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.     

Improving Efficiency of Organic Photovoltaic Cells Using PEDOT:PSS and MWCNT Nanocomposites as a Hole Conducting Layer

In this study, polymeric nanocomposites of poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) and functionalized multi-walled carbon nanotubes (MWCNTs) were spin coated on a pre-patterned ITO glass and used as a hole conducting layer in organic photovoltaic cells. The multi-layered ITO/MWCNT-PEDOT:PSS/CuPc/C60/Al devices were fabricated to investigate the current density-voltage characteristics and power conversion efficiency. The power conversion efficiency obtained from the device with a concentration of 1.0 wt% MWCNT in the PEDOT:PSS layer was increased twice as those adopted from device without MWCNT doping in the PEDOT:PSS layer and current density-voltage characteristics was also improved well with incorporation of MWCNTs.     

8-羟基喹啉镧两亲性配合物LB膜的双层电致发光器件

以具有不同层数的两亲配合物二[2-(N-十六烷基氨基甲酰基)-8-羟基喹啉]合镧[La(HQ)₂Cl]的LB膜为发光层,PBD为电子传输层,制备了双层结构的电致发光(EL)器件:ITO/LB膜/PBD/Al.器件产生黄绿色注入式发光.LB膜的层数和沉积压对器件的性能具有重要影响.在16V激发电压下,5,11和21层LB膜双层EL器件的电流密度分别为48,29和16.4mA/cm²,启亮电压阀值为7.5,8.5和9.5V.器件的亮度随电流密度和驱动电压的增加而增加.在相同偏压下,21层LB膜EL器件的亮度大于5和11层LB膜的器件.在25mN/m沉积的LB膜制备的EL器件具有较高的亮度(1219cd/m₂)和击穿电压.     

输运层厚度对双层有机器件复合发光的影响

采用ITO/PVK/Alq/Al双层电致发光(EL)结构,制备了三种载流子输运层厚度分别为30、 60、 120 nm,发光层厚度均为300 nm的有机薄膜EL器件,测试其EL谱及J-V特性曲线.根据有机EL器件中载流子的产生和输运过程导出了载流子复合几率及电子和空穴密度分布表示式,用以解释其发光强度随输运层厚度的变化关系,用一维无序结构载流子随机跃迁模型讨论输运层厚度对器件电流密度及启动电压的影响,探讨了载流子在薄膜中的输运过程,其理论与实验符合得很好.     

两亲8-氨基喹啉衍生物的空穴传输特性及LB膜电致发光器件

在过去的20年里,电致发光(EL)领域的研究显得异常活跃,EL已应用于通讯、信息、显示等许多领域,而占领这一领域的是P-N结无机半导体发光二级管,其发光效率已超过了白炽灯.但由于无机半导体很难实现大面积平面显示,加之成本较高,因此,限制了其进一步的发展[1].有机荧光材料的种类繁多,荧光量子效率高,且可以通过分子结构修饰有目的地控制其发光效率、发光颜色和电学性能[2],因而,越来越多的学术界和工业界的研究小组进入了有机电致发光研究领域[3.4].     

Organic electroluminescent device based on electropolymerized polybithiophene as the hole-transport layer

An ultrathin film of polybithiophene (PBTh), used in organic electroluminescent (EL) devices, was generated by an electrochemical method with a conducting indium tin oxide (ITO) glass as the working electrode. The light-emitting layer could be deposited directly onto the PBTh by using spin coating for fabrication of the organic EL devices. It was found that the film of PBTh as the hole-transport layer for the EL device could effectively raise the EL intensity and efficiency. The EL intensity of the ITO/PBTh/emitting layer/Al device is about 100 times as strong as that of the ITO/emitting layer/Al device at the same current density of 50 mA/cm².     

