一种共轭聚合物单分子发色团吸收和发射特性动态演变过程的实时测量

利用频域信息重构的散焦宽场成像测量了Poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子发色团的吸收与发射特性及其动态演变过程.通过调制用于激发共轭聚合物单分子的超短脉冲对的相对相位,对单分子荧光进行傅里叶变换的频域测量,跟踪发色团吸收偶极取向变化;通过测量散焦荧光成像光斑探测发色团发射偶极取向变化.研究发现, PFO-DBT共轭聚合物单分子发色团存在吸收和发射偶极取向均保持不变、其中之一变化以及两者同时变化三种情况.这种对共轭聚合物单分子发色团吸收和发射偶极取向演化过程的实时测量可用于分析共轭聚合物构象变化及其对能量转移过程的影响.     

链构象对稀溶液中MEH-PPV的光致发光的影响

聚(2-甲氧基-5-(2’-乙基己氧基)-1,4-对苯乙炔)(MEH-PPV)在溶液中的链构象依赖于溶剂的性质,共轭聚合物的发光特性受链构象影响明显。在稀溶液中,不良溶剂含量的增加使MEH-PPV分子链更加紧缩卷曲,单个分子链内更多共轭链段发生聚集,光激发形成的链间激子增加。通过对MEH-PPV稀溶液的光谱分析,发现链间激子的形成过程依赖于激发光的能量(hv)。在激发光能量大于聚合物的最低激发能(E4)的情况下,大部分链内激子通过辐射复合发光,少部分链内激子沿分子链转移到聚集的共轭链段上形成链间激子。在hv＜Ea的情况下,单个分子链内聚集共轭链段吸收光子能量形成链问激子并复合发光。     

沉积亚单层荧光染料提高有机发光器件的发光效率

结合掺杂薄层作为发光探针层的方法和亚单层（sub-monolayer）有机发光技术，利用沉积在有机发光器件发光层中的亚单层奎丫啶酮（Quinacridone，QAD）分子作为探针，同时改变QAD层的位置，对有机发光器件中激子的形成与扩散进行了研究，器件结构为ITO/NPB(60 nm)/ Alq3(x nm)/QAD(0.05 nm)/Alq3［(60－x) nm］/LiF/Al（其中x=0，2.5，5，7.5 nm）.通过对各器件不同条件下的电致发光谱、发光强度和发光效率的对比研究，得到在x＝5 nm处引入亚单层QAD可以使QAD分子通过能量转移而获得的激子数量最多，进而可以实现高效率的发光.     

光学材料 发光材料、荧光材料

O482．31 2005032312 链构象对稀溶液中MEH-PPV的光致发光的影响=Effect of chain conformations on photoluminescence of MEH- PPV in dilute solutions[刊,中]／孔凡(南京大学物理系 江 苏,南京(210093)),欧昌刚…∥发光学报．-2004,25 (6)．-731-736 聚(2-甲氧基-5-(2'-乙基己氧基)-1,4-对苯己炔) (MEH-PPV)在溶液中的链构象依赖于溶剂的性质,共轭 聚合物的发光特性受链构象影响明显。在稀溶液中,不良 溶剂含量的增加使MEH-PPV分子链更加紧缩卷曲,单个     

利用磁致发光曲线研究Rubrene器件中激子分裂和湮没过程

为了研究Rubrene分子中激发态的能量共振和分子间π-π共轭的特性对有机磁效应的影响, 本文制备了基于不同浓度和厚度的Rubrene有机发光器件, 并在不同温度下测量了器件的电致发光磁效应(magneto-electroluminescence, MEL). 实验发现, 发光层中Rubrene的厚度和浓度均可以对器件中的MEL产生较大的影响, 室温下MEL的高场值随Rubrene层厚度的增加而增加, 并在30 nm之后逐步趋于饱和; 随着Rubrene分子的浓度和测量温度的降低, MEL高场增加的幅度逐渐减小, 甚至在低温时出现高场下降. 通过对实验曲线进行数值拟合, 认为Rubrene分子之间形成的π-π共轭结构有助于双分子相互作用的发生, 单重态激子分裂、三重态激子之间的湮没和单-三重态极化子对的系间窜越三种过程在器件中相互竞争导致了所得MEL的变化. 本工作有助于加深对有机光电子器件内部机理的认识.     

