A Study on Liquid Hybrid Material for Waveguides—Synthesis and Property of PSQ‐Ls for Waveguides

Silicate‐based inorganic‐organic hybrid polymer systems have many unique properties including thermal stability and photo‐stability, chemical resistance with the combination of tunable optical properties. Two kinds of new UV‐patternable hybrid materials PSQ‐Ls were synthesized by a sol‐gel process at room temperature, which can be used for low cost fabrication of optical waveguides. Thick films (up to 8.31 µm) can be coated by a single spin‐coating process without any cracking and the average surface roughness (Ra), detected by atomic force microscopy (AFM), is below 0.5 nm. The optical properties (refractive index, birefringence, and optical loss at 1310 nm and 1550 nm, respectively) of the PSQ‐Ls films are investigated by a prism coupler. The refractive index of PSQ‐Ls can be exactly tuned from 1.4483 to 1.5212 by blending PSQ‐LH (n_TE=1.5212 @ 1310 nm) and PSQ‐LL (n_TE=1.4483 @ 1310 nm). The maximum refractive index contrast is about 4.8%. After post‐baking, birefringences of the films are below 0.0005 and optical losses are about 0.2 dB · cm^?1 at 1310 nm, 0.7 dB · cm^?1 at 1550 nm, respectively. Furthermore, the PSQ‐Ls films also show outstanding thermal stability in air atmospheres.     

Hybrid Plasmonic–Aerogel Materials as Optical Superheaters with Engineered Resonances

Solar radiation is a versatile source of energy, convertible to different forms of power. A direct path to exploit it is the generation of heat, for applications including passive building heating, but it can also drive secondary energy-conversion steps. We present a novel concept for a hybrid material which is both strongly photo-absorbing and with superior characteristics for the insulation of heat. The combination of that two properties is rather unique, and make this material an optical superheater. To realize such a material, we are combining plasmonic nanoheaters with alumina aerogel. The aerogel has the double function of providing structural support for plasmonic nanocrystals, which serve as nanoheaters, and reducing the diffusion rate of the heat generated by them, resulting in large local temperature increases under a relatively low radiation intensity. This work includes theoretical discussion on the physical mechanisms impacting the system's balanced thermal equilibrium.     

Photocurable Sol-Gel Coatings: Channel Waveguides for Use at 1.55 μm

The development and characterization of channel waveguides using wet-process, low temperature sol-gel chemistry is described. Two structures have been developed. The first one is a one-layer structure, composed of a sol-gel solution which is a mixture of photopolymerizable organosilicate and organozirconate precursors. The other is a multilayer structure with a buffer under the guide and a protective coating. The layers are deposited by the dipping technique. The devices are obtained by UV light exposure of the coating through a predefined mask (channel waveguides). The refractive index increase is sufficient enough to allow the use of waveguides in the 1.55 m telecommunication window.These waveguides are thick enough to reduce the coupling losses with an optical fiber below 0.5 dB. Also, because of our sandwich structure, the propagation losses are less than 0.1 dB.     

Hybrid Sol-Gel Coatings Produced from TEOS and γ-MPS

Hybrids sols from tetraetoxysilane (TEOS) and 3-(methacryloxypropyl) trimethoxysilane (-MPS) were prepared in acid medium for different TEOS/-MPS ratios and were modified by the addition of a colloidal silica suspension. The stability of the different sols was evaluated by viscosity measurements; the sols showed a Newtonian behaviour and the ageing effect was negligible even after two months from their preparation. Coatings were obtained by dipping at different withdrawal rates and heat-treated between 150 and 250°C. Transparent coatings with thickness higher than 4 m were reached for most of the studied compositions. The surface microhardness of coatings for each composition and thermal treatment was evaluated by the pencil hardness test. The thermal stability was followed by simultaneous thermogravimetric and differential thermal analysis (TGA-DTA) determining the limit temperatures at which the coatings can be treated without losingits hybrid character. A structural analysis was made by deconvolution of Fourier transformed infrared spectra (FTIR) of self-supported films observing the influence of the organic groups on the silica network.     

