JP2014215549A - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition which causes few development defects even after long-term storage and suppresses deterioration of LWR.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition contains (A) at least two photoacid generators and (B) a resin decomposed by the action of an acid to increase in its solubility in an alkali developer. The photoacid generators include at least a photoacid generator represented by general formula (A-1) and a photoacid generator represented by general formula (A-2).

Description

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, and more particularly to an actinic ray-sensitive or radiation-sensitive resin composition containing two or more photoacid generators having different cations.
The present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition.

Conventionally, in a manufacturing process of a semiconductor device such as an IC or LSI, fine processing by lithography using a photoresist composition has been performed.
In recent years, as integrated circuits have been highly integrated, ultrafine pattern formation has been required. For example, Patent Document 1 proposes a method using a composition containing a novel photoacid generator. Yes. In particular, Patent Document 1 specifically discloses an embodiment using a composition containing two types of photoacid generators.

JP 2009-167156 A

On the other hand, the actinic ray-sensitive or radiation-sensitive resin composition (resist film forming composition) used for pattern formation is usually used after being stored for a predetermined time after purchase. Therefore, a desired effect is required even after storage.
The present inventors have stored a composition containing two types of photoacid generators specifically disclosed in Patent Document 1 for a predetermined time, and then evaluated the characteristics thereof. As a result, development defects occurred during pattern formation. It was easy to find and LWR (line width roughness) was also increased.

In view of the above circumstances, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition in which development defects are less likely to occur even after long-term storage and LWR deterioration is also suppressed.
Another object of the present invention is to provide a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition.

As a result of intensive studies on the problems of the prior art, the present inventors have used the above-mentioned problems by using an actinic ray-sensitive or radiation-sensitive resin composition containing two kinds of photoacid generators containing a predetermined cation. It was found that can be solved.
That is, it has been found that the above object can be achieved by the following configuration.

(1) contains at least two photoacid generators (A) and a resin (B) that decomposes by the action of an acid to increase the solubility in an alkali developer,
The actinic ray, wherein the photoacid generator includes at least a photoacid generator represented by the general formula (A-1) described later and a photoacid generator represented by the general formula (A-2) described later. Or radiation sensitive resin composition.
(2) Among Z ¹ and Z ² , one is a cation represented by general formula (C-1) or (C-2), and the other is a cation represented by general formula (C-3). The actinic ray-sensitive or radiation-sensitive resin composition according to (1).
(3) In formula (A-1) A ¹ and the general formula in (A-2) A ² in are both an anion represented by the general formula (B-1), (1) or ( The actinic ray-sensitive or radiation-sensitive resin composition according to 2).
(4) The actinic ray according to any one of (1) to (3), wherein the total content of the photoacid generator is 12 to 30% by mass relative to the total solid content in the composition. Or radiation sensitive resin composition.
(5) Content of the photo-acid generator which has a cation represented by general formula (C-1) or (C-2) is 6-25 mass% with respect to the total solid in a composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (4).
(6) The total mass W1 of the photoacid generator having a cation represented by formula (C-1) or (C-2) and the photoacid generation having a cation represented by formula (C-3) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5), wherein the mixing ratio (W1 / W2) with the mass W2 of the agent is 1.0 to 9.0. .
(7) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (6), wherein p is 1.
(8) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (7), wherein q is 2.
(9) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (8), wherein Y is a substituted or unsubstituted adamantyl group.
(10) Any ^one of (1) to (9), wherein L ² is a * ¹ -OCO- * ² group (bonded to (CR ¹ R ² ) q at * ¹ and bonded to Y at * ² ) The actinic ray-sensitive or radiation-sensitive resin composition according to one.
(11) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (10), wherein L ¹ is a single bond.
(12) L ¹ is a * ¹ -COO- * ² group (bonded to (CQ ¹ Q ² ) p at * ¹ and (CR ¹ R ² ) q at * ² ), (1) to The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (10).
(13) The actinic ray-sensitive or sensation according to any one of (1) to (12), wherein the resin (B) has a repeating unit represented by the general formula (nI) or (nII) described later. Radiation resin composition.
(14) A film forming step of forming a film containing the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (13);
An exposure step of irradiating the film with actinic rays or radiation;
And a development step of developing a film irradiated with actinic rays or radiation using a developer.
(15) The pattern forming method according to (14), wherein the developing step includes a step of developing with a developer containing an organic solvent.
(16) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (13), which is used in a pattern forming method including a step of developing with a developer containing an organic solvent. .

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition in which development defects hardly occur even after long-term storage and LWR deterioration is suppressed.
Moreover, according to this invention, the pattern formation method using the said actinic-ray-sensitive or radiation-sensitive resin composition 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).
Further, in the present specification, “active light” or “radiation” means, for example, an 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. Means. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

  In the present specification, the “organic group” means a functional group containing at least one or more carbon atoms (for example, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof) A hetero atom (for example, an oxygen atom) may be contained.

  A feature of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is that two or more photoacid generators containing specific cations are used. As a result of intensive studies on the problems of the prior art, the present inventors have found that crystallization of the photoacid generator during long-term storage is the cause of the above problems. That is, when the composition is stored for a long period of time, the photoacid generator in the composition is crystallized and aggregates, so that it has been found that the development defects occur and the LWR deteriorates. Therefore, the present inventors can suppress the crystallization of the photoacid generator during long-term storage of the composition by using two or more kinds of photoacid generators containing a specific cation, resulting in the desired effect. It has been found that it can be obtained.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as “composition”) is decomposed by the action of at least two photoacid generators (A) and an acid. Resin (B) whose solubility with respect to a developing solution increases is contained.
Below, each component contained in a composition is explained in full detail first.

<Photoacid generator (A)>
In the composition of the present invention, at least two kinds of photoacid generators (A) are contained, and the photoacid generator represented by formula (A-1) and formula (A-2) At least the photoacid generator represented is included. As will be described later, the photoacid generator represented by the general formula (A-1) and the photoacid generator represented by the general formula (A-2) differ in at least the structure of the cation moiety.
Hereinafter, first, the photoacid generator represented by the following formula will be described in detail.

Formula ^(A-1) A 1 and the general formula in ^(A-2) A 2 in the anion represented by the general formula anion and represented by general formula (B-1) (B- 2) And at least one of A ¹ and A ² represents an anion represented by General Formula (B-1). Especially, it is preferable that both A < ¹ > and A < ² > are anions represented by general formula (B-1) from the point that a development defect does not occur easily after long-term storage. Furthermore, it is more preferable that both A ¹ and A ² are anions represented by formula (B-1) and have the same structure. When both are anions having the same structure, salt exchange occurring between the two photoacid generators can be prevented even after the composition has been stored for a long time, and as a result, a desired effect can be obtained.

In formula (B-1), Q ¹ and Q ² each independently represent a hydrogen atom, a fluorine atom or an organic group, and at least one of Q ¹ and Q ² is a fluorine atom or at least one fluorine An alkyl group substituted with an atom is represented.
Preferred examples of the organic group represented by Q ¹ and Q ² include CF ₃ .
Among them, an actinic ray-sensitive or radiation-sensitive resin composition in which development defects are less likely to occur even after long-term storage and LWR deterioration is further suppressed can be obtained (hereinafter referred to as “the effect of the present invention is more excellent. Q ¹ and Q ² are each independently preferably a fluorine atom or an alkyl group substituted with at least one fluorine atom, and a fluorine atom or a C 1-4 perfluoro It is more preferably an alkyl group, further preferably a fluorine atom or CF ₃ , and particularly preferably both are fluorine atoms.
In addition, it is preferable that carbon number of the said alkyl group is 1-10, and it is more preferable that it is 1-4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Examples of the alkyl group include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , and CH ₂ CF _3. CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , or CH ₂ such as CH ₂ C ₄ F can be mentioned.

L ¹ represents a single bond, —O—, —COO—, or OCO—. Among them, a single bond or * ¹ -COO- * ² group (* ¹ is bonded to (CQ ¹ Q ² ) p and * ² is (CR ¹ R ² ) in that the effect of the present invention is more excellent. It is preferable that it is bonded to q).

R ¹ and R ² each independently represents a hydrogen atom or an organic group.
Examples of the organic group represented by R ¹ and R ² include an alkyl group and a cycloalkyl group.
Especially, it is preferable that R < ¹ > and R < ² > are respectively independently a hydrogen atom and an alkyl group at the point which the effect of this invention is more excellent, and it is more preferable that both are hydrogen atoms.
The alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include groups exemplified as the alkyl groups for Q ¹ and Q ² .

L ² represents a single bond or 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), cycloalkylene group (preferably having 3 to 10 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group in which a plurality of these are combined. . Among these, —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO ₂ —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable. In particular, L ² is more preferably a * ¹ —OCO— * ² group (bonded to (CR ¹ R ² ) q at * ¹ and bonded to Y at * ² ).

Y represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.
The alicyclic hydrocarbon group has 3 to 18 carbon atoms, and among them, 6 to 15 is preferable and 10 to 12 is more preferable in that the effect of the present invention is more excellent.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like are preferable, and an adamantyl group is particularly preferable because the effects of the present invention are more excellent.
In addition, as a substituent contained in the said alicyclic hydrocarbon group, a hydroxyl group, an oxygen atom (= O), and a carboxyl group are mentioned, for example.
In addition, when the alicyclic hydrocarbon group includes a plurality of substituents, they may be bonded to each other to form a ring structure. That is, you may form the bivalent coupling group represented by * -L- *. In addition, * is a coupling | bonding position with respect to an alicyclic hydrocarbon group, and L represents a bivalent coupling group. The definition of a divalent linking group, has the same meaning as the divalent linking group represented by L ^2, among others -COO -, - O-, an alkylene group, and combinations thereof are preferred. Examples of the alicyclic hydrocarbon group further having such a ring structure include norbornane lactone.

p represents an integer of 1 to 3. Especially, 1 or 2 is preferable and 1 is more preferable at the point which the effect of this invention is more excellent.
q represents an integer of 2 to 8. Especially, 2-4 are preferable at the point which the effect of this invention is more excellent, 2 or 3 is more preferable, and 2 is especially preferable.

