JP2018115158A - Salt, acid generator, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a salt capable of producing a resist pattern with good line edge roughness, a resist composition containing the same, and a method for producing a resist pattern.SOLUTION: The salt is represented by formula (I) [where Qand Q, and Rand Reach independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group, or the like; z represents an integer of 0-6; Xrepresents *-CO-O-, *-O-CO-, or the like; Aand Aeach independently represent a divalent hydrocarbon group which may have a substituent; Rand Reach independently represent a hydrogen atom or a saturated hydrocarbon group; Rrepresents a hydroxy group or a group represented by formula (aa1) or formula (aa2); R-Reach independently represent an alkyl group, an alicyclic hydrocarbon group, or the like; na represents 0 or 1; Rand Reach independently represent a hydrogen atom or a hydrocarbon group; Rrepresents a hydrocarbon group; and Zrepresents an organic cation].SELECTED DRAWING: None

Description

  The present invention relates to a salt, an acid generator, a resist composition, a method for producing a resist pattern using the resist composition, and the like.

Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generator.
Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator.
Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator.

JP 2012-229206 A JP 2012-234155 A JP 2007-145822 A

  An object of the present invention is to provide a salt that improves the line edge roughness (LER) of a resist pattern.

The present invention includes the following inventions.
[1] A salt represented by the formula (I).
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, * —O—CO—O— or * —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ) Represents the bonding position with (Q ² ).
A ¹ and A ² each independently represent a divalent hydrocarbon group having 2 to 36 carbon atoms which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is —O— , —S—, —C (═O) —, or —SO ₂ — may be substituted.
R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents a hydroxy group, a group represented by the formula (aa1) or the formula (aa2).
(In the formula (aa1),
R ¹² , R ¹³ , and R ¹⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof, or R ¹² and R ¹³ Are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 1.
In formula (aa2),
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ¹⁶ and R ¹⁷ are mutually A divalent heterocyclic group having 3 to 20 carbon atoms is formed together with a carbon atom and an oxygen atom to which they are bonded, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is -O- or -S- may be substituted. )
Z ⁺ represents an organic cation. ]
[2] The salt according to [1], wherein X ¹ is * —CO—O—.
[3] A ¹ and A ² are each independently a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms and an alkane having 1 to 18 carbon atoms. The salt according to [1] or [2], which is a divalent hydrocarbon group formed from a diyl group.
[4] The salt according to any one of [1] to [3], wherein R ⁵ is a hydrogen atom.
[5] An acid generator containing the salt according to any one of [1] to [4].
[6] A resist composition comprising the acid generator according to [5] and a resin containing a structural unit having an acid labile group.
[7] The resist composition according to [6], further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator.
[8] (1) The process of apply | coating the resist composition as described in [6] or [7] on a board | substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer,
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  According to the present invention, a resist pattern can be manufactured with good line edge roughness (LER).

In this specification, the “(meth) acrylic monomer” has a structure of “CH ₂ ═CH—C (═O) —” or “CH ₂ ═C (CH ₃ ) —C (═O) —”. Means at least one of the monomers it has. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively. Notations such as “(meth) acryloyl” have the same meaning.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

[Salt represented by formula (I) and anion constituting it]
The salt of the present invention is a salt represented by the formula (I) (hereinafter sometimes referred to as “salt (I)”).
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, * —O—CO—O— or * —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ) Represents the bonding position with (Q ² ).
A ¹ and A ² each independently represent a divalent hydrocarbon group having 2 to 36 carbon atoms which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is —O— , —S—, —C (═O) —, or —SO ₂ — may be substituted.
R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents a hydroxy group, a group represented by the formula (aa1) or the formula (aa2).
(In the formula (aa1),
R ¹² , R ¹³ , and R ¹⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof, or R ¹² and R ¹³ Are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 1.
In formula (aa2),
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ¹⁶ and R ¹⁷ are mutually A divalent heterocyclic group having 3 to 20 carbon atoms is formed together with a carbon atom and an oxygen atom to which they are bonded, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is -O- or -S- may be substituted. )
Z ⁺ represents an organic cation. ]

As the perfluoroalkyl group for Q ¹ , Q ² , R ¹ and R ² , a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group , Perfluoropentyl group, perfluorohexyl group and the like.
Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.
R ¹ and R ² are each independently preferably a hydrogen atom or a fluorine atom.
z is preferably 0.

X ¹ is * —CO—O— or * —O—CO—O— (* represents a bond with C (R ¹ ) (R ² ) or C (Q ¹ ) (Q ² )). Preferably there is.

Examples of the divalent hydrocarbon group having 2 to 36 carbon atoms of A ¹ and A ² include alkanediyl group, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and divalent aromatic carbon group. A hydrogen group etc. are mentioned, The bivalent hydrocarbon group which combined 2 or more types among these groups may be sufficient.

Examples of the alkanediyl group in A ¹ and A ² include an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a 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, A linear alkanediyl group such as a 12-diyl group;
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- Examples thereof include branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.
Examples of the monocyclic divalent alicyclic saturated hydrocarbon group include cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1, And cycloalkanediyl groups such as a 5-diyl group.
Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6- A diyl group etc. are mentioned.
Examples of the divalent aromatic hydrocarbon group include phenylene group, naphthylene group, anthrylene group, p-methylphenylene group, p-tert-butylphenylene group, p-adamantylphenylene group, tolyl group, xylylene group, cumenylene group, mesitylene group. Group, biphenylene group, phenanthrylene group, 2,6-diethylphenylene group, aryl group such as 2-methyl-6-ethylphenylene group, and the like.
As a bivalent hydrocarbon group combining two or more types, a divalent hydrocarbon group formed from a C3-C18 alicyclic hydrocarbon group and a C1-C18 alkanediyl group (- Cycloalkanediyl-alkanediyl-, -alkanediyl-cycloalkanediyl-alkanediyl-), a divalent group formed from an aromatic hydrocarbon group having 6 to 18 carbon atoms and an alkanediyl group having 1 to 18 carbon atoms. A hydrocarbon group (-alkanediyl-aromatic hydrocarbon group-) and the like.

The substituent having a hydrocarbon group of A ¹ and ^{A 2,} hydroxy group, a cyano group, a carboxy group, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, 2 to 13 carbon atoms Examples include an alkylcarbonyloxy group and a group obtained by combining two or more of these groups.
Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
The divalent hydrocarbon group having 2 to 36 carbon atoms represented by A ¹ and A ² may have one substituent or a plurality of substituents.

—CH ₂ — contained in the divalent hydrocarbon group having 2 to 36 carbon atoms of A ¹ and A ² is replaced by —O—, —S—, —C (═O) — or —SO ₂ —. May be.
When the divalent hydrocarbon group having 2 to 36 carbon atoms represented by A ¹ and A ² has a substituent, or —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —C When (═O) — or —SO ₂ — is substituted, the number of carbons before the substitution is defined as the number of carbons of the hydrocarbon group.

The divalent hydrocarbon group having 2 to 36 carbon atoms represented by A ¹ is a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms. is preferably a divalent hydrocarbon group formed by group and the alkanediyl group having 1 to 18 carbon atoms, a cyclohexyl-diyl group, adamantane-diyl ^{group, * 1A 11 -X 1A -A 12} - * 2 a group represented ^{by, * 1A 13 -X 1A - *} 2 , a group represented ^{by, * 1-X 1A -A 14} - is more preferably a group represented by * 2. In particular, divalent carbon atoms 2 to 36 represented by where A ¹ and A ² hydrocarbon group is preferably one containing an alicyclic hydrocarbon group having a polycyclic, A ¹ and A ² are both polycyclic Those containing an alicyclic hydrocarbon group are more preferred.
X ^1A represents a C 3-18 divalent alicyclic hydrocarbon group, and is preferably a cyclohexanediyl group or an adamantanediyl group.
A ¹¹ , A ¹² , A ¹³ and A ¹⁴ each independently represent an alkanediyl group having 1 to 17 carbon atoms. A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are preferably each independently an alkanediyl group having 1 to 6 carbon atoms.
* 1 represents a bond to ^{X 1,} * 2 represents a bond to -O-.

The divalent hydrocarbon group having ² to 36 carbon atoms of A ² is a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms and carbon. It is preferably a divalent hydrocarbon group formed from an alkanediyl group of 1 to 18, represented by cyclohexyldiyl group, adamantanediyl group, * 3-A ¹⁵ -X ^11A -A ^16- * 4. that ^{group, * 3-a 17 -X 11A} - * 4 , a group represented ^{by, * 3-X 11A -A 18} - is more preferably a group represented by * 4.
X ^11A represents a C 3-18 divalent alicyclic hydrocarbon group.
A ¹⁵ , A ¹⁶ , A ¹⁷ and A ¹⁸ each independently represent an alkanediyl group having 1 to 17 carbon atoms. A ¹⁵ , A ¹⁶ , A ¹⁷ and A ¹⁸ are preferably each independently an alkanediyl group having 1 to 6 carbon atoms.
* 3 represents a bond with —O—, and * 4 represents a bond with R ⁵ .

