WO2021220851A1

WO2021220851A1 - Active light ray-sensitive or radiation-sensitive resin composition, active light ray-sensitive or radiation-sensitive film, mask blank, method for forming pattern, and method for producing electronic device

Info

Publication number: WO2021220851A1
Application number: PCT/JP2021/015782
Authority: WO
Inventors: 明弘金子; 雅史小島; 佑太奥秋; 研由後藤; 啓太加藤
Original assignee: 富士フイルム株式会社
Priority date: 2020-04-28
Filing date: 2021-04-16
Publication date: 2021-11-04
Also published as: JP7373059B2; JPWO2021220851A1; TW202146477A

Abstract

According to the present invention, provided is an active light ray-sensitive or radiation-sensitive resin composition which contains: a resin that has a specific repeating unit having a group having a cyclic structure containing a carbonic acid ester group or a group having a cyclic structure containing a SO₂ group, and that has a repeating unit having an acid-dissociable group; and a compound that generates an acid upon irradiation with active light rays or radiation. Also provided are: an active light ray-sensitive or radiation-sensitive resin film formed from the composition; a mask blank provided with the film; a method for forming a pattern using the composition; and a method for producing an electronic device.

Description

Actinic or Radiation-Sensitive Resin Compositions, Actinic or Radiation-Sensitive Films, Mask Blanks, Pattern Formation Methods and Manufacturing Methods for Electronic Devices

The present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition, a sensitive light-sensitive or radiation-sensitive film, mask blanks, a pattern forming method, and a method for manufacturing an electronic device.

In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits, integrated circuits) and LSIs (Large Scale Integrated Circuits, large-scale integrated circuits), microfabrication by lithography using a photosensitive composition is performed.
Examples of the lithography method include a method of forming a resist film with a photosensitive composition, exposing the obtained film, and then developing the film. In particular, in recent years, studies have been made on the use of EB (Electron Beam) and EUV (Extreme ultraviolet) during exposure.

Patent Document 1 describes a sensitive light-sensitive or radiation-sensitive resin composition containing a resin containing a repeating unit having a specific group and a compound that generates an acid by irradiation with active light or radiation. ..
Patent Document 2 describes a positive radiation-sensitive resin composition containing a polymer having a specific structural unit and a structural unit containing a cyclic ether structure or a cyclic carbonate structure, and an acid generator.

International Publication No. 2017/169626 Japanese Patent Application Laid-Open No. 2014-137454

In recent years, ultra-miniaturization of patterns formed using EB and EUV has been required. For example, in the formation of ultra-fine patterns having a pitch of 50 nm or less, pattern collapse is suppressed while ensuring the roughness performance of the obtained pattern. There is a demand for a sensitive light-sensitive or radiation-sensitive resin composition that can be produced.
The above-mentioned Patent Document 1 describes an actinic light-sensitive or radiation-sensitive resin composition capable of suppressing pattern collapse in pattern formation having a pitch of 90 nm, but in forming an ultrafine pattern having a finer pitch of 50 nm or less. , A specific composition capable of suppressing pattern collapse has not been disclosed. In addition, there was no description about roughness performance, leaving room for consideration.
The above-mentioned Patent Document 2 describes a positive radiation-sensitive resin composition, but does not specifically describe ultrafineness of a pattern formed by using EB and EUV, and the pattern collapses and roughness. There is no description about performance.

The present invention is a sensitive ray-sensitive or radiation-sensitive resin composition capable of forming a pattern capable of suppressing pattern collapse and having excellent roughness performance in an ultrafine pattern (for example, a pattern having a pitch of 50 nm or less). Alternatively, a sensitive light-sensitive or radiation-sensitive resin film formed of the radiation-sensitive resin composition, a mask blank having the above-mentioned sensitive light-sensitive or radiation-sensitive resin film, the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. An object of the present invention is to provide a pattern forming method using an object and a method for manufacturing an electronic device.

The present inventors have studied diligently and found that the above problems can be solved by the following means.

[1]
A resin (A) containing a repeating unit (1a) represented by the following general formula (1) and a repeating unit (1b) having an acid-degradable group,
Compound (B) that generates acid by irradiation with active light or radiation, and
A sensitive light-sensitive or radiation-sensitive resin composition containing.

In general formula (1),
R ¹ represents a group having a cyclic structure containing a carbonic acid ester group or a group having a cyclic structure containing _{SO 2 groups.} However, neither of the two bonds of the sulfur atom in the _{SO 2 group is bonded to the oxygen atom.}
R ² represents a hydrogen atom, a halogen atom, a hydroxyl group or an organic group.
R ³ represents a hydrogen atom, a halogen atom or an alkyl group.
L ¹ represents a single bond or a divalent linking group.
L ² represents a single bond or a divalent linking group.
X is ^{-COO -, - O -, -} CONR 4 -, - SO 3 -, - SO 2 NR 4 - or -C _(CF ₃₎ 2 O- and represents, ^{R 4} represents a hydrogen atom or an alkyl group.
m ¹ and n ¹ each represent an integer of 1 to 4. However, m ¹ + n ¹ = 5 is satisfied.
If R ^1, ^R 2, X and ^{L 1} there are a plurality, the plurality of ^R ^{1, R} 2, X and ^{L 1} may be different from one another respectively the same.
[2]
The actinic or radiation-sensitive resin composition according to [1], wherein ^{L 2} in the general formula (1) represents a single bond.
[3]
^{R 1} in the above general formula (1) is a group having a cyclic structure containing a carbonic acid ester group, or a cyclic containing _{SO 2} groups in which two bonds of a sulfur atom are both bonded to a carbon atom or a nitrogen atom. The sensitive light-sensitive or radiation-sensitive resin composition according to [1] or [2], which represents a group having a structure.
[4]
The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit (1a) is represented by the following general formula (2).

In the general formula (2), R ¹ , R ² , R ³ , L ¹ , m ¹ and n ¹ have the same meanings as those in the general formula (1).
X 'is ^{_{-COO -, - CONR 4 -,}} - SO 3 -, - SO 2 NR 4 - or -C _(CF ₃₎ 2 O- and represents, ^{R 4} represents a hydrogen atom or an alkyl group.
'If and ^{L 1} there are a plurality, the plurality of ^{^{R 1, R 2, X'}} R 1, R 2, X and ^{L 1} may be different from one another respectively the same.
[5]
The active photosensitivity or photosensitivity according to [4], wherein the resin (A) further contains a repeating unit (1c) having at least one selected from the group consisting of a lactone structure, a carboxyl group, a hydroxyl group and a sulfonamide group. Radiation sensitive resin composition.
[6]
The actinic or radiation-sensitive resin composition according to [4] or [5], wherein X'in the general formula (2) represents -COO-.
[7]
The ^{actinic cheilitis according to any one of [4] to [6], wherein R 1} in the general formula (2) is represented by the following general formula (4-1) or (4-2). Radiation-sensitive resin composition.

In general formula (4-1),
R ₄₁₁ , R ₄₁₂ , R ₄₁₃ , R ₄₁₄ and R ₄₁₅ each independently represent a hydrogen atom or an alkyl group.
p ₄₁ and p ₄₂ each independently represent an integer of 0 to 2. However, p ₄₁ + p ₄₂ ≤ 2 is satisfied. If R _411, R _412, R ₄₁₄ and R ₄₁₅ there are a plurality, a plurality of R _411, R _412, R ₄₁₄ and R ₄₁₅ may be different from one another respectively the same.
In general formula (4-2),
R ₄₂₁ , R ₄₂₂ , R ₄₂₃ , R ₄₂₄ and R ₄₂₅ each independently represent a hydrogen atom or an alkyl group.
p ₄₃ and p ₄₄ each independently represent an integer of 0 to 2. However, p ₄₃ + p ₄₄ ≤ 2 is satisfied. If R _421, R _422, R ₄₂₄ and R ₄₂₅ there are a plurality, a plurality of R _421, R _422, R ₄₂₄ and R ₄₂₅ may be different from one another respectively the same.
In the general formulas (4-1) and (4-2), * represents the bonding position.
[8]
The actinic or radiation-sensitive resin composition according to [7], wherein ^{R 1} in the general formula (2) is represented by the general formula (4-1).
[9]
The repeating unit (1a) is represented by the following general formula (5), and the resin (A) further has at least one selected from the group consisting of a lactone structure, a carboxyl group, a hydroxyl group and a sulfonamide group. The sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], which comprises the unit (1c).

In the general formula (5), R ¹ , R ² , R ³ , L ¹ , m ¹ and n ¹ have the same meanings as those in the general formula (1).
If R ^1, ^{R 2} and ^{L 1} there are a plurality, the plurality of ^R 1, ^{R 2} and ^{L 1} may be different from one another respectively the same.
[10]
^{The actinic or radiation-sensitive resin composition according to [9], wherein R 1} in the general formula (5) is represented by the following general formula (6-1) or (6-2).

In general formula (6-1),
R ₆₁₁ , R ₆₁₂ , R ₆₁₃ , R ₆₁₄ and R ₆₁₅ each independently represent a hydrogen atom or an alkyl group.
p ₆₁ and p ₆₂ each independently represent an integer of 0 to 2. However, p ₆₁ + p ₆₂ ≤ 2 is satisfied. If R _611, R _612, R ₆₁₄ and R ₆₁₅ there are a plurality, a plurality of R _611, R _612, R ₆₁₄ and R ₆₁₅ may be different from one another respectively the same.
In general formula (6-2),
R ₆₂₁ , R ₆₂₂ , R ₆₂₃ , R ₆₂₄ and R ₆₂₅ each independently represent a hydrogen atom or an alkyl group.
p ₆₃ and p ₆₄ each independently represent an integer of 0 to 2. However, p ₆₃ + p ₆₄ ≤ 2 is satisfied. If R _621, R _622, R ₆₂₄ and R ₆₂₅ there are a plurality, a plurality of R _621, R _622, R ₆₂₄ and R ₆₂₅ may be different from one another respectively the same.
In the general formulas (6-1) and (6-2), * represents the bonding position.
[11]
The actinic or radiation-sensitive resin composition according to [10], wherein ^{R 1} in the general formula (5) is represented by the general formula (6-1).
[12]
The actinic cheilitis according to any one of [1] to [11], wherein the content of the repeating unit (1a) is 10 to 60% by mass with respect to all the repeating units of the resin (A). Radiation-sensitive resin composition.
[13]
The actinic or radiation-sensitive resin composition according to any one of [1] to [12], wherein the compound (B) is an ionic compound containing an anion and a cation.
[14]
Any of [1] to [13], wherein the compound (B) is composed of one or more anionic molecules and one or more cationic molecules, and at least one of the cationic molecules contains a fluorine atom. The sensitive light-sensitive or radiation-sensitive resin composition according to item 1.
[15]
The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [13], wherein the compound (B) is represented by any of the following general formulas (a) to (c). ..
_{^{_{^{_{M a1 + A a - -L a}}}}} -B a - M a2 + (a)
_{^{_{^{_{(M b1 + A b -)}}}}} nb -L b -B b - M b2 + (b)
_{^{_{^{_{(M c + A c -)}}}}} nc -L c (c)
In the general formula _{(a), M a1} ⁺ and _{M a2} ⁺ each independently represent an organic cation, _{L a} represents a divalent organic group, _{A a} ^- and _{B a} ^- are each independently an anionic functional Represents a group.
However, in the general formula (a) _HA a _-L a -B represented by _a H _{compound M a1} ⁺ and _{M a2} ⁺ is substituted with a hydrogen atom each of the compounds represented by the represented by HA _a pKa groups is less than the pKa of the groups represented by _{B a} H.
In the general formula (b), M _b1 ⁺ and M _b2 ⁺ each independently represent an organic cation, L _b represents a (nb + 1) -valent organic group, _{and Ab} ⁻ and B _b ⁻ each independently represent an anion. It represents a sex functional group, and nb represents an integer of 2 or more. The plurality of M _b1 ⁺ and _Ab ⁻ may be the same or different from each other.
However, in the general formula (b) _{M b1} ⁺ and _{M b2} ⁺ of the compound represented by is substituted with hydrogen atoms, respectively _(HA _b) a compound represented by nb _-L _b -B b H, in HA _b The pKa of the group represented is smaller than the pKa of the group represented by _{B b H.}
In the general formula (c), _Mc ⁺ represents an organic cation, _Ac ⁻ represents an anionic functional group, L _c represents a nonionic organic moiety capable of neutralizing an acid, and nc represents 2 or more. Represents an integer. The plurality of _Mc ⁺ and _Ac ⁻ may be the same or different from each other.
[16]
A sensitive light-sensitive or radiation-sensitive film formed by the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [15].
[17]
[16] A mask blank having the sensitive light-sensitive or radiation-sensitive film according to [16].
[18]
A step of forming a resist film on a substrate using the actinic cheilitis or radiation-sensitive resin composition according to any one of [1] to [15].
The process of exposing the resist film and
The step of developing the exposed resist film with a developing solution to form a pattern, and
Pattern forming method including.
[19]
A method for manufacturing an electronic device, which comprises the pattern forming method according to [18].

According to the present invention, in an ultrafine pattern (for example, a pattern having a pitch of 50 nm or less), a sensitive ray-sensitive or radiation-sensitive resin composition capable of suppressing pattern collapse and forming a pattern having excellent roughness performance, the above-mentioned sensitivity Sensitive ray-sensitive or radiation-sensitive resin film formed of a light-sensitive or radiation-sensitive resin composition, mask blanks provided with the above-mentioned sensitive light-sensitive or radiation-sensitive resin film, the above-mentioned sensitive light-sensitive or radiation-sensitive resin film. A pattern forming method using a resin composition and a method for producing an electronic device can be provided.

Hereinafter, an example of a mode for carrying out the present invention will be described.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.

In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The bonding direction of the divalent group described in the present specification is not limited unless otherwise specified. For example, when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".

In the present specification, "(meth) acrylic" is a general term including acrylic and methacryl, and means "at least one of acrylic and methacrylic". Similarly, "(meth) acrylic acid" means "at least one of acrylic acid and methacrylic acid".

As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB:). It means Electron Beam) and the like. As used herein, the term "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. It also includes drawing with particle beams such as beams.

In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (HLC manufactured by Toso Co., Ltd.). GPC measurement by (-8120 GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detector: It is defined as a polystyrene-equivalent value by a differential refractometer (Refractive Index Detector).

1 Å is 1 x ^10-10 m.

In the present specification, the acid dissociation constant (pKa) represents pKa in an aqueous solution, and specifically, using the following software package 1, the value based on the Hammett substituent constant and the database of publicly known literature values is used. , It is a value obtained by calculation. The values of pKa described in the present specification are all values obtained by calculation using software package 1 except for the cases described later.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

On the other hand, pKa can also be obtained by the molecular orbital calculation method. As a specific method for this, there is a method of ^{calculating H +} dissociation free energy in a solvent based on a thermodynamic cycle. In the present specification, water is usually used as the solvent, and DMSO (dimethyl sulfoxide) is used when pKa cannot be obtained with water.
The calculation method of H ⁺ dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature and are not limited thereto. There are a plurality of software capable of performing DFT, and examples thereof include Gaussian16.

As described above, pKa in the present specification refers to a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using software package 1, and pKa is calculated by this method. If it cannot be calculated, the value obtained by Gaussian 16 based on DFT (Density Functional Theory) shall be adopted.

Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, the following substituent T can be selected.

(Substituent T)
Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and metoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group ; And combinations of these.

[Actinic cheilitis or radiation-sensitive resin composition]
The actinic or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) will be described.
The composition of the present invention is typically a resist composition, which may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development.
The composition of the present invention is preferably a chemically amplified resist composition.

The composition of the present invention comprises a resin (A) containing a repeating unit (1a) represented by the general formula (1) and a repeating unit (1b) having an acid-degradable group, and an acid by irradiation with active light or radiation. Is contained with the compound (B) that generates the above.
According to such a configuration, for example, in an ultrafine pattern having a pitch of 50 nm or less, pattern collapse (falling front width) can be reduced, and a pattern having excellent roughness performance can be formed.
Here, the "falling front width" means a line width that can be formed (resolved) without the line portion falling.
The mechanism by which the present invention can exert the above effects is not always clear, but the present inventors consider it as follows.

The composition of the present invention contains a resin (A) containing a repeating unit (1a) represented by the general formula (1). Repeating unit (1a) is represented by R ^1, polar moderately high, and has a group having a cyclic structure containing a carbonate group, or a group having a cyclic structure containing an SO ₂ group.
In general, a compound (also referred to as a "photoacid generator") that generates an acid by irradiation with active light or radiation contained in a sensitive light-sensitive or radiation-sensitive resin composition has a polar group or has a polar group. Since it is an ionic compound, it tends to agglomerate between photoacid generators.
However, in the present invention, the highly polar R ¹ of the resin (A) interacts with the compound (B) to suppress the aggregation of the compound (B). Therefore, in the sensitive light-sensitive or radiation-sensitive film (typically a resist film) formed by the composition of the present invention, it is considered that the photoacid generator can be uniformly present and the roughness performance is improved. Be done.
^{Here, the R 1} of the resin (A) has a polarity sufficient to suppress the aggregation of the photoacid generator as described above, but the polarity is not too high, so that development failure is unlikely to occur, and the resin (A) Compatibility with the non-polar unit in A) (for example, the acid-degradable group in the repeating unit (1b) having an acid-degradable group) can also be maintained. Therefore, it is considered that the roughness performance is further improved.
In this way, it is presumed that the excellent roughness performance makes the distance between adjacent patterns in the obtained pattern more uniform, so that the capillary force applied between the adjacent patterns is made uniform and pattern collapse can be suppressed. NS.

Further, the repeating unit (1a) contained in the resin (A) has one benzene ring in its structure.
In the case of a resin having no benzene ring, the glass transition point (Tg) of the obtained sensitive light-sensitive or radiation-sensitive film is lowered, and the acid generated from the photoacid generator is easily diffused, so that the roughness performance is improved. It gets worse. Further, it is considered that the insufficient strength of the obtained pattern causes the etching resistance to deteriorate and the pattern to collapse easily.
On the other hand, in the case of a resin having a polycyclic aromatic ring such as a naphthalene ring, since the hydrophobicity is high, it is ^{difficult to obtain the effect of the polarity of R 1} , and it is easy to cause aggregation of the photoacid generator. It is considered that such roughness performance cannot be obtained.

Hereinafter, the components that can be contained in the composition of the present invention will be described in detail.

