Porous low dielectric constant compositions and methods for making and using same

A composition comprising:

• (a) at least one organosilane and/or organosiloxane precursor selected from the group consisting of:
• 1) the formula SiR1n(OR2)p(O(O)CR3)4-(n+p) where R1 is independently H or C1 to C4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon;
• R2 is independently C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R3 is independently H, C1 to C6 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, provided there is at least one Si—H bond in the molecule;
• 2) the formula R1n(OR2)p(O(O)CR4)3-n-pSi—O—SiR3m(O(O)CR5)q(OR6)3-m-q where R1 and R3 are independently-H or C1 to C4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon;
• R2 and R6 are independently C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R4 and R5 are independently H, C1 to C6 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, n+m≧1 n+p≦3 and m+q≦3, provided there is at least one Si—H bond in the molecule;
• 3) the formula R1n(OR2)p(O(O)CR4)3-n-pSi—SiR3m(O(O)CR5)q(OR6)3-m-q where R1 and R3 are independently H or C1 to C4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon;
• R2 and R6 are independently C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R4 and R5 are independently H, C1 to C6 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, n+m≧1, n+p≦3 and m+q≦3, provided there is at least one Si—H bond in the molecule;
• 4) the formula R1n(OR2)p(O(O)CR4)3-n-pSi—R7—SiR3m(O(O)CR5)q(OR6)3-m-q where R1 and R3 are independently H or C1 to C4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon;
• R2, R6 and are independently C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R4 and R5 are independently H, C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R7 is C2 to C6 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, and n+m≧1, and n+p≦3, and m+q≦3, provided there is at least one Si—H bond in the molecule;
• 5) the formula (R1n(OR2)p(O(O)CR3)4-(n+p)Si)tCH4-t where R1 is independently H or C1 to C4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon;
• R2 is independently C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R3 is independently H, C1 to C6 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, and n+p≦4, provided there is at least one Si—H bond in the molecule;
• 6) the formula (R1n(OR2)p(O(O)CR3)4-(n+p)Si)tNH3-t where R1 is independently H or C1 to C4 linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated hydrocarbon;
• R2 is independently C1 to C6 linear or branched, saturated, singly or multiply unsaturated, cyclic, aromatic, partially or fully fluorinated hydrocarbon, R3 is independently H, C1 to C6 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, and n+p≦4, provided there is at least one Si—H bond in the molecule;
• 7) the formula (N(R1)Si(R1R2))x, where R1 and R2 are independently H, C1 to C4, linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated, and x may be any integer from 2 to 8;
• 8) the formula (C(R1R2)Si(R1R2))x, where R1 and R2 are independently H, C1 to C4, linear or branched, saturated, singly or multiply unsaturated, cyclic, partially or fully fluorinated, and x may be any integer from 2 to 8, provided there is at least one Si—H bond in the molecule;
• 9) and mixtures thereof;
• (b) a porogen, distinct from the at least one organosilane and/or organosiloxane precursor, selected from the group consisting of:
• 1) the formula CnH2n+2-2x-2y-z(OH)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of alcohol groups in the compounds and is between 1 and 4, and where the alcohol functionality can be exo- and/or endocyclic;
• 2) the formula CnH2n+2-2x-2yOz where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of ether linkages in the structure and is between 1 and 4, and where the ether linkage(s) can be exo- and/or endocyclic;
• 3) the formula CnH2n+2-2x-2y-2zOz where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of epoxide groups in the structure and is between 1 and 4, and where the epoxide groups can be attached to a cyclic ring or a linear chain;
• 4) the formula CnH2n+2-2x-2y-2zOz where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of aldehyde groups in the structure and is between 1 and 4;
• 5) the formula CnH2n+2-2x-2y-2zOz where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of aldehyde groups in the structure and is between 1 and 4, and where the ketone group(s) can be exo- and/or endocyclic;
