Resist composition, method of forming resist pattern, compound, and acid generator
A resist composition containing a compound represented by the general formula (bd1-1), (bd1-2) or (bd1-3); in the formula, Rx 1 to Rx 4 represent a hydrocarbon group or a hydrogen atom or may be mutually bonded to form a ring structure; Ry 1 to Ry 2 represent a hydrocarbon group or a hydrogen atom or may be mutually bonded to form a ring structure, Rz 1 to Rz 4 represent a hydrocarbon group or a hydrogen atom or may be mutually bonded to form a ring structure. At least one of Rx 1 to Rx 4 , Ry 1 to Ry 2 and Rz 1 to Rz 4 has an anion group, M 1 m+ represents a sulfonium cation having a sulfonyl group, R 001 to R 003 each independently represent a monovalent organic group; provided that at least one of R 001 to R 003 is an organic group having an acid dissociable group; and M 3 m+ represents an m-valent organic cation having an electron-withdrawing group.
1. A resist composition which generates an acid upon exposure and exhibits a changed solubility in a developing solution under the action of acid, the resist composition comprising:
a base component (A) that exhibits a changed solubility in a developing solution under the action of acid; and
a compound (BD1-1) having an anion moiety and a cation moiety and which is represented by the following general formula (bd1-1):
wherein Rx 1 to Rx 4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of Rx 1 to Rx 4 may be mutually bonded to form a ring structure; Ry 1 and Ry 2 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or Ry 1 and Ry 2 may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 1 to Rx 4 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, and the anion moiety as a whole forms an anion having a valency of n; n represents an integer of 1 or more; m represents an integer of 1 or more; and M 1 m+ is a cation represented by general formula (ca-0) shown below:
wherein R b1 represents an aryl group which may have a substituent; R b2 and R b3 each independently represent an aryl group which may have a substituent or an alkyl group which may have a substituent; R b2 and R b3 may be mutually bonded to form a ring with the sulfur atom; provided that at least one of R b1 to R b3 has a substituent containing a sulfonyl group.
2. The resist composition according to claim 1 ,
wherein at least one of Rx 1 to Rx 2 and at least one of Rx 3 to Rx 4 are mutually bonded to form a ring structure.
3. The resist composition according to claim 1 ,
wherein the anion moiety in the compound (BD1-1) is an anion represented by the following general formula (bd1-an1):
wherein Rx 5 and Rx 6 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent; Rx 7 and Rx 8 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or alternatively, may be mutually bonded to form a ring structure; p is 1 or 2, and when p=2, a plurality of Rx 7 and Rx 8 may be different from each other; and Ry 1 and Ry 2 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent or may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 5 to Rx 8 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, and the anion moiety as a whole forms an anion having a valency of n; n represents an integer of 1 or more.
4. The resist composition according to claim 3 ,
wherein the anion moiety in the compound (BD1-1) is an anion represented by the following general formula (bd1-an2):
wherein Rx 5 and Rx 6 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent; a plurality of Rx 7 and Rx 8 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent or two or more thereof may be mutually bonded to form a ring structure; and Ry 1 and Ry 2 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent or may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 5 to Rx 8 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, and the entire anion moiety may be an n-valent anion; and n represents an integer of 1 or more.
5. The resist composition according to claim 3 ,
wherein Rx 7 to Rx 8 are mutually bonded to form a ring structure.
6. The resist composition according to claim 3 ,
wherein at least one of Rx 5 and Rx 6 has an anion group.
7. The resist composition according to claim 1 ,
wherein Ry 1 to Ry 2 are mutually bonded to form a ring structure.
8. The resist composition according to claim 1 ,
wherein at least one of Rz 1 to Rz 4 has an anion group.
9. The resist composition according to claim 1 ,
wherein the sulfonyl group that a cation represented by the general formula (ca-0) has is a bivalent sulfonyl group in which one carbon atom of a ring formed of R b2 to R b3 that are mutually bonded to form a ring together with a sulfur atom in the formula is substituted.
10. The resist composition according to claim 1 ,
wherein the sulfonyl group that a cation represented by the general formula (ca-0) has is a monovalent group represented by —SO 2 —R b4 , wherein R b4 is a linear or branched linear alkyl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent.
11. The resist composition according to claim 1 ,
wherein the compound (BD1-1) has only one anionic group,
wherein Rx 1 to Rx 4 , Ry 1 and Ry 2 and Rz 1 to Rz 4 have only one anionic group, and the whole anion moiety is a monovalent anion; n represents an integer of 1; m represents an integer of 1; and M m+ represents a monovalent organic cation.