[Resin (A)]
The composition of the present invention contains a resin (A) containing a repeating unit (1a) represented by the following general formula (1) and a repeating unit (1b) having an acid-degradable group.

In general formula (1),
R ¹ represents a group having a cyclic structure containing a carbonic acid ester group or a group having a cyclic structure containing _{SO 2 groups.} However, neither of the two bonds of the sulfur atom in the _{SO 2 group is bonded to the oxygen atom.}
R ² represents a hydrogen atom, a halogen atom, a hydroxyl group or an organic group.
R ³ represents a hydrogen atom, a halogen atom or an alkyl group.
L ¹ represents a single bond or a divalent linking group.
L ² represents a single bond or a divalent linking group.
X is ^{-COO -, - O -, -} CONR 4 -, - SO 3 -, - SO 2 NR 4 - or -C _(CF ₃₎ 2 O- and represents, ^{R 4} represents a hydrogen atom or an alkyl group.
m ¹ and n ¹ each represent an integer of 1 to 4. However, m ¹ + n ¹ = 5 is satisfied.
If R ^1, ^R 2, X and ^{L 1} there are a plurality, the plurality of ^R ^{1, R} 2, X and ^{L 1} may be different from one another respectively the same.

In the general formula (1), R ¹ is a group having a cyclic structure containing a carbonic acid ester group (a group represented by the following formula (G1)) or _two SO groups (a group represented by the following formula (G2)). Represents a group having a cyclic structure containing.

In the formula (G1) and the formula (G2), * 1 to * 4 represent the coupling position. However, neither of the two bonds of the sulfur atom in the _{SO 2 group is bonded to the oxygen atom.} That is, neither * 3 nor * 4 in the formula (G2) represents the bond position with the oxygen atom.
It is preferable that both of the two bonds of the sulfur atom in the SO _{2 group are bonded to the carbon atom or the nitrogen atom.} That is, it is preferable that * 3 and * 4 in the formula (G2) independently represent the bond positions with the carbon atom or the nitrogen atom, respectively.

^{R 1} in the general formula (1) is a group having a cyclic structure containing a carbonic acid ester group, or a cyclic structure containing _{SO 2} groups in which two bonds of a sulfur atom are both bonded to a carbon atom or a nitrogen atom. It is preferable to represent a group having.

In ^{the cyclic structure of R 1,} the number of atoms (number of ring member atoms) that contribute to ring formation is preferably 4 to 15, more preferably 4 to 10, and even more preferably 4 to 8. Type of atoms contributing to ring formation than ₂ group carbonic acid ester group and SO is not particularly limited, (it may be a carbonyl carbon) of carbon atoms, oxygen atom, sulfur atom, nitrogen atom and the like, carbon atoms Is preferable.

The cyclic structure of R ¹ may be monocyclic or polycyclic, but is preferably monocyclic.

The cyclic structure of R ¹ is preferably composed of a carbonic acid ester group or SO ₂ group and a hydrocarbon group.
Ring structure of R ¹ is preferably a structure in which a portion of the hydrocarbon group in the cycloalkyl or cycloalkenyl group or a monocyclic or polycyclic is replaced by carbonate group or a SO ₂ group.
Here, the replacing part of the hydrocarbon group in the cycloalkyl group or cycloalkenyl group carbonate group or a SO ₂ group, in the cycloalkyl or cycloalkenyl group - (CH ₂₎ 3 _- group and carbonate group It means to replace with, or to replace the-(CH ₂ ) -group with _{2 SO groups.}

Cyclic structure R ¹ is, part of the hydrocarbon group carbonate group in monocyclic cycloalkyl group, or a structure substituted with a SO ₂ group, examples of the cycloalkyl group, having 4 to 15 carbon atoms Examples thereof include a cycloalkyl group, preferably a cycloalkyl group having 4 to 10 carbon atoms, more preferably a cycloalkyl group having 4 to 8 carbon atoms, and specifically, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

Cyclic structure R ¹ is, in part in polycyclic cycloalkyl group hydrocarbon group carbonate group, or a structure substituted with a SO ₂ group, examples of the cycloalkyl group, having 4 to 15 carbon atoms Cycloalkyl groups are mentioned, and cycloalkyl groups having 4 to 10 carbon atoms are preferable. The cycloalkyl group preferably has a 5- or 6-membered ring structure. Examples of the polycyclic cycloalkyl group having a 5- or 6-membered ring structure include a tricyclodecanyl group and a bicyclo [4,3,0] nonyl group.

The cyclic structure of R ¹ may further have a substituent. The further substituent is not particularly limited, and examples thereof include the above-mentioned substituent T.

In the general formula (1), R ² represents a hydrogen atom, a halogen atom, a hydroxyl group or an organic group.

Examples of the halogen atom when R ² represents a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

When R ² represents an organic group, the organic group is not particularly limited, and specific examples thereof include an alkyl group and a cycloalkyl group.
The alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and methyl. Groups are particularly preferred.
The cycloalkyl group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms.

The organic group may further have a substituent. The further substituent is not particularly limited, but the above-mentioned Substituent T is preferable, a halogen atom is more preferable, and a fluorine atom is further preferable.

When R ² represents an organic group, the organic group is preferably an alkyl group, more preferably a fluorine-substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a methyl group or a trifluoromethyl group. Is even more preferable.

R ² is preferably a hydrogen atom, a fluorine atom, a hydroxyl group, a methyl group or a trifluoromethyl group, and more preferably a hydrogen atom.

In the general formula (1), R ³ represents a hydrogen atom, a halogen atom or an alkyl group.

Examples of the halogen atom when R ³ represents a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

When R ³ represents an alkyl group, examples of the alkyl group include a linear or branched alkyl group having 1 to 12 carbon atoms, and a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
When the alkyl group has a substituent, the substituent includes the above-mentioned Substituent T, which is preferably a halogen atom and more preferably a fluorine atom.

R ³ is preferably a hydrogen atom, a fluorine-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a fluorine atom, and more preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a fluorine atom. , Hydrogen atom or methyl group is more preferable.

In the general formula (1), L ¹ represents a single bond or a divalent linking group.

Examples of the divalent linking group when L ¹ represents a divalent linking group include an alkylene group, -O-, -C (= O)-, or a divalent group formed by combining these.

Examples ^{of the alkylene group in which L 1} represents an alkylene group include a chain or branched alkylene group having 1 to 18 carbon atoms, and specifically, a methylene group, an ethylene group, an n-propylene group, and i-. Examples thereof include a propylene group, an n-butylene group, an n-hexylene group and an n-octylene group.
The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably a methylene group.
The alkylene group may have a substituent, and examples of the substituent when the alkylene group has a substituent include the above-mentioned Substituent T.

L ¹ is preferably a single bond, a methylene group, an ethylene group, -O-, -C (= O)-, or a divalent group formed by combining these.

In the general formula (1), L ² represents a single bond or a divalent linking group.

Examples of the divalent linking group when L ² represents a divalent linking group include an alkylene group, —O—, —C (= O) −, or a divalent group formed by combining these groups.

Examples of the alkylene group when L ² represents an alkylene group include the alkylene group mentioned as L ¹ , and the same applies to preferred examples.
The alkylene group may have a substituent, and examples of the substituent when the alkylene group has a substituent include the above-mentioned Substituent T.

L ² is preferably a single bond or —C (= O) O—, and more preferably a single bond. When L ² is a single bond, it is preferable because it is possible to prevent a decrease in Tg by maintaining the rigidity in the vicinity of the main chain of the resin (A).

, - - -COO In the general formula (1), X is ^{_{O -, - CONR 4 -,}} - SO 3 -, - SO 2 NR 4 - or -C _(CF ₃₎ 2 O- and represents, ^{R 4} is hydrogen Represents an atom or an alkyl group.

When R ⁴ represents an alkyl group, the alkyl group may be linear or branched, preferably having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
R ⁴ is preferably a hydrogen atom.

X more preferably represents -COO-, -O- or -SO _3-, and particularly preferably -COO- or -O-.

In the general formula (1), m ¹ and n ¹ each represent an integer of 1 to 4. However, m ¹ + n ¹ = 5 is satisfied.
m ¹ preferably represents 1 or 2, and more preferably 1. That is, n ¹ preferably represents 4 or 3, and more preferably 4.

The repeating unit (1a) represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).

(Repeating unit represented by general formula (2))

In the general formula (2), R ¹ , R ² , R ³ , L ¹ , m ¹ and n ¹ have the same meanings as those in the general formula (1), respectively.
X 'is ^{_{-COO -, - CONR 4 -,}} - SO 3 -, - SO 2 NR 4 - or -C _(CF ₃₎ 2 O- and represents, ^{R 4} represents a hydrogen atom or an alkyl group.
'If and ^{L 1} there are a plurality, the plurality of ^{^{R 1, R 2, X'}} R 1, R 2, X and ^{L 1} may be different from one another respectively the same.

In the general formula ^{^{(2), R 2, R}} 3, L 1, m 1 and ^{n 1} are respectively synonymous with ^{^{^{R 2, R 3, L 1}}} , m 1 and ^{n 1} in the general formula (1) The same applies to preferred examples.

^{R 1} in the general formula (2) is synonymous with ^{R 1} in the general formula (1).
R ¹ is preferably represented by the following general formula (4-1) or (4-2).

In general formula (4-1),
R ₄₁₁ , R ₄₁₂ , R ₄₁₃ , R ₄₁₄ and R ₄₁₅ each independently represent a hydrogen atom or an alkyl group.
p ₄₁ and p ₄₂ each independently represent an integer of 0 to 2. However, p ₄₁ + p ₄₂ ≤ 2 is satisfied. If R _411, R _412, R ₄₁₄ and R ₄₁₅ there are a plurality, a plurality of R _411, R _412, R ₄₁₄ and R ₄₁₅ may be different from one another respectively the same.
In general formula (4-2),
R ₄₂₁ , R ₄₂₂ , R ₄₂₃ , R ₄₂₄ and R ₄₂₅ each independently represent a hydrogen atom or an alkyl group.
p ₄₃ and p ₄₄ each independently represent an integer of 0 to 2. However, p ₄₃ + p ₄₄ ≤ 2 is satisfied. If R _421, R _422, R ₄₂₄ and R ₄₂₅ there are a plurality, a plurality of R _421, R _422, R ₄₂₄ and R ₄₂₅ may be different from one another respectively the same.
In the general formulas (4-1) and (4-2), * represents the bonding position.

_{When R 411} , R ₄₁₂ , R ₄₁₃ , R ₄₁₄ and R _{415 in the} general formula (4-1) represent an alkyl group, the alkyl group has a linear or branched carbon number of 1 to 12. Alkyl groups are mentioned, and a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
When the alkyl group has a substituent, the substituent includes the above-mentioned Substituent T, which is preferably a halogen atom and more preferably a fluorine atom.

R ₄₁₁ , R ₄₁₂ , R ₄₁₃ , R ₄₁₄ and R ₄₁₅ are preferably hydrogen atoms.

In the general formula (4-1), p ₄₁ and p ₄₂ preferably represent 0 or 1, respectively, and one represents 0 and the other represents 1, or both represent 1. It is preferable that one represents 0 and the other represents 1.

_{When R 421} , R ₄₂₂ , R ₄₂₃ , R ₄₂₄ and R _{425 in the} general formula (4-2) represent an alkyl group, the alkyl group in the above general formula (4-1) is R ₄₁₁ , R _412. , R ₄₁₃ , R ₄₁₄ and R ₄₁₅ are described as alkyl groups when they represent alkyl groups, and preferred examples thereof are also the same.

R ₄₂₁ , R ₄₂₂ , R ₄₂₃ , R ₄₂₄ and R ₄₂₅ are preferably hydrogen atoms.

In the general formula (4-2), p ₄₃ and p ₄₄ preferably represent 0 or 1, respectively, and one represents 0 and the other represents 1, or both represent 1. It is preferable that one represents 0 and the other represents 1.

It is particularly preferable that R ¹ is a group represented by the above general formula (4-1).

In the general formula (2), X 'is ^{_{-COO -, - CONR 4 -,}} - SO 3 -, - SO 2 NR 4 -, or -C _(CF ₃₎ 2 O- and represents, ^{R 4} is a hydrogen atom or Represents an alkyl group.

The above R ⁴ ^{has the same meaning as the R 4} described in the general formula (1), and the same applies to preferred examples.

X'is preferably -COO- or -SO _3- , and more preferably -COO-.

It is also preferable that the repeating unit (1a) represented by the above general formula (1) is a repeating unit represented by the following general formula (5).

(Repeating unit represented by the general formula (5))

In the general formula (5), R ¹ , R ² , R ³ , L ¹ , m ¹ and n ¹ have the same meanings as those in the general formula (1), respectively.
If R ^1, ^{R 2} and ^{L 1} there are a plurality, the plurality of ^R 1, ^{R 2} and ^{L 1} may be different from one another respectively the same.

In the general formula ^{^{(5), R 2, R}} 3, L 1, m 1 and ^{n 1} are respectively synonymous with ^{^{^{R 2, R 3, L 1}}} , m 1 and ^{n 1} in the general formula (1) The same applies to preferred examples.

^{R 1} in the general formula (5) is synonymous with ^{R 1} in the general formula (1).
R ¹ is preferably a group represented by the following general formula (6-1) or (6-2).

In general formula (6-1),
R ₆₁₁ , R ₆₁₂ , R ₆₁₃ , R ₆₁₄ and R ₆₁₅ each independently represent a hydrogen atom or an alkyl group.
p ₆₁ and p ₆₂ each independently represent an integer of 0 to 2. However, p ₆₁ + p ₆₂ ≤ 2 is satisfied. If R _611, R _612, R ₆₁₄ and R ₆₁₅ there are a plurality, a plurality of R _611, R _612, R ₆₁₄ and R ₆₁₅ may be different from one another respectively the same.
In general formula (6-2),
R ₆₂₁ , R ₆₂₂ , R ₆₂₃ , R ₆₂₄ and R ₆₂₅ each independently represent a hydrogen atom or an alkyl group.
p ₆₃ and p ₆₄ each independently represent an integer of 0 to 2. However, p ₆₃ + p ₆₄ ≤ 2 is satisfied. If R _621, R _622, R ₆₂₄ and R ₆₂₅ there are a plurality, a plurality of R _621, R _622, R ₆₂₄ and R ₆₂₅ may be different from one another respectively the same.
In the general formulas (6-1) and (6-2), * represents the bonding position.

_{R 611} , R ₆₁₂ , R ₆₁₃ , R ₆₁₄ , R ₆₁₅ , p ₆₁ and p ₆₂ in the general formula (6-1) _{are R 411} , R ₄₁₂ and R _{413 in the} general formula (4-1), respectively. , R ₄₁₄ , R ₄₁₅ , p ₄₁ and p _42, and so are the preferred examples.

_{R 621} , R ₆₂₂ , R ₆₂₃ , R ₆₂₄ , R ₆₂₅ , p ₆₃ and p ₆₄ in the general formula (6-2) _{are R 421} , R ₄₂₂ and R _{423 in the} general formula (4-2), respectively. , R ₄₂₄ , R ₄₂₅ , p ₄₃ and p _44, and so are the preferred examples.

It is particularly preferable that R ¹ is a group represented by the general formula (6-1).

When the repeating unit (1a) is a repeating unit represented by the general formula (5), the resin (A) is further selected from the group consisting of a lactone structure, a carboxyl group, a hydroxyl group and a sulfonamide group, which will be described later. It is particularly preferable to include a repeating unit (1c) having.

Specific examples of the repeating unit (1a) represented by the general formula (1) are shown below, but the present invention is not limited thereto.

In the resin (A), the repeating unit (1a) may be used alone or in combination of two or more.

The content of the repeating unit (1a) in the resin (A) is preferably 5 to 75% by mass, more preferably 5 to 70% by mass, based on all the repeating units of the resin (A). It is more preferably 10 to 60% by mass.

<Repeating unit having an acid-degradable group (1b)>
The resin (A) contains a repeating unit (1b) having an acid-degradable group.

The acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) that is eliminated by the action of an acid.
Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkylcarbonyl). Imid group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) Examples thereof include acidic groups such as methylene groups (typically, groups dissociating in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the α-position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

Among them, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.

Examples of the group desorbed by the action of an acid (leaving group) include groups represented by the formulas (Y1) to (Y4).
Equation (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Equation (Y2): -C (= O) OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Equation (Y3): -C (R ₃₆ ) (R ₃₇ ) (OR ₃₈ )
Formula (Y4): -C (Rn) (H) (Ar)

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ are independently alkyl groups (linear or branched chain), cycloalkyl groups (monocyclic or polycyclic), or aryl groups (monocyclic or polycyclic), respectively. Represents monocyclic or polycyclic).
Among them, Rx ₁ to Rx ₃ preferably independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear alkyl group. Is more preferable.
Two of Rx ₁ to Rx ₃ may be combined to form a monocyclic or polycyclic ring.
The alkyl group of Rx ₁ to Rx ₃ is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Further, an alkyl group having 1 to 4 carbon atoms such as a t-butyl group is preferable.
The cycloalkyl group of Rx ₁ to Rx ₃ is not particularly limited, and examples thereof include a cycloalkyl group having 3 to 20 carbon atoms, a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group. , Tetracyclodecanyl group, tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The alkyl group, cycloalkyl group, and aryl group may have a substituent.

Examples of the _{cycloalkyl group formed by combining two of Rx 1} to Rx ₃ include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as an nyl group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The _{cycloalkyl group formed by combining two of Rx 1} to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
The cycloalkyl group formed by bonding two of _{Rx 1} to Rx _{3 may have a substituent.}

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be combined with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. It is also preferable that R _{36 is a hydrogen atom.}

As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.

Here, _LY3 and _LY4 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined). ..
M represents a single bond or a divalent linking group.
Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, and an aldehyde. Represents a group or a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).
As for the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.
It is preferable that one of _LY3 and _LY4 is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
At least two of Q, M and _LY3 may be combined to form a ring (preferably a 5- or 6-membered ring).
From the viewpoint of pattern miniaturization, _LY4 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group and a norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group and an adamantan group. In these aspects, Tg (glass transition temperature) and activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.

In the formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be combined with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

The repeating unit (1b) having an acid-decomposable group is preferably a repeating unit represented by the following general formula (A).

In the general formula (A), L _1A represents a divalent linking group, R _1A to R _3A independently represent a hydrogen atom or a monovalent substituent, and R _4A is decomposed and eliminated by the action of an acid. Represents a group.
L _1A represents a divalent linking group. Examples of the divalent linking group include -CO- _{, -O-, -S-, -SO-, -SO 2-} , a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkaneylene group, an arylene group, etc.). In addition, a linking group in which a plurality of these are linked can be mentioned. Of these, -CO- and an arylene group are preferable as _{L 1A.}
As the arylene group, a phenylene group is preferable.
The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.