In formula (B-2), Q ^{1 ′} and Q ^{2 ′} each independently represent a hydrogen atom, a fluorine atom or an organic group, and at least one of Q ^{1 ′} and Q ^{2 ′} is a fluorine atom, or at least An alkyl group substituted with one fluorine atom is represented.
Definition of Q 1 ^'and Q ^2' is synonymous with Q ¹ and Q ² in the above-mentioned general formula (B-1), preferred embodiments are also the same.

R ^{1 ′} and R ^{2 ′} each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. Especially, it is more preferable that both are hydrogen atoms at the point which the effect of this invention is more excellent.
The number of carbon atoms in the alkyl group and the alkyl group substituted with at least one fluorine atom is not particularly limited, but those having 1 to 4 carbon atoms are preferable. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

L ′ represents a single bond, —O—, —COO—, or —OCO—. Among these, a single bond or a * ¹ -COO- * ² group (* ¹ is bonded to (CQ ^{1 ′} Q ^{2 ′} ) p ′ and * ² is (CR ¹ ) in that the effect of the present invention is more excellent. It is preferable that ^“ R ^{2 ′} ” is bonded to q ′).
L ″ represents a single bond or a divalent linking group. Definition of the divalent linking group are the same as defined for L ² in the above-mentioned general formula (B-1), preferred embodiments are also the same.

Y ′ represents an alicyclic hydrocarbon group or a non-aromatic heterocyclic group.
Although carbon number of an alicyclic hydrocarbon group is not specifically limited, 3-18 are preferable, 6-15 are more preferable, and 10-12 are still more preferable at the point which the effect of this invention is more excellent.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like are preferable in that the effect of the present invention is more excellent.

Although carbon number of a non-aromatic heterocyclic group is not specifically limited, 3-20 are preferable and 5-12 are more preferable at the point which the effect of this invention is more excellent.
The kind in particular of hetero atom contained in a non-aromatic heterocyclic group is not restrict | limited, For example, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned.
Examples of the non-aromatic heterocyclic group include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

p ′ represents an integer of 1 or more. Especially, 1-3 are preferable and 1 is more preferable at the point which the effect of this invention is more excellent.
q ′ represents 0 or 1.

  Below, the anion represented by general formula (B-1) and (B-2) is illustrated.

In General Formula (A-1), Z ¹ is any one of the cations represented by General Formulas (C-1) to (C-3), and Z ^{2 in} General Formula (A-2) Is any one of the cations represented by formulas (C-1) to (C-3), and is different from Z ¹ . That is, Z ¹ and Z ² are different cations, and both are selected from cations represented by general formulas (C-1) to (C-3).
Below, each group of general formula (C-1)-(C-3) is explained in full detail.

In general formula (C-1), R < ³ > -R < ⁹ > represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an organic group each independently. In addition, at least one of R ^{3 to} R ⁹ represents a hydroxyl group, a carboxyl group, a halogen atom, or an organic group.
Among these, R ^{3 to} R ⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen, It preferably represents an atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.
R ⁸ and R ⁹ each independently preferably represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group.

Any two of R ^{3 to} R ⁷ may be bonded to each other to form a ring. R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form a ring. Note that the ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

The alkyl group as R ^{3 to} R ⁷ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group. The alkyl group may have a substituent, and examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

The cycloalkyl group as R ^{3 to} R ⁷ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. The cycloalkyl group may have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.

The aryl group as R ^{3 to} R ⁷ is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group. The aryl group may have a substituent, and preferred substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, and an arylthio group.

The alkoxy group as R ^{3 to} R ⁷ is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an isopropyloxy group, a t-butyloxy group, a t-amyloxy group, and an n-butyloxy group. The alkoxy group may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R ^{3 to} R ^{7 are the same} as the specific examples of the alkoxy group.
Specific examples of the alkyl group in the alkylcarbonyloxy group and the alkylthio group as R ^{3 to} R ^{7 are the same} as the specific examples of the alkyl group.
Specific examples of the cycloalkyl group in the cycloalkylcarbonyloxy group as R ^{3 to} R ^{7 are the same} as the specific examples of the cycloalkyl group.
Specific examples of the aryl group in the aryloxy group and arylthio group as R ^{3 to} R ^{7 are the same} as the specific examples of the aryl group.

The definition of each group of the R ⁸ and R ⁹ are the same definitions of each group in R ³ to R ^7. The embodiment of R ⁸ and R ^9, at least one of R ⁸ and R ^9, an alkyl group, a cycloalkyl group, preferably represents an aryl group.
R ⁸ and R ⁹ may be connected to each other to form a ring, and when R ⁸ and R ⁹ are connected to each other to form a ring, carbon atoms that contribute to the formation of the ring included in R ⁸ and R ⁹ The total number of is preferably 4 to 7, and particularly preferably 4 or 5.

The alkyl group represented by R ¹⁰ and R ¹¹ is preferably an alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl Groups and the like.

The cycloalkyl group represented by R ¹⁰ and R ¹¹ is preferably a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like.

