Silsesquioxane resins
View Patent ↗This invention pertains to silsesquioxane resins useful in antireflective coatings wherein the silsesquioxane resin is comprised of the units (Ph(CH 2 ) r SiO (3−x)/2 (OR′) x ) m (HSiO (3−x)/2 (OR′) x ) n (MeSiO (3−x)/2 (OR′) x ) o (RSiO (3−x)/2 (OR′) x ) p (R 1 SiO (3−x)/2 (OR′) x ) q where Ph is a phenyl group, Me is a methyl group; R′ is hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; R is selected from a hydroxyl producing group; and R 1 is selected from substituted phenyl groups, ester groups, polyether groups; mercapto groups, and reactive or curable organic functional groups; and r has a value of 0, 1, 2, 3, or 4; x has a value of 0, 1 or 2; wherein in the resin m has a value of 0 to 0.95; n has a value of 0.05 to 0.95; o has a value of 0.05 to 0.95; p has a value of 0.05 to 0.5; q has a value of 0 to 0.5; and m+n+o+p+q≈1.
1. A silsesquioxane resin wherein comprising the units
(Ph(CH 2 ) r SiO (3−x)/2 (OR″) x ) m
(HSiO (3−x)/2 (OR″) x ) n
(MeSiO (3−x)/2 (OR″) x ) o
(RSiO (3−x)/2 (OR″) x ) p
(R 1 SiO (3−x)/2 (OR″) x ) q
where Ph is a phenyl group, Me is a methyl group; R″ is hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; R is selected from a hydroxyl producing group; and R 1 is selected from substituted phenyl groups, ester groups, polyether groups; mercapto groups, aryl sulphonic ester groups, carboxylic acid containing groups, and reactive or curable organic functional groups; and r has a value of 0, 1, 2, 3, or 4; x has a value of 0, 1 or 2; wherein in the resin m has a value of greater than 0 to 0.95; n has a value of 0.05 to 0.95; o has a value of greater than 0.05 to 0.95; p has a value of 0.05 to 0.5; q has a value of greater than 0 to 0.5; and m+n+o+p+q≈1.
2. The resin as claimed in claim 1 wherein m has a value of greater than 0 to 0.25, n has a value of 0.15 to 0.40, o has a value of 0.25 to 0.80, p has a value of 0.025 to 0.35 and q has a value of greater than 0 to 0.3.
3. The resin as claimed in claim 1 wherein m has a value of >0 to 0.15, n has a value of 0.10 to 0.3, o has a value of 0.25 to 0.75, p has a value of 0.05 to 0.15 and q has a value of >0 to 0.15.
4. The resin as claimed in claim 1 wherein the hydroxyl producing group, R, has the formula
—R 2 OR 3
where R 2 is any organic bridging group and R 3 is a protecting group.
5. The resin as claimed in claim 4 wherein the hydroxyl producing group has the formula
R 2 —O—SiMe 3 or R 2 —O— t Bu.
6. The resin as claimed in claim 1 wherein R 1 is an alkenyl group.
7. The resin as claimed in claim 1 wherein the resin contains 6 to 38 mole % of units having —OR″ groups.
8. The resin as claimed in claim 1 wherein the resin has an average molecular weight (Mw) of 700 to 30,000.
9. An antireflective coating composition comprising
(i) silsesquioxane resin comprising the units
(Ph(CH 2 ) r SiO (3−x)/2 (OR″) x ) m
(HSiO (3−x)/2 (OR″) x ) n
(MeSiO (3−x)/2 (OR″) x ) o
(RSiO (3−x)/2 (OR″) x ) p
(R 1 SiO (3−x)/2 (OR″) x ) q
where Ph is a phenyl group, Me is a methyl group; R″ is hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; R is selected from an a hydroxyl producing group; and R 1 is selected from substituted phenyl groups, ester groups, polyether groups; mercapto groups, aryl sulphonic ester groups, and reactive or curable organic functional groups; and r has a value of 0, 1, 2, 3, or 4; x has a value of 0, 1 or 2; wherein in the resin m has a value of greater than 0 to 0.95; n has a value of 0.05 to 0.95; o has a value of 0.05 to 0.95; p has a value of 0.05 to 0.5; q has a value of greater than 0 to 0.5; and m+n+o+p+q≈1.; and
(ii) a solvent.
10. The antireflective coating composition as claimed in claim 9 wherein m has a value of greater than 0 to 0.25, n has a value of 0.15 to 0.40, o has a value of 0.25 to 0.80, p has a value of 0.025 to 0.35 and q has a value of greater than 0 to 0.3.
