Carboxylate salt, carboxylic acid generator, resist composition, and method for producing resist patterns

Abstract

To provide a carboxylate and a carboxylic acid generator which can produce a resist pattern having excellent line edge roughness, and a resist composition comprising the same.SOLUTION: The present invention provides a carboxylate represented by the formula (I), a carboxylic acid generator and a resist composition [where L1 and L2 each denote a single bond or an optionally substituted hydrocarbon group, -CH2- in the group being optionally substituted with -O-, -S-, -SO2- or -CO-. X2 is *-CO-O-, *-O-CO-, *-O-CO-O- or the like. L3 is a single bond or a saturated hydrocarbon group. A1 is a ring shown above optionally having an alkyl group or a hydroxy group, -CH2- in the ring being optionally substituted with -CO-. R1 is a halogen atom or a haloalkyl group. R2 is a halogen atom, a hydroxy group, a haloalkyl group or the like. Z+ is an organic cation].SELECTED DRAWING: None

Claims

1. A carboxylic acid generator containing a carboxylic acid salt represented by formula (I). [In formula (I), L １ and L ２ Each of these independently represents a hydrocarbon group having 1 to 28 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. X ２ * represents *-CO-O-, *-O-CO-, *-O-CO-O-, or *-O-, where * is A １ or L ２ This represents the connection point. L ３ This represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms. A １ represents a ring represented by the following, and the -CH 2 - in the ring may be replaced by -CO-, and the ring may have an alkyl group or a hydroxy group having 1 to 6 carbon atoms. * is L １ and L ２ represents the bonding site with. R １ This represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms. R ２ -CH represents a halogen atom, a hydroxyl group, a C1-C12 haloalkyl group, or a C1-C12 alkyl group, and the -CH contained in the haloalkyl group and the alkyl group 2 The dash may be replaced by -O- or -CO-. m2 represents an integer from 0 to 4, and when m2 is 2 or greater, multiple R ２ They may be identical or different from one another. Z ＋ This represents an organic cation.

2. R １ The carboxylic acid generator according to claim 1, wherein the atom is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms.

3. L １ However, single bond, *-L １２ - or * - L １２ -X １３ -L １３ - (L １２ This represents a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents, a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, or a group formed by combining a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents and a chain hydrocarbon group having 1 to 4 carbon atoms which may have substituents, and the cyclic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - may be replaced by -CH contained in the chain hydrocarbon group. 2 The - symbol may be replaced by -O- or -CO-. * indicates a bond site with a carbonyl group. X １３ represents **-CO-O-, **-O-CO-, **-O-CO-O-, or **-O-, where ** is L １２ This represents the bonding site with L. １３ The carboxylic acid generator according to claim 1, wherein represents a single bond or a chain hydrocarbon group having 1 to 8 carbon atoms.

4. L ２ However, a chain hydrocarbon group having 1 to 8 carbon atoms may have single bonds or substituents (the chain hydrocarbon group contains -CH 2 The carboxylic acid generator according to claim 1, wherein - may be replaced with -O- or -CO-.

5. A resist composition containing a carboxylic acid generator according to any one of claims 1 to 4, an acid generator other than the carboxylic acid generator, and a resin having an acid-unstable group.

6. The resist composition according to claim 5, wherein the resin having an acid-unstable group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2). [In formulas (a1-0), (a1-1), and (a1-2), L a01 , L ａ１ and L ａ２ These are, independently, -O- or *-O- (CH ２ ) ｋ１ This represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bonding site with -CO-. R a01 , R ａ４ and R ａ５ Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R a02 , R a03 and R a04 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R ａ６ and R ａ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

7. The resist composition according to claim 5, wherein the resin having an acid-unstable group comprises a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or ＊ -X a51 - (A a52 -X a52 ) nｂ - represents -R a50 This represents the bonding site with the carbon atom to which it is bonded. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent, independently, -O-, -CO-O-, or -O-CO-. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, then multiple R a51 They may be identical or different from one another.

8. (1) A step of applying the resist composition according to claim 5 onto a substrate, (2) A step of drying the coated composition to form a composition layer, (3) Exposure step of the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element].

9. A carboxylate salt represented by formula (I). [In formula (I), L １ and L ２ Each of these independently represents a hydrocarbon group having 1 to 28 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. X ２ * represents *-CO-O-, *-O-CO-, *-O-CO-O-, or *-O-, where * is A １ or L ２ This represents the connection point. L ３ This represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms. A １ This represents a ring, and the ring contains -CH 2 The - may be replaced with -CO-, and the ring may have an alkyl group or hydroxyl group having 1 to 6 carbon atoms. * is L １ and L ２ This represents the connection point. R １ This represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms. R ２ -CH represents a halogen atom, a hydroxyl group, a C1-C12 haloalkyl group, or a C1-C12 alkyl group, and the -CH contained in the haloalkyl group and the alkyl group 2 The dash may be replaced by -O- or -CO-. m2 represents an integer from 0 to 4, and when m2 is 2 or greater, multiple R ２ They may be identical or different from one another. Z ＋ This represents an organic cation.

10. R １ The carboxylate salt according to claim 9, wherein the atom is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms.

11. L １ However, single bond, *-L １２ - or * - L １２ -X １３ -L １３ - (L １２ This represents a chain hydrocarbon group having 1 to 8 carbon atoms which may have substituents, a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, or a group formed by combining a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents and a chain hydrocarbon group having 1 to 4 carbon atoms which may have substituents, and the cyclic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - may be replaced by -CH contained in the chain hydrocarbon group. 2 The - symbol may be replaced by -O- or -CO-. * indicates a bond site with a carbonyl group. X １３ represents **-CO-O-, **-O-CO-, **-O-CO-O-, or **-O-, where ** is L １２ This represents the bonding site with L. １３ The carboxylate salt according to claim 9 or 10, wherein represents a single bond or a chain hydrocarbon group having 1 to 8 carbon atoms.

12. L ２ is a chain hydrocarbon group having 1 to 8 carbon atoms which may have a single bond or a substituent (in the chain hydrocarbon group, -CH 2 - may be replaced by -O- or -CO-). The carboxylate according to claim 9 or 10.

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