The alkenyl group represented by R ¹⁰ and R ¹¹ is preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, and a styryl group.

As the aryl group represented by R ¹⁰ and R ¹¹ , for example, an aryl group having 6 to 20 carbon atoms is preferable. Specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a penalenyl group, a phenyl group, Examples thereof include a nantracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, and a benzopyrenyl group. Preferred are a phenyl group and a naphthyl group, and more preferred is a phenyl group.

The alkyl group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R ¹⁰ and R ^11, for example, those listed as the alkyl group represented by R ¹⁰ and R ¹¹ above.

The cycloalkyl moiety of the 2-oxocycloalkyl group and alkoxycarbonyl cycloalkyl group represented by R ¹⁰ and R ^11, for example, those listed as the cycloalkyl group represented by R ¹⁰ and R ¹¹ above Can be mentioned.
R ¹⁰ and R ¹¹ may be bonded to each other to form a ring structure. As the ring structure, R ¹⁰ and R ¹¹ (for example, a methylene group, an ethylene group, a propylene group, etc.) are represented by the general formula (C-1 5) or a 6-membered ring formed together with the sulfur atom in the above), particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

R ^{3 to} R ¹¹ may further have a substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cyclo group. Alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, etc. Can be mentioned.

  As a suitable aspect of the cation represented by the said general formula (C-1), the cation represented by general formula (C-4) and general formula (C-5) is mentioned.

The definitions of R ^{3 to} R ^{9 in} the general formulas (C-4) and (C-5) are as described above.
Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m1, n1, m2, and m2 represent integers, preferably 0 to 3, more preferably 1 to 2, and particularly preferably 1. The alkylene group connecting S ⁺ and Y may have a substituent, and preferred examples of the substituent include an alkyl group.

R _x represents a monovalent organic group when Y is a nitrogen atom, and is absent when Y is an oxygen atom or a sulfur atom. R _x is preferably a group containing an electron withdrawing group, and particularly preferably a group represented by the following general formulas (ZI-3a-1) to (ZI-3a-4).

In the above (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, preferably an alkyl group.
In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond connected to a nitrogen atom as Y in the compound represented by the general formula (C-4).

When Y is a nitrogen atom, R _x is particularly preferably a group represented by —SO ₂ —R _y . _Ry represents an alkyl group, a cycloalkyl group or an aryl group, and preferably an alkyl group.

In addition, as a suitable aspect of the cation represented by general formula (C-4) and (C-5), the cation represented by general formula (C-6) and (C-7) is mentioned.
The definition of each group in general formula (C-6) and (C-7) is as above-mentioned.

  Below, the cation represented by general formula (C-1) is illustrated.

  Hereinafter, Formula (C-2) will be described in detail.

In General Formula (C-2), R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. R ¹² and R ¹³ may be bonded to each other to form a ring, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. These groups may have a substituent.
R ¹⁴ preferably represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a group having a monocyclic or polycyclic cycloalkyl group, or an alkylene oxide chain.
R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Among them, R ¹⁵ represents a group having a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. preferable. In addition, when there are a plurality of R ^{15 s} , they may be the same or different.

The alkyl group for R ^{12 to} R ¹⁵ is linear or branched and preferably has 1 to 10 carbon atoms.
Examples of the cycloalkyl group represented by R ^{12 to} R ¹⁵ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy group for R ^{14 to} R ¹⁵ is linear or branched and preferably has 1 to 10 carbon atoms.
The alkoxycarbonyl group for R ^{14 to} R ¹⁵ is linear or branched and preferably has 2 to 11 carbon atoms.
Examples of the group having a cycloalkyl group as R ¹⁵ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
Specific examples of the alkyl group of the alkylcarbonyl group represented by R ¹⁵ include the same examples as the above alkyl group.
The alkylsulfonyl group and cycloalkylsulfonyl group represented by R ¹⁵ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

R ¹² and R ¹³ may combine with each other to form a ring, and the formed ring structure includes a 5-membered or 6-membered ring formed by R ¹² and R ¹³ together with a sulfur atom, particularly preferably a 5-membered ring. (That is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This ring structure may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxy group. A carbonyloxy group etc. can be mentioned. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.
The R ¹² and R ^13, a methyl group, an ethyl group, a naphthyl group, and the like divalent group R ¹² and R ¹³ form a tetrahydrothiophene ring structure bonded to together with the sulfur atom to each other are preferable, R ¹² and A divalent group in which R ¹³ is bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

r represents an integer of 0-2. Especially, 0 or 1 is preferable and 1 is more preferable.
m15 represents an integer of 0 to 8. Especially, 0-2 are preferable.

  Below, the cation represented by general formula (C-2) is illustrated.

  Hereinafter, General Formula (C-3) will be described in detail.

In General Formula (C-3), R ^{16 to} R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, a halogen atom, or an organic group.
Especially, it is preferable that R < ¹⁶ > -R < ¹⁸ > represents a methyl group, a tert- butyl group, a methoxy group, a fluorine atom, and a chlorine atom.
Any two of R ^{16 to} R ¹⁸ may be bonded to each other to form a ring. The ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

  m16 to m18 each independently represents an integer of 0 to 5. Especially, 1-3 are preferable and 1 is more preferable.

