Photo-patternable dielectric materials and formulations and methods of use
View Patent ↗Silsesquioxane polymers, silsesquioxane polymers in negative tone photo-patternable dielectric formulations, methods of forming structures using negative tone photo-patternable dielectric formulations containing silsesquioxane polymers, and structures made from silsesquioxane polymers.
1. A composition of matter comprising:
a silsesquioxane polymer consisting essentially of the four repeat units of the structural formulas (1), (2), (3), (4):
wherein R 1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties;
wherein R 2 is selected from the group consisting of vinyl, substituted-vinyl, acetylenic, substituted acetylenic and nitrile moieties;
wherein R 3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties;
wherein R 4 is selected from the group consisting of linear alkoxy, branched alkoxy, cycloalkoxy, acetoxys, hydroxyl, silyloxy and silanol moieties; and
wherein m, n, o, and p represent the mole percent (mol %) of repeating units with m+n+o+p equal to about 100 mol % and wherein when only three repeat units are present either o or p is zero.
2. The composition of matter of claim 1 , wherein said silsesquioxane polymer is soluble in aqueous basic solution.
3. The composition of matter of claim 1 , wherein said silsesquioxane polymer has a molecular weight of between about 1500 Daltons and about 20,000 Daltons.
4. The composition of matter of claim 1 , wherein said silsesquioxane polymer consists essentially of repeat units of structural formulas (1), (2), (3) and (4), R 1 is a methyl moiety and m is between about 70 mol % and about 80 mol %, R 2 is a vinyl moiety and n is between about 3 mol % and about 13 mol %, R 3 is an ethylene moiety and o is between about 0.5 mol % and about 6 mol %, and R 4 is a hydroxyl moiety and p is between about 2 mol % and about 10 mol %.
5. A photoactive formulation, comprising:
a photoacid generator;
a casting solvent; and
a silsesquioxane polymer consisting essentially of the four repeat units of the structural formulas (1), (2), (3), (4):
wherein R 1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties;
wherein R 2 is selected from the group consisting of vinyl, substituted-vinyl, acetylenic, substituted acetylenic and nitrile moieties;
wherein R 3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties;
wherein R 4 is selected from the group consisting of linear alkoxy, branched alkoxy, cycloalkoxy, acetoxys, hydroxyl, silyloxy and silanol moieties; and
wherein m, n, o, and p represent the mole percent (mol %) of repeating units with m+n+o+p equal to about 100 mol % and wherein when only three repeat units are present either o or p is zero.
6. The photoactive formulation of claim 5 , wherein said silsesquioxane polymer consists essentially of repeat units of structural formulas (1), (2), (3) and (4), R 1 is a methyl moiety and m is between about 70 mol % and about 80 mol %, R 2 is a vinyl moiety and n is between about 3 mol % and about 13 mol %, R 3 is an ethyl moiety and o is between about 0.5 mol % and about 6 mol %, and R 4 is a hydroxyl moiety and p is between about 2 mol % and about 10 mol %.
7. The photoactive formulation of claim 5 , further including:
an additive silsesquioxane polymer of structure (5):
wherein R 5 is selected from the group consisting of alkyl, cycloalkyl and aryl moieties; and
wherein s is an integer between about 10 and about 1000.
8. The photoactive formulation of claim 5 , further including:
one or more cross-linking agents, one or more organic bases or combinations thereof.
9. The photoactive formulation of claim 5 , wherein said silsesquioxane polymer is soluble in aqueous solution of an organic base.
10. The photoactive formulation of claim 5 , wherein said photoacid generator is selected from the group consisting of triphenylsulfonium nonaflate, co (trifluoro -methylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), N-hydroxy-naphthalimide (DDSN), onium salts, aromatic diazonium salts, sulfonium salts, diaryliodonium salts, and sulfonic acid esters of N-hydroxyamides, imides, or combinations thereof.
11. The photoactive formulation of claim 5 , wherein said casting solvent is selected from the group consisting of ethoxyethylpropionate (EEP), a combination of EEP and γ-butyrolactone, propylene-glycol monomethylether acetate (PGMEA), propylene-glycol monomethylether alcohol, propylene-glycol monopropyl alcohol, propyleneglycol monopropyl acetate, ethyl lactate, or combinations thereof.
12. The photoactive formulation of claim 5 , further including:
one or more a cross-linking agents selected from the group consisting of methylphenyltetramethoxymethyl glycouril, tetramethoxymethyl glycouril, methylpropyltetramethoxymethyl glycouril, and 2,6-bis(hydroxymethyl)-p-cresol.
13. The photoactive formulation of claim 5 , further including:
a silsesquioxane polymer additive having silanol end groups.
14. The photoactive formulation of claim 5 , further including:
a silsesquioxane polymer additive having halosilane, acetoxysilane, silylamine, or alkoxysilane endgroups.
15. A composition of matter comprising:
a silsesquioxane polymer consisting essentially of repeat units of structural formulas (1), (2), (3) and (4);
wherein R 1 is a methyl moiety and m is between about 70 mol % and about 80 mol %, R 2 is a vinyl moiety or substituted vinyl moiety and n is between about 3 mol % and about 13 mol %, R 3 is an ethylene moiety and o is between about 0.5 mol % and about 6 mol %, and R 4 is a hydroxyl moiety and p is between about 2 mol % and about 10 mol %.