R _1A to R _3A independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include an alkyl group, a cycloalkyl group, and a halogen atom.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of this cycloalkyl group is preferably 3 to 8.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R _4A represents a group (leaving group) that is eliminated by the action of an acid.
Among them, examples of the leaving group include groups represented by the above formulas (Y1) to (Y4), and groups represented by the above formula (Y3) are preferable.

When each of the above groups has a substituent, the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like. The number of carbon atoms in the substituent is preferably 8 or less.

It is also preferable that the repeating unit (1b) having an acid-decomposable group is a repeating unit represented by the following general formula (3).

In general formula (3),
X ³ represents a hydrogen atom, an alkyl group, or a halogen atom.
Z represents a group having a group that is eliminated by the action of an acid.

In the general formula (3), ^{X 3} represents a hydrogen atom, an alkyl group, or a halogen atom.

When X ³ represents an alkyl group, the alkyl group includes a linear or branched alkyl group having 1 to 12 carbon atoms, and a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. Preferably, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
Examples of the substituent when the alkyl group has a substituent include the substituent described in the Substituent T, which is preferably a halogen atom and more preferably a fluorine atom.

Examples of the halogen atom when X ³ represents a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

X ³ is preferably a hydrogen atom, a fluorine-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a fluorine atom, a methyl group, and more preferably a trifluoromethyl group or a fluorine atom.

In the general formula (3), Z represents a group having a group eliminated by the action of an acid.

In the general formula (3), the polar group in the structure (acid-degradable group) in which the polar group is protected by the leaving group desorbed by the action of an acid is a carboxylic acid group. By using a carboxylic acid group as the polar group, the change in dissolution contrast before and after the elimination of the leaving group can be increased, so that the LWR performance can be improved.

In the general formula (3), Z may be the leaving group itself. That is, in this case, a structure (acid-degradable group) in which the polar group (carboxylic acid group) is protected by the leaving group (Z) is formed, and -COO-Z in the general formula (3) is an acid-degradable group as a whole. Consists of. Further, a part of Z in the general formula (3) may contain an acid-degradable group whose polar group is a carboxylic acid group, or Z as a whole is an acid-degradable group whose polar group is a carboxylic acid group. May be configured.
Examples of the leaving group that are eliminated by the action of an acid include groups represented by the above formulas (Y1) to (Y4).

In the desorbing group that protects the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the non-aromatic ring in the non-aromatic ring, from the viewpoint of excellent acid decomposition property of the repeating unit, It is also preferable that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have a halogen atom such as a fluorine atom as a substituent.

Other leaving groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, and 1,1,4. , A cyclohexyl group having a substituent (alkyl group, etc.) such as 4-tetramethylcyclohexyl group may be used.

-Repeating unit (1b-1)
The repeating unit (1b) is a repeating unit in which Z in the general formula (3) is represented by the above formula (Y1), that is, a repeating unit (1b-1) represented by the following general formula (3-1). It is preferable to have.

In general formula (3-1),
X ³ represents a hydrogen atom, an alkyl group, or a halogen atom.
R ^Z1 to R ^Z3 independently represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Any two of R ^Z1 to R ^Z3 may be bonded to form a ring structure.

^{X 3} in the general formula (3-1) ^{has the same meaning as X 3} in the general formula (3), and the same applies to preferred examples.

^{R Z1} to R ^Z3 in the general formula (3-1) _{are synonymous with Rx 1} to Rx _{3 in} the above formula (Y-1), and preferred examples are also the same.

・ Repeat unit (1b-2)
The repeating unit (1b) is more preferably a repeating unit (1b-2) represented by the following general formula (3-2).

In general formula (3-2),
X ³ represents a hydrogen atom, an alkyl group, or a halogen atom.
R ^3b represents an alkyl group, a cycloalkyl group, or an aryl group.
m ³ represents an integer of 1 or more.

^{X 3} in the general formula (3-2) ^{has the same meaning as X 3} in the general formula (3), and the same applies to preferred examples.

In the general formula (3-2), R ^3b represents an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group, cycloalkyl group, and aryl group may have a substituent.

When R ^3b represents an alkyl group, the alkyl group and the substituent that the alkyl group may have include an alkyl group as _{Rx 1} to Rx _{3 in the above formula (Y-1) and an alkyl group.} Substituents may be mentioned, and preferred examples are the same.

Examples of the cycloalkyl group when R ^3b represents a cycloalkyl group include cycloalkyl groups as Rx ₁ to Rx _{3 in} the above formula (Y-1), and preferred examples thereof are also the same.

Examples of the aryl group when R ^3b represents an aryl group include aryl groups as Rx ₁ to Rx _{3 in} the above formula (Y-1), and a phenyl group or a naphthyl group is preferable.

R ^3b is preferably a linear or branched alkyl group, more preferably a methyl group, an ethyl group, an i-propyl group, an n-butyl group, a t-butyl group, or a cyclohexyl group. More preferably, it is a methyl group, an ethyl group, an i-propyl group, or a t-butyl group.

In the general formula (3-2), m ³ represents an integer of 1 or more. m ³ is preferably 1 to 10, more preferably 1 to 6, and even more preferably 3 or 4.

The repeating unit (1b) having an acid-decomposable group is illustrated below, but the present invention is not limited thereto.

In the resin (A), the repeating unit (1b) may be used alone or in combination of two or more.

The content of the repeating unit (1b) is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and 30 to 70% by mass with respect to all the repeating units of the resin (A). Is more preferable.

<Repeating unit (1c)>
The resin (A) further preferably contains a repeating unit (1c) having at least one selected from the group consisting of a lactone structure, a carboxyl group, a hydroxyl group and a sulfonamide group. The repeating unit (1c) is a repeating unit different from the repeating unit (1a) and the repeating unit (1b).
As mentioned above, the repeating unit (1a) includes the highly polar R ¹ , but the repeating unit (1b) is typically less polar. Therefore, by including the repeating unit (1c) having a polarity between the repeating unit (1a) and the repeating unit (1b), each repeating unit of the resin (A) is contained in the film formed from the composition of the present invention. It is considered that the state of existence becomes more uniform, the uniformity of the distribution of the compound (B) increases, and the effect of suppressing the aggregation of the compound (B) becomes more remarkable.

-Repeating unit having a lactone structure The lactone structure may have a lactone ring, and a lactone structure having a 5- to 7-membered lactone ring is preferable.
A lactone structure in which a 5- to 7-membered ring lactone ring is fused with another ring to form a bicyclo structure or a spiro structure is also preferable. A sultone structure in which another ring is condensed into a 5- to 7-membered sultone ring in the form of forming a bicyclo structure or a spiro structure is also preferable.

Among them, the resin (A) preferably contains a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-22). Further, the lactone structure may be directly bonded to the main chain.
Among them, the general formula (LC1-1), the general formula (LC1-4), the general formula (LC1-5), the general formula (LC1-8), the general formula (LC1-16), and the general formula (LC1-21). Alternatively, a lactone structure represented by the general formula (LC1-22) is preferable.

The lactone structure may or may not have a _{substituent (Rb 2).} Examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. A halogen atom, a hydroxyl group, a cyano group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other to form a ring.

As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (LS1) is preferable.

In the above general formula (LS1),
A ^LS represents an ester bond (-COO- group represented by) or an amide bond (a group represented by -CONH-).

t is the ^{number of repetitions of the structure represented by −R LS2} −R ^LS3− , represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When t is 0, (-R ^LS2- ^{R LS3-} ) t is a single bond.

R ^LS2 represents an alkylene group, a cycloalkylene group, or a combination thereof. When a ^{plurality of R LS2s} are present, the plurality of R ^LS2s may be the same or different from each other.
The alkylene group or cycloalkylene group of ^{RLS2 may have a substituent.}

^RLS3 represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When a ^{plurality of R LS3s} are present, the plurality of R ^LS3s may be the same or different from each other.
Among them, R ^LS3 is preferably an ether bond or an ester bond, and more preferably an ester bond.

^RLS4 represents a monovalent organic group having a lactone structure.
Among them, in any of the structures represented by the above-mentioned general formulas (LC1-1) to (LC1-22), one hydrogen atom is removed from one carbon atom constituting the lactone structure. It is preferably a group consisting of It is preferable that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting a _{substituent (Rb 2).}

^RLS1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).

As a specific example of the repeating unit having a lactone structure, the description in paragraph [0088] of International Publication No. 2018/193954 can be taken into consideration, and these contents are incorporated in the present specification. Further, the resin (A) of the present invention may have a repeating unit having a lactone structure other than the above.

-Repeat unit having a hydroxyl group Examples of the hydroxyl group include an alcoholic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a phenolic hydroxyl group.

The repeating unit having an alcoholic hydroxyl group is preferably a repeating unit represented by the general formula (A5).

In the general formula (A5),
X ^Q5 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
^RQ5 represents an alkylene group (linear or branched chain, preferably 1 to 5 carbon atoms) or a non-aromatic ring group.

Examples of the non-aromatic ring group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group. Examples of the monocyclic hydrocarbon ring group include a cycloalkane ring group having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and a cycloalkene ring group having 3 to 12 carbon atoms.
Examples of the polycyclic hydrocarbon ring group include a ring-assembled hydrocarbon ring group and a crosslinked ring-type hydrocarbon ring group.
Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring and the like. Further, the crosslinked cyclic hydrocarbon ring may be a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
The crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclo [5, 2, 1, 02, 6] decane ring group.

It is also preferable that the alkylene group and the non-aromatic ring group do not have a substituent other than _{− (OH) q5.}

In the general formula (A5), q5 represents an integer of 1 to 5.
The repeating unit having a fluorinated alcohol group is preferably a repeating unit represented by the general formula (A6).

In the general formula (A6),
X ^Q6 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
^RQ6 represents an alkylene group (linear or branched chain, preferably 1 to 5 carbon atoms), a non-aromatic ring group, an aromatic ring group, or a group composed of a combination of two or more of these. ..

The aromatic ring group preferably has an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, an anthracene ring group, or a biphenylene ring group.

It is also preferable that the alkylene group, the non-aromatic ring group, and the aromatic ring group do not have a substituent other than _{− (−C (CF 3} ) ₂ OH) _q6.

In the general formula (A6), q6 represents an integer from 1 to 5.

When the resin (A) has a repeating unit having a hydroxyl group, the content thereof is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and 7 to 7 to all the repeating units of the resin (A). 45 mol% is more preferred.
The repeating unit having a hydroxyl group may be used alone or in combination of two or more.

The repeating unit having a phenolic hydroxyl group is preferably a repeating unit having a phenolic hydroxyl group represented by the following general formula (B2).

In the general formula (B2), X represents a hydrogen atom, an alkyl group, or a halogen atom.
The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms.
The substituent of the alkyl group is preferably a hydroxyl group or a halogen atom. When the alkyl group has a substituent, it is preferable that the alkyl group has only a hydroxyl group and / or a halogen atom as the substituent. The alkyl group is preferably _{-CH 3.}

In the general formula (B2), X ₄ represents a single bond, -COO-, or -CONR _64- , and R ₆₄ is a hydrogen atom or an alkyl group (which may be linear or branched, preferably having a number of carbon atoms). Represents 1 to 5). The carbonyl carbon in -COO- is preferably directly attached to the main chain of the repeating unit.

In the general formula (B2), L ₄ represents a single bond or an alkylene group (which may be linear or branched, preferably having 1 to 20 carbon atoms).

In the general formula (B2), Ar ₄ represents an (n + 1) -valent aromatic ring group. The aromatic ring group is an arylene group having 6 to 18 carbon atoms such as a benzene ring group, a naphthalene ring group, and an anthracene ring group, or a thiophene ring group, a furan ring group, a pyrrole ring group, a benzothiophene ring group, and a benzofuran. Aromatic ring groups containing heterocycles such as a ring group, a benzopyrol ring group, a triazine ring group, an imidazole ring group, a benzoimidazole ring group, a triazole ring group, a thiadiazol ring group, and a thiazole ring group are preferable, and a benzene ring group is preferable. More preferred.

In the general formula (B2), n represents an integer from 1 to 5. The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent that the above-mentioned _{alkyl group of R 64} , alkylene group of L ₄ and Ar ₄ (n + 1) -valent aromatic ring group can have include a halogen atom (preferably a fluorine atom) and a methoxy group. Examples thereof include an alkoxy group such as an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like. Further _{, examples of the substituent that the (n + 1) -valent aromatic ring group of Ar 4} can have include an alkyl group (which may be linear or branched, preferably having 1 to 20 carbon atoms).

As a specific example of the repeating unit having a hydroxyl group, the description in paragraphs [0068] to [0072] of International Publication No. 2018/193954 can be taken into consideration, and these contents are incorporated in the present specification. Further, the resin (A) of the present invention may have a repeating unit having a hydroxyl group other than the above. Specific examples of the repeating unit having a hydroxyl group other than the above are shown below, but the present invention is not limited thereto. However, the following specific examples show the structure as a raw material monomer.

It is also preferable that the repeating unit (1c) is the repeating unit described in paragraphs [0370] to [0433] of the US Patent Application Publication No. 2016/0070167A1.

When the resin (A) contains a repeating unit (1c), the type of the repeating unit (1c) contained in the resin (A) may be one or more.

When the resin (A) contains the repeating unit (1c), the content of the repeating unit (1c) contained in the resin (A) (if there are a plurality of repeating units (1c), the total content thereof) is the resin. It is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass with respect to all the repeating units in (A).

<Other repeating units>
In addition, the resin (A) may further contain other repeating units.
As other repeating units, the description in paragraphs [0122] to [0133] of International Publication No. 2018/193954 can be referred to, and these contents are incorporated in the present specification.

The resin (A) may contain a repeating unit other than the above as the other repeating unit as long as the effect of the present invention is not impaired. For example, the resin (A) may have a repeating unit having a photoacid generating group. good.
As the repeating unit having a photoacid generating group, the description in paragraphs [0090] to [0106] of JP-A-2014-413327 can be referred to, and these contents are incorporated in the present specification.

The resin (A) may further contain a repeating unit having a sultone structure.

The sultone structure may have a sultone ring, and a sultone structure having a 5- to 7-membered sultone ring is preferable.
A sultone structure in which another ring is condensed into a 5- to 7-membered sultone ring in the form of forming a bicyclo structure or a spiro structure is also preferable.

Among them, it is preferable to include a repeating unit having a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3). Further, the sultone structure may be directly bonded to the main chain.
Of these, the sultone structure represented by the general formula (SL1-1) is preferable.

The sultone structure may or may not have a _{substituent (Rb 2).} Examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. A halogen atom, a hydroxyl group, a cyano group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other to form a ring.

When the resin (A) contains a repeating unit having a sultone structure, the content thereof is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, based on all the repeating units of the resin (A). It is more preferably to 30% by mass.

The resin (A) may further have other repeating units other than the above.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
As a polystyrene conversion value by the GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 4,500 to 15,000. When the weight average molecular weight of the resin (A) is set to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and further, deterioration of developability and high viscosity can be prevented. It is possible to prevent the film property from deteriorating.
The dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.

The content of the resin (A) in the composition of the present invention is preferably 50 to 99.9% by mass, preferably 60 to 99.0% by mass, based on the total solid content in the composition of the present invention. More preferably. Further, the resin (A) may be used alone or in combination of two or more. The solid content means a component other than the solvent.

[Compound (B) that generates acid by irradiation with active light or radiation]
The composition of the present invention contains a compound (B) (also referred to as a photoacid generator) that generates an acid upon irradiation with active light or radiation. The photoacid generator is a compound that generates an acid by exposure (preferably exposure to electron beam (EB) or EUV).
The photoacid generator may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
When the photoacid generator is in the form of a small molecule compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less.
When the photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A).
In the present invention, the photoacid generator is preferably in the form of a small molecule compound.
The photoacid generator is not particularly limited, and among them, a compound that generates an organic acid by irradiation with electron beam (EB) or EUV is preferable, and a photoacid generator having a fluorine atom or an iodine atom in the molecule is more preferable.
Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), and carbonyl. Examples thereof include sulfonylimide acid, bis (alkylsulfonyl) imide acid, and tris (alkylsulfonyl) methidoic acid.

Regarding the acid generated from the photoacid generator, the description in paragraphs [0136] to [0141] of International Publication No. 2018/193954 can be taken into consideration, and these contents are incorporated in the present specification.

The photoacid generator is preferably an ionic compound containing an anion and a cation because the effect of the present invention is more excellent.
The photoacid generator may be an ionic compound having an anionic molecule and a cationic molecule, respectively, or may be a betaine compound having a structure in which an anionic portion and a cationic portion are covalently linked.
The photoacid generator is more preferably an ionic compound having an anionic molecule and a cationic molecule, respectively, and is composed of one or more anionic molecules and one or more cationic molecules, and is composed of the above-mentioned cationic molecule. It is more preferable that at least one of them contains a fluorine atom.
The photoacid generator is particularly preferably represented by any of the following general formulas (a) to (c). Details of the general formulas (a) to (c) will be described later.
_{^{_{^{_{M a1 + A a - -L a}}}}} -B a - M a2 + (a)
_{^{_{^{_{(M b1 + A b -)}}}}} nb -L b -B b - M b2 + (b)
_{^{_{^{_{(M c + A c -)}}}}} nc -L c (c)
In the general formula _{(a), M a1} ⁺ and _{M a2} ⁺ each independently represent an organic cation, _{L a} represents a divalent organic group, _{A a} ^- and _{B a} ^- are each independently an anionic functional Represents a group.
However, in the general formula (a) _HA a _-L a -B represented by _a H _{compound M a1} ⁺ and _{M a2} ⁺ is substituted with a hydrogen atom each of the compounds represented by the represented by HA _a pKa groups is less than the pKa of the groups represented by _{B a} H.
In the general formula (b), M _b1 ⁺ and M _b2 ⁺ each independently represent an organic cation, L _b represents a (nb + 1) -valent organic group, _{and Ab} ⁻ and B _b ⁻ each independently represent an anion. It represents a sex functional group, and nb represents an integer of 2 or more. The plurality of M _b1 ⁺ and _Ab ⁻ may be the same or different from each other.
However, in the general formula (b) _{M b1} ⁺ and _{M b2} ⁺ of the compound represented by is substituted with hydrogen atoms, respectively _(HA _b) a compound represented by nb _-L _b -B b H, in HA _b The pKa of the group represented is smaller than the pKa of the group represented by _{B b H.}
In the general formula (c), _Mc ⁺ represents an organic cation, _Ac ⁻ represents an anionic functional group, L _c represents a nonionic organic moiety capable of neutralizing an acid, and nc represents 2 or more. Represents an integer. The plurality of _Mc ⁺ and _Ac ⁻ may be the same or different from each other.

