Underlayer composition for promoting self assembly and method of making and using

1. An underlayer formulation, said underlayer for promoting the formation of self assembled structures, comprising:

a. a polymer comprising at least one monomer repeat unit having the structure

 wherein X is a crosslinking group chosen from

 and wherein p is 0-5, q is 1-2, m is 1-2 and R is H, C 1 -C 4 alkyl or tri(C 1 -C 4 alkyl)silyl;

b. at least one thermal acid generator; and

c. a solvent.

2. The formulation of claim 1 , wherein the one or more thermal acid generator is chosen from a substituted or unsubstituted halogenated alkyl compound, a substituted or unsubstituted alkane sulfonate, a substituted or unsubstituted 2-nitrobenzyl sulfonic acid ester, an acid salt of a primary amine, an acid salt of a secondary amine, an acid salt of a tertiary amine, a dicarboximidyl sulfonic acid ester, or an oxime sulfonate ester.

3. The formulation of claim 1 , wherein the one or more thermal acid generator is chosen from tri-C 1 -C 8 -alkylammonium p-toluenesulfonate, tri-C 1 -C 8 -alkylammonium dodecylbenzenesulfonate, tri-C 1 -C 8 -alkylammonium perfluorobutane-1-sulfonate, tri-C 1 -C 8 -alkylammonium trifluoromethane-sulfonate, 1,2,3-tris(perfluoro C 1 -C 8 alkane sulfonyloxy) benzene, 1,2,3-tris(C 1 -C 8 alkane sulfonyloxy) benzene, 1,2,3-tris(p-toluene sulfonyloxy) benzene, 4-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing.

4. The formulation of claim 1 , wherein the polymer further comprises one or more monomer repeat units chosen from C 1 -C 10 alkyl (meth)acrylate, styrene, vinyl pyridine, butadiene, Isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, itaconic acid, hydroxyethyl methacrylate, 4-hydroxystyrene, isobornyl methacrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.

5. The formulation of claim 4 , wherein the polymer is a random copolymer.

6. The formulation of claim 1 , wherein the polymer further comprises one or two monomer repeat units chosen from styrene or methyl methacrylate.

7. A process for producing a formulation for depositing a cured underlayer for promoting the formation of self assembled structures, comprising:

a. agitating a mixture, comprising

i. a polymer comprising at least one monomer repeat unit having the structure

 wherein X is a crosslinking group chosen from

 and wherein p is 0-5, q is 1-2, in is 1-2 and R is H, C 1 -C 4 alkyl or tri(C 1 -C 4 alkyl)silyl;

 at least one thermal acid generator; and

ii. a solvent;

whereby a homogenous solution is produced;

b. filtering the resulting homogeneous solution with a filter.

8. The process of claim 7 , wherein the one or more thermal acid generator is chosen from a substituted or unsubstituted halogenated alkyl compound, a substituted or unsubstituted alkane sulfonate, a substituted or unsubstituted 2-nitrobenzyl sulfonic acid ester, an acid salt of a primary amine, an acid salt of a secondary amine, an acid salt of a tertiary amine, a dicarboximidyl sulfonic acid ester, or an oxime sulfonate ester.

9. The process of claim 7 , wherein the one or more thermal acid generator is chosen from tri-C 1 -C 8 -alkylammonium p-toluenesulfonate, tri-C 1 -C 8 -alkylammonium dodecylbenzenesulfonate, tri-C 1 -C 8 -alkylammonium perfluorobutane-1-sulfonate, tri-C 1 -C 8 -alkylammonium trifluoromethane-sulfonate, 1,2,3-tris(perfluoro C 1 -C 8 alkane sulfonyloxy) benzene, 1,2,3-tris(C 1 -C 8 alkane sulfonyloxy) benzene, 1,2,3-tris(p-toluene sulfonyloxy) benzene, 4-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing.

10. The process of claim 7 , wherein the polymer further comprises one or more monomer repeat units chosen from C 1 -C 10 alkyl (meth)acrylate, styrene, vinyl pyridine, butadiene, isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, itaconic acid, hydroxyethyl meth acrylate, 4-hydroxystyrene, isobornyl meth acrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.

11. The process of claim 10 , wherein the polymer is a random copolymer.

12. The process of claim 7 , wherein the polymer further comprises one or two monomer repeat units chosen from styrene or methyl methacrylate.

