Influences of Branched Side Chains and Cross‐linking Network on the Solid State Structures of Oligo‐ and Poly (p‐phenyleneethynylene)s

To investigate the influences of side chains and cross‐linking network on the packing fashion and the formation of aggregates and excimers of poly(p‐phenyleneethynylene)s (PPEs) chains in the solid state, a series of cross‐linkable unsubstituted oligo (p‐phenyleneethynylene)s (OPEVs) and alkoxy‐substituted PPEs (EO‐PPEVs) with vinyl end‐groups were synthesized and characterized. By a thermal cross‐linking reaction, cross‐linked polymers were obtained. The oligomer chains in the cross‐linked polymers containing no residual vinyls are packed randomly, forming no aggregates or excimers; however, aggregates and excimers exist in the cross‐linked polymers if they contain residual vinyls. The chains of EO‐PPEVs with sterically hindered side chains form aggregates in films. The network, leading to a pronounced increase of the film photoluminescence quantum yields, can depress these aggregates. These EO‐PPEVs are fully processable and can become insoluble in normal organic solvents after thermal curing; therefore, they are favorable candidates as active layers for fabrication of high performance multilayer devices.     

Optical and Thermal Stability of Oligofluorene/Rubber Luminescent Blend

This paper proposes to obtain homogeneous and stable blends of oligo(9,9-dioctylfluorene)-co-phenylene (OF), a conjugated oligomer with strong tendency of formation of excimers in the solid state, and nitrile rubber (NBR). This rubber protection reduces the formation of polymer excimers in the films. The fluorene oligomer was synthesized via Suzuki reaction and incorporated in the nitrile rubber. The films were formed by spin coating and casting techniques on the proportions of 1, 5, 10, 20 and 50 % (w/w) of OF in the nitrile rubber (NBR). The structural, optical and thermal properties of the films were evaluated with infrared, UV–Vis, fluorescence and thermogravimetry, respectively. The nitrile rubber proved to be essential for the preparation of homogeneous and stable films, since it was not possible to obtain films with only fluorene using the above-mentioned techniques. Furthermore, luminescent properties of OF are unchanged and the excimers formation in the solid state decrease suggesting the efficiency of nitrile rubber as the matrix for making films.     

Effect of uniaxial compression on traps of excitons and charge carriers in poly(9-vinylcarbazole) films

The effect of uniaxial pressure (1 × 10⁸ Pa) on the photoluminescence spectra and thermally stimulated luminescence curves of poly(9-vinylcarbazole) has been investigated in the temperature range of 5–295 K. The thermally stimulated luminescence curve of crystalline carbazole has been measured for comparison. The high-temperature wings of the thermally stimulated luminescence curves are approximated by a Gaussian function, the half-width of which characterizes the disorder of energy states of deep structural traps. It is concluded that the pressure inhibits conformational changes of polymer chains of poly(9-vinylcarbazole), which leads to the formation of sandwich-like excimers as well as to an ordering of the spatial arrangement of the side carbazolyl groups. As a result, the concentration of “excimer-forming” centers increases, whereas the degree of disorder of energy states of deep structural traps of charge carriers is reduced by almost half and remains unchanged after the depressurization.     

共轭支链含腈基的聚对苯乙烯衍生物的合成及光谱特征

通过HECK法共聚将腈基引入聚对苯乙烯(PPV)的共轭支链,得到聚合物DiCN-PPV。通过核磁共振(¹H-NMR)、质谱(MS)、元素分析及GPC确定了组成和分子量。探索了聚合反应时间和温度对聚合物分子量及产率的影响。结果表明,该聚合物具有较高的热稳定性(T_d>247℃),在100℃反应62 h可以得到产物分子量M_n=1.76×10⁴,分散度P_d=1.9,产率50%。以紫外吸收光谱及荧光光谱分析了该聚合物溶液及其膜的基本光谱特征,表明D iCN-PPV中D-A(Donor-Acceptor)给受体的结构发生分子内的能量转移,从而导致了新的能级结构。它的荧光为红光λ_max=645 nm,是一种潜在的有机红光新材料。     

Luminescence properties of a new green emitting Eu2+-doped barium chlorosilicate phosphor

A new intense green light-emitting phosphor, the Eu²⁺-doped (BaO–BaCl₂–SiO₂) phosphor system, was synthesized at 800°C by the conventional high-temperature solid-state reaction. Its structure and luminescence properties were investigated by using thermogravimetry-differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), diffuse reflection spectra, photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The photoluminescence spectrum reveals that this phosphor can be efficiently excited by near-ultraviolet (UV) light and blue light in the wavelength region covering 280 and 480 nm, which perfectly matches the emission wavelength of near-UV light-emitting diodes (LEDs). It emits an intense green light peaking at 502 nm, which is promising to develop possible applications for white LEDs.     

