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 (LER) to be produced, and a resist composition containing the same.SOLUTION: There are provided a carboxylate represented by a formula (I), a carboxylic acid generator, and a resist composition. [In the formula, R4, R5, R7 and R8 each represent a halogen atom, a haloalkyl group or a hydrocarbon group and A1 and A2 each represent a hydrocarbon group, provided that the hydrocarbon groups may have a substituent and -CH2- contained in the hydrocarbon groups may be substituted with -O-, -CO-, -S- or -SO2-; m1 represents an integer of 1-5, m2, m4, m5 and m8 represent integers of 0-5, and m7 represents an integer of 0-4, provided that 1≤m1+m7≤5 and 0≤m2+m8≤5; and X0 represents an optionally substituted hydrocarbon group, provided that -CH2- contained in the group may be substituted with -O- or the like.]SELECTED DRAWING: None

Claims

1. A carboxylic acid generator containing a carboxylic acid salt represented by formula (I). [In formula (I), R ４ , R ５ , R ７ and R ８ Each of these independently represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, and the hydrocarbon group may have substituents, and the haloalkyl group and the hydrocarbon group contain -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. However, R ４ At least one of them is an iodine atom. A １ and A ２ each independently represents a hydrocarbon group having 2 to 20 carbon atoms, the hydrocarbon group may have a substituent, and -CH 2 - in the hydrocarbon group may be replaced by -O-, -CO-, -S- or -SO ２ -. m1 represents an integer from 1 to 5, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m² represents an integer between 0 and 5, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer from 1 to 5, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another. m5 represents an integer from 0 to 5, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m7 represents an integer from 0 to 4, and when m7 is 2 or greater, multiple R ７ They may be identical or different from one another. m8 represents an integer from 0 to 5, and when m8 is 2 or greater, multiple R ８ They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 5 and 0 ≤ m2 + m8 ≤ 5. X ０ represents a hydrocarbon group having 1 to 72 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -, except when X 0 -COO - is an anion represented by formula (I - A') or formula (IP - A'). [In formulas (I-A') and (IP-A'), X0 represents a hydrocarbon group having 1 to 72 carbon atoms, which may have a single bond or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2-. R bb1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X 10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenylene group which may have substituents. Ax represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. * indicates the bonding site with the carbon atom to which R bb1 is bonded, and ** indicates the bonding site with L 10. L 10 represents a hydrocarbon group having 1 to 36 carbon atoms, which may have a single bond or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -SO2-, or -CO-.

2. A １ However, *-X ０１ -L ０１ - or * - L ０１ -X ０１ - and A ２ However, *-X ０２ -L ０２ - or * - L ０２ -X ０２ - is (X ０１ and X ０２ These are, independently, -O-, -CO-, -S-, or -SO-, respectively. ２ Represents -. L ０１ and L ０２ Each of these independently represents a hydrocarbon group having 1 to 19 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group may contain -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. * is R ４ or R ５ This represents the bonding site with the benzene ring to which it can be bonded. ) The carboxylic acid generator according to claim 1.

3. X ０１ and X ０２ The carboxylic acid generator according to claim 2, wherein each is independently -O- or -S-.

4. L ０１ and L ０２ However, each independently, an alkanediyl group having 1 to 6 carbon atoms (the alkanediyl group contains -CH 2 The carboxylic acid generator according to claim 2, wherein - may be replaced by -O- or -CO-.

5. If m4 or m5 is an integer of 1 or greater, R ４ and R ５ However, each independently contains a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the alkyl group contains -CH 2 The carboxylic acid generator according to claim 1, wherein - may be replaced by -O- or -CO-.

6. If m7 or m8 is an integer of 1 or greater, R ７ and R ８ However, each independently contains a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the alkyl group contains -CH 2 The carboxylic acid generator according to claim 1, wherein - may be replaced by -O- or -CO-.

7. X ０ However, an aliphatic hydrocarbon group having 1 to 72 carbon atoms may have substituents (the aliphatic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ The carboxylic acid generator according to claim 1, which is a C6 to C36 aromatic hydrocarbon group, which may have substituents, a group represented by formula (aa), or a group represented by formula (bb). [In formula (aa), X a and X b These represent either -O- or -S- independently. X １ａ represents a hydrocarbon group having 1 to 24 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. X ２ａ represents a hydrocarbon group having 1 to 48 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. * is -COO － This represents the bonding site with the carbon atom. [In formula (bb), L Ａ This represents a C1-C6 alkanediyl group which may have a fluorine atom, or a C6-C14 aromatic hydrocarbon group which may have a halogen atom or a C1-C4 perfluoroalkyl group. L Ｂ This represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. R Ａ represents a hydrocarbon group having 1 to 36 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. * is -COO － This represents the bonding site with the carbon atom.

8. X ０ However, a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a hydroxyl group (the alicyclic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - May be replaced by -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - may be replaced by -CH contained in the chain hydrocarbon group. 2 The - may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a C1-C4 perfluoroalkyl group or a hydroxyl group.), the carboxylic acid generator according to claim 7, wherein the - is a C6-C36 aromatic hydrocarbon group which may have a fluorine atom, a C1-C4 perfluoroalkyl group or a hydroxyl group, a group represented by formula (aa), or a group represented by formula (bb).

