Anhydrous Sol-Gel Synthesis of Titania-Doped Siloxane Polymer for Integrated Optics

Sol-gel synthesis of organic-inorganic hybrid materials for planar waveguides and devices has received growing interest due to its low-cost processing and good suitability for doping. Titania is an important optical dopant, but homogeneous incorporation of titania in silica is difficult to be achieved by the conventional sol-gel process (aqueous system) because of the significant difference between the hydrolysis rates of the precursors. In this paper, we report an anhydrous sol-gel process for synthesising titania-doped siloxane polymers. The process consists of a hydrolysis of 3-methacryloxypropyltrimethoxysilane (MPS) with boric acid under anhydrous conditions, and a condensation with dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPhDMS) and titanium ethoxide (TET). Optical characterisations for the produced titania-doped polymer were performed, and results showed that TET doping is useful for reducing the OH concentration of the synthesised polymer and is also effective for improving the optical quality of spin coatings. DMDMS and DPhDMS are favourable in reducing the birefringence and in increasing the thermostability of the material, and the methacryl groups of MPS are UV-polymerizable, which is useful for low cost fabrication of waveguides by photolithographic process. The results of ellipsometry scanning measurements show that titania is homogeneously incorporated in the hybrid matrix, suggesting that the anhydrous sol-gel process is useful for preparation of UV-sensitive titania-doped siloxane polymers for optical applications.     

纳米二氧化钛粒子分散性能的研究

以四氯化钛为原料，采用溶胶-凝胶法技术合成路线，获得了平均粒径为63nm的二氧化钛粉末。采用分散技术，不仅可以改善粒子的分散性能，而且对粒子的生长也起到一定的抑制作用。研究表明：(1)采用SDS作为分散剂时，其极性基团和非极性基团分别与水和纳米TiO2粒子相结合，从而阻隔了TiO2粒子的团聚，起到分散作用。(2)以稀土元素La作为分散剂，其独特的轨道结构，不仅扩大了能量吸收的范围，更重要的是它与TiO2形成的络合物，使其成为相对独立的小团体，而它本身很小的固溶度使其难于形成合金化组元，结果被释放出来，从而形成更小的纳米TiO2粒子，起到分散纳米TiO2粒子的作用，并同时抑制纳米TiO2粒子的生长。     

Fullerene Derivatives Embedded in Hybrid Sol-Gel Glasses: Nonlinear Optical Properties and Optical Limiting Performances

Hybrid organic-inorganic materials are investigated as suitable materials for inclusion of fullerene derivatives and for fabrication of laser protection devices. A specific synthesis has been developed in order to optimize non-linear optical performances of fullerene derivatives. 3-glicydoxypropyltrymethoxysilane has been used as an inorganic and organic network former to obtain the host material. The sol-gel synthesis consists of the hydrolysis and condensation in acidic conditions of the inorganic network. Epoxy polymerization has been achieved by using zirconium or BF₃ alkoxides precursors. Bulk and multilayer materials doped with a fullerene derivative have been fabricated. They show good optical requirements: high fullerenes concentration, high microstructural homogeneity, high laser damage threshold and high optical limiting efficiency. Optical limiting (OL) mechanisms have been investigated. The most effective in the sol-gel materials is the reverse saturable absorption (RSA) one. However, different mechanisms, like non-linear (NL) scattering and NL refraction contribute to a different extent. Open- and closed-aperture OL and z-scan measurements on sol-gel samples show the contribution of NL scattering and NL refraction at 690 nm. Laser damage threshold has been characterized as a function of the structure of the samples and of the optical configurations (f/66 and f/5).     

溶胶凝法制备LiFePO4正极材料

本文介绍了溶胶凝胶法制备LiFePO4正极材料的基本原理及近几年这一领域的研究进展。对碳包覆活性物质、掺杂和多形态纳米化制备技术三种改性方法以及它们对LiFePO4正极材料性能的提高进行了总结。取得的成效主要有，容量得到提高、颗粒尺寸和碳含量有所减小，热处理过程所需时间大大缩短。文中进一步指出目前存在的若干问题，包括对制备过程的深入认识，产品成本以及环境污染。最后对其商业化的可能性进行了讨论。     

Synthesis of halide glasses by reactive processing of sol-gel materials

This paper aims to introduce fluoride materials, their conventional processing and how sol-gel processing can be used both to simplify processing and to improve properties. A multistep process incorporating sol-gel synthesis and reactive treatment is used to prepare a monolithic ZBLA fluoride glass. The first step is synthesis of a porous, monolithic, atomically homogeneous hydrous oxide gel containing zirconium, barium, lanthanum, aluminum and possibly sodium as components (ZBLA or ZBLAN). The second step is a relatively low-temperature reactive treatment of the gel with a fluorinating agent to achieve a porous fluoride glass. Subsequently, the gel is viscous sintered to a dense glass. The present status and future challenges in the preparation of optical-quality fluoride glasses via this method will be presented.     

