两亲性卟啉-紫精化合物LB膜的结构及光电性质研究

本文制备了两亲性卟啉-紫精化合物的LB膜材料, 用π-A等温曲线、吸收光谱、小角和低角X射线衍射以及扫描隧道电镜(STM)等方法研究了LB膜的结构。结果表明, LB膜内分子排列是二维有序的超晶格结构, 卟啉环在基片上的排列呈"站立"状态。单个分子占有面积为1.15nm^2, 单层高度为2.35nm, 相邻裂间的距离为1.07nm。这种规则有序的两亲性卟啉-紫精化合物呈现出良好的光量子收率和光电响应特性。     

8-羟基喹啉两亲配合物的LB膜及其电致发光器件研究

制备了两亲配体N-十六烷基-8-羟基-2-喹啉甲酰胺(HL)十个配合物的LB膜。采用π-A等温线和小角X射线衍射等方法研究了这些LB膜的性质和结构。两亲配合物的单分子占有面积为(1.25±0.06)nm^2和(0.75±0.06)nm^2,分别对应于两亲分子中两个喹啉环平躺和环与环之间以一定的角度倾斜于气/水界面。LB膜内分子排列是二维有序的超晶格结构,双层高度(5.0±0.1)nm;LB膜具有导电各向异性,其平面和垂直直流电导率分别为10^-^5S.m^-^1和10^-^9S.m^-^1;LB膜的高荧光性质使之可以用作为电致发光器件的发光材料。以LaL~2(H~2O)~4Cl的LB膜为发光层的单层电致发光器件的驱动电压为9V,发光亮度330cd/m^2,为黄绿色发光。     

导电聚合物有序超薄膜的合成及其作为有机电致发光器件空穴注入层

采用修饰多层LB膜的方法制备了导电聚合物聚-3,4-乙烯二氧噻吩/二十烷酸(PEDOT:AA)复合层状有序膜, 构筑了一种导电聚合物镶嵌的多层有序膜结构. 将这种导电聚合物有序薄膜沉积于ITO电极表面, 将其作为有机电致发光二极管(OLED)的空穴注入层, 并研究了ITO/(PEDOT:AA)/MEH-PPV/Al器件的性能. 研究结果表明, 与采用聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸(PEDOT:PSS)自组装膜和旋涂膜作为空穴注入层的ITO/(PEDOT:PSS)/MEH-PPV/Al器件相比, 器件的发光效率增加, 起亮电压降低. 我们认为这是由于PEDOT:AA薄膜提供了一种有序层状结构后, 减小了ITO与MEH-PPV间的接触势垒, 改善了空穴载流子注入效率. 进一步的研究表明, 由于PEDOT:AA多层膜间靠较弱的亲水、疏水作用结合, 这种导电多层有序膜的热稳定性与普通LB膜相似, 在较高温度下发生从层状有序态到无序态的变化, 这是导致OLED器件性能发生劣化的主要原因.     

有机超晶格的制备与结构表征

在常温、常压下利用LB膜技术制备了磺化酞菁铜-脂肪酸有机超晶格,利用红外偏振光谱、紫外偏振光谱及小角X射线衍射技术对其结构进行了表征.利用光学模拟法对X射线衍射峰位进行的计算机拟合结果与实验值一致.     

5,10,15,20-四-(4-N,N,N-二甲基十六烷基氨基苯基)卟啉LB膜结构的研究

研究了两亲性卟啉5,10,15,20-四-(4-N,N,N-二甲基十六烷基氨基苯基)卟啉(TDMC₁₆PP)在气/液界面上的成膜性能,制备了其多层LB膜。用UV-Vis吸收光谱、荧光光谱、偏振UV-Vis吸收光谱和小角X射线衍射对LB膜进行了测试表征。结果表明:两亲性卟啉TDMC₁₆PP具有良好的成膜性能,其LB膜性质稳定,有较好的结构均匀性和周期性。在LB膜内,脂肪链并不是直立的,卟啉大环平面与基片平面成42.5°排列。     

一个对称萘酞菁的LB膜及其二阶非线性光学性质的研究

用水平提拉法制备了四叔丁基萘酞菁锌的LB膜。利用表面压-面积曲线、紫外-可见吸收光谱、小角X-射线衍射等表征了LB膜的结构,结果表明该化合物可以形成较高质量的具有很好层状结构的多层LB膜,在膜中分子大环平面垂直于基片平面并且以分子平面并不完全重合的H-聚集体存在。采用透射SHG方法测量了相应LB膜的二阶非线性光学性质,结果显示在实验条件下该化合物LB膜的宏观二阶非线性系数以及分子超极化率分别为X     

有序纳米金颗粒的多层组装

采用LB技术组装了一种三维有序的由十八胺修饰的纳米金颗粒多层结构.这是一种新的组装纳米颗粒三维有序聚集体的方法.为了扩大这种方法的适用范围,在组装过程中,将有机小分子1-苯基-5-巯基四氮唑引进结构,形成了新的纳米金颗粒多层聚集体.这两种多层膜经透射电子显微镜和小角X射线衍射测量证明构成多层膜的单层膜上的纳米金颗粒是有序的,并且颗粒在层与层之间的排列也是有序的.     

