稀土有机－无机杂化材料的制备及发光性能

本论文旨在开发能使无机材料和有机材料的功能互补、协同优化的无机/有机复合发光材料的制备方法，并研究其发光性质，以发展一类新型的高性能发光材料。基于无机组份与有机组份的物理和化学性质的差异，采用能保持其性质均不改变的低温软化学合成法-溶胶-凝胶技术。无机组份选择具有优良光、热稳定性的SiO_2，有机组份选择具有和无机SiO_2相似折射率和优良力学性能的有机硅烷TMSPM和甲基丙烯酸羟乙酯(HEMA)。采用溶胶-凝胶法制备了两种杂化基质材料SiO_2/P (TMSPM)和SiO_2/P(HEMA)，所得的杂化材料具有良好的光学透明性。由于原位聚合物与无机SiO_2基质同时形成，不仅使杂化基质具有一定的韧性，而且可有效降低无机SiO_2凝胶基质的热聚集和光损耗，是制备复合发光材料的优良基质材料。稀土 (Tb~(3+), Eu~(3+))配合物分别以预掺杂法，原位(in-situ)掺杂法掺入溶胶中，制备了块状杂化材料和用旋转涂覆法(spin-coating method)制成了杂化发光薄膜。利用荧光光谱、红外光谱等现代谱学方法对材料的性能进行了分析。采用预掺杂法制备了稀土Eu~(3+)的1，10-菲罗啉、β-二酮类有机配合物掺杂的杂化发光薄膜。当以稀土Eu~(3+)离子的特征发射波长监控时，得到的激发谱均匀260-450 cm范围内的宽带代替了稀土离子的特征窄带激发光谱，可以判断在凝胶薄膜中已经形成了配合物，而且杂化凝胶薄膜的发射峰值比纯硅胶薄膜的发光强度高数倍，杂化薄膜的荧光寿命大于纯硅胶薄膜，表明与纯硅胶相比，杂化基质更能使稀土配合物分子与外界隔绝，避免了稀土配合物分子与周围环境的相互作用，从而降低了非辐射去活化过程，是一种更好的保护性基质。采用原位掺杂法制备了掺杂稀土Tb~(3+)的羧酸类配合物的杂化块状发光材料。除部分羧酸自由基外，羧酸配体已经通过原位合成法成功地掺入到了杂化基质中。羧酸配体与稀土离子所形成的结构、给电子效应、共轭效应及空间位阻效应特性对于其杂化材料的发光强度、荧光寿命等均会产生影响。

颗粒表面包覆的研究

纳米材料以其特有的优异性能成为下一代信息技术、能源技术和生物医学等技术的重要基础.随着对纳米材料研究的不断深入,对纳米材料的认识不断加深和丰富,对其的研究也逐渐集中在具有功能性质的纳米结构材料方面.对于应用纳米技术制备具有某种性质的材料来说,有必要建立可靠和可以预期结果的合成纳米结构材料的手段.制备具有纳米结构的表面包覆的颗粒材料的技术则是一种行之有效的手段.由于表面包覆的颗粒材料在材料改性和新功能性质的附加方面均有特点,具有实用及潜在应用价值,已广泛地应用在现代材料合成中.结合当今科学研究的前沿领域内,通过大量文献调研,选择具有纳米结构的表面包覆的颗粒材料作为研究的重点.在该论文中我们制备了一些表面包覆的颗粒材料,并对样品进行了表征,取得了一些创新性结果.