主链含电子传输型团的可溶性PPV聚合物载流子传输特性研究

合成了一种聚苯撑乙烯撑(PPV)主链上含有电子传输基团的新型结构电子聚合物(O-PPV).该低聚物的M_w=1000,T_g=197℃,可溶于氯仿和四氢呋喃.单层O-PPV器件的发光效率约为单层PPV器件的5～8倍.进一步构造了结构为空穴传输特性材料/O-PPV和O-PPV/电子传输特性材料的双层器件来研究O-PPV的载流子传输特性,实验结果表明,O-PPV是一种具有明显两性载流子传输的特性材料.     

Molecular assembled self-doped polyaniline interlayer for application in polymer light-emitting diode

Self-doped polyaniline (SPANI) ultrathin films were prepared by using a self-assembly process consisting of a self-doping monomer (o-aminobenzenesulfonic acid, SAN) and aniline (AN). SAN-AN copolymerization and film formation were simultaneously performed in aqueous solution. An immersing self-assembly method was developed to build up a SPANI nanofilm on an ITO glass, providing a hole injection layer in a double-layer electroluminescence (EL) device ITO/SPANI nanofilm//MEH-PV//Ca/Al. This device produces an orange EL as compared with a single-layer EL device of ITO//MEH-PV//Ca/Al. A double-layer device demonstrates that a SPANI film is capable of transporting holes in a polymer light-emitting diode (PLED).     

氟化吡唑啉蓝色电致发光器件的制备

自从Tang等[1]首次报道了多层有机电致发光器件以来, 人们研究了大量的新型材料[2,3], 其中较吸引人的方法是将高量子产率的荧光染料掺杂于传输层中制备电致发光器件[4～9]. 三芳基吡唑啉化合物具有较高的荧光产率和蓝色发射特性. 这些化合物具有分子内电荷传输性能, 在激发状态下分子可发生扭曲形成电子给体-受体结构[10], 因此在EL器件制备过程中既可以作为载流子传输材料, 又可以作为发光材料来应用. 虽然吡唑啉类化合物在固态下具有空穴传输特性[11], 也有较高的荧光产率, 但它们的玻璃转化转变温度较低, 在制备EL器件时, 如单独作为传输层或发射层时, 该类材料易于结晶, 从而使得器件的性能快速衰减. 如果将它们分散于聚合物等主体中, 就会避免重结晶问题. 我们在三苯基吡唑啉中引入强吸电子基团CF3, 导致分子的刚性增强和荧光强度增加, 熔点升高. 将氟化三苯基吡唑啉(FTPP)作为发光中心制作了两类EL器件, 均获得蓝光发射. FTPP分子结构见图1.     

Photoconductive properties of organic-inorganic hybrid films of layered perovskite-type niobate

A hybrid film of layered niobate and an organic amphiphile was prepared by the Langmuir-Blodgett (LB) method. Trimethylammonium-exchanged perovskite-type niobates ((CH(3))(3)NHSr(2)Nb(3)O(10)) were exfoliative to form an aqueous suspension. A monolayer of octadecylamine was produced on such an aqueous dispersion as a template for a hybrid film. A hybrid film was transferred as a Y-type LB film onto a hydrophilic glass plate or an ITO substrate. The structure of a deposited film was investigated with X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and atomic force microscopy (AFM) measurements, indicating a layer-by-layer structure with a single or double sheet of niobate as an inorganic composite. From the cyclic voltammogram on an ITO electrode modified with the Y-type 10 layered film, the lower edge of the conduction band of a niobate layer was determined to be - 0.6 V (vs Ag/AgCl). ac impedance and dc measurements were carried out on 1, 5, and 10-layered LB films (2 mm (electrode spacing) x 8 mm (width)) with aluminum electrodes. The freshly deposited samples behaved as an insulator under the illumination of 280 nm light (2.04 x 10(16) quanta s(-1)). Photoconductivities appeared, however, when they were preirradiated with a 150 W Xe lamp (ca. 2 x 10(18) quanta s(-1)) for 0.5-8.5 h. The process was denoted as photomodification. From the FT-IR and XRD results, it was deduced that the photomodification of LB films caused the decomposition of organic templates (octadecylammonium) accompanied by the collapse of layer-by-layer structures. dc analyses on the 5- and 10-layered films after photomodification also showed that they behaved as a photosemiconductor under UV light illumination.     

