Blue laser dye spectroscopic properties in solgel inorganic-organic hybrid films

A blue solid-state laser material based on 4,4' dibenzyl carbamido stilbene-2,2' disulfonic acid incorporated into solgel zirconia and inorganic-organic hybrid matrices is presented. The absorption maxima of the dye in various matrices are around 339-361 nm, and the broad fluorescence peaks are at 411-413 nm. Optical gain measurements using the variable stripe method show amplified spontaneous emission peaking at 437 nm.     

富勒烯有机-无机杂化材料的非共珍三阶非线性光学特性

采用中心波长800 nm、脉宽30 fs的超短激光脉冲,通过飞秒光开关技术(Optical Kerr Shutter,OKS)对富勒烯有机-无机杂化材料的飞秒超快非线性特性进行了实验研究.获得270 fs的开关时间,所得的富勒烯有机-无机杂化材料的三阶非线性系数X~(3)约为4.5×10~(-4) esu,比C_(60)分子的三阶非线性系数X~(3)高一个数量级.通过实验测定的光克尔信号强度与激发光和探测光偏振方向夹角的依赖关系表明:30 fs的超短激光脉冲激发富勒烯有机-无机杂化材料的克尔信号主要是源于光诱导双折射效应,而非用200 fs的超短激光脉冲时来自瞬态栅的自衍射效应.     

富勒烯有机-无机杂化材料的非共珍三阶非线性光学特性

采用中心波长800 nm、脉宽30 fs的超短激光脉冲,通过飞秒光开关技术（Optical Kerr Shutter,OKS）对富勒烯有机-无机杂化材料的飞秒超快非线性特性进行了实验研究.获得270 fs的开关时间,所得的富勒烯有机-无机杂化材料的三阶非线性系数χ(3)约为4.5×10－14 esu,比C60分子的三阶非线性系数χ(3)高一个数量级.通过实验测定的光克尔信号强度与激发光和探测光偏振方向夹角的依赖关系表明：30 fs的超短激光脉冲激发富勒烯有机-无机杂化材料的克尔信号主要是源于光诱导双折射效应,而非用200 fs的超短激光脉冲时来自瞬态栅的自衍射效应.     

Zero thermal expansion in a nanostructured inorganic-organic hybrid crystal

There are very few materials that exhibit zero thermal expansion (ZTE), and of these even fewer are appropriate for electronic and optoelectronic applications. We find that a multifunctional crystalline hybrid inorganic-organic semiconductor, beta-ZnTe(en)(0.5) (en denotes ethylenediamine), shows uniaxial ZTE in a very broad temperature range of 4-400 K, and concurrently possesses superior electronic and optical properties. The ZTE behavior is a result of compensation of contraction and expansion of different segments along the inorganic-organic stacking axis. This work suggests an alternative route to designing materials in a nanoscopic scale with ZTE or any desired positive or negative thermal expansion (PTE or NTE), which is supported by preliminary data for ZnTe(pda)(0.5) (pda denotes 1,3-propanediamine) with a larger molecule.     

The effect of C60 cluster ion beam bombardment in sputter depth profiling of organic-inorganic hybrid multiple thin films

The effects of C₆₀ cluster ion beam bombardment in sputter depth profiling of inorganic-organic hybrid multiple nm thin films were studied. The dependence of SIMS depth profiles on sputter ion species such as 500 eV Cs⁺, 10 keV C₆₀⁺, 20 keV C₆₀²⁺ and 30 keV C₆₀³⁺ was investigated to study the effect of cluster ion bombardment on depth resolution, sputtering yield, damage accumulation, and sampling depth.     

Novel luminescent RE/TiO2 (RE = Eu, Gd) catalysts prepared by in-situation sol-gel approach construction of multi-functional precursors and their photo or photocatalytic oxidation properties

In this context, a novel synthesis method was used to fabricate rare earth/TiO₂ catalyst for the first time. Lanthanide (Eu, Gd) coordination polymers with picolinic acids were applied as precursors of titania oxide components, in particular, polyethylene glycol and polyacrylamide were added to assemble inorganic-organic hybrid polymeric network through an in-situation sol-gel technique. After sintering treatment of the multi-component precursor under 600 °C for 3 h, fluorescence excitation and emission spectra show that Eu/TiO₂ crystalline phosphor exhibits strong red luminescence under excitation wavelength at 394 and 464 nm. SEM and BET indicate the two hybrids are porous and homogenous. The oxidation experiments from trivalent arsenite As(III) to pentavalent arsenate As(V) by the above two catalysts substantiate that their surfaces have higher affinity to arsenate and can enhance photocatalytic oxidation activity in comparison with pure titania.     

