Today cross-cutting approaches, where molecular engineering and clever processing are synergistically coupled, allow the chemist to tailor complex hybrid systems of various shapes with perfect mastery at different size scales, composition, functionality, and morphology. Hybrid materials with organic–inorganic or bio–inorganic character represent not only a new field of basic research but also, via their remarkable new properties and multifunctional nature, hybrids offer prospects for many new applications in extremely diverse fields. The description and discussion of the major applications of hybrid inorganic–organic (or biologic) materials are the major topic of this critical review. Indeed, today the very large set of accessible hybrid materials span a wide spectrum of properties which yield the emergence of innovative industrial applications in various domains such as optics, micro-electronics, transportation, health, energy, housing, and the environment among others (526 references).

Applications of advanced hybrid organic–inorganic nanomaterials: from laboratory to market

Degradation Mechanisms and Reactions in Organic Light-Emitting Devices.

Since the mid 1990s soluble, well-characterized high molecular weight metal-containing and metallosupramolecular polymers have become readily available for the first time, even in some cases, with narrow molecular weight distributions and controlled architectures such as block copolymers. This has led to a rapidly expanding interest in their properties and uses. The review provides a survey of the range of applications for these new materials, which combine the processing advantages of polymers with the functionality provided by the presence of metal centers.

Metallopolymers: New Multifunctional Materials

Periodic Mesoporous Organosilicas (PMOs) were developed in 1999 and are basically ordered templated mesoporous organosilicas, prepared by the combination of a surfactant as template and a silsesquioxane as the organosilica precursor. They were one of the first examples of the so-called "hybrid" organic/inorganic materials. In the years that followed, an amazing variety of functional groups, morphologies and applications has been developed. Some of these high-end applications, like low-k buffer layers in microelectronics, chiral catalysts, chromatographic supports, selective adsorbents and light-harvesting devices, have clearly shown their potential. In this review, we will give a comprehensive overview of all these different functionalities and applications that have been created for Periodic Mesoporous Organosilicas.

Periodic mesoporous organosilicas : from simple to complex bridges : a comprehensive overview of functions, morphologies and applications

Polymer brush coatings for combating marine biofouling

Direct Writing of Patterned Ceramics Using Electron‐Beam Lithography and Metallopolymer Resists

Adv. Mater. 2010, 22, 99–102 2010 WILEY-VCH Verlag Gm Since the conceptual and experimental breakthrough in 1992 on a soft-templating method to synthesize periodic mesoporous silica materials, their synthesis has evolved to the level of being able to adroitly control composition, pore size, mesopore architecture, and morphology. A significant advance in controlling the composition of periodic mesoporous silica materials is the successful integration of bridging organic groups into the siliceous pore wall to create periodic mesoporous organosilicas (PMOs). The enabling power of PMOs to fuse organic synthesis and inorganic materials chemistry has created opportunities for application in numerous areas, encompassing catalysis, separation, drug delivery, photonics, and nanoelectronics. Most PMOs synthesized to date are powders but many technologically relevant applications, such as sensors, membranes, displays, optical coatings, and microelectromechanical systems, require thin-film morphology because of the ease of materials property characterization and device fabrication on thin films. A quintessential example of the need for thin-film PMOs is their application as a lowdielectric-constant (low-k) insulating material on microelectronic chips in the semiconductor industry. The synthesis of PMO thin films has been achieved primarily through evaporation-induced self-assembly liquid-phase delivery techniques, such as spin-coating and dip-coating. However, the best-controlled and preferred techniques for fabricating insulating dielectrics in the semiconductor industry are vaporphase delivery techniques, such as chemical vapor deposition. An aerosol-deposition strategy for fabricating mesostructured thin films combines the advantages of vapor-phase delivery and evaporation-induced self-assembly and, at the same time, circumvents the difficulty of vaporizing low-volatility templates. Here, we report a vacuum-assisted aerosol deposition evaporation-induced self-assembly (VAAD-EISA) approach for fabricating highly ordered PMO thin films. The aerosol is generated by atomizing a solution of PMO precursors, surfactant, acid catalyst, and water in a chosen organic solvent. During aerosol transport, vacuum assists the evaporation of the solvent to induce self-assembly of themesostructure inside sub-micrometer aerosol droplets at room temperature. The aerosol is then forced through a specially designed converging nozzle to facilitate its deposition on a spinning substrate to form thin films with uniform surface coverage. After aging at room temperature, the as-synthesized films are heated under a nitrogen flow to remove templates. The structural, dielectric, and mechanical characterization of the thin films are subsequently carried out, and the results are reported herein. Figure 1 shows the VAAD system. It consists of an atomizer (TSI Model 3076), a transport tube, a deposition chamber with a spinning stage and a vacuum system. To achieve thin-film deposition, a de Laval nozzle design is used in order to accelerate the aerosol flow at the nozzle exit. A higher aerosol flow rate and a shorter nozzle-to-substrate distance (usually 0.5–1mm) significantly increase the deposition rate and decrease the deposition time from a few minutes to 10–20 seconds. The solution preparation is based on the previous spin-coating procedure with an increased amount of ethanol so as to extend the window of optimum deposition time.

Vacuum‐Assisted Aerosol Deposition of a Low‐Dielectric‐Constant Periodic Mesoporous Organosilica Film

This paper demonstrates for the first time thermally induced gradual hydrophobization, monitored quantitatively by ellipsometric porosimetry, of four prototypical periodic mesoporous organosilicas (PMOs) that are tailored through materials chemistry for use as low-dielectric-constant (low k) materials in microprocessors. Theoretical aspects of this quantification are briefly discussed. A comparison of structural, mechanical, dielectric, and hydrophobic properties of ethane, methane, ethene, and 3-ring PMOs is made. Particularly, ethane, methane, and 3-ring PMOs show impressive water repellency at post-treatment temperatures as low as 350 °C, with corresponding Young’s modulus values greater than 10 GPa and k values smaller than 2, a figure of merit that satisfies the technological requirements of future generation microchips.

Water Repellent Periodic Mesoporous Organosilicas

Water-stable diblock polystyrene-block-poly(2-vinyl pyridine) and diblock polystyrene-block-poly(methyl methacrylate) cylindrical patterned surfaces inhibit settlement of zoospores of the green alga Ulva.

The effect of temperature during solvent annealing on the microdomain orientation of block copolymer ultrathin films was investigated using symmetric polystyrene-block-poly(methyl methacrylate) dib...

Daniel Grozea

Papers

Direct Writing of Patterned Ceramics Using Electron‐Beam Lithography and Metallopolymer Resists

Vacuum‐Assisted Aerosol Deposition of a Low‐Dielectric‐Constant Periodic Mesoporous Organosilica Film

Water Repellent Periodic Mesoporous Organosilicas

Water-stable diblock polystyrene-block-poly(2-vinyl pyridine) and diblock polystyrene-block-poly(methyl methacrylate) cylindrical patterned surfaces inhibit settlement of zoospores of the green alga Ulva.

Microdomain Orientation of Diblock Copolymer Ultrathin Films Solvent Annealed at Low Temperatures