Examples of the saturated hydrocarbon group having 1 to 6 carbon atoms of R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; and a group formed by combining these.
R ³ and R ⁴ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and one is a hydrogen atom and the other is a methyl group. Further preferred.

Examples of the alkyl group of R ^{12 to} R ¹⁴ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
The alicyclic hydrocarbon group for R ^{12 to} R ¹⁴ may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). The alicyclic hydrocarbon group of R ^{12 to} R ¹⁴ is preferably an alicyclic hydrocarbon group having 3 to 16 carbon atoms.
Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group. Can be mentioned.

Examples of —C (R ¹² ) (R ¹³ ) (R ¹⁴ ) in the case where R ¹² and R ¹³ are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

  Examples of the group represented by the formula (aa1) include a tert-butyl group, a 2-alkyladamantan-2-yl group, a 1-alkylcyclopentan-1-yl group, and a 1-alkylcyclohexane-1-yl group. It is done.

Examples of the hydrocarbon group of R ^{15 to} R ¹⁷ include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
The aromatic hydrocarbon group includes phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the combined group include a group obtained by combining the above-described alkyl group and an alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aryl-cyclohexyl group such as a phenylcyclohexyl group.
Examples of the divalent heterocyclic group formed together with the carbon atom and oxygen atom to which R ¹⁶ and R ¹⁷ are bonded to each other include the following groups. * Represents a bond.
X represents an oxygen atom or a sulfur atom.
Of R ¹⁵ and R ¹⁶ , at least one is preferably a hydrogen atom.

Examples of the group represented by the formula (aa2) include the following groups. * Represents a bond.

Examples of the anion in the salt (I) include anions represented by the following formulas (Ia-1) to (Ia-50). Among them, formula (Ia-1) to formula (Ia-11), formula (Ia-13) to formula (Ia-20), formula (Ia-22), formula (Ia-23) to formula (Ia-33) An anion represented by formula (Ia-35) to formula (Ia-42), formula (Ia-44), formula (Ia-49) to formula (Ia-58), Formula (Ia-2), Formula (Ia-13) to Formula (Ia-16), Formula (Ia-23), Formula (Ia-24), Formula (Ia-35) to Formula (Ia-38), Formula An anion represented by (Ia-49) to formula (Ia-58) is more preferable.

Z ⁺ is preferably an organic onium cation.
Examples of the organic onium cation include an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation, preferably an organic sulfonium cation or an organic iodonium cation, and more preferably an arylsulfonium cation. It is.
Among these, a cation represented by any one of the formulas (b2-1) to (b2-4) (hereinafter may be referred to as “cation (b2-1)” or the like depending on the formula number) is preferable.
[In Formula (b2-1)-Formula (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group which may be substituted is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may together form a ring containing a sulfur atom to which they are bonded, and —CH ₂ — contained in the ring is —O— or —S (═O) —. Alternatively, -C (= O)-may be substituted.
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represents an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may together form a ring containing a sulfur atom to which they are bonded, and —CH ₂ — contained in the ring is —O—, —S (═O) —. Alternatively, -C (= O)-may be substituted.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the aliphatic hydrocarbon. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkoxy group having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may together form a ring containing —CH—C (═O) — to which they are bonded, and —CH ₂ — contained in the ring is —O— , -S (= O)-or -C (= O)-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more The plurality of R ^b15 may be the same or different. When r2 is 2 or more, the plurality of R ^b16 may be the same or different. When s2 is 2 or more, the plurality of R ^b17 is ^They may be the same or different, and when t2 is 2 or more, the plurality of R ^b18 may be the same or different. ]

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable.
Examples of the cation (b2-1) include the following cations.

Examples of the cation (b2-2) include the following cations.

Examples of the cation (b2-3) include the following cations.

Examples of the cation (b2-4) include the following cations.
Among them, formulas (b2-c-1), (b2-c-10), (b2-c-12), (b2-c-14), (b2-c-27), (b2-c-30) And a cation represented by (b2-c-31) is preferable.

<Specific examples of salt (I)>
The salt (I) is a combination of the above-described anion and organic cation. These anions and organic cations can be arbitrarily combined. Specific examples of the salt (I) are shown in the following table.

In the following table, salt (I-1) is a salt shown below.

  Among them, the salt (I) is a salt (I-1), a salt (I-2), a salt (I-9), a salt (I-23), a salt (I-24), a salt (I-49), Salt (I-50), salt (I-51), salt (I-52), salt (I-73), salt (I-74), salt (I-99), salt (I-100), salt (I-101), salt (I-102), salt (I-123), salt (I-124), salt (I-149), salt (I-150), salt (I-151), salt ( I-152), salt (I-173), salt (I-174), salt (I-199), salt (I-200), salt (I-201), salt (I-202), salt (I -223), salt (I-224), salt (I-249), salt (I-250), salt (I-251), salt (I-252), salt (I-273), salt (I- 274), salt (I-299), salt (I-300), salt (I-3) 1), salt (I-302), salt (I-323), salt (I-324), salt (I-349), salt (I-350) and salt (I-351) to salt (I-406) ) Is preferred.

<Method for producing salt (I)>
In the salt (I), R ⁵ is a group represented by the formula (aa2) (a salt represented by the formula (I1)), for example, a salt represented by the formula (I1-a), The compound represented by (I1-b) can be obtained by reacting in a solvent in the presence of a catalyst.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ¹⁵ , R ¹⁶ , R ¹⁷ , A ¹ , A ² , z and Z ⁺ represent the same meaning as described above. R ^{15 ′} represents a group obtained by removing a hydrogen atom from R ¹⁵ . ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the catalyst include camphorsulfonic acid or a salt represented by the following.

Examples of the compound represented by the formula (I1-b) include a compound represented by the following formula.

The salt represented by the formula (I1-a) includes, for example, a salt represented by the formula (I1-c) and a compound represented by the formula (I1-d) in a solvent in the presence of a catalyst. , Can be obtained by reacting.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ³ , R ¹⁵ , R ^{15 ′} , R ¹⁶ , z, A ¹ , A ² and Z ⁺ represent the same meaning as described above. R ^4'represents a group obtained by removing a hydrogen atom from ^{R 4.} ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the catalyst include salts represented by the following.

Examples of the compound represented by the formula (I1-d) include a compound represented by the following formula.

Examples of the salt represented by the formula (I1-c) include a salt represented by the formula (I1-e) and a compound represented by the formula (I1-f) in a solvent in the presence of a catalyst. It can be obtained by reacting.
^{Wherein, Q 1, Q 2, R} 1, R 2, R 3, R 4' is, z, X ^1, A ¹ and ^{Z +} are as defined above. X ^{1 ′} represents a group obtained by removing an oxygen atom at the A ¹ bond position from X ¹ . ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the catalyst include carbonyldiimidazole and potassium hydroxide.

Examples of the salt represented by the formula (I1-e) include the following salts, and the methods described in JP2007-197718A and JP2012-193170A are referred to. Can be manufactured.
Examples of the compound represented by the formula (I1-f) include a compound represented by the following formula.

In the salt (I), R ⁵ is a group represented by the formula (aa1) (a salt represented by the formula (I2)), for example, a salt represented by the formula (I2-a), The compound represented by (I2-b) can be obtained by reacting in a solvent in the presence of a base.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ¹² , R ¹³ , R ¹⁴ , A ¹ , A ² , z and Z ⁺ represent the same meaning as described above. ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the base include triethylamine, pyridine, dimethylaminopyridine and the like.
Examples of the compound represented by the formula (I2-b) include a compound represented by the following formula.

The salt represented by the formula (I2-a) includes, for example, a salt represented by the formula (I1-c) and a compound represented by the formula (I2-d) in a solvent in the presence of a catalyst. , Can be obtained by reacting.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ³ , R ¹⁵ , R ^{15 ′} , R ¹⁶ , z, A ¹ , A ² and Z ⁺ represent the same meaning as described above. R ^4'represents a group obtained by removing a hydrogen atom from ^{R 4.} ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the catalyst include salts represented by the following.

Examples of the compound represented by the formula (I2-d) include a compound represented by the following formula.

