Silicon containing block copolymers for direct self-assembly application
View Patent ↗The present invention relates to a novel diblock copolymer comprising a repeat unit (1) and a repeat unit (2), where R 1 is hydrogen or C 1 -C 4 alkyl, R 2 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and halide, R 3 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl and C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently chosen from a C 1 -C 4 alkyl and n=1-6. The invention also relates to a novel composition comprising the novel polymer and a solvent. The invention further relates to a process utilizing the novel composition for affecting directed self-assembly of the block copolymer.
1. A composition for use in directed self-assembly comprising;
i) a block copolymer comprising a repeat unit of structure (1) and a repeat of structure (2), where R 1 is hydrogen or C 1 -C 4 alkyl, R 2 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and halide, R 3 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl and C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently chosen from C 1 -C 4 alkyl and n=1-6; and,
ii) solvent.
2. The composition according to claim 1 where the block copolymer has a molar ratio of repeat unit (1) to repeat unit (2) in the range of 1.2 to 0.8.
3. The composition according to claim 1 where R 1 is hydrogen, R 2 is hydrogen or C 1 -C 4 alkyl, R 3 is C 1 -C 4 alkyl or C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each methyl and n=2-6.
4. The composition according to claim 1 where R 1 is hydrogen, R 2 is hydrogen, R 3 is C 1 -C 4 alkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each methyl and n=2-6.
5. The composition according to claim 1 where R 1 is hydrogen, R 2 is hydrogen, R 3 is methyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each methyl and n=3.
6. The composition according to claim 1 where the block copolymer has a molar ratio of repeat (1) to repeat unit (2) in the range of 5.3 to 8.0.
7. The composition according to claim 1 where the block copolymer has a molar ratio of repeat unit (1) to repeat unit (2) in the range of 7.3 to 6.0.
8. The composition of claim 1 wherein the concentration of the block copolymer in the solvent is between 0.5 to 5 wt % of the total composition.
9. The composition of claim 1 where the solvent is selected from a group chosen from 1,2-propanediol C 1 -C 4 alkyl ether C 1 -C 4 alkylcarboxylate, C 1 -C 4 alkyl C 1 -C 4 alkylcarboxylate and mixtures thereof.
10. A process for directed self-assembly patterning comprising steps of;
i) coating the block copolymer composition of claim 1 over a substrate to form a block copolymer film;
ii) applying a flow bake to the block copolymer film;
iii) applying an annealing bake to cause self-assembly of the block copolymer; and,
iv) developing the self-assembled polymer structure to form a pattern array.
11. The process of claim 10 where in step iv) the development is done by dry plasma etching with a plasma containing oxygen.
12. The process of claim 10 where in step ii) the flow bake is in the range of 100° C. to 160° C.
13. The process of claim 10 where in step iii) the annealing bake is in the range of 150° C. to 200° C. and is done in air.
14. The process of claim 10 where in step iii) the annealing bake is in the range of 150° C. to 250° C. and is done in nitrogen.
15. A block copolymer comprising a repeat unit (1) and a repeat unit (2), where R 1 is hydrogen or C 1 -C 4 alkyl, R 2 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and halide, R 3 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl and C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently chosen from a C 1 -C 4 alkyl and n=1-6
16. The block copolymer according to claim 15 where the block copolymer has a molar ratio of repeat unit (1) to repeat unit (2) of 5.3 to 8.0.
17. The block copolymer according to claim 16 where R 1 is hydrogen, R 2 is hydrogen or C 1 -C 4 alkyl, R 3 is C 1 -C 4 alkyl or C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each methyl and n=2-6.
18. The block copolymer according to claim 17 where R 1 is hydrogen, R 2 is hydrogen or C 1 -C 4 alkyl, R 3 is C 1 -C 4 alkyl or C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each methyl and n=3-6.
19. The block copolymer according to claim 15 where the block copolymer has a molar ratio of repeat unit (1) to repeat unit (2) in the range of 7.3 to 6.0.
20. The block copolymer according to claim 15 where the block copolymer has a molar ratio of repeat unit (1) to repeat unit (2) of 1.2 to 0.8.
21. A composition for use in directed self-assembly comprising;
i) a block copolymer comprising a repeat unit of structure (1) and a repeat of structure (2), where R 1 is hydrogen or C 1 -C 4 alkyl, R 2 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and halide, R 3 is selected from a group chosen from hydrogen, C 1 -C 4 alkyl and C 1 -C 4 fluoroalkyl, and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently chosen from C 1 -C 4 alkyl
ii) solvent.