L'air Liquide Société Anonyme Pour L'etude Et L'exploitation Des Procédés Georges Claude

American Air Liquide, Inc.

Air Liquide Advanced Materials, Inc.

Manish Khandelwal

Peng Zhang

Gennadiy Itov

Antonio Sanchez

Jean-Marc Girard

Matthew Damien Stephens

Reno Pesaresi

Sean Kerrigan

Glenn Kuchenbeiser

Cole Ritter

Yang Wang

David Orban

Zhiwen Wan

Guillaume Husson

Nicolas Blasco

Grigory Nikiforov

Larry Kit-wing Leung

Compounds and method of preparation of Si&#x2014;X and Ge&#x2014;X compounds (X&#x2550;N, P, As and Sb) via dehydrogenative coupling between the corresponding unsubstituted silanes and amines (including ammonia) or phosphines catalyzed by metallic catalysts is described. This new approach is based on the catalytic dehydrogenative coupling of a Si&#x2014;H and a X&#x2014;H moiety to form a Si&#x2014;X containing compound and hydrogen gas (X&#x2550;N, P, As and Sb). The process can be catalyzed by transition metal heterogenous catalysts such as Ru(0) on carbon, Pd(0) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The &#x2014;Si&#x2014;X products produced by dehydrogenative coupling are inherently halogen free. Said compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si-containing films.

Halogen free syntheses of aminosilanes by catalytic dehydrogenative coupling

A Si-containing film forming composition comprising a catalyst and/or a polysilane and a N&#x2014;H free, C-free, and Si-rich perhydropolysilazane having a molecular weight ranging from approximately 332 dalton to approximately 100,000 dalton and comprising N&#x2014;H free repeating units having the formula [&#x2014;N(SiH3)x(SiH2-)y], wherein x=0, 1, or 2 and y=0, 1, or 2 with x+y=2; and x=0, 1 or 2 and y=1, 2, or 3 with x+y=3. Also disclosed are synthesis methods and applications for using the same.

Perhydropolysilazane compositions and methods for forming oxide films using same

Methods are disclosed for forming a Silicon Metal Oxide film using a mono-substituted TSA precursor. The precursors have the formula: (SiH3)2N&#x2014;SiH2-X, wherein X is selected from a halogen atom; an isocyanato group; an amino group; an N-containing C4-C10 saturated or unsaturated heterocycle; or an alkoxy group.

Si-containing film forming precursors and methods of using the same

Si-containing film forming compositions are disclosed comprising a precursor having the formula [&#x2014;NR&#x2014;RRSi&#x2014;(CH)&#x2014;SiRR&#x2014;]wherein n=2 to 400; R, R, R, R, and Rare independently H, a hydrocarbon group, or an alkylamino group, and provided that at least one of R, R, R, and Ris H; and R is independently H, a hydrocarbon group, or a silyl group. Exemplary pre-cursors include, but are not limited to, [&#x2014;NH&#x2014;SiH&#x2014;CH&#x2014;SiH&#x2014;], and [&#x2014;N(SiH&#x2014;CH&#x2014;SiH)&#x2014;SiH&#x2014;CH&#x2014;SiH&#x2014;].

Si-containing film forming compositions and methods of making and using the same

Compounds and method of preparation of Si&#x2014;X and Ge&#x2014;X compounds (X=N, P, As and Sb) via dehydrogenative coupling between the corresponding unsubstituted silanes and amines (including ammonia) or phosphines catalyzed by metallic catalysts is described. This new approach is based on the catalytic dehydrogenative coupling of a Si&#x2014;H and a X&#x2014;H moiety to form a Si&#x2014;X containing compound and hydrogen gas (X=N, P, As and Sb). The process can be catalyzed by transition metal heterogenous catalysts such as Ru(O) on carbon, Pd(O) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The &#x2014;Si&#x2014;X products produced by dehydrogenative coupling are inherently halogen free. Said compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si&#x2014;containing films.

Selective reduction methods for halogenated carbosilanes and carbodisilanes are disclosed. More particularly, high yields of the desired carbosilanes and carbodisilanes are obtained by reduction of their halogenated counterparts using a reducing agent and tetrabutylphosphonium chloride (TBPC) as a catalyst.

Catalytic reduction of halogenated carbosilanes and halogenated carbodisilanes

Solid or liquid N&#x2014;H free, C-free, and Si-rich perhydropolysilazane compositions comprising units having the following formula [&#x2014;N(SiH)(SiH&#x2014;)], wherein x=0, 1, or 2 and y=0, 1, or 2 when x+y=2; and x=0, 1 or 2 and y=1, 2, or 3 when x+y=3 are disclosed. Also disclosed are synthesis methods and applications for the same.