In the salt (I), X ¹ is * —CO—O—, and R ⁵ is a group represented by the formula (aa2) (salt represented by the formula (I3)). It can be obtained by reacting the salt represented by (I3-a) and the compound represented by formula (I3-b) in a solvent in the presence of a catalyst.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , A ¹ , A ² , z and Z ⁺ represent the same meaning as described above. R ^{15 ′} represents a group obtained by removing a hydrogen atom from R ¹⁵ . ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the catalyst include camphorsulfonic acid or a salt represented by the following.

Examples of the salt represented by the formula (I3-a) include a salt represented by the formula (I3-c) and a compound represented by the formula (I1-d) in a solvent in the presence of a catalyst. , Can be obtained by reacting.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ⁴ , R ³ , R ¹⁵ , R ^{15 ′} , R ¹⁶ , z, A ¹ , A ² and Z ⁺ have the same meaning as above] Represents. R ^4'represents a group obtained by removing a hydrogen atom from ^{R 4.} ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.
Examples of the catalyst include salts represented by the following.

The salt represented by the formula (I3-c) is obtained by, for example, reacting a salt represented by the formula (I3-e) with a compound represented by the formula (I1-f) in a solvent. Can be obtained.
^{Wherein, Q 1, Q 2, R} 1, R 2, R 3, R 4, R 4', z, A 1 and ^{Z +} are as defined above. ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform and acetonitrile.

Examples of the salt represented by the formula (I1-e) include compounds represented by the following.

In the salt (I), a salt in which X ¹ is * —CO—O— and R ⁵ is a hydroxy group (a salt represented by the formula (I4)) is represented by, for example, the formula (I3). The salt can be obtained by reacting in a solvent in the presence of an acid catalyst.
[Wherein, Q ¹ , Q ² , R ¹ , R ² , R ³ , R ⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , A ¹ , A ² , z and Z ⁺ represent the same meaning as described above. ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the solvent include chloroform, acetonitrile, methanol and the like.
Examples of the acid catalyst include hydrochloric acid and p-toluenesulfonic acid.

[Acid generator]
The acid generator of the present invention contains a salt (I). In the acid generator of the present invention, the salt (I) may be contained alone, or two or more kinds may be contained.
The acid generator of the present invention may contain an acid generator known in the resist field other than the salt (I) (hereinafter sometimes referred to as “acid generator (B)”).
In the acid generator, the ratio of the content of the salt (I) and the acid generator (B) (mass ratio; salt (I): acid generator (B)) is usually 100: 0 to 0: 100 or The ratio is 1:99 to 99: 1, preferably 2:98 to 98: 2, more preferably 5:95 to 95: 5, and still more preferably 10:90 to 90:10.

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of the acid generators (B) of the resist composition of the present invention may be used. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include ionic acid generators comprising a combination of a known cation and a known anion, and onium salts containing an onium cation (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) are representative. Is. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. And the acid generators described in JP2013-68914A, JP2013-3155A, JP2013-11905A, and the like. Moreover, you may use the compound manufactured by the well-known method.

The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).
[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ —, or —CO—.
Z1 ⁺ represents an organic cation. ]

^Examples of the perfluoroalkyl group represented by Q ^b1 and Q ^b2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and A perfluorohexyl group etc. are mentioned.
Q ^b1 and Q ^b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and these It may be a group formed by combining two or more of the groups.
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-diyl group Alkanediyl group;
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- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced by —O— or —CO— include, for example, formula (b1-1) to formula (b1-3) Or a group represented by any of the above. In formulas (b1-1) to (b1-3) and formulas (b1-4) to (b1-11) which are specific examples thereof, * represents a binding site with -Y.

[In the formula (b1-1),
L ^b2 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 substituted with a fluorine atom.
L ^b3 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 substituted with a fluorine atom or a hydroxy group, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—.
However, the total number of carbon atoms of L ^b2 and L ^b3 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 substituted with 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 substituted with a fluorine atom or a hydroxy group, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—.
However, the total number of carbon atoms of L ^b4 and L ^b5 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 substituted with 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 substituted with a fluorine atom or a hydroxy group, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In the formulas (b1-1) to (b1-3), when —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O— or —CO—, the number of carbons before the replacement is changed to the saturated carbon group. The carbon number of the hydrogen group.
Examples of the divalent saturated hydrocarbon group include the same divalent saturated hydrocarbon group of L ^b1.

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.

The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced by —O— or —CO— is represented by the formula (b1-1) or the formula (b1-3). Preferred are the groups

Examples of formula (b1-1) include groups represented by formula (b1-4) to formula (b1-8).
[In the formula (b1-4),
L ^b8 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 substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
^Lb9 represents a C1-C20 bivalent saturated hydrocarbon group.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a C1-C21 divalent saturated hydrocarbon group.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b13 to} L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a C1-C18 divalent saturated hydrocarbon group.
L ^b17 represents a C1- ^C18 divalent saturated hydrocarbon group.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b16 to} L ^b18 is 19 or less. ]

L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a C 1-8 divalent saturated hydrocarbon group.
L ^b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 is preferably a ^C 1-6 divalent saturated hydrocarbon group.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

Examples of formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11), respectively.
In formula (b1-9),
L ^b19 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 substituted with a fluorine atom.
L ^b20 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 is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, L ^b24, the total number of carbon atoms of L ^b25 and L ^b26 is 21 or less.

  In formulas (b1-9) to (b1-11), when a hydrogen atom contained in a saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution is changed to the saturated hydrocarbon group. The number of carbons.

  Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

Examples of the group represented by the formula (b1-4) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-5) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-6) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-7) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-8) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-2) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-9) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-10) include the following.
(* Represents a binding site with Y)

Examples of the group represented by the formula (b1-11) include the following.
(* Represents a binding site with Y)

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38), and formula (Y39) to formula (Y40). It is done.
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced by —O—, —S (O) ₂ — or —CO—, the number may be one, or two or more. Good. Examples of such a group include groups represented by formula (Y12) to formula (Y35).

The alicyclic hydrocarbon group represented by Y is preferably a group represented by any one of formulas (Y1) to (Y20), formula (Y30), and formula (Y31), and more preferably a formula. (Y11), Formula (Y15), Formula (Y16), Formula (Y20), Formula (Y30), Formula (Y31), Formula (Y39), or Group represented by Formula (Y40), and more preferably Formula It is a group represented by (Y11), formula (Y15), formula (Y30), formula (Y39) or formula (Y40).
When the alicyclic hydrocarbon group represented by Y is a spiro ring containing an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39) to formula (Y40), etc., two oxygen atoms The alkanediyl group in between preferably has one or more fluorine atoms. Of the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

Examples of the substituent for the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, or-( CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms). Represents a hydrocarbon group, and ja represents an integer of 0 to 4).
Examples of the substituent for the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, and an alicyclic group having 3 to 16 carbon atoms. A hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, a glycidyloxy group or-( CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms). Represents a hydrocarbon group, and ja represents an integer of 0 to 4. —CH ₂ — contained in an alkyl group having 1 to 16 carbon atoms and an alicyclic hydrocarbon group having 3 to 16 carbon atoms is , -O-, -S (O) ₂ -or -CO- Good).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and the like.
The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.
The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group (tolyl group) having a chain hydrocarbon group having 1 to 18 carbon atoms. Xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and alicyclic hydrocarbon group having 3 to 18 carbon atoms. Aromatic hydrocarbon groups (p-adamantylphenyl group, p-cyclohexylphenyl group, etc.) are preferred.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, and nonyl. Group, decyl group, undecyl group, dodecyl group and the like.
Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of Y include the following.

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, —CH ₂ — adjacent to Y in L ^b1 is —O—. Alternatively, it is preferably replaced by -CO-.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and the alicyclic carbonization —CH ₂ — constituting the hydrogen group or adamantyl group may be replaced by —CO—, —S (O) ₂ — or —CO—. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by the following.

  As an anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-54) [hereinafter referred to as an anion (B1-A -1) ". ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula It is represented by any one of (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-54). An anion is more preferable.

Here, R ^{i2 to} R ⁱ⁷ are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is formed by, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. More preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ^A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ^b1 and Q ^b2 represent the same meaning as described above.
Specific examples of the anion in the salt represented by the formula (B1) include anions described in JP 2010-204646 A.

Preferable examples of the anion in the salt represented by the formula (B1) include anions each represented by the formula (B1a-1) to the formula (B1a-30).

  Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) To (B1a-30) are preferred.

Z1 ⁺ in the formula (B1) includes the same cation as in the salt (I).

  The acid generator (B1) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably an anion represented by any one of formulas (B1a-1) to (B1a-3) and (B1a-7) to (B1a-16), and a cation ( and a combination with b2-1) or a cation (b2-3).