一种新型共轭聚合物发光二极管老化的拉曼光谱研究

通过显微共焦拉曼光谱 ,对一种以新型的共轭聚合物半导体材料 3,4 (2 乙基己氧基 )苯基 1,3 丙二醇酯 (poly(2 (4 Ethylhexyl) phenyl 1,4 phenylenevinylene) (P PPV) )为发光层的聚合物发光二极管(PLEDs)器件进行了老化研究 ,无论是光致发光光谱还是拉曼光谱都提供证据说明造成器件老化的原因主要是发光层的聚合物的主链结构 ,即聚合物的共轭结构被破坏 ,这对提高以P PPV作为发光层的PLEDs器件的性能提出有用信息。     

高效饱和红光聚电解质的发光及电子注入特性研究

以新型的环境友好的水/醇溶性胺基化或者季铵盐化的芴和含硫窄带隙共聚物4,7-二噻吩-2-基-2,1,3-苯并噻二唑的共轭聚电解质为发光层，以高功函数金为电极，制备了一系列高效饱和红色单层发光二极管. 对PFN-DBT10，在38.7mA/cm²下外量子效率达到0.42%，色坐标位于(0.67，0.33). 这类聚电解质解决了发光器件层间的互溶问题，以它和高功函数金组成双层复合阴极，制成了高效三基色双层发光二极管. 通过单层和双层器件结构系统地研究了这类新型聚电解质的发光特性和电子注入特性，器件效率的提高与这类聚电解质和高功函数金电极界面相互作用有关.     

掺磷光材料有机电致发光器件的能量传递

将高量子效率的磷光材料fac-tris-2-phenylpyridine iridium(III) (Ir(ppy)3)按不同的比例掺杂到具有载流子传输能力的主体材料poly(N-vinylcarbazole) (PVK)中作为发光层制备磷光电致发光器件。通过对器件发光机制的研究,发现光致发光过程中起主导作用的是Fo¨ster能量转移机制;而在电致发光过程中,器件的发光性能受Dexter能量转移和电荷陷获2种能量传递形式的影响。器件的I-V-L特性表明：Ir(ppy)3的掺杂比例为5%时,器件的光功率效率最大,能量转移最充分。     

聚苯撑苯并双噁唑的电致发光

通过光谱技术、电化学特性等对聚苯撑苯并双噁唑(PBO)的性能进行了系统研究。通过电化学分析获得该聚合物最高占有分子轨道能级(HOMO)大约为EHOMO=5.69eV,通过光谱分析计算得到最低空轨道能级(LUMO)大约为ELUMO=2.99eV。PBO的溶液光致发光在430～500nm范围,呈现明显的浓度效应;其薄膜的光致发光峰大约位于500nm。研究制作了以PBO为发光层的单层电致发光器件ITO/PBO(60nm)/Al和双层电致发光器件ITO/CuPc(25nm)/PBO(60nm)/Al,其电致发光峰位具有聚集态发光的特征。器件的发光亮度和稳定性在双层器件中获得提高,器件的发光峰位随驱动电压大小在520～555nm范围变化。     

TCTA在外电场下的双分子发光现象

制备了三苯胺化合物4,4′,4″-三(咔唑-9-基)三苯胺(TCTA)的单层器件ITO/MoO_3/TCTA/LiF/Al和TCTA/TPBi双层异质结器件ITO/NPB/TCTA/TPBi/Bphen/LiF/Al,研究了TCTA的双分子发光现象。通过测试器件的光电性能和薄膜的稳态光谱,得出以下结论:(1)单层器件的电致发光光谱有425 nm和600 nm两个发光峰。与TCTA薄膜的光致发光光谱对比,可知425 nm附近的蓝色发光峰来源于TCTA单体发光,而600 nm附近的橙色发光应为TCTA二聚体electromer的发光。蓝色和橙色发光混合,使单层器件发光颜色表现为白色,对应色坐标为(0.381,0.343)。(2)TCTA/TPBi双层异质结器件的电致发光光谱为440 nm的单峰,器件的最大发光亮度为930 cd/m~2,发光性能明显优于单层器件。结合薄膜TCTA、TPBi和TCTA/TPBi的光致发光光谱和紫外-可见光吸收光谱,可知双层器件的发光来自TCTA~+TPBi~-电致激基复合物。双层器件表现出良好的色稳定性,电压在6～11 V范围,CIE色坐标为(0.18±0.01,0.14±0.01)。     

