Method for manufacturing resist compositions and resist patterns, and compounds

Abstract

To provide a compound which allows a resist pattern having good CD uniformity to be produced, and a resist composition containing the same.SOLUTION: The resist composition contains a compound represented by formula (I), a resin having an acid-labile group, and an acid generator. [In the formula, R1 represents an optionally substituted cyclic hydrocarbon group, provided that -CH2- contained in the group may be substituted with -O-, -S-, -SO2- or -CO-; L1 represents a single bond or an optionally substituted alkanediyl group; R2 and R3 each represent a hydrogen atom or a hydrocarbon group; Rf1 and Rf2 each represent a fluorine atom or a perfluoroalkyl group; R4 represents a halogen atom, a haloalkyl group or the like; and m1 represents an integer of 1-6 and m4 represents an integer of 0-5, provided that 1≤m1+m4≤6.]SELECTED DRAWING: None

Claims

[Claim 1] The compound represented by formula (I), A resin having an acid-unstable group represented by formula (1) or formula (2), It contains an acid generator, A resist composition in which the acid generator comprises an onium cation and an anion selected from a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion. [In formula (I), 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-, -SO ２ It may be replaced with - or -CO-. L 1 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or substituents. R ２ and R ３ Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Rf １ and Rf ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. m1 represents an integer from 1 to 6, and when m1 is 2 or greater, the bases within the parentheses may be the same or different from each other. R ４ represents a halogen atom, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH 2 - in the haloalkyl group and the alkyl group may be replaced by -O- or -CO-. m4 represents an integer from 0 to 5, and when m4 is 2 or greater, multiple R ４ They may be identical or different from each other, provided that 1 ≤ m1 + m4 ≤ 6. [In formula (1), Ra1, Ra2, and Ra3 each independently represent 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 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group having a combination thereof. Alternatively, Ra1 and Ra2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. ma and na each independently represent either 0 or 1, and at least one of ma and na represents 1. * indicates a connection site. [In formula (2), Ra1' and Ra2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Ra3' represents a hydrocarbon group having 1 to 20 carbon atoms, or Ra2' and Ra3' are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded and X, and the -CH2- contained in the hydrocarbon group and the heterocycle may be replaced with -O- or -S-. X represents either an oxygen atom or a sulfur atom. 'na' represents 0 or 1. * indicates a connection site. [Claim 2] R １ The resist composition according to claim 1, wherein the resist group is an alicyclic hydrocarbon group having 3 to 16 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. [Claim 3] Rf １ and Rf ２ The resist composition according to claim 1 or 2, wherein the resist is a fluorine atom or a trifluoromethyl group. [Claim 4] The resist composition according to claim 1 or 2, wherein m1 is an integer of any one of 1 to 3. [Claim 5] The resist composition according to claim 1 or 2, wherein the resin having the 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. [Claim 6] The resist composition according to claim 1 or 2, wherein the resin having the 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. [Claim 7] The resist composition according to claim 1 or 2, wherein the acid generator comprises a salt represented by formula (B1). [In formula (B1), Q ｂ１ and Q ｂ２ Each of these independently represents a hydrogen atom, a fluorine atom, a C1-C6 alkyl group, or a C1-C6 perfluoroalkyl group. L ｂ１ This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH contained in this divalent saturated hydrocarbon group is ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y represents a methyl group which may have substituents or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the alicyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. Z1 ＋ This represents an organic cation. [Claim 8] 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. [Claim 9] (1) A step of applying the resist composition according to claim 1 or 2 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]. [Claim 10] A compound represented by formula (I). [In formula (I), 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-, -SO ２ It may be replaced with - or -CO-. L 1 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or substituents. R ２ and R ３ Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Rf １ and Rf ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. m1 represents an integer from 1 to 6, and when m1 is 2 or greater, the bases within the parentheses may be the same or different from each other. R ４ -CH represents a halogen atom, 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-. m4 represents an integer from 0 to 5, and when m4 is 2 or greater, multiple R ４ They may be identical or different from each other, provided that 1 ≤ m1 + m4 ≤ 6. [Claim 11] R １ The compound according to claim 10, wherein the compound is an alicyclic hydrocarbon group having 3 to 16 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. [Claim 12] Rf １ and Rf ２ The compound according to claim 10 or 11, wherein the compound is a fluorine atom or a trifluoromethyl group. [Claim 13] The compound according to claim 10 or 11, wherein m1 is an integer of any one of 1 to 3.

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