Leonard V. Interrante

Rensselaer Polytechnic Institute

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J. S. Kasper

Hidradenitis Suppurativa Foundation

I. S. Jacobs

General Electric (United States)

H. R. Hart

General Electric (United States)

J. W. Bray

General Electric (United States)

Qionghua Shen

The University of Texas Southwestern Medical Center

J. C. Bonner

University of Rhode Island

G. D. Watkins

Aalto University

David Larkin

University of Sydney

K. W. Browall

General Electric (United States)

John B. Hudson

Rensselaer Polytechnic Institute

Cooperative Institutions

Rensselaer Polytechnic Institute

Centre National de la Recherche Scientifique

General Electric (United States)

American Ceramic Society

Massachusetts Institute of Technology

University of California, Berkeley

Brookhaven National Laboratory

Materials Science & Engineering

General Electric (Israel)

University of Illinois Urbana-Champaign

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Ultra Low‐k Films Derived from Hyperbranched Polycarbosilanes (HBPCS)

Advanced Functional Materials (2008)

Jitendra S. Rathore Leonard V. Interrante Géraud Dubois

Abstract Dense and porous hyperbranched carbosiloxane thin films (HBCSO) are obtained by sol–gel processing using methylene‐bridged hyperbranched polycarbosilanes (HBPCSs) with the general compositional formula {(OMe) 2 Si(CH 2 )}. Introduction of porosity is achieved using a porogen templating approach, allowing the control of the films' dielectric constant from 2.9 to as low as 1.8. Over the entire dielectric range, the HBCSO films exhibit exceptional mechanical properties, 2–3 times superior to those obtained for non‐alkylene bridged organosiloxanes such as methylsilsesquioxanes (MSSQs) of similar densities and k ‐values.

Methylene

10.1002/adfm.200801197

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Citations (71)

Selective Deposition of a Cross-Linked Low-Permittivity Polycarbosilane on Copper

ACS Applied Materials & Interfaces (2010)

Binay Singh Jaeyong Hyun Amit Pratap Singh D. D. Gandhi Ziling Wu

Differential scanning calorimetry studies of the reaction of a cyclolinear polycarbosilane [cyclo-(CH3Si(CH2)2SiCH3)-(CH2)6]n on air-exposed Cu surfaces reveal a substantial enhancement of the cross-linking rate compared to noncatalytic surfaces, e.g., Au, Ag, Al, Si. The increased rate is attributed to surface Cu(II)-catalyzed opening of the embedded disilacyclobutane rings in the polymer. This rate enhancement is used to selectively deposit a cross-linked polycarbosilane on copper patterns in exclusion to the silicon substrate surface. These results could be attractive for realizing metal-dielectric interfaces for applications in nanodevice wiring and packaging.

Deposition

10.1021/am100441t

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Citations (10)

Synthesis, Characterization, and Glass Transitions of Some Asymmetrically Substituted Poly(siloxanes)

Macromolecules (1997)

Qionghua Shen Leonard V. Interrante

A homologous series of poly(n-alkylmethylsiloxanes), [SiMe(R)O]n, were prepared by cationic ring-opening polymerization (ROP) of cyclotrisiloxanes containing n-alkyl substituents, such as C2H5, n-C3H7, n-C4H9, n-C5H11, and n-C6H13, on the Si. The resultant polymers were characterized by NMR, GPC, and DSC measurements. All of these asymmetrically substituted polymers were obtained in high molecular weight form and were found to have an atactic configuration. Their glass transitions were found to increase smoothly from Et to n-Hex (i.e., −139, −120, −115, −111.9, and −108 °C, for Et to n-Hex, respectively). These Tgs are much lower than those of the corresponding polyolefins, [C(H)(R)CH2]n. Moreover, in the case of these polyolefins, the Tgs decrease continuously from R = Me to n-Hex. The calculated Tgs for the polysiloxanes that were obtained by using published empirical equations show the same general trend as the experimental values.

Cationic polymerization

Homologous series

Characterization

10.1021/ma970026j

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Citations (15)

ChemInform Abstract: Synthesis and Crystal Structure of (Ni(hMedbtaa)) (TCNQ). A Mixed‐Stack Donor‐Acceptor Molecular Solid.

ChemInform (1989)

Peter Spellane Leonard V. Interrante Rudolph K. Kullnig F.S. Tham

Acceptor

10.1002/chin.198931251

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Synthesis of Cyclolinear Poly(carbosilane)-g-poly(methyl methacrylate or styrene) Random Copolymers

Macromolecules (2006)

Jaeyong Hyun Junwon Han Chang Y. Ryu Leonard V. Interrante

The cyclolinear polycarbosilane, (poly(1-hexyl-1,3-ditolyl-1,3-disilacyclobutane) poly(HDTDSCB)), which has tolyl groups attached to the main chain Si atoms, was prepared by ADMET polymerization with the second-generation Grubbs catalyst, and 10%, 5%, and 2% of the tolyl groups were brominated by reactions with N-bromosuccinimide. A series of well-controlled poly(methyl methacrylate) (PMMA) anions of 2.5K, 5K, and 10K molecular weight were introduced via the "grafting onto" strategy at low temperature to the randomly 10%, 5%, and 2% brominated poly(HDTDSCB), respectively, without any lithiation or ring opening of the disilacyclobutane in the main chain. Because of side reactions initiated by the PS anion under similar conditions, a "grafting from" strategy by ATRP was employed to yield the corresponding poly(HDTDSCB)-g-PS random copolymers. The product poly(HDTDSCB)-g-(PMMA or PS) random copolymers were purified by using total adsorption−desorption interaction chromatography, which involves selective adsorption of the polycarbosilane on a C18 HPLC column from a CH2Cl2/CH3CN (50/50) eluent, while the excess PMMA or PS homopolymer eluted. This method was also successfully applied to the separation of larger quantities of the copolymers by using multiple injections onto the C18 column.