16. The composition of matter of claim 15 , wherein said silsesquioxane polymer is soluble in aqueous basic solution.
17. The composition of matter of claim 15 , wherein said silsesquioxane polymer has a molecular weight of between about 1500 Daltons and about 20,000 Daltons.
18. A photoactive formulation, comprising:
a photoacid generator;
a casting solvent; and
a silsesquioxane polymer consisting essentially of repeat units of structural formulas (1), (2), (3) and (4);
wherein R 1 is a methyl moiety and m is between about 70 mol % and about 80 mol %, R 2 is a vinyl moiety or substituted vinyl moiety and n is between about 3 mol % and about 13 mol %, R 3 is an ethylene moiety and o is between about 0.5 mol % and about 6 mol %, and R 4 is a hydroxyl moiety and p is between about 2 mol % and about 10 mol %.
19. The composition of matter of claim 18 , wherein said silsesquioxane polymer is soluble in aqueous basic solution.
20. The composition of matter of claim 18 , wherein said silsesquioxane polymer has a molecular weight of between about 1500 Daltons and about 20,000 Daltons.
21. A composition of matter, comprising:
(i) a silsesquioxane polymer additive having silanol end groups or (ii) a silsesquioxane polymer additive having halosilane, acetoxysilane, silylamine, or alkoxysilane endgroups or (iii) an additive silsesquioxane polymer of structure (5):
wherein R 5 is selected from the group consisting of alkyl, cycloalkyl and aryl moieties;
and wherein s is an integer between about 10 and about 1000; and
a silsesquioxane polymer comprising three or four repeat units of the structural formulas (1), (2), (3), (4):
wherein two of said three or four repeat units are structures (1) and (2);
wherein R 1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties;
wherein R 2 is selected from the group consisting of vinyl, substituted-vinyl, acetylenic, substituted acetylenic and nitrile moieties;
wherein R 3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties;
wherein R 4 is selected from the group consisting of linear alkoxy, branched alkoxy, cycloalkoxy, acetoxys, hydroxyl, silyloxy and silanol moieties; and
wherein m, n, o, and p represent the mole percent (mol%) of repeating units with m+n+o+p equal to or greater than about 40 mol % and wherein when only three repeat units are present either o or p is zero.
22. A photoactive formulation, comprising:
a photoacid generator;
a casting solvent;
(i) a silsesquioxane polymer additive having silanol end groups or (ii) a silsesquioxane polymer additive having halosilane, acetoxysilane, silylamine, or alkoxysilane endgroups or (iii) an additive silsesquioxane polymer of structure (5):
wherein R 5 is selected from the group consisting of alkyl, cycloalkyl and aryl moieties;
and wherein s is an integer between about 10 and about 1000; and
a silsesquioxane polymer comprising three or four repeat units of the structural formulas (1), (2), (3), (4):
wherein two of said three or four repeat units are structures (1) and (2);
wherein R 1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties;
wherein R 2 is selected from the group consisting of vinyl, substituted-vinyl, acetylenic, substituted acetylenic and nitrile moieties;
wherein R 3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties;
wherein R 4 is selected from the group consisting of linear alkoxy, branched alkoxy, cycloalkoxy, acetoxys, hydroxyl, silyloxy and silanol moieties; and
wherein m, n, o, and p represent the mole percent (mol %) of repeating units with m+n+o+p equal to or greater than about 40 mol % and wherein when only three repeat units are present either o or p is zero.
23. A photoactive formulation, comprising:
a photoacid generator;
a casting solvent;
one or more a cross-linking agents selected from the group consisting of methylphenyltetramethoxymethyl glycouril, tetramethoxymethyl glycouril, methylpropyltetramethoxymethyl glycouril, and 2,6-bis(hydroxymethyl)-p-creso; and
a silsesquioxane polymer comprising three or four repeat units of the structural formulas (1), (2), (3), (4):
wherein two of said three or four repeat units are structures (1) and (2);
wherein R 1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties;
wherein R 2 is selected from the group consisting of vinyl, substituted-vinyl, acetylenic, substituted acetylenic and nitrile moieties;
wherein R 3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties;
wherein R 4 is selected from the group consisting of linear alkoxy, branched alkoxy, cycloalkoxy, acetoxys, hydroxyl, silyloxy and silanol moieties; and
wherein m, n, o, and p represent the mole percent (mol %) of repeating units with m+n+o+p equal to or greater than about 40 mol % and wherein when only three repeat units are present either o or p is zero.
24. A composition of matter comprising:
one or more a cross-linking agents selected from the group consisting of methylphenyltetramethoxymethyl glycouril, tetramethoxymethyl glycouril, methylpropyltetramethoxymethyl glycouril, and 2,6-bis(hydroxymethyl)-p-creso; and
a silsesquioxane polymer comprising three or four repeat units of the structural formulas (1), (2), (3), (4):
wherein two of said three or four repeat units are structures (1) and (2);
wherein R 1 is selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aromatic, arene and ester moieties;
wherein R 2 is selected from the group consisting of vinyl, substituted-vinyl, acetylenic, substituted acetylenic and nitrile moieties;
wherein R 3 is selected from the group consisting of linear alkyl, branched alkyl and cycloalkyl moieties;
wherein R 4 is selected from the group consisting of linear alkoxy, branched alkoxy, cycloalkoxy, acetoxys, hydroxyl, silyloxy and silanol moieties; and
wherein m, n, o, and p represent the mole percent (mol%) of repeating units with m+n+o+p equal to or greater than about 40 mol % and wherein when only three repeat units are present either o or p is zero.