Development of Anti-Reflection (AR) Coating on Plastic Panels for Display Applications

Traditionally, various vacuum-based processes have been used for producing interference-type anti-reflection (AR) coatings on large area substrates for different commercial applications. In this paper, the development of sol-gel derived AR coating on large plastic substrates for display application is presented. The sol-gel dip coating process was used to deposit thin films on large size plastic panels. By developing sols with different refractive indices, multi-layer thin-film AR coating stacks were designed and fabricated. These coatings possess good uniformity and meet stringent automotive specifications. This technology has been commercialized successfully for dashboard instrument panel application in Toyota's new hybrid engine car, named Prius.In this paper, AR coatings prepared by the sol-gel process are reviewed. The basic design concept for an AR coating, the coating preparation procedure, and important parameters of the solution coating process are discussed. Optical constants of the coating materials were characterized by using spectroscopic ellipsometry. Optical, mechanical and environmental tests were performed on the sol-gel derived AR coating stack. The sol-gel derived AR coating possesses equivalent or superior properties when compared to the major commercially available AR coating products.     

Low Dielectric Constant Organosilicate Films Prepared by Sol-Gel and Templating Methods

Low dielectric constant organosilicate films with controllable microstructure have been successfully synthesized by multiple-step sol-gel process and templating method, which are the two basic methods to establish porous network in the films. Ultra-low dielectric constant (k) of around 2.0 can be achieved for both films. The microstructure such as porosity, pore interconnection and pore size of the two types of the films have been studied and compared. It has been found that the sol-gel films have a higher level of porosity comparing to the templating films to obtain the same k value. The sol-gel film has a majority of closed pores with pore size around 5 nm. The templating film has a closed pore structure with pore size around 10 nm. Preliminary results present a very positive prospective for intermetal dielectric applications.     

Doping the Backbone of π‐Conjugated Polymers with Tricoordinate Boron: Synthetic Strategies and Emerging Applications

The doping of π‐conjugated organic compounds with trivalent boron atoms produces materials with intriguing properties and functions that result from the interaction of the π‐electron system with the vacant p orbital on boron. This offers unique opportunities in various applications such as organic (opto)electronics, biomedical imaging, and sensors for physiologically relevant anions or amines, as demonstrated by numerous examples on the molecular scale. Recently, the B‐doping strategy has been expanded to polymer chemistry with a view to benefit from the best of both worlds. Herein, recent advances in the synthesis of π‐conjugated polymers doped with tricoordinate boron in the backbone are reviewed. Selected applications are described where these functional materials have already been successfully implemented.     

锐钛矿型纳米氧化钛及其复合材料的低温制备技术

探索低温合成高催化活性纳米TiO2及其复合材料的有效方法,突破传统的高温煅烧法制备锐钛矿相纳米TiO2光催化剂带来的局限,已成为该领域研究的热点问题。本文综述了近年来低温合成锐钛矿型纳米TiO2光催化剂的研究进展,讨论了目前所报道的各种方法（胶溶－相转移法、衍生溶胶－凝胶法、水热法、超声水解法、微波照射法、微乳液法和低温直接氧化法）的原理、操作步骤、反应进程以及优缺点。针对纳米TiO2晶体用作光催化剂时固有的缺陷,即量子效率低且无法利用可见光,进一步评述了离子掺杂、贵金属沉积以及半导体复合等纳米TiO2复合材料的低温制备技术,展望了该领域今后的发展方向和研究重点。     

Considerations about the sol-gel process: From the classical sol-gel route to advanced chemical nanotechnologies

