Perfect and nearly perfect silsesquioxane (SQs) nanoconstruction sites and Janus SQs

Laine, Richard M.; Roll, Mark F.; Asuncion, Michael Z.; Sulaiman, Shahril Irwan; Popova, Vera; Bartz, D.; Krug, Dave J.; Mutin, P. Hubert

doi:10.1007/s10971-008-1700-9

Cited by 47 publications

(36 citation statements)

References 44 publications

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“…A range of nanocomposites [ 25 ] and nanoporous materials can be achieved with applicability in a range of technologies including low-dielectric constant-interlayer dielectrics for semiconductor interconnects, [ 26 ] hydrogen storage materials, encapsulants for drug delivery, porous media for trapping pollutants and other condensates, and functional coatings for scratch resistance or diffusion barriers. [ 27 ] Elsewhere some of the coauthors have developed a series of low-cost bifunctional (having two types of organic pendants R on the same inorganic cage core) SSQs from rice hull ash, a renewable, abundant agricultural waste product, providing a sustainable route for these versatile materials. [ 27 ] Here, we demonstrate that these low-cost, readily available bifunctional SSQs can be engineered into high-performance imprint mold materials that combine the ease of processing found in the soft organic templates with the thermal resistance, structural rigidity, and patterning resolution of the hard template materials.…”

Section: Doi: 101002/adma201001761mentioning

confidence: 99%

“…[ 27 ] Elsewhere some of the coauthors have developed a series of low-cost bifunctional (having two types of organic pendants R on the same inorganic cage core) SSQs from rice hull ash, a renewable, abundant agricultural waste product, providing a sustainable route for these versatile materials. [ 27 ] Here, we demonstrate that these low-cost, readily available bifunctional SSQs can be engineered into high-performance imprint mold materials that combine the ease of processing found in the soft organic templates with the thermal resistance, structural rigidity, and patterning resolution of the hard template materials. These hybrids offer superior performance as a NIL mold material compared to their wholly organic or inorganic analogs.…”

Section: Doi: 101002/adma201001761mentioning

confidence: 99%

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Cubic Silsesquioxanes as a Green, High‐Performance Mold Material for Nanoimprint Lithography

Popova

Chen

et al. 2010

Advanced Materials

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Optical lithography deep in the UV spectrum is the predominate route for high-resolution, high-volume nanoscale pattering. However, state-of-the-art optical lithography tools are exceedingly expensive and this places serious limitations on the applications, technical sectors, and markets where highresolution patterning can be implemented. To date the only substantial market for high-end optical lithography tools has been semiconductor fabrication. Nanoimprint lithography (NIL) has recently emerged as an alternative to optical lithography and combines the potential of sub-fi ve-nanometer patterning resolution with the low cost and simplicity of a stamping process. [1][2][3][4] This has led to signifi cant efforts to implement NIL methods, not only for semiconductor logic devices, but also in fi elds as diverse as the direct patterning of interlayer dielectrics (ILDs) for back-end-of-line (BEOL) interconnect structures, [5][6][7] bitpatterned magnetic media for data storage, [ 8 , 9 ] and high-brightness light-emitting diodes (LEDs). [ 10 ] Some of these are new areas where nanoscale patterning has previously not been considered, and are made possible here by the low cost and simplicity of the NIL stamping processes.NIL and other stamping processes are direct write (1 × ) technologies. There is a one-to-one correlation between the features in the mold and the imprint, meaning that high-quality imprint molds are critical. In fact, one of the biggest impediments to the widespread implementation of NIL is the limited availability of high-quality molds. High-resolution imprint molds are usually fabricated by slow, serial patterning techniques such as electron-beam (e-beam) lithography. While the NIL tools themselves are relatively inexpensive, the fabrication of highresolution 1 × molds can be prohibitive in terms of the fabrication time and cost. Furthermore, the notion of stamping these expensive master templates into contact with a resist material under high-temperature and elevated pressure radiation raises concerns regarding template durability. Ideally they should be cheap, simple, and easy to replace.There are several critical properties, in addition to patternability, that must be achieved when designing NIL molds. In the thermal embossing form of NIL, [ 1 , 2 ] a hard mold is pressed into a molten polymer fi lm at elevated temperature and a squeezefl ow process generates the pattern. The NIL mold material needs to have appropriate mechanical properties to resist deformation under the imprinting conditions and to withstand the elevated temperatures. With the UV forms of NIL, [ 3 , 4 ] a monomeric liquid fl ows into the cavities of the mold and is crosslinked into a rigid pattern upon exposure to the radiation. Here, the mold must not only be mechanically robust, but also UV transparent. In all forms of NIL, a low-energy surface is critical to facilitate the release of the high surface area mold from the imprint; the adhesive forces between mold and the template can become signifi cant.A range of materials ha...

