Thermophysical properties of fluorinated acrylate homopolymers: Mixing and phase separation

The thermophysical properties of fluorinated acrylate homopolymers are investigated by differential scanning calorimetry (DSC) and optical microscopy and discussed in terms of relative lengths of the fluorinated chain and the hydrocarbon spacer between the acrylate moiety and the fluorinated chain. These compounds exhibit an intrinsic microphase-separation (Isotropic+Isotropic morphology) occurring between the fluorinated chains and the acrylate polymer backbone. It is shown that the enthalpy of mixing is a function of the length of the lateral fluorocarbon chains. The thermophysical behaviour of these materials may be regarded as demixed systems exhibiting an Upper Critical Solution Temperature. The photopolymerization process of one of the monomer is studied by isothermal photocalorimetry. High acrylate double-bond conversion and fast curing rates were obtained thus demonstrating the promising use of these materials for coating and film processing applications using UV-curing techniques. Received 30 January 2002     

Microstructure and interfacial interaction of polyimide/silica hybrid nanocomposites prepared with 3-aminopropyltriethoxysilane

A series of polyimide (PI)-silica hybrid nanocomposites are prepared from 3,3′,4,4′biphenyltetracarboxylic dianhydride (BPDA)-4,4′-oxydianiline (ODA) polyamic acid (PAA) and tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS) by the sol-gel process. 3-Aminopropyltriethoxysilane (3-APS) is used to enhance the interfacial interaction between polyimide and silica. The morphology, interfacial interaction, and properties of the hybrids are investigated using scanning electron microscope (SEM), UV-vis spectroscopy, atomic force microscope (AFM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). SEM and AFM images indicate that silica particles of ca. 45-55 nm size are uniformly distributed in polyimide matrices and that the interfacial interaction between PI and TEOS is better than that between PI and TMOS. The optical transparencies of the PI/TEOS hybrids are better than that of the PI/TMOS hybrids. FTIR spectra confirm the Si O Si bond as well as the conversion of PAA to polyimide and PI/silica hybrid films. The thermal stability is increased after incorporation of the silicas in the polyimide matrix.     

Investigation on slot-die coating of hybrid material structure for OLED lightings

With an attempt to fabricate large-area OLED lighting panels, we investigate slot-die coating of a small molecule (SM) hole transport layer (HTL). It is observed that SM HTL films formed by spin coating exhibit pinhole-like surface, whereas the films by slot-die coating show micro-sized hillocks due to agglomeration. As the plate temperature of the slot coater is increased, smaller hillocks appear more densely. To tackle it, a small amount of a polymer HTL is added into the SM HTL (Hybrid HTL). By the aid of entangled polymer chains, small molecules are prohibited from migrating and thus agglomerations disappear. The peak-to-peak roughness of the slot-coated hybrid HTL films is measured to be about 11.5 nm, which is slightly higher than that (~7 nm) of the polymer HTL film, but much lower than that (~1071 nm) of the SM HTL film. Similar results are also observed in spin-coated films. It is also addressed that OLED with the hybrid HTL shows higher luminous efficacy, compared to OLED with the SM HTL or the polymer HTL. We have further demonstrated that the dissolution problem occurring between two stacked layers with different solvents during slot-die coating can be suppressed to a great extent using such a combination of materials in hybrid structure.     

Red colored transparent PMMA-SiO2 hybrid films

Red colored transparent organic-inorganic hybrids films of a cross-linked polymethyl-methacrylate (PMMA) and silica were prepared via the sol-gel route using tetraethoxy-silane (TEOS) as precursor and a commercial organic red dye. 3-(Trimethoxysilyl) propyl methacrylate (TMSPM) was used to make compatible the organic and inorganic components of the precursor solution mixture. Four type of colored hybrid films were deposited using precursor solutions with the reactants molar ratio 1:0.5:1 for TEOS: TMSPM:MMA, respectively, and four different weight contents of the organic red dye. The hybrid films were studied by Fourier transform infrared spectroscopy, atomic force microscopy and optical transmission and reflection spectroscopy. The hardness of the films was determined from a pencil hardness test referred to ASTM Standard D 3363-92. The results showed that the colored hybrid films have a thickness of about 2 μm and consist of a homogeneous cross-linked organic-inorganic matrix with embedded dye molecules very well dispersed. The hardness of the hybrid films was enhanced with respect to that of the pure organic component. The AFM measurements showed very flat and smooth film surfaces with rms average roughness about 0.3 nm. The optical properties of the hybrid films including their color properties were determined from optical transmission and reflection spectroscopy. We found that the intensity of the color in the hybrid films and the corresponding color coordinates depend on the amount of red dye in the hybrid films. Photodegradation studies were performed by monitoring the optical density of the films as a function of the exposure time to illumination for several values of illumination intensity.     