<Compound represented by the general formula (PA-1)>
The photoacid generator is preferably a compound represented by the following general formula (PA-1).

In formula ^{(PA-1), A} 1 and ^{A 2} are each independently, _-SO 2 -R ^P, or represents ^{-CO-R P.} R ^P represents an organic group.
R ^P present two in the general formula (PA-1) may be the same or different.
Formula number of carbon atoms in ^{R P} present two to (PA-1) in each independently, preferably 1 to 25, more preferably from 1 to 15.
The number of the general formula (PA-1) atoms excluding two hydrogen atoms of the present ^{R P} during each independently 2 to 30, and more preferably from 4 to 20.
R ^P is a group represented by the general formula (RF) is preferred.
-L ^RF- R ^RF (RF)

In the general formula (RF), ^LRF represents a single bond or a divalent linking group.
Examples of the divalent linking group include -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO _2- , and an alkylene group (linear or branched chain). It may be preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkaneylene group (linear or branched chain, preferably 2 to 6 carbon atoms), and these. A divalent linking group obtained by combining a plurality of the above can be mentioned.
Further, as the substituent that can be possessed when these divalent linking groups are possible, a halogen atom is preferable, and a fluorine atom is more preferable. For example, it is also preferable that the alkylene group (including an alkylene group that can be contained in a divalent linking group in which a plurality of them are combined) is a perfluoroalkylene group.
The divalent linking group is preferably -alkylene group-COO- or -alkylene group-SO _2- . For the -alkylene group-COO- and the -alkylene group-SO _2- , the alkylene group is preferably present on the N- side.

In the general formula (RF), R ^RF represents a cycloalkyl group or an alkyl group.
When R ^RF is a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic.
The cycloalkyl group preferably has 3 to 15 carbon atoms, and more preferably 5 to 10 carbon atoms.
Examples of the cycloalkyl group include a norbornyl group, a decalynyl group, and an adamantyl group.
The substituent that the cycloalkyl group may have is preferably an alkyl group (linear or branched chain, preferably 1 to 5 carbon atoms). It is also preferable that the cycloalkyl group does not have any other substituent.
One or more of the carbon atoms which are ring member atoms of the cycloalkyl group may be replaced with carbonyl carbon atoms and / or heteroatoms. ^{For example, the carbon atom (-CH <) bonded to L RF} in the cycloalkyl group may be replaced by the nitrogen atom (-N <).
When R ^RF is an alkyl group, the alkyl group may be linear or branched.
The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
The substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group. It is also preferable that the above alkyl group has no substituent other than these.
Examples of the cycloalkyl group as the substituent include, for example, the cycloalkyl group described in the case where ^{R RF is a cycloalkyl group.}
When the alkyl group has a fluorine atom as the substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as the substituent, it is also preferable that a part or all of the alkyl group is a perfluoromethyl group.

In formula (PA-1), - two ^{R P} included in ^"A 1 ^-N -A ² 'are bonded to each other may form a ring.

In the general formula (PA-1), M ⁺ represents a cation.
The M ⁺ cation is preferably an organic cation.
The organic cations are preferably cations represented by the general formula (ZaI) (cations (ZaI)) or cations represented by the general formula (ZaII) (cations (ZaII)) independently.

In the above general formula (ZaI)
R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent an organic group.
The carbon number of the organic group as R ²⁰¹ , R ²⁰² , and R ²⁰³ is usually 1 to 30, preferably 1 to 20. Further, two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. The two of the group formed by bonding of the R ²⁰¹ ~ ^{R 203,} for example, an alkylene group (e.g., butylene, pentylene), _{_{_{and, -CH 2 -CH 2 -O-CH}}} 2 -CH 2 - Can be mentioned.

Examples of the cation in the general formula (ZaI) include a cation (ZaI-1), a cation (ZaI-2), and a cation represented by the general formula (ZaI-3b) (cation (ZaI-3b)), which will be described later. In addition, a cation represented by the general formula (ZaI-4b) (cation (ZaI-4b)) can be mentioned.

First, the cation (ZaI-1) will be described.
The cation (ZaI-1) is an aryl sulfonium cation in which at least one ^{of R 201} to R ^{203 of the above general formula (ZaI) is an aryl group.}
As the aryl sulfonium cation, ^{all of R 201} to R ²⁰³ may be an aryl group, or ^{a part of R 201} to R ²⁰³ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
Further, one of R ²⁰¹ to R ²⁰³ may be an aryl group, and ^{the remaining two of R 201} to R ²⁰³ may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, and the like may be formed in the ring. It may contain an ester group, an amide group, or a carbonyl group. As ^{a group formed by bonding two of R 201} to R ²⁰³ , for example, one or more methylene groups are substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group. also an alkylene group (e.g., butylene group, pentylene group, or _{_{_{-CH 2 -CH 2 -O-CH 2}}} -CH 2 -) and the like.
Examples of the aryl sulfonium cation include a triaryl sulfonium cation, a diallyl alkyl sulfonium cation, an aryl dialkyl sulfonium cation, a diallyl cycloalkyl sulfonium cation, and an aryl dicycloalkyl sulfonium cation.

The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like. When the aryl sulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that the arylsulfonium cation has as needed is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms. A cycloalkyl group of 15 is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and substituent that the cycloalkyl group of R ²⁰¹ to R ²⁰³ may have are independently an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, carbon number of carbon atoms). 3 to 15), aryl group (for example, 6 to 14 carbon atoms), alkoxy group (for example, 1 to 15 carbon atoms), cycloalkyl alkoxy group (for example, 1 to 15 carbon atoms), halogen atom, hydroxyl group, or phenylthio group. preferable.
The substituent may further have a substituent if possible. For example, the alkyl group may have a halogen atom as a substituent and may be an alkyl halide group such as a trifluoromethyl group. good.

Next, the cation (ZaI-2) will be described.
The cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in the formula (ZaI) independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
The ^{organic group having no aromatic ring as R 201} to R ²⁰³ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and are linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.

Examples of the alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, and a propyl group). Groups, butyl groups, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl groups, cyclohexyl groups, and norbornyl groups) can be mentioned.
R ²⁰¹ to R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the cation (ZaI-3b) will be described.
The cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).

In the general formula (ZaI-3b),
R _1c to R _5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom and hydroxyl group. , Nitro group, alkylthio group, or arylthio group.
R _6c and R _7c independently represent a hydrogen atom, an alkyl group (t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R _x and R _y independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group, respectively.

Any two or more of R _1c to R _5c _{, R 5c} and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be combined to form a ring, respectively. , This ring may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of the group formed by combining any two or more of R _1c to R _5c _{, R 6c} and R _7c , and R _x and R _y include an alkylene group such as a butylene group and a pentylene group. .. The methylene group in the alkylene group may be substituted with a hetero atom such as an oxygen atom.
The _{group formed by bonding R 5c} and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).

In the general formula (ZaI-4b),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ is a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group (the cycloalkyl group itself may be used, or a group containing a cycloalkyl group as a part). May be). These groups may have substituents.
R ₁₄ is a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be a cycloalkyl group). It may be a group containing a group as a part). These groups may have substituents. When _{a plurality of R 14} are present, each independently represents the above group such as a hydroxyl group.
R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents. Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, in the ring skeleton, an oxygen atom, or may contain a hetero atom such as nitrogen atom. In one embodiment, two R ₁₅ is an alkylene group, it is preferable to form a ring structure.

In the general formula (ZaI-4b), _{the alkyl groups of R 13} , R ₁₄ and R ₁₅ are linear or branched chain. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group or the like.

Next, the general formula (ZaII) will be described. In the general formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group of R ²⁰⁴ and R ²⁰⁵ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ²⁰⁴ and R ²⁰⁵ may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl groups and cycloalkyl groups of R ²⁰⁴ and R ²⁰⁵ are linear alkyl groups having 1 to 10 carbon atoms or branched chain alkyl groups having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group). A group or a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group) is preferable.

The aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ^{205 may each independently have a substituent.} Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms). ~ 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like.

<Other photoacid generators>
In the composition of the present invention, other photoacid generators other than those described above may be used.
Other photoacid generators, for example, "M ^{⁺ Z} - ^(M ⁺ represents a cation and Z ^- represents an anion)" include compounds represented by (onium salt).

^"M + Z ^-" in a compound represented by, ^{M +} represents a cation, include the same cations as the cation in formula (PA-1).
In the compounds represented by, Z ^- "M ⁺ Z" ^- represents an anion, the ability of causing a nucleophilic reaction is extremely low anion preferred.
Examples of the anion include sulfonic acid anions (aliphatic sulfonic acid anions such as fluoroalkyl sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.) and carboxylic acid anions (aliphatic carboxylic acid anions, aromatics, etc.). Group carboxylic acid anions, aralkyl carboxylic acid anions, etc.), and tris (alkylsulfonyl) methide anions.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and may be a linear or branched alkyl group having 1 to 30 carbon atoms. , A cycloalkyl group having 3 to 30 carbon atoms is preferable.

The aromatic ring group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the substituents that the alkyl group, cycloalkyl group, and aryl group mentioned above can have include a halogen atom such as a nitro group and a fluorine atom, a carboxylic acid group, a hydroxyl group, an amino group, a cyano group, and an alkoxy group. (Preferably 1 to 15 carbon atoms), cycloalkyl group (preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), aryloxy group (preferably 6 to 14 carbon atoms), alkoxycarbonyl Group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkyl A sulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably carbon number 1 to 15). 7 to 20), cycloalkylaryloxysulfonyl group (preferably 10 to 20 carbon atoms), alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms), and cycloalkylalkyloxyalkyloxy group (preferably carbon number of carbons). 8 to 20) can be mentioned.

The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

The alkyl group in the tris (alkylsulfonyl) methideanion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group. A fluorine atom or an alkyl group substituted with a fluorine atom is preferable.

As other non-nucleophilic anions, e.g., fluorinated phosphorus (e.g., PF ₆ ^-), fluorinated boron (e.g., BF ₄ ^-), and fluorinated antimony (e.g., SbF ₆ ^-) and the like.

The non-nucleophilic anion is an aliphatic sulfonic acid anion in which at least the α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which a fluorine atom or a group having a fluorine atom is substituted, or an alkyl group in which fluorine is used. Atomically substituted tris (alkylsulfonyl) methideanions are preferred. Among them, a perfluoroaliphatic sulfonic acid anion (preferably 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom is more preferable, and a nonafluorobutane sulfonic acid anion, a perfluorooctane sulfonic acid anion, and a pentafluorobenzene sulfone are used. Acid anions or 3,5-bis (trifluoromethyl) benzenesulfonic acid anions are more preferred.

From the viewpoint of acid strength, it is preferable that the pKa of the generated acid is -1 or less in order to improve the sensitivity.

Further, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) is also preferable.

In the formula, Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of them are present, R ¹ and R ² may be the same or different, respectively.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The number of carbon atoms of the alkyl group in the alkyl group substituted with the fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4. The alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is, for example, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C. ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among others, fluorine atom or CF. ₃ is preferable. In particular, it is preferable that both Xfs are fluorine atoms.

The alkyl groups of R ¹ and R ² may have a substituent (preferably a fluorine atom), and the number of carbon atoms in the substituent is preferably 1 to 4. The substituent is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Alkyl groups having substituents for R ¹ and R ² include, for example, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C. ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F _{9 and the} like can be mentioned, and among them, CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF _3.

x is preferably an integer of 1 to 10, and more preferably 1 to 5.
y is preferably an integer of 0 to 4, more preferably 0.
z is preferably an integer of 0 to 5, more preferably an integer of 0 to 3.
Examples of the divalent linking group of L include -COO-, -CO- _{, -O-, -S-, -SO-, -SO 2-} , alkylene group, cycloalkylene group, alkaneylene group, and these. Examples thereof include a linking group in which a plurality of the above groups are linked, and a linking group having a total carbon number of 12 or less is preferable. Among them, -COO-, -CO-, or -O- is preferable, and -COO- is more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and has an alicyclic group, an aromatic ring group, and a heterocyclic group (not only those having aromaticity but also aromaticity). (Including those that do not), etc.
The alicyclic group may be monocyclic or polycyclic, and a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group is preferable, and in addition, a norbornyl group, a tricyclodecanyl group, and a tetracyclo Polycyclic cycloalkyl groups such as a decanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable. Among them, alicyclic groups having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are used in the post-exposure heating step. It is preferable from the viewpoint of suppressing the diffusibility in the membrane and improving the MEEF (Mask Error Enhancement Factor).
Examples of the aromatic ring group include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring and the like.
Examples of the heterocyclic group include groups derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring and the like. Of these, a group derived from a furan ring, a thiophene ring, or a pyridine ring is preferable.

Further, examples of the cyclic organic group include a group having a lactone structure, and specific examples thereof include lactone structures represented by the above-mentioned general formulas (LC1-1) to (LC1-22).

The cyclic organic group may have a substituent. The substituent may be an alkyl group (linear or branched chain, and may contain a cyclic structure, preferably having 1 to 12 carbon atoms) or a cycloalkyl group (monocyclic or polycyclic). It may be a spiro ring in the case of a polycycle, preferably having a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, and an amide. Examples thereof include a group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be carbonyl carbon.

Examples of the photoacid generator include paragraphs [0368] to [0377] of Japanese Patent Application Laid-Open No. 2014-41328 and paragraphs [0240] to [0262] of Japanese Patent Application Laid-Open No. 2013-228681 (corresponding US Patent Application Publication No. [0339]) of the specification of 2015/004533 can be incorporated, and these contents are incorporated in the specification of the present application.
Moreover, the following compound is mentioned as a preferable specific example. In the following compounds, anions and cations can be optionally exchanged, if possible.

<Compound (P)>
The composition of the present invention preferably contains, as a photoacid generator, a compound (P) having two or more (preferably two or three) cation sites and the same number of anion sites as the above cation sites.
Hereinafter, the specific configurations of the cation moiety and the anion moiety will be described, and then the specific configurations that the compound (P) can take will be described.

(Cation site)
The cation moiety is a structural moiety containing a positively charged atom or atomic group. For example, when the compound (P) has an organic cation, the organic cation may be used as the cation moiety.

As the organic cation, the organic cation mentioned in ^{the description of M +} in the above general formula (PA-1) can be used in the same manner.

・ General formula (I)
At least one (preferably all) of the two or more cation sites (preferably organic cations) of compound (P) preferably has a group represented by the general formula (I).
* -Ar ^x- (RI) ni (I)

In the general formula (I), * represents the bonding position. * Is preferably a bond position with respect to a cationized atom (S ⁺ or I ^{+, etc.).} ^{That is, it is preferable that Ar x} in the general formula (I) is directly bonded to a cationized atom (S ^+, I ^{+, etc.).}

In the general formula (I), Ar ^x represents an aromatic hydrocarbon ring group.
The aromatic hydrocarbon ring group has no substituent other than − (RI) ni.
The aromatic hydrocarbon ring group may be monocyclic or polycyclic, and a monocyclic ring is preferable.
Examples of the aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, and an anthracene ring group. Among them, the aromatic hydrocarbon ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

In the general formula (I), ni represents an integer of 1 or more.
ni is preferably an integer of 1 to 5.

In general formula (I), RI represents a substituent having no cationic functional group.
RI, which is a substituent, has a cationic functional group (a cationized atom such as> S ⁺ -, -I ⁺ -,> C ⁺ -, or> N ⁺ <and a group containing the above-mentioned atom). If not, there is no limitation, for example, a halogen atom, an alkyl group (which may be linear or branched. The number of carbon atoms is, for example, 1 to 6), and a cycloalkyl group (which may be monocyclic or polycyclic. The number of carbon atoms is, for example, 5). ~ 20) or an alkoxy group (which may be linear or branched; the number of carbon atoms is, for example, 1 to 6) is preferable. The RI may have additional substituents where possible, with the additional substituents preferably a halogen atom (preferably a fluorine atom). It is also preferred that these substituents have no additional substituents other than the halogen atom (eg, fluorine atom). For example, RI may be a perhalogenated alkyl group (preferably a perfluoroalkyl group) in which an alkyl group is further substituted with a halogen atom. The RI may also be, for example, a cycloalkylalkoxy group. The total carbon number of one RI (in the case of having a substituent, the number of carbon atoms including the number of carbon atoms contained in the substituent) is preferably 1 to 20.
When ni is 2 or more, a plurality of RIs may be bonded to each other to form a non-aromatic ring.

It is preferable that at least one (preferably all) of the two or more cation sites of the compound (P) is an organic cation having a group represented by the general formula (I). Hereinafter, the organic cation having a group represented by the general formula (I) is also referred to as a specific organic cation.
The specific organic cation is preferably an organic cation represented by the general formula (II), an organic cation represented by the general formula (III), or an organic cation represented by the general formula (IV).
That is, the compound (P) is selected from the group consisting of an organic cation represented by the general formula (II), an organic cation represented by the general formula (III), and an organic cation represented by the general formula (IV). It is preferable to have one or more kinds of organic cations.
The organic cations represented by the general formulas (II) to (IV) have a specific substituent and structure to make the entire compound (P) hydrophobic. Therefore, the compatibility with the acid-degradable resin is further improved, the compound (P) is easily dispersed uniformly even in the film formed by using the composition of the present invention, and the LWR performance is more excellent. Further, since the compatibility between the compound (P) and the acid-decomposable resin is good, the dispersibility of the compound (P) in the composition of the present invention is excellent, and the compound (P) is less likely to aggregate, which is excellent. The LWR performance is easily exhibited, and the effect of the present invention is more excellent.

・ General formula (II)
The organic cation represented by the general formula (II) is shown below.

