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JP-7856477-B2 - Salt, acid generator, resist composition, and method for producing resist patterns

JP7856477B2JP 7856477 B2JP7856477 B2JP 7856477B2JP-7856477-B2

Inventors

  • 小室 勝洋
  • 市川 幸司

Assignees

  • 住友化学株式会社

Dates

Publication Date
20260511
Application Date
20220428
Priority Date
20210506

Claims (20)

  1. An acid generator containing a salt represented by formula (I). [In formula (I), R1 , R2 , and R3 each independently represent * -O-R 10 , *-O-CO-O-R 10 , or *-O-L 10 -CO-O-R 10 , where * represents the bonding site with the benzene ring. L10 represents an alkanediyl group with 1 to 6 carbon atoms. R 10 represents an acid-unstable group. R4 , R5 , R6 , R7 , R8 , and R9 each independently represent a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, the hydrocarbon group may have substituents, and the -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . A1 , A2 , and A3 each independently represent a hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S-, or -SO2- . 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 4, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 4, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer between 0 and 4, and when m4 is 2 or greater, multiple R4s may be the same or different from each other. m5 represents an integer between 0 and 4, and when m5 is 2 or greater, multiple R5s may be the same or different from each other. m6 represents an integer between 0 and 4, and when m6 is 2 or greater, multiple R6s may be the same or different from each other. m7 represents an integer between 0 and 4, and when m7 is 2 or greater, multiple R7s may be the same or different from each other. m8 represents an integer between 0 and 4, and when m8 is 2 or greater, multiple R8s may be the same or different from each other. m9 represents an integer from 0 to 4, and when m9 is 2 or greater, multiple R9s may be the same or different from each other. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 4, and 0 ≤ m3 + m9 ≤ 4. X4 represents a single bond, -CH2- , -O-, -S-, -CO-, -SO-, or -SO2- . AI- represents organic anions other than carboxylate anions.
  2. An acid generator containing a salt represented by formula (I). [In formula (I), R1 , R2 , and R3 each independently represent * -O-R 10 , *-O-CO-O-R 10 , or *-O-L 10 -CO-O-R 10 , where * represents the bonding site with the benzene ring. L10 represents an alkanediyl group with 1 to 6 carbon atoms. R 10 represents an acid-unstable group. R4 , R5 , R6 , R7 , R8 , and R9 each independently represent a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, the hydrocarbon group may have substituents, and the -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . A1 represents *-L 011 -X 01 -L 012- , A2 represents *-L 021 -X 02 -L 022- , and A3 represents *-L 031 - X 03 -L 032- . X01 , X02 , and X03 each independently represent -O-, -CO-, -S-, or -SO2- . L011 , L012 , L021 , L022 , L031 , and L032 each independently represent a single bond or a hydrocarbon group having 1 to 19 carbon atoms, and the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S-, or -SO2- . However, the total number of carbon atoms in L011 and L012 is 1 to 19, the total number of carbon atoms in L021 and L022 is 1 to 19, and the total number of carbon atoms in L031 and L032 is 1 to 19. * indicates the bonding site with the benzene ring to which R1 , R2 , or R3 is bonded. m1 represents an integer between 0 and 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 4, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 4, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer between 0 and 4, and when m4 is 2 or greater, multiple R4s may be the same or different from each other. m5 represents an integer between 0 and 4, and when m5 is 2 or greater, multiple R5s may be the same or different from each other. m6 represents an integer between 0 and 4, and when m6 is 2 or greater, multiple R6s may be the same or different from each other. m7 represents an integer between 0 and 5, and when m7 is 2 or greater, multiple R7s may be the same or different from each other. m8 represents an integer between 0 and 4, and when m8 is 2 or greater, multiple R8s may be the same or different from each other. m9 represents an integer from 0 to 4, and when m9 is 2 or greater, multiple R9s may be the same or different from each other. However, 0 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 4, and 0 ≤ m3 + m9 ≤ 4, and at least one of m1, m2, and m3 represents an integer greater than or equal to 1. X4 represents a single bond, -CH2- , -O-, -S-, -CO-, -SO-, or -SO2- . AI- represents organic anions other than carboxylate anions.
  3. A1 is *-X01- L01- or *-L01- X01- , A2 is * -X02-L02- or *-L02- X02- , and A3 is * -X03 - L03- or * -L03 - X03- ( X01 , X02 and X03 each independently represent -O-, -CO-, -S- or -SO2- . L01 , L02 and L03 each independently represent a hydrocarbon group having 1 to 19 carbon atoms, the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2- . * is R1 , R2 or R 3 represents the bonding site with the benzene ring to which it is bonded.) The acid generator according to claim 1 or 2.
  4. The acid generator according to claim 3, wherein X01 , X02 , and X03 are each independently -O- or -S-.
  5. The acid generator according to claim 3, wherein L01 , L02 , and L03 are each independently an alkanediyl group having 1 to 6 carbon atoms (the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-).
  6. The acid generator according to claim 1 or 2, wherein R1 , R2 , and R3 are each independently * -O- R10 or *-O- L10 -CO-O- R10 (where * represents a bonding site with a benzene ring).
  7. The acid generator according to claim 1 or 2, wherein the acid-unstable group of R 10 is a group represented by formula (1a) or a group represented by formula (2a). [In formula (1a), R aa1 , R aa2 , and R aa3 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, or R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. * indicates a connection site. [In formula (2a), R aa1' and R aa2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2' and R aa3' are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X a- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced with -O- or -S-. Xa represents an oxygen atom or a sulfur atom. * indicates a connection site.
  8. The acid generator according to claim 1 or 2, wherein when m4, m5 or m6 is an integer of 1 or more, R4 , R5 and R6 are each independently 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 -CH2- contained in the alkyl group may be replaced with -O- or -CO-).
  9. The acid generator according to claim 1 or 2, wherein when m7, m8 or m9 is an integer of 1 or more, R7 , R8 and R9 are each independently 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 -CH2- contained in the alkyl group may be replaced with -O- or -CO-).
  10. The acid generator according to claim 1 or 2, wherein AI- is a sulfonate anion, a sulfonylimide anion, or a sulfonylmethide anion.