掺杂LaF3∶Er,Yb纳米颗粒的有机无机复合型平面光波导放大器的制备及增益测试

采用油酸修饰的铒镱共掺氟化镧纳米颗粒掺杂的有机-无机杂化材料做为光波导放大器的有源层,同时采用光学性质良好的甲基丙烯酸甲酯-甲基丙烯酸环氧丙酯共聚物制作光波导的上下包层,首先说明了芯层材料不能刻蚀制备传统矩形波导的原因,其次设计了一种倒脊结构的平面光波导放大器,并采用蒸镀铝掩膜、紫外光刻和反应离子刻蚀等工艺,制备出放大器的样品,同时对样品端面进行了化学机械抛光处理,在信号光（1 550 nm）功率为1 mW的条件下,在1.9 cm长度的波导上获得了3.2 dB的相对增益.     

有机/无机复合功能材料倒脊型波导热光开关

利用溶胶-凝胶技术自主合成了一种具有优良光学特性和高热稳定性的有机/无机复合芯层材料.这种功能材料的分子中含有有机柔性侧链,可形成环氧交联.与无机SiO2-TiO2体系相比,具有较高的热光系数(量级为10-4/K),以及更好的成膜性和可加工性.通过与实验室自行配制的P(MMA-GMA)包层材料相匹配,设计制备了基于这种有机/无机复合功能材料的倒脊型波导马赫-曾德尔型热光开关.器件的波导与热电极性能良好.插入损耗为10dB,驱动功率15mW,开关时间小于1ms,消光比15dB.     

Two-layer hybrid anti-reflection film prepared on the plastic substrates

Two-layer hybrid anti-reflection (AR) and anti-static (AS) films are formed on the flexible substrates such as polyethylene terephthalate and triacetyl cellulose. The AR layer is composed of two layers; indium-tin oxide (ITO) and thermo-curable fluorinated alkoxy silane compounds (JN7) made by DC magnetron roll sputtering and direct wet coating method, respectively. The polymer for an upper layer was used as the low refractive index (n_F=1.35) material, while ITO was chosen as the high refractive index (n_ITO=2.0) material with good electrical conductivity. The AR property (R<0.8%) and the AS and electromagnetic shielding properties (i.e. the electrical conductivity) were almost the same as the conventional transparent multi-layer AR system.     

有机-无机复合ZrO2-SiO2平面光波导

采用溶胶-凝胶法合成ZrO2-SiO2有机一无机复合光波导材料,通过改变其中ZrO2的含量来调节材料的折射率,使材料分别适用于平面光波导的导光层(ng≈1．497)和衬底层、包层(mb=nc≈1．479)。采用旋转涂膜工艺和相应的热处理,在单晶硅基片上制备衬底层、导光层和包层等薄膜,其中导光层介质因具有感光性而可通过紫外光刻来制备光路图案。所得有机一无机复合ZrO2-SiO2板型平面光波导(衬底层 导光层),用棱镜耦合截断法测试其光损耗在632．8nm波长处约为0．8dB／cm。对板型平面波导的导光层薄膜进行紫外光刻和异丙醇淋洗,制备出脊状光波导通道,在覆盖包层后,即获得埋层沟道式平面光波导。采用端耦合截断法测试了埋层沟道式平面光波导的光损耗(小于0．1dB／cm),并观察了其近场图像以及导光材料在近红外窗口的吸收光谱。     

TMOS based water repellent silica thin films by co-precursor method using TMES as a hydrophobic agent

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings on glass substrates using trimethylethoxysilane (TMES) as a co-precursor. Silica sol was prepared by keeping the molar ratio of tetramethoxysilane (TMOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:29.27:2.09 respectively, with 0.5 M NH₄OH throughout the experiments and the TMES/TMOS molar ratio (M) was varied from 0 to 3.8. It was found that with an increase in M value, the roughness and hydrophobicity of the films increased, however the optical transmission decreased from 93% to 57% in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 250 °C and above this temperature the films became hydrophilic. The hydrophobic silica thin films were characterized by taking into consideration the surface roughness studies, Fourier transform infrared (FT-IR) spectroscopy, percentage of optical transmission, scanning electron microscopy (SEM) and contact angle measurements.     