  Below, the cation represented by general formula (C-3) is illustrated.

As a preferred embodiment of the photoacid generator (A), ^one of Z ¹ and Z ² is represented by the general formula (C-1) or (C-2) in that the effect of the present invention is more excellent. The aspect which is a cation and the other is a cation represented by (C-3) is mentioned.

The photoacid generator (A) can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

The content of the photoacid generator (A) in the composition is not particularly limited, but is preferably 12 to 30% by mass with respect to the total solid content in the composition in terms of more excellent effects of the present invention. -20 mass% is more preferable.
The total solid content means the total mass of components constituting the resist film described later, and other components excluding the solvent.

Especially, content of the photo-acid generator which has the cation represented by the said general formula (C-1) or (C-2) is the point which the effect of this invention is more excellent, and the total solid content in a composition On the other hand, the aspect which is 6-25 mass% (6-12 mass% is especially preferable) is mentioned preferably.
The total mass W1 of the photoacid generator having a cation represented by the general formula (C-1) or (C-2) and the photoacid generation having a cation represented by the general formula (C-3) The mixing ratio (W1 / W2) with the mass W2 of the agent is not particularly limited, but is preferably 1.0 to 9.0, more preferably 2.0 to 9.0, and particularly preferably 3.0 to 9.0.

<Resin (B) which is decomposed by the action of an acid to increase the solubility in an alkali developer>
The composition of the present invention contains a resin (hereinafter also referred to as “acid-decomposable resin” or “resin (B)”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer.
The acid-decomposable resin is a group capable of decomposing under the action of an acid into an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”) on the main chain or side chain of the resin, or both of the main chain and side chain. Have
The resin (B) is preferably insoluble or hardly soluble in an alkali developer.
The acid-decomposable group preferably has a structure protected with a group capable of decomposing and leaving an alkali-soluble group by the action of an acid.

Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The repeating unit having an acid-decomposable group that can be contained in the resin (B) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI):
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the alkyl group which may have a substituent represented by Xa ₁ include a group represented by a methyl group or —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group or the like.

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

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

The repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.
Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.
The total content of repeating units having an acid-decomposable group is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, based on all repeating units in the resin (B), 30 More preferably, it is -70 mol%.
As the resin (B), specifically, specific examples disclosed in [0265] of US Patent Application Publication No. 2012/0135348 can be used, but the present invention is not limited thereto. .

  The resin (B) has, for example, at least one of a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably, it is a resin.

In formulas (I) and (II), R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R _11. . R ₁₁ represents a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with the carbon atom to which R ₂ is bonded.
R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₁₁ are the same as those described for R ₁₁ in formula (AI).

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group, an ethyl group, or an isopropyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.
R ₃ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

The alkyl group in R ₄ , R ₅ and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

Examples of the substituent that each of the groups may have include the same groups as those described above as the substituent that each group in the general formula (AI) may have.
The acid-decomposable resin is a resin containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferred.

  In another embodiment, a resin containing at least two kinds of repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI) is more preferable. When two or more repeating units of the general formula (I) are included, the alicyclic structure formed by R together with the carbon atom is a monocyclic alicyclic structure, and the alicyclic structure formed by R together with the carbon atom. It is preferable that both the repeating unit which is a polycyclic alicyclic structure is included. The monocyclic alicyclic structure preferably has 5 to 8 carbon atoms, more preferably 5 or 6 carbon atoms, and particularly preferably 5 carbon atoms. As the polycyclic alicyclic structure, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable.

  As the repeating unit having an acid-decomposable group contained in the resin (B), the repeating units shown below can also be used.

  One type of repeating unit having an acid-decomposable group contained in the resin (B) may be used, or two or more types may be used in combination. When used together, the specific examples disclosed in paragraph [0287] of US Patent Application Publication No. 2012/0135348 can be used, but the present invention is not limited thereto.

  In one embodiment, the resin (B) preferably contains a repeating unit having a cyclic carbonate structure. This cyclic carbonate structure is a structure having a ring including a bond represented by —O—C (═O) —O— as an atomic group constituting the ring. The ring containing a bond represented by —O—C (═O) —O— as the atomic group constituting the ring is preferably a 5- to 7-membered ring, and most preferably a 5-membered ring. Such a ring may be condensed with another ring to form a condensed ring.

The resin (B) preferably contains a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure.
Any lactone group or sultone group can be used as long as it has a lactone structure or sultone structure, but a lactone structure or sultone structure having a 5- to 7-membered ring is preferable, and a lactone having a 5- to 7-membered ring is preferable. A structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the structure or sultone structure is preferable. Any of the general formulas (LC1-1) to (LC1-17) and the following general formulas (SL1-1) and (SL1-2) disclosed in paragraph [0318] of US Patent Application Publication No. 2012/0135348 It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by: A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR and development defects are improved.

The lactone structure part or sultone structure part may or may not have a substituent (Rb ₂ ). When n ₂ is 2 or more, the plural substituents (Rb ₂ ) may be the same or different, and the plural substituents (Rb ₂ ) may be bonded to form a ring. .