Intermolecular interactions in Langmuir-Blodget films of liquid crystalline perylene derivatives

Langmuir-Blodgett (LB) films formed of some discotic liquid crystals, namely 3,4,9,10-tetra-(n-alkoxy-carbonyl)-perylenes, mixed with arachid acid have been studied. The absorption and fluorescence spectra were recorded. The results obtained have led to conclusions about formation of self-aggregates of dye molecules both in ground and excited states at the air-solid substrate interface. It was found that some fraction of J-aggregates can be created in the ground state. In the excited state, mostly excimers appear and the number of this kind of aggregates depends on the length of the alkyl chains substituted to the perylene core, as well as on the dye concentration and the number of layers in LB films.     

The Aggregation Enhanced Photoluminescence of Gold Nanorods in Aqueous Solutions

The photoluminescence (PL) properties of single gold nanorod (AuNR) under one-photon excitation (OPE) have been reported recently. In this work, the PL of AuNRs in aqueous solutions were studied with OPE of 514 or 633 nm to characterize the emissions of transverse and longitudinal surface Plasmon resonance (TSPR and LSPR) bands, because the AuNRs aqueous solution was frequently used in bio-medical applications. We found that under 514 nm OPE the TSPR emissions of four groups of AuNRs with different aspect ratios in aqueous solutions were all strong dominating the PL emission with the quantum yield (QY) of 10^?4, which is at least three orders of magnitude higher than that of single AuNR. We further found that the aggregate was the basic form of AuNRs in aqueous solution and living cells, measured by the elastic light scattering and transmission electron microscopy measurements. The Plasmon coupling particularly the TSPR coupling between the neighbored AuNRs in aggregates enhanced the PL and increased the QY, because the conjugation of the rod side to side was a main aggregate mode. Under 633 nm OPE, only LSPR emissions of AuNRs aqueous solutions occurred with the QY level of 10^?5 which is very similar to that of singe AuNR, because of the negligible LSPR coupling.     

基于Cu掺杂ZnInS和ZnCdS量子点的高显色性白光LED

利用胶体化学方法合成了发光波长可调的Cu掺杂量子点, 其波长范围可从绿光到深红光连续调节.通过将绿光ZnInS :Cu和红光ZnCdS :Cu量子点与蓝光GaN芯片相结合, 制备了高显色性的白光LED, 其流明效率为71 lm·W^-1, 色温为4 788 K, 显色指数高达94, CIE色坐标为(0.352 4, 0.365 1).通过测量Cu掺杂量子点的荧光衰减曲线, 发现不存在从绿光ZnInS :Cu到红光ZnCdS :Cu量子点的能量传递过程, 因为红光ZnCdS :Cu量子点在绿光波段没有吸收. 实验结果表明, Cu掺杂量子点有望应用于固态照明领域.     

AFM studies on formation of new phase responsible for enhanced photoluminescence in light-emitting small molecular thin films

Tris(8-hydroxyquinoline) metal complex (AlQ₃) is a widely used light-emitting material in organic light-emitting devices (OLEDs). The environmental stability is still a major problem with OLEDs and needs further improvements. In this report, we examine the optical properties of the thin films of this material and the effect of environment on it. The annealing in different ambients were done with the aim to understand the physical phenomenon involved in AlQ₃ thin films. An enhanced photoluminescence intensity is observed for the samples annealed in oxygen near 100 °C. Sudden change in roughness which may be as a consequence of change in surface morphology due to phase change and fraction of new phase is estimated by phase images taken by Atomic Force Microscopy (AFM). The enhanced photoluminescence is understood in terms of formation of a new phase.     

