Resist composition and method for producing resist patterns, as well as salt and acid generator

Abstract

To provide a salt, a resist composition, etc. that can produce a resist pattern having good line edge roughness. 【Solution means】An acid generator containing a salt represented by formula (I), a resist composition, etc. TIFF2026097770000164.tif60160 [Q 1 , Q 2 , Q 11 , Q 12 , R 1 , R 2 , R 11 and R 12 each represent a hydrogen atom, a fluorine atom, etc.; z and z1 each represent an integer of 0 to 6; X 0 and X 01 each represent a single bond, -O-, -CO-, -NR 13 -, or a group combining these; etc.]

Claims

1. An acid generator containing a salt represented by formula (I). [In formula (I), Q １ Q ２ Q １１ Q １２ , R １ , R ２ , R １１ and R １２ Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. z and z1 each independently represent an integer of any one of 0 to 6, and when z is 2 or more, a plurality of Rs １ and R ２ may be the same as or different from each other, and when z1 is 2 or more, a plurality of Rs 11 and R 12 may be the same as or different from each other. X ０ and X ０1 These are, independently, single bonds, -O-, -CO-, -S-, -SO-, and -SO-. ２ -, -NR １３ - Or represents a base that combines these elements. R １１Ｎ , R １２Ｎ and R １３ Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L １ and L ０1 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 -, -SO-, -NR １３ It may be replaced with - or -CO-. L ２ and L ０２ Each of these independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group contains -CH 2 The dash may be replaced by -O- or -CO-. R ５ , R ６ , R ７ and R ８ Each of these independently represents a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １３ It may be replaced with - or -CO-. m5 represents an integer from 0 to 4, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 4, and when m6 is 2 or greater, multiple R ６ 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 4, and when m8 is 2 or greater, multiple R ８ They may be identical or different from one another. Z ＋ and Z11 ＋ Each of these independently represents an organic cation.

2. X ０ and X ０1 However, each is independent of *-CO-, *-CO-O-, and *-CO-NR １３ -, *-O-CO- or *-O-CO-O- (* is C(R 1 ) (Caution 2 ) or C (Q 1 ) (Q 2 ), or C (R 11 ) (Caution 12 ) or C (Q 11 ) (Q 12 The acid generator according to claim 1, which represents the binding site with ).

3. L １ and L ０1 However, each can be independently a single bond, a chain hydrocarbon group having 1 to 4 carbon atoms which may have substituents, or a group formed by combining a chain hydrocarbon group having 1 to 4 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the chain hydrocarbon group and the cyclic hydrocarbon group contain -CH 2 The acid generator according to claim 1 or 2, wherein - may be replaced with -O- or -CO-.

4. L ２ and L ０２ The acid generator according to claim 1 or 2, wherein each is independently a single bond, a methylene group, *-CO- or *-O-CO- (where * represents a bonding site with a benzene ring).

5. A resist composition containing the acid generator described in claim 1 or 2.

6. Furthermore, the resist composition according to claim 5 contains a resin comprising a structural unit represented by formula (a2-A). [In formula (a2-A), R ａ２ 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 ａ２７ This represents a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 alkyl group which may have a halogen atom, 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 ａ２１ This represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group contains -CH ２ - stands for -O-, -CO-, or -NR ａ２８ It may be replaced with -. R ａ２８ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ａ２ This represents a single bond or a carbonyl group. nA2 represents an integer from 1 to 5, and when nA2 is 2 or greater, the bases within the parentheses may be the same or different from each other. na21 represents an integer from 0 to 4, and when na21 is 2 or greater, multiple R ａ２７ They may be the same or different from one another. mc represents an integer between 0 and 2.