12. A method of forming a resist pattern, comprising:
forming a resist film on a support using the resist composition according to claim 1 ;
exposing the resist film; and
developing the exposed resist film to form a resist pattern.
13. The method of forming a resist pattern according to claim 12 ,
wherein the resist film is exposed with extreme ultraviolet (EUV) or an electron beam (EB).
14. A resist composition which generates an acid upon exposure and exhibits changed solubility in a developing solution under the action of acid, the resist composition comprising:
a compound having an anion moiety and a cation moiety (BD1-2) and which is represented by the following general formula (bd1-2); and
a base component (A) that exhibits a changed solubility in a developing solution under the action of acid:
wherein R 001 to R 003 each independently represent a monovalent organic group; provided that at least one of R 001 to R 003 represents an organic group having an acid dissociable group which has a cyclic structure; and two or more of R 001 to R 003 may be mutually bonded to form a ring with the sulfur atom; Rx 1 to Rx 4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of Rx 1 to Rx 4 may be mutually bonded to form a ring structure; Ry 1 and Ry 2 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or Ry 1 and Ry 2 may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of R b2 and R b3 may be mutually bonded to form a ring structure; provided that at least one of Rz 1 to Rz 4 has an anion group, and the anion moiety as a whole forms an anion having a valency of n; and n represents an integer of 1 or more.
15. The resist composition according to claim 14 ,
wherein the acid dissociable group has a tertiary alkyl ester structure having 5 or more carbon atoms.
16. The resist composition according to claim 14 ,
wherein the compound (BD1-2) has only one anionic group,
wherein Rx 1 to Rx 4 , Ry 1 and Ry 2 and Rz 1 to Rz 4 have only one anionic group, and the whole anion moiety is a monovalent anion; n represents an integer of 1; m represents an integer of 1; and M m+ represents a monovalent organic cation.
17. A method of forming a resist pattern, comprising:
forming a resist film on a support using the resist composition according to claim 14 ;
exposing the resist film; and
developing the exposed resist film to form a resist pattern.
18. The method of forming a resist pattern according to claim 17 ,
wherein the resist film is exposed with extreme ultraviolet (EUV) or an electron beam (EB).
19. A compound having an anion moiety and a cation moiety and which is represented by the following general formula (bd1-2):
wherein R 001 to R 003 each independently represent a monovalent organic group; provided that at least one of R 001 to R 003 represents an organic group having an acid dissociable group which has a cyclic structure; and two or more of R 001 to R 003 may be mutually bonded to form a ring with the sulfur atom; Rx 1 to Rx 4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of Rx 1 to Rx 4 may be mutually bonded to form a ring structure; Ry 1 and Ry 2 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or Ry 1 and Ry 2 may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of Rz 1 to Rz 4 may be mutually bonded to form a ring structure; provided that at least one of Rz 1 to Rz 4 has an anion group, and the anion moiety as a whole forms an anion having a valency of n; and n represents an integer of 1 or more.
20. The compound according to claim 19 ,
wherein the compound has only one anionic group,
wherein Rx 1 to Rx 4 , Ry 1 and Ry 2 and Rz 1 to Rz 4 have only one anionic group, and the whole anion moiety is a monovalent anion; n represents an integer of 1; m represents an integer of 1; and M m+ represents a monovalent organic cation.
21. An acid generator including the compound according to claim 19 .
22. A resist composition which generates an acid upon exposure and exhibits a changed solubility in a developing solution under the action of acid, the resist composition comprising:
a base component (A) that exhibits a changed solubility in a developing solution under the action of acid; and
a compound having an anion moiety and a cation moiety (BD1-3) and which is represented by the following general formula (bd1-3):
wherein Rx 1 to Rx 4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of Rx 1 to Rx 4 may be mutually bonded to form a ring structure; Ry 1 and Ry 2 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or Ry 1 and Ry 2 may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 1 to Rx 4 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, and the anion moiety as a whole forms an anion having a valency of n; n represents an integer of 1 or more; m represents an integer of 1 or more; and M 3 m+ represents an m-valent organic cation having an electron-withdrawing group.