N&#x2014;H free and Si-rich per-hydridopolysilzane compositions, their synthesis, and applications

Methods for halogenation of a hydrosilazane include contacting the hydrosilazane with a halogenating agent in a liquid phase to produce the halosilazane having a formula(SiH(NR)X)N(SiHX),wherein each a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n&#x2265;1; wherein X is selected from a halogen atom selected from F, Cl, Br or I; each R is selected from H, a C-Clinear or branched, saturated or unsaturated hydrocarbyl group, or a silyl group [SiR']; further wherein each R&#x2032; of the [SiR&#x2032;] is independently selected from H, a halogen atom selected from F, Cl, Br or I, a C-Csaturated or unsaturated hydrocarbyl group, a C-Csaturated or unsaturated alkoxy group, or an amino group [&#x2014;NRR] with each Rand Rbeing further selected from H or a C-Clinear or branched, saturated or unsaturated hydrocarbyl group.

Methods of synthesizing Si&#x2014;H containing iodosilanes, such as diiodosilane or pentaiododisilane, using a halide exchange reaction are disclosed.

Preparation of Si-H containing iodosilanes via halide exchange reaction

N&#x2014;H free and SI-rich per-hydridopolysilzane compositions, their synthesis, and applications

Halogen free amine substituted trisilylamine and tridisilylamine compounds and a method of their preparation via dehydrogenative coupling between the corresponding unsubstituted trisilylames and amines catalyzed by transition metal catalysts is described. This new approach is based on the catalytic dehydrocoupling of a Si&#x2014;H and a N&#x2014;H moiety to form an Si&#x2014;N containing compound and hydrogen gas. The process can be catalyzed by transition metal heterogenous catalysts such as Ru(0) on carbon, Pd(0) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The &#x2014;Si&#x2014;N containing products are halide free. Such compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si containing films.

Amine substituted trisilylamine and tridisilylamine compounds and synthesis methods thereof

Compounds and method of preparation of Si&#x2014;X and Ge&#x2014;X compounds (X=N, P, As and Sb) via dehydrogenative coupling between the corresponding unsubstituted silanes and amines (including ammonia) or phosphines catalyzed by metallic catalysts is described. This new approach is based on the catalytic dehydrogenative coupling of a Si&#x2014;H and a X&#x2014;H moiety to form a Si&#x2014;X containing compound and hydrogen gas (X=N, P, As and Sb). The process can be catalyzed by transition metal heterogenous catalysts such as Ru(0) on carbon, Pd(0) on MgO) as well as transition metal organometallic complexes that act as homogeneous catalysts. The &#x2014;Si&#x2014;X products produced by dehydrogenative coupling are inherently halogen free. Said compounds can be useful for the deposition of thin films by chemical vapor deposition or atomic layer deposition of Si-containing films.

Mono-substituted TSA precursor Si-containing film forming compositions are disclosed. The precursors have the formula: (SiH)N&#x2014;SiH&#x2014;X, wherein X is selected from a halogen atom; an isocyanato group; an amino group; an N-containing C-Csaturated or unsaturated heterocycle; or an alkoxy group. Methods for forming the Si-containing film using the disclosed mono-substituted TSA precursor are also disclosed.

Preparation of Si&#x2014;H containing iodosilanes via halide exchange reaction

Si-containing film forming compositions comprising Si&#x2014;C free and volatile silazane-containing precursors are disclosed. The compositions may be used to deposit high purity thin films. The Si&#x2014;C free and volatile silazane-containing precursors have the formulae:[(SiR)NSiH]&#x2014;NH&#x2014;C&#x2261;N, with=1 or 2;&#x2003;&#x2003;(a)[(SiR)NSiH]&#x2014;NL,with=2 or 3;&#x2003;&#x2003;(b)(SiH)NSiH&#x2014;O&#x2014;SiHN(SiH); and&#x2003;&#x2003;(c)(SiR')N&#x2014;SiH&#x2014;N(SiR&#x2032;);&#x2003;&#x2003;(d)with each R independently selected from H, a dialkylamino group, or an amidinate; each R&#x2032; independently selected from H, a dialkylamino group, or an amidinate, with the provision that all R&#x2032; are not H; and L is selected from H or a C-Chydrocarbyl group.

Growing community of inventors

Somerset, NJ, United States of America

Manish Khandelwal