Pattern shrink methods
Pattern shrink methods comprise: (a) providing a semiconductor substrate comprising one or more layers to be patterned; (b) providing a resist pattern over the one or more layers to be patterned; (c) coating a shrink composition over the pattern, wherein the shrink composition comprises a polymer and an organic solvent, wherein the polymer comprises a group containing a hydrogen acceptor effective to form a bond with an acid group and/or an alcohol group at a surface of the resist pattern, and wherein the composition is free of crosslinkers; and (d) rinsing residual shrink composition from the substrate, leaving a portion of the polymer bonded to the resist pattern. Also provided are pattern shrink compositions, and coated substrates and electronic devices formed by the methods. The invention find particular applicability in the manufacture of semiconductor devices for providing high resolution patterns.
1. A pattern shrink method, comprising:
(a) providing a semiconductor substrate comprising one or more layers to be patterned;
(b) providing a resist pattern over the one or more layers to be patterned;
(c) coating a shrink composition over the pattern, wherein the shrink composition comprises a polymer and an organic solvent, wherein the polymer comprises a group containing a hydrogen acceptor effective to form a bond with an acid group and/or an alcohol group at a surface of the resist pattern, wherein the group containing the hydrogen acceptor is an oxygen-containing group or a nitrogen-containing group chosen from primary amine, amide, pyridine, indole, imidazole, triazine, pyrrole, purine, diazetidine, dithiazine, quinoline, carbazole, acridine, indazole, and benzimidazole groups; and wherein the composition is free of crosslinkers; and
(d) rinsing residual shrink composition from the substrate, leaving a portion of the polymer bonded to the resist pattern.
2. The pattern shrink method of claim 1 , wherein providing the resist pattern comprises:
(b1) applying a layer of a photoresist composition over the one or more layers to be patterned, wherein the photoresist composition comprises: a polymer comprising an acid cleavable leaving group, the cleavage of which forms an acid group and/or an alcohol group; a photoacid generator; and a solvent;
(b2) exposing the photoresist layer to activating radiation through a patterned photomask;
(b3) heating the photoresist layer, wherein acid generated by the acid generator causes cleavage of the acid cleavable leaving group, thereby forming the acid group and/or the alcohol group;
(b4) developing the exposed photoresist composition layer with an organic solvent developer to form a negative resist pattern comprising the acid group and/or the alcohol group.
3. The pattern shrink method of claim 1 , wherein the group containing the hydrogen acceptor group is a nitrogen-containing group.
4. The pattern shrink method of claim 3 , wherein the group containing the hydrogen acceptor group is a primary amine.
5. The pattern shrink method of claim 1 , wherein the group containing the hydrogen acceptor is an oxygen-containing group.
6. The pattern shrink method of claim 1 , wherein the polymer further comprises a unit formed from a vinyl aromatic monomer.
7. The pattern shrink method of claim 1 , wherein the polymer further comprises a unit formed from an (alkyl)acrylate monomer.
8. The pattern shrink method of claim 7 , wherein the (alkyl)acrylate monomer is of general formula (5):
wherein R 1 is a hydrogen or an alkyl group having 1 to 10 carbon atoms; and R 2 is a C 1 -C 10 alkyl, a C 3 -C 10 cycloalkyl, or a C 7 -C 10 aralkyl group.
9. The pattern shrink method of claim 1 , wherein the polymer contains silicon.
10. The pattern shrink method of claim 1 , wherein the polymer comprises a block polymer comprising a first block and a second block.
11. The pattern shrink method of claim 10 , wherein the first block forms an ionic bond with an acid group or a hydrogen bond with an alcohol group of the resist pattern.
12. The pattern shrink method of claim 10 , wherein the second block has a T g that is lower than a reflow temperature of the resist pattern.
13. The pattern shrink method of claim 1 , wherein the polymer has an Ohnishi parameter lower than 3.5, or a silicon content greater than 15 wt % based on the polymer.
14. The pattern shrink method of claim 1 , further comprising baking the substrate after the rinsing.
15. The pattern shrink method of claim 1 , wherein the group containing the hydrogen acceptor is a pyridine group.
16. The pattern shrink method of claim 15 , wherein the pyridine group is present in the polymer as a unit formed from 2-vinylpyridine.
17. The pattern shrink method of claim 15 , wherein the pyridine group is present in the polymer as a unit formed from 4-vinylpyridine.