基于溶液加工小分子材料发光层的有机-无机复合发光器件

报道了基于溶液加工有机小分子材料发光层、聚乙烯亚胺电子注入层的有机-无机复合发光器件. 优化了空穴传输层和磷光染料的掺杂浓度, 得到最佳发光效率的器件. 蓝光、黄光和红光器件的最大外量子效率为17.3%, 10.7% 和7.3%. 在发光亮度为1000 cd/m² 时, 蓝光、黄光和红光器件的外量子效率分别为17.0%, 10.6% 和5.8%, 器件效率下降较小. 原因在于同时采用空穴传输型和电子传输型的小分子材料作为共同主体材料, 器件具有较宽的载流子复合区域, 降低了三线激发态-三线激发态湮灭和三线激发态-极化子相互作用对器件发光效率的影响. 白光器件在亮度为1000 cd/m²时, 发光效率和功率效率为31 cd/A和 14.8 lm/W. 器件的色度为(0.32, 0.42), 色度比较稳定, 随电流的变化微小. 器件的效率较以往报道的有机-无机复合发光器件有显著的提高, 主要归因于在聚乙烯亚胺上能够制备特性良好的小分子材料薄膜, 以及小分子主体材料拥有较高的三线态能量和平衡的载流子传输特性, 能够获得高效的磷光发射.     

HFCVD法制备纳米晶态SiC及其室温下的光致发光

用热丝化学气相沉积(HFCVD)法以CH4和SiH4作为反应气体在Si衬底上制备了纳米晶态6H-SiC。为减小6H-SiC与Si衬底之间的晶格失配,在HFCVD系统中通过对Si衬底表面碳化处理制备了缓冲层,确立了形成缓冲层的最佳条件。采用扫描电镜、傅里叶红外吸收谱和X射线衍射等分析手段对样品进行了结构和组分分析。结果表明,在较低的衬底温度下所沉积的是晶态纳米SiC,纳米晶粒平均尺寸约为60nm,并在室温下观察到所制备的纳米SiC位于380～420nm范围内的短波可见光。研究和分析了碳化时间对发光峰及红外吸收峰位置的影响。     

掺杂4-苯基卟啉的聚苯乙烯／二氧化硅复合纳米微球的制备

采用溶胶-凝胶法,首先利用苯乙烯与3-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)化学反应合成共聚前驱物,利用TEOS在一定的条件下水解与缩合,一步合成了有机-无机复合纳米微球。用扫描电镜、红外光谱对共聚物及复合纳米粒子进行了表征。将非水溶性发光材料四苯基卟啉掺杂其中,制备出荧光复合纳米粒子。该粒子表现出了良好的发光性能,染料泄漏与猝灭几乎为零,可以作为一种新型的高效率的生物标记材料。     

Electron transport in dye-sensitized solar cells based on TiO2 nanowires

Anatase titanium dioxide nanowire arrays were prepared by hydrothermally oxidizing titanium foils in aqueous alkali and transferred onto fluorinated tin oxide(FTO)glass for use as the photoanodes of front side illuminated dye-sensitized solar cells(DSCs).Electrochemical impedance spectroscopy(EIS)measurement was applied to compare the electron transport and recombination properties of DSCs using TiO2nanowire films and TiO2nanoparticle films as photoanodes.It was found that the nanowire array films possess smaller electron transport resistance(Rt)and larger electron diffusion length(Le)in the photoanodes,suggesting that the nanowire arrays can enhance the electron transport rate and have a potential to improve the charge collection efficiency of DSCs.     

Structure of graphene nanotube hybrid materials produced via single-stage CVD

The structures of graphene layer-carbon nanotube hybrid films produced via CVD with a single-stage flow of acetylene into a chamber containing a prepared substrate are studied. It is shown that such films have a hybrid double-layer structure consisting of a graphene layer and a dense continuous network of nanotubes. The graphene layer contains continuous extended areas 10–50 μm in size and island areas ～0.1 μm in size. TEM images lead to the conclusion that the graphene layer and carbon nanotubes are bound by covalent bonds.     

