Pattern-forming method and composition
A pattern-forming method includes forming a prepattern that is insoluble or hardly soluble in an organic solvent. A resin layer is provided on at least a lateral face of the prepattern. The prepattern and the resin layer are heated such that an adjacent portion of the resin layer to the prepattern is made insoluble or hardly soluble in the organic solvent, without being accompanied by an increase of a molecular weight of the prepattern and the resin layer. A portion of the resin layer other than the adjacent portion of the resin layer is removed. The resin layer is formed from a first composition including a first polymer and an organic solvent. Solubility of the first polymer in the organic solvent does not substantially change due to an action of an acid. A weight average molecular weight of the first polymer is 15,000-150,000.
1. A pattern-forming method comprising:
forming a prepattern that is insoluble or hardly soluble in an organic solvent;
providing a resin layer on at least an entirety of a lateral face of the prepattern;
heating the prepattern and the resin layer such that a portion of the resin layer adjacent to and in contact with the entirety of the lateral face of the prepattern is made insoluble or hardly soluble in the organic solvent, without being accompanied by an increase of a molecular weight of the portion of the resin layer; and
removing with the organic solvent, a portion of the resin layer other than the portion of the resin layer such that a resist pattern is obtained,
wherein the resin layer is formed from a first composition comprising: a first polymer; and an organic solvent, solubility of the first polymer in the organic solvent not substantially changing due to an action of an acid,
wherein the first polymer comprises a first structural unit that comprises a lactone structure, a cyclic carbonate structure, a sultone structure or a combination thereof, and
wherein a weight average molecular weight of the first polymer is no less than 15,000 and no greater than 150,000.
2. The pattern-forming method according to claim 1 , wherein (i) the first polymer comprises a basic group; (ii) the first composition further comprises a basic compound; or both of (i) and (ii).
3. The pattern-forming method according to claim 1 , wherein a heating temperature in the heating is no less than 60° C. and no greater than 250° C.
4. The pattern-forming method according to claim 1 , wherein the forming of the prepattern comprises:
forming a resist film made from a resist composition comprising: a second polymer; a radiation-sensitive acid generator; and a solvent, wherein solubility of the second polymer in the organic solvent is capable of decreasing due to an action of an acid;
exposing the resist film; and
developing the exposed resist film with a developer solution comprising the organic solvent.
5. The pattern-forming method according to claim 4 , wherein the second polymer comprises an acid-labile group.
6. The pattern-forming method according to claim 2 , wherein the basic group is a group represented by formula (a), a group represented by formula (b), or both thereof:
wherein, in the formula (b), L represents a single bond, a divalent linear hydrocarbon group having 1 to 20 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; and R A and R B each independently represent a hydrogen atom, a monovalent linear hydrocarbon group having 1 to 20 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or L and R A optionally taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which L and R A bond.
7. The pattern-forming method according to claim 1 , further comprising after forming the prepattern and before providing the resin layer,
bringing a second composition into contact with the at least an entirety of the lateral face of the prepattern, wherein the second composition comprises a basic compound and an organic solvent, and does not comprise a polymer solubility of which in the organic solvent does not substantially change due to an action of an acid.
8. The pattern-forming method according to claim 2 , wherein the basic compound is a compound represented by formula (X), a compound represented by formula (Y), or both thereof:
wherein,
in the formula (X), X + represents a monovalent onium cation; and Y − represents a monovalent carboxylate anion or a monovalent sulfonamide anion, and
in the formula (Y), R X represents an unsubstituted or hydroxy-substituted monovalent linear hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or hydroxy-substituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; R Y and R Z each represent an unsubstituted or hydroxy-substituted monovalent linear hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or hydroxy-substituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R Y and R Z taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which R Y and R Z bond.
9. The pattern-forming method according to claim 1 , wherein a proportion of the first structural unit contained with respect to total structural units constituting the first polymer is no less than 10 mol % and no greater than 80 mol %.
10. The pattern-forming method according to claim 1 , wherein the first polymer further comprises a second structural unit which comprises a hydroxy group, a carboxy group, an oxo group or a combination thereof.