Synthesis and Characterization of Fluoro- and Chloro- bimetallic Alkoxides as Precursors for Luminescent Metal Oxide Materials via Sol-Gel Technique

Heterobimetallic alkoxides are broadly recognized as versatile precursors for luminescence materials, and efforts are being made to develop novel routes by applying the concept of geometrical molecular design, for their synthesis and to design a single source precursor suited to photoluminescent materials. Novel and new series of bimetallic alkoxides has been prepared by metathesis route. They exhibit a lower sensitivity towards hydrolysis and so they are easier to handle as compared to other alkoxides. All the compounds were characterized by elemental analysis, FT-IR and multinuclear NMR spectroscopies. FT-IR revealed that the molecular structure of these metal alkoxides was retained to a large extent in 4 ： 1 halogenated alcohol-benzene solution. The heteronuclear NMR spectroscopy provided useful information about chemical shifts for better understanding the likely structure based on interactions with their coordinate metals. The mass spectra show similar types of fragmentation pattern. SEM-EDS analyses showed consistency with the formulation. XRD patterns show an enhanced homogeneity at high temperature. TGA measurements show that thermal decomposition occured in steps that depended entirely on the chemical compositions and the synthesis routes. SEM observation reveals that the morphology and particle size strongly depend on synthesis routes for their precursors.     

Sol–Gel Derived Organic and Inorganic Hybrid Materials for Photonic Applications: Contribution to the Correlation Between the Material Structure and the Transmission in the Near Infrared Region

A promising way of fabricating integrated optics components is based on the sol–gel synthesis and photocuring of organic-inorganic hybrid materials. However, the main factor limiting the development of passive devices is the propagation losses. Moreover, the possibility to compensate these attenuations by optical amplification is competed with the multiphonon relaxation associated to the presence of OH groups. To our knowledge, OH groups were always shown as the main responsible for attenuation at the telecommunication wavelengths, namely at 1310 and 1550 nm, although the matrix is composed of organic species which can contribute to absorptions in this spectral range. This paper deals with spectroscopic and optical characterizations of a well established organic and inorganic hybrid material in order to determine the contribution of each molecular groups to the attenuation at the aforementioned wavelengths.     

Lanthanide Metal–Organic Framework Microrods: Colored Optical Waveguides and Chiral Polarized Emission

Lanthanide metal–organic frameworks (Ln-MOFs) have received much attention owing to their structural tunability and widely photofunctional applications. However, successful examples of Ln-MOFs with well-defined photonic performances at micro-/nanometer size are still quite limited. Herein, self-assemblies of 1,3,5-benzenetricarboxylic acid (BTC) and lanthanide ions afford isostructural crystalline Ln-MOFs. Tb-BTC, Eu@Tb-BTC, and Eu-BTC have 1D microrod morphologies, high photoluminescence (PL) quantum yields, and different emission colors (green, orange, and red). Spatially PL resolved spectra confirm that Ln-MOF microrods exhibit an optical waveguide effect with low waveguide loss coefficient (0.012≈0.033 dB μm⁻¹) during propagation. Furthermore, these microrods feature both linear and chiral polarized photoemission with high anisotropy.     

LC Packing Materials for Pharmaceutical and Biomedical Analysis

 The author has prepared novel liquid chromatography (LC) packing materials for pharmaceutical and biomedical analysis. Those include LC packing materials for direct serum injection assays of drugs and their metabolites, LC packing materials for resolution of enantiomeric drugs, and uniformly sized molecularly imprinted polymers for drugs and their metabolites.     

Highly Luminescent One-Dimensional Organic–Inorganic Hybrid Double-Perovskite-Inspired Materials for Single-Component Warm White-Light-Emitting Diodes

Double perovskites (DPs) are one of the most promising candidates for developing white light-emitting diodes (WLEDs) owing to their intrinsic broadband emission from self-trapped excitons (STEs). Translation of three-dimensional (3D) DPs to one-dimensional (1D) analogues, which could break the octahedral tolerance factor limit, is so far remaining unexplored. Herein, by employing a fluorinated organic cation, we report a series of highly luminescent 1D DP-inspired materials, (DFPD)₂M^IInBr₆ (DFPD=4,4-difluoropiperidinium, M^I=K⁺ and Rb⁺). Highly efficient warm-white photoluminescence quantum yield of 92 % is achieved by doping 0.3 % Sb³⁺ in (DFPD)₂KInBr₆. Furthermore, single-component warm-WLEDs fabricated with (DFPD)₂KInBr₆:Sb yield a luminance of 300 cd/m², which is one of the best-performing lead-free metal-halides WLEDs reported so far. Our study expands the scope of In-based metal-halides from 3D to 1D, which exhibit superior optical performances and broad application prospects.     

Polyampholytic Graft Copolymers as Matrix for TiO2/Eosin Y/[Mo3S13]2− Hybrid Materials and Light-Driven Catalysis

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO₂ core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO₂). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO₂ core. This resulted in high visible-light-driven H₂ generation. The enhanced light-driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO₂ was possible by introducing [Mo₃S₁₃]²⁻ cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.     

Synthesis and Characterization of Fully-Functionalized Polysilanes for Photorefractive Materials

Photorefractive (PR) polymers have attracted much interest since 1991 1. Furthermore,because fully-functionalized polymeric systems can overcome the shortcomings such asphase-separation and composite sublimation in composite systems they have gainedespecial attention.Polysilanes can be used as novel photoconductors because of a-electionsdelocalization in the polymeric backbone2. Silence3 and Nishida4 have stUdied thepolysilane composite photorefractive materials and found that the response t…     

Sol-Gel Method for Preparation of LiLaNiO/γ-Al_2O_3 Catalyst over Monoliths used in POM Reaction

Partial oxidation of methane (POM) has several advantages over the traditional industrial method of steam reforming, such as much higher space velocity, reduced capital and operation cost and optimized the ratio of the products (H2/CO). Many investigators are interested in the POM reaction over monolith now1-3. Monolith is a kind of ceramic-like metal oxide material. It has relative high surface to volume ratio compared to commercial pellets, low pressure drop during the reaction process2,…     

Thickness, Morphology and Structure of Sol-Gel Hybrid Films: II—The Role of the Solvent

The influence of the solvent on the thickness, morphology and structure of silica-polytetrahydrofuran hybrid films, prepared by spin coating, has been analysed. The inorganic precursor, tetraethylorthosilicate, was hydrolysed under acid catalysis, the hydrolysis molar ratio being 4. Polymers of average molecular weight (M _n) 650 and 2900 were incorporated in the initial colloidal solutions, in a low concentration (organic/inorganic molar ratio 0.01). Two solvents were compared: ethanol, protic, and tetrahydrofuran, aprotic and a little less polar. The thickness and surface texture parameters of the films were determined by profilometry, their morphology characterized by SEM and their structure studied by FTIR. It is shown that the solvent has no effect on the molecular structure of the films, but strongly influences the surface texture and the morphology of both pure silica and hybrid films. The solutions prepared in tetrahydrofuran present shorter gelation times (t _G) and allow the deposition of good quality films almost up to the gelation point (to a reduced time, t/t _G, of 0.9). The films are thinner than those prepared from corresponding ethanolic solutions at the same reduced ageing times. For pure silica films, tetrahydrofuran is the best choice, since it reduces the fractured region on the edge of the substrate. For hybrid films, this effect is achieved by the polymer and tetrahydrofuran is responsible for a higher arithmetical mean roughness. Therefore, ethanol becomes the preferable solvent.     

Hydrophobic Metal−Organic Frameworks and Derived Composites for Microelectronics Applications

The extraordinary characteristic features of metal−organic frameworks (MOFs) make them applicable for use in a variety of fields but their conductivity in microelectronics over a wide relative humidity (RH) range has not been extensively explored. To achieve good performance, MOFs must be stable in water, i. e., under humid conditions. However, the design of ultrastable hydrophobic MOFs with high conductivity for use in microelectronics as conducting and dielectric materials remains a challenge. In this Review, we discuss applications of an emerging class of hydrophobic MOFs with respect to their use as active sensor coatings, tunable low-κ dielectrics and conductivity, which provide high-level roadmap for stimulating the next steps toward the development and implementation of hydrophobic MOFs for use in microelectronic devices. Several methodologies including the incorporation of long alkyl chain and fluorinated linkers, doping of redox-active 7,7,8,8-tetracyanoquinodimethane (TCNQ), the use of guest molecules, and conducting polymers or carbon materials in the pores or surface of MOFs have been utilized to produce hydrophobic MOFs. The contact angle of a water droplet and a coating can be used to evaluate the degree of hydrophobicity of the surface of a MOF. These unique advantages enable hydrophobic MOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Classic representative examples of each category are discussed in terms of coordination structures, types of hydrophobic design, and potential microelectronic applications. Lastly, a summary and outlook as concluding remarks in this field are presented. We envision that future research in the area of hydrophobic MOFs promise to provide important breakthroughs in microelectronics applications.     

Synthesis and Characterization of Polystyrene/Nanosilica Organic-Inorganic Hybrid

IntroductionIn the past two decades, because of its potentialindustrial applications, organic-inorganic compositeshave attracted the attention of both researchers andacademicians. Organic-inorganic hybrids offer the pos-sibility to combine both the advant…     

Synthesis and Characterization of a Sol–Gel Derived Ureasilicate Hybrid Organic-Inorganic Matrix Containing CdS Colloidal Particles

The electrical properties of sol–gel-derived films can be tailored by embedding conductive particles of ruthenium dioxide or carbon black in an insulating amorphous SiO₂ silica matrix. The preparation process included an acid hydrolysis of tetraethoxysilane and methyltrimethoxysilane. Then alcohol solutions of ruthenium chloride or carbon black were added. Films of filler concentration up to 60 vol.% were prepared by dip coating and then dried and heat-treated at various temperatures up to 600_°C. The D.C. resistance of the films can be varied within the range of 10⁹ to 10^–2 cm. A non-linear dependence on filler composition in the films was observed for both systems, which is explained by a modified percolation theory. A percolation threshold of 5.5 vol.% for SiO₂-RuO₂ or 50 vol.% for SiO₂-C films, whereby the resistance drastically decreases, was determined. Moreover the temperature dependency of resistance and the current-voltage characteristics of the films can also be explained by this geometric model.     