10.1021/ma061642v

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Citations (14)

Rotating Ring-Disk Electrodes II. Digital Simulation of First and Second-Order Following Chemical Reactions

D. T. Sawyer Leonard V. Interrante Grace E. M. Lewis M. Randell

A digital simulation technique has been employed to treat the steady-state and transient ring current behavior at the rotating ring-disk electrode (RRDE) for cases where the intermediate generated at the disk electrode undergoes a first- or second-order homogeneous chemical reaction leading to a nonelectroactive species. Where comparisons were possible, the results were found to be in good agreement with previous approximate theoretical treatments. Working curves are provided which allow determination of rate constants of the homogeneous reactions from ring-current-rot ation rate data.

Transient (computer programming)

Rotating ring-disk electrode

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Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes Part A Polymer chemistry

Journal of Polymer Science (2017)

Xinxing Liu Jitendra Singh Rathore Géraud Dubois Leonard V. Interrante

Alkylene‐ and arylene‐bridged cyclolinear polycarbosilanes (CLPCS) with 1,3‐disilacyclobutane (DSCB) rings incorporated in the main chain of the polymer were prepared by polycondensation between corresponding di‐functional DSCB derivatives and di‐Grignard reagents. Well‐defined, low molecular weight (Mₙ = 3–5K; DP = 17–26), hexylene‐ and phenylene‐bridged CLPCS polymers were obtained without appreciable ring opening of the DSCB rings. Large exothermic peaks were observed in the DSC for these CLPCSs, which indicated, along with the IR spectra, that crosslinking occurred on heating to about 250 °C via the ring opening of the embedded, alternating, DSCB rings. Moreover, PB‐CLPCS undergoes photochemically induced crosslinking on UV irradiation to form crosslinked polycarbosilane network films. The spin‐cast, cured, films of these CLPCSs exhibit relatively low dielectric constants and promising thermal and mechanical properties for applications in electronics, for example, directly UV‐photoimprinted low‐k dielectrics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1547–1557

Arylene

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Chemical vapor deposition of silicon carbide using a novel organometallic precursor. Technical report

W. Lee Leonard V. Interrante Corinna L. Czekaj John B. Hudson Klaus Lenz

Dense silicon carbide films were prepared by low pressure chemical vapor deposition (LPCVD) using a volatile, heterocyclic, carbosilane precursor. At deposition temperatures between 700 and 800 deg C, polycrystalline, stoichiometric SiC films were deposited on single crystal silicon and fused silica substrates. Optical microscopy and SEM analyses indicated formation of a transparent yellow film with a uniform, featureless surface and good adherence to the Si(111) substate. The results of preliminary studies of the nature of the gaseous by-products of the CVD processes and ultrahigh vacuum physisorption and decomposition of the precursor on Si(100) substrates are discussed.

Stoichiometry

Physisorption

Deposition

Silanes

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Structures of Side Chain Liquid Crystalline Poly(silylenemethylene)s

Macromolecules (2002)

Soo‐Young Park Tao Zhang Leonard V. Interrante Barry L. Farmer

The structures of side chain liquid crystalline poly(silylenemethylene)s (−(SiCH3R−CH2)−: R = O(CH2)NO−Ph−Ph, Ph = phenyl) (PSM-N; N = 3, 6, 8, 11) have been studied by X-ray diffraction, differential scanning calorimetry (DSC), polarized optical microscopy, and transmission electron microscopy (TEM). DSC study showed that PSM-Ns have multiple transitions that are dependent on the side chain length. All PSM-Ns studied show a series of sharp equatorial reflections in the X-ray fiber pattern at room temperature, a characteristic of well-ordered smectic phases. Layered smectic structures of PSM-Ns persist up to the isotropic temperature during heating, although the specific kinds of smectic phases changed. In each, the layer thickness corresponds to the single side chain length and increases with slope of ∼1.3 Å per methylene spacer. This is a single-layer structure. For PSM-3 and PSM-6, the mesogens pack in a two-dimensional orthorhombic cell, a characteristic of a smectic E (SE) phase, with dimensions a = 8.14 Å and b = 5.14 Å. The SE phase of PSM-3 and PSM-6 converts directly to the isotropic phase. For PSM-8 and PSM-11, the mesogens pack in a hexagonal smectic B (SB) cell at room temperature. This is manifest from the hexagonal six-point arrangement of reflections at d = 4.4 Å in the X-ray fiber pattern. During room temperature annealing, PSM-8 and PSM-11 crystallize into orthorhombic cells with parameters a = 8.80 Å, b = 5.08 Å, c = 50.8 Å for PSM-8 and a = 8.90 Å, b = 5.14 Å, c = 58.6 Å for PSM-11. Upon heating, the crystalline structures change to smectic A (SA) before becoming isotropic. Micrographs of PSM-11 show a layered structure with thickness matching that observed in X-ray pattern.

Orthorhombic crystal system

Side chain

10.1021/ma010449s

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Citations (26)

Poly(silylenemethylenes) — a novel class of organosilicon polymers

Journal of Organometallic Chemistry (1996)

Leonard V. Interrante Quan Liu Ilya L. Rushkin Qionghua Shen

Organosilicon

10.1016/0022-328x(96)06362-0

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Citations (69)