Environment effects on the lasing photostability of Rhodamine 6G incorporated into organic-inorganic hybrid materials

The effect on the lasing photostability of Rhodamine 6G (Rh6G), and the rigidity of a hybrid inorganic-organic matrix by controlled addition of di-, tri- and tetrafunctionalized alkoxides has been evaluated. The dye was incorporated into hybrid matrices of (2-hydroxyethyl methacrylate) (HEMA) or vol/vol copolymers of methyl methacrylate (MMA) and HEMA with different weight proportions of polycondensated dimethyldiethoxysilane (DEOS), methyltriethoxysilane (TRIEOS), and tetraethoxysilane (TEOS). The laser samples were transversaly pumped at 534 nm at 5.5 mJ/pulse and up to a 10 Hz repetition rate. The dependence of the laser photostability on organic-inorganic composition, pH of the medium, and thermal treatment of the samples was studied. Good stability, with a drop of the initial laser output of only 13% after 10000 pump pulses at 10 Hz in a thermally postcured (HEMA-15 wt%TRIEOS) matrix was obtained. Careful control of the synthesis process is required to reach the necessary photostability for a solid-state dye laser based on hybrid matrices to become competitive with liquid dye lasers. PACS 81.05.Lg; 81.05.Zx; 81.20.Fw; 42.55.Mv; 42.55.Rz; 42.60.Lh; 42.62.b; 42.70a; 42.70-Hj; 42.70.Jk     

Preparation and fluorescent sensing applications of novel CdSe-chitosan hybrid films

A novel CdSe-chitosan hybrid fluorescent film has been fabricated by dipping a chitosan film containing Cd(Ac)₂ into NaHSe aqueous solution under a nitrogen atmosphere at room temperature. It has been demonstrated that utilization of a chitosan film as a substrate prohibits the aggregation of the as formed CdSe micro-nano-particles, and enhances the sensing performance of the inorganic-organic hybrid film. It has been also revealed that the amount of CdSe embedded in the hybrid film can be altered by varying the initial concentration of Cd(Ac)₂. Importantly, the photoluminescence emission of the hybrid film is selectively sensitive to the presence of polyamines. Furthermore, the response is reversible. Accordingly, it is anticipated that the film may be developed into a polyamine sensor.     

Synthesis of novel magnetic phosphazene-containing polymer microspheres with active hydroxyl groups

Monodisperse magnetic phosphazene-containing polymer microspheres with active hydroxyl groups were prepared at room temperature by ultrasonic irradiation. The morphology and structure of the magnetic poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres were characterized and the coordination behavior between magnetic nanoparticles and PZS microspheres was investigated. The magnetic measurements reveal that the magnetic microspheres are superparamagnetic with saturation magnetization of 34.9 emu/g. The paper presents a simple, economic and environmentally friendly route to preparing monodisperse magnetic hybrid inorganic-organic microspheres with functional groups.     

在有限空间内生成的晶格高度取向的ZnO纳米颗粒

应用固态反应的方法,在260和300 oC空气中分别热分解层状锌油酸固体得到氧化锌纳米颗粒/团簇．高分辨透射电子显微镜和选区电子衍射表明,这种团簇是带有各种缺陷的单晶．光致发光激发光谱表明这两个样品在272和366 nm有两个频段．前者可能是由于不到200个氧化锌分子组成的团簇从价带到导带的电子转移引起的．     

Simple reflow technique for fabrication of a microlens array in solgel glass

A simple reflow method for fabrication of refractive microlens arrays in inorganic-organic SiO2-ZrO2 solgel glass is presented. To our knowledge, this is the first report that presents a simple reflow technique for transforming a negatively induced hybrid solgel material into desirable spherical microlenses. It is shown that the microlenses have excellent smooth surfaces and uniform dimensions. The reflow technique is considerably cheaper than use of a high-energy beam-sensitive gray-scale mask and is suitable for mass production.     