In the general formula (II), Ar ¹ , Ar ² and Ar ³ each independently represent an aromatic hydrocarbon ring group.
At least one of ^{Ar 1} , Ar ² and Ar ³ represents an aromatic hydrocarbon ring group having a substituent having _{-CF 3.}
However, none of the aromatic hydrocarbon ring groups represented by ^{Ar 1} , Ar ² and Ar ^{3 has a substituent having a cationic functional group.}

Examples of the aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, and an anthracene ring group, and a benzene ring group is preferable.
The substituent that the aromatic hydrocarbon ring group may have is preferably a halogen atom, an alkyl group, a cycloalkyl group, or an alkoxy group. The substituent may be one kind alone or two or more kinds.
The alkyl group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group has, for example, 5 to 20 carbon atoms.
The alkoxy group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The alkyl group, the cycloalkyl group, and the alkoxy group may each independently have an additional substituent. The further substituent is preferably a halogen atom (preferably a fluorine atom). It is also preferred that these substituents have no additional substituents other than the halogen atom (eg, fluorine atom). The alkyl group may be a perhalogenated alkyl group (preferably a perfluoroalkyl group).
When the aromatic hydrocarbon ring group has a substituent, the number of the substituents of the aromatic hydrocarbon ring group is preferably 1 to 5 independently.
^{Of Ar 1} , Ar ² , and Ar ^{3 in} the general formula (II), at least one is an aromatic hydrocarbon ring group having a substituent, and at least two (two or three) are substituents. It is preferably an aromatic hydrocarbon ring group having.

^{Of Ar 1} , Ar ² , and Ar ^{3 in} the general formula (II), at least one (1 to 3) represents an aromatic hydrocarbon ring group having a substituent having _{−CF 3.}
Substituents having the -CF ₃ is substituent itself may be a -CF _3, may have a -CF ₃ as part of the overall substituent.
Aromatic hydrocarbon ring group having a substituent having a -CF ₃ preferably have one to 5 substituent having -CF _3.
Aromatic hydrocarbon ring group having a substituent having a -CF ₃ may further have a substituent having no -CF _3.
Of Ar ¹ , Ar ² , and Ar ³ , one or two may be aromatic hydrocarbon ring groups having _{-CF 3 and having no substituent.}
The organic cation represented by the general formula (II) preferably has 1 to 8 _{−CF 3} existing in a form of being directly bonded to the ring member atom of the aromatic hydrocarbon ring group.

The aromatic hydrocarbon ring groups which may have the substituents represented by ^{Ar 1} , Ar ² , and Ar ³ in the general formula (II) all have a substituent having a cationic functional group. Do not. In other words, the organic cation represented by the general formula (II) has no cationic functional group other than ^{S +} that directly binds to ^{Ar 1} , Ar ² , and Ar ^3.
As for the substituent having a cationic functional group, the substituent itself may be a cationic functional group, or the substituent may have a cationic functional group as a part of the whole substituent.

The organic cation represented by the general formula (II) is preferably different from the organic cation represented by the general formula (III) described later. For example, the organic cation represented by the general formula (II) has a fluorine atom in a form directly connected to the ring member atom of the above aromatic hydrocarbon ring group represented by ^{Ar 1} , Ar ² , and Ar ^3. It is also preferable that there is no such thing.

・ General formula (III)
The organic cation represented by the general formula (III) is shown below.

In the general formula (II), Ar ⁴ , Ar ⁵ and Ar ⁶ each independently represent an aromatic hydrocarbon ring group.
At ^{least two of Ar 4} , Ar ⁵ and Ar ⁶ represent aromatic hydrocarbon ring groups having substituents.
At ^{least one of Ar 4} , Ar ⁵ and Ar ⁶ represents an aromatic hydrocarbon ring group having a fluorine atom as a substituent.
At ^{least two of Ar 4} , Ar ^5, and Ar ⁶ represent groups of different structures.
However, none of the aromatic hydrocarbon ring groups represented by ^{Ar 4} , Ar ⁵ and Ar ^{6 has a substituent having a cationic functional group.}

The substituent that the aromatic hydrocarbon ring group may have is preferably a halogen atom (preferably a fluorine atom), an alkyl group, a cycloalkyl group, or an alkoxy group. The substituent may be one kind alone or two or more kinds.
The alkyl group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group has, for example, 5 to 20 carbon atoms.
The alkoxy group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The alkyl group, the cycloalkyl group, and the alkoxy group may each independently have an additional substituent.
When the aromatic hydrocarbon ring group has a substituent, the number of the substituents of the aromatic hydrocarbon ring group is preferably 1 to 5 independently.
^{Of Ar 4} , Ar ⁵ , and Ar ^{6 in} the general formula (III), at least two (two or three) are aromatic hydrocarbon ring groups having substituents.

^{Further, at least one (preferably 1 to 3) of Ar 4} , Ar ⁵ , and Ar ^{6 in} the general formula (III) is an aromatic hydrocarbon ring group having a fluorine atom as a substituent. ..
In other words, in Ar ⁴ , Ar ⁵ , and Ar ⁶ in the general formula (III), at least two (two or three) "aromatic hydrocarbon ring groups having substituents" are present. One (1 to 2 of 2 or 1 to 3 of 3) is an "aromatic hydrocarbon ring group having a fluorine atom as a substituent".
The above-mentioned "aromatic hydrocarbon ring group having a fluorine atom as a substituent" means at least one fluorine atom (fluorine atom which is the substituent itself) directly bonded to a ring member atom in the aromatic hydrocarbon ring group (preferably). Means an aromatic hydrocarbon ring group having 1 to 5).
The "aromatic hydrocarbon ring group having a fluorine atom as a substituent" may have a substituent other than the substituent which is a fluorine atom.

^{Of Ar 4} , Ar ⁵ , and Ar ^{6 in the} general formula (III), at least two represent groups having different structures. In other words, Ar ⁴ , Ar ⁵ , and Ar ⁶ are not all based on the same structure.
It should ^{be noted that Ar 4} , Ar ⁵ , and Ar ⁶ are all groups having the same structure. For example, the aromatic hydrocarbon ring groups of ^{Ar 4} , Ar ⁵ , and Ar ^{6 are all benzene ring groups.} In addition, the types and arrangements (bonding positions) of the groups of the benzene ring groups of ^{Ar 4} , Ar ⁵ , and Ar ^{6 are also the same.} In other words, ^{if all the combinations of group types of the benzene ring groups of Ar 4} , Ar ⁵ , and Ar ⁶ are the same, but not all of the arrangements of those groups are the same, then Ar ⁴ , Not all Ar ⁵ and Ar ⁶ are the basis of the same structure.

The aromatic hydrocarbon ring groups which may have a substituent represented by ^{Ar 4} , Ar ⁵ , and Ar ⁶ in the general formula (III) all have a substituent having a cationic functional group. Do not. In other words, the organic cation represented by the general formula (III) has no cationic functional group other than ^{S +} that directly binds to ^{Ar 4} , Ar ⁵ , and Ar ^6.

The organic cation represented by the general formula (III) is preferably different from the organic cation represented by the general formula (II). For example, none of the aromatic hydrocarbon ring groups which may have a substituent represented by ^{Ar 4} , Ar ⁵ , and Ar ⁶ preferably has a substituent having _{−CF 3.}

・ General formula (IV)
The organic cation represented by the general formula (IV) is shown below.

In the general formula (IV), Ar ⁷ , Ar ⁸ and Ar ⁹ each independently represent an aromatic hydrocarbon ring group.
At ^{least one of Ar 7} , Ar ⁸ and Ar ⁹ is an aromatic hydrocarbon ring group having one or more specific hydrocarbon groups selected from the group consisting of an alkyl group and a polycyclic cycloalkyl group as substituents. Represents.
However, none of the aromatic hydrocarbon ring groups represented by ^{Ar 7} , Ar ⁸ and Ar ^{9 has a substituent having a cationic functional group.}
None of the aromatic hydrocarbon ring groups represented by Ar ⁷ , Ar ⁸ and Ar ^{9 has a substituent having a fluorine atom.}

Examples of the substituent that the aromatic hydrocarbon ring group may have include a halogen atom other than the fluorine atom, an alkyl group, a cycloalkyl group, and an alkoxy group. The substituent may be one kind alone or two or more kinds.
The alkyl group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group has, for example, 5 to 20 carbon atoms.
The alkoxy group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The alkyl group, the cycloalkyl group, and the alkoxy group may each independently have an additional substituent.
When the aromatic hydrocarbon ring group has a substituent, the number of the substituents of the aromatic hydrocarbon ring group is preferably 1 to 5 independently.

^{Of Ar 7} , Ar ⁸ and Ar ^{9 in} the general formula (IV), at least one (1 to 3) consists of a group consisting of an alkyl group and a polycyclic cycloalkyl group as substituents. It is an aromatic hydrocarbon ring group having one or more specific hydrocarbon groups selected.
The alkyl group in the specific hydrocarbon group may be linear or branched. The alkyl group has, for example, 1 to 6 carbon atoms.
The polycyclic cycloalkyl group in the specific hydrocarbon group is not particularly limited as long as it is a polycyclic ring, and may be a polycyclic ring of a crosslinked ring system, a polycyclic ring of a fused ring system, or a polycyclic ring of a spiro ring system. It may be a polycyclic compound having a plurality of modes of these systems. The number of ring-membered atoms of the polycyclic cycloalkyl group is preferably 8 to 20. The cycloalkyl groups of the polycyclic, for example, a norbornyl group, an adamantyl group, a bicyclooctanyl group, and, include tricyclo [5,2,1,0 ^2,6] decanyl, among others adamantyl group.
The specific hydrocarbon group may or may not have an additional substituent. However, the above-mentioned additional substituents are other than the fluorine atom and the group having a fluorine atom as a part.
The specific hydrocarbon group directly bonds to the ring member atom of the aromatic hydrocarbon ring group.
When the aromatic hydrocarbon ring group has a specific hydrocarbon group, the number thereof is preferably 1 to 5 independently.
Further, the aromatic hydrocarbon ring group having a specific hydrocarbon group may or may not have a substituent other than the specific hydrocarbon group.

The aromatic hydrocarbon ring groups which may have the substituents represented by ^{Ar 7} , Ar ⁸ and Ar ⁹ in the general formula (IV) all have a substituent having a cationic functional group. Do not. In other words, the organic cation represented by the general formula (IV) has no cationic functional group other than ^{S +} that directly binds to ^{Ar 7} , Ar ⁸ , and Ar ^9.

None of the aromatic hydrocarbon ring groups having a substituent represented by ^{Ar 7} , Ar ⁸ and Ar ⁹ in the general formula (IV) has a substituent having a fluorine atom. .. In other words, the organic cation represented by the general formula (IV) does not have a fluorine atom.
That is, in the general formula (IV), the fluorine atom and the group having a fluorine atom as a part are excluded from the substituents that the aromatic hydrocarbon ring groups ^{of Ar 7} , Ar ⁸ and Ar ^{9 can have.} NS.

The specific organic cation may be another specific organic cation other than the organic cations represented by the general formulas (II) to (IV) described above.
For example, the following specific organic cations can be mentioned.
-In the cation represented by the general formula (ZaII) mentioned in the description ^{of M +} in the above general formula (PA-1) ^{, at least one of R 204} and R ²⁰⁵ is a substitution having a cationic functional group. A cation that is an aryl group that has no group and no heteroatom.
-In the cation represented by the general formula (ZaI-3b) mentioned in the description ^{of M +} in the above general formula (PA-1), at least one (1 to 5 _{) of R 1c} to R _5c. One) represents a group other than a hydrogen atom, and the group other than the hydrogen atom is a cation having a cationic functional group and not a substituent.
-In the cation represented by the general formula (ZaI-4b) mentioned in the explanation ^{of M +} in the above general formula (PA-1) _{, "R 13} is a group other than a hydrogen atom" and " A cation that meets at least one of the requirements of "r represents an integer of 1-8". It should be _{noted that each group of R 13} and R ₁₄ is not a substituent having a cationic functional group.

The two or more cation sites (preferably organic cations, more preferably specific organic cations) of compound (P) may be the same or different.

(Anion site)
The anion moiety is a structural moiety containing a negatively charged atom or atomic group, and for example, an anionic functional group that may be present in the compound (P) may be used as the anion moiety.
The compound (P) preferably has an organic anion having the same number of anionic functional groups as the cation site (preferably an organic cation) of the compound (P).
As described above, compound (P) has two or more (preferably two or three) cation sites and the same number of anion sites as the above cation sites.
That is, compound (P) has two or more (preferably two or three) anionic moieties (preferably anionic functional groups).

Examples of the anionic functional group, for example, -SO ₃ ^- group having as part, -COO ^- ^-, and -SO ₃ and -COO ^- groups having as part, -N ^- - group having as part, and, carbanions (-C ^- <) include groups having as part.
Among them, as the anion moiety, groups represented by the general formulas (B-1) to (B-13) are preferable.

In the general formulas (B-1) to (B-13), * represents the bonding position.
It is also preferable that * in the general formula (B-12) is a bond position with respect to a group that is neither _{-CO- nor -SO 2-.}

In the general formulas (B-1) to (B-5) and (B-12), ^RX1 represents an organic group.
^RX1 includes an alkyl group (which may be linear or branched, preferably having 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms). Alternatively, an aryl group (either monocyclic or polycyclic, preferably 6 to 20 carbon atoms) is preferable.
Incidentally, in formula (B-5) in ^{R X1,} N ^- directly attached to atoms and carbon atoms in -CO-, and, -SO ₂ - is also preferred not one of sulfur atoms in the.

The cycloalkyl group in R ^X1 may be monocyclic or polycyclic.
The cycloalkyl group in R ^X1, for example, a norbornyl group, and, adamantyl group.
Substituents which may have a cycloalkyl group at R ^X1 represents an alkyl group (a straight-chain or branched-chain. Preferably 1-5 1 carbon atoms) preferably.
One or more of the carbon atoms are ring member atoms of the cycloalkyl group in R ^X1 may be replaced by carbonyl carbon atom.
The number of carbon atoms in the alkyl group in R ^X1 is preferably 1 to 10, 1 to 5 and more preferable.
Substituent which may be possessed by the alkyl group in R ^X1 is a cycloalkyl group, a fluorine atom, or a cyano group.
Examples of the cycloalkyl group as the substituent include the cycloalkyl group described in the case where ^{RX1 is a cycloalkyl group.}
Alkyl group in R ^X1 is, if they have a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group.
The alkyl group in R ^X1 is one or more -CH 2 _- may be substituted with a carbonyl group.
Aryl group in R ^X1 is a benzene ring group.
Substituent which may be possessed by the aryl group in R ^X1 is an alkyl group, a fluorine atom, or a cyano group. Examples of the alkyl group as the substituent include the alkyl groups ^{described in the case where RX1} is a cycloalkyl group, and a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.

In the general formulas (B-7) and (B-11), ^RX2 represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group.
Substituent other than fluorine atom and a perfluoroalkyl group represented by R ^X2 is an alkyl group other than a perfluoroalkyl group, or a cycloalkyl group are preferable.
Examples of the alkyl groups include alkyl groups other than the perfluoroalkyl group from the alkyl group for R ^X1. Further, it is preferable that the alkyl group does not have a fluorine atom.
Examples of the cycloalkyl groups include cycloalkyl groups in R ^X1.
Further, it is preferable that the cycloalkyl group does not have a fluorine atom.

In the general formula (B-8), ^RXF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the plurality of ^RXF1 represents a fluorine atom or a perfluoroalkyl group.
The ^{perfluoroalkyl group represented by RXF1} preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.

In the general formula (B-10), ^RXF2 represents a fluorine atom or a perfluoroalkyl group.
The ^{perfluoroalkyl group represented by RXF2} preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.

In the general formula (B-9), n represents an integer of 0 to 4.

Compound (P) preferably has at least two anionic functional groups (preferably two selected from the general formulas (B-1) to (B-13)). In this case, the combination of the anionic functional groups of the compound (P) is not particularly limited.
For example, when the compound (P) has a group represented by the general formula (B-8) or (B-10), the general formulas (B-1) to (B-7), (B-9) are further added. ) Or may have a group represented by (B-11) to (B-13). Further, when the compound (P) is a group represented by the general formula (B-7), it may further have a group represented by the general formula (B-6). These compounds (P) may have further different anionic functional groups.

Among them, the compound (P) is anionic part, anionic sites _{A B} ^- preferably has a ^- (anionic functional group _{A B).}
Anionic part _{A B} ^- (anionic functional groups _{A B} ^-) is a group represented by any one of formulas (BX-1) ~ (BX -4).

In the general formulas (BX-1) to (BX-4), * represents a bonding position.
In the general formula (BX-1) ~ (BX -4), R B represents an organic group.
Examples of the organic group for R ^B has the general formula (B-1) ~ (B -5), and examples of the organic group ^{R X1} can be mentioned as well in (B-12).

Further, compound (P) as an anion site, the anionic sites _{A B} ^- in addition to further anionic sites _{A A} ^- (anionic functional group _{A B)} ^- (anionic functional group _{A A} ^-) to have Is preferable.
Anionic part _{A A} ^- (anionic functional group _{A A} ^-) is a group represented by any one of formulas (AX-1) ~ (AX -2).

In the general formulas (AX-1) to (AX-2), * represents a bonding position.
In the general formula (AX-2), ^RA represents an organic group.
^RA is preferably an alkyl group.
The alkyl group may be linear or branched.
The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
The substituent that the alkyl group may have is preferably a fluorine atom.
The alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.

Compound (P) as anionic sites, the anionic sites _{A B} ^- (anionic functional groups _{A B} ^-), and, the anionic part _{A A} ^- (anionic functional group _{A A} ^-) in addition to a further anion It may or may not have a site (preferably an additional anionic functional group).

(Structure of compound (P))
The compound (P) is preferably a compound represented by the general formula (AD0).
_{_{^{_{L 0 - (A 0 -)}}}} nk (M 0 +) nk formula (AD0)

In the general formula (AD0), nk represents an integer of 2 or more.
The nk is preferably 2 to 10, more preferably 2 to 3.
The two nks existing in the general formula (AD0) have the same value.

In the general formula (AD0), _{L 0} represents a nk-valent linking group.
However, when nk is 2, L ₀ represents a single bond or a divalent linking group.
Examples of the divalent organic group include -COO-, -CONH-, -CO-, -O-, an alkylene group (preferably 1 to 6 carbon atoms, which may be linear or branched), and cyclo. Examples thereof include an alkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group obtained by combining a plurality of these groups.
One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
These divalent linking groups may further, -S -, - SO -, - SO 2 -, and, ^-NR N - has the ^{(R N} represents a hydrogen atom or a substituent) group is selected from the group consisting of Is also preferable.
Examples of the nk-valent linking group include a single bond and / or each group that the divalent linking group can take, and -CR ^nk <, -N <,> C <, a trivalent or higher valent hydrocarbon ring group. And / or a group in which a trivalent or higher valent heterocyclic group is combined can be mentioned. R ^nk represents a hydrogen atom or a substituent.
When L ₀ is other than a single bond, the _{total number of atoms other than hydrogen atoms constituting L 0} is preferably 1 to 100, more preferably 1 to 50.