磷脂酸Langmuir-Blodgett膜分子结构的原子力显微术研究——分子排列有序性,分子间氢键作用,超分子结构以及晶格结构转变

利用原子力显微镜(AFM)研究了二棕榈酰磷脂酸(DPPA)的单层,双层和三层Langmuir-Blodgett膜的分子排列结构,发现相邻的(2～6个)DPPA分子的极性头磷酸基团通过分子间氢键形成局域超分子结构.分子分辨的AFM图象表明,DP-PA LB膜中分子排列具有长程的取向和位置有序.DPPA分子的晶格排列随着LB膜层数的增加由单层和双层的六方晶格转变成三层的正交(四方)晶格.探讨了不同的pH下的DPPA极性头磷酸基团的分子间氢键作用及其对膜分子有序排列以及云母基片对DPPALB膜中分子排列的晶格结构的影响.     

壳层悬挂β-环糊精单元的两亲性超支化聚合物的分子包合与识别行为

采用紫外分光光度法研究了两种壳层悬挂β-环糊精单元的两亲性超支化聚合物在缓冲溶液(25 ℃, pH=11)中的分子包合与识别行为. 结果表明, 两种聚合物具有来自环糊精单元和两亲性超支化聚合物的双重包合能力, 可分别与水溶性染料分子酚酞(PP)、甲基橙(MO)、有机小分子对硝基苯酚(p-NP)等3种客体分子发生单客体包合效应, 而且其包合能力强于单一的环糊精或两亲性超支化聚合物; 通过客体分子PP和MO证实了这两种聚合物还具有双重识别能力, 可以与PP和MO发生双客体包合效应.     

非两亲性四硫代富瓦烯导电LB膜的研究

近年来，利用LB技术制备电活性的有机超薄膜受到广泛的关注．导电LB膜的膜材料主要是含有受体化合物7，7’，8，8’-四氰基二亚甲基苯醌（TCNQ）的电荷转移复合物[1~3]以及给体分子[4，5]，特别是四硫代富瓦烯（TTF）衍生物[6~8]．尽管LB膜多由带长链的两亲性分子组装而成，但是对非两亲性TTF衍生物LB膜的研究[9~11]结果表明，引入长链烷基并非制备TTF类电荷转移复合物LB膜的先决条件．该结果极大地拓展了LB膜材料的研究范围．本文报道非两亲性TTF衍生物与花生酸混合导电LB膜的制备、结构表征与导电性能研究．1实验部分利用亚磷…     

On the Complementary Photoluminescent and Electroluminescent Images of Poly(phenylenevinylene)‐Based Light‐Emitting Diodes with a Thin Active Layer

A clear complementary relationship between photoluminescent (PL) and electroluminescent (EL) images was observed for organic light‐emitting diodes (OLEDs) based on poly(phenylenevinylene) (PPV) and dye‐doped PPV. So‐called ‘black spots' (dark circular regions observed on the active area of running OLEDs) become bright ones, when the photoluminescence of the same area is excited. A very small thickness of the active layer (ca. 10 nm) was the crucial point to observe this anticorrelation between EL and PL. A substantial increase of the PL yield (‘anti‐burning' effect) was observed after strong light exposure (ca. 10 mJ/cm²) of the polymer covered by an aluminium layer. The same light exposure without aluminium protection resulted in complete photobleaching of the polymer. The presence of a thin insulating layer between the polymer and aluminium was proposed to be responsible for these effects. This layer prevents electron injection and PL quenching due to exciton dissociation at the metal‐polymer interface. The former effect leads to black spots in the EL image, the latter one gives rise to bright spots on the PL image situated on the same places. The intermediate layer can be also induced by light exposure. A very efficient energy transfer from the polymer to the dye and to the J‐aggregates of the dye was demonstrated in PPV/dye composite films.     

CHARACTERIZATION AND LUMINESCENCE PROPERTIES OF THE DYE-DOPED POLYMER LANGMUIR-BLODGETT FILMS*

1,1,4,4-Tetraphenyl-1,3-butadiene (TPB) was successfully introduced into the polymer multilayerfilms by means of Langmuir-Blodgett (LB) technique. Results of UV-VIS spectra and X-ray diffractionshowed that the uniform films had a layer structure similar to the superlattice of organic multiple quantumwells. The electroluminescence (EL) devices fabricated from the doped polymer LB films emitted blue light.Compared with the casting films, the photoluminescence (PL) and EL spectra showed that the exciton energyshifts to higher and the half-width of the emission peak becomes narrower due to exciton confinement effect.     

