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

Abstract

To provide a carboxylate which allows a resist pattern having good line edge roughness to be produced, a carboxylic acid generator, and a resist composition containing the same.SOLUTION: There are provided a carboxylate represented by formula (I), a carboxylic acid generator, and a resist composition. [In the formula, L1 represents a single bond or an optionally substituted C1-40 hydrocarbon group, provided that -CH2- contained in the hydrocarbon group may be substituted with -O-, -S-, -SO2- or -CO-; R1 represents a halogen atom or a C1-12 haloalkyl group; R2 represents a halogen atom, a hydroxy group, a C1-12 haloalkyl group or a C1-12 alkyl group, provided that -CH2- contained in the haloalkyl group and the alkyl group may be substituted with -O- or -CO-; m2 represents an integer of 0-6; and Z+ represents 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 -CH represents a single bond or a hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group may have substituents selected from a hydroxyl group, a carboxyl group, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group consisting of these, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. R １ This represents an iodine atom. 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 6, 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. L １ is a single bond, *-L ２ - or *-L ２ -X ３ -L ３ -(L ２ represents a linear hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, or a group combining a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent and a linear hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and -CH 2 - contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -, and -CH 2 - contained in the linear hydrocarbon group may be replaced by -O- or -CO-. * represents the bonding site with the carbonyl group. X ３ represents **-CO-O-, **-O-CO-, **-O-CO-O- or **-O-, and ** represents the bonding site with L ２ L ３ represents a single bond or a linear hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and -CH 2 - contained in the linear hydrocarbon group may be replaced by -O- or -CO-. ) The carboxylic acid generator according to claim 1

3. If m2 is an integer greater than or equal to 1, then R ２ However, iodine atoms, fluorine atoms, hydroxyl groups, C1-C6 haloalkyl groups or C1-C6 alkyl groups (the haloalkyl groups and the alkyl groups contained in the -CH 2 The carboxylic acid generator according to claim 1, wherein - may be replaced by -O- or -CO-.

4. A resist composition containing a carboxylic acid generator according to any one of claims 1 to 3, an acid generator other than the carboxylic acid generator, and a resin having an acid-unstable group.

5. The resist composition according to claim 4, 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 an alkyl group having 1 to 6 carbon atoms that may contain 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.

6. The resist composition according to claim 4, 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 This 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 the same or different from each other.

7. (1) A step of applying the resist composition according to claim 4 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].

8. A carboxylate salt represented by formula (I). [In formula (I), L 1 -CH represents a single bond or a hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group may have substituents selected from a hydroxyl group, a carboxyl group, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group consisting of these, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. R １ This represents an iodine atom. 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 6, 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.

9. L １ However, single bond, *-L ２ - or * - L ２ -X ３ -L ３ - (L ２ This represents a chain hydrocarbon group having 1 to 10 carbon atoms which may have substituents, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, or a group formed by combining a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents and a chain hydrocarbon group having 1 to 8 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 ３ represents **-CO-O-, **-O-CO-, **-O-CO-O-, or **-O-, where ** is L ２ This represents the bonding site with L. ３ This represents a chain-like hydrocarbon group having 1 to 8 carbon atoms, which may have single bonds or substituents, and the chain-like hydrocarbon group contains -CH 2 The carboxylate salt according to claim 8, wherein - may be replaced by -O- or -CO-.

10. If m2 is an integer greater than or equal to 1, then R ２ However, iodine atoms, fluorine atoms, hydroxyl groups, C1-C6 haloalkyl groups or C1-C6 alkyl groups (the haloalkyl groups and the alkyl groups contained in the -CH 2 The carboxylate salt according to claim 8 or 9, wherein - may be replaced by -O- or -CO-.

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