This paper was given on occasion of receiving the first Life Time Award by the International Society on Sol-Gel Science and Technology. Its intention is to provide an insight on the development of this field, its driving forces and especially on its impact on application and industrial technologies. The motivation of the work carried out in the last decades is that in the early days of the sol-gel technologies, where this route started to interest industry as well as scientists, the author got interested in a field which was clearly application-driven and strongly anchored in the material scientist community rather than in fundamental chemistry. If one is talking about application-oriented technologies, of course, markets and industrial needs have to be taken into consideration, because the restrictions or bottle-necks, but also chances provided by economical needs strongly may govern the field. In opposition to these fields, only driven by science, may not have these restrictions as far as it is possible to raise funds for the scientific work. For this reason, the attempt is made to point out the connections between application and science in the sol-gel field. Since I am working in the sol-gel field since 1975, strongly focused on industrial applications, it should be understandable that many of my own development examples are used to demonstrate this way. Another problem, of course, is connected to the sol-gel field: This is a question of appropriate definitions as well as to draw a clear borderline of the field. Especially in the last decade, the connection of sol-gel materials to nanostructured materials has become closer, so that it is difficult to clearly divide these fields. On the other hand, the fabrication of nanoparticles by hydrolysis and condensation processes or controlled precipitation processes can be defined as a sol-gel technology, but in many cases is just not done. This leads to the fact that in many areas, sol-gel types of processes are used, but called different. Due to the fact that the properties of small particles either in solution or dispersed in an appropriate matrix show highly interesting material properties, it would be desirable that the sol-gel community would try to interact stronger with these developments (e.g. the “particle” community). This also might include a focus of the sol-gel area a little bit more back to the routes, to material science development and engineering. According to my opinion, this would be a very interesting supplement for the field as it is represented today.     

Optical and Structural Properties of Doped ZnS Nanoparticles Produced by the Sol-Gel Method

Optical and structural properties of Mn2+-doped ZnS nanoparticles in an organic matrix are experimentally and theoretically studied. The nanoparticles, which were produced by the sol-gel method, are nearly monodisperse with a diameter of approximately 3 nm and show the characteristic orange-red luminescence of Mn2+ centers in a crystalline ZnS matrix. The absorption spectrum of the embedded ZnS nanoparticles is slightly blue shifted and broadened compared to the reference system containing ZnS microparticles. This blue shift is caused by quantum size effects, whereas the broadening is due to defects such as lattice distortions, and vacancies, which are probably located close to the surface in the case of small particles. With increasing temperature the absorption spectra shift to the red and are broadened due to thermal activated diffusion of ions close to the surface. In contrast, the spectral feature of the emission spectra via the Mn2+ center is nearly unchanged compared to the ZnS microparticles. Furthermore, the quantum efficiency is increased and the decay time of the electron-hole pairs is shortened to the nanosecond regime because of the enhanced probability of the electron-hole pairs to see the Mn2+ center. Therefore, the only effect of doping of ZnS nanoparticles with Mn2+ center is the suppression of the relaxation of electron-hole pairs via surface defects generating a highly efficient and fast relaxation of the electron-hole pairs via the Mn2+ center.     

Study of Hybrid Silica-Polyethyleneglycol Xerogels by Eu3+ Luminescence Spectroscopy

Good optical quality Eu3+-doped silica-polyethyleneglycol hybrids were prepared by the sol-gel process. Thermomechanical analysis showed an increase of the glass transition temperature, due to the stiffness of the polymeric network, as the amount of Eu3+ increased. Europium luminescent properties were used to study structural evolution during the sol-gel transition. For lower doping concentrations dried gels present statistical distributions of Eu3+, typical of an amorphous environment, while for higher concentrations a crystalline-like environment of Eu3+ was observed. A broad emission band was observed in the visible part of the electromagnetic spectrum and assigned to the intrinsic emission from the hybrid polymeric network.     

Thermal behaviour study of some sol-gel TiO2 based materials

Among the great number of sol-gel materials prepared, TiO₂ holds one of the most important places due to its photocatalytic properties, both in the case of powders and coatings. Impurity doping is one of the typical approaches to extend the spectral response of a wide band gap semiconductor to visible light. This work has studied some un-doped and Pd-doped sol-gel TiO₂ nanopowders, presenting various surface morphologies and structures. The obtained powders have been embedded in vitreous TiO₂ matrices and the corresponding coatings have been prepared by dipping procedure, on glass substrates. The relationship between the synthesis conditions and the properties of titania nanosized materials, such as thermal stability, phase composition, crystallinity, morphology and size of particles, and the influence of dopant was investigated. The influence of Pd on TiO₂ crystallization both for supported and unsupported materials was studied (lattice parameters, crystallite sizes, internal strains). The hydrophilic properties of the films were also connected with their structure, composition and surface morphology. The methods used for the characterization of the materials have been: simultaneous thermogravimetry and differential thermal analysis, powder X-ray diffraction, electron microscopy (TEM, SAED) and AFM.     

