Method for manufacturing resist compositions and resist patterns

Abstract

To provide a resist composition from which a resist pattern having good CDU can be produced.SOLUTION: The resist composition contains: an acid generator containing a salt represented by a specific structure; and a resin containing a structural unit having an acid-labile group and a structural unit having a specific structure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist composition used for fine processing of semiconductors and a method for manufacturing a resist pattern.

Background Art

[0002] Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Composition is described. TIFF0007842065000001.tif2874

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a salt that forms a resist pattern with better CD uniformity (CDU) than the resist pattern formed by the above resist composition.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF0007842065000002.tif9491 [In formula (I), R 1 、R 2 and R 3 each independently represents an iodine atom or a fluorine atom. R 4 、R 5 、R 6 、R 7 、R 8 and R 9These are, independently, a halogen atom and a hydroxyl atom. The C1 group represents a C1-C12 haloalkyl group or a C1-C12 alkyl group, and the halo The alkyl group and the -CH2- contained in the alkyl group are replaced with -O- or -CO-. It's fine if you do that. X 1 , X 2 and X 3 Each of these independently represents either an oxygen atom or a sulfur atom. m1 represents an integer from 1 to 5, and when m1 is 2 or greater, the bases in multiple parentheses are mutual They may be the same or different. m2 represents an integer between 0 and 5, and when m2 is 2 or greater, the bases within multiple parentheses are mutually exclusive. They may be the same or different. m3 represents an integer between 0 and 5, and when m3 is 2 or greater, the bases within multiple parentheses are mutually exclusive. They may be the same or different. m4 represents an integer between 0 and 4, and when m4 is 2 or greater, multiple R 4 They are the same It can be one or different. m5 represents an integer between 0 and 4, and when m5 is 2 or greater, multiple R 5 They are the same It can be one or different. m6 represents an integer between 0 and 4, and when m6 is 2 or greater, multiple R 6 They are the same It can be one or different. m7 represents an integer between 0 and 4, and when m7 is 2 or greater, multiple R 7 They are the same It can be one or different. m8 represents an integer between 0 and 5, and when m8 is 2 or greater, multiple R 8 They are the same It can be one or different. m9 represents an integer between 0 and 5, and when m9 is 2 or greater, multiple R 9 They are the same It can be one or different. However, 1 ≤ m1 + m7 ≤ 5, 0 ≤ m2 + m8 ≤ 5, and 0 ≤ m3 + m9 ≤ 5. AI - This represents an organic anion. [2]X 1 , X 2 and X 3 The salt described in [1] is an oxygen atom. [3] AI - However, sulfonate anions, sulfonylimide anions, sulfonylmethides The salt described in [1] or [2] is an anion or a carboxylic acid anion. [4] AI - This is a sulfonate anion, and the sulfonate anion is represented by formula (IA). The salts listed in any of the following [1]-[3] are anions that are subjected to the treatment. TIFF0007842065000003.tif2352[In formula (IA), Q 1 and Q 2 Each of these independently contains a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. It represents the 'L' group. L 1 This represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the saturated hydrocarbon group contains -CH 2- may be replaced by -O- or -CO-, and the water contained in the saturated hydrocarbon group The elementary atoms may be substituted with fluorine atoms or hydroxyl groups. Y 1 This is a methyl group which may have substituents or a carbon 3- which may have substituents It represents 18 alicyclic hydrocarbon groups, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, It may be replaced with -SO2- or -CO-. An acid generator containing a salt described in any of [5][1] to [4]. A resist composition containing the acid generator described in [6][5] and a resin having an acid-unstable group. [7] Structural units having an acid-unstable group are structural units represented by formula (a1-1) and formula (a The resist composition according to [6], comprising at least two of the structural units represented by 1-2). TIFF0007842065000004.tif3985[In formulas (a1-1) and (a1-2), L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents k1 represents an integer from 1 to 7, and * represents the association with -CO-. R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a6 and R a7 These are, independently, an alkyl group with 1 to 8 carbon atoms and an alicyclic group with 3 to 18 carbon atoms. This represents a hydrocarbon group or a group formed by combining 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. [8] Further contains a salt that generates an acid that is less acidic than the acid generated by the acid generator. The resist composition according to [6] or [7]. [9](1)[6]~[8] is applied to a substrate. To the extent, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) A method for manufacturing a resist pattern, comprising the step of developing the composition layer after heating. [Effects of the Invention]

[0006] By using a resist composition containing the salt of the present invention, good CD uniformity (CDU) can be achieved. ) can be used to manufacture resist patterns. [Modes for carrying out the invention]

[0007] In this specification, "(meth)acrylic monomer" means "CH2=CH-CO-" monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" It means at least one selected from the group. Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to the group consisting of "acrylates and methacrylates." "At least one selected from" and "selected from the group consisting of acrylic acid and methacrylic acid" This means "at least one type". "CH2=C(CH3)-CO-" or "CH2=CH-C" When structural units having "O-" are given as examples, structural units having both groups are similar As illustrated in the example, the groups described herein include linear and branched structures. For things that can take both forms, either form is acceptable. "Combined base" means, for example... This refers to a group formed by combining two or more of the indicated groups, with their valencies appropriately changed. (Stereoisomer) If present, it includes all stereoisomers. In this specification, "solid content of the resist composition" means the amount of solids of the resist composition that is added to the total amount of solids of the resist composition. This refers to the sum of the components excluding the solvent (E) described above.

[0008] <Salt represented by formula (I)> This invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salt (I), the side with a negative charge is called "anion (I)," and the side with a positive charge is called "antion (I)." It is sometimes referred to as "On (I)". R 4 , R 5 , R 6 , R 7 , R8 and R 9 Examples of halogen atoms include fluorine atoms and chlorine atoms. Examples include ions, bromine atoms, and iodine atoms. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 What are haloalkyl groups with 1 to 12 carbon atoms in this context? , represents an alkyl group having 1 to 12 carbon atoms and containing a halogen atom, such as a chloromethyl group or bromomethyl group. Tyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoro Examples include butyl. The number of carbon atoms in the haloalkyl group is preferably 1 to 9, and more preferably Or, it is 1 to 4. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of alkyl groups with 1 to 12 carbon atoms include methyl propyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-propyl group Examples of alkyl groups include tyl, pentyl, hexyl, octyl, and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, and more preferably 1 to 4. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 The haloalkyl group or alkyl group represented by If the -CH2- group is replaced by -O- or -CO-, the original carbon atom is considered to be the same as the original carbon atom. The number is the total number of carbon atoms in the haloalkyl group or the alkyl group. Also, R 4 , R 5 , R 6 , R 7 , R 8 and R 9This is where the hydroxyl group (the -CH2- contained in the methyl group) is placed at -O- (The replaced group), carboxyl group (the -CH2-CH2- contained in the ethyl group is -O-CO - (a group replaced by), alkoxy groups with 1 to 11 carbon atoms (in alkyl groups with 2 to 12 carbon atoms) (A group in which the -CH2- contained in is replaced by -O-), an alkoxycal with 2 to 11 carbon atoms. Bonyl group (the -CH2-CH2- contained in alkyl groups with 3 to 12 carbon atoms) (a group that has been replaced by) an alkylcarbonyl group with 2 to 12 carbon atoms (an alkylcarbonyl group with 2 to 12 carbon atoms) Alkyl groups (groups in which the -CH2- contained in the group is replaced by -CO-), and alkyl groups with 2 to 11 carbon atoms. The carbonyloxy group (the -CH2-CH2- contained in an alkyl group with 3 to 12 carbon atoms) It may have a group that is replaced by -CO-O-. Examples of alkoxy groups having 1 to 11 carbon atoms include methoxy, ethoxy, propoxy, and b Toxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl Examples include the ruoxy group, nonyloxy group, decyloxy group, and undecyloxy group. Alkoxycarbonyl groups having 2 to 11 carbon atoms, alkylcarbonyl groups having 2 to 12 carbon atoms, and The alkylcarbonyloxy group having 2 to 11 carbon atoms is the alkyl or alkoxy group described above. This represents a group to which a carbonyl group or a carbonyloxy group is bonded. Examples of alkoxycarbonyl groups having 2 to 11 carbon atoms include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include carbonyl groups and butoxycarbonyl groups, which are alkylcarbonyl groups with 2 to 12 carbon atoms. Examples of acetyl groups include acetyl groups, propionyl groups, and butyryl groups, with 2 to 1 carbon atoms. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, Examples include butyryloxy groups. X 1 It is preferable that it is an oxygen atom. X 2 It is preferable that it is an oxygen atom. X 3 It is preferable that it is an oxygen atom. m1 is preferably 1 or 2. m2 is preferably 0 or 1. m3 is preferably 0 or 1. m4 is preferably 0, 1, 2, or 4. m5 is preferably 0 or 1. m6 is preferably 0 or 1. m7 is preferably 0, 1, or 2, and more preferably 0 or 1. m8 is preferably 0 or 1. m9 is preferably 0 or 1. 4 , R 5 and R 6 Each of them operates independently. Iodine atom, fluorine atom, hydroxyl group, C1-C4 alkyl group, C1-C4 hydroxyl group A rhalkyl group, preferably an alkoxy group having 1 to 3 carbon atoms, and containing an iodine atom, a fluorine atom, and a hydride. A oxy group, a carbon-1 to carbon-3 alkoxy group is more preferred, along with an iodine atom, a fluorine atom, and a hydride. A roxy group is even more preferred. 7 , R 8 and R 9 These are, independently, iodine atoms and f Electrolyte atom, hydroxyl group, alkyl group with 1 to 4 carbon atoms, haloalkyl group with 1 to 4 carbon atoms, A carbon-1 to carbon-3 alkoxy group is preferred, along with an iodine atom, a fluorine atom, and a carbon-1 to carbon-3 alkoxy group. A coxy group is more preferable.

[0009] Examples of cation (I) include the following cations: TIFF0007842065000005.tif188140

[0010] TIFF0007842065000006.tif185157

[0011] AI - Examples of the organic anion represented by AI include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, and the like. AI Examples of the organic anion represented by AI include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, and the like. AI - represented The organic anion represented by AI is preferably, independently of each other, a sulfonate anion, and more preferably, independently of each other, an anion represented by formula (I-A). 、式(I-A)で表されるアニオンであることがより好ましい。 TIFF0007842065000007.tif2965[In formula (I-A), Q 1 and Q 2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. ル基を表す。 L 1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. 2-は、-O-又は-CO-に置き換わっていてもよく、該飽和炭化水素基に含まれる水 素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。 Y 1 represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-.] 18の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる-CH2-は、-O-、 -SO2-又は-CO-に置き換わっていてもよい。]

[0012] In the anion represented by formula (I-A), when -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. Also, when -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the alicyclic hydrocarbon group. O-又は-CO-に置き換わっている場合、置き換わる前の炭素数を該飽和炭化水素基の 炭素数とする。また、脂環式炭化水素基に含まれる-CH2-が-O-、-SO2-又は -CO-に置き換わっている場合、置き換わる前の炭素数を該脂環式炭化水素基の炭素数 It should be noted that there are some parts in the original text that seem a bit unclear or might have some formatting issues. The translation is done as accurately as possible based on the provided text.Let's assume that.

[0013] Q 1 and Q 2 Examples of perfluoroalkyl groups with 1 to 6 carbon atoms include trifluoromethyl Group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, pe Perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples include perfluoropentyl groups and perfluorohexyl groups. Q 1 and Q 2 Each of these independently consists of a fluorine atom or a trifluoromethyl group. Preferably, both are fluorine atoms, and more preferably, both are fluorine atoms.

[0014] L 1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups and branched alkanediyl groups. Examples include dipropyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of these types. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; 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 Branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as n-1,4-diyl group and cyclooctane-1,5-diyl group A monocyclic, divalent, alicyclic saturated hydrocarbon group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbon such as 1,5-diyl group and adamantane-2,6-diyl group Examples include hydrogen groups.

[0015] L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The substituted base can be represented, for example, by any of the following equations: (b1-1) to (b1-3). The bases are listed. Furthermore, the bases represented by formulas (b1-1) to (b1-3) and their specific examples are In the example groups represented by formulas (b1-4) to (b1-11), * and ** are bond positions. This represents -Y 1 This represents the bonding position with [the specified element].

[0016] TIFF0007842065000008.tif26117[In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- contained in the hydrocarbon group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms of and is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms of and is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms of and is 23 or less.

[0017] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. ru. L b2 The bond is preferably a single bond. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, the divalent saturated hydrocarbon group has 1 to 8 carbon atoms, and the divalent saturated hydrocarbon water The hydrogen atoms in the elementary group may be substituted with fluorine atoms. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The saturated hydrocarbon group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms. L b7 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. The -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. That's good too. L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The replaced group is preferably the group represented by formula (b1-1) or formula (b1-3).

[0018] As for equation (b1-1), the bases expressed by equations (b1-4) to (b1-8) are listed. It can be done. TIFF0007842065000009.tif48120[In formula (b1-4), L b8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and contains The -CH2- group may be replaced by -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), Lb16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- group may be replaced by -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0019] L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0020] The base represented by equation (b1-3) is given by equations (b1-9) to (b1-11), respectively. The bases that can be represented are listed below. TIFF0007842065000010.tif23139 formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b20 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b22 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b25 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b26 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0021] Note that the groups represented by formulas (b1-9) to (b1-11) are saturated hydrocarbon groups. If the hydrogen atom contained in is substituted with an alkylcarbonyloxy group, before replacement The number of carbon atoms in the saturated hydrocarbon group is defined as the number of carbon atoms in the saturated hydrocarbon group.

[0022] Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group These are some examples.

[0023] The following are examples of bases represented by formula (b1-4): TIFF0007842065000011.tif16154

[0024] The following are examples of bases represented by formula (b1-5): TIFF0007842065000012.tif69148

[0025] The following are examples of bases represented by formula (b1-6): TIFF0007842065000013.tif44148

[0026] The following are examples of bases represented by formula (b1-7): TIFF0007842065000014.tif63153

[0027] The following are examples of bases represented by formula (b1-8): TIFF0007842065000015.tif23150

[0028] The following are examples of bases represented by formula (b1-2): TIFF0007842065000016.tif31161

[0029] The following are examples of bases represented by formula (b1-9): TIFF0007842065000017.tif44137

[0030] The following are examples of bases represented by formula (b1-10): TIFF0007842065000018.tif92165

[0031] The following are examples of bases represented by formula (b1-11): TIFF0007842065000019.tif85164

[0032] Y 1 Examples of alicyclic hydrocarbon groups represented by formulas (Y1) to (Y11), and (Y36) are: The base represented by formula (Y38) is an example. Y 1 The -CH2- contained in the alicyclic hydrocarbon group represented by -O-, -S(O)2- or When replaced by -CO-, the number of replacements may be one or two or more. For example, the bases represented by equations (Y12) to (Y35) and (Y39) to (Y41) can be listed. * is L 1 This represents the bonding position with [the specified element].

[0033] TIFF0007842065000020.tif75146Y 1 The alicyclic hydrocarbon group represented by formula (Y1) to formula (Y20) is preferably formula (Y1) to formula (Y20), formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), Formula (Y39) ~ Formula (Y41) A group represented by any of the following, more preferably formula (Y11), formula (Y15), or formula (Y1 6), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula ( A group represented by formula (Y39) or formula (Y40), more preferably formula (Y11), formula (Y 15), Formula (Y20), Formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), Formula It is a group represented by formula (Y39) or formula (Y40). Y 1 The alicyclic hydrocarbon group represented by formulas (Y28) to (Y35), (Y39) to ( In the case of a spiro ring containing oxygen atoms, such as Y40, the alkanes between the two oxygen atoms The fluorine group preferably has one or more fluorine atoms. Also, the ketal structure contains In the lucandiyl group, the methylene group adjacent to the oxygen atom has a fluorine atom substituted on it. It is preferable not to have it.

[0034] Y 1 The substituents of the methyl group represented by this symbol include halogen atoms, hydroxyl groups, and carbon 3- 16 alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, glycidyloxy groups, - (CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth , alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, or groups having 6 to 18 carbon atoms This represents an aromatic hydrocarbon group or a group formed by combining these groups. ja is one of the integers from 0 to 4. Represents a number. Included in alkyl groups with 1 to 16 carbon atoms and alicyclic hydrocarbon groups with 3 to 16 carbon atoms. The -CH2- group may be replaced by -O-, -S(O)2-, or -CO-. These are some examples. Y 1 The substituents of the alicyclic hydrocarbon group represented by this formula include halogen atoms, hydroxyl groups, and hydroxyl groups. C1-C12 alkyl groups and C3-C16 alicyclic groups, which may be substituted with a droxy group. Formula hydrocarbon groups, alkoxy groups with 1 to 12 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, carbon Aralkyl groups with prime numbers 7-21, alkylcarbonyl groups with 2-4 carbon atoms, glycidyl oxy Group, -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, Rb1 This refers to an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a group having 6 carbon atoms. Represents up to 18 aromatic hydrocarbon groups or combinations thereof. ja is any of 0 to 4. Represents an integer. Alkyl groups with 1 to 16 carbon atoms, and alicyclic hydrocarbon groups with 3 to 16 carbon atoms. The -CH2- contained in may be replaced by -O-, -S(O)2-, or -CO-. Examples include: (i) and others.

[0035] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and methyl cyclohexyl groups. Chlohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, no Examples include rubornyl groups and adamantyl groups. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, and biphenyl groups. Examples include aryl groups such as nyl groups and phenanthryl groups. Aromatic hydrocarbon groups are chain carbon It may have a hydrogenated group or an alicyclic hydrocarbon group, and may have an aromatic carbon having a chain hydrocarbon group Examples of hydrogen groups include tolyl group, xylyl group, coumenyl group, mesityl group, and p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6- Examples include ethylphenyl groups, and aromatic hydrocarbon groups having alicyclic hydrocarbon groups include: Examples include p-cyclohexylphenyl groups and p-adamantylphenyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, and b Tyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group These are some examples. Alkyl groups substituted with hydroxyl groups include hydroxymethyl groups and hydroxy Examples include hydroxyalkyl groups such as ethyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups, etc. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, and naphthyl group. Examples include tyl groups and naphthylethyl groups. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. These are some examples.

[0036] Y 1 The following are some examples: TIFF0007842065000021.tif140163

[0037] Y 1 This is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. More preferably, an alicyclic hydrocarbon group substituted with a hydroxyl group, even more preferably, a hydroxyl group. an adamantyl group which may have a conversion group, and said alicyclic hydrocarbon group or adamantyl group The -CH2- groups that make up the compound may be replaced with -CO-, -S(O)2-, or -CO-. Y. 1 More preferably, an adamantyl group, a hydroxyadamantyl group, or an oxoada A mantyl group or a group represented below, particularly preferably a hydroxyadamantyl group or These are oxoadamantyl groups, and groups that contain them. TIFF0007842065000022.tif89156

[0038] The anions represented by formula (IA) are given by formulas (IA-1) to (IA-55). The anion represented [Hereafter, depending on the formula number, it may be referred to as "anion (IA-1)," etc.] The following is preferred: formulas (IA-1) to (IA-4), formula (IA-9), formula (I- A-10), Equations (IA-24) to (IA-33), Equations (IA-36) to (I- A-40), an anion represented by any of the formulas (IA-47) to (IA-55) More preferable.

[0039] TIFF0007842065000023.tif100142

[0040] TIFF0007842065000024.tif95156

[0041] TIFF0007842065000025.tif142151

[0042] TIFF0007842065000026.tif106141

[0043] TIFF0007842065000027.tif113161

[0044] Here R i2 ~R i7 Each of these is independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 For example, a chain-like hydrocarbon group having 1 to 12 carbon atoms. These include alkyl groups having 1 to 4 carbon atoms, alicyclic hydrocarbon groups having 5 to 12 carbon atoms, or combinations thereof. Groups formed by combining, more preferably methyl groups, ethyl groups, and cyclohexyl groups. Or it is an adamantyl group. L A41 These are single bonds or alkanediyl groups having 1 to 4 carbon atoms. Q 1 and Q 2This expresses the same meaning as above. Specifically, the anion represented by formula (IA) is as described in Japanese Patent Publication No. 2010-204646. Anions listed in the official gazette are among those mentioned.

[0045] Preferably, the anion represented by formula (IA) is formula (Ia-1)~(Ia- The anions represented in 34) are listed below. TIFF0007842065000028.tif189154

[0046] TIFF0007842065000029.tif34138

[0047] TIFF0007842065000030.tif159166

[0048] In particular, equations (Ia-1) to (Ia-3) and equations (Ia-7) to (Ia- 19) An anion represented by any of the formulas (Ia-22) to (Ia-34) is preferred. It's nice.

[0049] AI - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007842065000031.tif40135

[0050] AI - Examples of sulfonylmethide anions represented by the formula include the following: TIFF0007842065000032.tif31128

[0051] AI - Examples of carboxylic acid anions represented by the formula include the following: TIFF0007842065000033.tif44154

[0052] Specific examples of salt (I) include salts formed by arbitrarily combining the cations and anions mentioned above. It can be produced. Specific examples of salt (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the anion or cation described above. For example, salt (I-1) is formed from the anion shown in formula (Ia-1) and formula (Ic-1) It is a salt consisting of the cation shown by and the following salt. TIFF0007842065000034.tif31117 [Table 1] TIFF0007842065000036.tif223154 TIFF0007842065000037.tif223154 TIFF0007842065000038.tif223154 TIFF0007842065000039.tif223154 TIFF0007842065000040.tif223154 TIFF0007842065000041.tif223154 TIFF0007842065000042.tif223154 TIFF0007842065000043.tif223154 TIFF0007842065000044.tif223154 TIFF0007842065000045.tif223154 TIFF0007842065000046.tif223154 TIFF0007842065000047.tif234157

[0053] In particular, salt (I) is divided into salt (I-1) to salt (I-5), and salt (I-13) to salt (I-25). Salt (I-30) to Salt (I-34), Salt (I-42) to Salt (I-54), Salt (I-59) ~Salt (I-63), Salt (I-71)~Salt (I-83), Salt (I-88)~Salt (I-92) , salt (I-100) ~ salt (I-112), salt (I-117) ~ salt (I-121), salt (I -129)~Salt (I-141), Salt (I-146)~Salt (I-150), Salt (I-158 )~Salt (I-170), Salt (I-175)~Salt (I-179), Salt (I-187)~Salt ( I-199), Salt (I-204) ~ Salt (I-208), Salt (I-216) ~ Salt (I-22 8) Salt (I-233) ~ Salt (I-237), Salt (I-245) ~ Salt (I-257), Salt (I-262)~Salt (I-266), Salt (I-274)~Salt (I-286), Salt (I-2 91) Salt (I-295), Salt (I-303), Salt (I-315), Salt (I-320) Salt (I-324), Salt (I-332) ~ Salt (I-344), Salt (I-349) ~ Salt (I- 353), Salt (I-361) ~ Salt (I-373), Salt (I-378) ~ Salt (I-382) , salt (I-390) ~ salt (I-402), salt (I-407) ~ salt (I-411), salt (I -419)~Salt (I-431), Salt (I-436)~Salt (I-440), Salt (I-448 )~Salt (I-460), Salt (I-465)~Salt (I-469), Salt (I-477)~Salt ( I-489), Salt (I-494) ~ Salt (I-498), Salt (I-506) ~ Salt (I-51 8) is preferable.

[0054] <Method for producing salt (I)> Salt (I) is a mixture of the salt represented by formula (Ia) and the salt represented by formula (Ib) in a solvent. It can be manufactured by reaction. TIFF0007842065000048.tif99162[In the formula, all signs have the same meaning as above. R A , R B and R C Each These independently represent hydrocarbon groups with 1 to 12 carbon atoms, or R A , R B and R C together They may form an aromatic ring. D This represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ] Examples of solvents include chloroform, monochlorobenzene, acetonitrile, and water. It can be done. The reaction temperature is typically between 15°C and 80°C, and the reaction time is typically between 0.5 and 24 hours.

[0055] Examples of salts represented by formula (Ib) include the salts represented by the following formulas. This is done by a method similar to the method described in Japanese Patent Publication No. 2011-116747, or by a known manufacturing method. It can be manufactured more easily. TIFF0007842065000049.tif92125

[0056] The salt represented by formula (Ia) is the same as the salt represented by formula (Ic) and the salt represented by formula (I-d1). The compound represented by formula (I-d2) and the compound represented by formula (I-d3) It can be produced by reacting potassium carbonate in a solvent. TIFF0007842065000050.tif85148[In this formula, all symbols have the same meaning as described above.] Examples of solvents include chloroform, monochlorobenzene, acetonitrile, and water. It can be done. The reaction temperature is typically between 15°C and 100°C, and the reaction time is typically between 0.5 and 24 hours. .

[0057] Examples of salts represented by formula (Ic) include those represented by the following formula, which are readily available on the market. It can be obtained. TIFF0007842065000051.tif36105

[0058] Compound represented by formula (I-d1), compound represented by formula (I-d2), and compound represented by formula (I-d3 Examples of compounds represented by ) include the following compounds, which are readily available from the market. It is possible. TIFF0007842065000052.tif19146

[0059] The salt represented by formula (Ia) is the same as the salt represented by formula (Ie) and the salt represented by formula (I-f1). The compound represented by formula (I-f2) and the compound represented by formula (I-f3) It can be produced by reacting it in a solvent in the presence of a base. TIFF0007842065000053.tif86151[In this formula, all symbols have the same meaning as described above.] Examples of bases include potassium hydroxide and sodium hydride. Examples of solvents include chloroform, monochlorobenzene, acetonitrile, and water. It can be done. The reaction temperature is typically between 15°C and 100°C, and the reaction time is typically between 0.5 and 24 hours. .

[0060] Examples of salts represented by formula (Ie) include those represented by the following formula, which are readily available on the market. It can be obtained. JPEG0007842065000054.jpg35105

[0061] Compound represented by formula (I-f1), compound represented by formula (I-f2), and compound represented by formula (I-f3 Examples of compounds represented by ) include the following compounds, which are readily available from the market. It is possible. TIFF0007842065000055.tif2196

[0062] <Acid Generator> The acid generator of the present invention contains salt(I). It may contain one type of salt(I), or salt( I) may contain two or more types. The acid generator of the present invention, in addition to salt (I), contains an acid generator known in the resist field (hereinafter referred to as "acid generator"). It may contain a herbal agent (B), which may be used alone. You may use one type, or you may use two or more types in combination.

[0063] The acid generator (B) may be either nonionic or ionic. As herbal preparations, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate ester) are used. Sulfonate, oximesulfonate, N-sulfonyloxiimide, sulfonyloxyke Ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, keto Examples include sulfones, sulfonyl diazomethanes, etc. Ionic acid generators include onions. Onium salts containing um cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples include salts (iodonium salts). An anion of anium salts is aniodonium sulfonate. Examples include sulfonylimide anions, sulfonylmethide anions, and others.

[0064] As for the acid generating agent (B), see Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. 55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 Japanese Patent Publication No. 62-153853, Japanese Patent Publication No. 63-146029, U.S. Patent No. 3,779, Patent No. 778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acid when exposed to radiation, as described in publications No. 126, 712, etc., can be used. Compounds manufactured by known methods may also be used. The acid generator (B) may consist of two or more types. They may be used in combination.

[0065] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a fluorine-containing acid generator of formula (B1). This is a salt represented by (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007842065000056.tif2862[In formula (B1), Q b1 and Q b2 Each of these independently contains a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. It represents the 'L' group. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the saturated hydrocarbon group contains -CH2- may be replaced by -O- or -CO-, and the saturated hydrocarbon group is contained The hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups. Y is a methyl group which may have substituents or a C3-C1 group which may have substituents 8 represents an alicyclic hydrocarbon group, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + This represents an organic cation.