18. A pattern shrink method, comprising:
(a) providing a semiconductor substrate comprising one or more layers to be patterned;
(b) providing a resist pattern over the one or more layers to be patterned;
(c) coating a shrink composition over the pattern, wherein the shrink composition comprises a polymer and an organic solvent, wherein the polymer comprises a group containing a hydrogen acceptor, wherein the group containing the hydrogen acceptor comprises a nitrogen-containing group chosen from primary amine, amide, pyridine, indole, imidazole, triazine, pyrrole, purine, diazetidine, dithiazine, quinoline, carbazole, acridine, indazole, and benzimidazole; and wherein the composition is free of crosslinkers; and
(d) rinsing residual shrink composition from the substrate, leaving a portion of the polymer on the resist pattern, thereby shrinking a spacing of the resulting pattern.
19. The pattern shrink method of claim 18 , wherein providing the resist pattern comprises:
(b1) applying a layer of a photoresist composition over the one or more layers to be patterned, wherein the photoresist composition comprises: a polymer comprising an acid cleavable leaving group, the cleavage of which forms an acid group and/or an alcohol group; a photoacid generator; and a solvent;
(b2) exposing the photoresist layer to activating radiation through a patterned photomask;
(b3) heating the photoresist layer, wherein acid generated by the acid generator causes cleavage of the acid cleavable leaving group, thereby forming the acid group and/or the alcohol group;
(b4) developing the exposed photoresist composition layer with an organic solvent developer to form a negative resist pattern comprising the acid group and/or the alcohol group.
20. The pattern shrink method of claim 18 , wherein the polymer further comprises a unit formed from a vinyl aromatic monomer.
21. The pattern shrink method of claim 18 , wherein the polymer further comprises a unit formed from an (alkyl)acrylate monomer.
22. The pattern shrink method of claim 18 , wherein the polymer contains silicon.
23. The pattern shrink method of claim 18 , wherein the polymer comprises a block polymer comprising a first block and a second block.
24. The pattern shrink method of claim 18 , wherein the group containing the hydrogen acceptor group is a primary amine.
25. The pattern shrink method of claim 18 , wherein the group containing the hydrogen acceptor is a pyridine group.
26. The pattern shrink method of claim 25 , wherein the pyridine group is present in the polymer as a unit formed from 2-vinylpyridine.
27. The pattern shrink method of claim 25 , wherein the pyridine group is present in the polymer as a unit formed from 4-vinylpyridine.
28. A pattern shrink method, comprising:
(a) providing a semiconductor substrate comprising one or more layers to be patterned;
(b) providing a resist pattern over the one or more layers to be patterned, wherein the resist pattern is formed by a negative tone development process;
(c) coating a shrink composition over the pattern, wherein the shrink composition comprises a block polymer and an organic solvent, wherein the block polymer comprises a first block and a second block, and the first block comprises a group containing a hydrogen acceptor, wherein the group containing the hydrogen acceptor comprises a nitrogen-containing group chosen from primary amine, amide, pyridine, indole, imidazole, triazine, pyrrole, purine, diazetidine, dithiazine, quinoline, carbazole, acridine, indazole, and benzimidazole; and wherein the composition is free of crosslinkers; and
(d) rinsing residual shrink composition from the substrate, leaving a portion of the polymer on the resist pattern, thereby shrinking a spacing of the resulting pattern.
29. The pattern shrink method of claim 28 , wherein providing the resist pattern comprises:
(b1) applying a layer of a photoresist composition over the one or more layers to be patterned, wherein the photoresist composition comprises: a polymer comprising an acid cleavable leaving group, the cleavage of which forms an acid group and/or an alcohol group; a photoacid generator; and a solvent;
(b2) exposing the photoresist layer to activating radiation through a patterned photomask;
(b3) heating the photoresist layer, wherein acid generated by the acid generator causes cleavage of the acid cleavable leaving group, thereby forming the acid group and/or the alcohol group;
(b4) developing the exposed photoresist composition layer with an organic solvent developer to form a negative resist pattern comprising the acid group and/or the alcohol group.
30. The pattern shrink method of claim 28 , wherein the second block of the block polymer comprises a unit formed from a vinyl aromatic monomer.
31. The pattern shrink method of claim 28 , wherein the block polymer further comprises a unit formed from an (alkyl)acrylate monomer.
32. The pattern shrink method of claim 28 , wherein the block polymer contains silicon.
33. The pattern shrink method of claim 28 , wherein the group containing the hydrogen acceptor group is a primary amine.
34. The pattern shrink method of claim 28 , wherein the group containing the hydrogen acceptor is a pyridine group.
35. The pattern shrink method of claim 34 , wherein the pyridine group is present in the polymer as a unit formed from 2-vinylpyridine.
36. The pattern shrink method of claim 34 , wherein the pyridine group is present in the polymer as a unit formed from 4-vinylpyridine.