In the general formula (AD0), _{A 0} ^- represents an anionic functional group. The anionic functional groups are as described above. More existing A ₀ ^- may each be the same or different.
A plurality of A ₀ ^- are, for example, "a group represented by the general formula (B-8) or (B-10) and the general formulas (B-1) to (B-7), (B-9). Or, it may have at least a group represented by (B-11) to (B-13), and a group represented by the general formula (B-7) and a group represented by the general formula (B-6). It may have at least a group represented by, and a group represented by any of the general formulas (BX-1) to (BX-4) and the general formulas (AX-1) to (AX-). It may have at least a group represented by any of 2).

In the general formula _{(AD0), M} ^{0 +} is an organic cation (specific organic cation, or an organic cation other than the specific organic cation) represents a.
nk number of M ₀ ⁺ at least one of the (preferably all) preferably represents a specific organic cation.
The specific organic cation is as described above.
The same applies to organic cations other than the specific organic cations.
A plurality of M ₀ ⁺ may be the same or different from each other.

Further, the compound (P) is preferably compound (I), compound (II), or compound (III).
Hereinafter, compounds (I) to (III) will be described.

-Compound (I)
Compound (I) will be described.
Compound (I) is the following compound.
Compound (I): A compound having one of the following structural sites X and one of the following structural sites Y, and the following first acidic site and the following structure derived from the following structural site X by irradiation with active light or radiation. A compound that generates an acid containing the following second acidic moiety derived from the moiety Y

Structural part X: Structural part consisting of anionic part A ₁ ⁻ and cation part M ₁ ⁺ , and forming the first acidic part represented _{by HA 1} by irradiation with active light or radiation Structural part Y: Anion part a ₂ ^- consists of a cationic sites M ₂ ⁺ and, and, by irradiation with actinic rays or radiation, the represented by HA ₂ having a structure different from that of the first acidic site formed by the above structural moiety X Structural part forming the acidic part of 2

However, compound (I) satisfies the following condition I.
Condition I: In the compound (I), the _{compound PI obtained by replacing the cation site M 1} ⁺ in the structural site X and the cation site M ₂ ⁺ in the structural site Y with H ⁺ is contained in the structural site X. The acid dissociation constant a1 derived from the acidic site represented by _{HA 1} , which is obtained by replacing the above-mentioned cation site M ₁ ⁺ with H ⁺ _{, and the above-mentioned cation site M 2} ⁺ in the above-mentioned structural part Y are replaced with H ^+. It _{has an acid dissociation constant a2 derived from an acidic moiety represented by HA 2} , and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
The acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above-mentioned method. More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI refer to the compound PI (the compound PI is a compound having HA ₁ and HA _{2) when the acid dissociation constant of the compound PI is obtained.} . corresponding to ") is" _{a 1} ^- and pKa when a compound "having a HA ₂ is the acid dissociation constant a1, the" _{a 1} ^- a compound having an HA ₂ "is" _{a 1} ^- and a ₂ ^- pKa when a compound "having a is an acid dissociation constant a2.
Further, the compound PI corresponds to an acid generated by irradiating compound (I) with active light or radiation.

In the compound PI, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, in that the effect of the present invention is more excellent. ..

Further, in the above-mentioned compound PI, the acid dissociation constant a2 is preferably -4.00 to 15.00, more preferably -2.00 to 12.00, in that the effect of the present invention is more excellent.

Further, in the above-mentioned compound PI, the acid dissociation constant a1 is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, in that the effect of the present invention is more excellent.

・ General formula (Ia)
The compound (I) is not particularly limited, and examples thereof include a compound represented by the following general formula (Ia).
M ₁₁ ⁺ A ₁₁ ^{－－} L ₁ － A ₁₂ ^－ M ₁₂ ⁺ (Ia)

In the general formula (Ia), _"M ^₁₁ + _A ¹¹ ^-" and _"A ^₁₂ - _M ¹² ^+" each correspond to structural moiety X and the structural moiety Y. Compound (Ia) produces an acid represented _{by HA 11-} L _1- A ₁₂ H by irradiation with active light or radiation. That is, _"M ^₁₁ + _A ¹¹ ^-" forms a first acidic moiety represented by _{HA 11,} _"A ^₁₂ - _M ¹² ^+" is _{HA 12} having a structure different from that of the aforementioned first acid sites It forms a second acidic moiety represented by.
However, Table above general formula _(Ia), in _{M 11} ⁺ and _{M 12} ⁺ organic cation represented by made by replacing the ^{H +} compound _{_{_{PIa (HA 11 -L 1 -A 12}}} H), at _{A 12} H The acid dissociation constant a2 derived from the acidic moiety is larger than the acid dissociation constant a1 derived from the acidic moiety represented by _{HA 11.} The preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.

In the general formula _{(Ia), M 11} ⁺ and _{M 12} ⁺ each independently, an organic cation (specific organic cation, or an organic cation other than the specific organic cation) represents a.
M ₁₁ ⁺ and _{M 12} ⁺ is at least one (preferably both) is preferably a specific organic cation.
The specific organic cation is as described above.
The organic cations other than the specific organic cations are as described above.

In the general formula _{(Ia), A 11} ^- and _{A 12} ^- independently represents an anionic functional group. However, A ₁₂ ⁻ represents a structure different from the anionic functional group represented by A ₁₁ ^−.
The anionic functional groups are as described above.
A ₁₁ ^- and _{A 12} ^- anionic functional group are each independently the general formula (B-1) a group represented by ~ (B-13) are preferred.
A ₁₁ ^- and _{A 12} ^- The combination of the anionic functional group represented by is not particularly limited, for _{example, A 11} ^- is a group represented by the general formula (B-8) or (B-10) _{If, A 12} ^- Table the anionic functional group represented by the general formula (B-1) ~ (B -7), (B-9), or (B-11) ~ (B -13) include groups, a ₁₁ ^- when is a group represented by the general formula _{(B-7), a 12} - as the anionic functional group represented by the table in the general formula (B-6) The groups to be used are mentioned.

In the general formula (Ia), L ₁ represents a divalent linking group.
In the general formula (I), the _{divalent linking group represented by L 1} is not particularly limited, and is an -CO-, -NR-, -CO-, -O-, alkylene group (preferably having 1 to 1 to carbon atoms). 6. Linear or branched chain), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), divalent aliphatic heterocyclic group (at least one) A 5- to 10-membered ring having an N atom, an O atom, an S atom, or a Se atom in the ring structure is preferable, a 5- to 7-membered ring is more preferable, and a 5- to 6-membered ring is further preferable), and a plurality of these. Examples thereof include a divalent linking group in which the above are combined. The above R may be a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, but for example, an alkyl group (preferably 1 to 6 carbon atoms) is preferable.
These divalent linking groups may further include a group selected from the group consisting of _{-S-, -SO-, and -SO 2-.}
Further, the alkylene group, the cycloalkylene group, the alkaneylene group, and the divalent aliphatic heterocyclic group may be substituted with a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

・ General formula (a)
Among them, as the compound (I), the compound represented by the general formula (a) is preferable.
_{^{_{^{_{M a1 + A a - -L a}}}}} -B a - M a2 + (a)

In the general formula (a), _Ma1 ⁺ and _Ma2 ⁺ independently represent organic cations (specific organic cations or organic cations other than specific organic cations).
It is preferable that at least one (preferably all) of _Ma ¹⁺ and _Ma ^{2+ represents a specific organic cation.}
The specific organic cation is as described above.
The same applies to organic cations other than the specific organic cations.

In the general formula _{(a), L} a represents a divalent organic group.
Examples of the divalent organic group include -COO-, -CONH-, -CO-, -O-, an alkylene group (preferably 1 to 6 carbon atoms, which may be linear or branched), and a cycloalkylene group. (Preferably, the number of carbon atoms is 3 to 15), an alkenylene group (preferably, the number of carbon atoms is 2 to 6), and a divalent linking group in which a plurality of these are combined can be mentioned.
One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
These divalent linking groups also preferably have a group selected from the group consisting of -S-, -SO-, and -SO _2-.

Among them, L _a is preferably a group represented by the following general formula (L).
* A-LA-LB-LC-LD-LE- * B (L)

In the general formula (L), * A represents the connection position with _{A a} ^{− in the general formula (a).}
In the general formula (L), * B is, _{B a} in the general formula (a) ^- shows the point of attachment with.

In the general formula (L), LA represents − (C (R _LA1 ) (R _LA2 )) _XA −.
The XA represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.
R _LA1 and R _LA2 independently represent a hydrogen atom or a substituent.
When R _LA1 and R _LA2 represent a substituent, a fluorine atom or a fluoroalkyl group is preferable, a fluorine atom or a perfluoroalkyl group is more preferable, and a fluorine atom or a perfluoromethyl group is further preferable.
When the number of XA is 2 or more, the R _{LA1s having} XA may be the same or different.
When the number of XA is 2 or more, the R _{LA2 having} XA may be the same or different.
-(C (R _LA1 ) (R _LA2 ))-is preferably -CH _2- , -CHF-, -CH (CF ₃ )-or -CF _2- .
Above all, formula (a) in the _{A a} ^- and a direct bond to _{- (C (R LA1) (} R LA2)) - _{is, -CH 2 -, - CHF -} , - CH (CF 3) - or -CF It is preferably _2-.
Formula (a) in the _{A a} ^- and a direct bond to _{- (C (R LA1) (} R LA2)) - other than the _{- (C (R LA1) (} R LA2)) - are each independently, -CH ₂ -, - CHF- or -CF ₂ - is preferably.

In the general formula (L), LB represents a single bond, an ester group (-COO-), or a sulfonyl group (-SO _2- ).

In the general formula (L), LC represents a single bond, an alkylene group, a cycloalkylene group, or a group composed of a combination thereof (such as "-alkylene group-cycloalkylene group-").
The alkylene group may be linear or branched.
The alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 2 carbon atoms, and even more preferably 1.
The cycloalkylene group preferably has 3 to 15 carbon atoms, and more preferably 5 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic.
Examples of the cycloalkylene group include a norbornanediyl group and an adamantandiyl group.
As the substituent that the cycloalkylene group may have, an alkyl group (which may be linear or branched, preferably 1 to 5 carbon atoms) is preferable.
One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
When the LC is "-alkylene group-cycloalkylene group-", the alkylene group portion is preferably present on the LB side.
When the LB is a single bond, the LC is preferably a single bond or a cycloalkylene group.

In the general formula (L), LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

In the general formula (L), LE is a single bond or _{- (C (R LE1) (} R LE2)) XE - represents a.
_XE _in- (C (R LE1) (R _LE2 )) XE- represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.
R _LE1 and R _LE2 independently represent a hydrogen atom or a substituent.
When the number of XEs is 2 or more, the R _LE1s having XEs may be the same or different.
When the number of XEs is 2 or more, the R _LE2s having XEs may be the same or different.
Above all,-(C (R _LE1 ) (R _LE2 ))-is preferably _{-CH 2-} or -CF _2-.
In the general formula (L), when LB, LC, and LD are single bonds, it is preferable that LE is also a single bond.

In the general formula (a), _A a ^- and _{B a} ^- each independently represent an anionic functional group.
The anionic functional groups are as described above.
Among them, A _a ⁻ is preferably a group represented by any of the general formulas (AX-1) to (AX-2).
B _a ^- preferably represents a general formula (BX-1) ~ a group represented by any one of (BX-4).
A _a ^- and _{B a} ^- is preferably respectively different structures.
Among them, _{A a} ^- is a group represented by the general formula (AX-1), and _{B a} ^- Do a group represented by any one of formulas (BX-1) ~ (BX -4) or, _{a a} ^- is a group represented by the general formula (AX-2), and _{B a} ^- general formula (BX-1), (BX -3), with either (BX-4) It is preferably the group represented.

However, in the general formula (a) _HA a _-L a -B represented by _a H _{compound M a1} ⁺ and _{M a2} ⁺ is substituted with a hydrogen atom each of the compounds represented by the represented by HA _a pKa groups is less than the pKa of the groups represented by _{B a} H.
More _{specifically,} HA _a _-L a -B a in the case of seeking the acid dissociation constant for the compound represented by H, _"HA _a _-L a -B a H" is ^{_{_"A} a} - -L ^a - the pKa at which the B _a H "as" pKa of the group represented by HA _a "further" ^{_{_a} a} - _-L ^a -B ^a H "is" ^{_{_a} a} ^- _-L ^a -B ^a - " _Let pKa at the time of becoming "pKa of the group represented by B a H".
“PKa _{of the group represented by HA a} ” and “pKa of the group represented by B _a H” are determined by using “Software Package 1” or “Gaussian 16”, respectively.
For example, _{the pKa of the group represented by HA a} corresponds to the acid dissociation constant a1 described above, and the preferred range is also the same.
The pKa of the group represented by B _a H corresponds to the acid dissociation constant a2 described above, and the preferable range is also the same.
The difference between the pKa of the groups represented by pKa and HA _a group represented by HB _a ( "pKa of the group represented by HB _a" - "pKa of the group represented by HA _a") is above Corresponds to the difference between the acid dissociation constant a1 and the acid dissociation constant a2, and the preferred range is also the same.

-Compound (II)
Next, compound (II) will be described.
Compound (II) is the following compound.
Compound (II): A compound having two or more structural sites X and the structural site Y, and having two first acidic sites derived from the structural site X by irradiation with active light or radiation. A compound that generates an acid containing the above and the second acidic moiety derived from the structural moiety Y. However, compound (II) satisfies the following condition II.
Condition II: In the compound (II), the _{compound PII obtained by replacing the cation site M 1} ⁺ in the structural site X and the cation site M ₂ ⁺ in the structural site Y with H ⁺ is contained in the structural site X. The acid dissociation constant a1 derived from the acidic site represented by _{HA 1 in} which the cation site M ₁ ⁺ is replaced with H ⁺ , and the HA obtained by replacing the _{cation site M 2} ⁺ in the structural site Y with H ^+. _It has an acid dissociation constant a2 derived from the acidic moiety represented by 2, and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
The acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above-mentioned method.
Here, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PII will be described more specifically. When compound (II) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y. , Compound PII corresponds to "a compound having _two _{HA 1} and HA 2". If asked for the acid dissociation constant of the compound PII, compound PII is ^- a pKa of acid dissociation constant a1 when the "one of _{A 1} and one HA ₁ and HA ₂ with a compound of", "two a ₁ ^- and HA ₂ compound having the "is" two _{a 1} ^- and _{a 2} ^- pKa when a compound "having a is an acid dissociation constant a2. That is, when the compound PII has a plurality of acid dissociation constants derived from the acidic site represented by _{HA 1 formed} by replacing the _{cation site M 1} ⁺ in the structural site X with H ^{+, the smallest value is acid.} It is regarded as the dissociation constant a1.

Further, the compound PII corresponds to an acid generated by irradiating compound (II) with active light rays or radiation.
The compound (II) may have a plurality of the structural sites Y.

In the compound PII, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.00 or more, and more preferably 3.00 or more, in that the effect of the present invention is more excellent. The upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is not particularly limited, but is, for example, 15.00 or less.

Further, in the above-mentioned compound PII, the acid dissociation constant a2 is preferably 2.00 or less, more preferably 1.00 or less, in that the effect of the present invention is more excellent. The lower limit of the acid dissociation constant a2 is preferably −2.00 or higher.

Further, in the above-mentioned compound PII, the acid dissociation constant a1 is preferably 2.00 or less, more preferably 0.50 or less, still more preferably −0.10 or less, in that the effect of the present invention is more excellent. The lower limit of the acid dissociation constant a1 is preferably -15.00 or higher.

The compound (II) is not particularly limited, and examples thereof include a compound represented by the following general formula (IIa).

In the general formula (IIa), _"M ^₂₁ + _A ²¹ ^-" and _"A ^₂₂ - ⁺ _M ^22" each correspond to structural moiety X and the structural moiety Y. Compound (IIa) generates an acid represented by the following general formula (IIa-1) by irradiation with active light or radiation. That is, _"M ^₂₁ + _A ²¹ ^-" forms a first acidic moiety represented by _{HA 21,} _"A ^₂₂ - _M ²² ^+" is a structure different from that of the first acid sites _{HA 22} It forms a second acidic moiety represented by.

In the general formula _(IIa), ^⁺ _{M 21} ⁺ and _{M 22} each independently represents an organic cation.
A ₂₁ ^- and _{A 22} ^- independently represents an anionic functional group. However, A ₂₂ ⁻ represents a structure different from the anionic functional group represented by A ₂₁ ^−.
L ₂ represents a (n1 + n2) valent organic group.
n1 represents an integer of 2 or more.
n2 represents an integer of 1 or more.
However, the following general formula _(IIa), corresponds to the compound represented by Compound PIIa comprising replacing organic cation represented by _{M 21} ⁺ and _{M 22} ⁺ to ^{H +} (the general formula (IIa-1) ), The acid dissociation constant a2 derived from the acidic moiety represented by _{A 22} H is larger than the acid dissociation constant a1 derived from the acidic moiety represented by _{HA 21.} The preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.

In the general formula _{^{_{^{(IIa), M 21 +,}}}} M 22 +, A 21 -, _{and, A 22} ^- is in each above-mentioned general formula _{^{_{^{(Ia) M 11 +, M}}}} 12 +, A 11 -,及fine _{a 12} ^- in the above formula, preferred embodiments are also the same.
In the general formula (IIa), n1 pieces of _{M 21} ⁺ each other, n1 pieces of _{A 21} ⁺ each other, represent each mutually identical groups.

In the general formula (IIa), is not particularly limited as expressed by (n1 + n2) valent organic group in _{L 2,} for example, include groups represented by the following (A1) and the following (A2). Incidentally, in the following (A1) and (A2), at least two of * _{A 21} ^- represents a bonding position to at least one of * the _{A 22} ^- represents a bonding site to the.

In the above (A1) and (A2), T ¹ represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group, and T ² is a carbon atom, a tetravalent hydrocarbon ring group, or a tetravalent. Represents the heterocyclic group of.

The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, and more preferably 6 to 14.
The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocycle is preferably a 5- to 10-membered ring having at least one N atom, an O atom, an S atom, or a Se atom in the ring structure, more preferably a 5- to 7-membered ring, and a 5- to 6-membered ring. Rings are more preferred.