Examples of the acid generator (B1) include organic sulfonic acid-organic sulfonium salts and the like, and examples thereof include acid generation described in JP2013-68914A, JP2013-3155A, and JP2013-11905A. Agents and the like. Specific examples include those represented by any one of formulas (B1-1) to (B1-48). As an acid generator (B), Formula (B1-1)-Formula (B1-3), Formula (B1-5)-Formula (B1-7), Formula (B1-11)-Formula (B1-14) , Formula (B1-17), Formula (B1-20) to Formula (B1-26), Formula (B1-29), Formula (B1-31) to Formula (B1-48) Is particularly preferred.

[Resist composition]
The resist composition of the present invention contains a resin having an acid labile group (hereinafter sometimes referred to as “resin (A)”) and the above-described acid generator containing salt (I). Here, the “acid labile group” has a leaving group, the leaving group is eliminated by contact with an acid, and the structural unit has a hydrophilic group (for example, a hydroxy group or a carboxy group). Means a group that converts to
The resist composition preferably further contains a quencher (hereinafter sometimes referred to as “quencher (C)”), and preferably contains a solvent (hereinafter sometimes referred to as “solvent (E)”). .

<Acid generator>
In the resist composition of the present invention, the content of the salt (I) is preferably 1 to 20% by mass and more preferably 2 to 15% by mass with respect to the resin (A).
The acid generator (B) may contain 1 type independently, and may contain 2 or more types.
It is preferable that content of an acid generator (B) is 1-20 mass% with respect to resin (A), and it is more preferable that it is 3-15 mass%.

<Resin (A)>
The resin (A) has a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no halogen atom and no acid labile group (hereinafter sometimes referred to as “structural unit (s)”), structural unit (a1), and Structural units other than the structural unit (s) (for example, the structural unit (a4) having a halogen atom, the structural unit (a5) having a non-leaving hydrocarbon group, the structural unit (a6) having a carboxy group, and decomposed by exposure. And other structural units derived from monomers known in the art, and the like.

<Structural unit (a1)>
The “acid labile group” has a leaving group, and the leaving group is eliminated by contact with an acid, and the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means group.
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”).
The acid labile group contained in the resin (A) is preferably the group (1) and / or the group (2).
[In the formula (1), R ^{a1 to} R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination of these, or R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma and na each independently represents 0 or 1, and at least one of ma and na represents 1.
* Represents a bond. ]
[In Formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and the hydrocarbon group and the divalent —CH ₂ — contained in the ring group may be replaced by —O— or —S—.
X represents an oxygen atom or a sulfur atom.
na ′ represents 0 or 1.
* Represents a bond. ]

^Examples of the alkyl group represented by R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). Carbon number of the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably 3 to 16.
Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include, for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl An ethyl group etc. are mentioned.
Preferably, ma is 0 and na is 1.
Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
The aromatic hydrocarbon group includes phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the combined group include a group obtained by combining the above-described alkyl group and an alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aryl-cyclohexyl group such as a phenylcyclohexyl group.
^{Examples of the} divalent heterocyclic group formed together with the carbon atom and X to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other and X include the following groups. * Represents a bond.
At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.
na ′ is preferably 0.

The group represented by the formula (1) is a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, ma = 0, na = 1, preferably tert-butoxycarbonyl Group), 2-alkyladamantan-2-yloxycarbonyl group (in formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded are adamantyl groups, R ^a3 is an alkyl group, ma = 0, na = 1 ) And 1- (adamantan-1-yl) -1-alkylalkoxycarbonyl group (in formula (1), R ^a1 and R ^a2 are alkyl groups, R ^a3 is an adamantyl group, ma = 0, na = 1), etc. Specific examples include the following groups. * Represents a bond.

Specific examples of the group represented by the formula (2) include the following groups. * Represents a bond.

  The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, more preferably a (meth) acrylic monomer having an acid labile group.

  Among the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. If the resin (A) having a structural unit derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter referred to as the structural unit (a1-0)). The structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)) or the structural unit represented by the formula (a1-2) (hereinafter, And may be referred to as a structural unit (a1-2).). These may be used alone or in combination of two or more.
[In Formula (a1-0), Formula (a1-1) and Formula (a1-2),
L ^a01 , L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents any integer of 1 to 7, and * represents It represents a bond with —CO—.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof.
R ^a6 and R ^a7 each independently represent 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 of 0 to 14.
n1 represents any integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ]

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (where k01 is preferably an integer of 1 to 4, more preferably Is 1.), more preferably an oxygen atom.
R ^a02 , R ^a03 , R ^a04 , R ^a6, R ^a7 , the alkyl group, the alicyclic hydrocarbon group, and the combination thereof are the same as those ^exemplified for R ^{a1 to} R ^a3 in formula (1). Groups.
The carbon number of the alkyl group of R ^a02 , R ^a03 and R ^a04 is preferably 1 to 6, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
The carbon number of the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 3-8, more preferably 3-6.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has 18 or less total carbon atoms in combination of the alkyl group and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.
The carbon number of the alkyl group in R ^a6 and R ^a7 is preferably 1 to 6, more preferably a methyl group, an ethyl group, or an isopropyl group, and still more preferably an ethyl group or an isopropyl group.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As the structural unit (a1-0), for example, a structural unit represented by any one of formulas (a1-0-1) to (a1-0-12) and a methyl group corresponding to R ^a01 can be a hydrogen atom. The substituted structural unit is mentioned, The structural unit represented by either the formula (a1-0-1)-a formula (a1-0-10) is preferable.

As a monomer which introduce | transduces structural unit (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among them, a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) and a structural unit in which a methyl group corresponding to R ^a4 is replaced with a hydrogen atom are preferable. -1-1)-the structural unit represented by any one of formula (a1-1-4) is more preferable.

As the structural unit (a1-2), the structural unit represented by any one of the formulas (a1-2-1) to (a1-2-6) and the methyl group corresponding to R ^a5 were replaced with hydrogen atoms. Examples of the structural unit include formula (a1-2-2), formula (a1-2-5), and formula (a1-2-6).

  When the resin (A) includes the structural unit (a1-0) and / or the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is the total structure of the resin (A). It is 10-95 mol% normally with respect to a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

As the structural unit (a1) having a group represented by the group (2), a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”). Can be mentioned.
[In the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ^a33 may be the same as or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other And C—O to which they are bonded to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group is —O— Alternatively, it may be replaced by -S-. ]

^Examples of the alkyl group for R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
Examples of the halogen atom for R ^a32 and R ^a33 include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,1. 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -A perfluorohexyl group etc. are mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
The R ^a34 and R ^a35, include the same groups as R ^{a1 'and} R ^a2' of formula (2).
^Ra36 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. It is done.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
As la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group.
The hydrocarbon group for R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. It is a group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. When the aromatic hydrocarbon group in R ^a36 has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

Examples of the monomer for deriving the structural unit (a1-4) include monomers described in JP 2010-204646 A, preferably formula (a1-4-1) to formula (a1-4-7). And monomers represented by formulas (a1-4-1) to (a1-4-5) are more preferred.

  When resin (A) has a structural unit (a1-4), it is preferable that the content rate is 10-95 mol% with respect to the sum total of all the structural units of resin (A), 15-90 More preferably, it is mol%, and further preferably 20-85 mol%.

As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (2), a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”) Is also included).
In formula (a1-5),
R ^a8 represents a C 1-6 alkyl group optionally having a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a1 represents a single bond or * — (CH ₂ ) _h3 —CO—L ⁵⁴ —, h3 represents an integer of 1 to 4, and * represents a bond to L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents any integer of 1 to 3.
s1 ′ represents any integer of 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. Groups.
In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
Of L ⁵² and L ⁵³ , one is preferably —O— and the other is preferably —S—.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

As a monomer which introduce | transduces structural unit (a1-5), the monomer described in Unexamined-Japanese-Patent No. 2010-61117 is mentioned, for example. Among these, structural units each represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and are represented by formula (a1-5-1) or formula (a1-5-2). A structural unit is more preferable.

  When resin (A) has a structural unit (a1-5), the content rate is preferable 1-50 mol% with respect to all the structural units of resin (A), and 3-45 mol% is more preferable. 5 to 40 mol% is more preferable.

In addition, examples of the structural unit (a1) include the following structural units.

  When resin (A) contains the said structural unit, the content rate is 10-95 mol% with respect to all the structural units of resin (A), 15-90 mol% is more preferable, 20-85 mol % Is more preferable.

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no halogen atom and no acid labile group (hereinafter sometimes referred to as “monomer (s)”). As the monomer for deriving the structural unit (s), a monomer having no acid labile group known in the resist field can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid labile group is preferable. A structure having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile group If a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When a resist pattern is produced from the resist composition of the present invention, when a high energy beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and the structural unit (a2-1) is more preferable. As a structural unit (a2), 1 type may be included independently and 2 or more types may be included.