• 6) the formula CnH2n+2-2x-2y-3z(OOH)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of carboxylic acid groups in the structure and is between 1 and 4;
• 7) the formula CnH2n+2-2x-2y-6z(O3)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of anhydride groups in the structure and is 1 or 2;
• 8) the formula CnH2n+2-2x-2y-2z(O2)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure, and where none of the unsaturated bonds are conjugated with the carbonyl group of the ester, and where z is the number of anhydride groups in the structure and is 1 or 2;
• 9) the formula CnH2n+2-2x-2y-2z(O2)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is greater than or equal to 1, and where at least of the unsaturated bonds are conjugated with the carbonyl group of the an ester, and where z is the number of ester groups in the structure and is 1 or 2;
• 10) the formula CnH2n+2-2w-2x-2y(O)y(O)z where n=1-12, and where w is the number of cyclic rings in the structure and is between 0 and 4, and where x is the number of unsaturated bonds in the structure and is between 0 and n, and where y is the number of carbonyl groups in the structure in which the carbonyl group can be ketones and/or aldehydes, and where z is the number of ether groups in the structure and is 1 or 2, and where the ether group(s) can be endocyclic or exocyclic;
• 11) the formula CnH2n+2-2w-2x-y(OH)y(O)z where n=1-12, and where w is the number of cyclic rings in the structure and is between 0 and 4, and where x is the number of unsaturated bonds in the structure and is between 0 and n, and where y is the number of alcohol groups in the structure, and where z is the number of ether groups in the structure and is 1 or 2, and where the ether group(s) can be endocyclic or exocyclic;
• 12) the formula CnH2n+2-2u-2v-w-2y-3z(OH)w(O)x(O)y(OOH)z where n=1-12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of alcohol groups in the structure and is between 0 and 4, and where x is the number of ether groups in the structure and is between 0 and 4 and where the ether group(s) can be endocyclic or exocyclic, and where y is the number of carbonyl groups in the structure and is between 0 and 3 in which the carbonyl group can be ketones and/or aldehydes, and where z is the number of carboxylic acid groups in the structure and is between 0 and 2;
• 13) the formula CnH2n+2-2x-2y-z(NH2)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of amine groups in the compounds and is between 1 and 4, and where the amine functionality can be exo- and/or endocyclic;
• 14) the formula CnH2n+2-2x-2y-2z(NH)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of secondary amine groups in the compounds and is between 1 and 4, and where the amine functionality can be exo- and/or endocyclic;
• 15) the formula CnH2n+2-2x-2y-3z(N)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of tertiary amine groups in the compounds and is between 1 and 4, and where the amine functionality can be exo- and/or endocyclic;
• 16) the formula CnH2n+2-2x-2y-z(NO2)z where n=1-12, and where x is the number of cyclic rings in the structure and is between 0 and 4, and where y is the number of unsaturated bonds in the structure and is between 0 and n, and where z is the number of nitro groups in the compounds and is between 1 and 4, and where the nitro functionality can be exo- and/or endocyclic;
• 17) the formula CnH2n+2-2u-2v-w-2x-3y-z(NH2)w(NH)x(N)y(OH)z where n=1-12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of primary amine groups, x is the number of secondary amine groups, y is the number of tertiary amine groups, and where 1<w+x+y<4, and where z is the number of alcohol groups in the compound and is between 1 and 4, and where the alcohol and/or amine groups can be exo- and/or endocyclic;
• 18) the formula CnH2n+2-2u-2v-w-2x-3y-z(NH2)w(NH)x(N)y(OH)z where n=1-12, and where u is the number of cyclic rings in the structure and is between 0 and 4, and where v is the number of unsaturated bonds in the structure and is between 0 and n, and where w is the number of primary amine groups, x is the number of secondary amine groups, y is the number of tertiary amine groups, and where 1<w+x+y<4, and where z is the number of ether groups in the compound and is between 1 and 4, and where the ether and/or amine groups can be exo- and/or endocyclic;
• 19) and mixtures thereof.