WO2014175201A1

WO2014175201A1 - Pattern formation method, active light-sensitive or radiation-sensitive resin composition used therein, resist film, and electronic device using resist film and method for producing electronic device

Info

Publication number: WO2014175201A1
Application number: PCT/JP2014/061133
Authority: WO
Inventors: 敬充冨賀
Original assignee: 富士フイルム株式会社
Priority date: 2013-04-26
Filing date: 2014-04-21
Publication date: 2014-10-30
Also published as: KR101783737B1; TWI607283B; JP2014215548A; KR20150127290A; TW201443569A

Abstract

The purpose of the present invention is to provide a pattern formation method that can form a pattern of good shape. This pattern formation method comprises the following: (a) a step for forming a film from an active light-sensitive or radiation-sensitive resin composition containing (A) and (B), where (A) is a resin that due to the action of an acid shows an increase in polarity and a decrease in solubility in a developer containing an organic solvent, and (B) is a compound represented by general formula (I) that generates acid by being irradiated with active light or radiation; (b) a step for irradiating the film with active light or radiation; and (c) a step for developing the film that has been irradiated with the active light or radiation using the developer containing the organic solvent.

Description

Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition used therefor, resist film, electronic device using these, and method for producing the same

The present invention relates to a pattern forming method, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therefor, and an electronic device manufacturing method and an electronic device using these. More specifically, the present invention relates to a pattern forming method suitable for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes, and the pattern forming method. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a resist film, and an electronic device manufacturing method and an electronic device using these. In particular, the present invention relates to an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, a pattern forming method suitable for exposure in an ArF immersion projection exposure apparatus, and an actinic ray used in the pattern forming method. The present invention relates to a photosensitive or radiation-sensitive resin composition, a resist film, a method for manufacturing an electronic device, and an electronic device.

Since the resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption.
In recent years, a pattern formation method using a developer (organic developer) containing an organic solvent has been developed (Patent Document 1). For example, in the Example column of Patent Document 1, the following photoacid generator is used.

JP 2011-123469 A

On the other hand, in recent years, various electronic devices have been required to have higher functions, and accordingly, further improvement in characteristics of resist patterns used for microfabrication has been required. In particular, there is a demand for further performance improvement of pattern shape characteristics such as line width roughness (LWR), pattern profile, CDU (pattern dimension uniformity), MEEF (Mask Error Enhancement Factor) and the like.
The present inventors evaluated the above various characteristics using the pattern forming method described in Patent Document 1. As a result, although the conventional required level was satisfied, the level required recently is not satisfied, and further improvement is necessary. It was.

An object of this invention is to provide the pattern formation method which can form a favorable-shaped pattern in view of the said situation.
Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition used therein, a resist film, an electronic device using these, and a method for producing the same.

As a result of intensive studies on the problems of the prior art, the present inventors have found that the above-described problems can be solved by using a radiation-sensitive resin composition containing a predetermined photoacid generator.
That is, it has been found that the above object can be achieved by the following configuration.

(1) (a) A step of forming a film with an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B):
(A) a resin whose polarity increases by the action of an acid and whose solubility in a developer containing an organic solvent decreases,
(B) A step of irradiating the compound (I) film represented by the general formula (I) described later, which generates an acid upon irradiation with actinic rays or radiation, and (c) development containing an organic solvent The process of developing the film | membrane which irradiated the actinic ray or the radiation using the liquid.
(2) The pattern forming method according to (1), wherein R is a group having a cyclic structure.
(3) The pattern forming method according to (1) or (2), wherein W is a polycyclic aliphatic group.
(4) The pattern forming method according to any one of (1) to (3), wherein W is an adamantylene group.
(5) The content of the organic solvent in the developer containing the organic solvent is 90% by mass or more and 100% by mass or less with respect to the total amount of the developer, according to any one of (1) to (4) Pattern forming method.
(6) Any of (1) to (5), wherein the developer contains at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. The pattern formation method as described in one.
(7) The actinic ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin (HR) different from the resin (A), according to any one of (1) to (6) Pattern forming method.
(8) The pattern forming method according to any one of (1) to (7), wherein the exposure in the step (A) is immersion exposure.
(9) An actinic ray-sensitive or radiation-sensitive resin composition used for the pattern forming method according to any one of (1) to (8).
(10) A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to (9).
(11) A method for manufacturing an electronic device, comprising the pattern forming method according to any one of (1) to (8).
(12) An electronic device manufactured by the method for manufacturing an electronic device according to (11).

ADVANTAGE OF THE INVENTION According to this invention, the pattern formation method which can form a favorable-shaped pattern can be provided.
Moreover, according to this invention, the actinic-ray-sensitive or radiation-sensitive resin composition used for it, a resist film, an electronic device using these, and its manufacturing method can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a 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).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
Unless otherwise specified, “exposure” in the present specification is not limited to exposure to deep ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
In this specification, "(meth) acrylic monomer" means at least one monomer having the structure of "CH ₂ = CH-CO-" or _{_{"CH 2 = C (CH 3)}} -CO- " To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

The characteristic point of the present invention is that a group having a cyclic structure of the photoacid generator is further substituted with an organic group. By including such an organic group, the molecular weight of the photoacid generator itself increases, and the diffusibility in the film decreases. Therefore, it becomes easy to form a pattern as a latent image after performing the exposure process. In particular, the organic group is a group having a bulky structure (a group having a cyclic structure), and the effect is great.

The pattern forming method of the present invention includes the following steps (a) to (c).
(A) forming a film with an actinic ray-sensitive or radiation-sensitive resin composition containing (A) and (B) described later,
(A) irradiating the film with actinic rays or radiation, and
(C) Step of developing the film irradiated with the actinic ray or radiation using a developer containing an organic solvent In the following, first, the actinic ray-sensitive or radiation-sensitive resin composition ( Hereinafter, these components are simply referred to collectively as “composition”) in detail, and then the procedure of each step is described in detail.

<Resin whose polarity increases by the action of an acid and its solubility in a developer containing an organic solvent decreases (hereinafter also referred to as resin (A))>
Resin (A) is a resin whose polarity increases due to the action of an acid and its solubility in an organic solvent decreases. In such a resin (A), a part or all of the hydrophilic group in the molecule is protected by a protecting group that can be removed by contact with an acid, and the resin (A) is in contact with an acid. Then, this protecting group is eliminated and the solubility of the resin (A) in the organic solvent decreases. The hydrophilic group protected by this protecting group is hereinafter also referred to as “acid labile group”. Examples of the hydrophilic group include a hydroxy group or a carboxy group, and a carboxy group is more preferable.
The resin (A) can be produced by polymerizing a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”). In the polymerization, only one type of monomer (a1) may be used, or two or more types may be used in combination.

<Monomer (a1)>
The monomer (a1) has an acid labile group. In the case where the hydrophilic group is a carboxy group, the acid labile group is a group in which the hydrogen atom of the carboxy group is replaced with an organic residue, and the atom of the organic residue bonded to the oxy group is a tertiary carbon atom. It is done. Among such acid labile groups, a preferred acid labile group is represented, for example, by the following formula (1) (hereinafter sometimes referred to as “acid labile group (1)”).

[In formula (1), R ^a1 , R ^a2 and R ^a3 (hereinafter referred to as “R ^a1 to R ^a3 ”, the same shall apply hereinafter) are each independently an aliphatic hydrocarbon having 1 to 8 carbon atoms. Represents a group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. When the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or the ring formed by combining R ^a1 and R ^a2 with each other has a methylene group, the methylene group is an oxy group, —S— or a carbonyl group. May be replaced. * Represents a bond. ]

Examples of the aliphatic hydrocarbon group represented by R ^a1 to R ^a3 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. The alicyclic hydrocarbon group of R ^a1 to R ^a3 may be either monocyclic or polycyclic, and may be either unsaturated or saturated that does not exhibit aromaticity.
Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and methylnorbornyl group, and groups shown below.

The alicyclic hydrocarbon group of R ^a1 to R ^a3 is preferably a saturated hydrocarbon group, and preferably has 3 to 16 carbon atoms.
In the ring formed by combining R ^a1 and R ^a2 , the following groups are ^exemplified as the group represented by —C (R ^a1 ) (R ^a2 ) (R ^a3 ).

The number of carbon atoms in the ring formed by combining R ^a1 and R ^a2 with each other is preferably 3-12.

Specific examples of the acid labile group (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^a1 to R ^a3 are all alkyl groups in the formula (1), one of these alkyl groups is a tert -Butoxycarbonyl group is preferred.), 2-alkyladamantan-2-yloxycarbonyl group (in formula (1), R ^a1 and R ^a2 are bonded to each other to form an adamantyl ring together with the carbon atom to which they are bonded) R ^a3 is an alkyl group) and 1- (adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is adamantyl). Group which is a group).

On the other hand, examples of the acid labile group in the case where the hydrophilic group is a hydroxy group include those in which the hydrogen atom of the hydroxy group is replaced with an organic residue to become a group containing an acetal structure. Among such acid labile groups, preferred acid labile groups are, for example, those represented by the following formula (2) (hereinafter sometimes referred to as “acid labile groups (2)”).

[In the formula (2), R ^b1 and R ^b2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^b3 represents a hydrocarbon group having 1 to 20 carbon atoms, Alternatively, R ^b2 and R ^b3 are bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom and the oxygen atom to which they are bonded. When the hydrocarbon group or the ring formed by combining R ^b2 and R ^b3 with each other has a methylene group, the methylene group may be replaced with an oxy group, —S— or a carbonyl group. * Represents a bond. ]

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. At least one of R ^b1 and R ^b2 is preferably a hydrogen atom.
Specific examples of the acid labile group (2) include the following groups.

The monomer (a1) having an acid labile group is preferably a monomer having an acid labile group and a carbon-carbon double bond, more preferably a (meth) acrylic monomer having an acid labile group.
In particular, the monomer (a1) is preferably a monomer having both an acid labile group (1) and / or an acid labile group (2) and a carbon-carbon double bond in the molecule, more preferably It is a (meth) acrylic monomer having an acid labile group (1).