Examples of the structural unit having a phenolic hydroxy group include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as “structural unit (a2-A)”).
[In the formula (a2-A),
R ^a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
A ^a50 represents a single bond or ^* —X ^a51 — (A ^a52 —X ^a52 ) _na —, and * represents a bond to the carbon atom to which —R ^a50 is bonded.
A ^a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent —O—, ^—CO —O— or —O—CO—.
na represents 0 or 1.
mb represents an integer of 0 to 4. When mb is an integer greater than or equal to 2, several ^Ra51 may mutually be same or different. ]

^Examples of the halogen atom for R ^a50 include a fluorine atom, a chlorine atom and a bromine atom.
^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R ^a50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, 1 , 1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3 , 3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl Groups and n-perfluorohexyl groups.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group for R ^a51 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
^Examples of the alkoxy group for R ^a51 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. A C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is more preferable.
^Examples of the alkylcarbonyl group for R ^a51 include an acetyl group, a propionyl group, and a butyryl group.
^Examples of the alkylcarbonyloxy group for R ^a51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
R ^a51 is preferably a methyl group.

^* —X ^a51 — (A ^a52 —X ^a52 ) _na — includes ^* —O—, ^* —CO—O—, ^* —O—CO—, ^* —CO—O—A ^a52 —CO—O—, ^* —O—CO—A ^a52 —O—, ^* —O—A ^a52 —CO—O—, ^* —CO—O—A ^a52 —O—CO—, ^* —O—CO—A ^a52 —O—CO -. Of these, ^* —CO—O—, ^* —CO—O—A ^a52 —CO—O— or ^* —O—A ^a52 —CO—O— is preferable.

Examples of the alkanediyl group 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 2 -Methylbutane-1,4-diyl group etc. are mentioned.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably a single bond, ^* —CO—O— or ^* —CO—O—A ^a52 —CO—O—, and is a single bond, ^* —CO—O— or ^* —CO—O—CH. _2- CO-O- is more preferable, and a single bond or ^* -CO-O- is more preferable.

mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
The hydroxyl group is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

As the structural unit (a2-A), structural units represented by the formulas (a2-2-1) to (a2-2-4) and a structural unit in which a methyl group corresponding to R ^a50 is replaced with a hydrogen atom are included. Can be mentioned. The structural unit (a2-A) includes a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), and a methyl group corresponding to R ^a50 in a hydrogen atom. A substituted structural unit is preferred.

  Examples of the monomer for deriving the structural unit (a2-A) include monomers described in JP 2010-204634 A and JP 2012-12577 A.

  When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably based on all structural units. It is 10-70 mol%, More preferably, it is 15-65 mol%.

Examples of the structural unit (a2) having an alcoholic hydroxy group include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).
In formula (a2-1),
L ^a3 represents —O— or ^* —O— (CH ₂ ) _k2 —CO—O—,
k2 represents any integer of 1 to 7. * Represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O- and is (wherein f1 is an integer of 1 to 4) More preferably, it is —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

As a structural unit (a2-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferred, and any one of formula (a2-1-1) to formula (a2-1-4) The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is more preferable.

  When resin (A) contains a structural unit (a2-1), the content rate is 1-45 mol% normally with respect to all the structural units of resin (A), Preferably it is 1-40 mol%. Yes, more preferably 1 to 35 mol%, still more preferably 2 to 20 mol%, and even more preferably 2 to 10 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. But you can. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure is used.

The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be contained independently and 2 or more types may be contained.
[In Formula (a3-1), Formula (a3-2), Formula (a3-3) and Formula (a3-4),
L ^a4 , L ^a5 and L ^a6 each represent a group represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). .
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each represent a hydrogen atom or a methyl group.
R ^a24 represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 represent a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer of 0 to 5.
q1 represents any integer of 0 to 3.
r1 represents any integer of 0 to 3.
w1 represents an integer of 0 to 8.
When p1, q1, r1, and / or w1 is 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group represented by R ^a21 , R ^a22 , R ^a23 and R ^a25 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. An alkyl group is mentioned.
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group for R ^a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
Examples of the alkyl group having a halogen atom of Ra ²⁴ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group of L ^a8 and L ^a9 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a 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, 2-methylbutane-1,4-diyl group, etc. are mentioned.

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are independently of each other preferably —O— or k3 is an integer of 1 to 4 * —O— ( A group represented by CH ₂ ) _{k 3} —CO—O—, more preferably —O— and * —O—CH ₂ —CO—O—, and still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

In formula (a3-4), R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group. It is.
R ^a25 is preferably a carboxy group, a cyano group, or a methyl group.
L ^a7 is preferably —O— or ^* —O—L ^a8 —CO—O—, more preferably —O—, —O—CH ₂ —CO—O— or —O—C ₂ H ₄ —. CO-O-.
In particular, the formula (a3-4) is preferably the formula (a3-4) ′.
(Wherein R ^a24 and L ^a7 represent the same meaning as described above.)

As the structural unit (a3), a monomer derived from JP2010-204646, a monomer described in JP2000-122294A, a structure derived from a monomer described in JP2012-41274A Units are listed. As the structural unit (a3), the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3-2-2), the formula (a3-3) 1), a structural unit represented by any one of formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and R ^a18 , R ^a19 , R ^a20 and R ^a24 A structural unit in which a methyl group corresponding to is replaced by a hydrogen atom is preferred.

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), and a structural unit (a3-4) is respectively with respect to all the structural units of resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more preferable.

<Structural unit (a4)>
As the structural unit (a4), a structural unit represented by formula (a4-0) can be given.
[In the formula (a4-0),
R ⁵⁶ represents a hydrogen atom or a methyl group.
L ⁴ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a perfluoroalkyl cycloalkanediyl group perfluoro alkanediyl group or 3 to 12 carbon atoms having 1 to 8 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

As the aliphatic saturated hydrocarbon group for L ⁴ , a linear alkanediyl group such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, ethane-1,1- Branched alkanediyl such as diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group Groups.

As the perfluoroalkanediyl group of L ³ , a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a 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-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3 , 3-diyl group, perfluorooctane-4,4-diyl group, and the like.
Examples of the L ³ perfluorocycloalkanediyl group include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

L ⁴ is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ³ is preferably a C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

The structural unit (a4-0), a methyl group have structural units replaced by a hydrogen atom corresponding to R ⁵⁵ in the structural unit and the following structural units shown below.

As the structural unit (a4), a structural unit represented by formula (a4-1) can be given.
[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—. Good.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). However, at least one of A ^a41 and R ^a42 has a fluorine atom as a substituent.
[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a C1-C5 saturated hydrocarbon group which may have a single bond or a substituent.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Is a bond, and * on the right side is a bond with —O—CO—R ^a42 . ]

^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.
The chain and cyclic aliphatic hydrocarbon groups may have a carbon-carbon unsaturated bond, but the chain and cyclic aliphatic saturated hydrocarbon groups are preferable. The aliphatic saturated hydrocarbon group includes a straight chain or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic group formed by combining an alkyl group and an alicyclic hydrocarbon group. Group hydrocarbon group and the like.

Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. Group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Cyclic aliphatic hydrocarbon groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other cycloalkyl groups; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* is a bond) And a polycyclic alicyclic hydrocarbon group such as).
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group, and a fluorenyl group.

R ^a42 may have a halogen atom and a group represented by the formula (a-g3) as a substituent. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.
[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents a bond. ]
However, in R ^a42 —X ^a43 —A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.

^As the aliphatic hydrocarbon group for A ^a45, the same groups as those exemplified for R ^a42 can be mentioned.
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). preferable.
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and still more preferably a carbon number. It is a 1-6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the carbon number contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

The aliphatic hydrocarbon having a group represented by the formula (a-g3) is more preferably a group represented by the formula (a-g2).
[In the formula (a-g2),
A ^a46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47, and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bond with a carbonyl group. ]

1-6 are preferable and, as for carbon number of the aliphatic hydrocarbon group of ^Aa46 , 1-3 are more preferable.
4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of A ^<a47> , 5-12 are more preferable, and A ^<a47> has a more preferable cyclohexyl group or an adamantyl group.

A more preferred structure of the partial structure represented by * -A ^a46 -X ^a44 -A ^a47 (* is a bond to a carbonyl group) is the following structure.