  11. The acid generator according to claim 1 or 2, wherein AI- is a sulfonate anion, and the sulfonate anion is an anion represented by the formula (I-A). [In formula (IA), Q1 and Q2 each independently represent a hydrogen atom, a fluorine atom, a C1-C6 alkyl group, or a C1-C6 perfluoroalkyl group. L1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. Y1 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 -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO2- , or -CO-.
  12. A resist composition containing the acid generator described in claim 1 or 2 and a resin having an acid-unstable group.
  13. The resist composition according to claim 12, 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 each independently represent -O- or *-O-(CH 2 ) k1 -CO-O-, where k1 is an integer from 1 to 7, and * represents the bond site with -CO-. Ra01 , Ra4 , and Ra5 each independently represent a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may contain a halogen atom. R a02 , R a03 , and R a04 each independently represent 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 combination thereof. Ra6 and Ra7 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 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.
  14. The resist composition according to claim 12, wherein the resin having an acid-unstable group comprises a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 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 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 represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 independently represent -O-, -CO-O-, or -O-CO-, respectively. 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, multiple R a51s may be identical or different from each other.
  15. The resist composition according to claim 12, further comprising a salt that generates an acid with a lower acidity than the acid generated by the acid generator.
  16. (1) A step of applying the resist composition according to claim 12 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, and (5) A step of developing the composition layer after heating. A method for manufacturing a resist pattern that includes a resist pattern.
  17. A salt represented by formula (I). [In formula (I), R1 , R2 , and R3 each independently represent * -O-R 10 , *-O-CO-O-R 10 , or *-O-L 10 -CO-O-R 10 , where * represents the bonding site with the benzene ring. L10 represents an alkanediyl group with 1 to 6 carbon atoms. R 10 represents an acid-unstable group. R4 , R5 , R6 , R7 , R8 , and R9 each independently represent a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, the hydrocarbon group may have substituents, and the -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . A1 , A2 , and A3 each independently represent a hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S-, or -SO2- . 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 4, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 4, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer between 0 and 4, and when m4 is 2 or greater, multiple R4s may be the same or different from each other. m5 represents an integer between 0 and 4, and when m5 is 2 or greater, multiple R5s may be the same or different from each other. m6 represents an integer between 0 and 4, and when m6 is 2 or greater, multiple R6s may be the same or different from each other. m7 represents an integer between 0 and 4, and when m7 is 2 or greater, multiple R7s may be the same or different from each other. m8 represents an integer between 0 and 4, and when m8 is 2 or greater, multiple R8s may be the same or different from each other. m9 represents an integer between 0 and 4, and when m9 is 2 or greater, multiple R9s may be the same or different from each other. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 4, and 0 ≤ m3 + m9 ≤ 4. X4 represents a single bond, -CH2- , -O-, -S-, -CO-, -SO-, or -SO2- . AI- represents organic anions other than carboxylate anions.
  18. A salt represented by formula (I). [In formula (I), R1 , R2 , and R3 each independently represent * -O-R 10 , *-O-CO-O-R 10 , or *-O-L 10 -CO-O-R 10 , where * represents the bonding site with the benzene ring. L10 represents an alkanediyl group with 1 to 6 carbon atoms. R 10 represents an acid-unstable group. R4 , R5 , R6 , R7 , R8 , and R9 each independently represent a halogen atom, a C1-C12 haloalkyl group, or a C1-C18 hydrocarbon group, the hydrocarbon group may have substituents, and the -CH2- contained in the haloalkyl group and the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . A1 represents *-L 011 -X 01 -L 012- , A2 represents *-L 021 -X 02 -L 022- , and A3 represents *-L 031 - X 03 -L 032- . X01 , X02 , and X03 each independently represent -O-, -CO-, -S-, or -SO2- . L011 , L012 , L021 , L022 , L031 , and L032 each independently represent a single bond or a hydrocarbon group having 1 to 19 carbon atoms, and the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S-, or -SO2- . However, the total number of carbon atoms in L011 and L012 is 1 to 19, the total number of carbon atoms in L021 and L022 is 1 to 19, and the total number of carbon atoms in L031 and L032 is 1 to 19. * indicates the bonding site with the benzene ring to which R1 , R2 , or R3 is bonded. m1 represents an integer between 0 and 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 4, and when m² is 2 or greater, the bases within the parentheses may be the same or different. m3 represents an integer between 0 and 4, and when m3 is 2 or greater, the bases within the parentheses may be the same or different. m4 represents an integer between 0 and 4, and when m4 is 2 or greater, multiple R4s may be the same or different from each other. m5 represents an integer between 0 and 4, and when m5 is 2 or greater, multiple R5s may be the same or different from each other. m6 represents an integer between 0 and 4, and when m6 is 2 or greater, multiple R6s may be the same or different from each other. m7 represents an integer between 0 and 5, and when m7 is 2 or greater, multiple R7s may be the same or different from each other. m8 represents an integer between 0 and 4, and when m8 is 2 or greater, multiple R8s may be the same or different from each other. m9 represents an integer from 0 to 4, and when m9 is 2 or greater, multiple R9s may be the same or different from each other. However, 0 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 4, and 0 ≤ m3 + m9 ≤ 4, and at least one of m1, m2, and m3 represents an integer greater than or equal to 1. X4 represents a single bond, -CH2- , -O-, -S-, -CO-, -SO-, or -SO2- . AI- represents organic anions other than carboxylate anions.
  19. A1 is *-X01- L01- or *-L01- X01- , A2 is * -X02-L02- or *-L02- X02- , and A3 is * -X03 - L03- or * -L03 - X03- ( X01 , X02 and X03 each independently represent -O-, -CO-, -S- or -SO2- . L01 , L02 and L03 each independently represent a hydrocarbon group having 1 to 19 carbon atoms, the hydrocarbon group may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO2- . * is R1 , R2 or R 3 represents the bonding site with the benzene ring to which it is bonded.) The salt according to claim 17 or 18.
  20. The salt according to claim 19, wherein X01 , X02 , and X03 are each independently -O- or -S-.