有机/无机复合功能材料倒脊型波导热光开关

利用溶胶-凝胶技术自主合成了一种具有优良光学特性和高热稳定性的有机/无机复合芯层材料.这种功能材料的分子中含有有机柔性侧链,可形成环氧交联.与无机SiO2-TiO2体系相比,具有较高的热光系数（量级为10－4/K）,以及更好的成膜性和可加工性.通过与实验室自行配制的P(MMA-GMA)包层材料相匹配,设计制备了基于这种有机/无机复合功能材料的倒脊型波导马赫-曾德尔型热光开关.器件的波导与热电极性能良好.插入损耗为10 dB,驱动功率15 mW,开关时间小于1 ms,消光比15 dB.     

键合型有机/无机杂化材料加载条形波导电光调制器

相对于普通的有机/无机杂化材料,侧链键合型有机/无机杂化材料能提高生色团的掺杂浓度,避免出现结晶、相分离等现象,同时生色团极化有序性的弛豫因生色团运动受阻而降低,具有较高的热稳定性.本文采用溶胶凝胶法合成了一种性能优良、稳定的侧链键合型有机/无机杂化材料,并将这种材料应用于电光调制器的电光层,利用传统的半导体工艺,采用加载条形波导结构,成功制备了马赫-曾德尔(Mach-Zehnder,M-Z)型电光调制器.测试得到电光调制器在1 550 nm波长下10 kHz的响应信号,为键合型杂化材料应用于光电器件的进一步研究打下了基础.     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅰ) sp结构与化学键分析

以CF₄，CH₄和N₂为源气体，利用射频等离子体增强化学气相沉积法，在不同功率下制备了含氮氟化类金刚石膜.用俄歇电子能谱、拉曼光谱、X射线光电子能谱和傅里叶变换红外光谱对薄膜的电子结构和化学键进行了表征，并结合高斯分峰拟合方法分析了薄膜中sp²，sp³结构比率.结果表明，制备的薄膜属于类金刚石结构，不同沉积功率下，薄膜内的sp²/sp³值在2.0—9.0之间，随着沉积功率的增加薄膜内sp²的相对含量增加.膜内主要有C—F_x(x=1，2)，C—C，C=C和C≡N等化学键.沉积功率增加，C—C基团增加，膜内F的浓度降低，C—F基团减少，薄膜的关联加强，稳定性提高. 关键词： 含氮氟化类金刚石膜 sp结构 化学键结构 射频功率     

新型稀土铕配合物Eu(o-BBA)3(phen)电致发光研究

研究了一种新的稀土配合物邻苯甲酰苯甲酸-1,10-菲咯啉-铕(Eu(o-BBA)3(phen))的电致发光特性.采用不同的电子传输层材料,制备了多种结构的有机电致发光器件及有机无机复合器件.比较了单层电致发光器件A:ITO/PVK:Eu/Al与有机无机复合器件B:ITO/PVK:Eu/ZnS/Al发光性能的不同.分析了采用无机半导体材料ZnS作为电子传输层的优点.研究结果表明采用无机的电子传输层,能有效地避免激基复合物的形成,提高器件的亮度同时保持稀土离子发光的色纯性.     

用低压反应离子镀的方法制备Ge_(1-x)C_x单层非均匀增透膜的研究

用低压反应离子镀(RLVIP)的方法在Ge基底上制备了Ge1-xCx单层非均匀增透薄膜。随着沉积速率在0.05~0.4nm/s之间的变化,其折射率在2.31~3.42之间可变。实验结果表明,镀制的Ge1-xCx单层非均匀增透保护薄膜均为无定形结构,并实现了从2000~8000nm的宽波段增透。当沉积速率为0.1nm/s时,单面平均透过率从68.6%提高到了80.9%,比单面未镀膜时提高了17.9%。通过对薄膜的稳定性和牢固度进行测试表明,制备的Ge1-xCx单层非均匀增透薄膜具有良好的性能。     

Inverted organic solar cells comprising low-temperature-processed ZnO films

Inverted organic solar cells are fabricated using low-temperature-annealed ZnO film as an electron transport layer. Uniform ZnO films were prepared by spin coating a diethylzinc (DEZ) precursor solution in air, followed by annealing at 100 °C. Organic solar cells prepared on these ZnO films with a 1:1 P3HT:PCBM blend as the active layer show a high power conversion efficiency of 4.03 %, which is more than 10 % higher than the PCE of solar cells comprising ZnO prepared via a high-temperature sol–gel route.