^As the alkanediyl group of ^Aa41 , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group Linear alkanediyl group such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, Examples include branched alkanediyl groups such as 2-methylbutane-1,4-diyl group.
^Examples of the substituent in the alkanediyl group of A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

The saturated hydrocarbon group of A ^a42 , A ^a43 and A ^{a44 in} the group represented by the formula (a-g1) is preferably a chain or cyclic saturated hydrocarbon group or a group formed by combining them. . Examples of the saturated hydrocarbon group include linear or branched alkanediyl groups and monocyclic alicyclic hydrocarbon groups, and saturated hydrocarbons formed by combining alkanediyl groups and alicyclic hydrocarbon groups. Groups and the like. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, Examples include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
^Examples of the substituent for the saturated hydrocarbon group of A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

Examples of the group represented by the formula (a-g1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group, or an oxycarbonyl group include the following groups. In the following examples, * and ** each represent a bond, and ** is a bond with —O—CO—R ^a42 .

Examples of the structural unit represented by the formula (a4-1) include the structural units shown below and structural units in which a methyl group corresponding to R ^a41 in the following structural units is replaced with a hydrogen atom.

Examples of the structural unit (a4) include a structural unit represented by the formula (a4-4).
[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents — (CH ₂ ) _j1 —, — (CH ₂ ) _j2 —O— (CH ₂ ) _j3 — or — (CH ₂ ) _j4 —CO—O— (CH ₂ ) _j5 —.
j1 to j5 each independently represents an integer of 1 to 6.
R ^f22 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

The hydrocarbon group for R ^f22 includes aliphatic hydrocarbon groups formed by chain, cyclic, and combinations thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
Examples of the hydrocarbon group having a fluorine atom include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Specifically, as the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoro (Ropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5- Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2, 2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentyl Examples thereof include fluorinated alkyl groups such as a methyl group and a perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.
R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, more preferably a C 1-10 alkyl group having a fluorine atom. Preferably, the C1-C6 alkyl group which has a fluorine atom is further more preferable.

In Formula (a4-4), A ^f21 is preferably — (CH ₂ ) _j1 —, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

Examples of the structural unit represented by formula (a4-4) include structural units in which the methyl group corresponding to R ^f21 is replaced with a hydrogen atom in the following structural units and structural units represented by the following formulas. It is done.

  When the resin (A) has a structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on all structural units of the resin (A). More preferably, it is 10 mol%.

<Structural unit (a5)>
Examples of the non-elimination hydrocarbon group that the structural unit (a5) has include a group having a linear, branched, or cyclic hydrocarbon group. Among these, the structural unit (a5) preferably includes an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.

[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. . However, the hydrogen atom bonded to the carbon atom at the coupling position with the L ⁵⁵ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group for R ⁵² may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include alkyl groups such as octyl group and 2-ethylhexyl group.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵⁵ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. .
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.
In formula (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total carbon number of L ^x1 and L ^x2 is 16 or less.
In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x3 and L ^x4 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.

L ^x1 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group, more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond.
L ^x3 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is 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.
L ^x9 is 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.
W ^x1 is preferably a C 3-10 divalent alicyclic saturated hydrocarbon group, more preferably a cyclohexanediyl group or an adamantanediyl group.

As group represented by a formula (L1-1), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-2), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-3), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-4), the bivalent group shown below is mentioned, for example.

L ⁵⁵ is preferably a group represented by a single bond or the formula (L1-1).

As the structural unit (a5-1), structural units shown below and structural units in which a methyl group corresponding to R ⁵¹ in the following structural units is replaced with a hydrogen atom can be mentioned.
When the resin (A) has the structural unit (a5), the content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on all structural units of the resin (A). More preferred is ˜15 mol%.

<Structural unit (a6)>
Examples of the structural unit (a6) having a carboxy group include the structural units represented below.

  When the resin (A) has the structural unit (a6), the content is preferably 1 to 40 mol%, more preferably 2 to 35 mol%, based on all structural units of the resin (A). More preferred is ˜30 mol%.

<Structural unit (II)>
Specific examples of the structural unit (II) that decomposes upon exposure to generate an acid include the structural units described in JP-A-2016-79235, and a side chain includes a sulfonate group or a carboxylate group and an organic cation. It is preferable that it is a structural unit which has a sulfonio group and an organic anion in a side chain.

The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by the formula (II-2-A ′).
[In the formula (II-2-A ′)
X ^III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —S— or —CO—. The hydrogen atom contained in the saturated hydrocarbon group may be replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxy group.
A ^x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
RA ^- represents a sulfonate or carboxylate groups.
R ^III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
Z ^{a +} represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3 , an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 and The same can be mentioned.
Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2, 4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Can be mentioned.

Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by ^XIII3 include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. These may be combined.
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 , Linear alkanediyl groups such as dodecane-1,12-diyl group; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Branched alkanediyl groups such as pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-diyl group, Cycloalkanediyl group such as looctane-1,5-diyl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group Bivalent polycyclic alicyclic saturated hydrocarbon groups and the like.

Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —S—, or —CO— include divalent groups represented by formula (X1) to formula (X53), for example. Can be mentioned. However, the number of carbon atoms before —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —S—, or —CO— is 17 or less. In the following formulas, * represents a bond to ^{A x1.}

X ³ represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
X ⁴ represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
X ⁵ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
X ⁶ represents an alkyl group having 1 to 14 carbon atoms.
X ⁷ represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁸ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

Examples of the organic cation represented by Z ^{a +} include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, organic benzothiazolium cation, and organic phosphonium cation. Organic sulfonium cation and organic iodonium cation Are preferred, and arylsulfonium cations are more preferred.
Specifically, the thing similar to what was illustrated with the organic cation in salt (I) is mentioned.

The structural unit represented by the formula (II-2-A ′) is preferably a structural unit represented by the formula (II-2-A).
[In formula (II-2-A), R ^III3 , X ^III3 and Z ^{a +} represent the same meaning as described above.
Z represents an integer of 0 to 6.
R ^III2 and R ^III4 each independently represent a hydrogen atom, a fluorine atom or a C 1-6 perfluoroalkyl group, and when z is 2 or more, the plurality of R ^III2 and R ^III4 are the same as each other It may be different or different.
Q ^a and Q ^b each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. ]

^{Examples of} the C 1-6 perfluoroalkyl group represented by R ^III2 , R ^III4 , Q ^a and Q ^b include the same as the C 1-6 perfluoroalkyl group represented by Q ¹ .

The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1).
[In the formula (II-2-A-1)
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b , z and Z ^{a +} represent the same meaning as described above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
X ² represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —S— or —CO—. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]

Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include linear or branched alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group.
Examples of the divalent saturated hydrocarbon group having 1 to 11 carbon atoms represented by X ² include those having up to 11 carbon atoms in the divalent saturated hydrocarbon group represented by X ^III3 .

As the structural unit represented by the formula (II-2-A), a structural unit represented by the formula (II-2-A-2) is more preferable.
[In Formula (II-2-A-2), R ^III3 , R ^III5 and Z ^{a +} represent the same meaning as described above.
m and n each independently represent 1 or 2. ]

Examples of the structural unit represented by the formula (II-2-A-1) include the following structural units and the structural units described in WO2012 / 050015. Z ^{a +} represents an organic cation.

The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1).
[In the formula (II-1-1),
A ^II1 represents a single bond or a divalent linking group.
R ^II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^II2 and R ^II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R ^II2 and R ^II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded.
R ^II4 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
A ⁻ represents an organic anion. ]
Examples of the divalent linking group represented by A ^II1 include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is: -O-, -S- or -CO- may be substituted. Specifically, the same thing as a C1-C18 bivalent saturated hydrocarbon group represented by ^XIII3 is mentioned.
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
As a C1-C18 hydrocarbon group represented by ^RII2 and ^RII3 , the same thing as the C1-C18 hydrocarbon group represented by R ^<a3>' of Formula (2) is mentioned.
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 , an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 ; The same can be mentioned.

Examples of the structural unit containing a cation in formula (II-1-1) include the structural units represented below.

A ^- The organic anion represented by a sulfonic acid anion, sulfonyl imide anion, methide anion and a carboxylate anion, and the like. A ^- organic anion represented by the sulfonate anion are preferable, and more preferably an anion contained in the above-mentioned acid generator (B1).

A ^- The sulfonyl imide anions represented by, the following may be mentioned.

Examples of the structural unit (II-1) include the structural units represented below.

  When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol% with respect to the total structural units of the resin (A). Preferably it is 2-15 mol%, More preferably, it is 3-10 mol%.

The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), that is, a copolymer of the monomer (a1) and the monomer (s).
The structural unit (a1) is preferably at least one selected from the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably the structural unit ( a1-1) or the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably a structural unit represented by formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4). And at least one selected from structural units represented by formula (a3-4-1) to formula (a3-4-2).

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do. The content rate of each structural unit which resin (A) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably 15,000 or less). In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.