Description

This invention relates to salts, acid generators, resist compositions, and methods for producing resist patterns. Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Patent Document 2 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Patent Document 3 describes a salt represented by the following formula. Japanese Patent Publication No. 2011-186248Japanese Patent Publication No. 2020-015713Japanese Patent Publication No. 2011-038091 In this specification, "(meth)acrylic monomer" means "at least one of acrylic monomers and methacrylic monomers." The notations "(meth)acrylate" and "(meth)acrylic acid" also have the same meaning. For groups described herein that can take both linear and branched structures, either is acceptable. When the -CH2- contained in hydrocarbon groups, etc., is replaced by -O-, -S-, -CO- or -SO2- , the same example shall apply to each group. "Combined group" means a group formed by bonding two or more of the exemplified groups, and the valencies of these groups may be appropriately changed depending on the bonding configuration. "Derived from" or "induced" means that the polymerizable C=C bond contained in the molecule becomes a -C-C- group (single bond) through polymerization. If stereoisomers exist, all stereoisomers are included. In this specification, "solid content of the resist composition" means the total amount of the resist composition excluding the solvent (E) described later. [Salt represented by formula (I)] This invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salts (I), the side with a positive charge is sometimes called a "cation (I)" and the side with a negative charge is sometimes called an "anion (I)". [In the formula, all signs have the same meaning as described above.] [Cation (I)] The cation (I) of the salt represented by formula (I) is the cation represented by formula (I-C). [In equation (I-C), all signs have the same meaning as in equation (I).] In formula (I), examples of alkanediyl groups in L10 contained in R1 , R2 , and R3 include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. L10 is preferably an alkanediyl group having 1 to 3 carbon atoms, and more preferably a methylene group. The acid-unstable group R10 in R1 , R2 , and R3 refers to a group that, upon contact with an acid (e.g., trifluoromethanesulfonic acid), undergoes the removal of a leaving group containing the group represented by R10 , thereby forming a carboxyl group or a hydroxyl group. Preferred acid-unstable groups are those represented by formula (1a) (hereinafter sometimes referred to as "acid-unstable group (1a)") and those represented by formula (2a) (hereinafter sometimes referred to as "acid-unstable group (2a)"). [In formula (1a), R aa1 , R aa2 , and R aa3 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, or R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. * indicates a connection site. [In formula (2a), R aa1' and R aa2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2' and R aa3' are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X a- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced with -O- or -S-. Xa represents an oxygen atom or a sulfur atom. * indicates a connection site. Examples of alkyl groups for R aa1 , R aa2 , and R aa3 include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. The number of carbon atoms in the alkyl groups for R aa1 , R aa2 , and R aa3 is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkenyl groups in R aa1 , R aa2 , and R aa3 include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. The alicyclic hydrocarbon groups of R aa1 , R aa2 , and R aa3 may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon g