SILICON PRECURSORS AND COMPOSITIONS COMPRISING SAME FOR DEPOSITING LOW DIELECTRIC CONSTANT FILMS
A chemical vapor deposition method for producing a porous organosilica glass film comprising: introducing into a reaction chamber gaseous reagents comprising a porogenated precursor; optionally a structure former precursor selected from the group consisting an organosilane, an organosiloxane, and combinations thereof; and optionally a porogen precursor; applying an energy source to the gaseous reagents in the chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the porogen; and removing from the preliminary film at least a portion of the porogen to provide the porous film with pores and a dielectric constant less than 2.6.
1 . A chemical vapor deposition method for producing a porous organosilica glass film represented by the formula Si v O w C x H y F z , where v+w+x+y+z=100%, v is from 10 to 35 atomic %, w is from 10 to 65 atomic %, x is from 5 to 30 atomic %, y is from 10 to 50 atomic % and z is from 0 to 15 atomic %, said method comprising:
providing a substrate within a reaction chamber; introducing into the reaction chamber reagents comprising a porogenated precursor comprising a silicon atom bonded to a porogen; optionally a structure former precursor selected from the group consisting of an organosilane and an organosiloxane; and optionally a porogen precursor wherein the porogen in the porogenated precursor comprises 10 carbon atoms or less;
applying at least one energy source to the gaseous reagents in the reaction chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the porogen; and
removing from the preliminary film at least a portion of the porogen to provide the porous film with pores and a dielectric constant less than 2.6.
2 . The method of claim 1 wherein the dielectric constant is less than 2.2.
3 . The method of claim 1 wherein v is from 20 to 30 atomic %, w is from 20 to 45 atomic %, x is from 5 to 20 atomic %, y is from 15 to 40 atomic % and z is 0.
4 . The method of claim 1 wherein the at least one energy source is plasma energy.
5 . The method of claim 1 , wherein the structure former precursor comprises an organosiloxane is diethoxymethylsilane.
6 . The method of claim 5 , wherein the organosiloxane comprises diethoxymethylsilane.
7 . The method of claim 1 , wherein the structure former precursor is a compound represented by one or more of the following:
(a) the formula R 1 n (OR 2 ) p (O(O)CR 3 ) 4−(n+p) Si where R 1 is independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 is independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 3 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3 and p is 0 to 3;
(b) the formula R 1 n (OR 2 ) p (O(O)CR 4 ) 3−n−p Si—O—SiR 3 m (O(O)CR 5 ) q (OR 6 ) 3−m−q where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 6 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 4 and R 5 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 0 to 3, m is 0 to 3, q is 0 to 3 and p is 0 to 3, provided that n+m≧1, n+p≦3 and m+q≦3;
(c) the formula R 1 n (OR 2 ) p (O(O)CR 4 ) 3−n−p Si—SiR 3 m (O(O)CR 5 ) q (OR 6 ) 3−m−q where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 and R 6 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 4 and R 5 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 0 to 3, m is 0 to 3, q is 0 to 3 and p is 0 to 3, provided that n+m≧1, n+p≦3 and m+q≦3;
(d) the formula R 1 n (OR 2 ) p (O(O)CR 4 ) 3−n−p Si—R 7 —SiR 3 m (O(O)CR 5 ) q (OR 6 ) 3−m−q where R 1 and R 3 are independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 , R 6 and R 7 are independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 4 and R 5 are independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 0 to 3, m is 0 to 3, q is 0 to 3 and p is 0 to 3, provided that n+m≧1, n+p≦3, and m+q≦3;
(e) the formula (R 1 n (OR 2 ) p (O(O)CR 3 ) 4−(n+p) Si) t CH 4−t where R 1 is independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 is independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 3 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3, p is 0 to 3, and t is 2 to 4, provided that n+p≦4;
(f) the formula (R 1 n (OR 2 ) p (O(O)CR 3 ) 4−(n+p) Si) t NH 3−t where R 1 is independently H or C 1 to C 4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon; R 2 is independently C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R 3 is independently H, C 1 to C 6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, n is 1 to 3, p is 0 to 3 and t is 1 to 3, provided that n+p≦4; or
(g) cyclic carbosilanes of the formula (CR 1 R 3 SiR 1 R 3 ) x , where R 1 and R 3 are independently H, C 1 to C 4 , linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated, and x is an integer from 2 to 8.
8 . The method of claim 1 , wherein the structure former precursor is a member selected from the group consisting of diethoxymethylsilane, dimethoxymethylsilane, di-isopropoxymethylsilane, di-t-butoxymethylsilane, methyltriethoxysilane, methyltrimethoxysilane, methyltri-isopropoxysilane, methyltri-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-isopropoxysilane, dimethyldi-t-butoxysilane, and tetraethoxysilane.