TBVB用作蓝光发光层的非掺杂有机电致蓝光和白光器件

利用一种来源于PPV的发蓝光的齐聚物材料2,5,2',5'-tetra(4'-biphenylenevinyl)-biphenyl(TBVB)制作非掺杂的有机电致蓝光和白光器件。蓝光器件的结构为ITO/NPB/TBVB/Alq₃/LiF/Al,其中TBVB用作发光层;白光器件的结构为ITO/NPB/TBVB/rubrene/Alq₃/LiF/Al,其中TBVB与超薄层(平均“厚度”0.05~0.20nm)的Rubrene相结合用作发光层,二者分别发蓝光和黄光。在蓝光器件中,当TBVB的厚度为30nm时,器件发出色坐标为(0.20,0.26)的蓝光,其最大亮度和效率分别达到2154cd/m²和1.62cd/A。在白光器件中,可通过调节TBVB和Rubrene的厚度实现对器件发光色度的调节。当TBVB和Rubrene的厚度分别为10,0.15nm时,器件在亮度为4000cd/m²时发光色坐标为(0.33,0.34),非常接近白光等能点,且随着电压的变化始终处于白光区。当电压为16V时该器件达到最高亮度4025cd/m²;当电压为6V时器件有最高的效率3.2cd/A。     

Photoelectric properties of a self-ordered molecular disperse structure based on a polar-dye solution in a liquid-crystal matrix

An analysis of photoluminescence spectra and nonlinear optical properties revealed the effect of polar-dye aggregates in a liquid-crystal matrix on the formation of an ordered molecular disperse structure. As the dye is aggregated in the liquid-crystal matrix, there is a certain concentration of the dye below which only second-harmonic generation occurs upon laser excitation at 1064 nm, while above this concentration, this generation occurs in combination with intense two-photon-induced photoluminescence. An applied electric field or intense ultraviolet illumination is found to change both the molecule orientation and the conditions of molecule aggregation.     

Synthesis and characterization of GaP nanochains with a twin-modulated quasi-periodic structure

GaP nanochains have been synthesized by hydrogen-assisted thermal evaporation, and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and Raman spectroscopy. GaP nanochains possess a (111) twin crystal plane-modulated quasi-periodic structure, that gives a strong green photoluminescence at 618 nm. While the Raman spectrum of the nanochains is similar to that of the GaP crystal, the intensity of the longitudinal optical (LO) peak is stronger than that of the transverse optical (TO) peak, which is supposedly related to the nanochain microstructures.     

一种基于咔唑的可溶性蓝光发光材料的合成与发光机理研究

通过SN1亲核反应机理及SUZUKI偶联反应,设计并合成了一种含有咔唑及8-苄氧基喹啉基团的有机蓝光发光材料,即N-[6-(8-苄氧基喹啉基)-己基]咔唑(CzBQ).通过紫外-可见吸收光谱和荧光光谱等测试方法对其结构及光物理性能等进行了表征.研究结果表明:CzBQ为一种蓝光有机发光材料,其光学带隙为3.02 eV,在...     

AlON:Ce3+荧光粉的制备及光谱研究

采用高温固相法合成了不同浓度Ce³⁺ 掺杂的AlON荧光粉. 通过X射线和扫描电镜分析了荧光粉的物相和显微结构, 且利用荧光光谱仪测试了AlON:Ce³⁺荧光粉的发光光谱.结果表明, 荧光粉在305 nm紫外激发下发射390 nm为中心的蓝光.温度依赖荧光谱测试发现, AlON:Ce³⁺荧光粉在150 ℃ 下发射强度能保持室温发射强度的86%.因此, 该荧光粉是大功率白光发光二极管用最佳荧光粉的候选材料之一. 关键词： 光致发光 浓度猝灭 热稳定性     

新型蓝绿色磷光配合物二(1-苯基吡唑)铱(吡啶三唑)的发光性能

利用1-苯基吡唑、吡啶三唑与水合三氯化铱反应合成了一种新型铱配合物Ir(2N)₂(PZ),研究了配合物的吸收光谱、光致发光光谱以及光致发光效率。利用该材料作为磷光客体,掺杂到高分子主体材料中制作了电致发光器件,研究了其电致发光光谱。结果表明,该配合物在228,250,328nm处存在自旋允许的¹π-π^*跃迁;荧光光谱结果显示在470nm处有较强的磷光发射;电致发光光谱与光致发光光谱相比却发生较大程度的红移。     

Comparison of the electroluminescence and its related properties of two cyclopentadiene derivatives

In order to fully understand the dependence of device electroluminescence (EL) on the chemical structure of two light-emitting materials: 1,2,3,4-tetraphenyl-1,3-cyclopentadiene (TPCP) and 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP), their properties in solution and as evaporated thin films of UV-Vis absorption, geometric structures, photoluminescence (PL), electrochemistry, glass transition temperature and EL were compared. Compared with that of TPCP, the first absorption band of PPCP shifts to the shorter wavelength region both in solution and thin film state; the photoluminescence in solution exhibits lower quantum efficiency but in thin film state has a higher intensity; the electrochemical oxidation happens at a higher potential; the solid powder exhibits higher glass transition temperature; and the electroluminescent device shows higher luminescence and efficiency. Reasons responsible for the differences were analyzed.     