<Resin (X) other than Resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of such a resin include a resin containing the structural unit (a4) (hereinafter sometimes referred to as “resin (X)”).
Examples of the structural unit that the resin (X) may further include the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit (a5), and other known structural units.
The resin (X) is more preferably a resin composed of the structural unit (a4) and / or the structural unit (a5).
When the resin (X) contains the structural unit (a4), the content is preferably 40 mol% or more, more preferably 45 mol% or more, and more preferably 50 mol% or more with respect to all the structural units of the resin (X). Is more preferable.
When the resin (X) contains the structural unit (a5), the content is preferably 10 to 60 mol%, more preferably 20 to 55 mol%, based on all the structural units of the resin (X). 50 mol% is more preferable.

Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do. The content rate of each structural unit which resin (X) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). Preferably it is 1-40 mass parts, Most preferably, it is 2-30 mass parts.

  80 mass% or more and 99 mass% or less are preferable with respect to solid content of a resist composition, and, as for the total content rate of resin other than resin (A) and resin (A), 90 mass% or more and 99 mass% or less are preferable. . The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, and 99.9% by mass or less, preferably 99% by mass or less in the resist composition. It is. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate Esters such as acetone, methyl isobutyl ketone, ketones such as 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be contained alone, or two or more kinds may be contained.

<Quencher (C)>
The resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as “quencher (C)”). The quencher (C) may be a basic nitrogen-containing organic compound or a salt that generates an acid having a lower acidity than the acid generator (B).

<Basic nitrogen-containing organic compound>
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

  Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyl Cyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldinonylamine Decylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4 , 4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methyl Imidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) 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′-dipyridyl sulfide, 4, 4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, and the like are preferable, diisopropylaniline is preferable, and 2,6-diisopropylaniline is particularly preferable.

  As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

<Salt that generates acid with low acidity>
The acidity in a salt that generates an acid having a weaker acidity than the acid generated from the acid generator is indicated by an acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pKa <7. More preferably, the salt is 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid inner salt represented by the formula (D) described in JP-A-2015-147926, and a salt. Examples thereof include salts described in JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A, and JP 2011-191745 A.

Examples of the weak acid inner salt represented by the formula (D) include the following salts.

  The content of the quencher (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 4% by mass, and particularly preferably 0.01 to 3% by mass in the solid content of the resist composition. % By mass.

<Other ingredients>
The resist composition of the present invention may contain components other than the above components (hereinafter sometimes referred to as “other components (F)”) as necessary. The other component (F) is not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (A) and salt (I) of the present invention, and the resin (X), acid generator (B), quencher (C), solvent (E) used as necessary. ) And other components (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention on a board | substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

  The resist composition can be applied onto the substrate by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do. In this specification, irradiating these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction in the acid labile group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., and the development time is preferably 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention includes a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly an electron. It is suitable as a resist composition for line (EB) exposure or a resist composition for EUV exposure, and is useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

  The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Model 1100 manufactured by Agilent, MASS: LC / MSD manufactured by Agilent). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

Example 1: Synthesis of a salt represented by the formula (I-1)
50.3 parts of the salt represented by the formula (I-1-a) and 250 parts of acetonitrile were mixed, and then stirred at 40 ° C. for 1 hour. To the obtained mixture, 23.8 parts of the compound represented by the formula (I-1-b) is added at 40 ° C. over 10 minutes, and the temperature is raised to 70 ° C., followed by stirring at 70 ° C. for 2 hours. Thus, a solution containing a salt represented by the formula (I-1-c) was obtained. After cooling the obtained solution containing the salt represented by the formula (I-1-c) to 23 ° C., a mixed solution of 13 parts of the compound represented by the formula (I-1-d) and 13 parts of acetonitrile was added. The solution containing the salt represented by the formula (I-1-e) was obtained by adding over 90 minutes and stirring at 23 ° C. for 1 hour. In the obtained solution containing the salt represented by the formula (I-1-e), 13 parts of the compound represented by the formula (I-1-d) and the salt represented by the formula (I-1-f) 0.1 part was added and it stirred at 23 degreeC for 18 hours. To the obtained reaction mixture, 500 parts of chloroform, 200 parts of ion-exchanged water and 50 parts of a saturated aqueous sodium hydrogen carbonate solution were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 200 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated twice. The collected organic layer was concentrated, and 200 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 40.30 parts of the salt represented by the formula (I-1-g).
After adding 1.8 parts of the salt represented by the formula (I-1-g), 0.6 part of the compound represented by the formula (I-1-h) and 14 parts of chloroform, the mixture was stirred at 23 ° C. for 30 minutes. did. To the resulting mixture, 1.4 parts of 0.2% camphorsulfonic acid in chloroform was added at 23 ° C., and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction solution, 30 parts of chloroform and 20 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. The recovered organic layer was concentrated, and 10 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.24 parts of the salt represented by the formula (I-1).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 543.2

Example 2: Synthesis of salt represented by formula (I-49)
After 1.8 parts of the salt represented by the formula (I-1-g), 0.4 parts of the compound represented by the formula (I-49-f) and 14 parts of chloroform were mixed, the mixture was stirred at 23 ° C. for 30 minutes. did. To the resulting mixture, 1.4 parts of 0.2% camphorsulfonic acid in chloroform was added at 23 ° C., and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction solution, 30 parts of chloroform and 20 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. The recovered organic layer was concentrated, and 10 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 0.99 parts of the salt represented by the formula (I-49).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 529.2

Example 3: Synthesis of salt represented by formula (I-23)
1.2 parts of the compound represented by the formula (I-1), 10 parts of chloroform and 10 parts of methanol were charged into a reactor and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.10 parts of hydrochloric acid and 10 parts of ion-exchanged water were added and stirred at about 50 ° C. for 1 hour. After concentrating the obtained reaction mixture, 25 parts of ethyl acetate was added to the obtained concentrate, stirred, allowed to stand, and separated to obtain an organic layer. To the obtained organic layer, 5 parts of 10% aqueous potassium carbonate solution was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. To the obtained organic layer, 5 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. Such washing operation was repeated 5 times. By concentrating the obtained organic layer and separating the concentrated mass by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: methanol / chloroform = 1/1), 0.31 part of a compound represented by the formula (I-23) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 471.2

Example 4: Synthesis of salt represented by formula (I-9)
5.03 parts of the salt represented by the formula (I-9-a) and 25 parts of acetonitrile were mixed and then stirred at 40 ° C. for 1 hour. To the obtained mixture, 2.38 parts of a compound represented by the formula (I-9-b) is added at 40 ° C. over 10 minutes, and the temperature is raised to 70 ° C. and then stirred at 70 ° C. for 2 hours. Thus, a solution containing a salt represented by the formula (I-9-c) was obtained. After cooling the obtained solution containing the salt represented by the formula (I-9-c) to 23 ° C., 1.09 parts of the compound represented by the formula (I-9-d) and 1.09 parts of acetonitrile. Was added over 10 minutes, and the mixture was stirred at 23 ° C. for 1 hour to obtain a solution containing the salt represented by the formula (I-9-e). In the obtained solution containing the salt represented by the formula (I-9-e), 1.09 parts of the compound represented by the formula (I-9-d) and the formula (I-9-f) are represented. 0.01 part of a salt was added and stirred at 23 ° C. for 18 hours. To the obtained reaction mixture, 50 parts of chloroform, 20 parts of ion-exchanged water and 5 parts of a saturated aqueous sodium hydrogen carbonate solution were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated twice. The collected organic layer was concentrated, and 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.88 parts of the salt represented by the formula (I-9-g).
1.67 parts of a salt represented by the formula (I-9-g), 0.6 part of a compound represented by the formula (I-9-h) and 14 parts of chloroform were added, followed by stirring at 23 ° C. for 30 minutes. did. To the resulting mixture, 1.4 parts of 0.2% camphorsulfonic acid in chloroform was added at 23 ° C., and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction solution, 30 parts of chloroform and 20 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. The recovered organic layer was concentrated, and 10 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.01 part of a salt represented by the formula (I-9).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 487.2