Among (meth) acrylic monomers having an acid labile group (1), the acid labile group (1) is preferably a group having an alicyclic hydrocarbon structure having 5 to 20 carbon atoms. A resin (A) obtained by polymerizing the monomer (a1) having a group having a sterically bulky alicyclic hydrocarbon structure is obtained by using the composition of the present invention containing the resin (A). When the resist pattern is manufactured, the resist pattern can be manufactured with better resolution. Here, (meth) acryl represents acryl and / or methacryl.

Among (meth) acrylic monomers having an acid labile group (1) containing an alicyclic hydrocarbon structure, a monomer represented by the formula (a1-1) (hereinafter referred to as “monomer (a1-1)”) And a monomer represented by the formula (a1-2) (hereinafter sometimes referred to as “monomer (a1-2)”) are preferable. When manufacturing resin (A), these may be used independently and may use 2 or more types together. Resin (A) contains at least one selected from a repeating unit derived from a monomer represented by formula (a1-1) and a repeating unit derived from a monomer represented by formula (a1-2) Is preferred. The resin (A) preferably contains at least one repeating unit derived from the monomer represented by the formula (a1-1) and one repeating unit derived from the monomer represented by the formula (a1-2). . In another embodiment, the resin (A) preferably contains two or more repeating units derived from the monomer represented by the formula (a1-2). In the resin (A), the ratio of the total amount of the repeating units derived from the monomer represented by the formula (a1-1) and the repeating units derived from the monomer represented by the formula (a1-2) to the total repeating units is: It is preferably 40 mol% or more, more preferably 45 mol% or more, and further preferably 50 mol% or more. In particular, the ratio of the repeating unit derived from the monomer represented by the formula (a1-2) to the total repeating units is preferably 30 mol% or more, more preferably 35 mol% or more, and 40 mol % Or more is more preferable. The content ratio of each repeating unit in the resin (A) can be measured by, for example, ¹³ C-NMR.

[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 each independently represent an oxy group or a group represented by * —O— (CH ₂ ) _k1 —CO—O—. Here, k1 represents an integer of 1 to 7, and * is a bond with a carbonyl group (—CO—).
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.
m1 represents an integer of 0 to 14, and n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]
In the formula (a1-1), the notation “— (CH ₃ ) _m1 ” in the adamantane ring represents a hydrogen atom bonded to a carbon atom constituting the adamantane ring (that is, a hydrogen atom of a methylene group and / or a methine group). Is replaced by a methyl group, and the number of the methyl group is m1.

In the formula (a1-1) and the formula (a1-2), L ^a1 and L ^a2 are preferably an oxy group or * —O— (CH ₂ ) _f1 —CO—O— (where f1 is 1 to 4 represents an integer of 4, and more preferably an oxy group. f1 is more preferably 1. R ^a4 and R ^a5 are preferably methyl groups.
The aliphatic hydrocarbon group for R ^a6 or R ^a7 is preferably a group having 6 or less carbon atoms. The alicyclic hydrocarbon group for R ^a6 or R ^a7 preferably has 8 or less carbon atoms, more preferably 6 or less.
When R ^a6 or R ^a7 is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be either saturated or unsaturated, but saturated hydrocarbon It is preferably a group.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

Examples of the monomer (a1-1) include the following.

Among these, as the monomer (a1-1), 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate and 2-isopropyladamantan-2-yl (meth) Acrylates are preferred, with 2-methyladamantan-2-yl methacrylate, 2-ethyladamantan-2-yl methacrylate and 2-isopropyladamantan-2-yl methacrylate being more preferred.
Examples of the monomer (a1-2) include the following. Among these, as the monomer (a1-2), 1-ethylcyclohexyl (meth) acrylate is preferable, and 1-ethylcyclohexyl methacrylate is more preferable.

When the resin (A) is produced using the monomer (a1-1) and / or the monomer (a1-2), when the total structural unit of the obtained resin (A) is 100 mol%, it is derived from these monomers. The total content of structural units is preferably in the range of 10 to 95 mol%, more preferably in the range of 15 to 90 mol%, and still more preferably in the range of 20 to 85 mol%. In order to bring the total content of the structural unit derived from the monomer (a1-1) and / or the structural unit derived from the monomer (a1-2) into such a range, when the resin (A) is produced, In addition, the amount of monomer (a1-1) and / or monomer (a1-2) used may be adjusted with respect to the amount of all monomers used.

In the production of the resin (A), in addition to the (meth) acrylic monomer (that is, the monomer (a1-1) and the monomer (a1-2)), an acid labile group (1), a carbon-carbon double bond, Other monomers having in the molecule can also be used.

The monomer (a1) having an acid labile group (2) is preferably a (meth) acrylic monomer. For example, a monomer represented by the formula (a1-5) (hereinafter referred to as “monomer (a1-5)”) There is a).

[In the formula (a1-5),
R ³¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
L ¹ to L ^{3 each} represents an oxy group, a group represented by —S— or * —O— (CH ₂ ) _k1 —CO—O—. Here, k1 represents an integer of 1 to 7, and * is a bond with a carbonyl group (—CO—).
Z ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms, and the methylene group contained in the alkylene group may be replaced with an oxy group or a carbonyl group.
s1 and s1 ′ each independently represents an integer of 0 to 4. ]

In the formula (a1-5), R ³¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably an oxy group.
One of L ² and L ³ is preferably an oxy group and the other is —S—.
s1 is preferably 1.
s1 ′ is preferably 0-2.
Z ¹ is preferably a single bond or —CH ₂ —CO—O—.

Specific examples of the monomer (a1-5) are as follows, for example.

When the resin (A) has a structural unit derived from the monomer (a1-5), the content thereof is in the range of 10 to 95 mol% with respect to all the structural units (100 mol%) of the resin (A). The range of 15 to 90 mol% is more preferable, and the range of 20 to 85 mol% is more preferable.

<Acid stable monomer>
The resin (A) used in the composition is a copolymer obtained using a monomer having no acid labile group (hereinafter sometimes referred to as “acid stable monomer”) in addition to the monomer (a1). It is preferable.

When the resin (A) is produced using an acid-stable monomer in combination, the amount of acid-stable monomer can be determined based on the amount of monomer (a1) used. The ratio of the amount of monomer (a1) used and the amount of acid-stable monomer used is expressed as [monomer (a1)] / [acid-stable monomer], and is preferably 10 to 80 mol% / 90 to 20 mol%. More preferably, it is 20 to 60 mol% / 80 to 40 mol%. Further, when a monomer having an adamantyl group (particularly, monomer (a1-1)) is used as the monomer (a1), the monomer having an adamantyl group with respect to the total amount (100 mol%) of the monomer (a1) used. It is preferable to use 15 mol% or more. Thereby, there exists a tendency for the dry etching tolerance of the resist pattern obtained from the resist composition containing resin (A) to become more favorable.

Examples of the acid-stable monomer include those having a hydroxy group or a lactone ring in the molecule. Acid-stable monomer having a hydroxy group (hereinafter sometimes referred to as “acid-stable monomer (a2)”) and / or acid-stable monomer having a lactone ring (hereinafter referred to as “acid-stable monomer (a3)”) The resin (A) having a structural unit derived from.) Is a coating film formed on the substrate or a composition layer obtained from the coating film when the resist composition containing the resin (A) is applied to the substrate. It becomes easy to express the outstanding adhesiveness between. Further, such a composition can produce a resist pattern with good resolution.

<Acid stable monomer (a2)>
When the acid-stable monomer (a2) is used for the production of the resin (A), a suitable acid-stable monomer (a2) is listed depending on the type of exposure source used to obtain a resist pattern from the composition containing the resin (A). be able to. That is, when the resist composition of the present invention is used for KrF excimer laser exposure (wavelength: 248 nm), high energy beam exposure such as electron beam or EUV light, a phenolic hydroxy group is used as the acid stable monomer (a2). It is preferable to use the acid-stable monomer (a2-0) [for example, hydroxystyrenes] having for the production of the resin (A). When short-wave ArF excimer laser exposure (wavelength: 193 nm) is used, an acid-stable monomer represented by the formula (a2-1) described later is used for the production of the resin (A) as the acid-stable monomer (a2). Is preferred. As described above, the acid-stable monomer (a2) used for the production of the resin (A) can be preferably selected depending on the exposure source used for producing the resist pattern. The acid-stable monomer (a2) The resin (A) may be produced using only one kind of monomer suitable for the kind of the resin, or the resin (A) may be produced using two or more kinds of suitable monomers for the kind of the exposure source. Alternatively, the resin (A) may be produced using a suitable monomer according to the type of exposure source and two or more of the other acid stable monomers (a2).

As the acid stable monomer (a2), a styrene monomer such as p- or m-hydroxystyrene represented by the following formula (a2-0) (hereinafter referred to as “acid stable monomer (a2-0)”). Can be mentioned. The formula (a2-0) is shown in a form in which the phenolic hydroxy group is not protected with a suitable protecting group.

[In the formula (a2-0),
R ^a30 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyl group, or methacryloyl Represents a group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 are independent of each other. ]

^Examples of the halogen atom of R ^a30 and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include the same groups as those exemplified in the description of R ^a32 of the monomer (a1-4). Among these, R ^a30 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
The alkyl group for R ³¹ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably a methyl group.
As the alkoxy group for R ^a31, the same groups as those exemplified above for R ^a33 of the monomer (a1-4) can be mentioned. Among these, R ^a31 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

When the resin (A) having a structural unit derived from such an acid stable monomer (a2-0) is produced, the phenolic hydroxy group in the acid stable monomer (a2-0) is protected with a protecting group. Monomers can be used. Examples of the protecting group include a protecting group that is eliminated with an acid. Since the phenolic hydroxy group protected with a protecting group capable of leaving with an acid can be deprotected by contact with an acid, a structural unit derived from an acid stable monomer (a2-0) can be easily formed. Can do.
However, as described above, since the resin (A) has the structural unit (a1) containing an acid labile group, an acid stable monomer in which a phenolic hydroxy group is protected with a protective group that can be deprotected with a base ( When carrying out the polymerization using a2-0) and deprotecting, it is preferable to deprotect by contact with a base so as not to significantly impair the acid labile group of the structural unit (a1). Examples of the protecting group that can be deprotected with a base include an acetyl group and the like. Examples of the base include 4-dimethylaminoviridine, triethylamine and the like.