11. The pattern-forming method according to claim 1 , wherein the first polymer comprises a third structural unit which comprises a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.
12. The pattern-forming method according to claim 1 , wherein the prepattern is a line-and-space pattern or a hole pattern.
13. The pattern-forming method according to claim 1 , further comprising after removing the portion of the resin layer, rinsing the resist pattern with an organic solvent that is other than the organic solvent used in removing the portion of the resin layer.
14. A pattern-forming method comprising:
forming a prepattern that is insoluble or hardly soluble in an organic solvent;
providing a resin layer on at least an entirety of a lateral face of the prepattern;
heating the prepattern and the resin layer such that a portion of the resin layer adjacent to and in contact with the entirety of the lateral face of the prepattern is made insoluble or hardly soluble in the organic solvent, without being accompanied by an increase of a molecular weight of the portion of the resin layer; and
removing with the organic solvent, a portion of the resin layer other than the portion of the resin layer such that a resist pattern is obtained,
wherein the resin layer is formed from a first composition comprising: a first polymer; and an organic solvent, solubility of the first polymer in the organic solvent not substantially changing due to an action of an acid,
wherein the first polymer comprises a first structural unit that comprises a lactone structure, a cyclic carbonate structure, a sultone structure or a combination thereof, and
wherein (i) the first polymer comprises a basic group; (ii) the first composition further comprises a basic compound; or both of (i) and (ii).
15. The pattern-forming method according to claim 14 , wherein a heating temperature in the heating is no less than 60° C. and no greater than 250° C.
16. The pattern-forming method according to claim 14 , wherein the forming of the prepattern comprises:
forming a resist film made from a resist composition comprising: a second polymer; a radiation-sensitive acid generator; and a solvent, wherein solubility of the second polymer in the organic solvent is capable of decreasing due to an action of an acid;
exposing the resist film; and
developing the exposed resist film with a developer solution comprising the organic solvent.
17. The pattern-forming method according to claim 16 , wherein the second polymer comprises an acid-labile group.
18. The pattern-forming method according to claim 14 , wherein the basic group is a group represented by formula (a), and a group represented by formula (b), or both thereof:
wherein, in the formula (b), L represents a single bond, a divalent linear hydrocarbon group having 1 to 20 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; and R A and R B each independently represent a hydrogen atom, a monovalent linear hydrocarbon group having 1 to 20 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or L and R A optionally taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which L and R A bond.
19. The pattern-forming method according to claim 14 , further comprising after forming the prepattern and before providing the resin layer,
bringing a second composition into contact with the at least an entirety of the lateral face of the prepattern, wherein the second composition comprises a basic compound and organic solvent, and does not comprise a polymer solubility of which in the organic solvent does not substantially change due to an action of an acid.
20. The pattern-forming method according to claim 14 , wherein the basic compound is a compound represented by formula (X), a compound represented by formula (Y), or both thereof:
wherein,
in the formula (X), X + represents a monovalent onium cation; and Y − represents a monovalent carboxylate anion or a monovalent sulfonamide anion, and
in the formula (Y), R X represents an unsubstituted or hydroxy-substituted monovalent linear hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or hydroxy-substituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; R Y and R Z each represent an unsubstituted or hydroxy-substituted monovalent linear hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or hydroxy-substituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R Y and R Z taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which R Y and R Z bond.
21. The pattern-forming method according to claim 14 , wherein a proportion of the first structural unit contained with respect to total structural units constituting the first polymer is no less than 10 mol % and no greater than 80 mol %.
22. The pattern-forming method according to claim 14 , wherein the first polymer further comprises a second structural unit which comprises a hydroxy group, a carboxy group, an oxo group or a combination thereof.
23. The pattern-forming method according to claim 14 , wherein the first polymer comprises a third structural unit which comprises a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.
24. The pattern-forming method according to claim 14 , wherein the prepattern is a line-and-space pattern or a hole pattern.
25. The pattern-forming method according to claim 14 , further comprising after removing the portion of the resin layer, rinsing the resist pattern with an organic solvent that is other than the organic solvent used in removing the portion of the resin layer.