稀土配合物掺杂的中孔杂化发光材料的制备及其表征

稀土配合物由于具有优良的窄带发光性能和较长的荧光寿命，因而在光电学领域比如激光材料或者荧光标记上引起了广泛的兴趣和应用。吸附在固体表面的稀土配合物的发光性质得到了广泛的研究。MCM-48中孔材料是M41S家族中的一种，具有直径20-30A三维结构的中孔孔道，比MCM-41的一维结构孔道更有优势，比如它可以最大可能的避免客体分子的堆积现象。因此本论文中我们研究了将稀土（Eu3+）β-二酮（DBM＝dibenzoylmethane）配合物掺杂到纯硅MCM-48以及三种有机基团嫁接的有机－无机杂化MCM-48的孔道中去，得到了各种不同的杂化中孔发光材料。首先烧结后的MCM-48被装载稀土Eu（OBM）3'2H2O配合物之后。XRD结果说明稀土配合物被组装到了MCM-48中，其有序结构因为稀土配合物的进入而受到一定的影响，但是样品仍保持了MCM-48的立方相结构。分别通过吸收光谱和热失重的方法计算了掺杂后的发光MCM-48样品进行洗涤后留在MCM一48中配合物的量。固体漫反射光谱在紫外区有一个OBM配体的Sn基态能级（π）到S1激发态能级份＊）的电子跃迁形成的吸收宽带。可见区还观察到E护”离子的4f-4畴征吸收线。与稀土配合物中的OBM配体相比，掺杂MCM-48样品的Sn-S1吸收带均发生蓝移，反映了S1能级向高能方向移动。然后采用了室温两步合成法合成MCM-48，模板剂的去除采用了溶剂萃取法。最佳掺杂浓度为6.98×10-3 mol/l；同时最佳掺杂时间为24小时。在同样的掺杂条件下，稀土配合物在基质中的掺杂量MCM-48＞MCM-41＞＞SiO2。萃取之后的MCM-48在外形上近乎于球形，粒子的直径在0.7-1.2μm之间。粒子显现出多孔的海绵状表面形态，并且具有晶体结构外形，呈菱形十二面体被削去顶端立方体的结构。而且在粒子的表面观察到了类似螺旋结构的孔道，我们认为这是MCM一48所特有的双螺旋型三维孔道结构，这是到目前为止首次报道利用扫描电镜观察到中孔分子筛的孔道结构。荧光光谱结果观察到了激发峰的最大值由于纳米粒子效应出现的蓝移现象。不同基质中的发射系数QZ和04比较可知配合物在三种基质SiO2、MCM-41和MCM-48中环境的极性相差不大。掺杂到中孔MCM-48材料中的稀土配合物的热稳定性比在MCM-41中强，这是由于MCM-48的三维孔道对配合物的保护作用。室温条件下合成的MCM-48分子筛利用后合成嫁接的方法[post-synthesis grajng（PSG）]进行表面修饰，修饰剂选用了带有功能性乙烯基的VTES，链长最短的MTES以及带有氨基的长链NTSED。稀土Eu（DBM）3'2H2O配合物被组装到杂化中孔分子筛材料中。红外光谱与2951核磁共振光谱表明MCM-48的表面被成功的接枝上了有机M下任S，盯任s，N丁s任D基团。与MCM-48相比，MCM-48-R的表面积、孔体积和孔径的减少有以下NTSED＞VTES＞MTES的顺序。这也许是修饰的有机基团不同的链的长度不同的原因。稀土配合物在这三种有机一无机杂化基质环境的极性比纯硅MCM-48要增大。同时配合物在三种基质的中的QZ的值及发光效率的顺序为：MCM-48-MTES＜MCM-48-VTES＜MCM-48-NTSED，说明MCM-48经过三种有机硅氧烷修饰之后孔道极性也遵循同样的顺序，可以认为这是由于三种有机基团的链长的不同造成的，链长越长则修饰之后孔道极性增大的就越多。最后通过溶胶一凝胶过程利用提拉法（Dip-coating method）制备了具有中孔结构的SiO2-CTAB-Tb（acac）3透明发光薄膜（Mesostructed Iuminescence thin film，略为MLTF），稀土配合物利用原位合成（In-situ）的办法掺入到透明薄膜中。对薄膜进行热处理过程表明薄膜中的稀土配合物在50℃的时候开始形成。XRO结果表明稀土离子及有机配体的掺入对薄膜中孔相的结构没有太大的影响，荧光薄膜仍保持层状结构。红外光谱结果说明制备的中孔薄膜是由CTAB和硅氧烷聚合物组成的复合薄膜。荧光薄膜的发射光谱给出了Th3+离子的特征发射峰，荧光薄膜中有机配体与丁b离子之间发生了能量传递现象。因为在热处理过程中有机配体逐渐代替了开始与Tb离子配位的OH基团，使得二者间的能量传递更加有效，从而导致了荧光的增强。

Polycrystalline silicon thin films and solar cells prepared by rapid thermal CVD

Polycrystalline silicon (poly-Si) films(similar to 10 mu m) were grown from dichlorosilane by a rapid thermal chemical vapor deposition (RTCVD) technique, with a growth rate up to 100 Angstrom/s at the substrate temperature (T-s) of 1030 degrees C. The average grain size and carrier mobility of the films were found to be dependent on the substrate temperature and material. By using the poly-Si films, the first model pn(+) junction solar cell without anti-reflecting (AR) coating has been prepared on an unpolished heavily phosphorus-doped Si wafer, with an energy conversion efficiency of 4.54% (AM 1.5, 100 mW/cm(2), 1 cm(2)).