9. A resist composition containing a carboxylic acid generator according to any one of claims 1 to 8, an acid generator other than the carboxylic acid generator, and a resin having an acid-unstable group.

10. The resist composition according to claim 9, 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.

11. The resist composition according to claim 9, 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 represents a single bond or *-X a51 -(A a52 -X a52 ) nｂ -, where * represents the bonding site with the carbon atom to which -R a50 is bonded. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 each independently represents -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.

12. (1) A step of applying the resist composition according to claim 9 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].

13. A carboxylate salt represented by formula (I). [In formula (I), R ４ , R ５ , R ７ and R ８ Each of these independently represents a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, and the hydrocarbon group may have substituents, and the haloalkyl group and the hydrocarbon group contain -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. However, R ４ At least one of them is an iodine atom. A １ and A ２ Each of these independently represents a hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group may contain -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. m1 represents an integer from 1 to 5, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m² represents an integer between 0 and 5, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer from 1 to 5, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another. m5 represents an integer from 0 to 5, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m7 represents an integer from 0 to 4, and when m7 is 2 or greater, multiple R ７ They may be identical or different from one another. m8 represents an integer from 0 to 5, and when m8 is 2 or greater, multiple R ８ They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 5 and 0 ≤ m2 + m8 ≤ 5. X ０ represents a hydrocarbon group having 1 to 72 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -, except when X 0 -COO - is an anion represented by formula (I - A') or formula (IP - A'). [In formulas (I-A') and (IP-A'), X0 represents a hydrocarbon group having 1 to 72 carbon atoms, which may have a single bond or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2-. R bb1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X 10 represents a single bond, *-O-**, *-CO-O-**, *-O-CO-O-**, or *-Ax-Ph-Ay-**. Ph represents a phenylene group which may have substituents. Ax represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. Ay represents one type of bond selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds. * indicates the bonding site with the carbon atom to which R bb1 is bonded, and ** indicates the bonding site with L 10. L 10 represents a hydrocarbon group having 1 to 36 carbon atoms, which may have a single bond or substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -SO2-, or -CO-.

14. A １ However, *-X ０１ -L ０１ - or * - L ０１ -X ０１ - and A ２ However, *-X ０２ -L ０２ - or * - L ０２ -X ０２ - is (X ０１ and X ０２ These are, independently, -O-, -CO-, -S-, or -SO-, respectively. ２ Represents -. L ０１ and L ０２ Each of these independently represents a hydrocarbon group having 1 to 19 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group may contain -CH 2 - stands for -O-, -CO-, -S-, or -SO ２ It may be replaced with -. * is R ４ or R ５ This represents the bonding site with a benzene ring to which it can be bonded.) The carboxylate salt according to claim 13.

15. X ０１ and X ０２ The carboxylate salt according to claim 14, wherein each is independently -O- or -S-.

16. L ０１ and L ０２ However, each independently, an alkanediyl group having 1 to 6 carbon atoms (the alkanediyl group contains -CH 2 The carboxylate salt according to claim 14 or 15, wherein - may be replaced by -O- or -CO-.

17. If m4 or m5 is an integer of 1 or greater, R ４ and R ５ However, each independently contains a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the alkyl group contains -CH 2 The carboxylate salt according to claim 13 or 14, wherein - may be replaced by -O- or -CO-.

18. If m7 or m8 is an integer of 1 or greater, R ７ and R ８ However, each independently contains a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms (the alkyl group contains -CH 2 The carboxylate salt according to claim 13 or 14, wherein - may be replaced by -O- or -CO-.

19. X ０ However, an aliphatic hydrocarbon group having 1 to 72 carbon atoms may have substituents (the aliphatic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ The carboxylate salt according to claim 13 or 14, wherein the group is an aromatic hydrocarbon group having 6 to 36 carbon atoms, which may have substituents, a group represented by formula (aa), or a group represented by formula (bb). [In formula (aa), X a and X b These represent either -O- or -S- independently. X １ａ represents a hydrocarbon group having 1 to 24 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. X ２ａ represents a hydrocarbon group having 1 to 48 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. * is -COO － This represents the bonding site with the carbon atom. [In formula (bb), L Ａ This represents a C1-C6 alkanediyl group which may have a fluorine atom, or a C6-C14 aromatic hydrocarbon group which may have a halogen atom or a C1-C4 perfluoroalkyl group. L Ｂ This represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. R Ａ represents a hydrocarbon group having 1 to 36 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ It may be replaced with -. * is -COO － This represents the bonding site with the carbon atom.

20. X ０ However, a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a hydroxyl group (the alicyclic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - May be replaced by -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - may be replaced by -CH contained in the chain hydrocarbon group. 2 The - may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a C1-C4 perfluoroalkyl group or a hydroxyl group.), the carboxylate salt according to claim 19, wherein the group is a C6-C36 aromatic hydrocarbon group which may have a fluorine atom, a C1-C4 perfluoroalkyl group or a hydroxyl group, a group represented by formula (aa), or a group represented by formula (bb).

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