11. The antireflective coating composition as claimed in claim 9 wherein m has a value of >0 to 0.15, n has a value of 0.10 to 0.3, o has a value of 0.25 to 0.75, p has a value of 0.05 to 0.15 and q has a value of >0 to 0.15.
12. The antireflective coating composition as claimed in claim 9 wherein the hydroxyl producing group has the formula —R 2 OR 3 where R 2 is any organic bridging group and R 3 is a protecting group.
13. The antireflective coating composition as claimed in claim 12 wherein the hydroxyl producing group has the formula
R 2 —O—SiMe 3 or R 2 —O— t Bu.
14. The antireflective coating composition as claimed in claim 9 wherein R 1 is an alkenyl group.
15. The antireflective coating composition as claimed in claim 9 wherein the resin contains 6 to 38 mole % of units having —OR″ groups.
16. The antireflective coating composition as claimed in claim 9 wherein the resin has an average molecular weight (Mw) of 700 to 30,000.
17. The antireflective coating composition as claimed in claim 9 wherein the solvent is selected from 1-methoxy-2-propanol, propylene glycol monomethyl ethyl acetate (PGMEA), gamma-butyrolactone, and cyclohexanone.
18. The antireflective coating composition as claimed in claim 9 wherein the composition comprises 80 to 95 wt % solvent based on the total weight of the composition.
19. The antireflective coating composition as claimed in claim 9 wherein the composition additionally comprises a free radical initiator.
20. A method of forming an antireflective coating on an electronic device comprising
(A) applying to an electronic device an anti-reflective coating composition comprising
(i) silsesquioxane resin comprising the units
(Ph(CH 2 ) r SiO (3−x)/2 (OR″) x ) m
(HSiO (3−x)/2 (OR″) x ) n
(MeSiO (3−x)/2 (OR″) x ) o
(RSiO (3−x)/2 (OR″) x ) p
(R 1 SiO (3−x)/2 (OR″) x ) q
where Ph is a phenyl group, Me is a methyl group; R″ is hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; R is selected from a hydroxyl producing group; and R 1 is selected from substituted phenyl groups, ester groups, polyether groups; mercapto groups, aryl sulphonic ester groups, and reactive or curable organic functional groups; and r has a value of 0, 1, 2, 3, or 4; x has a value of 0, 1 or 2; wherein in the resin m has a value of greater than 0 to 0.95; n has a value of 0.05 to 0.95; o has a value of 0.05 to 0.95; p has a value of 0.05 to 0.5; q has a value of greater than 0 to 0.5; and m+n+o+p+q≈1.; and
(ii) a solvent, and
(B) removing the solvent and curing the silsesquioxane resin to form an antireflective coating on the electronic device.
21. The method as claimed in claim 20 wherein m has a value of greater than 0 to 0.25, n has a value of 0.15 to 0.40, o has a value of 0.25 to 0.80, p has a value of 0.025 to 0.35 and q has a value of greater than 0 to 0.3.
22. The method as claimed in claim 20 wherein m has a value of >0 to 0.15, n has a value of 0.10 to 0.3, o has a value of 0.25 to 0.75, p has a value of 0.05 to 0.15 and q has a value of >0 to 0.15.
23. The method as claimed in claim 20 wherein the hydroxyl producing group has the formula —R 2 OR 3 where R 2 is any organic bridging group and R 3 is a protecting group.
24. The method as claimed in claim 23 wherein the hydroxyl producing group has the formula
R 2 —O—SiMe 3 or R 2 —O— t Bu.
25. The method as claimed in claim 20 wherein R 1 is an alkenyl group.
26. The method as claimed in claim 20 wherein the resin contains 6 to 38 mole % of units having —OR″ groups.
27. The method as claimed in claim 20 wherein the resin has an average molecular weight (Mw) of 700 to 30,000.
28. The method as claimed in claim 20 wherein the solvent is selected from 1-methoxy-2-propanol, propylene glycol monomethyl ethyl acetate (PGMEA), gamma-butyrolactone, and cyclohexanone.
29. The method as claimed in claim 20 wherein the composition comprises 80 to 95 wt % solvent based on the total weight of the composition.
30. The method as claimed in claim 20 wherein the composition additionally comprises a free radical initiator.
31. The method as claimed in claim 20 wherein the antireflective coating composition is applied by spin-coating, dip-coating, spray-coating, flow-coating, or screen printing.
32. The method as claimed in claim 31 wherein the antireflective coating composition is applied by spin-coating.
33. The method as claimed in claim 20 wherein removing the solvent and curing comprises heating the coated substrate to 80° C. to 450° C. for 0.1 to 60 minutes.
34. The method as claimed in claim 20 wherein the curing takes place in an inert atmosphere.