[0066] Q in equation (B1) b1 Q b2 , L b1 And Y are, respectively, in the above-mentioned equation (IA). ruQ 1 Q 2 , L 1 and Y 1 Similar examples can be given. The sulfonic acid anion in formula (B1) is the anion represented by formula (IA) and Similar examples can be given.

[0067] Z1 + Examples of organic cations include organic onium cations and organic sulfonium cations. Organic iodium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cationic cations are particularly noteworthy. N and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) ( Examples include the following, which may be referred to as "cation(b2-1)" depending on the formula number.

[0068] In formulas (b2-1) to (b2-4) of TIFF0007842065000057.tif77115, R b4 ~R b6 These are, independently, chain hydrocarbon groups with 1 to 30 carbon atoms and groups with 3 to 36 carbon atoms. This term represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and is contained in the chain-like hydrocarbon group. The hydrogen atoms present are found in hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and lipid groups with 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms and aliphatic hydrocarbon groups with 1 to 18 carbon atoms. They may also be substituted with an alkylcarbonyl group or glycidyloxy group having 2 to 4 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, hydroxyl groups, or C1 groups. It may be substituted with ~12 alkoxy groups. R b4 and R b5 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. Even if the -CH2- contained in the ring is replaced by -O-, -S-, or -CO- good. R b7 and R b8 These are, independently, a hydroxyl group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or more, multiple Number R b8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. It may be done, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. That's good too. R b11 This consists of a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, and an alicyclic carbon group with 3 to 36 carbon atoms. This represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This refers to a chain-type hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or This represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in this chain hydrocarbon are carbon atoms. It may be substituted with 6 to 18 aromatic hydrocarbon groups, and the aromatic hydrocarbon groups contained The hydrogen atom is part of an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with a xy group. R b11 and R b12 These molecules bond to each other, forming a ring including the -CH-CO- groups to which they are joined. It is also possible that the -CH2- contained in the ring is replaced by -O-, -S-, or -CO-. That's fine. R b13 ~R b18 These are, independently, a hydroxyl group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 12 carbon atoms. L b31 This represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5. q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, r2 When there are 2 or more R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 teeth If the same or different, and t2 is 2 or more, multiple R b18 They are either the same or different.

[0069] Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples include alkyl groups with a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and monocyclic alicyclic carbon Examples of hydrogen groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Cycloalkyl groups such as cycloheptyl, cyclooctyl, and cyclodecyl groups Examples include the decahydronaphthyl group and adamantyl group, which are polycyclic alicyclic hydrocarbon groups. Examples include the norbornyl group and the following groups. TIFF0007842065000058.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably These have 4 to 12 carbon atoms.

[0070] As an example of an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, methylcyclohex xyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl Ruadamantan-2-yl group, 2-isopropyladamantan-2-yl group, methyl nor Examples include bornyl groups and isobornyl groups. Hydrogen atoms are substituted with aliphatic hydrocarbon groups. In alicyclic hydrocarbon groups, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferable. The number is 20 or less.

[0071] Aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthryl groups. Examples include aryl groups and the like. Aromatic hydrocarbon groups are chain hydrocarbon groups or alicyclic hydrocarbon groups. Aromatic hydrocarbon groups that may have hydrogen groups, including tolyl groups, xyl groups, and chain-type hydrocarbon groups. Lyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group) and alicyclic groups Aromatic hydrocarbon groups having hydrocarbon groups (p-cyclohexylphenyl group, p-adamantine group) Examples include phenyl groups, etc. Furthermore, if the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, Chain-type hydrocarbon groups with 1 to 18 prime numbers and alicyclic hydrocarbon groups with 3 to 18 carbon atoms are preferred. As an aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group, p-methoxyphenyl Examples include the 'L' group. Examples of chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include the benzyl group and the ferrous hydrocarbon group. Netyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples include aralkyl groups.

[0072] Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups, etc. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It is possible. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group and ethylcarbonyl Oxy group, propyl carbonyloxy group, isopropyl carbonyloxy group, butylcarbon Bonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy C group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include oxy groups and 2-ethylhexylcarbonyloxy groups.

[0073] R b4 and R b5 The ring formed when these atoms bond to each other and together with the sulfur atom they bond to is The rings may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may have 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Furthermore, the ring containing the sulfur atom can be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. For example, the following rings can be cited. * indicates a bonding position. TIFF0007842065000059.tif23144

[0074] R b9 and R b10 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothi Examples include the ophenium ring, thian-1-ium ring, and 1,4-oxatian-4-ium ring. It can be done. R b11 and R b12 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring Examples include oxonorbornane rings and oxoadamantane rings.

[0075] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) Examples of cations (b2-1) include the following: TIFF0007842065000060.tif73149

[0076] TIFF0007842065000061.tif69136

[0077] Examples of cations (b2-2) include the following: TIFF0007842065000062.tif16131

[0078] Examples of cations (b2-3) include the following: TIFF0007842065000063.tif25122

[0079] Examples of cations (b2-4) include the following: TIFF0007842065000064.tif108153

[0080] The acid generator (B) is a combination of the anion and the organic cation described above, and these are They can be combined in any way. Preferably, the acid generator (B) is formula (Ia-1)~ Equations (Ia-3) and (Ia-7) to (Ia-16), (Ia-18), An Ani represented by (Ia-19), or any of equations (Ia-22) to (Ia-34) Examples include combinations of ON and cation (b2-1) or cation (b2-3).

[0081] The acid generator (B) is preferably represented by formulas (B1-1) to (B1-48), respectively. Examples include those that are used. Among them, those containing arylsulfonium cations are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B 1-31) The one represented by formula (B1-48) is particularly preferred. TIFF0007842065000065.tif119149

[0082] JPEG0007842065000066.jpg77147

[0083] JPEG0007842065000067.jpg147147

[0084] JPEG0007842065000068.jpg60154

[0085] TIFF0007842065000069.tif60166

[0086] When the acid generator contains salt (I) and acid generator (B), salt (I) and acid generator (B) The ratio of the content of each (mass ratio; salt (I): acid generator (B)) is usually 1:99 to 99:1. Yes, preferably 2:98 to 98:2, and more preferably 5:95 to 95:5. More preferably 10:90~90:10, and especially preferably 15:85~85: It is 15. In the resist composition of the present invention, the total content of the acid generator is as follows: resin (A)1 Preferably 1 to 40 parts by mass, more preferably 3 parts by mass, per 00 parts by mass The amount is 35 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less.

[0087] <Resist Composition> The resist composition of the present invention comprises an acid generator containing salt (I) and a resin having an acid-unstable group ( It contains the following (sometimes referred to as "resin (A)"). Here, "acid-unstable group" refers to the elimination group. It has a group, and upon contact with an acid, the leaving group is removed, and the constituent unit becomes a hydrophilic group (for example, hydroxy This refers to a group that converts into a constituent unit having a carboxyl group or a carboxyl group. The resist composition of the present invention generates an acid that is less acidic than the acid generated by the acid generator. It may contain a quencher such as salt (hereinafter sometimes referred to as "quencher (C)"). Preferably, it contains a solvent (which may be referred to as "solvent (E)" below).

[0088] <Resin (A)> Resin (A) is a structural unit having an acid-unstable group (hereinafter referred to as "structural unit (a1)"). The resin (A) may further contain structural units other than structural unit (a1). Preferred. Structural units other than structural unit (a1) include structural units that do not have acid-unstable groups ( (Hereinafter referred to as "structural unit (s)"), structural unit (a1), and other structural units (s) Structural units (for example, structural units having halogen atoms as described later (hereinafter referred to as "structural unit (a4)") In some cases, this may be referred to as "structural unit ( a5) In some cases) and other structural units derived from monomers known in the field. These are some examples.

[0089] <Structural unit (a1)> Structural unit (a1) is a monomer having an acid-unstable group (hereinafter referred to as "monomer (a1)"). It is derived from (in some cases). The acid-unstable group contained in resin (A) is the group represented by formula (1) (hereinafter also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007842065000070.tif1988[In formula (1), R a1 , R a2 and R a3 These are, independently, alkyl groups with 1 to 8 carbon atoms. R represents a group consisting of a cyclic hydrocarbon group with 3 to 20 carbon atoms, or a group consisting of a combination thereof. a1 Reach biR a2 These are non-aromatic carbon atoms with 3 to 20 carbon atoms that bond to each other and together with the carbon atoms they bond to. It forms a hydrogenated ring. ma and na each independently represent 0 or 1, and at least one of ma and na This represents 1. * indicates a bond position. TIFF0007842065000071.tif2171[In formula (2), R a1’ and R a2’ Each of these is independently a hydrogen atom or a carbon atom with 1 to 1 carbon atoms. Represents two hydrocarbon groups, R a3’ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2’ Reach biR a3’ They bond with each other, and together with the carbon atoms and X they bond to, they have 3 to 20 carbon atoms. A heterocycle is formed, and the hydrocarbon group and the -CH2- contained in the heterocycle are -O- or -S- It can be replaced with this. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a bond position.

[0090] R a1 , R a2 and R a3 Examples of alkyl groups in this context include methyl group, ethyl group, and propyl group. Examples include the hydroxyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. R a1 , R a2and R a3 In this context, the alicyclic hydrocarbon group is either monocyclic or polycyclic. This is also acceptable. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, and cyclopentyl group. Examples include cycloalkyl groups such as chloroheptyl and cyclooctyl groups. Polycyclic and alicyclic groups. The hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following: Examples include the group (* indicates a bonding position). a1 , R a2 and R a3 Alicyclic carbonized water The number of carbon atoms in the elemental group is preferably 3 to 16. TIFF0007842065000072.tif10150 Examples of groups combining alkyl groups and alicyclic hydrocarbon groups include methylcyclohexyl Xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group Examples include adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. ru. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 Examples of such rings include the following: The non-aromatic hydrocarbon ring is preferably carbon The numbers range from 3 to 12. * represents the bonding position with -O-. TIFF0007842065000073.tif30139

[0091] R a1’ , R a2’ and R a3’ Examples of hydrocarbon groups in this context include alkyl groups and alicyclic carbon groups. Examples include hydrogenated groups, aromatic hydrocarbon groups, and groups formed by combining these. It is possible. Alkyl and alicyclic hydrocarbon groups are R a1 , R a2 and R a3 Similar to the base mentioned above This is one example. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclophenyl group) Xylphenyl group, p-adamantylphenyl group, etc., phenylcyclohexyl group, etc. Examples include reel-cycloalkyl groups. R a2’ and R a3’ They bond with each other and together with the carbon atoms and X they bond to, complex When forming a ring, -C(R a1’ )(R a3’ )-XR a2’ The following rings are examples: * indicates a bonding position. TIFF0007842065000074.tif19130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0092] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. A tert-butoxycarbonyl group is preferred as this group. In equation (1), R a1 , R a2 However, together with the carbon atoms to which these bond, adamant Forms a chill group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2 Each of them is an alkyl group independently, and R a3 Adama A methyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates the bonding position. TIFF0007842065000075.tif73158

[0093] The following are specific examples of group (2). * indicates the bonding position. TIFF0007842065000076.tif66153

[0094] The monomer (a1) preferably has an acid-unstable group and an ethylenically unsaturated bond. Mer, more preferably a (meth)acrylic monomer having an acid-unstable group.

[0095] Among (meth)acrylic monomers having an acid-unstable group, preferably those having 5 to 20 carbon atoms. Examples include those having alicyclic hydrocarbon groups. A resin (A) having structural units derived from monomer (a1) is used in the resist composition. This allows for an improvement in the resolution of the resist pattern.

[0096] As a structural unit derived from a (meth)acrylic monomer having group (1), formula (a1- A structural unit represented by (0) (hereinafter sometimes referred to as structural unit (a1-0)), formula (a1 A structural unit represented by -1) (hereinafter sometimes referred to as structural unit (a1-1)) or formula ( The structural units represented by a1-2) (hereinafter sometimes referred to as structural units (a1-2)) are listed below. Preferably, from the group consisting of structural unit (a1-1) and structural unit (a1-2) These are at least one selected structural unit. These may be used individually or in combination of two or more. They can be used together. TIFF0007842065000077.tif39127[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or * -O-(CH2) k1 -CO -O- represents -O-, k1 represents an integer from 1 to 7, and * represents the association with -CO-. R a01 , R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a02 , R a03 and R a04 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkyl groups with 3 to 8 carbon atoms. This represents 18 alicyclic hydrocarbon groups or groups formed by combining these groups. R a6 and R a7 These are, independently, an alkyl group with 1 to 8 carbon atoms and an alicyclic group with 3 to 18 carbon atoms. This represents a hydrocarbon group or a group formed by combining these groups. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[0097] R a01 , R a4 and R a5 The group is preferably a methyl group. La01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 -CO- It is O- (where k01 is preferably an integer from 1 to 4, more preferably 1) It exists. ), more preferably it is an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Alkyl groups, alicyclic hydrocarbon groups and so As a base formed by combining these, R in equation (1) a1 ~R a3 The same groups as those listed above can be cited. R a02 , R a03 , and R a04 The alkyl group in the alkyl group preferably has 1 to 6 carbon atoms. More preferably, it is a methyl group or an ethyl group, and even more preferably a methyl group. R a6 and R a7 The alkyl group in is preferably having 1 to 6 carbon atoms, more The group is a methyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. It is a pill group. R a02 , R a03 and R a04 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12. More preferably, it is 5 to 10. Groups that combine alkyl groups and alicyclic hydrocarbon groups are formed by combining these alkyl groups and alicyclic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. R a02 and R a03 The alkyl group is preferably a C1-C6 alkyl group, and more preferably a methyl group. It is either an ethyl group or an ethyl group. R a04Preferably, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. The group is a methyl group, more preferably an ethyl group, a cyclohexyl group, or an adamantyl group. be. R a6 and R a7 The alkyl group is preferably a C1-C6 alkyl group, and more preferably a methyl group. The group is an ethyl group or an isopropyl group, and more preferably an ethyl group or an isopropyl group. That is the case. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0098] Examples of structural units (a1-0) are given by equations (a1-0-1) to (a1-0-12). A structural unit represented by one of the following and R in the structural unit (a1-0) a01 Methi equivalent to Examples of structural units in which the ∫ group is replaced by a hydrogen atom include equations (a1-0-1) to (a1-0 A structural unit represented by any of the following (-10) is preferred. TIFF0007842065000078.tif65159

[0099] As for the structural unit (a1-1), for example, as described in Japanese Patent Publication No. 2010-204646 Examples of structural units derived from monomers include those from formula (a1-1-1) to formula (a1 -1-4) A structural unit represented by any of the above and R in the structural unit (a1-1) a4 Equivalent to A structural unit in which the methyl group is replaced by a hydrogen atom is preferred, and formulas (a1-1-1) to ( A structural unit represented by any of a1-1-4) is more preferable. TIFF0007842065000079.tif43119

[0100] The structural unit (a1-2) is one of the following equations: (a1-2-1) to (a1-2-6). Structural units represented by and R in structural units (a1-2) a5 The methyl group corresponding to the hydrogen source Examples of structural units that have been replaced by children are given by equations (a1-2-2), (a1-2-5), and equation A structural unit represented by (a1-2-6) is preferred. TIFF0007842065000080.tif33156

[0101] If resin (A) contains structural unit (a1-0), its content is the total structural unit of resin (A). For each position, it is usually 5-60 mol%, preferably 5-50 mol%, and more preferably The percentage is between 10 and 40 mol%. If resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), The total content of these is typically 10 to 95 mol% relative to the total structural units of resin (A), and is preferable. More preferably 15-90 mol%, more preferably 20-85 mol%, and even more preferably More preferably, it is 25-80 mol%, and even more preferably 30-75 mol%.