13. The process of claim 7 , wherein the filter is an absolute filter having a pore size of less than 100 nm.

14. A process for directing a multiplied pattern in a block copolymer film, said process comprising:

a. providing a block copolymer having two or more spontaneously separating blocks;

b. providing a substrate;

c. coating, on the substrate, a first formulation for depositing a first coating and thermally curing the first coating; and

d. disposing the block copolymer on at least a portion of the cured first coating;

wherein the first formulation comprises (i) a polymer comprising at least one monomer repeat unit having the structure

 and wherein X is a crosslinking group chosen from

 and wherein p is 0-5, q is 1-2, and m is 1-2;

(ii) at least one thermal acid generator; and (iii) a solvent.

15. The process of claim 14 , wherein the first polymer further comprises at least one combination of monomer repeat units, said combination chosen from methyl (meth)acrylate and styrene, butadiene and butyl (meth)acrylate, butadiene and dimethyl siloxane, butadiene and methyl(meth) acrylate, butadiene and vinyl pyridine, isoprene and methyl(meth)acrylate, isoprene and vinyl pyridine, butyl (meth)acrylate and methyl(meth)acrylate, butyl (meth)acrylate and vinyl pyridine, hexyl(meth)acrylate and vinyl pyridine, isobutylene and butyl (meth)acrylate, isobutylene and dimethylsiloxane, isobutylene and methyl (meth)acrylate, isobutylene and vinyl pyridine, isoprene and ethylene oxide, butyl (meth)acrylate and vinyl pyridine, ethylene and methyl (meth)acrylate, methyl (meth)acrylate and butyl (meth)acrylate, styrene and butadiene, styrene and butyl (meth)acrylate, styrene and dimethylsiloxane, styrene and isoprene, styrene and vinylpyridine, ethylene and vinyl pyridine, vinyl pyridine and methyl (meth)acrylate, ethylene oxide and isoprene, ethylene oxide and butadiene, ethylene oxide and styrene, ethylene oxide and methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and butadiene, 2-hydroxyethyl (meth)acrylate and butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and dimethyl siloxane, 2-hydroxyethyl (meth)acrylate and ethylene, 2-hydroxyethyl (meth)acrylate and hexyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate and isobutylene, 2-hydroxyethyl (meth)acrylate and isoprene, 2-hydroxyethyl (meth)acrylate and styrene, 2-hydroxyethyl (meth)acrylate and vinyl pyridine, (meth)acrylonitrile and butadiene, (meth)acrylonitrile and butyl (meth)acrylate, (meth)acrylonitrile and dimethyl siloxane, (meth)acrylonitrile and ethylene oxide, (meth)acrylonitrile and ethylene, (meth)acrylonitrile and hexyl(meth)acrylate, (meth)acrylonitrile and 2-hydroxyethyl (meth)acrylate(meth), acrylonitrile and isobutylene, (meth)acrylonitrile and isoprene, (meth)acrylonitrile and methyl (meth)acrylate, (meth)acrylonitrile and styrene, or (meth)acrylonitrile and vinyl pyridine.

16. The process of claim 14 , wherein the at least one thermal acid generator is chosen from tri-C 1 -C 8 -alkylammonium p-toluenesulfonate, tri-C 1 -C 8 -alkylammonium dodecylbenzenesulfonate, tri-C1-C8-alkylammonium perfluorobutane-1-sulfonate, tri-C 1 -C 8 -alkylammonium trifluoromethane-sulfonate, 1,2,3-tris(perfluoro C1-C8 alkane sulfonyloxy) benzene, 1,2,3-tris(C 1 -C 8 alkane sulfonyloxy)benzene, 1,2,3-tris(p-toluene sulfonyloxy)benzene, 4-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesutfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing.

17. A process for directing a multiplied pattern in a block copolymer film, said process comprising:

a. providing a block copolymer having two or more spontaneously separating blocks;

b. providing a substrate;

c. coating, on the substrate, a first formulation for depositing a first coating and thermally curing the first coating; and

d. disposing the block copolymer on at least a portion of the cured first coating;

e. before disposing the block copolymer, forming a pattern in the cured first coating by a lithographic process; and

f. optionally, providing a second coating in the pattern from a second formulation; and thereafter rinsing with a rinse solution;

wherein the second formulation comprises: (i) a polymer comprising at least one monomer repeat unit having the structure

and wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, and m is 1-2;

(ii) at least one thermal acid generator; and (iii) a solvent.

18. The process of claim 17 , wherein the first coating is a pinning layer and the second coating is a neutral layer.

19. The process of claim 17 , wherein the first coating is a neutral layer and the second coating is a pinning layer.

20. The process of claim 17 , wherein the second polymer comprises at least one monomer repeat unit chosen from C 1 -C 10 alkyl (meth)acrylate, styrene, vinyl pyridine, butadiene, isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, itaconic acid, hydroxyethyl methacrylate, 4-hydroxystyrene, isobornyl methacrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.