The effects of photochemical oxidation and chain conformation on green emission of poly(9,9-dioctylfluorene)

The effects of chain conformation on the photo-oxidation and green emission of poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) has been investigated at both single-molecule and ensemble levels. Single-molecule studies reveal the conformation of PFO chains to be more globular when cast from THF than from toluene solutions. Intensity transients of the single molecules show that the elongated molecules cast from toluene have more fluctuations due to limited energy transfer along the polymer chains. The more globular chains show monotonic decays with isotropic polarization. Emission spectra of the single molecules show that photochemical oxidation leads to a reduction in the emission of the molecule with no change in the emission spectra. No green emission is ever detected for single molecules, indicating that formation of emissive ketone defects is a rare event. Ensemble studies of chains show that molecules cast from THF develop some green emission upon photodegradation, while those cast from toluene do not. The increase in green emission in the globular molecules suggests that interchain contacts improve energy transfer for emissive ketone defects in the PFO cast from THF.     

聚芴共轭聚合物在稀薄溶液中形态变化的静态光散射研究

PF8聚芴共轭高分子材料是应用于制作蓝色光激发光器件的一种有潜力功能材料, 故本文利用静态光散射技术研究了PF8聚芴共轭高分子在稀薄甲苯溶液中的形态结构变化特点。研究结果显示, PF8共轭高分子在甲苯稀薄溶液中单一分子链的持续长度与Kuhn链结长度均明显受到温度的影响。这表明在较高温度下高分子与溶剂间的相互作用力较大, 导致其呈现较伸展的虫状形态结构; 而在较低温度下高分子与溶剂间相互作用力较小, 导致其呈现收缩的结构形态。因此在较高温度状态下PF8共轭高分子应该具有比较刚硬的特征。     

Linear dipole behavior of single quantum dots encased in metal oxide semiconductor nanoparticles films

Understanding of charge/energy exchange processes and interfacial interactions that occur between quantum dots (QDs) and the metal oxides is of critical importance to these QD-based optoelectronic devices. This work reports on linear dipole behavior of single near-infrared emitting CdSeTe/ZnS core/shell QDs which are encased in indium tin oxide (ITO) semiconductor nanoparticles films. A strong polarization anisotropy in photoluminescence emission is observed by defocused wide-field imaging and polarization measurement techniques, and the average polarization degree is up to 0.45. A possible mechanism for the observation is presented in which the electrons, locating at single QD surface from ITO by electron transfer due to the equilibration of the Fermi levels, result in a significant Stark distortion of the QD electron/hole wavefunctions. The Stark distortion results in the linear polarization property of the single QDs. The investigation of linear dipole behavior for single QDs encased in ITO films would be helpful for further improving QD-based device performance.     

Imaging single quantum dots in three-dimensional photonic crystals

Performing fluorescence wide-field microscopy we have imaged single semiconductor quantum dots deep inside a 3-dimensional photonic crystal prepared from colloidal polymer beads. Exploring the emission diffraction patterns in defocused images of quantum dots we demonstrate that the direction-dependent photonic stop band imprints an anisotropy to the angular emission of a single quantum dot. Hence a single, quasi-point-like emitter is manipulated to radiate its photons only to certain well-defined directions by means of the anisotropic light propagation in photonic crystals. The experiments thus provide new routes to evaluate local, frequency selective optical properties in 3-dimensional photonic crystals employing single emitters.     

Room-temperature fluctuations in the fluorescence of a single polymer molecule

A theoretical model of light absorption and emission by a polymer molecule has been developed using recent experimental data on the room-temperature fluctuations in the fluorescence intensity of single molecules of a PPV-PPyV copolymer containing several tens of chromophores. An analysis of the experimental data based on the proposed model shows evidence of a change in the conformation of a polymer molecule in the triplet state. By applying the theory to the PPV-PPyV copolymer, it is possible to determine the rate constants of the conformation variation, the rates of the transition from the singlet to the triplet state, and the lifetime of the triplet state of the molecule. The theory also predicts some new effects which can be verified by experiment.     