[0102] A structural unit having a base (2) in structural unit (a1) is represented by formula (a1-4). Examples of structural units (hereinafter sometimes referred to as "structural units (a1-4)") include the following. TIFF0007842065000081.tif4071[In formula (a1-4), R a32 This is a hydrogen atom, a halogen atom, or a carbon-1 atom which may have a halogen atom. Represents alkyl groups up to 6. R a33 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer between 0 and 4. If la is 2 or greater, multiple R a33 They are intertwined They may be the same or different. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 they combine with each other and Together with the -CO- to which they bond, they form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the carbonized water The -CH2- contained in the elementary group and the divalent hydrocarbon group is replaced by -O- or -S- That's good too.

[0103] R a32 and R a33 The alkyl groups in this context are methyl, ethyl, propyl, and iso. Examples include propyl groups, butyl groups, pentyl groups, and hexyl groups. The alkyl group is carbon A alkyl group with prime numbers 1 to 4 is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even better. R a32 and R a33 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. Examples of C1-C6 alkyl groups that may have halogen atoms include trifluoromethyl Tyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-triflu Oroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group Pyr group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoro Chil group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, Perf Luolopentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pe Examples include ethyl groups, hexyl groups, and perfluorohexyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Examples include oxy groups and hexyloxy groups. In particular, alkoxy groups having 1 to 4 carbon atoms. A group is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred. . Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It can be done. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b Examples include thyryloxy groups. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining these. Alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples include syl groups, heptyl groups, and octyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Monocyclic alicyclic hydrocarbon group Examples include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Examples of cycloalkyl groups include decahydrona. Examples include the phthyl group, adamantyl group, norbornyl group, and the following groups (* indicates the bond position). It can be done. TIFF0007842065000082.tif10152 Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclophenyl group) Xylphenyl group, p-adamantylphenyl group, etc., phenylcyclohexyl group, etc. Examples include the reel-cyclohexyl group. In particular, R a36 As for, A Lukyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or Examples of groups formed by combining these include

[0104] In equation (a1-4), R a32 A hydrogen atom is preferred as the element. R a33 Preferably, the group is an alkoxy group having 1 to 4 carbon atoms, and also includes methoxy and ethoxy groups. A methoxy group is more preferable, and a methoxy group is even more preferable. For la, 0 or 1 is preferred, and 0 is more preferred. R a34 Preferably, it is a hydrogen atom. R a35 Preferably, it is an alkyl group or alicyclic hydrocarbon group having 1 to 12 carbon atoms. Preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, or a C3 to 18 carbon atom Alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof The group formed is more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms. It is an 8-cell alicyclic aliphatic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. a36 in The alkyl group and alicyclic hydrocarbon group are preferably unsubstituted. a36 Aroma in The hydrocarbon group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0105] -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 is an acid (for example) It is eliminated upon contact with p-toluenesulfonic acid, forming a hydroxyl group.

[0106] As for structural units (a1-4), for example, see Japanese Patent Publication No. 2010-204646. Examples include monomer-derived structural units. Preferably, formulas (a1-4-1) to (a1 -4-12) The structural units and R in the structural unit (a1-4) a32 in relation to Examples include structural units in which the corresponding hydrogen atom is replaced by a methyl group, and more preferably, formula (a 1-4-1) Structural units represented by equations (a1-4-5) and (a1-4-10), respectively. These are some examples. TIFF0007842065000083.tif68157

[0107] If resin (A) contains structural units (a1-4), the content of these units is the total structural content of resin (A). Preferably, the percentage of the total units is 10 to 95 mol%, and more preferably 15 to 90 mol%. It is more preferable that it be 20-85 mol%, and even more preferably 20-70 mol% It is even more preferable that it be 20 to 60 mol%, and particularly preferable that it be 20 to 60 mol%.

[0108] As structural units derived from (meth)acrylic monomers having group (2), formula (a1 Structural units represented by -5) (hereinafter sometimes referred to as "structural units (a1-5)") are also mentioned. It can be done. TIFF0007842065000084.tif4558 formula (a1-5), R a8 This may have a halogen atom, or it may have a C1-C6 alkyl group, a hydrogen atom, or a halogen atom. This represents a chlorogenic atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents a value, and h3 is one of 1 to 4. Represents an integer of L, where * is L 51 This represents the bonding position with [the specified element]. 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.

[0109] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may have a halogen atom include methyl and ethyl groups. Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluorine Examples include methyl and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0110] Examples of structural units (a1-5) are described in Japanese Patent Publication No. 2010-61117. Examples of monomer-derived structural units include those from formula (a1-5-1) to formula (a1-5- 4) The structural units represented by formula (a1-5-1) or formula (a1-5-2 A structural unit represented by ) is more preferable. TIFF0007842065000085.tif33133

[0111] If resin (A) contains structural units (a1-5), the percentage of these units is the total structural content of resin (A). The amount is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and 5 to 40 mol% relative to the unit. A % of 10% is more preferable, and 5 to 30 mol% is even more preferable.

[0112] In addition, the following structural units (a1) can also be listed. TIFF0007842065000086.tif31162

[0113] When resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above The content is preferably 10 to 95 mol% relative to the total structural units of resin (A), and 15 ~90 mol% is more preferred, 20~85 mol% is even more preferred, and 20~70 mol% is More preferably, 20-60 mol% is even more preferable, and 10-40 mol% is particularly preferable. It seems so.

[0114] <Structural unit (s)> A structural unit (s) is a monomer that does not have an acid-unstable group (hereinafter referred to as "monomer (s)"). It is derived from (there is a combination). The monomer that derives the structural unit (s) is an acid-resistant monomer known in the field of resists. Monomers without a stable group can be used. The structural unit (s) preferably has a hydroxyl group or a lactone ring. A structural unit having a xyl group and not having an acid-unstable group (hereinafter referred to as "structural unit (a2)") A structural unit having a lactone ring and / or not having an acid-unstable group (hereinafter referred to as "structural unit") If a resin having a "production unit (a3)" is used in the resist composition of the present invention, This improves the resolution of the resist pattern and its adhesion to the substrate.

[0115] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) can be an alcoholic hydroxyl group or a phenolic group. A hydroxyl group may also be used. When manufacturing a resist pattern from the resist composition of the present invention, KrF is used as the exposure light source. High-energy beams such as excimer lasers (248 nm), electron beams, or EUV (ultra-ultraviolet light) are used. If present, the structural unit (a2) is a structural unit having a phenolic hydroxyl group ( It is preferable to use a2). Alternatively, use an ArF excimer laser (193 nm), etc. In that case, the structural unit (a2) may be the structural unit (a2-1) or structural unit (a2) described later. -A) is more preferable. The structural unit (a2) includes one type alone. It is acceptable to include two or more types.

[0116] The structural unit (a2) having a phenolic hydroxyl group is defined as the structural unit of formula (a2 Examples of structural units represented by -A) (hereinafter sometimes referred to as "structural unit (a2-A)") include It can be done. TIFF0007842065000087.tif4349[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents an alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy 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 they combine This indicates the bonding position with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. 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, Number R a51 They may be the same or different from each other.

[0117] R a50 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. It can be done. R a50 C1-C6 alkyl groups that may have a halogen atom include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pe fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, Tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a50 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a51 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. It is possible. R a51 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Examples include propoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. A carbon-1 to carbon-4 alkoxy group is preferred, and a methoxy group or ethoxy group is more preferred. A toxic group is even more preferable. R a51 The alkylcarbonyl groups in this context include acetyl, propionyl, and butyric groups. Examples include the lyl group. R a51 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the luoxy group and the butyryloxy group. R a51 A methyl group is preferred.

[0118] *-X a51 -(A a52 -X a52 ) nb - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, These include *-CO-O- and *-CO-OA. a52 -CO-O- or *- OA a52 -CO-O- is preferred.

[0119] Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and Examples include 2-methylbutane-1,4-diyl groups. A a52 It is preferable that this is a methylene group or an ethylene group.

[0120] A a50 These are single bonds, *-CO-O- or *-CO-OA a52 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-.

[0121] mb is preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxyl group is preferably bonded to the ortho- or para-position of the benzene ring, and at the para-position It is more preferable for them to combine.

[0122] As for the structural unit (a2-A), see Japanese Patent Publication No. 2010-204634, Japanese Patent Publication No. 2012- Examples include monomer-derived structural units described in Publication No. 12577.

[0123] The structural unit (a2-A) is represented by equations (a2-2-1) to (a2-2-6). In structural units and structural units represented by formulas (a2-2-1) to (a2-2-6), R in the manufacturing unit (a2-A) a50 A structural unit in which the methyl group equivalent to a hydrogen atom is replaced by a hydrogen atom. The following can be listed. The structural unit (a2-A) is the structural unit represented by formula (a2-2-1), formula Structural units represented by (a2-2-3), structural units represented by formula (a2-2-6), and formula ( a2-2-1) Structural unit represented by formula (a2-2-3) or formula (a In the structural unit represented in 2-2-6), R in structural unit (a2-A) a50 Equivalent to It is preferable that the structural unit is one in which the methyl group is replaced by a hydrogen atom. TIFF0007842065000088.tif42166

[0124] Content of structural unit (a2-A) when structural unit (a2-A) is present in resin (A) This is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, relative to the total structural units. It is mol%, more preferably 15-65 mol%, and even more preferably 20- The concentration is 65 mol%, and more preferably 20-50 mol%. Structural unit (a2-A) is polymerized using structural unit (a1-4), for example, and then p-Tol It can be incorporated into resin (A) by treating it with an acid such as ene sulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0125] Structural units having an alcoholic hydroxyl group in structural unit (a2) include those with the formula ( The structural unit represented by a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") It can be listed. TIFF0007842065000089.tif3954 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents the associative position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0126] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14 The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0127] As for the structural unit (a2-1), for example, see Japanese Patent Publication No. 2010-204646. Examples of structural units derived from monomers are given by equations (a2-1-1) to (a2-1-6). A structural unit represented by any of the following formulas is preferred, from formula (a2-1-1) to formula (a2-1-4) A structural unit represented by either formula (a2-1-1) or formula (a2-1- The structural unit represented in 3) is even more preferable. TIFF0007842065000090.tif50138

[0128] If resin (A) contains structural units (a2-1), the content of these units is the total structural unit content of resin (A). For each position, it is usually 1 to 45 mol%, preferably 1 to 40 mol%, and more preferably The amount is 1 to 35 mol%, more preferably 2 to 20 mol%, and even more preferably The percentage is between 2 and 10 mol%.

[0129] <Structural unit (a3)> The lactone rings of structural unit (a3) ​​are a β-propiolactone ring and a γ-butyrolactone ring. It can be a monocyclic ring such as a δ-valerolactone ring, and the contraction of a monocyclic lactone ring with other rings. A ring compound is also acceptable. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or γ - A bridged ring containing a butyrolactone ring structure (e.g., a structural unit represented by the following formula (a3-2)) These are some examples.

[0130] The structural unit (a3) ​​is preferably formula (a3-1), formula (a3-2), formula (a3-3) Alternatively, it is a structural unit represented by formula (a3-4). These may be contained individually. It may contain two or more types. TIFF0007842065000091.tif46147[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 These are, independently, -O- or *-O-(CH2) k3 - This represents a base represented by CO-O-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- represents vinegar. L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This includes an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom, or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently comprises a carboxyl group, a cyano group, or a carbon Represents aliphatic hydrocarbon groups with prime numbers 1 through 4. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 They may be the same or different from each other.

[0131] R a21 , R a22 , R a23 and R a25 As for aliphatic hydrocarbon groups in this context, methyl ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and ter Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in this include fluorine, chlorine, bromine, and iodine. Atoms are one example. R a24 The alkyl groups in this context include methyl, ethyl, propyl, and isopropyl groups. butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Examples include alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups. Alternatively, an ethyl group may be used. R a24 Examples of alkyl groups having a halogen atom include the trifluoromethyl group. Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perf Perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Lufluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl Examples include the 14-3 group and the triiodomethyl group.

[0132] L a8 and L a9 Examples of alkanediyl groups in this context include methylene groups, ethylene groups, and pro groups. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, tan-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Examples include tan-1,4-diyl groups and 2-methylbutane-1,4-diyl groups.

[0133] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is independently preferred Alternatively, -O- or *-O-(CH2) k3 In -CO-O-, k3 is 1 to 4 A base that is any integer, more preferably -O- and *-O-CH2-CO-O-, and further Preferably, it is an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a melanin group. It is a chill group. p1, q1, and r1 are each independently, preferably integers between 0 and 2. More preferably, it is 0 or 1.