  The resin (B) preferably has a repeating unit having a hydroxyl group or a cyano group other than the general formula (AI). This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In general formula (VIIa), it is more preferable that _two members out of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.
Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.
The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (B).
Specific examples of the repeating unit having a hydroxyl group or a cyano group include the repeating unit disclosed in paragraph [0340] of US Patent Application Publication No. 2012/0135348, but the present invention is not limited thereto.

  The resin (B) preferably contains a repeating unit represented by the following general formula (nI) or general formula (nII).

In general formula (nI) and general formula (nII),
R ₁₃ ′ to R ₁₆ ′ each independently have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, or a lactone structure. Represents a group or a group having an acid-decomposable group.
X ₁ and X ₂ each independently represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom.
n represents an integer of 0 to 2.

Examples of the acid-decomposable group in the group having an acid-decomposable group as R ₁₃ ′ to R ₁₆ ′ include cumyl ester group, enol ester group, acetal ester group, tertiary alkyl ester group, etc. This is preferably a tertiary alkyl ester group represented by —C (═O) —O—R ₀ .
In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy. 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned.
At least one of R ₁₃ ′ to R ₁₆ ′ is preferably a group having an acid-decomposable group.
Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
The alkyl group represented by R ₁₃ ′ to R ₁₆ ′ is more preferably a group represented by the following general formula (F1).

In general formula (F1),
R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx is a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group), preferably a hydrogen atom.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Specific examples of the repeating unit represented by the general formula (nI) or the general formula (nII) include the following specific examples, but the present invention is not limited to these compounds. Especially, the repeating unit represented by (II-f-16)-(II-f-19) is preferable.

  The resin (B) may have a repeating unit represented by the following general formula (VIII).

In the general formula (VIII),
Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  It is preferable that resin (B) contains the repeating unit represented by the general formula (nI) or the general formula (nII) described above and the repeating unit represented by the general formula (VIII). This improves the adhesion of the resist film to the substrate.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

Resin (B) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included.
Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, the performance required for the resin (B) used in the composition of the present invention, in particular, (1) solubility in a coating solvent, (2) film formability (glass transition point), (3) alkali developability (4) Slip film (selection of hydrophilicity / hydrophobicity, alkali-soluble group), (5) Adhesion of unexposed part to substrate, (6) Dry etching resistance, etc. can be finely adjusted.

As such a monomer, for example, it has one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. A compound etc. can be mentioned.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (B), the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and the general required performance of the resist, resolving power, heat resistance, sensitivity. It is set appropriately in order to adjust etc.

When the composition of the present invention is used for ArF exposure, the resin (B) used in the composition of the present invention preferably has substantially no aromatic group from the viewpoint of transparency to ArF light. . More specifically, the repeating unit having an aromatic group is preferably 5% by mole or less, more preferably 3% by mole or less, and more preferably 3% by mole or less of the entire repeating unit of the resin (B). More preferably, it is 0 mol%, that is, it does not have a repeating unit having an aromatic group. The resin (B) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (B) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

  The resin (B) used in the composition of the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

  The resin (B) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). Specifically, synthesis methods disclosed in paragraphs [0126] to [0128] of US Patent Application Publication No. 2012/0164573 can be used.

The weight average molecular weight of the resin (B) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 15 as a polystyrene-converted value by the GPC method. 1,000, particularly preferably 3,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

  As for the content rate in the whole composition of resin (B), 30-99 mass% is preferable in a total solid, More preferably, it is 55-95 mass%. In addition, the resins of the present invention may be used alone or in combination.

<Other ingredients>
In the composition, components other than the photoacid generator (A) and the resin (B) may be contained.
Below, arbitrary components are explained in full detail.

(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 photoacid generator or the like. Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and 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, light An onium salt that is a weak acid relative to the acid 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 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) 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.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
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 US Patent Application Publication No. 2012/0219913.

  Preferable basic compounds 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, or 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 C6-C12) may be bonded to a 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 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. 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. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (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 1 or more, preferably 3 to 9, more preferably 4 to 6 in the molecule. 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 JP 2011-22560 A, paragraphs [0218] to [0219] of JP 2012-137735 A, 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, but when it is contained, the content of the basic compound is usually 0.001 to 10 relative to the total solid content of the composition. % By mass, preferably 0.01 to 5% by mass.
The use ratio of the photoacid generator (A) and the basic compound in the composition is preferably photoacid generator (A) / 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 photoacid generator (A) / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

A low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter, also referred to as compound (C)) has an acetal group, a carbonate group, a carbamate group, A tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable.
100-1000 are preferable, as for the molecular weight of a compound (C), 100-700 are more preferable, and 100-500 are especially preferable.
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 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably it represents C1-C10) or an alkoxyalkyl group (preferably C1-C10). 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 a structure disclosed in paragraph [0466] of US Patent Application Publication No. 2012/0135348, but are not limited thereto. Is not to be done.

  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 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 preferred compound (C) include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348.