Energy migration and transfer between chromophores embedded in Gaussian space

We have used a Monte Carlo method to investigate energy migration and transfer between chromophores embedded in Gaussian space. In using this method we have obtained fluorescence quantum yields, fluorescence depolarization, and the respective decay profiles of donor fluorescence. It was shown that all photophysical observables are dependent upon the number of donor and acceptor chromophores and upon the Förster radii ratio. The latter feature is particularly interesting, and it indicates the existence of correlations between donor and acceptor chromophores. It was shown that the excitation of the donor chromophore at the origin leads to different values of observables, in comparison with an excitation of a randomly selected donor chromophore. The results presented show the importance of the averaging procedures needed to be developed while dealing with specific distribution functions, as, for example, in the case of energy migration and trapping in aromatic polymers and copolymers.     

Electrochemical,thermal,and photophysical properties of novel two-photon absorption chromophores

Electrochemical, thermal, and photophysical properties of novel two- （BPODPA）, four- （BBPOPA）, and six-branch （TBPOA） triphenylamine chromophores are studied. The decomposition temperature of chro- mophores reaches 373 - 412 ℃. The electrochemical properties is explored by cyclic voltammetry. The ionization potential of chromophores is in the range of 5.14 - 5.18 eV. Excitation at 400 nm reveals emission peaks at 483 - 487 nm and the fluorescence quantum yields are 0.73 - 0.75 in CH2Cl2. Two-photon absorption （TPA） properties of chromophores are measured by nonlinear transmission method. The maximum TPA cross-section values are measured at 758 nm to be 20369 GM （1 GM=10^-50 cm^4 -s/photon） for TBPOA, 7024 GM for BBPOPA, and 1227 GM for BPODPA, respectively. When pumped with 800-nm laser irradiation, chromophores show strong two-photon excited blue-green fluorescence at 502 - 518 nm. These results provide a basis for understanding the electronic and optical properties of the conjugated multi-branch chromoohore in terms of the underlying molecular and electronic structures.     

含联二萘的PPV类共轭聚合物发蓝光材料的设计合成

利用Wittig和Wittig-Horner反应合成了四种含有联二萘和不同芳香基团的具有线性或超支化结构的发光共聚物,并对共聚物的光物理性质和电化学性质进行了研究。结果表明,这些线性共聚物都具有较高效率的蓝光发射。具有超支化结构的共聚物BN-TPPV在氯仿溶液中的荧光量子效率高达95%,在氯仿溶液和膜中的发射光谱峰值分别位于393,428nm,实现了高效率的蓝光发射。说明将联二萘生色团引入聚合物是一种实现发蓝光材料的重要途径。     

新型联苯胺基窄带隙共轭聚合物的光学及电化学性能研究

随着化石燃料的日益枯竭,人类社会对能源的需求在不断增长。为了平衡能量应用需求并提升能量使用效率,开发高效能量转换材料与电化学储能材料成为当前研究的重要课题。导电聚合物基电极材料面临着相应储能器件能量密度、功率密度、循环性能不高的挑战,需进行结构改性提高电导率、改善界面性质。鉴于共轭高分子的电子结构、光学及电化学性质由共轭链骨架结构决定,对导电共轭聚合物进行结构修饰以提升其电荷传输性能和载流子迁移率,进而设计合成新型高迁移率导电聚合物基共轭聚合物是提高相应器件特性的关键所在。已有研究大多借助复杂的结构设计来实现提升迁移率,设计合成了结构简单,有助提升电荷迁移的新型窄带隙聚联苯胺基共轭聚合物聚物。通过光谱学及电化学方法对材料结构与性能进行了表征分析。采用核磁共振氢谱、红外光谱,X射线粉末衍射对单体及聚合物进行了结构表征,通过紫外光谱、紫外可见漫反射、循环伏安、计时电位、交流阻抗对其进行了光学及电化学性能测试。结果表明,成功制得具有预期结构的共轭聚合物,所得聚合物结晶性较佳,光学带隙Eopt_g为1.85 eV,HOMO及LUMO能级分别为-5.44和-3.59 eV,前者高于,后者则低于大部分文献值,呈现可同时促进p-型和n-型掺杂的结构特性,具备增强材料容纳电荷能力的性能优势。聚合物储能特性受化学结构、晶体结构及微观形貌综合影响。改善材料微观结构特性有助于提升其电子电导率,但层状致密块体形貌特征又使其离子电导率受限。电化学性能测试结果显示,聚合物具有一定电化学活性,具有较小的电荷转移阻抗,具备基本满足使离子顺利扩散的条件,0.05 A·g-1时的放电比电容达256.6 F·g-1。研究结果表明,制得的联苯胺基窄带隙共轭聚合物在光电转换、储能及微型电子器件中有广阔的应用前景。