[0134] In equation (a3-4), R a24 Preferably, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is a group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a group of the same type. It is either a hydrogen atom or a methyl group. R a25 The group is preferably a carboxyl group, a cyano group, or a methyl group. L a7 Preferably -O- or *-OL a8 -CO-O- and, far It is -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer between 0 and 2, and more preferably 0 or 1. In particular, formula (a3-4)' is preferred over formula (a3-4). TIFF0007842065000092.tif4326 (in the formula, Ra24 , L a7 (This expresses the same meaning as above.)

[0135] The structural unit (a3) ​​is the monomer described in Japanese Patent Publication No. 2010-204646. , monomers described in Japanese Patent Publication No. 2000-122294, Japanese Patent Publication No. 2012-41274 Examples of structural units derived from monomers described in the publication are listed below. Structural unit (a3) ​​is , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , equation (a3-3-1), equation (a3-3-2), and equation (a3-4-1) ~ equation (a3-4-1 2) A structural unit represented by any of the above, and in the said structural unit, formula (a3-1) to formula ( R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to water Structural units that are replaced by elementary atoms are preferred.

[0136] TIFF0007842065000093.tif115164

[0137] If resin (A) contains structural units (a3), the total content of these units is the total structural unit content of resin (A). The amount is usually 5-70 mol%, preferably 10-65 mol%, and more preferably It is either 10-60 mol% or 10-60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of units (a3-4) is 5 to 60 units relative to the total structural units of resin (A), respectively. % is preferred, 5 to 50 mol% is more preferred, and 10 to 50 mol% is even more preferred.

[0138] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007842065000094.tif2553[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and the saturated hydrocarbon water The -CH2- group in the element may be replaced by -O- or -CO. R 42 The saturated hydrocarbon groups represented by these terms include chain-type saturated hydrocarbon groups and monocyclic or polycyclic alicyclic saturated hydrocarbon groups. Examples include hydrocarbon groups, and groups formed by combining these.

[0139] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic groups such as adamantyl groups, norbornyl groups, and the following groups (* indicates bonding position). Examples include saturated hydrocarbon groups. TIFF0007842065000095.tif10146 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic saturated hydrocarbon groups include -Alkanediyl group-alicyclic saturated hydrocarbon group, -Alkanediyl group-alkyl Examples include AL groups, -alkanediyl groups, -alicyclic saturated hydrocarbon groups, -alkyl groups, etc.

[0140] The structural unit (a4) is the structural unit represented by formula (a4-0) and the structural unit represented by formula (a4-1). Examples include structural units and structural units represented by formula (a4-4). TIFF0007842065000096.tif3844[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a This is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. This represents a luorocycloalkanediyl group. R 64 This represents a hydrogen atom or a fluorine atom.

[0141] L 4a The alkanediyl groups in this include methylene group, ethylene group, propane-1, Linear alkanediyl groups such as 3-diyl groups and butane-1,4-diyl groups, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylprop Branched alkanes such as pan-1,3-diyl groups and 2-methylpropane-1,2-diyl groups A diyl group is one example.

[0142] L 3a In this context, perfluoroalkanediyl groups include difluoromethylene groups and per Fluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane -1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane -2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2 ,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1, 5-diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3, 3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2, 2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1, 7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3, 4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1, 8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3, Examples include 3-diyl groups and perfluorooctane-4,4-diyl groups. L 3a As for the perfluorocycloalkanediyl group in this context, perfluorocyclo xandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl Examples include yl groups and perfluoroadamantanediyl groups.

[0143] L 4a The is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond. The bond is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably Alternatively, it is a perfluoroalkanediyl group with 1 to 3 carbon atoms.

[0144] The structural units (a4-0) include the structural units shown below and the structural units within the following structural units ( a4-0) R 54 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007842065000097.tif59166

[0145] TIFF0007842065000098.tif34112

[0146] TIFF0007842065000099.tif4866[In formula (a4-1), Ra41 represents a hydrogen atom or a methyl group. R a42 This represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. A a41 This is an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a compound of formula (ag 1) represents the base. However, A a41 and R a42 At least one of them is a substituent. It has a halogen atom (preferably a fluorine atom). TIFF0007842065000100.tif1588 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these is independently a divalent carbon atom having 1 to 5 carbon atoms, which may have substituents. This represents a saturated hydrocarbon group. A a43 This is a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have single bonds or substituents. It represents. X a41 and X a42 These are, independently, -O-, -CO-, -CO-O-, or -O-CO - represents However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * represents a bond position, and the * on the right is -O-CO-R a42 This is the bonding position with [the other element].

[0147] R a42 The saturated hydrocarbon groups in this context include chain-type saturated hydrocarbon groups and monocyclic or polycyclic saturated hydrocarbon groups. Examples include alicyclic hydrocarbon groups, and groups formed by combining these. ru.

[0148] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic saturated alicyclic hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic groups such as adamantyl groups, norbornyl groups, and the following groups (* indicates bonding position). Examples include the compound hydrocarbon group. TIFF0007842065000101.tif11159 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more saturated alicyclic hydrocarbon groups include -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl Examples include -alkanediyl groups, -saturated alicyclic hydrocarbon groups, -alkyl groups, etc.

[0149] R a42 The substituents that may be present are halogen atoms and those represented by formula (a-g3) At least one selected from the group consisting of groups is mentioned. As for halogen atoms, Examples include elementary atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. TIFF0007842065000102.tif855[In formula (a-g3), X a43 * represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O- (* represents an oxygen atom, a carbonyl group, or *-O-CO-O-). R a42 (Represents the bonding position with [another element].) A a45 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. * indicates a bond position. However, R a42 -X a43 -A a45 In R a42 If it does not have a halogen atom, then A a4 5 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom.

[0150] A a45 The saturated hydrocarbon groups in this context include methyl, ethyl, propyl, and butyl groups. pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentade Alkyl groups such as syl, hexadecyl, heptadecyl, and octadecyl groups; cyclop Monocyclic alicyclic groups such as thyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Hydrocarbon groups; as well as decahydronaphthyl groups, adamantyl groups, norbornyl groups and the following Examples include polycyclic alicyclic hydrocarbon groups such as the group (* indicates a bonding position). TIFF0007842065000103.tif11158 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0151] R a42 The halogen atom is preferably a saturated hydrocarbon group which may have a halogen atom. Alkyl groups having and / or saturated hydrocarbon groups having a group represented by formula (a-g3) are suitable. It is preferable. R a42 If it is a saturated hydrocarbon group having a halogen atom, it preferably has a fluorine atom. A saturated hydrocarbon group, more preferably a perfluoroalkyl group or perfluoroalkyl group. It is a chloroalkyl group, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. The perfluoromethyl group, perfluoroethyl group, and perfluoropropyl group are examples of perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples include oroheptyl groups and perfluorooctyl groups. Examples of the 'l' group include the perfluorocyclohexyl group. R a42 However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then formula (a- Including the number of carbon atoms in the group represented by g3), R a42 The total number of carbon atoms should preferably be 15 or less. Furthermore, 12 or less is more preferable. When the group represented by formula (a-g3) is used as a substituent, The number should preferably be one.

[0152] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 is, More preferably, the group is represented by the formula (a-g2). TIFF0007842065000104.tif872[In formula (a-g2), A a46 This comprises a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may have a halogen atom. represent. X a44 This represents *-O-CO- or *-CO-O- (* is A a46 (Represents the bonding position with [another element].) . A a47 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. However, A a46, A a47 and X a44 The total number of carbon atoms is 18 or less, A a46 and A a47 of Of these, at least one has at least one halogen atom. * indicates the bonding position with the carbonyl group.

[0153] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. A a47 The number of carbon atoms in the saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, A a 47 A cyclohexyl group or an adamantyl group is more preferable.

[0154] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the bonding position with [the other party].) TIFF0007842065000105.tif14160

[0155] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents in the alkanediyl group represented by are a hydroxyl group and a carbon 1- Examples include 6 alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0156] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups. , and formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Examples of such groups include methylene groups, ethylene groups, and propane-1,3-di Iyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane -1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1 Examples include 2-diyl groups. A a42 , A a43 and A a44 The substituents of the divalent saturated hydrocarbon group represented by are hydroxyl groups. Examples include alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0157] In the group represented by formula (a-g1), X a42 -O-, -CO-, -CO-O- or The following are examples of groups that are -O-CO-. In the following examples, * and ** represents the bond position, and ** is -O-CO-R a42 This is the bonding position with [the other party]. TIFF0007842065000106.tif47140

[0158] The structural units represented by formula (a4-1) are the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to this is placed on a hydrogen atom. Examples of replaced structural units include: TIFF0007842065000107.tif154136

[0159] TIFF0007842065000108.tif59122

[0160] The structural units represented by formula (a4-1) are the structural units represented by formula (a4-2) and Examples of structural units are given by formula (a4-3). TIFF0007842065000109.tif4156[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -C contained in the alkanediyl group H2- may be replaced by -O- or -CO-. R f6 This represents a saturated hydrocarbon group having 1 to 20 fluorine atoms. However, L 44 and R f6 The upper limit for the total number of carbon atoms is 21.

[0161] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41 Similar to the examples given above, It can be done. R f6 The saturated hydrocarbon group is R 42 Similar to the examples given earlier, the same types of bases can be cited. L 44 In this context, an alkanediyl group having 2 to 4 carbon atoms is preferred. An ethylene group is more preferable.

[0162] Examples of structural units represented by formula (a4-2) include formulas (a4-1-1) to (a4 The structural units represented in (a4-2) are as follows. R f5The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be cited as a structural unit.

[0163] TIFF0007842065000110.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. vinegar. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 (Represents the bonding position with [another element].) . A f14 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom. However, A f13 and A f14 At least one of them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0164] L 5 The alkanediyl group in A is a41 The same as the example with the alkanediyl group. The basis for this can be cited.

[0165] A f13 A preferred divalent saturated hydrocarbon group which may have a fluorine atom is A divalent chain-type saturated hydrocarbon group which may have a fluorine atom and a fluorine atom A divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanedi It is a lu group. Examples of divalent chain-type saturated hydrocarbon groups that may contain a fluorine atom include methylene groups and ethyl acetate groups. Alkanediyl groups such as len group, propanediyl group, butanediyl group and pentanediyl group ; Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, Perfluoroalkanes such as the fluorobutanediyl group and the perfluoropentanediyl group. Examples include diyl groups. Divalent alicyclic saturated hydrocarbon groups, which may contain a fluorine atom, are monocyclic and polycyclic. A slight misalignment is also acceptable. Examples of monocyclic groups include cyclohexanediyl groups and perfluorocyclodiyl groups. Examples include the xandiyl group. Polycyclic groups include the adamantanediyl group and norbol. Examples include the nandiyl group and the perfluoroadamantanediyl group.

[0166] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in Similar groups to those exemplified can be cited. Among them, the trifluoromethyl group and the difluoromethyl group are particularly noteworthy. Tyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-Pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and per Fluoroctyl groups and other alkyl fluorides, cyclopropylmethyl groups, cyclopropyl groups Cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group Xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbol Nyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl A methyl group is preferred.

[0167] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon group is a divalent chain-type saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent A group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is also preferred. A saturated hydrocarbon group is even more preferred. A f14 The saturated hydrocarbon group is a chain-type saturated hydrocarbon group having 3 to 12 carbon atoms and a group having 3 to 12 carbon atoms. Groups containing alicyclic saturated hydrocarbon groups are preferred, and chain-type saturated hydrocarbon groups having 3 to 10 carbon atoms and Groups containing alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms are even more preferred. Among them, A f14 teeth Preferably, the group contains an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably, Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and It is a damantyl group.

[0168] Examples of structural units represented by equation (a4-3) include equation (a4-1'-1) ~ equation (a The structural units represented in 4-1'-11) are listed below. Keru R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also shown in formula (a4-3). It can be cited as a structural unit.

[0169] As a structural unit (a4), the structural unit represented by formula (a4-4) can also be cited. TIFF0007842065000111.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is, -(CH2) j1 -,-(CH2) j2 -O-(CH2) j3 - or - (CH2) j4 - CO-O-(CH2) j5 - represents j1 through j5 each independently represent an integer from 1 to 6. R f22 This represents a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom.

[0170] R f22 The saturated hydrocarbon group is R a42 Examples include saturated hydrocarbon groups similar to those represented by the symbol. R f22 This refers to an alkyl group having 1 to 10 carbon atoms that contains a fluorine atom, or a carbon atom containing a fluorine atom. A cycloaliphatic saturated hydrocarbon group having 1 to 10 prime atoms is preferred, and a group having 1 to 10 carbon atoms and a fluorine atom is preferred. Alkyl alkyl groups are more preferred, and C1-C6 alkyl groups having a fluorine atom are even more preferred. It's nice.

[0171] In equation (a4-4), A f21 As for, -(CH2) j1 - is preferred, ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0172] Examples of structural units represented by formula (a4-4) include the following structural units and the following formula In the structural unit shown, R in structural unit (a4-4) f21 The methyl group corresponding to One example is a structural unit in which a hydrogen atom has been replaced. TIFF0007842065000112.tif86160

[0173] If resin (A) has structural units (a4), the content of these units is the total structural unit content of resin (A). A percentage of the position is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3 to 10 mol%. A percentage is even more preferable.

[0174] <Structural Unit (a5)> The non-leaved hydrocarbon groups possessed by structural unit (a5) include linear, branched, or cyclic hydrocarbons. Groups having a group are examples. In particular, structural unit (a5) has an alicyclic hydrocarbon group. The base is preferable. Examples of structural units (a5) include the structural unit represented by formula (a5-1). . TIFF0007842065000113.tif3149[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in this alicyclic hydrocarbon group The elementary atoms may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- group contained in may be replaced by -O- or -CO-.

