Silsesquioxane resin systems with base additives bearing electron-attracting functionalities
View Patent ↗Silsesquioxane-based compositions that contain (a) silsesquioxane resins that contain HSiO3/2 units and RSiO 3/2 units wherein; R is an acid dissociable group, and (b) least one organic base additive selected from bulky tertiary amines, imides, amides and the polymeric amines wherein the organic base additive contains an electron-attracting group with the provision that the organic base additive is not 7-diethylamino-4-methylcoumarin. The silsesquioxane-based compositions are useful as positive resist compositions in forming patterned features on substrate, particularly useful for multi-layer layer (i.e. bilayer) 193 nm & 157 nm photolithographic applications.
1. A composition comprising:
(I) a silsesquioxane resin comprising HSiO 3/2 units and RSiO 3/2 units where R is an acid dissociable group having the formula
wherein each R 3 is independently a linking group;
R 4 is a second linking group;
L is selected from the group consisting of linear or branch alkylene groups having 1 to 10 carbon atoms, fluoroalkylene groups having 2 to 20 carbon atoms, substituted and unsubstituted arylene groups, substituted and unsubstituted cycloalkylene groups, and substituted and unsubstituted alkarylene groups;
R 5 is hydrogen, linear or branched alkyl or fluoroalkyl;
R 6 is alkyl or fluoroalkyl;
Z is an acid-cleavable group;
f is 0 or 1;
g is 0 or 1;
h is 0 or 1; and
(II) an organic base selected from 2-(2-amino-phenyl)-isoindole-1,3-dione, 1-(2-((1H-1,2,3-benzotriazol-1-ylmethyl)amino)phenyl)ethanone, N-benzyl-N-ethylaniline, 1-((2,3-dimethyl-phenylamino)-methyl)-pyrroilidine-2,5-dione, 1-(2-methyl-4-phenylamino-3,4-dihydro-2H-quinolin-1-yl)-heptan-1-one and 2-((3-fluoro-4-methyl-phenylamino)-methyl)-phenol.
2. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b wherein a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, and 0.9<a+b<1.0.
3. The composition as claimed in claim 2 wherein a has a value of 0.6 to 0.8 and b has a value of 0.2 to 0.4.
4. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (HSi(OR 1 )O 2/2 ) c wherein R 1 is selected from H or a linear or branched C 1 to C 6 alkyl group, a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, c has a value of 0.01 to 0.4, and 0.9<a+b+c<1.0.
5. The composition as claimed in claim 4 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4 and c has a value of 0.05 to 0.15.
6. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (Si(OR 1 )xO( 4-x)/2 ) d wherein R 1 is selected from H or a linear or branched C 1 to C 6 alkyl group, a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, d has a value of 0.05 to 0.45, 0.9<a+b+d<1.0, and x has a value of 0 to 3.
7. The composition as claimed in claim 6 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4 and d has a value of 0.1 to 0.25.
8. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (HSi(OR 1 )O 2/2 ) c (Si(OR 1 ) x O( 4.x)/2)d wherein R 1 is selected from H or a linear or branched C 1 to C 6 alkyl group, a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, c has a value of 0.01 to 0.4, d has a value of 0.05 to 0.45, 0.9<a+b+c+d<1.0 and x has a value of 0 to 3.
9. The composition as claimed in claim 8 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4, c has a value of 0.05 to 0.15 and d has a value of 0.1 to 0.25.
10. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (R 2 SiO 3/2 ) e wherein R 2 is a property modifying functional group, a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, e has a value of 0.01 to 0.25, and 0.9<a+b+e<1.0.
11. The composition as claimed in claim 10 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4, and e has a value of 0.05 to 0.15.
12. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (HSi(OR 1 )O 2/2 ) c (R 2 SiO 3/2 ) e wherein R 1 is selected from H or a linear or branched C 1 to C 6 alkyl group; R 2 is a property modifying functional group; a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, c has a value of 0.01 to 0.4, e has a value of 0.01 to 0.25, and 0.9<a+b+c+e<1.0.
13. The composition as claimed in claim 12 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4, c has a value of 0.05 to 0.15 and e has a value of 0.05 to 0.15.
14. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (Si(OR 1 )xO( 4-x)/2)d (R 2 SiO 3/2 ) e wherein R 1 is selected from H or a linear or branched C 1 to C 6 alkyl group, R 2 is a property modifying functional group, a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, d has a value of 0.05 to 0.41 e has a value of 0.01 to 0.25, 0.9<a+b+d+e<1.0 and x has a value of 0 to 3.
15. The composition as claimed in claim 14 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4 and d has a value of 0.1 to 0.25 and e has a value of 0.05 to 0.15.
16. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula
(HSiO 3/2 ) a (RSiO 3/2 ) b (HSi(OR 1 )O 2/2 ) c (Si(OR 1 )xO( 4-x )/2)d (R 2 SiO 3/2 ) e
wherein R 1 is selected from H or a linear or branched C 1 to C 6 alkyl group, R 2 is a property modifying functional group, a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6, c has a value of 0.01 to 0.4, d has a value of 0.05 to 0.45, e has a value of 0.01 to 0.25, 0.9<a+b+c+d+e<1.0 and x has a value of 0 to 3.
17. The composition as claimed in claim 16 wherein a has a value of 0.6 to 0.8, b has a value of 0.2 to 0.4, c has a value of 0.05 to 0.15 and d has a value of 0.1 to 0.25 and e has a value of 0.05 to 0.15.