Examples of the acid stable monomer (a2-0) include the following monomers. In the following examples, the phenolic hydroxy group is not protected by a protecting group.

Of these, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferable.
When the resin (A) is produced using 4-hydroxystyrene or 4-hydroxy-α-methylstyrene, it is preferable to use those obtained by protecting the phenolic hydroxy group in these with a protective group.

When the resin (A) has a structural unit derived from the acid-stable monomer (a2-0), the content thereof is 5 to 95 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range of 10 to 80 mol% is more preferable, and the range of 15 to 80 mol% is more preferable.
Examples of the acid stable monomer (a2-1) include monomers represented by the following formula (a2-1).

[In the formula (a2-1),
L ^a3 represents an oxy group or * —O— (CH ₂ ) _k2 —CO—O—,
k2 represents an integer of 1 to 7. * Represents a bond with —CO—.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably an oxy group, —O— (CH ₂ ) _f1 —CO—O— (where f1 is an integer of 1 to 4), more preferably Is an oxy group.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1. ]

Examples of the acid stable monomer (a2-1) include the following. Among these, 3-hydroxyadamantan-1-yl (meth) acrylate, 3,5-dihydroxyadamantan-1-yl (meth) acrylate and (meth) acrylic acid 1- (3,5-dihydroxyadamantan-1-yl Oxycarbonyl) methyl is preferred, 3-hydroxyadamantan-1-yl (meth) acrylate and 3,5-dihydroxyadamantan-1-yl (meth) acrylate are more preferred, 3-hydroxyadamantan-1-yl methacrylate and 3, More preferred is 5-dihydroxyadamantan-1-yl methacrylate.

When the resin (A) has a structural unit derived from the acid-stable monomer (a2-1), the content thereof is 3 to 40 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range of 5 to 35 mol% is more preferable, the range of 5 to 30 mol% is more preferable, and the range of 5 to 15 mol% is particularly preferable.

<Acid stable monomer (a3)>
The lactone ring possessed by the acid-stable monomer (a3) may be monocyclic such as β-propiolactone ring, γ-butyrolactone ring and δ-valerolactone ring, and the monocyclic lactone ring and other rings Or a condensed ring. Among these lactone rings, a γ-butyrolactone ring and a condensed ring of γ-butyrolactone ring with other rings are preferable.

The acid stable monomer (a3) is preferably represented by the following formula (a3-1), formula (a3-2) or formula (a3-3). In manufacture of resin (A), only 1 type may be used among these and 2 or more types may be used together. The resin (A) more preferably contains at least one repeating unit derived from the monomer represented by the formula (a3-1). In addition, the resin (A) includes at least one repeating unit derived from the monomer represented by the formula (a3-1) and at least one repeating unit derived from the monomer represented by the formula (a3-2). It is particularly preferable to include it. In the following description, the acid-stable monomer (a3) represented by the formula (a3-1) is referred to as “acid-stable monomer (a3-1)”, and the acid-stable monomer represented by the formula (a3-2) ( a3) is referred to as “acid-stable monomer (a3-2)”, and acid-stable monomer (a3) represented by formula (a3-3) is referred to as “acid-stable monomer (a3-3)”.

[In Formula (a3-1), Formula (a3-2) and Formula (a3-3),
L ^a4 , L ^a5 and L ^a6 (hereinafter referred to as “L ^a4 to L ^a6 ”) are each independently —O— or * —O— (CH ₂ ) _k3 —CO—O—. To express.
k3 represents an integer of 1 to 7. * Represents a bond with —CO—.
R ^a18 , R ^a19 and R ^a20 (hereinafter referred to as “R ^a18 to R ^a20 ”) each independently represent a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1, q1 or r1 is 2 or more, a plurality of R ^a21 , R ^a22 or R ^a23 may be the same as or different from each other. ]

Examples of L ^a4 to L ^{a6 in} formula (a3-1) to formula (a3-3) include those described for L ^a3 .
L ^a4 to L ^a6 are preferably each independently —O— or * —O— (CH ₂ ) _d1 —CO—O— (where d1 is an integer of 1 to 4), -O- is preferable.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

Examples of the acid stable monomer (a3-1) include the following.

Examples of the acid-stable monomer (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring include the following.

Examples of the acid-stable monomer (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring include the following.

Among the acid stable monomers (a3) having a lactone ring, (meth) acrylic acid (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl, (meth) acrylic Acid tetrahydro-2-oxo-3-furyl, 2- (5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yloxy) -2-oxoethyl (meth) acrylate Such methacrylate esters are more preferred.

The resin (A) is a structural unit selected from the group consisting of a structural unit derived from the monomer (a3-1), a structural unit derived from the monomer (a3-2), and a structural unit derived from the monomer (a3-3) [ In the case of having the structural unit derived from the acid-stable monomer (a3)], the total content thereof is preferably 5 to 60% by mole, based on all the structural units (100% by mole) of the resin (A). The range of mol% is more preferable, the range of 10 to 40 mol% is more preferable, and the range of 15 to 40 mol% is particularly preferable.
The contents of the structural unit derived from the monomer (a3-1), the structural unit derived from the monomer (a3-2), and the structural unit derived from the monomer (a3-3) are the total structure of the resin (A). The amount is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, still more preferably 20 to 50 mol%, based on the unit (100 mol%).

<Acid-stable monomer (a4)>
Further, acid-stable monomers other than the acid-stable monomer (a2) and the acid-stable monomer (a3) (hereinafter sometimes referred to as “acid-stable monomer (a4)”) include anhydrous anhydrides represented by the formula (a4-1) In some cases, maleic acid, itaconic anhydride represented by formula (a4-2) and an acid-stable monomer having a norbornene ring represented by formula (a4-3) (hereinafter referred to as “acid-stable monomer (a4-3)”) There are).

[In the formula (a4-3),
R ^a25 and R ^a26 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a cyano group, a carboxy group, or —COOR ^a27 [wherein R ^a27 Represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is: It may be replaced with an oxy group or a carbonyl group. However, those in which —COOR ^a27 is an acid labile group are excluded (that is, R ^a27 does not include those in which a tertiary carbon atom is bonded to —O—). ] Or
Alternatively, R ^a25 and R ^a26 combine with each other to form —CO—O—CO—. ]

In R ^a25 and R ^a26 of the monomer (a4-3), ^examples of the aliphatic hydrocarbon group which may have a hydroxy group include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and 2-hydroxyethyl. Groups and the like.
The aliphatic hydrocarbon group for R ^a27 is preferably a group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. The alicyclic hydrocarbon group is preferably a group having 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. ^Examples of R ^a27 include a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.

Examples of the acid-stable monomer (a4-3) having a norbornene ring include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylate, Examples thereof include 2-hydroxy-1-ethyl norbornene-2-carboxylic acid, 5-norbornene-2-methanol, and 5-norbornene-2,3-dicarboxylic acid anhydride.

The resin (A) is a structural unit derived from maleic anhydride represented by the formula (a4-1), a structural unit derived from itaconic anhydride represented by the formula (a4-2), and a monomer (a4-3) In the case where it has a structural unit selected from the group consisting of structural units derived from (a structural unit derived from an acid-stable monomer (a4)), the total content is based on all structural units (100 mol%) of the resin (A). On the other hand, the range of 2 to 40 mol% is preferable, the range of 3 to 30 mol% is more preferable, and the range of 5 to 20 mol% is more preferable.

Examples of the acid stable monomer (a4) include an acid stable monomer having a sultone ring represented by the formula (a4-4) (hereinafter sometimes referred to as “acid stable monomer (a4-4)”). Is mentioned.

[In the formula (a4-4),
L ^a7 represents —O— or * —O— (CH ₂ ) _k2 —CO—O—, and k2 represents an integer of 1 to 7. * Represents a bond with —CO—.
R ^a28 represents a hydrogen atom or a methyl group.
W ¹ represents a residue containing a sultone ring which may have a substituent. ]

Examples of the sultone ring include those shown below. Residues containing sultone ring, for example, one of the hydrogen atoms in the sultone ring include those replaced by bond to L ^a7.

The residue containing a sultone ring which may have a substituent is a group in which a hydrogen atom other than the hydrogen atom replaced with a bond to the above-mentioned ^{La 7} is further substituted with a substituent. As a hydroxy group, a cyano group, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Examples thereof include an alkoxycarbonyl group having 1 to 7 carbon atoms, an acyl group having 1 to 7 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms.

Examples of the fluorinated alkyl group include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) Tyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoro Pentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2, 3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group And perfluorohexyl groups. Among them, the number of carbon atoms is preferably 1 to 4, more preferably a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group, and particularly preferably a trifluoromethyl group.
Examples of the hydroxyalkyl group include a hydroxymethyl group and a 2-hydroxyethyl group.

Specific examples of the acid stable monomer (a4-4) are shown below.

When the resin (A) has a structural unit derived from the acid stable monomer (a4-4), the content thereof is 2 to 40 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range of 3 to 35 mol% is more preferable, and the range of 5 to 30 mol% is more preferable.

Preferred resin (A) is a copolymer obtained by polymerizing the monomer (a1), the acid stable monomer (a2) and / or the acid stable monomer (a3). In this preferable copolymer, it is preferable to use at least one of the above-mentioned monomer (a1-1) and monomer (a1-2) as monomer (a1), and more preferable to use monomer (a1-1). . The acid stable monomer (a2) is preferably an acid stable monomer (a2-1), and the acid stable monomer (a3) is at least one of an acid stable monomer (a3-1) and an acid stable monomer (a3-2). Is preferred.

Resin (A) uses monomer (a1) and, if necessary, an acid-stable monomer selected from the group consisting of acid-stable monomer (a2), acid-stable monomer (a3) and acid-stable monomer (a4), After adjusting the amount of use such that these are suitable for the total structural unit of the resin (A) as described above, it can be produced by a known polymerization method (for example, radical polymerization method).

In one embodiment, the resin (A) preferably has a structural unit represented by the formula (II) (hereinafter sometimes referred to as “structural unit (II)”).

[In the formula (II), R ³ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Ring X1 represents a heterocyclic ring having 2 to 36 carbon atoms, and the hydrogen atom contained in the heterocyclic ring is a halogen atom, a hydroxy group, a hydrocarbon group having 1 to 24 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, It may be substituted with an acyl group having 2 to 4 carbon atoms or an acyloxy group having 2 to 4 carbon atoms. ]
In the formula (II), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the alkyl group which may have a halogen atom include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl. Group, perfluorohexyl group and the like.
The heterocyclic ring of the ring X1 is not limited as long as it contains —CO— and a nitrogen atom as atoms constituting the ring, and may be an aromatic heterocyclic ring or has no aromaticity It may be. Moreover, any of monocyclic and polycyclic may be sufficient.
Specific examples of the following groups include the following.

Examples of the hydrocarbon group include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and dimethylcyclohexane. Examples thereof include cycloalkyl groups such as a hexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, methylnorbornyl group, and the following groups.

Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.
In the formula (II), R ³ is preferably a hydrogen atom or a methyl group.
Ring X1 is preferably a 4- to 7-membered heterocyclic ring containing a nitrogen atom or a heterocyclic ring containing this 4- to 7-membered ring, and a 4- to 6-membered heterocyclic ring containing a nitrogen atom or such a 4 to 6-membered ring Heterocycles containing rings are more preferred. It is preferable that —CO— is arranged at a position bonded to a nitrogen atom, that is, the ring X1 is a lactam ring.
The structural unit (II) is preferably a structural unit derived from a compound represented by the following formula (IID).

[In the formula (IID), R ³¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. R ³² represents a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms. n9 represents an integer of 0 to 8, and when n9 is 2 or more, the plurality of R ³² are the same or different. n9 is preferably 0 or 1, and more preferably 0. ]

The structural unit (II) includes the following structural units.

In the above structural unit, a structural unit in which a methyl group corresponding to R ³ is replaced by a hydrogen atom can also be given as a specific example of the structural unit (II).

The weight average molecular weight of the resin (A) is preferably 2,500 or more, more preferably 3,000 or more, and further preferably 4,000 or more. The upper limit of the weight average molecular weight is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less. In addition, the weight average molecular weight here is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis.
Resin (A) may use only 1 type and may mix and use 2 or more types.

The content of resin (A) in the composition (total amount when two or more are used) is not particularly limited, but is 50% relative to the total solid content in the composition in that the effect of the present invention is more excellent. ~ 99 mass% is preferable, and 70-97 mass% is more preferable.
In addition, the total solid content intends the total mass of components constituting the film described later, and intends other components excluding the solvent.

<Compound represented by general formula (I) that generates acid upon irradiation with actinic ray or radiation>
The compound represented by the general formula (I) is a photoacid generator that generates an acid upon irradiation with actinic rays or radiation. By using this compound, a desired effect can be obtained.
Hereinafter, each group of general formula (I) is explained in full detail.

In the general formula (I), Z ⁺ represents a cation.
Examples of the cation include an onium cation, a sulfonium cation, an iodonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among these, a sulfonium cation and an iodonium cation are preferable, and an arylsulfonium cation is more preferable.

The cation (Z ⁺ ) is preferably a sulfonium cation or an iodonium cation, more preferably an organic cation represented by any one of the following formulas (b2-1) to (b2-4) [hereinafter, each of the formulas Depending on the number, they may be referred to as “cation (b2-1)”, “cation (b2-2)”, “cation (b2-3)” and “cation (b2-4)”. ].

[In the formulas (b2-1) to (b2-4),
R ^b4 , R ^b5 and R ^b6 are each independently an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. Represents. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon The hydrogen atom contained in the group may be substituted with a halogen atom, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The aromatic hydrocarbon group may be a halogen atom, a hydroxy group, or a carbon number of 1 to 18 May be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group with 3 to 18 carbon atoms, or an alkoxy group with 1 to 12 carbon atoms.

R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represents an integer of 0 to 5.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b9 to R ^b11 are each independently an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and when these are aliphatic hydrocarbon groups, the carbon number thereof is preferably 1 to 12, In the case of an alicyclic hydrocarbon group, the carbon number thereof is preferably 3 to 18, and more preferably 4 to 12.

R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or 1 carbon atom. It may be substituted with ˜12 alkylcarbonyloxy groups.

R ^b9 and R ^b10 may be bonded together with the sulfur atom to which they are bonded to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) alicyclic hydrocarbon ring. The methylene group contained in the alicyclic hydrocarbon ring may be replaced with an oxy group, a thioxy group or a carbonyl group.

^{^{^{R b13, R b14, R b15}}} , R b16, R b17 and R ^b18 (hereinafter, may be referred to as "R ^b13 ~ R ^b18".) Are each independently a hydroxy group, of 1 to 12 carbon atoms It represents an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms.

L ^b11 represents —S— or —O—.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different from each other. When p2 is 2 or more, the plurality of R ^b14 may be the same or different from each other, and s2 is 2 or more. Sometimes, the plurality of R ^b17 may be the same or different from each other, and when t2 is 2 or more, the plurality of R ^b18 may be the same or different from each other.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl. In particular, the alkyl group of R ^b9 to R ^b12 preferably has 1 to 12 carbon atoms.
Preferred alicyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 2-alkyladamantan-2-yl, 1- (adamantan-1-yl) -1 -Alkyl groups and isobornyl groups. In particular, the alicyclic hydrocarbon group of R ^b9 to R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
Preferred aromatic hydrocarbon groups include a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, a 4-methoxyphenyl group, a biphenylyl group, and a naphthyl group. Etc. are preferable.
An aromatic hydrocarbon group substituted with an alkyl group is typically an aralkyl group, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the ring formed together with the sulfur atom to which R ^b9 and R ^b10 are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium. Examples include rings.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among these, a cation (b2-1) is preferable, and an organic cation represented by the following formula (b2-1-1) [hereinafter referred to as “cation (b2-1-1)”. ], More preferably a triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0) or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = X2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups).

In formula (b2-1-1),
R ^b19 to R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic ring having 3 to 18 carbon atoms. Represents a hydrocarbon group.
v2, w2 and x2 each independently represents an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, the plurality of R ^b19 may be the same as or different from each other. When w2 is 2 or more, the plurality of R ^b20 may be the same or different from each other. R ^b21 may be the same as or different from each other.
Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is preferable that

Specific examples of the cation (b2-1-1) include the following.

Specific examples of the cation (b2-2) include the following.

Specific examples of the cation (b2-3) include the following.

Specific examples of the cation (b2-4) include the following.

Q ¹ and Q ² each independently represents fluorine or an alkyl group substituted with at least one or more fluorine atoms. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Perfluoroalkyl groups include, for example, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl. Group and perfluorohexyl group.
Q ¹ and Q ² are preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, Q ¹ and Q ² are preferably fluorine atoms.

L represents a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, and an alkylene group. (Preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent linking group in which a plurality of these are combined. .
Among them, L is preferably a divalent saturated hydrocarbon group having 1 to 30 carbon atoms, and when the divalent saturated hydrocarbon group has a methylene group, the methylene group is replaced with an oxy group or a carbonyl group. It may be.
Examples of the divalent saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and 2 of these groups. It may be a combination of more than one species. For example, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6- Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane- 1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl A linear alkanediyl group such as a group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group; an alkyl group (particularly, carbon Alkyl group of 1 to 4, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec- butyl group, te
rt-butyl group etc.) having a side chain, such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane Branched alkanediyl groups such as 1,4-diyl group, 2-methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, 1,3-cyclopentane-1,3-diyl group, cyclohexane A monocyclic divalent alicyclic hydrocarbon group which is a cycloalkanediyl group such as a cycloalkanediyl group such as a 1,4-diyl group silylene group, a cyclooctane-1,5-diyl group; norbornane- Polycyclic divalent alicyclic carbonization such as 1,4-diyl group, norbornane-2,5-diyl group, 1,5-adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. A hydrogen group etc. are mentioned.

Examples of the group in which the methylene group contained in the divalent saturated hydrocarbon group is replaced by an oxy group or a carbonyl group include, for example, groups represented by any of the following formulas (b1-1) to (b1-8) Is mentioned. L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), more preferably a group represented by formula (b1-1) or a formula (b1-2). It is the group shown. Incidentally, the formula (b1-1) ~ formula (b1-8) are described together left and right to the general Formula (I), the left bond * is C (Q ¹⁾ and (Q ²⁾ The right hand * is bonded to W. The same applies to specific examples of the following formulas (b1-1) to (b1-8).

[In the formulas (b1-1) to (b1-8),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 20.
L ^b5 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b6 and L ^b7 each independently represent a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b9 and L ^b10 each independently represent a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 12.
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b12 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b14 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.

Examples of the divalent group represented by the formula (b1-1) include the following.

Examples of the divalent group represented by the formula (b1-2) include the following.

Examples of the divalent group represented by the formula (b1-3) include the following.

Examples of the divalent group represented by the formula (b1-4) include * —CH ₂ —O—CH ₂ — *.

Examples of the divalent group represented by the formula (b1-5) include the following.

Examples of the divalent group represented by the formula (b1-6) include the following.

Examples of the divalent group represented by the formula (b1-7) include the following.

Examples of the divalent group represented by the formula (b1-8) include the following.

The divalent saturated hydrocarbon group for L ^b1 may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, and a glycidyloxy group. Etc.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group.

W represents a group having a cyclic structure (group having a divalent cyclic structure). Examples of the group having a cyclic structure include a cyclic aliphatic group, an arylene group, and a group having a heterocyclic structure.

The cyclic aliphatic group (alicyclic hydrocarbon group) as W may have a monocyclic structure or a polycyclic structure. The cycloaliphatic group having a monocyclic structure is preferably a monocyclic cycloalkylene group such as a cyclopentylene group, a cyclohexylene group and a cyclooctylene group. Examples of the cyclic aliphatic group having a polycyclic structure (polycyclic aliphatic group) include polycyclic ring groups such as norbornylene group, tricyclodecanylene group, tetracyclodecanylene group, tetracyclododecanylene group and adamantylene group. A cycloalkylene group is preferred. In particular, it is preferable to employ an adamantylene group as W.

The methylene group contained in the cyclic aliphatic group is an oxy group or a sulfonyl group (—SO ₂ —).
Or it may be replaced by a carbonyl group. Examples of the group in which the methylene group contained in the cycloaliphatic group is replaced with an oxy group, a sulfonyl group or a carbonyl group include, for example, a cyclic ether group (one or two of the methylene groups contained in the alicyclic hydrocarbon group are oxy groups) ), Cyclic ketone groups (groups in which one or two of the methylene groups contained in the alicyclic hydrocarbon group are replaced by carbonyl groups), sultone ring groups (methylene groups contained in the alicyclic hydrocarbon groups) Two adjacent methylene groups are groups in which the oxy group and the sulfonyl group are substituted, respectively, and lactone ring groups (two methylene groups adjacent to each other among the methylene groups contained in the alicyclic hydrocarbon group are respectively A group in which an oxy group and a carbonyl group are substituted).

As the cyclic aliphatic group, for example, two hydrogen atoms of the cycloalkane represented by the following formulas (KA-1) to (KA-7) were removed as a monocyclic aliphatic hydrocarbon group. Groups. Examples of the polycyclic aliphatic hydrocarbon group include groups in which two hydrogen atoms of cycloalkane represented by the following formulas (KA-8) to (KA-22) are removed. Specific examples of the group in which the methylene group constituting the alicyclic hydrocarbon group is replaced by an oxygen atom, a sulfonyl group or a carbonyl group include any of the following formulas (Y1) to (Y15): The group represented by these is mentioned. In the groups represented by these formulas (Y1) to (Y15), * represents a bond bonded to L ^b1 . Note that the bond that is bonded to R is omitted in the following figures.

The arylene group as W is, for example, a phenylene group, a naphthylene group, a phenanthrylene group, or an anthrylene group.
The group having a heterocyclic structure as W may have aromaticity or may not have aromaticity. The heteroatom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include lactone ring, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, piperidine ring and morpholine ring. Among these, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.

R represents an organic group. In the present specification, the “organic group” means a functional group having at least one or more carbon atoms (for example, a linear aliphatic group, a cyclic aliphatic group, an aromatic group, or a group obtained by combining them) ) And may contain a heteroatom (such as an oxygen atom).

One preferred embodiment of R is a group having a cyclic structure. Examples of the group having a cyclic structure include a cyclic aliphatic group, an aryl group, and a group having a heterocyclic structure.
The cycloaliphatic group may have a monocyclic structure or a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable. The cycloaliphatic group having a polycyclic structure is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
The aryl group is, for example, a phenyl group, a naphthyl group, a phenanthryl group, or an anthryl group.
The group having a heterocyclic structure may have aromaticity or may not have aromaticity. The heteroatom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include lactone ring, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, piperidine ring and morpholine ring. Among these, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.
The group having a cyclic structure represented by R may have a substituent. Examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxy group, Examples include an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.

One preferred embodiment of R includes a hydroxy group protected by a protecting group (hereinafter also referred to as “protected hydroxy group” in some cases).
This protecting group refers to a group that can be deprotected by the action of an acid. As such a protecting group, as long as deprotection is caused by the action of an acid, a protecting group well known in the organic synthesis field can be adopted as a protecting group for a hydroxy group.
Here, when the suitable example of a protected hydroxy group is shown, group represented by the following formula | equation (1A) and group represented by a formula (2A) are mentioned. Among these, the group represented by the formula (2A) is more preferable.

[In the formula (1A),
R ^a61 to R ^a63 each independently represents an alkyl group having 1 to 6 carbon atoms. * Represents a bond. ]

[In the formula (2A),
R ^{a61 ′} and R ^{a62 ′} each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ^{a63 ′} represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ^{a62 ′} and R ^{a63 ′} are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be replaced with an oxygen atom or a sulfur atom, and the methylene group constituting the divalent hydrocarbon group may be replaced with an oxygen atom or a sulfur atom. ]

The alkyl groups of R ^a61 to R ^{a63 in} the formula (1A) include those already exemplified in the range of 1 to 6 carbon atoms, and it is preferable that all of R ^a61 to R ^a63 are methyl groups.

R ^{a61 ′} to R ^{a63 ′ in the} formula (2A) are a hydrogen atom or a hydrocarbon group, and this hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is An alkyl group or an alicyclic hydrocarbon group may be used. R ^{a62 ′} and R ^{a63 ′} may be bonded to each other to form a divalent hydrocarbon group, and the divalent hydrocarbon group may contain a hetero atom. At least one of R ^{a61 ′} and R ^{a62 ′} is preferably a hydrogen atom.

Another preferred embodiment of R is a group represented by -L ₁₀ -R ₁₀ .
L ₁₀ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group is an oxygen atom, a carbonyl group, or —NR ₁₁ — ( R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Examples of the group in which the methylene group constituting the aliphatic saturated hydrocarbon group of L ₁₀ is replaced by an oxygen atom or a carbonyl group include * —CO—O—, * —CO—O— (CH ₂ ) v— ( v represents an integer of 0 to 4), * —CO—O—CH ₂ —, * —O—CO—, * —O—CH ₂ —CO—O—, * —O—CO—O—, * —O—CO—O—CH ₂ —, * —O—CO—CH ₂ —O—, * —O—CH ₂ —CO—O—CH ₂ —, * —O—CO—CH ₂ —O—CH ₂ — and * —O—CH ₂ —CH ₂ —O— and the like are mentioned. Among them, L ₁₀ represents * —CO—O— (CH ₂ ) v— (v represents an integer of 0 to 4). .) Is preferred. In the specific examples of L ₁₀ shown here, * represents a bond with a carbon atom of the ring W, that is, a bond with a carbon atom constituting the ring of the ring W.

R ₁₀ is a monovalent organic group containing an anthracene ring, a fluorene ring or a phenanthrene ring, and the organic group may have a substituent. More specific examples of R ₁₀ include those represented by the following formulas (R ¹ -1) to (R ¹ -22). Note that * in each of the specific examples of R ¹ is a bond to L ₁₀ .

As one alternative preferred embodiment of the R, include groups represented by _{-O-CO-O-L 11} -Y 11.
L ₁₁ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms (alkylene group), and the methylene group constituting the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
Examples of the alkanediyl group in L ₁₁ include linear alkanediyl and branched alkanediyl.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl group such as, 6-diyl group;
A straight chain alkanediyl group having a side chain of an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), for example, butane-1,3-diyl group, 2-methylpropane-1,3- Examples thereof include branched alkanediyl groups such as diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.
Among these, L ₁₁ is preferably a single bond or a methylene group.

Y ₁₁ represents an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the methylene group constituting the alicyclic hydrocarbon group includes an oxygen atom, a sulfonyl group, or It may be replaced with a carbonyl group.
The alicyclic hydrocarbon group for Y ₁₁ may be monocyclic or polycyclic. Further, it is not limited to an alicyclic hydrocarbon group having a carbon atom only as a ring atom, and may be a group in which an alkyl group having 1 to 12 carbon atoms is bonded to a carbon atom of the ring atom.
Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group and methylnorbornyl group, and groups shown below.

This alicyclic hydrocarbon group optionally has a substituent. The “substituent alicyclic hydrocarbon group” means a group in which a hydrogen atom in the alicyclic hydrocarbon group is substituted with a substituent.
Examples of the substituent include a halogen atom (excluding a fluorine atom), a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 21 carbon atoms. , An acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or — (CH ₂ ) _j2 —OC
Group (wherein represented by O-R _{_i1,} R _i1 is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, alicyclic hydrocarbon group or aromatic having 6 to 18 carbon atoms having 3 to 16 carbon atoms Represents a hydrocarbon group, j2 represents an integer of 0 to 4, and the like. The aromatic hydrocarbon group and aralkyl group which are substituents of the alicyclic hydrocarbon group may have, for example, an alkyl group having 1 to 8 carbon atoms, a halogen atom or a hydroxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, Examples thereof include aryl groups such as biphenyl group, phenanthryl group, 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl.
Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl group, naphthylethyl group and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the aliphatic hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

The methylene group constituting the alicyclic hydrocarbon group is an oxygen atom, a sulfonyl group (—SO ₂ —)
Examples of the group replaced with a carbonyl group include a cyclic ether structure (a group in which one or two methylene groups constituting an alicyclic hydrocarbon group are replaced with oxygen atoms), a cyclic ketone group (an alicyclic group). A group in which one or two of the methylene groups constituting the hydrocarbon group are replaced by a carbonyl group), a sultone ring group (two methylene groups adjacent to each other among the methylene groups constituting the alicyclic hydrocarbon group) , A group substituted with an oxygen atom and a sulfonyl group, respectively, and a lactone ring group (the two adjacent methylene groups among the methylene groups constituting the alicyclic hydrocarbon group are replaced with an oxygen atom and a carbonyl group, respectively. Group) and the like.
As the alicyclic hydrocarbon group for Y ₁₁ , for example, the following formulas (Y1) to (Y29) are preferable. * Represents a bond to L _11.

Examples of the alicyclic hydrocarbon group having a substituent of Y ₁₁ include the following.

Y ₁₁ is preferably an adamantyl group which may have a substituent, and more preferably an adamantyl group, an oxoadamantyl group or a hydroxyadamantyl group.

The content of the compound represented by the general formula (I) in the composition is not particularly limited, but 3 to 30% by mass with respect to the total solid content in the composition in that the effect of the present invention is more excellent. 3 to 15% by mass is more preferable.
In addition, the total solid content intends the total mass of components constituting the film described later, and intends other components excluding the solvent.
In addition, the compound represented by general formula (I) may be used individually by 1 type, and may use 2 or more types together.

<Other ingredients>
The composition of the present invention may contain components other than the compound represented by the resin (A) and the general formula (I).
Below, an arbitrary component is explained in full detail.

<Compound capable of generating acid upon irradiation with actinic ray or radiation (B2)>
The composition in the present invention comprises a compound (B2) that generates an acid upon irradiation with actinic rays or radiation other than the compound represented by the above general formula (I) (hereinafter referred to as “acid generator” or “compound (B2)”. May also be included.
The compound (B2) is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.
The compound (B2) may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the compound (B2) is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the compound (B2) is in a form incorporated into a part of the polymer, it may be incorporated into a part of the acid-decomposable resin described above, or may be incorporated into a resin different from the acid-decomposable resin. .
In the present invention, the compound (B2) is preferably in the form of a low molecular compound.

As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Further, two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and an oxygen atom in the ring,
It may contain a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion.
Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the actinic ray-sensitive or radiation-sensitive resin composition is improved.
Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.
The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. An alkyl group,
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.
Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), fluorinated antimony and the like (eg, SbF ₆ ⁻ ). .

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which at least α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, Pentafluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.
Among the acid generators, particularly preferable examples include compounds exemplified in paragraph [0143] of US2012 / 0207978A1.

The acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
When two or more acid generators are used in combination, the total content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 0.8%, based on the total solid content of the composition. It is 5 to 25% by mass, more preferably 3 to 20% by mass, particularly preferably 3 to 15% by mass.

<(HR) hydrophobic resin>
The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (HR)”), particularly when applied to immersion exposure. The hydrophobic resin (HR) is a resin having a relatively small surface free energy as compared with the resin (A). As a result, the hydrophobic resin (HR) is unevenly distributed on the surface of the resist film, and the immersion medium is In the case of water, the static / dynamic contact angle of the film surface with respect to water can be improved, and the immersion liquid followability can be improved.
Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

The hydrophobic resin (HR) preferably contains a fluorine atom and / or a silicon atom. The fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be contained in the side chain. The hydrophobic resin (HR) has a hydrophobic group such as a branched alkyl group or a long-chain alkyl group (preferably having 4 or more carbon atoms, more preferably 6 or more carbon atoms, and particularly preferably 8 or more carbon atoms). It is also preferable.

The content of the hydrophobic resin (HR) in the composition can be appropriately adjusted and used so that the receding contact angle of the film formed from the composition falls within the preferred range described later, but based on the total solid content of the composition Is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, and particularly preferably 0.2 to 8% by mass. is there.

The hydrophobic resin (HR) may have a structural unit derived from a compound represented by the formula (a) (hereinafter referred to as “compound (a)”).

[In the formula (a),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent.
A ¹ represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1).

(In the formula (a-g1),
s represents 0 or 1.
A ¹⁰ and A ¹² each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ¹¹ represents an optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms or a single bond. X ¹⁰ and X ¹¹ are each independently an oxygen atom (in this specification, the oxygen atom may be represented by “—O—”), a carbonyl group (herein, the carbonyl group is represented by “—CO—”). ), A carbonyloxy group (in the present specification, the carbonyloxy group may be represented by “—CO—O—”) or an oxycarbonyl group (in the present specification, the oxycarbonyl group is represented by It may be represented by “—O—CO—”. However, the total number of carbon atoms of A ¹⁰ , A ¹¹ , A ¹² , X ¹⁰ and X ¹¹ is 6 or less. ]]

A ¹ is an alkanediyl group having 1 to 6 carbon atoms or a group represented by the above formula (a-g1) (hereinafter referred to as “group (a-g1)”).
The alkanediyl group of A ¹ may be linear or branched, for example, methylene group, ethylene group, propanediyl group, propanediyl group, butanediyl group, pentanediyl group, pentanediyl group and hexanediyl. Groups and the like.
The hydrogen atom constituting the alkanediyl group may be replaced with a substituent. Examples of the substituent include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

Specific examples of the group (a-g1) are shown below. In the following specific examples, the left and right sides are described in accordance with the formula (a), and of the two bonds indicated by *, the left bond is bonded to the oxygen atom on the R ¹ side and the right These bonds are bonded to the oxygen atom on the R ² side.
As the group having an oxygen atom (a-g1),

(* Represents a bond).

As the group (ag1) having a carbonyl group,

(* Represents a bond).

As the group (ag1) having a carbonyloxy group,

(* Represents a bond).

As the group having an oxycarbonyl group (a-g1),

(* Represents a bond).

Among them, A ¹ is preferably an alkanediyl group, more preferably an alkanediyl group having no substituent, further preferably an alkanediyl group having 1 to 4 carbon atoms, and particularly preferably an ethylene group.

The aliphatic hydrocarbon group for R ² may have a carbon-carbon unsaturated bond, but is preferably an aliphatic saturated hydrocarbon group.
As the aliphatic saturated hydrocarbon group, an alkyl group (the alkyl group may be linear or branched) and an alicyclic hydrocarbon group, and an aliphatic combination of an alkyl group and an alicyclic hydrocarbon group A hydrocarbon group etc. are mentioned.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the groups shown below.

Aliphatic hydrocarbon group R ² may not have even have a substituent, R ² is preferably an aliphatic hydrocarbon group having a substituent.
The substituent for R ² is preferably a halogen atom or a group represented by the formula (ag3) (hereinafter referred to as “group (ag3)”).

(In the formula (a-g3),
X ¹² represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom. )

The aliphatic hydrocarbon group having a halogen atom is typically an alkyl group having a halogen atom and an alicyclic hydrocarbon group having a halogen atom (preferably a cycloalkyl group having a halogen atom).
An alkyl group having a halogen atom is one in which a hydrogen atom constituting the alkyl group is substituted with a halogen atom. Similarly, an alicyclic hydrocarbon group having a halogen atom is a group in which a hydrogen atom constituting the alicyclic hydrocarbon group is substituted with a halogen atom.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, Preferably it is a fluorine atom.

The aliphatic hydrocarbon group having a halogen atom for R ² is a perfluoroalkyl group in which all of the hydrogen atoms constituting the alkyl group are substituted with fluorine atoms, or all of the hydrogen atoms constituting the cycloalkyl group are substituted with fluorine atoms. Perfluorocycloalkyl groups are preferred. Among these, a perfluoroalkyl group is preferable, a perfluoroalkyl group having 1 to 6 carbon atoms is more preferable, and a perfluoroalkyl group having 1 to 3 carbon atoms is still more preferable.
Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group.
X ¹² is preferably a carbonyloxy group or an oxycarbonyl group.

Examples of the compound (a) in which R ² is an aliphatic hydrocarbon group having a fluorine atom and A ¹ is an ethylene group include compounds represented by the following formulas (a1) to (a16).

As the compound (a) in which R ² is a perfluoroalkyl group or a perfluorocycloalkyl group, among the above specific examples, the formula (a3), the formula (a4), the formula (a7), the formula (a8), the formula The compound represented by any of (a11), formula (a12), formula (a15), and formula (a16) is applicable.

The aliphatic hydrocarbon group having a group represented by the formula (a-g3) may have one or a plurality of groups (ag3), but is included in the group (ag3). The total number of carbon atoms of the aliphatic hydrocarbon group including the number of carbon atoms is preferably 15 or less, and more preferably 12 or less. In order to satisfy such a preferable total carbon number, a group having one group (ag3) is preferable as R ² .

An aliphatic hydrocarbon group having the group (ag3), that is, R ² having the group (ag3) is
A group represented by the following formula (a-g2) (hereinafter referred to as “group (a-g2)”) is preferable.

(In the formula (a-g2),
A ¹³ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom.
X ¹² represents a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom. However, the total number of carbon atoms of A ¹³ , A ¹⁴ and X ¹² is 18 or less. )

Among the groups (ag2) (* is a bond to a carbonyl group), the following structures are preferable.

R ² is a compound which is an aliphatic hydrocarbon group having one group represented by the formula (a-g3) (a) , i.e., compounds wherein R ² is a group represented by the formula (a-g2) Specifically, (a) is represented by the following formula (a ′) (hereinafter referred to as “compound (a ′)”).

[In the formula (a ′),
A ¹³ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom.
X ¹² represents a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom. However, the total number of carbon atoms of A ¹³ and A ¹⁴ is 17 or less.
A ¹ and R ¹ are as defined above. ]
The compound (a ′) is a useful compound as a raw material for producing the hydrophobic resin (HR) contained in the composition.

In the compound (a ′), both A ¹³ and A ¹⁴ may have a halogen atom, but only A ¹³ is an aliphatic hydrocarbon group having a halogen atom, or only A ¹⁴ has a halogen atom. The aliphatic hydrocarbon group is preferable. Further, only A ¹³ is preferably an aliphatic hydrocarbon group having a halogen atom, and among them, A ¹³ is more preferably an alkanediyl group having a fluorine atom, and more preferably a perfluoroalkanediyl group. The “perfluoroalkanediyl group” refers to an alkanediyl group in which all of the hydrogen atoms are substituted with fluorine atoms.

Examples of the compound (a ′) in which R ² is a perfluoroalkanediyl group and A ¹ is an ethylene group include compounds represented by the following formulas (a′1) to (a′10).

A ¹³ and A ¹⁴ are arbitrarily selected within a range where the total number of carbon atoms is 17 or less, and the carbon number of A ¹³ is preferably 1 to 6, and more preferably 1 to 3. The number of carbon atoms of A ¹⁴ is preferably 4-15, and more preferably 5-12. Further preferred A ¹⁴ is an alicyclic hydrocarbon group having 6 to 12 carbon atoms, and the alicyclic hydrocarbon group is preferably a cyclohexyl group or an adamantyl group.

<Acid diffusion control agent>
The composition of the present invention preferably contains an acid diffusion controller. The acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like. Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid, a basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, and an acid. An onium salt that is a weak acid relative to the generator can be used.

Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

Regarding the 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.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
Specific examples of preferred compounds include those exemplified in paragraph [0379] of US2012 / 0219913A1.

Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably 6 to 12 carbon atoms may be bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. In addition to the alkyl group, the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
The following compounds are also preferable as the basic compound.

As basic compounds, in addition to the above-mentioned compounds, paragraphs [0180] to [0225] of JP2011-22560A, paragraphs [0218] to [0219] of JP2012-137735A, international publication pamphlet The compounds described in paragraphs [0416] to [0438] of WO2011 / 158687A1 can also be used.
These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The composition of the present invention may or may not contain a basic compound. When it is contained, the content of the basic compound is usually 0.001 to 10 mass based on the solid content of the composition. %, Preferably 0.01 to 5% by mass.
The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

A low molecular weight compound having a nitrogen atom and a group capable of leaving by the action of an acid has an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, a hemi group as a group leaving by the action of an acid. Aminal ether groups are preferred, with carbamate groups and hemiaminal ether groups being particularly preferred.
The molecular weight of the compound (C) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (C), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

Compound (C) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( Preferably, it represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.
Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

Specific examples of the group represented by the general formula (d-1) include US2012 / 013534.
The structure disclosed in paragraph [0466] of 8A1 can be exemplified, but is not limited thereto.

It is particularly preferable that the compound (C) has a structure represented by the following general formula (6).

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and preferred examples thereof are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include Rb The same group as the specific example mentioned above about is mentioned.

Specific examples of the particularly preferable compound (C) include, but are not limited to, compounds disclosed in paragraph [0475] of US2012 / 0135348A1.
The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the low molecular compound (C) having a group capable of leaving by the action of an acid on the nitrogen atom can be used singly or in combination of two or more.
The content of the compound (C) in the composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, further based on the total solid content of the composition. Preferably, the content is 0.01 to 5% by mass.

A basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation has a proton acceptor functional group, and decomposes upon irradiation with actinic rays or radiation, resulting in a decrease or disappearance of proton acceptor properties. Or a compound that changes from proton acceptor properties to acidic properties. Hereinafter, it is also referred to as compound (PA).

The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. 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 represented by the following general formula.

Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Means that when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
Proton acceptor property can be confirmed by measuring pH.

In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. More preferably, −13 <pKa <−3.

In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.
Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or the proton acceptor property is reduced. It is a compound that has changed to acidic.

In general formula (PA-1),
Q represents —SO ₃ H, —CO ₂ H, or —W ₁ NHW ₂ R _f . Here, R _f represents an alkyl group, a cycloalkyl group or an aryl group, and W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or may be bonded to R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

The general formula (PA-1) will be described in more detail.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferred is an alkylene group having at least one fluorine atom, and the preferred carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

The monovalent organic group for R _x preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.
The alkyl group for R _x may have a substituent, and preferably has 1 to
20 linear and branched alkyl groups, which may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.
Preferred _examples of the divalent organic group for R _y include an alkylene group.
Examples of the ring structure that R _x and R _y may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

The proton acceptor functional group in R is as described above, and examples thereof include azacrown ether, primary to tertiary amines, and groups having a heterocyclic aromatic structure containing nitrogen such as pyridine and imidazole.
The organic group having such a structure preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group containing a proton acceptor functional group or an ammonium group in R is _exemplified as R _x. Alkyl groups,
The same as the cycloalkyl group, aryl group, aralkyl group and alkenyl group.

When B is —N (R _x ) R _y —, R and R _x are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.

Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures.

As R _f in -X ₁ NHX ₂ R _f represented by Q, preferred is an alkyl group which may have a fluorine atom of 1 to 6 carbon atoms, more preferably perfluoroalkyl of 1 to 6 carbon atoms It is a group. As X ₁ and X ₂ , at least one is preferably —SO ₂ —, and more preferably, both X ₁ and X ₂ are —SO ₂ —.
Q is particularly preferably —SO ₃ H or —CO ₂ H from the viewpoint of the hydrophilicity of the acid group.
Of the compounds represented by the general formula (PA-1), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, but is preferably contained in the anion portion.
Preferred examples of the compound (PA) include compounds represented by the following general formulas (4) to (6).

In the general formulas (4) to (6), A, X, n, B, R, Rf, X ₁ and X ₂ have the same meanings as in the general formula (PA-1).
C ⁺ represents a counter cation.
The counter cation is preferably an onium cation. Among them, the sulfonium cation described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in the general formula (ZI) described above, as I ⁺ (R ₂₀₄ ) (R ₂₀₅ ) in the general formula (ZII) The iodonium cation described is a preferred example.
Hereinafter, specific examples of the compound (PA) include compounds exemplified in paragraph [0280] of US2011 / 0269072A1.

In the present invention, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.
Specific examples of X ⁻ include the same as the anion moiety of the acid generator.
Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N has the previously described formula (PA-1)
It is the same as the proton acceptor functional group described in 1.
Specific examples of the ionic compound having a proton acceptor moiety in the cation moiety include the compounds exemplified in paragraph [0291] of US2011 / 0269072A1.
Such a compound can be synthesized with reference to methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

Compound (PA) may be used alone or in combination of two or more. The content of the compound (PA) is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content of the composition.

In the composition of the present invention, an onium salt that becomes a weak acid relative to the acid generator can be used as an acid diffusion control agent.
When an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, the acid generated from the acid generator by irradiation with actinic rays or radiation When it collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ is an optionally substituted hydrocarbon group, and Z ^2c is an ^optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon adjacent to S R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation represented by S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) described above, I ⁺ (R ₂₀₄ ) (R ₂₀₅ ). The iodonium cation represented by these is mentioned.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include
The structure exemplified in paragraph [0198] of JP-A-2-242799 can be exemplified.
Preferred examples of the anion moiety of the compound represented by the general formula (d1-2) include
The structure exemplified in paragraph [0201] of JP-A-2-242799 can be exemplified.
Preferable examples of the anion part of the compound represented by the general formula (d1-3) include
The structures exemplified in paragraphs [0209] to [0210] of JP-A-2-242799 can be given.

An onium salt that is a weak acid relative to an acid generator is a compound that has a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond. Good.
The compound is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
-X ^- it is, -COO ^{^-,} -SO ₃ ^- represents an anion portion selected from -R ₄ ^-, -SO ₂ -, and ^-N. R ₄ is a group having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.
Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.
L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.
The content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.

<Solvent (hereinafter referred to as “solvent (D)”)>
The composition may contain a solvent (D). The solvent (D) is used on the substrate in the production of a resist pattern, which will be described later, according to the type and amount of the resin (A) and the type and amount of the compound represented by the general formula (I). From the viewpoint that the applicability when applying the composition is improved, an optimum one can be selected.

As the solvent (D), glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate (PGMEA); glycol ethers such as propylene glycol monomethyl ether (PGME); ethyl lactate, butyl acetate, acetic acid Examples thereof include esters such as amyl and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone, and carbonates such as propylene carbonate. Only 1 type may be used for a solvent (D) and it may use 2 or more types together. Preferred solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone and γ-butyrolactone. A solvent containing at least one of 2-heptanone and γ-butyrolactone is more preferable, and a mixed solvent of two or more containing 2-heptanone and γ-butyrolactone is particularly preferable.
Specifically, two kinds of mixed solvents selected from PGMEA / ethyl lactate, PGMEA / PGME, PGMEA / cyclohexanone, PGMEA / ethyl lactate / γ-butyrolactone, PGMEA / cyclohexanone / γ-butyrolactone, PGMEA / 2-heptanone / propylene Carbonate, PGME / cyclohexanone / propylene carbonate, PGMEA / PG
A mixed solvent of three kinds selected from ME / γ-butyrolactone, a mixed solvent of four kinds of PGMEA / PGME / cyclohexanone / γ-butyrolactone, and the like are preferable.

<Other ingredients>
The composition may contain components other than the above-described components (for example, the resin (A), the acid generator (B), the solvent (D), the basic compound (E), etc.) as necessary. . This component is referred to as “component (F)”. Such component (F) is not particularly limited, and examples thereof include additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes.

<Pattern formation method>
Next, the pattern forming method according to the present invention will be described.
The pattern forming method (negative pattern forming method) of the present invention includes at least the following steps.
(A) a step of forming a film (resist film) containing the composition of the present invention (film forming step),
(A) a step of irradiating the film with actinic rays or radiation (exposure step); and (c) a step of developing the film irradiated with actinic rays or radiation using a developer containing an organic solvent (organic solvent development step). )

The exposure (irradiation with actinic rays or radiation) in the step (a) may be immersion exposure.
The pattern formation method of the present invention preferably includes (i) a heating step after (b) the exposure step.
The pattern forming method of the present invention may further include (e) a step of developing using an alkali developer. By including the step (e), it is expected that a resist pattern finer than the optical pattern can be formed by a single exposure as described in JP-A-2008-292975.
The pattern forming method of the present invention may include (a) an exposure step a plurality of times.
The pattern forming method of the present invention may include (d) a heating step a plurality of times.

The resist film of the present invention is formed from the above-described composition of the present invention, and more specifically, is preferably a film formed by applying the composition to a substrate. In the pattern forming method of the present invention, the step of forming a film of the composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
Also, a post-exposure heating step (PEB; Post Exp) after the exposure step and before the development step.
(osake Bake) is also preferable.

The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

Although there is no restriction | limiting in the light source wavelength used for the exposure apparatus in this invention, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less. More preferably 220 nm or less, particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.

In the exposure process of the present invention, an immersion exposure method can be applied.
The immersion exposure method is a technology for filling and exposing a projection lens and a sample with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) as a technique for increasing the resolving power.
This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to the air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The resolution and the focus margin (DOF) can be expressed by the following equations. Here, k ₁ and k ₂ are coefficients related to the process.

(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(DOF) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage is obtained that the refractive index change as a whole liquid can be made extremely small.