[0175] R 52 The alicyclic hydrocarbon group in this can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopene. Examples include chill groups and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include, for example, Examples include adamantyl groups and norbornyl groups. Aliphatic hydrocarbon groups with 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, and iso groups. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl Examples include alkyl groups such as the octyl group and the 2-ethylhexyl group. Examples of alicyclic hydrocarbon groups with substituents include the 3-methyladamantyl group. ru. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably k is an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0176] L 55 In this context, divalent saturated hydrocarbon groups include divalent chain saturated hydrocarbon groups and divalent lipids. Examples include cyclic saturated hydrocarbon groups, preferably divalent chain saturated hydrocarbon groups. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, and propanedi groups. Examples include alkanediyl groups such as the yl group, butanediyl group, and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl groups and cyclohexanediyl groups. Examples include the roalkanediyl group. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include ada Examples include mantanediyl groups and norbornanediyl groups.

[0177] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by can be replaced with -O- or -CO-. Examples of the replaced groups include those represented by formulas (L1-1) to (L1-4). In the following formula, * and ** represent bonding positions, respectively, with * representing the bonding position with the oxygen atom. TIFF0007842065000114.tif18165 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is Lx1 (Represents the bonding position.) L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently consists of a single bond or a divalent aliphatic saturated carbon with 1 to 14 carbon atoms. It represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0178] L x1 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x2 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x6 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably The group is either a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. L x9 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. W x1 Preferably, a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably It is either a cyclohexanediyl group or an adamantanediyl group.

[0179] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007842065000115.tif53136

[0180] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007842065000116.tif23130

[0181] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007842065000117.tif15145

[0182] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007842065000118.tif26114

[0183] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0184] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R 51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007842065000119.tif77157

[0185] TIFF0007842065000120.tif39159 If resin (A) has structural units (a5), the content of these units is the total structural unit content of resin (A). A value of 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% is preferred. A percentage is even more preferable.

[0186] <Structural Unit (II)> Resin (A) further decomposes upon exposure to generate acid, resulting in structural units (hereinafter referred to as "structural units") It may contain (II) in some cases. Specific structural units (II) include Examples include the structural unit described in Japanese Patent Publication No. 2016-79235, with sulfonates in the side chains. A structural unit having a group or carboxylate group and an organic cation, or a side chain containing a sulfonio It is preferable that the structural unit has a group and an organic anion.

[0187] Structural units having a sulfonate group or carboxylate group and an organic cation in the side chain It is preferable that the structural unit is represented by formula (II-2-A'). TIFF0007842065000121.tif3189 [In formula (II-2-A'), X III3 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and contains -CH2- may be replaced with -O-, -S-, or -CO- in the saturated carbonized water. The hydrogen atoms contained in the elementary group are halogen atoms, or C1-C2 atoms which may contain halogen atoms. It may be replaced by an alkyl group or hydroxyl group of 6. A x1 This represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen contained in the alkanediyl group The atoms may be substituted with fluorine atoms or perfluoroalkyl groups having 1 to 6 carbon atoms. . RA - This represents a sulfonate group or a carboxylate group. R III3 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents an alkyl group. ZA + This represents an organic cation.

[0188] R III3 The halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Examples include atoms, etc. R III3 A C1-C6 alkyl group which may have a halogen atom represented by the following is: , R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by These are some examples. Ax1 Examples of alkanediyl groups with 1 to 8 carbon atoms, represented by the following: methylene group, ethylene group, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group Iyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples include the group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. . A x1 Examples of perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted include truffles. Peromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl Ropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl Examples include the syl group, perfluoropentyl group, and perfluorohexyl group. X III3 As a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, the following are examples: linear or branched a Examples include lucandiyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of these groups. They can be placed together. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, do Linear alkanediyl groups such as decane-1,12-diyl groups; butane-1,3-diyl groups, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Branched alkanedi such as tan-1,4-diyl group and 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclo Cycloalkanes such as xane-1,4-diyl groups and cyclooctane-1,5-diyl groups Divalent monocyclic or alicyclic saturated hydrocarbon groups such as the 1,4-diyl group; norbornane-1,4-diyl group, Lunan-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6- Examples include divalent polycyclic and alicyclic saturated hydrocarbon groups such as diyl groups.

[0189] The -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. Examples include the divalent groups represented by equations (X1) to (X53). However, Furthermore, the -CH2- group contained in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. The number of carbon atoms in each preceding atom is 17 or less. In the following formula, * and ** represent bond positions, and * is A x1 This represents the bonding position with [the specified element]. TIFF0007842065000122.tif145161

[0190] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0191] ZA + The organic cation represented is cation Z1 in salt (B1). + Similar to It can be listed.

[0192] The structural unit represented by formula (II-2-A') is the structural unit represented by formula (II-2-A) It is preferable that this be the case. TIFF0007842065000123.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z2A represents an integer between 0 and 6. R III2 and R III4 Each of these is independently a hydrogen atom, a fluorine atom, or a carbon atom with 1 to 6 carbon atoms. Represents a fluoroalkyl group, and when z is 2 or greater, multiple R III2 and R III4 They are identical to each other. It may be one way, or it may be different. Q a and Q b Each is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.] R III2 , R III4 Q a and Q b As a perfluoroalkyl group having 1 to 6 carbon atoms, So, as mentioned above, Q b1 Examples include perfluoroalkyl groups with 1 to 6 carbon atoms, as shown below. It can be done.

[0193] The structural unit represented by formula (II-2-A) is the same as the structural unit represented by formula (II-2-A-1). It is preferable that it be in that position. TIFF0007842065000124.tif5576 [In formula (II-2-A-1), RIII2 , R III3 , R III4 Q a Q b and ZA + This expresses the same meaning as above. R III5 This represents a saturated hydrocarbon group with 1 to 12 carbon atoms. z2A1 represents an integer between 0 and 6. X I2 This represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group contains -CH2- may be replaced by -O-, -S-, or -CO-, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with halogen atoms or hydroxyl groups. R III5 Examples of saturated hydrocarbon groups with 1 to 12 carbon atoms represented by these groups include methyl group, ethyl group, and propyl group. Ropyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentium hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and do Examples include linear or branched alkyl groups such as decyl groups. X I2 As a divalent saturated hydrocarbon group represented by , X III3 Divalent saturated hydrocarbons represented by Similar examples can be given.

[0194] The structural unit represented by formula (II-2-A-1) is represented by formula (II-2-A-2). A structural unit that can be made is even more preferable. TIFF0007842065000125.tif4880[In formula (II-2-A-2), R III3 , R III5 and ZA + This expresses the same meaning as above. m and n each independently represent either 1 or 2.

[0195] Examples of structural units represented by formula (II-2-A') include the following structural units and international Examples of structural units include those described in Publication No. 2012 / 050015. ZA + This is an organic cation. It represents. TIFF0007842065000126.tif150149

[0196] A structural unit having a sulfonio group and an organic anion in its side chain is represented by formula (II-1-1). It is preferable that the structural unit is such that it can be formed. TIFF0007842065000127.tif3281[In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3 Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, and R II2 Reach biR II3 These atoms may bond to each other, forming a ring with the sulfur atom to which they are bonded. R II4 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. This represents a luquill group. A - This represents an organic anion. R II1 Divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, as represented by the phenylene group, Examples include naphthylene groups. R II2 and R II3 Examples of hydrocarbon groups represented include alkyl groups, alicyclic hydrocarbon groups, and aromatic groups. Examples include hydroxyl groups and groups formed by combining them. Examples of alkyl groups and alicyclic hydrocarbon groups are the same as those described above. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. , aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl Nyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesityl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group), alicyclic carbon Aromatic hydrocarbon groups having a hydrogenated group (p-cyclohexylphenyl group, p-adamantyl group) Examples include phenyl groups, phenylcyclohexyl groups, and other aryl-cycloalkyl groups. It can be done. R II4 The halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Examples include atoms, etc. R II4 A C1-C6 alkyl group which may have a halogen atom represented by the following is: , R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by These are some examples. A II1 Examples of divalent linking groups represented by this formula include divalent saturated carbon dioxide with 1 to 18 carbon atoms. Examples include the elemental group, and the -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or It may be replaced with -CO-. Specifically, X III3 Two carbon atoms represented by 1 to 18 Examples include the same saturated hydrocarbon groups as those with a valence.

[0197] The structural units containing cations in formula (II-1-1) are the structural units represented below. Some examples include: TIFF0007842065000128.tif74130

[0198] TIFF0007842065000129.tif97135

[0199] A - Examples of organic anions represented by this include sulfonic acid anions and sulfonylimido anions. Examples include sulfonylmethide anions and carboxylic acid anions. - It is represented The organic anion is preferably a sulfonate anion, and is a sulfonate anion, sulfonylurea As anions, sulfonylmethide anions, and carboxylic acid anions, the formula described above is ( Examples include anions similar to those found in the salt represented in I).

[0200] Examples of structural units represented by formula (II-1-1) include the following structural units. It is possible. TIFF0007842065000130.tif98155

[0201] When resin (A) contains structural unit (II), the content of structural unit (II) is: The amount is preferably 1 to 20 mol%, and more preferably 2 to 1 mol%, relative to the total structural units of fat (A). The percentage is 15 mol%, and more preferably 3 to 10 mol%.

[0202] Resin (A) may have structural units other than those described above, and such structural units In terms of rank, well-known structural units in this field can be cited.

[0203] The resin (A) is preferably a resin consisting of structural unit (a1) and structural unit (s). . The structural unit (a1) is preferably structural unit (a1-0), structural unit (a1-1) and structural unit (a1-0) Manufacturing unit (a1-2) (preferably having a cyclohexyl group and a cyclopentyl group) At least one selected from the group consisting of building units and structural units (a1-4), and more Preferably, there are at least two types, and more preferably, structural unit (a1-1) and structural unit It consists of at least two types selected from the group (a1-2). The structural unit (s) is preferably from the group consisting of structural unit (a2) and structural unit (a3). At least one of the selected structural units (a2) is preferably structural unit (a2-1). Alternatively, it is a structural unit (a2-A). The structural unit (a3) ​​is preferably expressed by formula (a3-1). The structural units that are formed, the structural units represented by formula (a3-2) and the structural units represented by formula (a3-4) It is at least one of the units selected from the group.

[0204] Each structural unit constituting resin (A) may be used individually or in combination of two or more types. Furthermore, using monomers that derive these structural units, known polymerization methods (e.g., radical polymerization) can be used. Therefore, it can be manufactured. The content of each structural unit in resin (A) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 (less than 15,000, more preferably less than 15,000). In this specification, weight average fraction The amount of molecules was determined by gel permeation chromatography under the conditions described in the examples. That is the case.

[0205] <Resins other than resin (A)> The resist composition of the present invention may further contain resins other than resin (A). Examples of resins other than resin (A) include structural unit (a4) or structural unit (a5). Examples include resins (hereinafter sometimes referred to as resin(X)).

[0206] Among the resins (X), resins containing structural units (a4) are preferred. It is preferable that the resin contains structural units having oxyatoms. In resin (X), the content of structural unit (a4) is equal to the sum of all structural units in resin (X). In contrast, it is preferable that the amount be 30 mol% or more, and more preferably 40 mol% or more. Furthermore, it is more preferable that the amount be 45 mol% or more. The structural units that resin (X) may further possess include structural unit (a2) and structural unit (a3) and other structural units derived from known monomers are examples. Among them, resin ( X) is preferably a resin consisting only of structural unit (a4) and / or structural unit (a5). It is more preferable that the resin consists solely of structural units (a4).

[0207] Each structural unit constituting the resin (X) may be used individually or in combination of two or more types. These monomers that induce structural units can be used in known polymerization methods (e.g., radical polymerization). Therefore, it can be manufactured. The content of each structural unit in resin (X) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of each resin (X) is preferably 6,000 or more. Preferably 7,000 or more, 80,000 or less (more preferably 60,000 or less) Yes, it exists. The method for measuring the weight-average molecular weight of resin (X) is the same as in the case of resin (A). Furthermore, if the resist composition contains resin (X), its content is equal to 100 mass of resin (A). Preferably, the amount is 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably 1 to 40 parts by mass, particularly preferably 2 to 30 parts by mass, and particularly preferred The amount is 2 to 8 parts by mass.

[0208] The content of resin (A) in the resist composition is 8 in relation to the solid content of the resist composition. Preferably, it is 0% by mass or more and 99% by mass or less, and preferably 90% by mass or more and 99% by mass or less. It is preferable. Also, if it contains resins other than resin (A), then resin (A) and resins other than resin (A) The total content of the resin is 80% by mass or more and 99% by mass or less relative to the solid content of the resist composition. The resist composition is preferably as follows: The solid content of a substance and the resin content thereto are determined by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as fluoroscopy.

[0209] <Solvent (E)> The solvent (E) content is typically 90% by mass or more and 99.9% by mass or less in the resist composition. Yes, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of solvent (E) is 99% by mass or less. The content of solvent (E) is determined, for example, by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as chromatography. The solvent (E) includes ethyl cellosolve acetate, methyl cellosolve acetate, and Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, vinegar Esters such as butyl acid, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl Ketones such as lucetone, 2-heptanone, and cyclohexanone; γ-butyrolactone, etc. Examples include cyclic esters; etc. One of the solvents (E) may be used alone. You may use two or more types.

[0210] <Quencher (C)> The quencher (C) consists of a basic nitrogen-containing organic compound and an acid generator (B). Examples include salts that produce an acid weaker than the acid produced. Quencher (C) content. It is preferable that this is about 0.01 to 5% by mass, based on the solid content of the resist composition. . Basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Aliphatic amines include primary amines. Examples include amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. Ruaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine Octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine mine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, methyldinonylamine, methylddecylamine, ethyl dibuty Luamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine Ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, dicyclo Xylmethylamine, Tris[2-(2-methoxyethoxy)ethyl]amine, Triiso Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine Mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmeth , 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridazole 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl (Lu)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide Examples include phyto, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Aromatic amines such as diisopropylaniline are preferred, and more preferably One example is 2,6-diisopropylaniline. Examples of ammonium salts include tetramethylammonium hydroxide and tetraisopropylammonium Ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl Ammonium hydroxide, tetraoctylammonium hydroxide, phenyl trim Tylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium Examples include nium hydroxide, tetra-n-butylammonium salicylate, and choline. It is possible.