纳米黑磷的改性及其在光催化析氢领域的应用

黑磷作为一种新型的二维材料,具有高载流子迁移率、强大的光吸收性、高比表面积以及各向异性等特点,在光催化领域表现出极强的应用潜力,如光催化析氢、光催化降解有机污染物和生物医学光热、光动力学治疗等。但黑磷存在易氧化且光生电子-空穴复合严重等问题,需要通过改性提高黑磷光催化剂的性能。本文综述了表面修饰、掺杂、复合以及构建异质结等黑磷改性方法,着重对黑磷基材料在光催化产氢领域的应用进行了详细介绍,并指出了黑磷基材料在光催化领域应用需要克服的问题并展望及前景。     

Preparation and Characterization of Fullerenes Containing Sol-Gel Glass

Transparent materials containing C₆₀ are interesting because of their optical limiting properties. Fullerenes can be incorporated in sol-gel matrices, but their poor solubility in the solvents commonly used in the process and their tendency to form clusters constitutes the main experimental problem. For this reason we have synthesized C₆₀ derivatives with high solubility and having reactive groups that could covalently bond to the inorganic network. By this way and by an optimization of the sol-gel preparation procedure, transparent films and bulks were obtained. Good optical limiting performances were demonstrated by experimental measurements.     

烷氧基硅烷溶胶-凝胶反应机理*

利用烷氧基硅烷作为前驱体之一,进行溶胶-凝胶(sol-gel)反应制备无机氧化物和有机－无机杂化材料,近几十年来一直是一个研究热点。对烷氧基硅烷的sol-gel反应过程,特别是起始的水解和初步缩合过程已有较多的研究。本文综述了烷氧基硅烷的sol-gel反应机理研究的进展,并对未来发展提出了看法。     

Characteristics of dye-impregnated tetraethylorthosilane (TEOS) derived sol-gel coatings

An investigation has been carried out on a cross-comparison study into several sol-gel coatings, impregnated with a pH-sensitive fluorescent dye, to determine their optimum characteristics, with the aim of their application as thin film sensor elements in fibre optic chemical sensors. In this test of the coatings, they were applied to standard, cleaned microscope slides and several characteristics, such as the ability of the sol to wet the glass substrate and the optical clarity of the subsequent coating were investigated and found to depend mainly on the water: tetraethylorthosilane (H₂O: TEOS) ratio used in their preparation but also on the extent of aging and the level of catalyst used. It was found that thicker coatings could be created through the use of suitable chemical additives in the preparation process.     

Control of Dopant Adsorption from Aqueous Solution into Nanoporous Sol-Gel Films

The doping of porous sol-gel films by adsorption of cations onto silica from aqueous solutions is demonstrated. The films are fabricated using the sol-gel method, giving nanometer scale porosity, high surface area, and homogeneity on the scale of optical wavelengths. After deposition by spin coating and initial heat treatment, the films are soaked in a salt solution of the desired dopant, and then given a further consolidating heat treatment.Doping with lead, aluminum and calcium has been demonstrated, and consistent and reproducible processes have been established. Results are presented showing control of doping level through pre-doping temperature and surface treatment, doping time and temperature, and doping solution pH. Potential applications in integrated optics are proposed.     

Ni^2＋／TiO2介孔材料光催化降解造纸废水影响因素的研究

溶胶-凝胶法合成了不同Ni掺杂量的Ni2 /TiO2介孔复合材料.用X射线衍射(XRD)、透射电子显微镜(TEM)、红外(FT - IR)光谱和N2吸附脱附等对产物结构进行了表征.考察了Ni掺杂量、催化剂的用量、初始pH、外加氧化剂等因素对光催化降解造纸废水的影响.结果表明: Ni2 /TiO2介孔复合材料光催化降解造纸废水的最佳反应条件为:Ni掺杂量为2%、催化剂用量1.5g/L、初始pH=4、通氧;光照4 h后,废水色度去除率达100%; 12 h后,废水CODCr去除率达到83.4%.     

钛掺杂对LiNi0.75Co0.25O2结构与性能的影响

应用溶胶-凝胶法合成LiNi(0.75-x)Co0.25TixO2(x=0,0.1,0.25)系列正极材料,其结构、形貌、粒度、电化学性能由TG、XRD、SEM和电池充放电测试表征研究表明,材料的电化学性能与钛掺杂量密切相关.在钴含量不变的情况下,随着Ti含量(x)的增加,材料由六方层状结构逐渐向立方结构转变,x=0.25时,出现了立方相与六方相共存.根据实验和理论计算结果简要讨论了钛掺杂对正极材料LiNi0.75Co0.25O2结构和电化学性能的影响.