Investigation of the two-photon polymerisation of a Zr-based inorganic-organic hybrid material system

Two-photon polymerisation of photo-sensitive materials allows the fabrication of three dimensional micro- and nano-structures for photonic, electronic and micro-system applications. However the usable process window and the applicability of this fabrication technique is significantly determined by the properties of the photo-sensitive material employed. In this study investigation of a custom inorganic-organic hybrid system, cross-linked by a two-photon induced process, is described. The material was produced by sol-gel synthesis using a silicon alkoxide species that also possessed methacrylate functionality. Stabilized zirconium alkoxide precursors were added to the precursor solution in order to reduce drying times and impart enhanced mechanical stability to deposited films. This enabled dry films to be used in the polymerisation process. A structural, optical and mechanical analysis of the optimised sol-gel material is presented. A Ti:sapphire laser with 80 MHz repetition rate, 100 fs pulse duration and 795 nm is used. The influence of both material system and laser processing parameters including: laser power, photo-initiator concentration and zirconium loading, on achievable micro-structure and size is presented.     

Complex nanostructured materials from segmented copolymers prepared by ATRP

The development of new controlled/living radical polymerization processes, such as Atom Transfer Radical Polymerization (ATRP) and other techniques such as nitroxide mediated polymerization and degenerative transfer processes, including RAFT, opened the way to the use of radical polymerization for the synthesis of well-defined, complex functional nanostructures. The development of such nanostructures is primarily dependent on self-assembly of well-defined segmented copolymers. This article describes the fundamentals of ATRP, relevant to the synthesis of such systems. The self-assembly of block copolymers prepared by ATRP is illustrated by three examples. In the first, block copolymers of poly(butyl acrylate) with polyacrylonitrile phase separate, leading to spherical, cylindrical or lamellar morphologies, depending on the block copolymer composition. At a higher temperature, polyacrylonitrile block converts to nanostructured carbon clusters, whereas poly(butyl acrylate) block serves as a sacrificial block, aiding the development of designed nanostructures. In the second example, conductive nanoribbons of poly(n-hexylthiophene) surrounded by a matrix of organic polymers are formed from block copolymers prepared by ATRP. The third example describes an inorganic-organic hybrid system consisting of hard nanocolloidal silica particles (20 nm) grafted by ATRP with well-defined polystyrene-poly(benzyl acrylate) block copolymer chains (1000 chains per particle). Silica cores in this system are surrounded by a rigid polystyrene inner shell and softer polyacrylate outer shell. Received 9 July 2002 Published online: 11 March 2003     

Nanosized multilayer films with concurrent photochromism and electrochromism based on Dawson-type polyoxometalate

An inorganic-organic composite multilayer film constructed of poly(vinyl alcohol) (PVA) with Dawson-type phosphotungstate anion [P₂W₁₈O₆₂]⁶⁻ (P₂W₁₈) and poly(allylamine hydrochloride) (PAH) were fabricated on quartz, ITO, silicon and CaF₂ substrates by a layer-by-layer self-assembly method. The film was provided with concurrent photochromism and electrochromism. IR spectra showed that the structure of the PVA was fully maintained in the multilayer film. And their photochromic and electrochromic properties were investigated by UV-vis spectra, cyclic voltammetry (CV), chronoamperometry (CA) measurement and X-ray photoelectron spectra (XPS). Atomic force microscopy (AFM) was used to investigate the surface topography. This study provides a new route to explore the possibility of application to polyoxometalate-based hybrid inorganic-organic materials.     

Electroluminescence from GaN-polymer heterojunction

Inorganic and organic semiconductor devices are generally viewed as distinct and separate technologies. Herein we report a hybrid inorganic-organic light-emitting device employing the use of an air stable polymer, Poly (9,9-dioctylfluorene-alt-benzothiadiazole) as a p-type layer to create a heterojunction, avoiding the use of p-type GaN, which is difficult to grow, being prone to the complex and expensive fabrication techniques that characterises it. I-V characteristics of the GaN-polymer heterojunction fabricated by us exhibits excellent rectification. The luminescence onset voltage is typically about 8-10 V. The device emits yellowish white electroluminescence with CIE coordinates (0.42, 0.44).     

Polarization dependence of optical Kerr effect in metallophthalocyanine-doped inorganic-organic hybrid materials

Ultrafast optical Kerr effect of metallophthalocyanine-doped inorganic-organic materials was investigated using a femtosecond optical Kerr shutter at wavelength of 800 nm. Experimental results showed that the dependence of the Kerr signals on the polarization angle between the pump beam and the probe beam could be controlled by changing the pump-probe intensity ratio. The pump-intensity dependence of the polarization characters of the Kerr signals probably arose from the contribution of light induced transient grating (LITG) to the Kerr signals.     