吡唑啉衍生物作为空穴传输层在电致发光材料中的应用

我们曾报道过有关1,3二苯基吡唑啉衍生物的光谱和光物理行为^[1,2],并详细地研究了它们在受激发后的辐射和非辐射衰变过程.该类化合物作为一种良好的光致发光材料,由于存在着分子内共轭的电荷转移结构,因此表现出较强的光诱导分子极化能力,可用作为有机非线性光学材料^[3]、光折变材料等.此外,还发现该类化合物在组合型光导器件中可用作空穴传输层材料.既然这类化合物兼具光致发光和空穴传输功能,很自然的会考虑到,它是否也能用作为一种有机的电致发光(EL)材料.有机电致发光材料的重要性自不待言,特别近年来许多科学家致力于此,因此进展很快.但寻找新的高效材料,不论是用作主要的发光层或其它的辅助性化合物,仍在继续.本简报即是对上述化合物用作EL材料的初步研究.     

Spectroscopic consideration of the surface potential built across phthalocyanine thin films on a metal electrode

The nonlinear optical properties of tert-butyl phthalocyanine copper Langmuir-Blodgett (CuttbPc LB) films and vacuum-evaporated phthalocyanine copper (CuPc) films deposited on a metal surface were investigated by second-harmonic generation (SHG) spectroscopy. At the organic/metal interface, a space charge field is formed due to the presence of excess charge injected from a metal electrode to the organic layer. Since the Pc molecule has D4h symmetry, an inversion center is present and the optical SH process is not allowed under the electric-dipole approximation. However, the space charge field at the interface directly influences the symmetric structure of the electrons in the Pc molecule. We investigated the contributions of the surface potential to the SHG using Pc LB and vacuum-evaporated films deposited on aluminum (Al) and gold (Au) metal electrodes, where a distinctive difference in the spectrum for the Pc films on the Al and Au surfaces was observed. The contribution of the surface potential was revealed based on the resonant conditions of the SH process, taking into account the electric-quadrupole transition and dc-field-induced electric-dipole transition.     

Influence of Poly(methylmethacrylate) on 8-hydroxyquinoline Derivative-Metal Complexes Electroluminescence

A new method is presented of enhancing the organic electroluminescent(EL) efficiency by using poly (methylmethacrylaie) (PMMA) as barrier layers which play the role of controlling the electron-hole recombination in the organic EL materials. The organic EL device with one layer of 8-hydroxyquinoline derivalive-metal complexes-(Alq3, Znq2) as the EL-emitting layers, and two layers of EL emitting materials deposited on PMMA Langmuir-Blodgett films (PMMA/Alq3, PMMA/Znq2) sandwiched between indium/tin oxide (ITO) and aluminum electrodes have been fabricated, respectively. The evidence reveals that the LB film takes an importance to raising the 8-hydroxyquinoline derivative-metal complexes EL efficiency.     

1，3—Diphenyl—5—（9—phenanthry1）—2—pyrazoline（DPPhP）：An Excellent Ho1e—Transport Material for Use in Organic Light—Emitting Diodes

An excellent hole-transport material,1,3-diphenyl-5-(9-phenanthryl)-2-pyrazoline(DPPhP)for OLEDs was studied.This compound not only offers hlgh glass transition temperature(Tg=96℃）,good film forming ability,and high HOMO energy level,but also displays excellent hole-transport property.The electrlumlnescent device with a simple structure of ITO/DPPhP(60nm)/AIQ(60mm)/LiF(0.8nm)/Al shows an external quantom efficiency as high as 1.6?     