Light-induced orientation of the molecules of nematic liquid crystals doped with comb-shaped polymers with different spatial distributions of chromophores

The orienting effect of light on nematic liquid crystals (NLCs) doped with comb-shaped polymers with different spatial distributions of side absorbing azobenzene fragments, i.e., a homopolymer (containing only azofragments), a block copolymer (containing additionally a block of non-absorbing fragments), and a statistical copolymer (containing randomly arranged absorbing and non-absorbing fragments) is experimentally studied. The light-induced Freedericksz transition threshold for the block copolymer is two times lower than that for the homopolymer. For NLC with statistical copolymer dopant, the first-order orientation transition with an extremely wide optical bistability region is observed.     

Syntheses and optical properties of triphenylene-containing conjugated polymers

In this paper, we report the detailed synthesis and optical properties of three new conjugated polymers containing triphenylene units in the backbone. Polymer PTPT exhibits strong folding propensity and forms foldamers in both polar and nonpolar solvents. PTPA, with two long alkyl chains attached to the bridging phenyl ring, exhibits mainly as interchain aggregates in “poor” solvents (DMSO and acetonitrile), but adopts a folding conformation in solvent mixtures with a high poor solvent content. PTPV, on the other hand, adopts a random nonfolding conformation in both polar and nonpolar solvents. The low folding propensity of PTPV is likely due to the added geometrical flexibility of the vinyl bonds. Among the three polymers, PTPV is most fluorescent with a fluorescence quantum yield as high as 0.87, suggesting its potential applications as light-emitting materials or fluorescence-based sensors. PTPT, on the other hand, with its strong folding property, may find applications as efficient charge-transporting materials.     

Structure, phase (aggregate) state, and optical properties of a new heat-resistant polymer with a nonlinear optical chromophore

A new heat-resistant copolymer (II) with a nonlinear optical chromophore in a side chain was synthesized by the etherification of side hydroxyl groups in chains of silicon-containing poly(o-hydroxyamide) (I) with 4′-{(6-chlorohexyl)methylamino}-4-nitroazobenzene (chromophore) under conditions of phase-transfer catalysis. The structure and phase (aggregate) states of copolymer II were investigated using x-ray diffraction and differential scanning calorimetry. It was shown that the substitution of chromophore molecules for up to 15% of hydrogen atoms in hydroxyl groups of amorphous copolymer I most likely leads to an independent arrangement of the chromophoric groups and the formation of crystal domains. It was established that this ordering substantially affects the stability and efficiency of the nonlinear optical properties of films prepared from copolymer II and is probably responsible for the slow decay of the second-harmonic generation signal in the sample.     

红外光谱法测定聚(乳酸-苯丙氨酸)共聚物的含量

分别以苯丙氨酸和乳酸为原料合成了3-苯甲基-2,5-吗啉二酮(PMD)与丙交酯(LA),以PMD和LA作为聚合单体经开环聚合分别得到PMD均聚物(PPMD)、丙交酯均聚物(PLA)及聚(乳酸-苯丙氨酸)共聚物。对合成的均聚物进行红外分析,确定1 671.53和870.82 cm-1处的吸收峰分别为PPMD和PLA的特征峰。根据以上两种特征吸收峰并以朗伯-比耳定律为理论依据,建立了利用红外光谱法测定聚(乳酸-苯丙氨酸)共聚物含量的方法。实验测定的标准工作曲线为y=0.055 67x+0.1091,r=0.999 3。利用该标准工作曲线定量测定了共聚物组分含量,其结果与1H NMR测定值一致,相对误差在2％以内,证明红外光谱法可方便、快捷地测定聚(乳酸-苯丙氨酸)共聚物组分含量,且适用于其他聚(乳酸-氨基酸)共聚物的含量测定,具有一定的实用性及推广性。