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Section: Doi: 101002/adma201001761mentioning

confidence: 99%

Section: Doi: 101002/adma201001761mentioning

confidence: 99%

Cubic Silsesquioxanes as a Green, High‐Performance Mold Material for Nanoimprint Lithography

Popova

Chen

et al. 2010

Advanced Materials

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“…POSS is a particularly intriguing class of versatile building blocks . The preparation of Janus silsesquioxane structures has been a great challenge . Recently, there has been some progress being made on the synthesis of Janus POSS compounds but the side chains are mostly inert .…”

Section: Introductionmentioning

confidence: 99%

Regioisomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes

Shao

Yin

Jin

et al. 2018

Chemistry A European J

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We report the design, synthesis and self-assembly of a series of tandem triblock shape amphiphile regioisomers composed of one rod-like fluorinated polyhedral oligomeric silsesquioxane (FPOSS) cage tethered with two spherical tert-butyl-POSS (tBPOSS) cages in para-, meta-, and ortho-configurations. Precision syntheses are achieved through sequential "click" reactions and the compounds are thoroughly characterized by combined techniques of NMR, FT-IR and MALDI-TOF MS spectroscopy. Only the ortho-isomer forms an ordered lamellae structure induced by the crystallization of perfluoroalkyl-chains and the other two remain amorphous due to frustrated packing by unfavorable regio-configuration. The distinct assembly behaviors of these three regioisomers reflect the delicate influence of a minute structural difference on precision macromolecular assembly.

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“…2(b)]. 27) We have also recently developed facile routes to functionalized T 10 / T 12 cages, such as thiol T 10 [ Fig. 2(c)] and the vinyl T 10 /T 12 compounds described further below.…”

Section: Introductionmentioning

confidence: 99%

Facile thiol-ene reactions of vinyl T<sub>10</sub>/T<sub>12</sub> silsesquioxanes for controlled refractive indices for transparent fiber glass reinforced composites

Asuncion

Krug

Abu-Seir

et al. 2015

J. Ceram. Soc. Japan

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A series of thioether-functionalized silsesquioxanes (SQs) was synthesized by radically initiated thiol-ene reactions of vinyl T 10 / T 12 SQ cages with a variety of commercially available thiols. The objectives of this study were to develop model reactions as the basis for using the vinyl T 10/12 compounds as novel crosslinking agents in the synthesis of new types of thiol-ene crosslinked polymers. A second motivation was to develop model compounds with controlled refractive indices and Abbe numbers as possibly modifiers of polymers used for a wide variety of optical and photonic applications. The reactions proceed under mild conditions over 24 h to give thioether SQs in high yields (>90%) and high purity without complex workup. The ease of synthesis coupled with the wide variety and availability of functionalized thiols provides a simple route to elaborating and functionalizing vinyl SQ cages. In addition, the resulting compounds exhibit refractive indices to 1.52 coupled with Abbe numbers to 51 due to the uniquely high electron density provided by the incorporated sulfur atoms, making them ideal compounds for use with optically transparent materials. In addition, cured forms of these compounds provide methods of raising the Abbe number of epoxy resins designed to index match fiberglass with the intent of making transparent fiberglass reinforced composites.

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Perfect and nearly perfect silsesquioxane (SQs) nanoconstruction sites and Janus SQs

Cited by 47 publications

References 44 publications

Cubic Silsesquioxanes as a Green, High‐Performance Mold Material for Nanoimprint Lithography

Cubic Silsesquioxanes as a Green, High‐Performance Mold Material for Nanoimprint Lithography

Regioisomeric Tandem Triblock Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxanes

Facile thiol-ene reactions of vinyl T<sub>10</sub>/T<sub>12</sub> silsesquioxanes for controlled refractive indices for transparent fiber glass reinforced composites

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