18. The composition as claimed in claim 1 wherein Z is selected from esters of the formula —COOR 7 , carbonates of the formula —OCOOR 8 , ethers of the formula —OR 9 , wherein R 7 , R 8 and R 9 are selected to render Z acid-cleavable.
19. The composition as claimed in claim 18 wherein Z is an ester of the formula —COOR 7 wherein R 7 is a tertiary alkyl group.
20. The composition as claimed in claim 1 wherein R is selected from 1,1 dimethylethyl bicyclo[2,2,1]heptane-2-carboxylate, isopropyl bicyclo[2,2,1]heptane-2-carboxylate, 2-methyladamantyl bicyclo[2,2,1]heptane-2-carboxylate, cyclohexyl bicyclo[2,2,1]heptane-2-carboxylate, 2-hydroxy-3-pinanyl bicyclo[2,2,1]heptane-2-carboxylate and t-butyl bicyclo[2,2,1]heptane-2-carboxylate.
21. The composition as claimed in claim 20 wherein R is t-butyl bicyclo[2,2,1]heptane-2-carboxylate.
22. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b where R is selected from isopropyl bicyclo[2,2,1]heptane-2-carboxylate, 2-methyladamantyl bicyclo[2,2,1]heptane-2-carboxylate, cyclohexyl bicyclo[2,2,1]heptane-2-carboxylate, 2-hydroxy-3-pinanyl bicyclo[2,2,1]heptane-2-carboxylate and t-butyl bicyclo[2,2,1]heptane-2-carboxylate and a has a value of 0.4 to 0.9, b has a value of 0.1 to 0.6 and 0.9<a+b<1.0.
23. The silsesquioxane resin as claimed in claim 1 wherein the silsesquioxane resin has the formula (HSiO 3/2 ) a (RSiO 3/2 ) b (R 1 OSiO 3/2 ) c (SiO 4/2 ) d where R is selected from isopropyl bicyclo[2,2,1]heptane-2-carboxylate, 2-methyladamantyl bicyclo[2,2,1]heptane-2-carboxylate, cyclohexyl bicyclo[2,2,1]heptane-2-carboxylate, 2-hydroxy-3-pinanyl bicyclo[2,2,1]heptane-2-carboxylate and t-butyl bicyclo[2,2,1]heptane-2-carboxylate; R 1 is H; a has a value of 0.5 to 0.7, b has a value of 0.2 to 0.45, c has a value of 0.05 to 0.2, d has a value of 0.01 to 0.1, and 0.9<a+b+c+d<1.0.
24. The composition as claimed in claim 1 wherein the silsesquioxane resin has the formula
(HSiO 3/2 ) a (RSiO 3/2 ) b (HSi(OR 1 )O 2/2 ) c (Si(OR 1 )xO( 4.x )/2)d (R 2 SiO 3/2 ) e
where R is selected from isopropyl bicyclo[2,2,1]heptane-2-carboxylate, 2-methyladamantyl bicyclo[2,2,1]heptane-2-carboxylate, cyclohexyl bicyclo[2,2,1]heptane-2-carboxylate, 2-hydroxy-3-pinanyl bicyclo[2,2,1]heptane-2-carboxylate and t-butyl bicyclo[2,2,1]heptane-2-carboxylate; R 1 is H; R 2 is selected from bicyclo[2,2,1]hept-5-ene-2-1,1,1-trifluoro-2-trifluoromethylpropane-2-ol, 2-trifluoromethyl bicyclo[2,2,1 ]hept-5-en-2-ol, 3,3,3-trifluoropropane-2-ol, 2-trifluoromethyl-3,3-difluoro-bicyclo[2,2,1]hept-5-en-2-ol; a has a value of 0.4 to 0.6, b has a value of 0.2 to 0.45, c has a value of 0.05 to 0.20, d has a value of 0.01 to 0.15, e has a value of 0.01 to 0.25, 0.9<a+b+c+d+e<1.0 and x has a value of 0 to 3.
25. A photoresist composition comprising
(I) a silsesquioxane resin comprising HSiO 3/2 units and RSiO 3/2 units where R is an acid dissociable group having the formula
wherein each R 3 is independently a linking group;
R 4 is a second linking group;
L is selected from the group consisting of linear or branch alkylene groups having 1 to 10 carbon atoms, fluoroalkylene groups having 2 to 20 carbon atoms, substituted and unsubstituted arylene groups, substituted and unsubstituted cycloalkylene groups, and substituted and unsubstituted alkarylene groups;
R 5 is hydrogen, linear or branched alkyl or fluoroalkyl;
R 6 is alkyl or fluoroalkyl;
Z is an acid-cleavable group;
f is 0 or 1;
g is 0 or 1;
h is 0 or 1; and
(II) an organic base selected from 2-(2-amino-phenyl)-isoindole-1,3-dione, 1-(2-((1H-1,2,3-benzotriazol-1-ylmethyl)amino)phenyl)ethanone, N-benzyl-N-ethylaniline, 1-((2,3-dimethyl-phenylamino)-methyl)-pyrroilidine-2,5-dione, 1-(2-methyl-4-phenylamino-3,4-dihydro-2H-quinolin-1-yl)-heptan-1-one and 2-((3-fluoro-4-methyl-phenylamino)-methyl)-phenol; and
(III) an acid generator.