Resist composition and method for producing resist patterns and salt

Abstract

An object is to provide a salt, a resist composition, etc. that can produce a resist pattern having good pattern collapse resistance. 【Solution means】A resist composition containing an acid generator containing a salt represented by formula (I). TIFF2026103864000179.tif2399[In the formula, X 0 and X 1 are each -O-, -CO- or a group combining these, etc.; W 1 represents a hydrocarbon group containing a cyclic hydrocarbon group, and a hydrogen atom contained in the hydrocarbon group may be replaced by a substituent; L 2 represents a single bond or an alkanediyl group, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-; R 1 is a substituted / unsubstituted cyclic hydrocarbon group; R 3 represents a halogen atom, a nitro group, a cyano group or a hydrocarbon group, and the hydrocarbon group may have a substituent; m3 represents an integer of 0 to 4; mn1 represents an integer of 1 to 5; Z + represents an organic cation.]

Claims

1. A resist composition containing an acid generator comprising a salt represented by formula (I). [In formula (I), X ０ and X １ These are, independently, -O-, -CO-, -S-, -SO-, and -SO ２ -, -NR １１ - Or represents a base that combines these elements. R １１ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. W １ represents a hydrocarbon group containing a cyclic hydrocarbon group having 3 to 36 carbon atoms, and the hydrogen atoms contained in the hydrocarbon group may be replaced by substituents, and the -CH ２ - may be replaced by -O-, -S-, -CO-, -SO-, -NR １１ - or -SO ２ -. L ２ This 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 １ This represents a cyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents, and the cyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -CO-, -SO-, -NR １１ - or - SO ２ It may be replaced with -. R ３ represents a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １１ It may be replaced with - or -CO-. m3 represents an integer from 0 to 4, and when m3 is 2 or greater, multiple R ３ They may be identical or different from one another. mn1 represents an integer between 1 and 5, and when mn1 is 2 or greater, the bases within the parentheses may be the same or different. Z ＋ This represents an organic cation.

2. The resist composition according to claim 1, wherein the salt represented by formula (I) is the salt represented by formula (IA). [In formula (IA), X ０ , R １１ , W １ , X １ , L ２ , R １ , R ３ , m3, mn1 and Z ＋ This has the same meaning as equation (I). W1 represents a cyclic hydrocarbon group with (5 + m11) carbon atoms, and the carbon atoms in the cyclic hydrocarbon group may form a double bond between two adjacent carbon atoms, and the cyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -SO ２ -, -SO-, -NR １１ It may be replaced by - or -CO-, and the hydrogen atoms contained in the cyclic hydrocarbon group may be substituted with substituents. R ４ represents a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １１ - or -CO- may be replaced, and the hydrocarbon group is W １ It bonds with the carbon atoms contained in the bridge to form a bridge, and the -CH contained in the bridge 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １１ The carbon atoms in the bridge may be replaced by - or -CO-, and the carbon atoms in the bridge may form a double bond with two adjacent carbon atoms, and the bridge may have substituents. m11 represents an integer between 0 and 3. m4 represents an integer between 0 and 10, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another.

3. R １ This refers to a C3-C16 alicyclic hydrocarbon group having a halogen atom or a C1-C3 haloalkyl group (the alicyclic hydrocarbon group contains -CH ２ The resist composition according to claim 1 or 2, wherein - may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group may have substituents other than halogen atoms and haloalkyl groups.

4. X １ However, *-CO-O- or *-O-CO- (* is W １ The resist composition according to claim 1 or 2, which represents the bonding site with ().

5. R ４ This includes a halogen atom or an alkyl group having 1 to 12 carbon atoms that may have a halogen atom (the alkyl group contains -CH 2 - is -O-, -NR １１ The resist composition according to claim 2, wherein it may be replaced by - or -CO-.

6. R １ However, a cycloaliphatic hydrocarbon group having 3 to 24 carbon atoms and containing a fluorine atom or an iodine atom (the cycloaliphatic hydrocarbon group contains -CH ２ The - may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group may have a hydroxyl group. R ４ However, hydroxyl group, amino group, -X ２１ -R ２１ (X ２１ R represents a group consisting of -O-, -NH-, -CO-, or a combination thereof. ２１ The resist composition according to claim 2, wherein (a) represents an alkyl group having 1 to 8 carbon atoms, and (b) is a halogen atom or a haloalkyl group having 1 to 8 carbon atoms.