The mode control of asymmetric Fabry-Perot optical modulators with multiple quantum wells

The asymmetric Fabry-Perot (ASFP) mode position with the thickness of different index coating layer is calculated. The reason for the blue shift of the ASFP mode with the increasing thickness of low index coating layer is analyzed and this phenomenon is observed in experiments. With the wet-etching method, the ASFP mode can be tuned to the desired wavelength and thus the deviation of growth can be compensated. This method is used to improve the contrast ratio of modulators. With the ASFP mode located at different positions relative to the unbiased e-hh peak, different modulation characteristics are demonstrated.

Optical and structural properties of anodized AlxGa1-xAs layers

The optical and structural properties of anodized AlxGa1-xAs films were investigated by using optical reflectance, X-ray photoemission and Auger electron spectroscopy (XPS and AES). II was found that the anodization process occurs progressively from the surface to the bulk of AlxGa1-xAs and the formed oxidation film comprises mainly oxides of Al and Ga together with a relatively small amount of As. The refractive indexes of the anodized Al0.8Ga0.2As film and Al0.8Ga0.2As film itself were deduced to be about 1.80 and 3.25, respectively, indicating that the anodization film is desirable for anti-reflection coating of the surface of AlxGa1-xAs/GaAs solar cells. (C) 1997 Elsevier Science S.A.

Ag surface plasmon enhanced double-layer antireflection coatings for GaAs solar cells

Surface plasmon enhanced antireflection coatings for GaAs solar cells have been designed theoretically. The reflectance of double-layer antireflection coatings (ARCs) with different suspensions of Ag particles is calculated as a function of the wavelength according to the optical interference matrix and the Mie theory. The mean dielectric concept was adopted in the simulations. A significant reduction of reflectance in the spectral region from 300 to 400 nm was found to be beneficial for the design of ARCs. A new SiO_2/Ag-ZnS double-layer coating with better antireflection ability can be achieved if the particle volume fraction in ZnS is 1%-2%.

Room temperature continuous wave operation of 1.33-micron InAs/GaAs quantum dot laser with high output power

Continuous wave operation of a semiconductor laser diode based on five stacks of InAs quantum dots (QDs) embedded within strained InGaAs quantum wells as an active region is demonstrated. At room temperature, 355-mW output power at ground state of 1.33-1.35 microns for a 20-micron ridge-waveguide laser without facet coating is achieved. By optimizing the molecular beam epitaxy (MBE) growth conditions, the QD density per layer is raised to 4*10^(10) cm^(-2). The laser keeps lasing at ground state until the temperature reaches 65 Celsius degree.

Contrastive study of two SESAMs for passive mode-locking in Nd:YVC>4 laser with low pump power

Two semiconductor saturable absorber mirrors (SESAMs), of which one is coated with 50% reflection film on the top and the other is not, were contrastively studied in passively mode-locked solid-state lasers which were pumped by low output power laser diode (LD). Experiments have shown that reducing the modulation depth of SESAM by coating partial reflection film, whose reflectivity is higher than that between SESAM and air interface, is an effective method to get continuous wave (CW) mode-locking instead of Q-switched mode-locking (QML) in low power pumped solid-state lasers. A simple Nd:YVO4 laser pumped by low power LD, in which no water-cooling system was used, could obtain CW mode-locking by the 50% reflector coated SESAM with average output power of ~ 20 mW

Thermally Stable Guest-Host Polyetherketone Poled Polymer for Electro-Optical Applications

The high glass transition temperature polymer polyetherketone doped with disperse red 13 (DR13/PEK-c) has been prepared by the spin-coating method. Through in situ second-harmonic generation, the corona poling temperature was optimized by measuring the temperature dependence of the in situ second-harmonic generation signal intensity under the poling electric field. The linear electro-optic coefficients of the poled polymer films have been determined at 632.8 nm by using a simple interferometric technique. The polymer system was measured after 13 000 h, and found that it remained at 80% of its initial value.