Electroluminescence and Photoluminescence of Conjugated Polymer Films Prepared by Plasma Enhanced Chemical Vapor Deposition of Naphthalene

Polymer light-emitting devices were fabricated utilizing plasma polymerized thin films as emissive layers. These conjugated polymer films were prepared by RF plasma enhanced chemical vapor deposition using naphthalene as monomer. The effect of different applied powers on the chemical structure and optical properties of the conjugated polymers was investigated. Fourier transform infrared (FTIR) and Raman spectroscopies confirmed that a conjugated polymer film with a 3-D cross-linked network was developed. By increasing the power, products tended to form as highly cross-linked polymer films. The fabricated devices showed broadband Electroluminescence (EL) emission peaks with center at 535–550 nm. Photoluminescence (PL) spectra of plasma polymers showed different excimeric emissions, resulted from crosslinked architecture. As the plasma power increased, the optical properties showed two different domains; up to 200 W, EL, PL and UV–Vis spectra red-shifted and broadened significantly. At higher powers, a reverse behavior was observed. Also, the relation between the film structure and plasma species was investigated using optical emission spectroscopy.     

Luminescence of monolayer thin films of the fully conjugated rigid‐rod polymer poly(p‐phenylenebenzobisthiazole)

Poly(p‐phenylenebenzobisthiazole) (PBT) is a heterocyclic, aromatic rigid‐rod polymer with a fully conjugated backbone and excellent dimensional, thermo‐oxidative, and solvent stabilities. A PBT polymer with an intrinsic viscosity of 18.0 dL/g was dissolved in methanesulfonic acid or Lewis acid. The PBT solution was spin‐coated and doctor‐bladed for freestanding films or onto an indium tin oxide (ITO) substrate. The acid was removed via coagulation. Scanning electron microscopy determined that the resultant film thicknesses were about 340 and 60 nm for PBT freestanding films and films on the ITO substrate, respectively. X‐ray scattering demonstrated that the freestanding films were in‐plane isotropic without long‐range order. The freestanding films were excited with a He‐Cd laser at 325 nm for photoluminescence (PL) response. PL spectra showed a distinct intensity maximum at 580 nm, regardless of the film‐forming conditions. After the films cooled to 67 K, the PL maximum shifted to 566 nm with enhanced intensity. Aluminum was evaporated onto the monolayer PBT thin film on the ITO substrate as an electron injector for electroluminescence (EL) response. Diodic electric behavior was observed for all monolayer PBT EL devices for the first time. A threshold voltage as low as 4 V was achieved for the monolayer EL devices. In addition, PBT EL spectra were tunable, with a maximum intensity at 570 nm at a bias voltage of 4.5 V changing to 496 nm at 7.5 V (i.e., a blueshift) with greatly increased intensity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1760–1767, 2002     

The Electroluminescence Characterization of Poly(p-phenyleneethynylene)——The π-conjugated Backbone Interrupted by a Butylene Unit

IntroductionSince the firstreport in1 990 of the electro- lu-minescence of the conjugated polymers in the filmof poly(p- phenylenevinylene) sandwiched betweenan anode and a cathode of appropriate work func-tions[1] ,enormous efforts have been devoted to thesynthesis of light emitting polymers[2— 4 ] .Owing toconjugated polymers′ photoluminescence and elec-troluminescence having been found out,their im-portant properties,polymer processability,bandgap tunability and mechanical flexibility mak…     

Luminescence properties of PPV derivatives carrying anthracene pendent groups

Photo- (PL) and electroluminescence (EL) properties of three different PPV derivatives carrying the 9,10-diphenylanthracene units are compared. One (polymer 1 ) of the polymers contains the 9,10-diphenylanthracene structure as an integral part of the main chain, but the other two have it as the pendent group attached to the main chain through either oxyethyleneoxy (polymer 2 ) or oxyhexamethyleneoxy (polymer 3 ) spacer. Polymers 1 and 2 exhibit very similar PL and EL spectra that are more or less of superimposed feature of the spectra from the backbones and the anthracene pendents. In contrast, polymer 3 shows an EL spectrum that is completely different from its PL spectrum. Whereas the PL spectrum of polymer 3 appears to be a combination of the spectra from the main chain and the pendents, as for polymer 1 and 2 , the EL spectrum of polymer 3 , however, looks as if the lights were emitted only from the backbone. This difference is explained in terms of excited state electronic interactions between the main chain and the pendents.     