Further, in the above (A1) and (A2), L ²¹ and L ²² independently represent a single bond or a divalent linking group, respectively.
The divalent linking group represented by ^{L 21} and L ²² has the same meaning as the divalent linking group represented by _{L 1 in the general formula (Ia), and the preferred embodiment is also the same.}
n1 represents an integer of 2 or more. The upper limit is not particularly limited, but is, for example, 6 or less, preferably 4 or less, and more preferably 3 or less.
n2 represents an integer of 1 or more. The upper limit is not particularly limited, but is, for example, 3 or less, preferably 2 or less.

・ General formula (b)
Among them, the compound represented by the general formula (b) is preferable as the compound (II).
_{^{_{^{_{(M b1 + A b -)}}}}} nb -L b -B b - M b2 + (b)

In the general formula (b), M _b1 ⁺ and M _b2 ⁺ independently represent organic cations (specific organic cations or organic cations other than specific organic cations).
In the general formula _{(b), M b1} ⁺ and _{M b2} ⁺ has the same meaning as each _{M a1} ⁺ and _M in general formula (a) _a2 ^+, it is also the same preferred embodiment.

In the general formula (b), L _b represents an organic group having a (nb + 1) valence.
Examples of the (nb + 1) -valent organic group include the groups represented by the above (A1) and the above (A2). Incidentally, in the above (A1) and (A2), at least nb number of * is _{A b} ^- represents a bonding site to the, at least one of * _{B b} ^- represents a bonding site to the.
Further, in the above (A1) and ^(A2), the divalent linking group represented by ^{L 21} and ^{L 22,} similar to the divalent linking group represented by _{L a} in the general formula (a) It is preferably a divalent linking group of.

In the general formula _{(b), A} b ^- and _{B b} ^- each independently represent an anionic functional group.
In the general formula _{(b), A} b ^- and _{B b} ^-, each _{A a} in general formula (a) ^- and _{B a} ^- has the same meaning as, and their preferred embodiments are also the same.

In the general formula (b), nb represents an integer of 2 or more. The plurality of M _b1 ⁺ and _Ab ⁻ may be the same or different from each other.
The upper limit of nb is not particularly limited, but is, for example, 6 or less, preferably 4 or less, and more preferably 3 or less.

However, in the general formula (b) _{M b1} ⁺ and _{M b2} ⁺ of the compound represented by is substituted with hydrogen atoms, respectively _(HA _b) a compound represented by nb _-L _b -B b H, in HA _b The pKa of the group represented is smaller than the pKa of the group represented by _{B b H.}

-Compound (III)
Next, compound (III) will be described.
Compound (III): A compound having two or more of the structural site X and the following structural site Z, wherein the first acidic site derived from the structural site X is 2 by irradiation with active light or radiation. A compound that generates an acid containing one or more of the above structural site Z Structural site Z: Nonionic organic site capable of neutralizing the acid

The nonionic organic moiety capable of neutralizing the acid in the structural moiety Z is not particularly limited, and is, for example, an organic moiety containing a functional group having a group or an electron capable of electrostatically interacting with a proton. Is preferable.
As a functional group having a group or an electron capable of electrostatically interacting with a proton, a functional group having a macrocyclic structure such as a cyclic polyether or a nitrogen atom having an unshared electron pair that does not contribute to π conjugation is used. Examples thereof include functional groups having. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Substructures of functional groups having groups or electrons that can electrostatically interact with protons include, for example, crown ether structure, aza-crown ether structure, 1-3 amine structure, pyridine structure, imidazole structure, and pyrazine structure. Etc., and among them, the 1st to 3rd grade amine structure is preferable.

In the compounds PIII which the compound in (III) formed by replacing the cationic sites _M ^{1 +} in the structural moiety X to ^{H +,} HA ₁ comprising substituting the cationic sites _M ^{1 +} in the structural moiety X to ^{H +} The acid dissociation constant a1 derived from the acidic moiety represented by is preferably 2.0 or less, more preferably 0.5 or less, still more preferably −0.1 or less, in that the effect of the present invention is more excellent. The lower limit of the acid dissociation constant a1 is preferably -15.0 or higher.
When compound PIII has a plurality of acid dissociation constants derived from the acidic site represented by _{HA 1 in} _{which the cation site M 1} ⁺ in the structural site X is replaced with H ^{+, the smallest value is acid.} It is regarded as the dissociation constant a1.
That is, when compound (III) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and the structural site Z, the compound PIII is "two HA _1". It corresponds to "a compound having." If asked for the acid dissociation constant of the compound PIII, compound PIII is ^- pKa when the "one of _{A 1} and a compound having one HA _1" is an acid dissociation constant a1. That is, when compound PIII has a plurality of acid dissociation constants derived from the acidic site represented by _{HA 1 in} _{which the cation site M 1} ⁺ in the structural site X is replaced with H ^{+, the smallest value is acid.} It is regarded as the dissociation constant a1.
In the compound (III), the _{compound PIII in which the cation site M 1} ⁺ in the structural site X is replaced with H ⁺ is, for example, a compound in which the compound (III) is represented by the compound (IIIa) described later. If, HA _31- L _3- N (R ^2X ) -L _4- A ₃₁ H corresponds.

The compound (III) is not particularly limited, and examples thereof include a compound represented by the following general formula (IIIa).

In the general formula (IIIa), _"M ^₃₁ + _A ³¹ ^-" corresponds to the structural moiety X. Compound (IIIa) produces an acid represented _{by HA 31-} L _3- N (R ^2X ) -L _4- A ₃₁ H by irradiation with active light or radiation. That is, _"M ^₃₁ + _A ³¹ ^-" forms a first acidic moiety represented by _{HA 31.}

In the general formula _{(IIIa), M 31} ⁺ represents an organic cation.
A ₃₁ ^- represents an anionic functional group.
L ₃ and L ₄ each independently represent a divalent linking group.
R ^2X represents a monovalent organic group.

In the general formula _{(IIIa), M 31 ^+,} and _{A 31} ^- each _{M 11} ⁺ in general formula (Ia), and _{A 11} ^- in the above formula, preferred embodiments are also the same.
In the general formula (IIIa), L ₃ and L ₄ _{are synonymous with L 1} in the general formula (Ia) described above, and the preferred embodiments are also the same.
In the general formula (IIIa), two _{M 31} ⁺ each other, and two _{A 31} ^- each other, represent each mutually identical groups.

In the general formula (IIIa), the ^{monovalent organic group represented by R 2X} is not particularly limited, and for example, -CH _2- is -CO-, -NH-, -O-, -S-,-. SO-, and -SO 2 _- may be substituted with one or more combinations selected from the group consisting of an alkyl group (preferably may be 1-10 either linear or branched carbon atoms. ), Cycloalkyl group (preferably 3 to 15 carbon atoms), alkenyl group (preferably 2 to 6 carbon atoms) and the like.
Moreover, the said alkylene group, the said cycloalkylene group, and the said alkaneylene group may be substituted with a substituent.

As the compound (III), a compound represented by the following general formula (c) is preferable.
_{^{_{^{_{(M c + A c -)}}}}} nc -L c (c)

In the general formula (c), _Mc ⁺ represents an organic cation (organic cation other than the specific organic cation or the specific organic cation).
In the general formula _{^(c), M} c ⁺ has the same meaning as _{M a1} ⁺ in general formula (a), and their preferred embodiments are also the same.

In the general formula (c), _Ac ⁻ represents an anionic functional group.
In the general formula (c), _Ac ⁻ _{has the same meaning as A a} ⁻ in the general formula (a) described above, and the preferred embodiment is also the same.

In the general formula (c), nc represents an integer of 2 or more. The plurality of _Mc ⁺ and _Ac ⁻ may be the same or different from each other.
The upper limit of nc is not particularly limited, but is, for example, 6 or less, preferably 4 or less, and more preferably 3 or less.

L _c represents a nonionic organic moiety capable of neutralizing the acid.
A preferred embodiment of L _c is the same as that of the structural part Z described above.

The molecular weight of compound (P) is preferably 300 to 3000, more preferably 500 to 2000, and even more preferably 700 to 1500.

The compound (P) is illustrated below.
The combination of the organic cation and the organic anion in the following compound (P) may be replaced as appropriate.
The numerical value attached to the organic anion of the compound (P) indicates the acid dissociation constant derived from each acidic site formed when ^{each anionic functional group in the organic anion is bonded to H + instead of the organic cation.}

The content of the photoacid generator in the composition of the present invention is not particularly limited, but is preferably 5% by mass or more based on the total solid content of the composition of the present invention in that the effect of the present invention is more excellent. 9% by mass or more is more preferable, and 15% by mass or more is further preferable. The content is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.
The photoacid generator may be used alone or in combination of two or more.

[(D) Acid diffusion control agent]
The composition of the present invention may further contain an acid diffusion control agent. The acid diffusion control agent acts as a quencher for trapping the acid generated from the photoacid generator, and plays a role of controlling the acid diffusion phenomenon in the resist film.
The acid diffusion control agent may be, for example, a basic compound.
The basic compound is preferably a compound having a structure represented by the following general formulas (A) to (E).

In the general formula (A) and the general formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), or a cycloalkyl group (preferably 1 to 20 carbon atoms). Represents an aryl group (preferably 6 to 20 carbon atoms), and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
It is more preferable that the alkyl groups in the general formula (A) and the general formula (E) are unsubstituted.

Regarding basic compounds, the descriptions in paragraphs [0190] to [0197] of International Publication No. 2018/193954 can be referred to, and these contents are incorporated in the present specification.

The acid diffusion control agent has a proton-accepting functional group and is decomposed by irradiation with active light or radiation to reduce or eliminate the proton accepting property, or generate a compound in which the proton accepting property is changed to acidic. It may be a compound (PA).
Regarding the above compound (PA), the description in paragraphs [0198] to [0203] of International Publication No. 2018/193954 can be referred to, and these contents are incorporated in the present specification.

As the compound (PA), for example, those described in paragraphs [0421] to [0428] of JP-A-2014-413328 and paragraphs [0108]-[0116] of JP-A-2014-134686 can be incorporated. , These contents are incorporated herein by reference.

Small molecule compounds having a nitrogen atom and having a group desorbed by the action of an acid can also be used as an acid diffusion control agent. The small molecule compound is preferably an amine derivative having a group on the nitrogen atom that is eliminated by the action of an acid.
The group eliminated by the action of the acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group, and a carbamate group or a hemiaminol ether group is more preferable. preferable.
The molecular weight of the small molecule compound is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
The small molecule compound may have a carbamate group having a protecting group on the nitrogen atom.

As a specific example of the acid diffusion control agent, the description in paragraphs [0204] to [0206] of International Publication No. 2018/193954 can be taken into consideration, and these contents are incorporated in the present specification. Further, the composition of the present invention may contain an acid diffusion control agent other than the above.

When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.001 to 15% by mass, preferably 0.01 to 15% by mass, based on the total solid content of the composition of the present invention. 8% by mass is more preferable.
The acid diffusion control agent may be used alone or in combination of two or more.

The ratio of the photoacid generator and the acid diffusion control agent in the composition of the present invention is preferably photoacid generator / acid diffusion control agent (molar ratio) = 2.5 to 300. The molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and the molar ratio is preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the resist pattern over time from exposure to heat treatment. The photoacid generator / acid diffusion control agent (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

Examples of the acid diffusion control agent include the compounds described in paragraphs [0140] to [0144] of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.). Can also be mentioned.

[(E) Hydrophobic resin]
The composition of the present invention may contain a hydrophobic resin different from the resin (A) in addition to the resin (A).

Hydrophobic resin from the viewpoint of uneven distribution in the film surface layer, "fluorine atom", "silicon atom", and has any one or more "CH ₃ partial structure contained in the side chain portion of the resin" It is preferable, and it is more preferable to have two or more kinds. Further, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.

Regarding the hydrophobic resin, the descriptions in paragraphs [0315] to [0415] of JP2014-010245A can be referred to, and these contents are incorporated in the present specification.

As the hydrophobic resin, the resins described in JP2011-24801A, JP2010-175859, and JP2012-032544 can also be preferably used.

When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the composition of the present invention. % Is more preferable.

[(F) Solvent]
The composition of the present invention may contain a solvent.
The solvent is not particularly limited, but (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and , At least one selected from the group consisting of alkylene carbonates. The solvent may further contain components other than the components (M1) and (M2).
Regarding the solvent, the description in paragraphs [0187] to [0197] of International Publication No. 2019/08890 can be referred to, and these contents are incorporated in the present specification.

The content of the solvent in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. In this way, the coatability of the composition of the present invention can be further improved.
The solid content concentration is the mass percentage of the mass of other components excluding the solvent with respect to the total mass of the composition of the present invention.

[(H) Surfactant]
The composition of the present invention may contain a surfactant. When a surfactant is included, a pattern having better adhesion and fewer development defects can be formed.
The surfactant is preferably a fluorine-based and / or silicon-based surfactant.
Regarding surfactants, the descriptions in paragraphs [0183] to [0184] of International Publication No. 2019/088900 can be referred to, and these contents are incorporated in the present specification.

When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.

[(G) Other additives]
The composition of the present invention comprises a dissolution inhibitory compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1000 or less, or a carboxylic acid). It may further contain an alicyclic or aliphatic compound containing an acid group).

The composition of the present invention may further contain a dissolution inhibitory compound. Here, the "dissolution-inhibiting compound" is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.

[Use]
The composition of the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation with active light or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit substrate manufacturing such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. The present invention relates to a lithographic printing plate or a radiation-sensitive or radiation-sensitive resin composition used for producing an acid-curable composition. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.

[Actinic cheilitis or radiation-sensitive film]
The present invention also relates to a sensitive light or radiation sensitive film formed by the sensitive light or radiation composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate. The thickness of this film is preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, it is applied on the substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., but spin coating is preferable, and the number of rotations thereof is high. 1000-3000 rpm (rotations per minute) is preferable. The coating film is prebaked at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes to form a thin film.
As the material forming the substrate to be processed and its outermost layer, for example, in the case of a semiconductor wafer, a silicon wafer can be used, and examples of the material to be the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, and the like. WSi, BPSG, SOG, organic antireflection film and the like can be mentioned.

[Mask blanks]
The present invention also relates to a mask blank provided with an actinic cheilitis or radiation-sensitive film coated with the actinic cheilitis or radiation-sensitive resin composition obtained as described above.
Regarding mask blanks, the descriptions in paragraphs [0265] to [0271] of JP-A-2018-10299 can be referred to, and these contents are incorporated in the present specification.

[Pattern formation method]
The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but it is preferable to have the following steps.
Step 1: A step of forming a resist film on a substrate using the composition of the present invention Step 2: A step of exposing the resist film (preferably with an electron beam (EB) or EUV) Step 3: Using a developing solution Steps for developing the exposed resist film and forming a pattern Hereinafter, the procedures for each of the above steps will be described in detail.

<Step 1: Resist film forming step>
Step 1 is a step of forming a resist film on a substrate using the composition of the present invention. The composition of the present invention is as described above.

Examples of the method of forming a resist film on a substrate using the composition of the present invention include a method of applying the composition of the present invention on a substrate.
It is preferable that the composition of the present invention is filtered by a filter as necessary before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The film thickness of the resist film is not particularly limited, but 10 to 65 nm is preferable, and 15 to 50 nm is more preferable, from the viewpoint of being able to form a fine pattern with higher accuracy.

Regarding the resist film forming step, the description in paragraphs [0227] to [0230] of International Publication No. 2018/193954 can be taken into consideration, and these contents are incorporated in the present specification.

<Process 2: Exposure process>
Step 2 is a step of exposing the resist film (preferably with an electron beam (EB) or EUV).
Examples of the exposure method include a method of irradiating the formed resist film with an electron beam (EB) or EUV through a predetermined mask.

It is preferable to bake (heat) after exposure and before developing. Baking accelerates the reaction of the exposed area, resulting in better sensitivity and pattern shape.
The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and even more preferably 80 to 130 ° C.
The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.
The heating can be carried out by means provided in a normal exposure machine and / or a developing machine, and may be carried out by using a hot plate or the like.
This process is also called post-exposure baking.

<Process 3: Development process>
Step 3 is a step of developing the exposed resist film using a developing solution to form a pattern.
The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method). ), A method of spraying the developer on the surface of the substrate (spray method), and a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic discharge method). ).
Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.
The development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.
Regarding the alkaline developer, the description in paragraph [0304] of JP-A-2019-174549 can be referred to, and these contents are incorporated in the present specification.

The organic developer is a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. It is preferable to have.

Regarding the ketone solvent, the description in paragraph [0306] of JP-A-2019-174549 can be referred to, and these contents are incorporated in the present specification.

Regarding the ester solvent, the description in paragraph [0307] of JP-A-2019-174549 can be referred to, and these contents are incorporated in the present specification.

As the alcohol solvent, the amide solvent, the ether solvent, and the hydrocarbon solvent, for example, the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167A1 can be used. ..

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less, based on the total amount of the developing solution. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.

<Other processes>
The pattern forming method preferably includes a step of washing with a rinsing liquid (rinsing step) after the step 3.
Regarding the rinsing step, the descriptions in paragraphs [0316] to [0320] of JP-A-2019-174549 can be referred to, and these contents are incorporated in the present specification.
Further, the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. In addition, this step has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250 ° C. (preferably 90 to 200 ° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate) to form the pattern on the substrate. Regarding this process, the description in paragraph [0238] of International Publication No. 2018/193954 can be taken into consideration, and these contents are incorporated in the present specification.

The composition of the present invention and various materials used in the pattern forming method of the present invention (for example, solvent, developing solution, rinsing solution, antireflection film forming composition, top coat forming composition, etc.) are made of metal. It is preferable that it does not contain impurities such as. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppt or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, examples of the metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, etc. W, Zn and the like can be mentioned.

Regarding the method for removing impurities such as metals from various materials, the description in paragraphs [0240] to [0242] of International Publication No. 2018/193954 can be referred to, and these contents are incorporated in the present specification.

Further, in the present invention, the matters described in paragraphs [0243] to [0247] of International Publication No. 2018/193954 can be incorporated, and these contents are incorporated in the present specification.

The present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on an electric electronic device (home appliance, OA (Office Automation), media-related device, optical device, communication device, etc.).

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below. Unless otherwise specified, "parts" and "%" are intended to be based on mass.