Example 5: Synthesis of salt represented by formula (I-351)
4.84 parts of the salt represented by the formula (I-351-a) and 30 parts of acetonitrile were mixed and then stirred at 23 ° C. for 30 minutes. To the obtained mixture, 2.41 parts of the compound represented by the formula (I-351-b) was added at 60 ° C. over 10 minutes, and the mixture was stirred at 60 ° C. for 2 hours to obtain the formula (I-351 A solution containing the salt represented by -c) was obtained. To the solution containing the salt represented by the formula (I-351-c) thus obtained, a mixed solution of 1.32 parts of the compound represented by the formula (I-351-d) and 1.32 parts of acetonitrile was added for 30 minutes. And the mixture was stirred at 60 ° C. for 2 hours to obtain a solution containing a salt represented by the formula (I-351-e). In the obtained solution containing the salt represented by the formula (I-351-e), 1.31 parts of the compound represented by the formula (I-351-d) and the formula (I-351-f) 0.01 part of a salt was added and stirred at 23 ° C. for 18 hours. To the obtained reaction mixture, 50 parts of chloroform, 20 parts of ion-exchanged water and 5 parts of a saturated aqueous sodium hydrogen carbonate solution were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated twice. The collected organic layer was concentrated, and 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 3.16 parts of the salt represented by the formula (I-351-g).
After 1.87 parts of the salt represented by the formula (I-351-g), 0.6 part of the compound represented by the formula (I-351-h) and 14 parts of chloroform were added, the mixture was stirred at 23 ° C. for 30 minutes. did. To the resulting mixture, 1.4 parts of 0.2% camphorsulfonic acid in chloroform was added at 23 ° C., and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction solution, 30 parts of chloroform and 20 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. The recovered organic layer was concentrated, and 10 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.18 parts of the salt represented by the formula (I-351).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 573.3

Example 6: Synthesis of salt represented by formula (I-353)
5.03 parts of the salt represented by the formula (I-353-a) and 25 parts of acetonitrile were mixed, and then stirred at 40 ° C. for 1 hour. To the obtained mixture, 2.38 parts of a compound represented by the formula (I-353-b) is added over 10 minutes at 40 ° C., the temperature is raised to 70 ° C., and the mixture is stirred at 70 ° C. for 2 hours. To obtain a solution containing a salt represented by the formula (I-353-c). After cooling the obtained solution containing the salt represented by the formula (I-353-c) to 23 ° C., 1.70 parts of the compound represented by the formula (I-353-d) and 1.70 parts of acetonitrile. Was added over 10 minutes, and the mixture was stirred at 23 ° C. for 1 hour to obtain a solution containing a salt represented by the formula (I-353-e). In the obtained solution containing the salt represented by the formula (I-353-e), 1.70 parts of the compound represented by the formula (I-353-d) and the formula (I-353-f) 0.01 part of a salt was added and stirred at 23 ° C. for 18 hours. To the obtained reaction mixture, 50 parts of chloroform, 20 parts of ion-exchanged water and 5 parts of a saturated aqueous sodium hydrogen carbonate solution were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated twice. The collected organic layer was concentrated, and 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 3.52 parts of the salt represented by the formula (I-353-g).
After adding 2.05 parts of the salt represented by the formula (I-353-g), 0.6 part of the compound represented by the formula (I-353-h) and 14 parts of chloroform, the mixture was stirred at 23 ° C. for 30 minutes. did. To the resulting mixture, 1.4 parts of 0.2% camphorsulfonic acid in chloroform was added at 23 ° C., and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction solution, 30 parts of chloroform and 20 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. To the recovered organic layer, 20 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. The recovered organic layer was concentrated, and 10 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.54 parts of the salt represented by the formula (I-353).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 647.3

Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.
Hereinafter, these monomers are referred to as “monomer (a1-1-1)” according to the formula number.

Synthesis Example 1 [Synthesis of Resin A1]
As the monomer, monomer (a1-4-2), monomer (a1-1-3), monomer (a1-2-6), monomer (a3-1-1) and monomer (II-2-A-1-1) The molar ratio [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2): monomer (II-2- A-1-1)] is mixed at a ratio of 32: 25: 35: 5: 3, and 1.5 mass times of methyl is added to this monomer mixture with respect to the total mass of all monomers. Isobutyl ketone was mixed. To the obtained mixture, azobisisobutyronitrile as an initiator was added so as to be 7 mol% with respect to the total number of moles of all monomers, and this was heated at 85 ° C. for about 5 hours to polymerize. Went. Thereafter, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 6 hours, followed by liquid separation. The recovered organic layer is poured into a large amount of n-heptane to precipitate a resin, and filtered and recovered to obtain a resin A1 (copolymer) having a weight average molecular weight of about 8.0 × 10 ³ in a yield of 68. %. This resin A1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A2]
As the monomer, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (a3-1-1) are used, and the molar ratio [monomer (a1-4 -2): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (a3-4-2)] were synthesized except that they were mixed at a ratio of 35: 25: 35: 5. In the same manner as in Example 1, resin A1 (copolymer) having a weight average molecular weight of about 8.0 × 10 ³ was obtained in a yield of 65%. This resin A2 has the following structural units.

Synthesis Example 3 [Synthesis of Resin A3]
As the monomer, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) were used, and the molar ratio [monomer (a1-4-2): monomer (a1-1) −3): Monomer (a1-2-6)] was mixed at a ratio of 35:25:40, and the weight average molecular weight was about 7.6 × 10 ³ in the same manner as in Synthesis Example 1. A resin A1 (copolymer) was obtained with a yield of 64%. This resin A3 has the following structural units.

Synthesis Example 4 [Synthesis of Resin A4]
As the monomer, monomer (a2-2-1), monomer (a1-1-3), monomer (a1-2-6) and monomer (a3-1-1) were used, and the molar ratio [monomer (a1-4 -2): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2)] are mixed at a ratio of 35: 25: 35: 5, and In this monomer mixture, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and this was heated at 75 ° C. for about 5 hours for polymerization. Went. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin is added to a methanol / water mixed solvent, repulped, and then subjected to a refining operation of filtering twice to obtain a resin A4 (copolymer) having a weight average molecular weight of about 8.1 × 10 ^3. Obtained in 61% yield. This resin A4 has the following structural units.

<Preparation of resist composition>
Each of the components shown below was mixed in parts by mass shown in Table 2, dissolved in a solvent, and filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

<Resin (A)>
A1 to A4: Resin A1 to Resin A4
<Acid generator (B)>
B1-25: salt represented by formula (B1-25); synthesized by the method described in JP2011-126869 B1-41: salt represented by formula (B1-41); B1-X1: synthesized by the method described in JP2012-229206 B1-X2: synthesized by the method described in JP2012-234155 B1-X3: described in JP2007-145822 Synthesis by the method
<Quencher (C)>
C1: synthesized by the method described in JP2011-39502A
D1: (Tokyo Chemical Industry Co., Ltd.)
<Solvent (E)>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

(Electron beam exposure evaluation of resist composition)
A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. This silicon wafer was spin-coated with a resist composition so that the film thickness of the composition layer was 0.04 μm. Thereafter, the composition layer was formed by pre-baking on a direct hot plate for 60 seconds at the temperature shown in the “PB” column of Table 2. A line-and-space pattern was directly drawn on the composition layer formed on the wafer using an electron beam drawing machine ("HL-800D 50 keV" manufactured by Hitachi, Ltd.) while changing the exposure stepwise. .
After the exposure, post exposure baking is performed for 60 seconds on the hot plate at the temperature indicated in the “PEB” column of Table 2 and paddle development is further performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. A resist pattern was obtained.
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and space width of the 60 nm line and space pattern were 1: 1 was defined as effective sensitivity.

  Line edge roughness evaluation (LER): The width of unevenness on the side wall surface of a resist pattern manufactured with effective sensitivity was measured with a scanning electron microscope to determine line edge roughness. The results are shown in Table 3.

  The resist composition of the present invention has good line edge roughness and is useful for fine processing of semiconductors.

Claims (8)

A salt represented by the formula (I).
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, * —O—CO—O— or * —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ) Represents the bonding position with (Q ² ).
A ¹ and A ² each independently represent a divalent hydrocarbon group having 2 to 36 carbon atoms which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is —O— , —S—, —C (═O) —, or —SO ₂ — may be substituted.
R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents a hydroxy group, a group represented by the formula (aa1) or the formula (aa2).
(In the formula (aa1),
R ¹² , R ¹³ , and R ¹⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof, or R ¹² and R ¹³ Are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 1.
In formula (aa2),
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ¹⁶ and R ¹⁷ are mutually A divalent heterocyclic group having 3 to 20 carbon atoms is formed together with a carbon atom and an oxygen atom to which they are bonded, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is -O- or -S- may be substituted. )
Z ⁺ represents an organic cation. ] The salt according to claim 1, wherein X ¹ is * —CO—O—. A ¹ and A ² are each independently a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 18 carbon atoms. The salt according to claim 1, which is a divalent hydrocarbon group formed from The salt according to any one of claims 1 to 3, wherein R ⁵ is a hydrogen atom.   The acid generator containing the salt of any one of Claims 1-4.   A resist composition comprising the acid generator according to claim 5 and a resin containing a structural unit having an acid labile group.   The resist composition according to claim 6, further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator. (1) The process of apply | coating the resist composition of Claim 6 or 7 on a board | substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: