In-situ study of sol–gel processing by time-resolved infrared spectroscopy

Sol–gel processing of thin films involves time dependent phenomena which are basically driven by solvent evaporation. An example is evaporation induced self-assembly that is used to prepare mesoporous ordered films through self-organization of templating micelles. The possibility to follow in situ as a function of time the evolution of the system can give a better knowledge of the process and the physics and chemistry beneath. Time-resolved infrared techniques have been applied to different sol–gel systems to study time-dependent phenomena, in particular rapid scan time resolved infrared spectroscopy has been used to monitor in situ the process and as a tool to design the sol–gel synthesis.     

Formamidines and triazenes as precursors for the preparation of rhenium imido-complexes

Summary The rhenium(V) imido-complexes [Re(NR)Cl₃(PPh₃)₂] have been obtained by heating the rhenium(V) derivative [ReOCl₃(PPh₃)₂] with RNHCHNR R = Ph (1a), p-MeC₆H₄ (1b), p-ClC₆H₄ (1c) andp-FC₆H₄ (1d) in THF under reflux. [Re(NR)Cl₃(PPh₃)₂] (R =p-MeQ₆H₄) has also been obtained by heating the rhenium(III)-triazenido complex [ReCl₂(RN N NR)(PPh₃)₂] in CCl₄ under reflux.     

Endpoint Bounds for the Quartile Operator

It is a result by Lacey and Thiele (Ann. of Math. (2) 146(3):693–724, 1997; ibid. 149(2):475–496, 1999) that the bilinear Hilbert transform maps $L^{p_{1}}(\mathbb{R}) \times L^{p_{2}}(\mathbb{R}) $ into $L^{p_{3}}(\mathbb{R})$ whenever (p ₁,p ₂,p ₃) is a Hölder tuple with p ₁,p ₂>1 and $p_{3}>\frac{2}{3}$ . We study the behavior of the quartile operator, which is the Walsh model for the bilinear Hilbert transform, when $p_{3}=\frac{2}{3}$ . We show that the quartile operator maps $L^{p_{1}}(\mathbb{R}) \times L^{p_{2}}(\mathbb{R}) $ into $L^{\frac{2}{3},\infty}(\mathbb{R})$ when p ₁,p ₂>1 and one component is restricted to subindicator functions. As a corollary, we derive that the quartile operator maps $L^{p_{1}}(\mathbb{R}) \times L^{p_{2},\frac{2}{3}}(\mathbb{R}) $ into $L^{\frac{2}{3},\infty}(\mathbb{R})$ . We also provide weak type estimates and boundedness on Orlicz-Lorentz spaces near p ₁=1,p ₂=2 which improve, in the Walsh case, the results of Bilyk and Grafakos (J. Geom. Anal. 16 (4):563–584, 2006) and Carro et al. (J. Math. Anal. Appl. 357(2):479–497, 2009). Our main tool is the multi-frequency Calderón-Zygmund decomposition from (Nazarov et al. in Math. Res. Lett. 17(3):529–545, 2010).     

Mesoporous aluminophosphate thin films with cubic pore arrangement

Mesoporous aluminophosphate thin films with 3D cubic (Im3m) pore arrangement were synthesized for the first time. Thin films were templated with block copolymer nonionic templates Pluronic F127 and F108 and deposited on a glass substrate by dip-coating. In situ SAXS investigations show the formation of a highly ordered mesostructure upon the dip-coating process, which remains stable up to at least 670 K. A cubic mesostructure was observed also by TEM. Template removal process was monitored by TG and FT-IR. A transition from an amorphous aluminophosphate gel to a well-defined aluminophosphate framework was observed by MAS NMR.     

Mesoporous hybrid thin films: the physics and chemistry beneath

Mesoporous films containing organic or biological functions within an organised array of cavities are produced by combining sol-gel, self-assembly of supramolecular templates and surface chemistry. This paper reviews the essential physics and chemical concepts behind the synthesis of these complex multifunctional materials.     

Structure of adsorbed polyelectrolyte monolayers investigated by combining optical reflectometry and piezoelectric techniques

Polyelectrolyte monolayers on solid substrates are studied with optical reflectivity and the quartz crystal microbalance (QCM). In particular, we investigate the adsorption of anionic poly(styrene sulfonate) (PSS) on amino-functionalized silica as well as cationic poly(allylamine hydrochloride) (PAH) and poly-L-lysine (PLL) on bare silica. By comparing the dry and wet masses measured on identical substrates with these two techniques, we obtain information on the layer thickness and water content of these layers. Monolayers typically feature an adsorbed dry mass of about 0.1-2 mg/m(2), a layer thickness of 0.5-2 nm, and a water content of 20-50%. One finds that the layer thickness increases with increasing concentrations of monovalent salts and polyelectrolytes.     

Top-down patterning of zeolitic imidazolate framework composite thin films by deep X-ray lithography

For the first time a top-down process was used to control the spatial location of Metal-Organic Frameworks on a surface. Deep X-ray lithography was utilised to micropattern a Zeolitic Imidazolate Framework layer on a sol-gel surface, with exposure hardening the sol-gel by inducing crosslinking while leaving the frameworks intact.     

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).     

Entrapping of Push-Pull Zwitterionic Chromophores in Hybrid Matrices for Photonic Applications

A new class of heterocycle-based push-pull chromophores showing enhanced nonlinear properties characterized by an aromatic and highly zwitterionic ground state and a quinoid/neutral excited state have been synthesized to be incorporated in sol-gel hybrid systems. This class of compounds shows very large first molecular hyperpolarizabilities ( as high as 27000 × 10^–48 esu) and is a promising candidate for photonic applications where large second order non-linearities are required. In spite of their very large hyperpolarizability and chemical and thermal stability, these chromophores are decomposed in presence of light and oxygen (photobleaching) and are sensitive to acidic environments due to the carbanionic nature of the donor moiety. A hybrid matrix, based on N-[(3-trimethoxysilyl)propyl]ethylenediamine and 3-glycidoxypropyltrimethoxysilane, has been specifically designed to allow the incorporation of such zwitterionic compounds assuring at the same time a good temporal stability of the optical properties. Amine functionalisation has been found very effective in reducing the photobleaching by acting on these chromophores via the singlet oxygen. Second harmonic generation has been observed on poled films, and an order parameter, , of 0.17 has been estimated. The nonlinear coefficient d_eff of the samples has been thus estimated at a value two times larger than for d₁₁ of quartz that, from literature data, is about 0.335 pm/V.