23. The resist composition according to claim 22 ,
wherein the cation moiety in the compound (BD1-3) is a cation represented by any of the following general formulae (ca0-1) to (ca0-4):
wherein R 201 to R 207 and R 211 to R 212 each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent; R 201 to R 203 , R 206 to R 207 , R 211 to R 212 may be mutually bonded to form a ring together with a sulfur atom in the formula; R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or may be mutually bonded to form a ring together with a sulfur atom in the formula; R 210 represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a —SO 2 — containing cyclic group which may have a substituent; provided that at least one of one of R 201 to R 203 , at least one of R 204 and R 205 , at least one of R 206 and R 207 , and at least one of R 211 and R 212 have an electron-withdrawing group as a substituent; L 201 represents —C(═O)— or —C(═O)—O—; a plurality of Y 201 's each independently represent an arylene group, an alkylene group or an alkenylene group; x is 1 or 2; and W 201 represents an (x+1)-valent linking group.
24. The resist composition according to claim 22 ,
wherein the electron-withdrawing group is a halogen atom or a halogenated alkyl group.
25. The resist composition according to claim 22 ,
wherein at least one of Rx 1 to Rx 2 and at least one of Rx 3 to Rx 4 are mutually bonded to form a ring structure.
26. The resist composition according to claim 22 ,
wherein the anion moiety in the compound (BD1-3) is an anion represented by the following general formula (bd1-an1):
wherein Rx 5 to Rx 6 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent; Rx 7 to Rx 8 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent, or alternatively, may be mutually bonded to form a ring structure; p is 1 or 2, and when p=2, a plurality of Rx 7 to Rx 8 may be different from each other; and Ry 1 to Ry 2 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent or may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 5 to Rx 8 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, the entire anion moiety may be an n-valent anion; and n represents an integer of 1 or more.
27. The resist composition according to claim 26 ,
wherein the anion moiety in the compound (BD1-3) is an anion represented by the following general formula (bd1-an2):
wherein Rx 5 to Rx 6 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent; a plurality of Rx 7 to Rx 8 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent or two or more thereof may be mutually bonded to form a ring structure; and Ry 1 and Ry 2 each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent or may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 5 to Rx 8 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, the entire anion moiety may be an n-valent anion; and n represents an integer of 1 or more.
28. The resist composition according to claim 26 ,
wherein Rx 7 and Rx 8 are mutually bonded to form a ring structure.
29. The resist composition according to claim 26 ,
wherein at least one of Rx 5 and Rx 6 has an anion group.
30. The resist composition according to claim 22 ,
wherein Ry 1 and Ry 2 are mutually bonded to form a ring structure.
31. The resist composition according to claim 22 ,
wherein at least one of Rz 1 to Rz 4 has an anion group.
32. The resist composition according to claim 22 ,
wherein the compound (BD1-3) has only one anionic group,
wherein Rx 1 to Rx 4 , Ry 1 and Ry 2 and Rz 1 to Rz 4 have only one anionic group, and the whole anion moiety is a monovalent anion; n represents an integer of 1; m represents an integer of 1; and M m+ represents a monovalent organic cation.
33. A method of forming a resist pattern, comprising:
forming a resist film on a support using the resist composition according to claim 22 ;
exposing the resist film; and
developing the exposed resist film to form a resist pattern.
34. The method of forming a resist pattern according to claim 33 ,
wherein the resist film is exposed with extreme ultraviolet (EUV) or an electron beam (EB).
35. A compound having an anion moiety and a cation moiety and which is represented by the following general formula (bd1-3):
wherein Rx 1 to Rx 4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or two or more of Rx 1 to Rx 4 may be mutually bonded to form a ring structure; Ry 1 and Ry 2 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, or Ry 1 and Ry 2 may be mutually bonded to form a ring structure;
represents a double bond or a single bond; Rz 1 to Rz 4 each independently represent, where valence allows, a hydrogen atom or a hydrocarbon group which may have a substituent, provided that two or more of Rz 1 to Rz 4 are mutually bonded to form a ring structure; provided that at least one of Rx 1 to Rx 4 , Ry 1 , Ry 2 and Rz 1 to Rz 4 has an anion group, and the anion moiety as a whole forms an anion having a valency of n; n represents an integer of 1 or more; m represents an integer of 1 or more; and M 3 m+ represents an m-valent organic cation having an electron-withdrawing group.
36. The compound according to claim 35 ,
wherein the compound has only one anionic group,
wherein Rx 1 to Rx 4 , Ry 1 and Ry 2 and Rz 1 to Rz 4 have only one anionic group, and the whole anion moiety is a monovalent anion; n represents an integer of 1; m represents an integer of 1; and M m+ represents a monovalent organic cation.
37. An acid generator including the compound according to claim 35 .