18 g of glycerol 1,2-carbonate and 108 g of methylene chloride are mixed, 15.9 g of N-methylmorpholine (NMM) is added with stirring at -10 ° C, and 43.8 g of trifluoromethanesulfonic anhydride (Tf ₂ O) is added. A mixed solution of 42 g of methylene chloride and 42 g of methylene chloride was carefully added dropwise so as not to generate excessive heat, and the mixture was stirred at 0 ° C. for 2 hours. After returning the reaction solution to 20 ° C., 300 g of acetone was added and concentrated under reduced pressure to obtain 120 g of an acetone solution of Intermediate A. 15.3 g of 4-hydroxystyrene and 126 g of acetone were mixed, 99 g of cesium carbonate was added under ice-cooling, and 120 g of an acetone solution of the above intermediate A was added dropwise. After stirring at 20 ° C. for another 2 hours, the mixture was filtered. The filtrate was concentrated under reduced pressure to distill off the solvent, and then recrystallized from 2-propanol to obtain 30 g of monomer a1 (yield 62%).
^{1 1} H-NMR (Acetone-d6: ppm) δ: 7.43 (d), 6.98 (d), 6.70 (dd), 5.68 (d), 5.23 (m), 5. 12 (d), 4.73 (dd), 4.54 (dd), 4.42-4.26 (dddd)

25.2 g of 4-vinylbenzoic acid, 20 g of glycerol 1,2-carbonate, 2.1 g of 4-dimethylaminopyridine and 315 g of tetrahydrofuran (THF) are mixed, and 1-ethyl-3- (3-dimethylamino) is cooled under ice. 36 g of propyl) carbodiimide hydrochloride (EDC) was added, and the mixture was stirred at 20 ° C. for 6 hours. After removing the insoluble matter by filtration, the filtrate was concentrated under reduced pressure. 560 g of ethyl acetate and 500 g of water were added to the residue to carry out a liquid separation operation, and the organic layer was washed 3 times with 500 g of water. After dehydration with sodium sulfate, the mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in 75 g of ethyl acetate, and 120 g of n-hexane was added dropwise while stirring under ice-cooling to precipitate white crystals. This was filtered to obtain 29 g of monomer a14 (yield 69%).
^{1 1} H-NMR (Acetone-d6: ppm) δ: 8.00 (d), 10.22 (s), 7.63 (d), 7.86 (d), 6.85 (dd), 6. 01 (d), 5.43 (d), 5.28 (m), 4.77 (dd), 4.69-4.54 (m)

<Synthesis Example 1: Synthesis of Resin A-1>
14 g of monomer (a1), 42 g of monomer (b1), 14 g of monomer (c4), 4.3 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), and 155 g of cyclohexanone. Was dissolved in. 41 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a reaction vessel, and the mixture was added dropwise to a system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours and then allowed to cool to 20 ° C. After adding 70 g of PGMEA to the above reaction solution, the mixture was added dropwise to 2450 g of a mixed solvent of ethyl acetate and n-heptane (ethyl acetate / n-heptane = 10/90 (mass ratio)) to precipitate the polymer, and the supernatant solvent was added. Was removed. To the remaining polymer, 1050 g of a mixed solvent of ethyl acetate and n-heptane (mass ratio similar to the above) was added, and the mixture was stirred for 30 minutes and then filtered. The obtained powder was dried under reduced pressure to obtain 51 g of a resin (A-1). The weight average molecular weight by GPC was 9000, and the dispersity (Mw / Mn) was 1.77. ¹³ The composition ratio of the resin A-1 calculated by C-NMR measurement was 20/60/20 (a1 / b1 / c4) in terms of mass ratio.

^{1 1} H-NMR (DMSO-d6: ppm) δ: 9.06, 7.07-6.22, 5.13, 4.63, 4.47-3.99, 2.15-0.12.

<Synthesis Example 2: Synthesis of Resin A-21>
14 g of monomer (a14), 42 g of monomer (b1), 14 g of monomer (c4), 5.1 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), and 155 g of cyclohexanone. Was dissolved in. 41 g of PGMEA was placed in a reaction vessel, and the mixture was added dropwise to a system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours and then allowed to cool to 20 ° C. After adding 70 g of PGMEA to the above reaction solution, the mixture was added dropwise to 2450 g of a mixed solvent of ethyl acetate and n-heptane (ethyl acetate / n-heptane = 10/90 (mass ratio)) to precipitate the polymer, and the supernatant solvent was added. Was removed. To the remaining polymer, 1050 g of a mixed solvent of ethyl acetate and n-heptane (mass ratio similar to the above) was added, and the mixture was stirred for 30 minutes and then filtered. The obtained powder was dried under reduced pressure to obtain 55 g of a resin (A-21). The weight average molecular weight by GPC was 9000, and the dispersity (Mw / Mn) was 1.67. ¹³ The composition ratio of the resin A-21 calculated by C-NMR measurement was 20/60/20 (a14 / b1 / c4) in terms of mass ratio.

^{1 1} H-NMR (DMSO-d6: ppm) δ: 9.08, 7.80, 7.40-6.32, 5.18, 4.78-4.22, 2.12-0.22

The resin (A) shown in Tables 1 to 3 was synthesized by the same method as in the synthesis example of the resin A-1 except that the monomer used was changed.
The composition ratio of the resin ^{was calculated by 1} H-NMR (nuclear magnetic resonance) or ¹³ C-NMR measurement. The weight average molecular weight (Mw: polystyrene conversion) and the dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement. In Tables 1 to 3, for each resin, the content of each repeating unit (mass ratio of each repeating unit to all repeating units of the resin (A) (unit: mass%)), Mw (weight average molecular weight), and Mw (weight average molecular weight). And the degree of dispersion are shown.
Although the resins (RA-1) to (RA-8) are not the resins (A) of the present invention, they are listed in Table 3 for convenience.
In Tables 1 to 3, the content of each repeating unit is described in the "content (% by mass)" column to the right of the "type" column of each repeating unit.

The structure of each repeating unit is shown below.

[Photoacid generator B]
The photoacid generator used is shown below.

[Acid diffusion control agent D]
The acid diffusion control agent used is shown below.

[Hydrophobic resin E]
The hydrophobic resin used is shown below.

The weight average molecular weight (Mw) and dispersity (Mw / Mn) of E-1 to E-4 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). The composition ratio (molar ratio) of the resin ^{was measured by 13} C-NMR.

[Surfactant]
The surfactants shown below were used.
H-1: Megafuck F176 (manufactured by DIC Corporation, fluorine-based surfactant)
H-2: Megafuck R08 (manufactured by DIC Corporation, fluorine and silicon-based surfactant)

〔solvent〕
The following solvents were used.
F1: Propylene glycol monomethyl ether acetate (PGMEA)
F2: Propylene glycol monomethyl ether (PGME)
F3: Propylene glycol monoethyl ether (PGEE)
F4: Cyclohexanone F5: Cyclopentanone F6: 2-Heptanone F7: Ethyl lactate F8: γ-Butyrolactone F9: Propylene carbonate

[Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition]
Each component shown in Tables 4 to 6 was mixed so that the solid content concentration was 2.0% by mass. Then, the obtained mixed solution is first filtered through a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 5 nm, thereby causing sensitive light or radiation. A sex resin composition (hereinafter, also referred to as a resin composition) was prepared. In the resin composition, the solid content means all components other than the solvent. The obtained resin composition was used in Examples and Comparative Examples.
In the following "resin (A)" column, "photoacid generator (B)" column, "acid diffusion control agent (D)" column, "hydrophobic resin (E)" column, and "surfactant" column The addition amount of each component described represents the ratio (mass%) of each component to the total solid content. The addition amount of each component is described in the "addition amount (%)" column on the right side of the "type" column of each component.

[Pattern formation (1): EUV exposure, organic solvent development]
The underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a base film having a film thickness of 20 nm. The resin composition shown in Table 7 was applied thereto and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
Using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech), pattern irradiation was performed on the silicon wafer having the obtained resist film. rice field. As the lectil, a mask having a line size of 20 nm and a line: space = 1: 1 was used.
The resist film after exposure was baked at 90 ° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

〔evaluation〕
[Roughness performance] (LWR (line width noise) performance)
A length-measuring scanning electron microscope (SEM Co., Ltd.) was used for a 20 nm (1: 1) line-and-space pattern resolved at the optimum exposure amount when resolving a line pattern with an average line width of 20 nm. When observing from the upper part of the pattern using Hitachi, Ltd. S-9380II)), the line width was observed at 50 points, and the measurement variation was evaluated by 3σ and used as LWR (nm). The smaller the value, the better the performance.

[Fall front width]
The line width of the line-and-space pattern was measured while changing the exposure amount. At this time, the average value of the minimum line widths at which the pattern was resolved without collapsing over 10 μm square was defined as the collapse front width. The smaller this value is, the wider the margin of pattern collapse is, and the better the performance is.

The evaluation results are shown in Table 7 below.

[Pattern formation (2): EUV exposure, alkaline aqueous solution development]
The underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a base film having a film thickness of 20 nm. The resin composition shown in Table 8 was applied thereto and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
Using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech), pattern irradiation was performed on the silicon wafer having the obtained resist film. rice field. As the lectil, a mask having a line size of 20 nm and a line: space = 1: 1 was used.
The resist film after exposure was baked at 90 ° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, this was spin-dried to obtain a positive pattern.
The LWR performance and the collapse front width were evaluated by the same method as described above.

The evaluation results are shown in Table 8 below.

[Pattern formation (3): EB (electron beam) exposure, alkaline aqueous solution development]
The resin composition shown in Table 9 was uniformly applied onto a silicon substrate treated with hexamethyldisilazane using a spin coater. Next, heat drying was performed on a hot plate at 120 ° C. for 90 seconds to form a resist film having a film thickness of 35 nm.
Using an electron beam irradiation device (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 keV), electron beam irradiation is performed on the obtained resist film through a 6% halftone mask with a line width of 24 nm and a 1: 1 line and space pattern. went. Immediately after the irradiation, the mixture was heated on a hot plate at 110 ° C. for 60 seconds. Further, it was developed at 23 ° C. for 60 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

〔evaluation〕
[Roughness performance] (LWR (line width noise) performance)
A length-measuring scanning electron microscope (SEM Co., Ltd.) was used for a 20 nm (1: 1) line-and-space pattern resolved at the optimum exposure amount when resolving a line pattern with an average line width of 24 nm. When observing from the upper part of the pattern using Hitachi, Ltd. S-9380II)), the line width was observed at 50 points, and the measurement variation was evaluated by 3σ and used as LWR (nm). The smaller the value, the better the performance.

The fall front width was evaluated by the same method as described above.

The evaluation results are shown in Table 9 below.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on April 28, 2020 (Japanese Patent Application No. 2020-0797747), the contents of which are incorporated herein by reference.

Claims

A resin (A) containing a repeating unit (1a) represented by the following general formula (1) and a repeating unit (1b) having an acid-degradable group,
Compound (B) that generates acid by irradiation with active light or radiation, and
A sensitive light-sensitive or radiation-sensitive resin composition containing.

In general formula (1),
R 1 represents a group having a cyclic structure containing a carbonic acid ester group or a group having a cyclic structure containing SO 2 groups. However, neither of the two bonds of the sulfur atom in the SO 2 group is bonded to the oxygen atom.
R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group or an organic group.
R 3 represents a hydrogen atom, a halogen atom or an alkyl group.
L 1 represents a single bond or a divalent linking group.
L 2 represents a single bond or a divalent linking group.
X is -COO -, - O -, - CONR 4 -, - SO 3 -, - SO 2 NR 4 - or -C (CF 3) 2 O- and represents, R 4 represents a hydrogen atom or an alkyl group.
m 1 and n 1 each represent an integer of 1 to 4. However, m 1 + n 1 = 5 is satisfied.
If R 1, R 2, X and L 1 there are a plurality, the plurality of R 1, R 2, X and L 1 may be different from one another respectively the same.
The actinic or radiation-sensitive resin composition according to claim 1, wherein L 2 in the general formula (1) represents a single bond.
R 1 in the general formula (1) is a group having a cyclic structure containing a carbonic acid ester group, or a cyclic containing SO 2 groups in which two bonds of a sulfur atom are both bonded to a carbon atom or a nitrogen atom. The sensitive light-sensitive or radiation-sensitive resin composition according to claim 1 or 2, which represents a group having a structure.
The actinic or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the repeating unit (1a) is represented by the following general formula (2).

In the general formula (2), R 1 , R 2 , R 3 , L 1 , m 1 and n 1 have the same meanings as those in the general formula (1), respectively.
X 'is -COO -, - CONR 4 -, - SO 3 -, - SO 2 NR 4 - or -C (CF 3) 2 O- and represents, R 4 represents a hydrogen atom or an alkyl group.
'If and L 1 there are a plurality, the plurality of R 1, R 2, X' R 1, R 2, X and L 1 may be different from one another respectively the same.
The active photosensitivity or photosensitivity according to claim 4, wherein the resin (A) further contains a repeating unit (1c) having at least one selected from the group consisting of a lactone structure, a carboxyl group, a hydroxyl group and a sulfonamide group. Radiation sensitive resin composition.
The actinic or radiation-sensitive resin composition according to claim 4 or 5, wherein X'in the general formula (2) represents -COO-.
The actinic cheilitis or radiation-sensitive radiation according to any one of claims 4 to 6, wherein R 1 in the general formula (2) is represented by the following general formula (4-1) or (4-2). Sex resin composition.

In general formula (4-1),
R 411 , R 412 , R 413 , R 414 and R 415 each independently represent a hydrogen atom or an alkyl group.
p 41 and p 42 each independently represent an integer of 0 to 2. However, p 41 + p 42 ≤ 2 is satisfied. If R 411, R 412, R 414 and R 415 there are a plurality, a plurality of R 411, R 412, R 414 and R 415 may be different from one another respectively the same.
In general formula (4-2),
R 421 , R 422 , R 423 , R 424 and R 425 each independently represent a hydrogen atom or an alkyl group.
p 43 and p 44 each independently represent an integer of 0 to 2. However, p 43 + p 44 ≤ 2 is satisfied. If R 421, R 422, R 424 and R 425 there are a plurality, a plurality of R 421, R 422, R 424 and R 425 may be different from one another respectively the same.
In the general formulas (4-1) and (4-2), * represents the bonding position.
The actinic or radiation-sensitive resin composition according to claim 7, wherein R 1 in the general formula (2) is represented by the general formula (4-1).
The repeating unit (1a) is represented by the following general formula (5), and the resin (A) further has at least one selected from the group consisting of a lactone structure, a carboxyl group, a hydroxyl group and a sulfonamide group. The sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, which comprises a unit (1c).

In the general formula (5), R 1 , R 2 , R 3 , L 1 , m 1 and n 1 have the same meanings as those in the general formula (1), respectively.
If R 1, R 2 and L 1 there are a plurality, the plurality of R 1, R 2 and L 1 may be different from one another respectively the same.
The actinic or radiation-sensitive resin composition according to claim 9, wherein R 1 in the general formula (5) is represented by the following general formula (6-1) or (6-2).

In general formula (6-1),
R 611 , R 612 , R 613 , R 614 and R 615 each independently represent a hydrogen atom or an alkyl group.
p 61 and p 62 each independently represent an integer of 0 to 2. However, p 61 + p 62 ≤ 2 is satisfied. If R 611, R 612, R 614 and R 615 there are a plurality, a plurality of R 611, R 612, R 614 and R 615 may be different from one another respectively the same.
In general formula (6-2),
R 621 , R 622 , R 623 , R 624 and R 625 each independently represent a hydrogen atom or an alkyl group.
p 63 and p 64 each independently represent an integer of 0 to 2. However, p 63 + p 64 ≤ 2 is satisfied. If R 621, R 622, R 624 and R 625 there are a plurality, a plurality of R 621, R 622, R 624 and R 625 may be different from one another respectively the same.
In the general formulas (6-1) and (6-2), * represents the bonding position.
The actinic or radiation-sensitive resin composition according to claim 10, wherein R 1 in the general formula (5) is represented by the general formula (6-1).
The actinic cheilitis or radiation-sensitive radiation according to any one of claims 1 to 11, wherein the content of the repeating unit (1a) is 10 to 60% by mass with respect to all the repeating units of the resin (A). Sex resin composition.
The actinic or radiation-sensitive resin composition according to any one of claims 1 to 12, wherein the compound (B) is an ionic compound containing an anion and a cation.
Any one of claims 1 to 13, wherein the compound (B) is composed of one or more anionic molecules and one or more cationic molecules, and at least one of the cationic molecules contains a fluorine atom. The sensitive light-sensitive or radiation-sensitive resin composition according to.
The actinic or radiation-sensitive resin composition according to any one of claims 1 to 13, wherein the compound (B) is represented by any of the following general formulas (a) to (c).
M a1 + A a - -L a -B a - M a2 + (a)
(M b1 + A b -) nb -L b -B b - M b2 + (b)
(M c + A c -) nc -L c (c)
In the general formula (a), M a1 + and M a2 + each independently represent an organic cation, L a represents a divalent organic group, A a - and B a - are each independently an anionic functional Represents a group.
However, in the general formula (a) HA a -L a -B represented by a H compound M a1 + and M a2 + is substituted with a hydrogen atom each of the compounds represented by the represented by HA a pKa groups is less than the pKa of the groups represented by B a H.
In the general formula (b), M b1 + and M b2 + each independently represent an organic cation, L b represents a (nb + 1) -valent organic group, and Ab − and B b − each independently represent an anion. It represents a sex functional group, and nb represents an integer of 2 or more. The plurality of M b1 + and Ab − may be the same or different from each other.
However, in the general formula (b) M b1 + and M b2 + of the compound represented by is substituted with hydrogen atoms, respectively (HA b) a compound represented by nb -L b -B b H, in HA b The pKa of the group represented is smaller than the pKa of the group represented by B b H.
In the general formula (c), Mc + represents an organic cation, Ac − represents an anionic functional group, L c represents a nonionic organic moiety capable of neutralizing an acid, and nc represents 2 or more. Represents an integer. The plurality of Mc + and Ac − may be the same or different from each other.
A sensitive light-sensitive or radiation-sensitive film formed by the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 15.
A mask blank having the sensitive light-sensitive or radiation-sensitive film according to claim 16.
A step of forming a resist film on a substrate using the actinic cheilitis or radiation-sensitive resin composition according to any one of claims 1 to 15.
The step of exposing the resist film and
A step of developing the exposed resist film with a developing solution to form a pattern, and
Pattern forming method including.
A method for manufacturing an electronic device, which comprises the pattern forming method according to claim 18.