Dissolution of copper phthalocyanine and fabrication of its nano-structure film

The mono-protonated and di-protonated forms of copper phthalocyanine (CuPc) were obtained by increasing concentrations of trifluoroacetic acid (TFA) solution to a fixed concentration of CuPc solutions. UV-Vis spectrum shows that the Q bands of these two derivatives split and shift to the red, which means successive protonation happened and caused the two derivatives to lose their symmetry. After the protonation step, the solubility of protonated CuPc in organic solvent increased 60 times. The CuPc film was fabricated by the electrophoretic deposition (EPD) method from the protonated CuPc dissolved in nitromethane containing TFA. Scanning electron microscopy (SEM) showed that the deposited CuPc film on the indium tin oxide (ITO) substrate is composed of thread-like nanobelts with diameters between 100 nm and 200 nm. Furthermore, the CuPc film is in α phase with stacking direction (b-axis) parallel to the substrate, which was detected by X-ray diffraction.     

聚吡咯(PPy)对细菌视紫红质(bR)的光电性能的影响

细菌视紫红质(bacteriorhodopsin,用bR表示)是嗜盐菌(halobacterium halobium)紫膜中发现的唯一蛋白质,由于具有独特质子泵和光色互变功能以及高稳定性,而成为理想的生物材料。在光照下,它产生典型的微分脉冲电信号^[1],而且响应快,这对于它在信息存储、仿视觉系统等应用方面有极大的应用前景。     

Red Light Emitting Devices Based on Organo-lanthanide(Ⅲ) Complex

An organic electroluminescent devices with Eu³⁺-complex as an emitter was fabricated. A device structure of ITO/emitting/electron transport layer/Al was empolyed. Its color was red.     

氧化铟锡(ITO)自组装修饰及其对有机电致发光器件性能的影响

设计合成了一种新型的有机硅氧烷Cz-Si,并将其用于ITO自组装修饰。制备的Cz-Si具有较好的稳定性,可以在空气中对ITO进行自组装修饰,实验操作简单。为考察ITO自组装修饰对有机电致发光器件性能的影响,分别以修饰后的ITO(ITO/SAM)及不修饰的ITO(unmodified)作阳极,制备了一系列有机电致发光器件ITO/SAM(or unmodified)/NPB(40~50 nm)/Alq₃(60 nm)/LiF(1.0 nm)/Al。实验结果表明,ITO自组装修饰后器件性能可以得到显著提升,研究认为这与其调控ITO/有机层界面的电子能级、粗糙度以及界面一致性有关。     

氧化铟锡(ITO)自组装修饰及其对有机电致发光器件性能的影响

设计合成了一种新型的有机硅氧烷Cz-Si,并将其用于ITO自组装修饰。制备的Cz-Si具有较好的稳定性,可以在空气中对ITO进行自组装修饰,实验操作简单。为考察ITO自组装修饰对有机电致发光器件性能的影响,分别以修饰后的ITO(ITO/SAM)及不修饰的ITO(unmodified)作阳极,制备了一系列有机电致发光器件ITO/SAM(orunmodified)/NPB(40~50nm)/Alq₃(60nm)/LiF(1.0nm)/Al。实验结果表明,ITO自组装修饰后器件性能可以得到显著提升,研究认为这与其调控ITO/有机层界面的电子能级、粗糙度以及界面一致性有关。     

PANI-CSA: An Easy Method to Avoid ITO Photolithography in PLED Manufacturing

In order to optimize polymer light emitting diode (PLED) performances, devices with holes injected through an Indium Tin Oxide (ITO) / Polyaniline (PANI) electrode into the polymer are much more efficient than devices fabricated with the anode made only by ITO. We demonstrated that by using doped PANI as hole injection layer in a polymer light emitting diode the manufacturing process can become simpler. Indeed, the pattern of conductive layer can be produced without ITO photolithography by UV exposition. As hole transporter layer, Poly(N-vinylcarbazole) (PVK) was spin coated over the doped PANI layer and a layer of tris (8-hydroxy) quinoline aluminum (Alq₃) was then thermally evaporated so as to form the electron transport layer. To complete the device structure, Aluminum contacts were deposited onto the organic layers by vacuum evaporation at low pressure. The layers were characterized by X-ray small-angle diffraction, IR Raman and UV-Vis spectroscopies. Devices without PANI and with PANI as HIL were studied.