9 . The method of claim 1 , wherein structure former precursor comprises a mixture of a first organosilicon precursor with two or fewer Si—O bonds with a second organosilicon precursor with three or more Si—O bonds, and the mixture is provided to tailor a chemical composition of the porous film.
10 . The method of claim 1 wherein the reagents comprise diethoxymethylsilane and tetraethoxysilane.
11 . A composition for depositing porous low dielectric constant film comprising:
(a)(i) a porogenated precursor selected from the group consisting of: octyltriethoxysilane, octyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltrimethoxysilane, octyltrimethoxysilane, octnyltriethoxysilane, hexyltriethoxysilane, isobutyltriethoxysilane, methylcyclohexyldiethoxysilane, cyclooctyltriethoxysilane, butyltriethoxysilane, cyclohexanetrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, neobutyltriethoxysilane, cyclopentyltriethoxysilane, cyclopentylmethyltriethoxysilane, (5-bicycloheptenyl)triethoxysilane, (5-bicycloheptenyl)methyldiethoxysilane, (5-bicycloheptenyl)dimethylethoxysilane, (5-bicycloheptenyl)trimethylsilane, (5-bycloheptyl)methyldiethoxysilane, (5-bicycloheptyl)dimethylethoxysilane, (5-bicycloheptyl)trimethylsiane, (5-bicycloheptyl)dimethylchlorosilane, cyclohexylmethyldimethoxysilane, isobutylmethyldimethoxysilane, 1-[2-(trimethoxysilyl)ethyl]cyclohexane-3,4-epoxide, 1,1, -dimethyl-1-silacyclopentane, (2-cyclohexen-1-yloxy)trimethylsilane, (cyclohexyloxy)trimethylsilane, 2,4-cyclopentadie-1-yltrimethylsilane, 1,1-dimethylsilacyclohexane, and combinations thereof;
(a)(ii) a structure former precursor selected from the group consisting of diethoxymethylsilane, dimethoxymethylsilane, di-isopropoxymethylsilane, di-t-butoxymethylsilane, methyldiethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methyltri-isopropoxysilane, methyltri-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethyldi-isopropoxysilane, dimethyldi-t-butoxysilane, tetraethoxysilane, methylsilane, dimethylsilane, trim ethylsilane, tetramethylsilane, phenylsilane, cyclohexylsilane, tert-butylsilane, ethylsilane, diethylsilane, methyltriacetoxysilane, methyldiacetoxysilane, methylethoxydisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, dimethyldiacetoxysilane, bis(trimethoxysilyl)methane, bis(dimethoxysilyl)methane, tetraethoxysilane, triethoxysilane, trimethylphenoxysilane, phenoxysilane, ditertbutylsilane, diethyoxysilane and mixtures thereof; and
(b) a porogen precursor selected from the group consisting of: alpha-terpinene, limonene, cyclohexane, cyclooctene, cycloheptene, cyclooctane, cyclooctadiene, cycloheptane, cycloheptadiene, cycloheptatriene, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, gamma-terpinene, dimethylhexadiene, ethylbenzene, decahydronaphthalene, 2-carene, 3-carene, vinylcyclohexene and dimethylcyclooctadiene, substituted dienes, bicycloheptadiene (BCHD), and decahydronaphthele.
12 . The composition of claim 11 wherein the structure former precursor is diethoxymethylsilane and the porogen precursor is alpha-terpinene.
13 . The composition of claim 11 provided in a kit, wherein the porogenated precursor, the structure former precursor, and the porogen precursor are maintained in separate vessels.
14 . The composition of claim 13 wherein at least one of the vessels is a pressurizable stainless steel vessel.
15 . The composition of claim 13 wherein the porogen and the precursor are maintained in a single vessel having a separation means for maintaining the porogens and the precursor separate.
16 . A composition for depositing porous low dielectric constant film comprising:
a porogenated precursor selected from the group consisting of: octyltriethoxysilane, octyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltrimethoxysilane, octyltrimethoxysilane, octnyltriethoxysilane, hexyltriethoxysilane, isobutyltriethoxysilane, methylcyclohexyldiethoxysilane, cyclooctyltriethoxysilane, butyltriethoxysilane, cyclohexanetrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, neobutyltriethoxysilane, cyclopentyltriethoxysilane, cyclopentylmethyltriethoxysilane, (5-bicycloheptenyl)triethoxysilane, (5-bicycloheptenyl)methyldiethoxysilane, (5-bicycloheptenyl)dimethylethoxysilane, (5-bicycloheptenyl)trimethylsilane, (5-bycloheptyl)methyldiethoxysilane, (5-bicycloheptyl)dimethylethoxysilane, (5-bicycloheptyl)trimethylsiane, (5-bicycloheptyl)dimethylchlorosilane, cyclohexylmethyldimethoxysilane, isobutylmethyldimethoxysilane, 1-[2-(trimethoxysilylethyl)cyclohexane-3,4-epoxide, 1,1, -dimethyl-1-silacyclopentane, (2-cyclohexen-1-yloxy)trimethylsilane, (cyclohexyloxy)trimethylsilane, 2,4-cyclopentadie-1-yltrimethylsilane, 1,1-dimethylsilacyclohexane, and combinations thereof.