On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of the water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

The receding contact angle of the resist film formed using the composition in the present invention is preferably 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, and is suitable for exposure through an immersion medium. More preferably 75 ° or more, and further preferably 75 to 85 °.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited.

When the resin (A) does not substantially contain a fluorine atom and a silicon atom, the receding contact angle on the resist film surface can be improved by adding the hydrophobic resin (HR) to the composition in the present invention.
From the viewpoint of improving the receding contact angle, the ClogP value of the hydrophobic resin (HR) is preferably 1.5 or more. Further, from the viewpoint of improving the receding contact angle, the mass content of the side chain portion in the hydrophobic resin (HR) in the CH ₃ partial structure in the hydrophobic resin (HR) is 12.0% or more. It is preferable.

In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed and form an exposure pattern. The contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

When the pattern forming method of the present invention further includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia. Inorganic alkalis such as water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, Alkaline aqueous solutions such as alcohol amines such as ethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.

Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

As the developer (hereinafter also referred to as an organic developer) in the step of developing using a developer containing an organic solvent, which is included in the pattern forming method of the present invention, a ketone solvent, an ester solvent, an alcohol solvent Polar solvents such as solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.

Examples of the alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbuta Glycol ether solvents such as Lumpur can be mentioned.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.
However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formic acid Ester solvents such as chill, propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, alcohol solvents such as n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy Glycol ether solvents such as butyl butanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and aromatic carbonization such as toluene and xylene Examples thereof include aliphatic hydrocarbon solvents such as hydrogen solvents, octane, and decane.

Specific examples having a vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ester solvents such as ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol Alcohol solvents such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, and glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol And glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, N-methyl-2 -Amido solvents of pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

The developer containing an organic solvent may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those described above for the basic compound that can be contained in the composition.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / m
m ² or less, more preferably 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.

By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer will decrease, and the resist film / resist pattern may be inadvertently scraped or broken. This is considered to be suppressed.

The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.
Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

The pattern formation method of the present invention can further include a step (e) (alkali development step) of performing development using an alkaline aqueous solution to form a resist pattern. Thereby, a finer pattern can be formed.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step (c), but a portion with high exposure strength is also removed by performing an alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]). The same mechanism).
The alkali development can be performed either before or after the development step (c) using a developer containing an organic solvent, but is more preferably performed before the organic solvent development step (c).

Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.
It is preferable to include the process of wash | cleaning using a rinse liquid after the process developed using the developing solution containing an organic solvent.

The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.

Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.
A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

Examples are shown below, but the present invention is not limited thereto.

<Preparation of composition (resist composition)>
A solution obtained by dissolving the components shown in Table 1 below in a solvent shown in the same table was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition.

Various components used in Table 1 are summarized below.
For each of the resins A1 to A9 described below, the composition ratio of the repeating units is a molar ratio.
Note that B-14 and B-15 described later do not contain an organic group represented by R in the general formula (I).

N-4: 2,6-diisopropylaniline

W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based) W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: KH-20 (Asahi Kasei Corporation)
W-6: PolyFox ^™ PF-6320 (manufactured by OMNOVA solution inc.) (Fluorine-based)

〔solvent〕
SL-1: Propylene glycol monomethyl ether acetate SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether SL-6: Cyclohexanone SL-7: γ-butyrolactone SL-8: propylene carbonate

<Line and space pattern evaluation>
(Line and space pattern forming method)
ARC29A (Nissan Chemical Co., Ltd.) for forming an organic antireflection film was applied onto a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. The resist composition was applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Using the ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML), the obtained silicon wafer was 1 with a line width of 45 nm. 1: exposed through a 6% halftone mask with a line and space pattern. Ultra pure water was used as the immersion liquid. After heating (PEB) at 105 ° C. for 60 seconds, developing with a developer (butyl acetate) for 30 seconds, paddle with pure water and rinsing, and rotating a silicon wafer at 4000 rpm for 30 seconds By performing post-baking at 90 ° C. for 60 seconds, a line and space (1: 1) resist pattern having a pitch of 90 nm and a line width of 45 nm was obtained.

(Evaluation of mask error enhancement factor (MEEF))
With respect to the masks used in each of the examples and comparative examples, the mask line width (the sum of the line width and the space width) was changed, the mask line width was changed, and the optimum exposure amount in each example and comparative example (above The absolute value of the slope of the change in line width of the obtained pattern when the pattern was formed according to the method of each example and comparative example was defined as MEEF. That is, MEEF defined by the following formula was calculated. The closer this value is to 1, the better the performance as a resist.
Pattern line width (nm) = a × mask line width variation (nm) + b
(Absolute value of a = MEEF, b = constant)

(Evaluation of line width roughness (LWR))
The line pattern of the size described above in each example and comparative example was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and the range of 2 μm in the longitudinal direction of the line pattern was equally spaced. LWR was evaluated by measuring 50 dotted line widths and calculating 3σ from the standard deviation. A smaller value indicates better performance.

(Evaluation of pattern cross section)
The cross-sectional shape of the pattern obtained by the above method was observed with a scanning electron microscope, and the line width Lb at the bottom of the resist pattern and the line width La at the top of the resist pattern were measured. The case where 0.9 ≦ (La / Lb) ≦ 1.1 is defined as “rectangular”, and the case where (La / Lb)> 1.1 is defined as “T-top shape”, and the cross-sectional shape of the obtained pattern Were observed with a scanning electron microscope, and A was obtained when the rectangular pattern was obtained, and B was obtained when the T top shape was obtained. The cross-sectional shape is preferably a rectangular pattern.

<Contact hole pattern evaluation>
(Contact hole pattern formation method)
ARC29A (Nissan Chemical Co., Ltd.) for forming an organic antireflection film was applied onto a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. The said resist composition was apply | coated on it, and it baked (PB) for 60 second at 100 degreeC, and formed the resist film with a film thickness of 100 nm. The obtained silicon wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) with a hole portion of 45 nm. Pattern exposure was performed through a square array of halftone masks having a pitch between holes of 90 nm. Ultra pure water was used as the immersion liquid. After heating (PEB) at 105 ° C. for 60 seconds, developing with a developer (butyl acetate) for 30 seconds, paddle with pure water, rinsing, and rotating a silicon wafer for 30 seconds at a rotational speed of 4000 rpm A contact hole pattern with a hole diameter of 45 nm was obtained by post-baking at 90 ° C. for 60 seconds.

(Evaluation of mask error enhancement factor (MEEF))
With respect to the masks used in each of the examples and comparative examples, the mask pitch (the sum of the hole size and the space width) was fixed, the mask hole size was changed, and the optimum exposure amount in the sensitivity evaluation (the contact hole pattern) The change in the diameter of the hole pattern obtained at the time of pattern formation was observed. And the absolute value of the inclination was set to MEEF. That is, MEEF defined by the following equation was calculated. The closer this value is to 1, the better the performance as a resist.
Pattern hole size (nm) = a × mask hole size variation (nm) + b
(Absolute value of a = MEEF, b = constant)

(Evaluation of critical dimension uniformity (CDU))
The hole pattern of the size described above in each example and comparative example was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and the diameters of 90 hole patterns were measured. CDU was evaluated by calculating 3σ from the standard deviation. A smaller value indicates better performance.

(Pattern cross-sectional shape)
The cross-sectional shape of the resist pattern is observed using a scanning electron microscope, the hole diameter Lb at the bottom of the resist pattern and the hole diameter La at the top of the resist pattern are measured, and 0.9 ≦ (La / Lb) ≦ 1 .1 was evaluated as “A (good)”, and when it was out of this range, it was evaluated as “B (defective)”.

The above evaluation results are summarized in Table 2 below.

As shown in the above table, in the pattern forming method of the present invention, it was confirmed that the pattern shape to be formed was excellent.
For example, as can be seen from the comparison between Example 5 and Example 17, when the compound represented by any one of the general formulas (C-1) to (C-3) was used as the basic compound, it was more excellent. It was confirmed that an effect was obtained.
Further, when Examples 6 and 18 using B-3 and B-10 having no cyclic structure as R are compared with other examples using a photoacid generator having no cyclic structure as R, In other examples, it was confirmed that LWR, CDU and the like were smaller, and a more excellent effect was obtained.

On the other hand, in Comparative Examples 1 and 2 using the compounds specifically disclosed in Patent Document 1 (compounds having no organic group represented by R in the general formula (I)), compared with Examples, The shape of the pattern formed was inferior.

Claims

(A) forming a film with an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B):
(A) a resin whose polarity increases by the action of an acid and whose solubility in a developer containing an organic solvent decreases,
(B) A compound represented by the general formula (I) that generates an acid upon irradiation with actinic rays or radiation (a) a step of irradiating the film with actinic rays or radiation, and (c) a developer containing an organic solvent. And developing a film irradiated with the actinic ray or radiation using a pattern.

In the general formula (I), Z + represents a cation. Q 1 and Q 2 each independently represents fluorine or an alkyl group substituted with at least one or more fluorine atoms. L represents a divalent linking group. W represents a group having a cyclic structure. R represents an organic group.
2. The pattern forming method according to claim 1, wherein R is a group having a cyclic structure.
The pattern forming method according to claim 1, wherein W is a polycyclic aliphatic group.
The pattern forming method according to any one of claims 1 to 3, wherein W is an adamantylene group.
The pattern formation according to any one of claims 1 to 4, wherein a content of the organic solvent in the developer containing the organic solvent is 90% by mass or more and 100% by mass or less with respect to the total amount of the developer. Method.
6. The developer according to claim 1, wherein the developer contains at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Pattern forming method.
The pattern forming method according to claim 1, wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin (HR) different from the resin (A). .
The pattern forming method according to claim 1, wherein the exposure in the step (a) is immersion exposure.
An actinic ray-sensitive or radiation-sensitive resin composition used for the pattern forming method according to any one of claims 1 to 8.
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 9.
A method for manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 8.
An electronic device manufactured by the electronic device manufacturing method according to claim 11.