Sulfur-/Nitrogen-Rich Albumen Derived “Self-Doping” Graphene for Sodium-Ion Storage

The development of sodium-ion batteries (SIBs) is hindered by the rapid reduction in reversible capacity of carbon-based anode materials. Outside-in doping of carbon-based anodes has been extensively explored. Nickel and NiS₂ particles embedded in nitrogen and sulfur codoped porous graphene can significantly improve the electrochemical performance. Herein a built-in heteroatom “self-doping” of albumen-derived graphene for sodium storage is reported. The built-in sulfur and nitrogen in albumen act as the doping source during the carbonization of proteins. The sulfur-rich proteins in albumen can also guide the doping and nucleation of nickel sulfide nanoparticles. Additionally, the porous architecture of the carbonized proteins is achieved through removable KCl/NaCl salts (medium) under high-temperature melting conditions. During the carbonization process, nitrogen can also reduce the carbonization temperature of thermally stable carbon materials. In this work, the NS-graphene delivered a specific capacity of 108.3 mAh g⁻¹ after 800 cycles under a constant current density of 500 mA g⁻¹. In contrast, the Ni/NiS₂/NS-graphene maintained a specific capacity of 134.4 mAh g⁻¹; thus the presence of Ni/NiS₂ particles improved the electrochemical performance of the whole composite.     

Internal Polarity of Class I and Class II Type Sol–Gel Hybrid Materials Using Aromatic Aminoketones as Solvatochromic Probes for Adsorbed Solvents and the Silicatic Cage

2-Hydroxyethylamino functionalized aromatic amino ketones bearing furyl and thienyl as well as 4-N, N-dimethylaminophenyl moieties have been used as solvatochromic probes when entrapped physically (Class I) and chemically bonded (Class II), respectively, to silicatic sol–gel hybrid materials. Class I hybrid materials have been obtained by encapsulation the dissolved probe during the acidically induced sol–gel procedure using various amounts of methyltrimethoxysilane and tetramethoxysilane as components. Class II xerogels have been synthesized by functionalization of the 2-hydroxyethylamino substituted aryl ketones with 3-isocyanatopropyltriethoxysilane and subsequent sol–gel process with TEOS (tetraethoxysilane). Molecular structures of the hybrid materials have been confirmed by solid-state MAS CP -²⁹Si and -¹³C NMR spectroscopy.Significant influences of the polarity of adsorbed solvents and of composition of the sol–gel material on the UV/Vis absorption spectrum of the encapsulated solvatochromic moiety are observed.Mobility of the entrapped probe and the associated influence of the adsorbed solvent upon the probe in the pores are significantly different for the two different classes of sol–gel materials studied.Solvatochromism of Class I xerogels shows that opposite effects of primary alcohols as function of alkyl chain length on the interfacial polarity are observed. They are caused by the influence of the internal surface modified with the solvent and origin solvent polarity on the UV/Vis spectrum of the encapsulated probe. Class II xerogels show related effects as observed for the probes studied in well behaved regular solvents.     

Hybrid organic–inorganic sol–gel materials for micro and nanofabrication

In this review hybrid organic–inorganic (HOI) resists as emerging materials alternative to organic polymers for micro and nanolithography are presented and discussed. In particular, results on sol–gel materials belonging to 3-glycidoxypropyltrimethoxysilane based HOI are presented and reviewed, highlighting as various lithographic techniques can be used to pattern their surface and showing examples of micro- and nano-patterned structures achieved with radiation assisted lithography (UV, X-rays and electron beam) or imprint techniques. It will be demonstrated the particular versatility shown by some of these materials, that in some case can be processed with all the lithographic methods herein considered, without any significant modification of their main composition and synthesis procedure. Moreover, results about the investigation of interaction between radiation and HOI materials and thermal treatment will be discussed, as well as possible synthesis strategies and composition modification developed in order to improve efficiency of curing, tailor HOI properties to specific needs (optical properties, resist composition, mechanical stability, etc.) and explore innovative and non conventional patterning techniques. The reported results highlight as these novel materials, thanks to their solution processability and higher performances respect to commercial polymeric resists, allow to use the above mentioned lithographic techniques in a direct patterning process, strongly simplifying conventional technique and reducing their processing time and costs.