17 . A composition for depositing porous low dielectric constant film comprising:
(a)(i) a porogenated precursor selected from the group consisting of: octyltriethoxysilane, octyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltrimethoxysilane, octyltrimethoxysilane, octnyltriethoxysilane, hexyltriethoxysilane, isobutyltriethoxysilane, methylcyclohexyldiethoxysilane, cyclooctyltriethoxysilane, butyltriethoxysilane, cyclohexanetrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, neobutyltriethoxysilane, cyclopentyltriethoxysilane, cyclopentylmethyltriethoxysilane, (5-bicycloheptenyl)triethoxysilane, (5-bicycloheptenyl)methyldiethoxysilane, (5-bicycloheptenyl)dimethylethoxysilane, (5-bicycloheptenyl)trimethylsilane, (5-bycloheptyl)methyldiethoxysilane, (5-bicycloheptyl)dimethylethoxysilane, (5-bicycloheptyl)trimethylsiane, (5-bicycloheptyl)dimethylchlorosilane, cyclohexylmethyldimethoxysilane, isobutylmethyldimethoxysilane, 142-(trimethoxysilyl)ethyl]cyclohexane-3,4-epoxide, 1,1, -dimethyl-1-silacyclopentane, (2-cyclohexen-1-yloxy)trimethylsilane, (cyclohexyloxy)trimethylsilane, 2,4-cyclopentadie-1-yltrimethylsilane, 1,1-dimethylsilacyclohexane, and combinations thereof; and
(a)(ii) a structure former precursor selected from the group consisting of diethoxymethylsilane, dimethoxymethylsilane, di-isopropoxymethylsilane, di-t-butoxymethylsilane, methyldiethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methyltri-isopropoxysilane, methyltri-t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethyldi-isopropoxysilane, dimethyldi-t-butoxysilane, tetraethoxysilane, methylsilane, dimethylsilane, trim ethylsilane, tetramethylsilane, phenylsilane, cyclohexylsilane, tert-butylsilane, ethylsilane, diethylsilane, methyltriacetoxysilane, methyldiacetoxysilane, methylethoxydisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, dimethyldiacetoxysilane, bis(trimethoxysilyl)methane, bis(dimethoxysilyl)methane, tetraethoxysilane, triethoxysilane, trimethylphenoxysilane, phenoxysilane, ditertbutylsilane, diethyoxysilane and mixtures thereof.
18 . A composition for depositing porous low dielectric constant film comprising:
(a) a porogenated precursor selected from the group consisting of: octyltriethoxysilane, octyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltrimethoxysilane, octyltrimethoxysilane, octnyltriethoxysilane, hexyltriethoxysilane, isobutyltriethoxysilane, methylcyclohexyldiethoxysilane, cyclooctyltriethoxysilane, butyltriethoxysilane, cyclohexanetrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, neobutyltriethoxysilane, cyclopentyltriethoxysilane, cyclopentylmethyltriethoxysilane, (5-bicycloheptenyl)triethoxysilane, (5-bicycloheptenyl)methyldiethoxysilane, (5-bicycloheptenyl)dimethylethoxysilane, (5-bicycloheptenyl)trimethylsilane, (5-bycloheptyl)methyldiethoxysilane, (5-bicycloheptyl)dimethylethoxysilane, (5-bicycloheptyl)trimethylsiane, (5-bicycloheptyl)dimethylchlorosilane, cyclohexylmethyldimethoxysilane, isobutylmethyldimethoxysilane, 1-[2-(trimethoxysilylethyl)cyclohexane-3,4-epoxide, 1,1, -dimethyl-1-silacyclopentane, (2-cyclohexen-1-yloxy)trimethylsilane, (cyclohexyloxy)trimethylsilane, 2,4-cyclopentadie-1-yltrimethylsilane, 1,1-dimethylsilacyclohexane, and combinations thereof; and
(b) a porogen precursor selected from the group consisting of: alpha-terpinene, limonene, cyclohexane, cyclooctene, cycloheptene, cyclooctane, cyclooctadiene, cycloheptane, cycloheptadiene, cycloheptatriene, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, gamma-terpinene, dimethylhexadiene, ethylbenzene, decahydronaphthalene, 2-carene, 3-carene, vinylcyclohexene and dimethylcyclooctadiene, substituted dienes, bicycloheptadiene (BCHD), and decahydronaphthele.