7. X ０ The resist composition according to claim 1 or 2, wherein the resist is *-CO-O-, *-O-CO-, *-O-CO-O-, or *-O- (where * represents a bonding site with a benzene ring).

8. A resist composition according to claim 1 or 2, comprising a resin containing 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.

9. The resin contains structural units having acid-unstable groups. The resist composition according to claim 8, 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 - 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 any integer from 1 to 4, and * represents the binding 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.

10. The resist composition according to claim 1 or 2, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

11. (1) A step of applying the resist composition according to claim 1 or 2 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].

12. A salt represented by formula (I). [In formula (I), X ０ and X １ These are, independently, -O-, -CO-, -S-, -SO-, and -SO ２ -, -NR １１ - Or represents a base that combines these elements. R １１ This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. W １ This represents a hydrocarbon group containing a cyclic hydrocarbon group having 3 to 36 carbon atoms, and the hydrogen atoms contained in the hydrocarbon group may be replaced by substituents, and the hydrocarbon group contains -CH ２ - is -O-, -S-, -CO-, -SO-, -NR １１ - or - SO ２ It may be replaced with -. L ２ This 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 １ This represents a cyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents, and the cyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -CO-, -SO-, -NR １１ - or - SO ２ It may be replaced with -. R ３ represents a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １１ It may be replaced with - or -CO-. m3 represents an integer from 0 to 4, and when m3 is 2 or greater, multiple R ３ They may be identical or different from one another. mn1 represents an integer between 1 and 5, and when mn1 is 2 or greater, the bases within the parentheses may be the same or different. Z ＋ This represents an organic cation.

13. The salt according to claim 12, wherein the salt represented by formula (I) is the salt represented by formula (IA). [In formula (IA), X ０ , R １１ , W １ , X １ , L ２ , R １ , R ３ , m3, mn1 and Z ＋ This has the same meaning as equation (I). W1 represents a cyclic hydrocarbon group with (5 + m11) carbon atoms, and the carbon atoms in the cyclic hydrocarbon group may form a double bond between two adjacent carbon atoms, and the cyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -SO ２ -, -SO-, -NR １１ It may be replaced by - or -CO-, and the hydrogen atoms contained in the cyclic hydrocarbon group may be substituted with substituents. R ４ represents a halogen atom, a nitro group, a cyano group, or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １１ - or -CO- may be replaced, and the hydrocarbon group is W １ It bonds with the carbon atoms contained in the bridge to form a bridge, and the -CH contained in the bridge 2 - is -O-, -S-, -SO ２ -, -SO-, -NR １１ The carbon atoms in the bridge may be replaced by - or -CO-, and the carbon atoms in the bridge may form a double bond with two adjacent carbon atoms, and the bridge may have substituents. m11 represents an integer between 0 and 3. m4 represents an integer between 0 and 10, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another.

14. R １ This refers to a C3-C16 alicyclic hydrocarbon group having a halogen atom or a C1-C3 haloalkyl group (the alicyclic hydrocarbon group contains -CH ２ The salt according to claim 12 or 13, wherein - may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group may have substituents other than halogen atoms and haloalkyl groups.

15. X １ However, *-CO-O- or *-O-CO- (* is W １ The salt according to claim 12 or 13, which represents the bonding site with ().

16. R ４ This includes a halogen atom or an alkyl group having 1 to 12 carbon atoms that may have a halogen atom (the alkyl group contains -CH 2 - is -O-, -NR １１ The salt according to claim 13, wherein it may be replaced by - or -CO-.

17. R １ However, a cycloaliphatic hydrocarbon group having 3 to 24 carbon atoms and containing a fluorine atom or an iodine atom (the cycloaliphatic hydrocarbon group contains -CH ２ The - may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group may have a hydroxyl group. R ４ However, hydroxyl group, amino group, -X ２１ -R ２１ (X ２１ R represents a group consisting of -O-, -NH-, -CO-, or a combination thereof. ２１ The salt according to claim 13, wherein (c) represents an alkyl group having 1 to 8 carbon atoms, and (d) is a halogen atom or a haloalkyl group having 1 to 8 carbon atoms.

18. X ０ The salt according to claim 12 or 13, wherein the compound is *-CO-O-, *-O-CO-, *-O-CO-O-, or *-O- (where * represents a bonding site with a benzene ring).

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