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JP-7855447-B2 - Carboxylate salt, carboxylic acid generator, resist composition, and method for producing resist patterns

JP7855447B2JP 7855447 B2JP7855447 B2JP 7855447B2JP-7855447-B2

Inventors

  • 嶋田 雅彦
  • 市川 幸司

Assignees

  • 住友化学株式会社

Dates

Publication Date
20260508
Application Date
20220720
Priority Date
20210720

Claims (16)

  1. A carboxylic acid generator containing a carboxylic acid salt represented by formula (I). [In formula (I), R1 , R2 , and R3 each independently represent *-O-R 10 , *-O-CO-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 a group having a cyclic carbonate ester structure represented by formula (Ix) . (In formula (Ix), Ring Wx represents a ring in a cyclic carbonate ester structure, which may have substituents. L 12 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-, -CO-, or -SO2- . * indicates a connection site. 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 5, 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 5, 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 5, 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 5, 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 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. X0 represents a hydrocarbon group having 1 to 72 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- .
  2. 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 carboxylic acid generator according to claim 1.
  3. The carboxylic acid generator according to claim 2, wherein X01 , X02 , and X03 are each independently -O- or -S-.
  4. The carboxylic acid generator according to claim 2, 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-).
  5. The carboxylic acid generator according to claim 1 , wherein X0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have substituents (the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2- ), 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 each independently represent -O- or -S-. X1a represents a hydrocarbon group having 1 to 24 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . X2a represents a hydrocarbon group having 1 to 48 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . * indicates the bond site with the carbon atom in -COO- . [In formula (bb), L A 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 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the -CH2- contained in the alkanediyl group may be replaced with -O-, -S-, -CO-, or -SO2- . R A represents a hydrocarbon group having 1 to 36 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . * indicates the bond site with the carbon atom in -COO- .
  6. X0 may have a fluorine atom, a C1-C4 perfluoroalkyl group, or a C3-C36 alicyclic hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- ), or a group combining a C3-C36 alicyclic hydrocarbon group and a C1-C18 chain hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- , and the -CH2- contained in the chain hydrocarbon group 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 5, which is a C6-C36 aromatic hydrocarbon group that 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).
  7. A resist composition containing a carboxylic acid generator according to any one of claims 1 to 6 , an acid generator other than the carboxylic acid generator , and a resin having an acid-unstable group represented by formula (1) or formula (2) . [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 an alicyclic hydrocarbon group 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), R a1' and R a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2' and R a3' are bonded to each other to form a heterocyclic group 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 heterocyclic group 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.
  8. The resist composition according to claim 7, 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 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. Ra02 , Ra03 , and Ra04 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.
  9. The resist composition according to claim 7 , wherein the resin having the 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.
  10. (1) A step of applying the resist composition according to claim 7 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 [the specified element].
  11. A carboxylate salt represented by formula (I). [In formula (I), R1 , R2 , and R3 each independently represent *-O-R 10 , *-O-CO-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 a group having a cyclic carbonate ester structure represented by formula (Ix) . (In formula (Ix), Ring Wx represents a ring in a cyclic carbonate ester structure, which may have substituents. L 12 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-, -CO-, or -SO2- . * indicates a connection site. 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 5, 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 5, 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 5, 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 5, 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 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. X0 represents a hydrocarbon group having 1 to 72 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- .
  12. 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 carboxylate salt according to claim 11 .
  13. The carboxylate salt according to claim 12 , wherein X01 , X02 , and X03 are each independently -O- or -S-.
  14. The carboxylate salt according to claim 12 or 13 , 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-).
  15. The carboxylate salt according to claim 11 or 12, wherein X0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have substituents (the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2- ), 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 each independently represent -O- or -S-. X1a represents a hydrocarbon group having 1 to 24 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . X2a represents a hydrocarbon group having 1 to 48 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . * indicates the bond site with the carbon atom in -COO- . [In formula (bb), L A 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 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the -CH2- contained in the alkanediyl group may be replaced with -O-, -S-, -CO-, or -SO2- . R A represents a hydrocarbon group having 1 to 36 carbon atoms, which may have substituents, and the -CH2- contained in the hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- . * indicates the bond site with the carbon atom in -COO- .
  16. X0 may have a fluorine atom, a C1-C4 perfluoroalkyl group, or a C3-C36 alicyclic hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- ), or a group combining a C3-C36 alicyclic hydrocarbon group and a C1-C18 chain hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2- , and the -CH2- contained in the chain hydrocarbon group 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 15, 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 ) .

Description

This invention relates to carboxylate salts, carboxylic acid generators, resist compositions, and methods for producing resist patterns. Patent Document 1 describes a carboxylate salt represented by the following formula and a resist composition containing the carboxylate salt as a carboxylic 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 and a resist composition containing the salt as an acid generator. Patent Document 4 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Patent Document 5 describes a carboxylate salt represented by the following formula and a resist composition containing the carboxylate salt as a carboxylic acid generator. Japanese Patent Publication No. 2011-039502Japanese Patent Publication No. 2012-236816Japanese Patent Publication No. 2011-085878Japanese Patent Publication No. 2020-015713Japanese Patent Publication No. 2020-046662 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 from" 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. [Carboxylate salt represented by formula (I)] The present invention relates to a carboxylate salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)" or "carboxylate salt (I)"). In carboxylate salts (I), the negatively charged side is sometimes called the "anion (I)," and the positively charged side is sometimes called the "cation (I)." [In the formula, all signs have the same meaning as described above.] [Cation (I)] The cation (I) of the carboxylate 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 cyclic carbonate ester structure of R10 contained in R1 , R2 , and R3 refers to a structure having -O-CO-O- as the atoms constituting the ring. The cyclic carbonate ester structure may be monocyclic or polycyclic, and may have heteroatoms such as oxygen atoms, sulfur atoms, or nitrogen atoms in addition to the oxygen atoms that form the carbonate ester structure. The number of carbon atoms in the cyclic carbonate ester structure is 2 to 30, preferably 2 to 24, more preferably 2 to 18, even more preferably 2 to 16, and even more preferably 3 to 12. The ring in the cyclic carbonate ester structure is preferably a 3-membered to 18-membered ring, more preferably a 3-membered to 16-membered ring, even more preferably a 4-membered to 12-membered ring, even more preferably a 4-membered to 10-membered ring, even more preferably a 5-membered to 8-membered ring, and even more preferably a 5-membered ring. Examples of cyclic carbonate ester structures include those represented by formulas (x1) to (x16), with any of formulas (x1) to (x3), (x9), and (x16) being preferred, any of formulas (x1) to (x3) being more preferred, and the structure represented by formula (x1) being even more preferred. The bonding site can be at any position. The cyclic carbonate ester structure may have substituents, and examples of substituents include alkyl groups having 1 to 12 carbon atoms, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, hydroxyl groups, alkoxy groups having 1 to 6 carbon atoms, and groups that combine two or more of these. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, b