Optical properties of hybrid polymers as barrier materials

The development of high barrier films for the encapsulation of organic electronics devices onto flexible polymeric substrates is attracting a considerable scientific interest, since it is important to protect the organic semiconductor layers of these devices from corrosion due to atmospheric gas molecule permeation. The barrier layers for encapsulation consist of a sequence of inorganic and hybrid polymer thin films that are deposited onto flexible polymeric substrates, such as polyethylene terephthalate (PET). In addition to their barrier response, these multilayer systems should also exhibit high transparency and good adhesion between the hybrid polymer and inorganic layers. The knowledge of their optical properties and the correlation of the optical response with their structure and the final barrier response are of major importance since it will contribute towards the optimization of their functionality. In this work, the optical properties of hybrid polymers deposited onto silicon oxide inorganic thin films that were grown onto flexible polymeric substrates, have been investigated by the use of spectroscopic ellipsometry in a wide spectral region from the infrared to the visible-ultra violet. As it has been found, the increase of the solid content in the hybrid polymers is associated with a reduction in the refractive index values. This behavior can be correlated to a lower density of the hybrid polymer, and furthermore to a poor barrier response, due to the less cohesive inorganic-organic bonding network. Finally, from the investigation of the optical response of the hybrid polymers in the IR spectral region has revealed information on their bonding structure that has been discussed together with their barrier response.     

基于电场调控的高性能紫外无机-有机复合结构光电探测器

通过溶液旋涂制备了结构为ITO/ZnO/P3HT:ITIC/Ag的紫外无机-有机复合结构光电探测器,混合膜中聚合物给体(P3HT)和非富勒烯小分子受体(ITIC)的质量比为100:1.由于载流子传输通道不连续,器件在零偏压下的暗电流密度很小,为5.8×10-10 A·cm-2,为器件实现外加电场可调和光电流倍增提供了条...     

新型杂化絮凝剂PAC-PDMDAAC对染料废水的脱色光谱分析

用新型杂化絮凝剂聚合氯化铝-聚二甲基二烯丙基氯化铵(PAC-PDMDAAC)处理分散紫和活性艳红两种染料废水。杂化絮凝剂投药量为400和450 mg·L-1时,分散紫和活性艳红的脱色率分别达到99%和86.8%,优于聚合氯化铝(PAC)和复配型PAC-PDMDAAC。杂化絮凝剂处理分散紫的最佳pH为7～12,而处理活性艳红的最佳pH为7～9。分别对两种染料及其杂化絮体进行傅里叶红外光谱扫描,结果表明杂化絮凝剂与两种染料分子的某些基团有络合作用,杂化絮体中羟基峰增大且宽化,杂化絮凝剂对染料废水的脱色以吸附电中和为主。对染料原水以及混凝后上清液进行紫外连续扫描,两种上清液的吸光度都大大降低,同时吸收曲线波峰偏移,进一步说明电中和与吸附架桥的协同作用是脱色的主要机理。同时,杂化絮凝剂对分散紫的脱色是通过破坏醚键以及与—NH₂反应,而对活性艳红的脱色则是通过对—SO₃的置换以及对Cl-的取代。为该新型无机-有机高分子杂化絮凝剂混凝脱色效能及脱色机理研究提供新方法,具有实际意义和应用价值。     

Effect of thermal treatment on the nonlinear optical response and stability of hybrid inorganic-organic films

Hybrid inorganic-organic second-order nonlinear optical (NLO) materials have been obtained through hydrolysis and co-condensation between tetraethyl silicate (TEOS), Vinyltriethoxysilane (VTES) and an alkoxysilane dye (ICTES-DR1). The hybrid materials showed a thermal stability up to 306 °C in thermogravimetric analysis (TGA) thermograms and no visible glass transition temperature (T_g) was observed in the range 50-200 °C in differential scanning calorimetry (DSC) thermograms. The poling profiles of the hybrid films were investigated by using the in situ second harmonic generation (SHG) measurement. The thermal stability of the second order NLO properties of the poled films were also investigated by the in situ SHG intensity probing. It has been shown that the NLO response and its thermal stability were strongly dependent on the thermal pretreatment of the films.