[0211] The acidity of a salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). An acid with a lower acidity than the acid generated from the acid generator (B) The salt that generates is a salt with an acid dissociation constant of the acid generated from the salt usually -3 < pKa, preferably is a salt of -1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter, may be referred to as " intramolecular salt of weak acid (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. As the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), preferably an intramolecular salt of weak acid (D). Examples of the intramolecular salt of weak acid (D) include the following salts. TIFF0007842065000131.tif113145 TIFF0007842065000131.tif113145

[0212] When the resist composition contains the quencher (C), the content of the quencher (C) is TIFF0007842065000132.tif95145

[0213] usually 0.01 to 5% by mass, preferably 0.01 to 3% by mass in the solid content of the resist composition. 3% by mass in the solid content of the resist composition.

[0214] <Other Components> The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter, "other components" It may be referred to as "F (F)". It may contain other components (F) in particular. There are no known additives in the resist field, such as sensitizers, dissolution inhibitors, surfactants, and stabilizers. Agents, dyes, etc. can be used.

[0215] <Preparation of resist composition> The resist composition of the present invention comprises a salt (I) and a resin (A), and, if necessary, an acid generator. Agent (B), resins other than resin (A), solvent (E), quencher (C) and other components ( It can be prepared by mixing F). The mixing order is arbitrary and not particularly limited. It is not. The temperature when mixing should be between 10 and 40°C, depending on the type of resin, etc. and the solvent used in the resin, etc. An appropriate temperature can be selected depending on the solubility of E). The mixing time depends on the mixing temperature. Depending on the situation, an appropriate time can be selected from 0.5 to 24 hours. Furthermore, a special mixing method is also available. There are no restrictions, and stirring and mixing can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0216] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of coating the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating. To coat the resist composition onto the substrate, a commonly used device such as a spin coater is used. Therefore, it can be done. Examples of substrates include inorganic substrates such as silicon wafers. Before applying the Dist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. It's fine if you do that. By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is performed. For example, evaporating a solvent using a heating device such as a hot plate (so-called private heating) This is done by (k) or by using a vacuum device. The heating temperature is 50-200°C. It is preferable that the heating time be 10 to 180 seconds. Also, vacuum drying The pressure used during this process is 1 to 1.0 × 10 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine is an immersion exposure machine. This is also good. As exposure light sources, KrF excimer laser (wavelength 248nm), ArF excimer Ultraviolet lasers such as lasers (wavelength 193nm) and F2 excimer lasers (wavelength 157nm) Laser light is emitted from solid-state laser sources (such as YAG or semiconductor lasers). These devices emit high-harmonic laser light in the far-ultraviolet or vacuum-ultraviolet region by wavelength conversion, such as electron beams and ultra-high-frequency lasers. Various methods can be used, such as those that irradiate with ultraviolet light (EUV). In some cases, the act of irradiating with these radiations is collectively referred to as "exposure." Typically, exposure is performed through a mask corresponding to the desired pattern. The exposure light source is electron In the case of lines, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated to promote the deprotection reaction at the acid-unstable groups. Perform a loose post-exposure bake. The heating temperature is usually around 50-200°C, or as preferred. The temperature is approximately 70-150°C. The heated composition layer is typically developed using a developing device and a developing solution. Examples include the dipping method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 It is preferable that the developing time is ~300 seconds. By selecting the type of developer as follows: Positive-type resist patterns or negative-type resist patterns can be manufactured. When producing a positive-type resist pattern from the resist composition of the present invention, the developer is used as follows: An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution will do. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). Alkaline developers may contain surfactants. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is washed away. It is preferable to remove it. When manufacturing a negative-type resist pattern from the resist composition of the present invention, the developer is used as A developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used. Organic solvents contained in organic developers include ketosols such as 2-hexanone and 2-heptanone. Solvents; glycol ethers such as propylene glycol monomethyl ether acetate Sterling solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole Examples include aromatic hydrocarbon solvents such as the like. In organic developer solutions, the content of organic solvents is preferably 90% by mass or more and 100% by mass or less. It is more preferable that the concentration be 95% by mass or more and 100% by mass or less, and that it be substantially composed of only organic solvents. It is preferable. Among organic developers, those containing butyl acetate and / or 2-heptanone are Preferred. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass. Preferably, the amount is 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the composition consists solely of butyl acetate and / or 2-heptanone. Organic developers may contain surfactants. Also, organic developers may contain trace amounts of surfactants. It may contain moisture. During development, by substituting a different type of solvent than the organic developer, development can be stopped. That's good too. It is preferable to wash the resist pattern with a rinsing solution after development. The rinsing solution can be: There are no particular restrictions as long as it does not dissolve the resist pattern, including general organic solvents. A liquid can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0217] <Application> The resist composition of the present invention is a resist composition for KrF excimer laser exposure, and ArF Resist compositions for Kishima laser exposure, resist compositions for electron beam (EB) exposure, or EU Resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure It is suitable as a resist composition for use and is useful for semiconductor microfabrication. [Examples]

[0218] The present invention will be described in more detail with reference to examples. In the examples, the content or amount used is expressed Unless otherwise specified, "%" and "parts" refer to mass. The weight-average molecular weight is a value obtained by gel permuration chromatography. The analytical conditions for gel permuration chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The compound structure was determined by mass spectrometry (LC: Agilent 1100, MASS: Agil This was confirmed by measuring molecular ion peaks using an ent LC / MSD (manufactured by ent). In the examples, the value of this molecular ion peak is indicated by "MASS".

[0219] Example 1: Synthesis of the salt represented by formula (I-2) TIFF0007842065000133.tif75164 1.58 parts of the salt represented by formula (I-2-a), 1.0 parts of the compound represented by formula (I-2-b) Mix 0 parts of the mixture with 10 parts of dimethylformamide and stir at 23°C for 30 minutes. The resulting mixture Add 0.44 parts potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then further stir at 90°C. By stirring at °C for 3 hours, a mixture containing the salt represented by formula (I-2-c) was obtained. After cooling the mixture to 23°C, add 12 parts of a 5% oxalic acid aqueous solution and heat at 23°C for 30 minutes. After stirring for minutes, add 2.00 parts of the salt represented by formula (I-2-d) and stir at 23°C for 7 hours. Mixed. To the resulting reaction product, 30 parts chloroform and 30 parts deionized water were added, and 23 After stirring at °C for 30 minutes, the organic layer was separated by liquid-liquid extraction. The resulting organic layer was subjected to ion exchange. 30 parts water was added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. The washing procedure was repeated seven times. After concentrating the resulting organic layer, acetonitrile 1 was added to the concentration residue. Add 0.5 parts and 30 parts of tert-butyl methyl ether, and stir at 23°C for 30 minutes. Subsequently, the supernatant liquid is removed and the solution is concentrated to obtain 2.02 parts of the salt represented by formula (I-2). Ta. MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 339.1

[0220] Example 2: Synthesis of the salt represented by formula (I-3) TIFF0007842065000134.tif69160 1.58 parts of the salt represented by formula (I-2-a), 1.0 parts of the compound represented by formula (I-2-b) Mix 0 parts of the mixture with 10 parts of dimethylformamide and stir at 23°C for 30 minutes. The resulting mixture Add 0.44 parts potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then further stir at 90°C. By stirring at °C for 3 hours, a mixture containing the salt represented by formula (I-2-c) was obtained. After cooling the mixture to 23°C, add 12 parts of a 5% oxalic acid aqueous solution and heat at 23°C for 30 minutes. After stirring for minutes, add 1.93 parts of the salt represented by formula (I-3-d) and stir at 23°C for 7 hours. Mixed. To the resulting reaction product, 30 parts chloroform and 30 parts deionized water were added, and 23 After stirring at °C for 30 minutes, the organic layer was separated by liquid-liquid extraction. The resulting organic layer was subjected to ion exchange. 30 parts water was added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. The washing procedure was repeated seven times. After concentrating the resulting organic layer, acetonitrile 1 was added to the concentration residue. Add 0.5 parts and 30 parts of tert-butyl methyl ether, and stir at 23°C for 30 minutes. Afterward, the supernatant is removed and the solution is concentrated to obtain 2.24 parts of the salt represented by formula (I-3). Ta. MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 323.0

[0221] Example 3: Synthesis of the salt represented by formula (I-14) TIFF0007842065000135.tif79166 1.58 parts of the salt represented by formula (I-2-a), 1.0 parts of the compound represented by formula (I-2-b) Mix 0 parts of the mixture with 10 parts of dimethylformamide and stir at 23°C for 30 minutes. The resulting mixture Add 0.44 parts potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then further stir at 90°C. By stirring at °C for 3 hours, a mixture containing the salt represented by formula (I-2-c) was obtained. After cooling the mixture to 23°C, add 12 parts of a 5% oxalic acid aqueous solution and heat at 23°C for 30 minutes. After stirring for 1 minute, add 1.93 parts of the salt represented by formula (I-14-d) and incubate at 23°C for 7 hours. Stirring was performed. To the resulting reaction product, 30 parts chloroform and 30 parts deionized water were added, and 2 After stirring at 3°C ​​for 30 minutes, the organic layer was separated by liquid-liquid extraction. The resulting organic layer was then subjected to ion exchange. After adding 30 parts of replacement water and stirring at 23°C for 30 minutes, the organic layer was separated. The washing procedure was repeated seven times. After the obtained organic layer was concentrated, the concentrated residue was treated with acetonitrile. Add 1.5 parts and 30 parts of tert-butyl methyl ether, and stir at 23°C for 30 minutes. Afterward, the supernatant is removed and the solution is concentrated to obtain 1.99 parts of the salt represented by formula (I-14). I obtained it. MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 323.1

[0222] Example 4: Synthesis of the salt represented by formula (I-437) Mix 1.24 parts of the compound represented by formula (I-437-b) and 10 parts of tetrahydrofuran. Combine the ingredients, stir at 23°C for 30 minutes, then cool to 5°C and add 0.14 parts of sodium hydride. Added. To the resulting mixture, 1.82 parts of the salt represented by formula (I-2-a) were added and heated at 5°C. The mixture was stirred for 3 hours. 6.30 parts of 1N hydrochloric acid were added to the resulting mixture, and then the temperature was raised to 23°C. The mixture was stirred at 23°C for 30 minutes. To the resulting mixture, 30 parts of chloroform and deionized water were added. 15 parts were added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. After concentrating the organic layer, add 1.5 parts acetonitrile and tert-butylmethyl methyl ester to the concentration residue. Add 30 parts of ether, stir at 23°C for 30 minutes, then remove the supernatant and concentrate. This yielded 2.11 parts of the salt represented by formula (I-437-c). Formula (I-437-c) 1.00 part of the salt represented by formula (I-2-d), 0.81 parts of the salt represented by formula (I-2-d), and chloroform 2 0 parts were added and stirred at 23°C for 3 hours. 15 parts of deionized water were added to the resulting reaction product. Then, after stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. After adding 15 parts of decontaminated water and stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. After concentrating the resulting organic layer, the concentrated residue was treated with acetonic acid. Add 1.5 parts of tolyl and 30 parts of tert-butyl methyl ether, and incubate at 23°C for 30 minutes. After stirring, the supernatant is removed and the liquid is concentrated to obtain salt 1 represented by formula (I-437). I obtained 12 copies. MASS(ESI(+)Spectrum):M + 499.0 MASS(ESI(-)Spectrum):M - 339.1

[0223] Example 5: Synthesis of the salt represented by formula (I-438) Mix 1.24 parts of the compound represented by formula (I-437-b) and 10 parts of tetrahydrofuran. Combine the ingredients, stir at 23°C for 30 minutes, then cool to 5°C and add 0.14 parts of sodium hydride. Added. To the resulting mixture, 1.82 parts of the salt represented by formula (I-2-a) were added and heated at 5°C. The mixture was stirred for 3 hours. 6.30 parts of 1N hydrochloric acid were added to the resulting mixture, and then the temperature was raised to 23°C. The mixture was stirred at 23°C for 30 minutes. To the resulting mixture, 30 parts of chloroform and deionized water were added. 15 parts were added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. After concentrating the organic layer, add 1.5 parts acetonitrile and tert-butylmethyl methyl ester to the concentration residue. Add 30 parts of ether, stir at 23°C for 30 minutes, then remove the supernatant and concentrate. This yielded 2.11 parts of the salt represented by formula (I-437-c). Formula (I-437-c) 1.00 part of the salt represented by formula (I-3-d), 0.80 parts of the salt represented by formula (I-3-d), and chloroform 2 0 parts were added and stirred at 23°C for 3 hours. 15 parts of deionized water were added to the resulting reaction product. Then, after stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. After adding 15 parts of decontaminated water and stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. After concentrating the resulting organic layer, the concentrated residue was treated with acetonic acid. Add 1.5 parts of tolyl and 30 parts of tert-butyl methyl ether, and incubate at 23°C for 30 minutes. After stirring, the supernatant is removed and the liquid is concentrated to obtain salt 1 represented by formula (I-438). I obtained 0.35 copies. MASS(ESI(+)Spectrum):M + 499.0 MASS(ESI(-)Spectrum):M - 323.0

[0224] Example 6: Synthesis of the salt represented by formula (I-448) TIFF0007842065000138.tif40164 1.00 parts of salt represented by formula (I-437-c), 1 part of salt represented by formula (I-448-d) 0.07 parts and 20 parts of chloroform were added, and the mixture was stirred at 23°C for 3 hours. Add 15 parts of deionized water, stir at 23°C for 30 minutes, then separate and remove the organic layer. Then, 15 parts of deionized water were added to the resulting organic layer, and after stirring at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was concentrated. Afterward, add 1.5 parts acetonitrile and 30 parts tert-butyl methyl ether to the concentrated residue. After adding and stirring at 23°C for 30 minutes, the supernatant is removed and concentrated to obtain formula ( 1.44 parts of the salt represented by I-448) were obtained. MASS(ESI(+)Spectrum):M + 499.0 MASS(ESI(-)Spectrum):M - 467.1