7. The resin further contains structural units having acid-unstable groups. The resist composition according to claim 6, wherein the structural unit having an acid-unstable group is selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a1-4), a structural unit represented by formula (a1-5), and a structural unit represented by formula (a1-6). [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 consisting of a combination thereof, and the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. 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 thereof, and the alkyl group, the alkenyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a halogen atom. m1' represents an integer between 0 and 14. n1 represents an integer between 0 and 14. n1' represents an integer between 0 and 3. [In formula (a1-4), R ａ１ 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 ａ１７ This represents a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 alkyl group which may have a halogen atom, 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 ａ１１ This represents a single bond or an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group contains -CH ２ - stands for -O-, -CO-, or -NR ａ１８ It may be replaced with -. R ａ１８ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X ａ１ This represents a single bond or a carbonyl group. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a34 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a35 and R a36 are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the -C-O- to which they are bonded, and -CH 2 - contained in the hydrocarbon group and the divalent heterocyclic group may be replaced by -O- or -S-. na1 represents an integer from 1 to 5, and when na1 is 2 or greater, the bases within the parentheses may be the same or different from each other. na11 represents an integer from 0 to 4, and when na11 is 2 or greater, multiple R ａ１７ They may be the same or different from one another. mc represents an integer between 0 and 2. [In formula (a1-5), R a8 This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. Z a1 represents a single bond or *-(CH 2 ), h3 -CO-L 54 -, h3 represents an integer of 1 to 4, and * represents the bonding site with L 51 . L 51 , L 52 , L 53 and L 54 These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3. [In formula (a1-6), R a61 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 a6２ , R a63 and R a6４ Each independently represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, or R a6２ and R a63 They bond to each other, forming a ring with 3 to 20 carbon atoms, R a6４ This represents an alkyl group having 1 to 6 carbon atoms or a cyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. X a61 These are single bonds, -CO-O-* or -CO-NR a65 - represents *, where * represents the bonding site with Ar, R a65 This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X a62 This is a single bond, *-O-L a61 - or * - CO-O-L a62 - represents the bonding site with Ar, and L a61 and L a62 Each of these independently represents an alkanediyl group having 1 to 4 carbon atoms. Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents.

8. The resist composition according to claim 5, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

9. (1) A step of applying the resist composition according to claim 5 onto a substrate, (2) A step of drying the coated resist 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].

10. A salt represented by formula (I). [In formula (I), Q １ Q ２ Q 11 Q 12 , R １ , R ２ , R 11 and R 12 Each of these independently represents a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. z and z1 each independently represent an integer from 0 to 6, and when z is 2 or greater, multiple R １ and R ２ They may be the same or different from each other, and when z1 is 2 or more, multiple R 11 and R 12 They may be identical or different from one another. X ０ and X ０1 These are, independently, single bonds, -O-, -CO-, -S-, -SO-, and -SO-. ２ -, -NR １３ - Or represents a base that combines these elements. R １１Ｎ , R １２Ｎ and R １３ Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L １ and L ０1 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 -, -SO-, -NR １３ It may be replaced with - or -CO-. L ２ and L ０２ Each of these independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group contains -CH 2 The dash may be replaced by -O- or -CO-. R ５ , R ６ , R ７ and R ８ Each of these independently represents a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 36 carbon atoms which may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １３ It may be replaced with - or -CO-. m5 represents an integer from 0 to 4, and when m5 is 2 or greater, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 4, and when m6 is 2 or greater, multiple R ６ 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 4, and when m8 is 2 or greater, multiple R ８ They may be identical or different from one another. Z ＋ and Z11 ＋ Each of these independently represents an organic cation.

11. X ０ and X ０1 However, each is independent of *-CO-, *-CO-O-, and *-CO-NR １３ -, *-O-CO- or *-O-CO-O- (* is C(R 1 ) (Caution 2 ) or C (Q 1 ) (Q 2 ), or C (R 11 ) (Caution 12 ) or C (Q 11 ) (Q 12 The salt according to claim 10, which represents the bonding site with ).

12. L １ and L ０1 However, each can be independently a single bond, a chain hydrocarbon group having 1 to 4 carbon atoms which may have substituents, or a group formed by combining a chain hydrocarbon group having 1 to 4 carbon atoms which may have substituents and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents (the chain hydrocarbon group and the cyclic hydrocarbon group contain -CH 2 The salt according to claim 10 or 11, wherein - may be replaced by -O- or -CO-.

13. L ２ and L ０２ The salt according to claim 10 or 11, wherein each is independently a single bond, a methylene group, *-CO- or *-O-CO- (where * represents a bond site with a benzene ring).

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