crosslink is observed. The common phenomenon of greenish blue emission of fluorene-based polymer around 525 nm has been effectively restrained in this polymer by introducing the isopropylidene group into the backbone of polymer.     

纳米银与基体P(AMPS-MMA)的相互作用研究

在无引发剂和还原剂的条件下超声辐射双原位合成出纳米银/2-丙烯酰氨基-2-甲基丙磺酸与甲基丙烯酸甲酯共聚物[P(AMPS-MMA)]复合物.TEM表明,纳米银粒子的粒径5~15nm,均匀地分散在聚合物基体中;UV-Vis表明,超声时间影响纳米银的粒径大小及粒径分布;FT-IR、UV-Vis和荧光光谱表明纳米银与基体P(AMPS-MMA)之间存在一定的化学作用力;XPS证明了纳米银与基体P(AMPS-MMA)的作用力为纳米银与聚合物中酯基氧原子之间通过配位作用形成的化学作用力.     

Charge carrier formation in polythiophene/fullerene blend films studied by transient absorption spectroscopy

We report herein a comparison of the photophysics of a series of polythiophenes with ionization potentials ranging from 4.8 to 5.6 eV as pristine films and when blended with 5 wt % 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]C61 (PCBM). Three polymers are observed to give amorphous films, attributed to a nonplanar geometry of their backbone while the other five polymers, including poly(3-hexylthiophene), give more crystalline films. Optical excitation of the pristine films of the amorphous polymers is observed by transient absorption spectroscopy to give rise to polymer triplet formation. For the more crystalline pristine polymers, no triplet formation is observed, but rather a short-lived (approximately 100 ns), broad photoinduced absorption feature assigned to polymer polarons. For all polymers, the addition of 5 wt % PCBM resulted in 70-90% quenching of polymer photoluminescence (PL), indicative of efficient quenching of polythiophene excitons. Remarkably, despite this efficient exciton quenching, the yield of dissociated polymer+ and PCBM- polarons, assayed by the appearance of a long-lived, power-law decay phase assigned to bimolecular recombination of these polarons, was observed to vary by over 2 orders of magnitude depending upon the polymer employed. In addition to this power-law decay phase, the blend films exhibited short-lived decays assigned, for the amorphous polymers, to neutral triplet states generated by geminate recombination of bound radical pairs and, for the more crystalline polymers, to the direct observation of the geminate recombination of these bound radical pairs to ground. These observations are discussed in terms of a two-step kinetic model for charge generation in polythiophene/PCBM blend films analogous to that reported to explain the observation of exciplex-like emission in poly(p-phenylenevinylene)-based blend films. Remarkably, we find an excellent correlation between the free energy difference for charge separation (deltaG(CS)rel) and yield of the long-lived charge generation, with efficient charge generation requiring a much larger deltaG(CS)rel than that required to achieve efficient PL quenching. We suggest that this observation is consistent with a model where the excess thermal energy of the initially formed polaron pairs is necessary to overcome their Coulombic binding energy. This observation has important implications for synthetic strategies to optimize organic solar cell performance, as it implies that, at least devices based on polythiophene/PCBM blend films, a large deltaG(CS)rel (or LUMO level offset) is required to achieve efficient charge dissociation.     

Ultrafast excited state dynamics of a bithiophene-isoindigo copolymer obtained by direct arylation polycondensation and its application in indium tin oxide-free solar cells

A low band gap copolymer, P2TI (E_g = 1.6.eV), with bithiophene as donor and isoindigo as acceptor units is designed and synthesized by the direct arylation polycondensation (DAP) method. Absorbance of the polymer spans from 300 to 780 nm. It exhibits an absorption coefficient (ε) of 96 L/g cm in solution at its maxima. A HOMO level of −5.42 eV and LUMO level of −3.72 eV is measured by square wave voltammetry. ITO-free solar cells fabricated using a P2TI :PCBM71 bulk heterojunction shows a moderate efficiency of 1.02% with a high open circuit voltage of 0.81 V. An intramolecular charge transfer state is found in the relaxation of P2TI in solution, which is generated with a time constant of 2 ps as measured by femtosecond-transient absorption spectroscopy. Charge carriers were generated in <250 fs in P2TI: PCBM71 films. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1475–1483     

水相中CdTe纳米晶的制备及其光学性质

用不同稳定剂(巯基乙酸(TGA)、巯基丙酸(MPA)、L-半胱氨酸(L-Cys)、3-巯基-1,2-丙二醇(TG))在水相中制备了CdTe纳米晶, 并用透射电子显微镜(TEM)、X射线光电子能谱(XPS)和X射线粉末衍射(XRD)等技术对其进行了表征. 研究了不同水相合成条件对CdTe纳米晶光学性质的影响, 结果表明, n(Cd):n(Te)、溶液pH值、回流时间以及稳定剂的性质, 对纳米晶的光学性质具有显著影响. 制得的CdTe纳米晶发射峰窄且对称(半高全宽达38 nm), 用不同稳定剂制备的纳米晶发光量子效率有所不同, 用不同的激发波长对纳米晶进行激发时, 发射峰并未表现出明显的移动.     

Synthesis, characterization and photovoltaic properties of poly(thiophenevinylene-alt-benzobisoxazole)s

Herein we report the synthesis of two solution processible, conjugated polymers containing the benzobisoxazole moiety. The polymers were characterized using (1)H NMR, UV-Vis and fluorescence spectroscopy. Thermal gravimetric analysis shows that the polymers do not exhibit significant weight loss until approximately 300 °C under nitrogen. Cyclic voltammetry shows that the polymers have reversible reduction waves with estimated LUMO levels at -3.02 and -3.10 eV relative to vacuum and optical bandgaps of 2.04-2.17 eV. Devices based on blends of the copolymers and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) exhibited modest power conversion efficiencies. Theoretical models reveal that there is poor electron delocalization along the polymer backbone, leading to poor performance. However, the energy levels of these polymers indicate that the incorporation of benzobisoxazoles into the polymer backbone is a promising strategy for the synthesis of new materials.