[0225] Example 7: Synthesis of the salt represented by formula (I-440) TIFF0007842065000139.tif38165 1.00 parts of salt represented by formula (I-437-c), 1 part of salt represented by formula (I-440-d) 0.20 parts and 20 parts of chloroform were added and the mixture was stirred at 23°C for 3 hours. Add 15 parts of deionized water, stir at 23°C for 30 minutes, then separate and remove the organic layer. Then, 15 parts of deionized water were added to the resulting organic layer, and after stirring at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was concentrated. Afterward, add 1.5 parts acetonitrile and 30 parts tert-butyl methyl ether to the concentrated residue. After adding and stirring at 23°C for 30 minutes, the supernatant is removed and concentrated to obtain formula ( 1.23 parts of the salt represented by I-440) were obtained. MASS(ESI(+)Spectrum):M + 499.0 MASS(ESI(-)Spectrum):M - 517.1

[0226] Example 8: Synthesis of the salt represented by formula (I-34) Mix 0.96 parts of the compound represented by formula (I-34-b) and 10 parts of tetrahydrofuran. Then, after stirring at 23°C for 30 minutes, it is cooled to 5°C and 0.14 parts of sodium hydride are added. To the resulting mixture, 1.82 parts of the salt represented by formula (I-2-a) were added, and the mixture was incubated at 5°C for 3 minutes. The mixture was stirred for a certain amount of time. 6.30 parts of 1N hydrochloric acid were added to the resulting mixture, and then the temperature was raised to 23°C. The mixture was stirred at 23°C for 30 minutes. To the resulting mixture, 30 parts chloroform and 1 part deionized water were added. Five parts were added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. After concentrating the chamber, add 1.5 parts acetonitrile and tert-butylmethyl ester to the concentrated residue. Add 30 parts of the solution, stir at 23°C for 30 minutes, then remove the supernatant and concentrate. This yielded 1.09 parts of the salt represented by formula (I-34-c). The salt represented by formula (I-42-c) 0.90 parts of the salt, 1.20 parts of the salt represented by formula (I-440-d), and 20 parts of chloroform The mixture was added and stirred at 23°C for 3 hours. 15 parts of deionized water were added to the resulting reaction product. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. Io was added to the resulting organic layer. After adding 15 parts of decontaminated water and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated five times. After concentrating the resulting organic layer, acetonite was added to the concentration residue. Add 1.5 parts of lyl and 30 parts of tert-butyl methyl ether, and stir at 23°C for 30 minutes. After mixing, the supernatant is removed and the mixture is concentrated to obtain salt 1.0 represented by formula (I-34). I got 5 copies. MASS(ESI(+)Spectrum):M + 445.1 MASS(ESI(-)Spectrum):M - 517.1

[0227] Example 9: Synthesis of the salt represented by formula (I-498) Mix 2.46 parts of the compound represented by formula (I-498-b) and 10 parts of tetrahydrofuran. Combine the ingredients, stir at 23°C for 30 minutes, then cool to 5°C and add 0.14 parts of sodium hydride. Added. To the resulting mixture, 1.82 parts of the salt represented by formula (I-2-a) were added and heated at 5°C. The mixture was stirred for 3 hours. 6.30 parts of 1N hydrochloric acid were added to the resulting mixture, and then the temperature was raised to 23°C. The mixture was stirred at 23°C for 30 minutes. To the resulting mixture, 30 parts of chloroform and deionized water were added. 15 parts were added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. After concentrating the organic layer, add 1.5 parts acetonitrile and tert-butylmethyl methyl ester to the concentration residue. Add 30 parts of ether, stir at 23°C for 30 minutes, then remove the supernatant and concentrate. This yielded 1.69 parts of the salt represented by formula (I-498-c). Formula (I-498-c) 1.44 parts of the salt represented by formula (I-440-d), 1.20 parts of the salt represented by formula (I-440-d), and chloroform Add 20 parts of the solution and stir at 23°C for 3 hours. Add 15 parts of deionized water to the resulting reaction product. After adding the mixture and stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. Add 15 parts of deionized water, stir at 23°C for 30 minutes, then separate and remove the organic layer. This washing operation was repeated five times. After concentrating the resulting organic layer, acetone was added to the concentrated residue. Add 1.5 parts tonitrile and 30 parts tert-butyl methyl ether, and bake at 23°C for 30 minutes. After stirring for minutes, the supernatant is removed and concentrated to obtain the product represented by formula (I-498). 1.89 parts of salt were obtained. MASS(ESI(+)Spectrum):M + 732.8 MASS(ESI(-)Spectrum):M - 517.1

[0228] Example 10: Synthesis of the salt represented by formula (I-5) TIFF0007842065000142.tif79166 1.58 parts of the salt represented by formula (I-2-a), 1.0 parts of the compound represented by formula (I-2-b) Mix 0 parts of the mixture with 10 parts of dimethylformamide and stir at 23°C for 30 minutes. The resulting mixture Add 0.44 parts potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then further stir at 90°C. By stirring at °C for 3 hours, a mixture containing the salt represented by formula (I-2-c) was obtained. After cooling the mixture to 23°C, add 12 parts of a 5% oxalic acid aqueous solution and heat at 23°C for 30 minutes. After stirring for 1 minute, add 2.91 parts of the salt represented by formula (I-440-d) and leave at 23°C for 7 hours. The mixture was stirred. To the resulting reaction product, 30 parts chloroform and 30 parts deionized water were added. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. Ions were added to the resulting organic layer. Thirty parts of replacement water were added, and the mixture was stirred at 23°C for 30 minutes. After separation, the organic layer was removed. The washing procedure was repeated seven times. After the obtained organic layer was concentrated, acetonite was added to the concentrated residue. Add 1.5 parts of ruthone and 30 parts of tert-butylmethyl ether, and stir at 23°C for 30 minutes. Afterward, the supernatant is removed and the solution is concentrated to obtain 2.88 parts of the salt represented by formula (I-5). I obtained it. MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 517.1

[0229] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. These are referred to as "monomers (a1-1-3)" etc., according to their formula numbers. TIFF0007842065000143.tif3997

[0230] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) is used, and its molar ratio [monomer (a1-4-2):monomer (a1-1 -3): Mix the monomers (a1-2-6) in a ratio of 38:24:38. Furthermore, this monomer mixture contains methyl methyl in an amount equal to 1.5 times the total mass of all monomers. Isobutyl ketone was mixed. To the resulting mixture, azobisisobutyronite was added as an initiator. Add lyl so that it is 7 mol% of the total number of moles of all monomers. Polymerization was carried out by heating at 85°C for approximately 5 hours. Afterwards, p-True was added to the polymerization reaction solution. An aqueous solution of sulfonic acid was added, and after stirring for 6 hours, the mixture was separated. The resulting organic layer contained a large amount of n -By pouring it into heptane to precipitate the resin, filtering and recovering it, the weight-average molecular weight is approximately 5. 3 x 10 3 Resin A1 (polymer) was obtained in a yield of 78%. This resin A1 has the following composition It has a manufacturing unit. TIFF0007842065000144.tif29126

[0231] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) is used, and its molar ratio [monomer (a1-4-2):monomer (a1-1 -3): Mix the monomers (a1-2-6) in a ratio of 49:21:30. Furthermore, this monomer mixture contains methyl methyl in an amount equal to 1.5 times the total mass of all monomers. Isobutyl ketone was mixed. To the resulting mixture, azobisisobutyronite was added as an initiator. Add lyl so that it is 7 mol% of the total number of moles of all monomers. Polymerization was carried out by heating at 85°C for approximately 5 hours. Afterwards, p-True was added to the polymerization reaction solution. An aqueous solution of sulfonic acid was added, and after stirring for 6 hours, the mixture was separated. The resulting organic layer contained a large amount of n -By pouring it into heptane to precipitate the resin, filtering and recovering it, the weight-average molecular weight is approximately 5. 8×10 3 Resin A2 (polymer) was obtained in a yield of 84%. This resin A2 has the following composition It has a manufacturing unit. TIFF0007842065000145.tif29126

[0232] Synthesis Example 3 [Synthesis of Resin A3] As monomers, monomer (a1-4-2) and monomer (a1-2-6) are used, The molar ratio [monomer(a1-4-2):monomer(a1-2-6)] is 49:51. Mix them together, and then add to this monomer mixture, relative to the total mass of all monomers. Then, 1.5 times the mass of methyl isobutyl ketone was mixed in. To the resulting mixture, as an initiator, Azobisisobutyronitrile is added at 7 mol% relative to the total number of moles of all monomers. The mixture was added in this manner, and polymerization was carried out by heating it at 85°C for about 5 hours. After that, the heavy A p-toluenesulfonic acid aqueous solution was added to the reaction mixture, stirred for 6 hours, and then separated. The prepared organic layer is poured into a large amount of n-heptane to precipitate the resin, which is then filtered and recovered. The weight-average molecular weight is approximately 5.9 × 10⁻⁶. 3 Resin A3 (polymer) was obtained in a yield of 88%. The resin A3 has the following structural units. TIFF0007842065000146.tif2791

[0233] <Preparation of the resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture contained fluorine with a pore size of 0.2 μm. The resist composition was prepared by filtering through a resin filter. [Table 2]

[0234] <Resin> A1-A3, Resin A1-Resin A3 <Salt (I)> I-2: Salt represented by formula (I-2) I-3: Salt represented by formula (I-3) I-5: Salt represented by formula (I-5) I-14: Salt represented by formula (I-14) I-34: Salt represented by formula (I-34) I-437: Salt represented by formula (I-437) I-438: Salt represented by formula (I-438) I-440: Salt represented by formula (I-440) I-448: Salt represented by formula (I-448) I-498: Salt represented by formula (I-498) <Acid Generator> IX-1: Salt represented by formula (IX-1) (WO2017 / 135003 pamphlet) (Synthesized according to the examples) TIFF0007842065000148.tif2669<Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007842065000149.tif4349<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0235] (Electron beam exposure evaluation of resist compositions) A 6-inch silicon wafer is subjected to hexamethyldisilaza on a direct hot plate. The silicon wafer was treated at 90°C for 60 seconds using a solvent. The resist composition was then applied to this silicon wafer. The layer was spin-coated to a thickness of 0.04 μm. Then, direct hot plated... On the grid, the composition layer was formed by pre-baking for 60 seconds at the temperature shown in the "PB" column of Table 2. A composition layer formed on the surface is subjected to electron beam lithography (ELS-F1 manufactured by Elionix Co., Ltd.). Using "25 125 keV", the exposure amount is changed in steps to create a contact hole pattern. (Hole pitch 40nm / Hole diameter 17nm) was directly drawn. After exposure, post-exposure is performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds. Perform jar baking and further perform paddle development for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern.

[0236] In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask becomes 17 nm was defined as the effective sensitivity.

[0237] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a mask having a hole diameter of 17 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The average hole diameters of the patterns formed with masks having a hole diameter of 55 nm within the same wafer were measured at 400 locations and used as the population to calculate the standard deviation. The results are shown in Table 3. The numerical values in parentheses indicate the standard deviation (nm).

Table 3

Industrial Applicability

[0238] Since the resist composition of the present invention can obtain a resist pattern having good CD uniformity (CDU), it is suitable for fine processing of semiconductors and is extremely useful industrially. ​​​

Claims

1. A resist composition comprising an acid generator containing a salt represented by formula (I), and a resin containing a structural unit having an acid-unstable group and a structural unit represented by formula (a2-A). [In formula (I), R １ , R ２ and R ３ Each of these independently represents either an iodine atom or a fluorine atom. R ４ 、 R ５ 、 R ６ 、 R ７ 、 R ８ and R ９ each independently represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms, and -CH 2 - in the haloalkyl group and the alkyl group may be replaced by -O- or -CO-. X １ , X ２ and X ３ Each of these independently represents either an oxygen atom or a sulfur atom. m1 represents either 1 or 2, and when m1 is 2, the bases within the parentheses may be the same or different from each other. m2 represents either 0 or 1. m3 represents either 0 or 1. m4 represents an integer from 0 to 4, and when m4 is 2 or greater, multiple R ４ They may be identical or different from one another. 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 2, and when m7 is 2, multiple R ７ They may be identical or different from one another. m8 represents an integer from 0 to 2, and when m8 is 2, multiple R ８ They may be identical or different from one another. m9 represents an integer from 0 to 2, and when m9 is 2, multiple R ９ They may be identical or different from one another. However, 1 ≤ m1 + m7 ≤ 4, 0 ≤ m2 + m8 ≤ 3, and 0 ≤ m3 + m9 ≤ 3. AI － This represents the anion expressed by formula (I-A). [In formula (IA), Q １ and Q ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L １ This represents a base that can be expressed by any of the formulas (b1-1) to (b1-3). Y １ This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents, and the alicyclic hydrocarbon group contains -CH ２ - is -O-, -SO ２ It may be replaced with - or -CO-. [In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the saturated hydrocarbon group contains -CH ２ The dash may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b5 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the saturated hydrocarbon group contains -CH ２ The dash may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the saturated hydrocarbon group contains -CH ２ The dash may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less. * and ** represent connection sites, where * is -Y １ This represents the connection point with [the other element]. [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-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.

2. X １ , X ２ and X ３ The resist composition according to claim 1, wherein is an oxygen atom.

3. The resist composition according to claim 1 or 2, wherein the structural unit having an acid-unstable group comprises at least one of the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2). [In formulas (a1-1) and (a1-2), L a1 and L a2 These are, independently, -O- or *-O- (CH ２ ) k1 -CO-O- represents -CO-O-, k1 is an integer from 1 to 7, and * represents the association with -CO-. R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining 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.

4. The resist composition according to any one of claims 1 to 3, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

5. (1) A step of applying the resist composition according to any one of claims 1 to 4 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 method for manufacturing a resist pattern, comprising the step of developing the composition layer after heating.

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