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 compound (C) can be used singly or in combination of two or more.
Although content in particular of the compound (C) in the composition of this invention is not restrict | limited, It is preferable that it is 0.001-20 mass% with respect to the total solid of a composition, More preferably, it is 0.001-10. It is 0.01 mass%, More preferably, it is 0.01-5 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, 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. And 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. The compound represented by the general formula (PA-1) has an acidic group as well as a proton acceptor functional group, so that the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. 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.
Specific examples of the compound (PA) include compounds exemplified in paragraph [0280] of US Patent Application Publication No. 2011/0269072.

  Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. 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 photoacid 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 are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).
Specific examples of the ionic compound having a proton acceptor site in the cation moiety include the compounds exemplified in paragraph [0291] of US Patent Application Publication No. 2011/0269072.
Such a compound can be synthesized with reference to methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

A compound (PA) may be used individually by 1 type, and may be used in combination of 2 or more type.
0.1-10 mass% is preferable with respect to the total solid of a composition, and, as for content of a compound (PA), 1-8 mass% is more preferable.

In the composition of the present invention, an onium salt that becomes a weak acid relative to the photoacid generator (A) can be used as an acid diffusion controller.
When the photoacid generator (A) and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator (A) are mixed and used, actinic radiation or radiation irradiation When the acid generated from the photoacid generator (A) 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 photoacid generator (A) is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a 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 ). And an iodonium cation represented by:
Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include a structure exemplified in paragraph [0198] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structure exemplified in paragraph [0201] of JP2012-242799A.
Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.

An onium salt that is a weak acid relative to the photoacid 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. Also good.
The compound is preferably a compound represented by any one of the following general formulas (E-1) to (E-3).

In general formulas (E-1) to (E-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 -,}} -N. R ₄ has 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 (E-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 an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino group. 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 (E-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [2013] of JP2013-8020A. The compounds exemplified in [0029] can be mentioned.
Preferable examples of the compound represented by the general formula (E-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
Preferable examples of the compound represented by the general formula (E-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 photoacid generator is preferably 0.5 to 10.0% by mass with respect to the total solid content of the composition, and is preferably 0.5 to 8%. More preferably, it is 0.0 mass%, and it is still more preferable that it is 1.0-8.0 mass%.

(Hydrophobic resin (D))
The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”), particularly when applied to immersion exposure. The hydrophobic resin (D) is preferably different from the resin (B).
As a result, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include those exemplified in paragraph [0500] of US Patent Application Publication No. 2012/0251948.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.
The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

The hydrophobic resin (D) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph [0519] of US Patent Application Publication No. 2012/0251948.

Further, as described above, the hydrophobic resin (D) preferably includes a CH ₃ partial structure in the side chain portion.
Here, CH ₃ partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH ₃ partial structure") The, CH ₃ partial structure an ethyl group, and a propyl group having Is included.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R _{11 to} R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R _{11 to} R ₁₄ each independently represents a side chain portion.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of monovalent organic groups for R _{11 to} R ₁₄ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyls. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).

  Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, more specifically, the organic group that is stable against an acid is preferably an organic group that does not have the “acid-decomposable group” described in the resin (B).

The alkyl group for X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

  Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

  Hereinafter, the repeating unit represented by formula (III) will be described in detail.

In the general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.
The alkyl group for X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group. X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable against acid, more specifically, R ₃ is preferably an organic group that does not have the “acid-decomposable group” described in the hydrophobic resin (B).
R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

  n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

  Preferred specific examples of the repeating unit represented by the general formula (III) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. The content is usually 100 mol% or less with respect to all repeating units of the hydrophobic resin (D).

  The hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ), The surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.

Further, the hydrophobic resin (D) includes the following (x) to (z) even when (i) contains a fluorine atom and / or silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
As for content of the repeating unit which has an acid group (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (D), More preferably, it is 3-35 mol%, More preferably, it is 5- 20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the acid-decomposable resin (B).
The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is more preferably 3 to 98 mol%, and further preferably 5 to 95 mol%.

  In the hydrophobic resin (D), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin (B). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). More preferably, it is 10-80 mol%, More preferably, it is 20-60 mol%.

  The hydrophobic resin (D) may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (III) is preferably 1 to 100 mol%, and preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin (D). Is more preferable, and it is still more preferable that it is 30-70 mol%.

  It is also preferable that the hydrophobic resin (D) further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol% with respect to all repeating units in the hydrophobic resin (D), preferably 10 to 90 mol%. More preferably, it is more preferably 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When the hydrophobic resin (D) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (D), and is 10 to 80% by mass. More preferably. Moreover, it is preferable that it is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mol%.
When the hydrophobic resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin (D). More preferably. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and it is more preferable that it is 20-100 mol%.

On the other hand, particularly in the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin (D) preferably has a form containing substantially no fluorine atom and silicon atom. Specifically, the content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, preferably 3 mol% or less, based on all repeating units in the hydrophobic resin (D). Is more preferably 1 mol% or less, and ideally 0 mol%, that is, it does not contain a fluorine atom and a silicon atom. Moreover, it is preferable that hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in all the repeating units of the hydrophobic resin (D). It is preferably 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, with respect to the total solid content in the composition, 7 mass% is still more preferable.