Photophysics,electrochemical properties,and electroluminescence of poly(p‐phenylenevinylene) derivatives with 1,3,5‐triphenylbenzene or 2,4,6‐triphenylpyridine segments along the backbone

The steady‐state and time‐resolved photoluminescence (PL), electrochemical behavior, and electroluminescence (EL) of didodecyloxy poly(p‐phenylenevinylene)‐based polymers that contained along the backbone structure 1,3,5‐triphenylbenzene (PC) or 2,4,6‐triphenylpyridine (PN) were studied. An intensive green PL broad‐band emission with maxima at 516 and 527 nm was observed from thin films of PC and PN polymers, respectively, redshifted in comparison with the PL emission spectra measured in tetrahydrofuran solutions. The PL decay dynamics revealed the existence of more than one excited species, and the decay curves were best described by three‐term exponential functions with a dominant lifetime of about 1 ns. The results of time‐resolved PL and steady‐state PL studies indicated excimer or aggregate formation. Both polymers oxidized irreversibly. A quasireversible reduction was observed in the PN polymer, whereas the PC polymer reduced irreversibly. For PC, slightly higher values of the ionization potential (E_IP) and electron affinity (E_A) were found (E_IP = 5.52 eV, E_A = 2.85 eV) than those for PN (E_IP = 5.37 eV, E_A = 2.77 eV). Light‐emitting devices with indium tin oxide hole‐injecting and aluminum electron‐injecting electrodes were prepared and studied. They emitted green light, and their EL spectra were similar to those of PL thin films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 524–533, 2006     

Azo dye doped polymer films for nonlinear optical applications

Azo dye doped polymer films were prepared on glass substrates using spin-coating technique. FTIR, UV-Vis spectra and PL measurements were recorded to characterize the structure of the metanil yellow doped PVA films. Surface morphology and thickness of the films were studied using AFM and FESEM. The magnitude of both real and imaginary parts of third-order nonlinear susceptibility χ3 of metanil yellow were determined by the Z-scan technique. The nonlinear refractive index n2 and the nonlinear absorption coefficient β of the azo dye doped polymer films were calculated respectively. The real part of the third-order susceptibility χ3 is much larger than its imaginary part indicating that the third-order optical response of the metanil yellow doped PVA films is dominated by the optical nonlinear refractive behavior.     

Metal induced photoluminescence quenching of a phenylene vinylene oligomer and its recovery

Metal/polymer interfaces play an important role in polymeric light emitting diodes (LEDs). In typical organic light-emitting devices, metallic electrodes are used to inject charged carriers into the organic electroluminescent (EL) medium. However, what other effects the metals have on the organic medium is not well known. In this work, we report severe photoluminescence (PL) quenching of organic thin films comprising of one of the most useful materials, namely 1,4-bis[4-(3,5-di-tert-butylstyryl)styryl]benzene (4PV), upon sub-monolayer deposition of Al, Ag, and Ca in an ultra high vacuum environment. The severity of the luminescence quenching may greatly affect the EL device performance. Gap states at the Ca/4PV interface are shown to be responsible for the PL quenching. The oxidation of Ca resulted in the removal of the gap states and the recovery of the quenched PL.     

Blue luminescence induced by confinement in self-assembled films

The fabrication and characterization by means of photoluminescence (PL), UV-vis absorption, electro-luminescence (EL) and X-ray reflectivity of multilayer heterostructures consisting of alternate layers of conjugated and non-conjugated polymers have been studied. The heterostructures are prepared by the layer-by-layer self-assembly technique, using two types of polyelectrolytes. The first are precursors of conjugated polymers such as poly(phenylenevinylene) (PPV) and other poly(arylenevinylene) polymers, and the second are non-conjugated polymers such as poly(styrene-4-sulfonate) (SPS), polyacrylic acid (PAA) and poly(allylamine hydrochloride) (PAH). The heterostructures consist of a repeated sequence of bilayers (layer pair) or multilayers, where the conjugated polymer is formed by heat treatment under vacuum. The thickness of each bilayer or multilayer was controlled by changing the non-conjugated polymer layer. Most importantly, we have found that the PL and EL spectral emissions can be ‘tuned’ by a proper ‘design’ of the heterostructure. Particularly, heterostructures in which the bilayer thickness is rather small and the electroluminescent layers are practically in contact show a blue shift upon decreasing the thickness of the assembly for ultrathin assemblies. In contrast, for assemblies where the electroluminescent layers are well separated by one or several non-conjugated layers (polyelectrolyte spacers), the emission is in the blue and independent of the assembly thickness (number of bilayers). We interpret the results as being due to confinement effects. Using this assembly technique, we were able to fabricate light emitting diodes (LEDs) which emit in the blue region.