  The hydrophobic resin (D), like the resin (B), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. Thereby, a composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (B), but in the synthesis of the hydrophobic resin (D), The reaction concentration is preferably 30 to 50% by mass.

  Specific examples of the hydrophobic resin (D) are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

(solvent)
The composition may contain a solvent.
Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, and cyclic lactone (preferably having 4 to 4 carbon atoms). 10), organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate and alkyl pyruvate.
Specific examples of these solvents include those described in paragraphs [0441] to [0455] of US Patent Application Publication No. 2008/0187860.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
The solvent containing a hydroxyl group and the solvent not containing a hydroxyl group can be selected as appropriate, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether, alkyl lactate or the like, and propylene glycol monomethyl ether (PGME, also known as 1- Methoxy-2-propanol) and ethyl lactate are more preferable. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

(Surfactant)
The composition may or may not further contain a surfactant. When it is contained, fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, fluorine atom and silicon atom It is more preferable to contain either one or two or more surfactants having both.

When the composition contains a surfactant, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

  These surfactants may be used alone or in several combinations.

When the composition contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. It is.
On the other hand, by making the addition amount of the surfactant 10 ppm or less with respect to the total amount of the composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased, thereby making the resist film surface more hydrophobic. It is possible to improve water followability at the time of immersion exposure.

(Other)
The composition of the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in paragraphs [0605] to [0606] of US Patent Application Publication No. 2008/0187860.
These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the composition contains a carboxylic acid onium salt, the content is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably based on the total solid content of the composition. Is 1-7 mass%.
If necessary, the composition may further include an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer (eg, molecular weight). 1000 or less phenolic compounds, alicyclic or aliphatic compounds having a carboxyl group) and the like can be contained.

Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

The composition of the present invention is preferably a resist film having a thickness of 80 nm or less from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and still more preferably 2.0 to 5.3% by mass. By setting the solid content concentration in the above range, the composition can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but it is likely that the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, thereby aggregating the material in the resist solution, particularly the photoacid generator (A). As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the composition.

  The composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably a mixed solvent, filtering the solution, and then applying the solution on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

  The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, production of imprint mold structures, and other photofabrication processes, lithographic printing plates, acid-curing properties. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the composition.

<Pattern formation method>
Next, the pattern forming method according to the present invention will be described.
The pattern forming method of the present invention is not particularly limited,
(A) a film forming step of forming a film containing the above composition (hereinafter also referred to as a resist film);
(B) an exposure step of irradiating the film with actinic rays or radiation; and (c) a development step of developing the film irradiated with the actinic rays or radiation using a developer.
It is preferable to contain at least.

The exposure in the step (ii) 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 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 above 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.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
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.

Moreover, the immersion exposure method can be applied in the step of performing exposure according to the present invention. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
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 reduces 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 film 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 that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

On the other hand, when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light, the optical image projected on the resist film is distorted. . Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of 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 film (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 when exposed through an immersion medium. It is more preferable that it is 75 degrees or more, and it is still more preferable that it is 75-85 degrees.

  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. In order to achieve a preferable receding contact angle, it is preferable to include the hydrophobic resin (D) in the composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film.

  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. Furthermore, if necessary, an antireflection film may be formed between the resist film and the substrate. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used.

  The developer used in the step of developing the resist film formed using the composition of the present invention is not particularly limited. For example, a developer containing an alkali developer or an organic solvent (hereinafter also referred to as an organic developer). ) Can be used.

When the pattern forming method of the present invention includes a step of developing using an alkali developer, usable alkali developers are not particularly limited, but generally, 2.38% by mass of tetramethylammonium hydroxide. An aqueous solution is desirable. In addition, 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.
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.

  When the pattern forming method of the present invention includes a step of developing using a developer containing an organic solvent, examples of the developer (hereinafter also referred to as an organic developer) include ketone solvents, ester solvents, and alcohols. Polar solvents and hydrocarbon solvents such as system solvents, amide solvents and ether solvents can be used.

  Examples of the ketone solvent 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. Examples include 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, and propyl lactate. be able to.

  Examples of the alcohol solvent 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, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent 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.

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 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. 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 the 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 2mL / sec / mm ² or less, more preferably 1.5mL / sec / mm ^2, more preferably not more than 1mL / sec / mm ^2. 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 by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. 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.
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, and specifically, 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 include 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 on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment 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 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The pattern forming method of the present invention uses both a step of developing using an alkali developer (alkali developing step) and a step of developing using an organic solvent-containing development (organic solvent developing step). can do. 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, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, only the intermediate exposure intensity region can be left as a pattern without being dissolved, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975). The same mechanism as in paragraph [0077] of the publication).
The alkali development step can be performed either before or after the organic solvent development, but is more preferably performed before the organic solvent development step.

The present invention also relates to an electronic device manufacturing method including the above-described negative 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.

<1. Synthesis of photoacid generator>
The photoacid generators (A-1 to A-23) used in Examples and Comparative Examples are shown in Table 3 below.
These photoacid generators were synthesized with reference to descriptions in JP2009-167156, JP2011-16794, JP2011-251961, JP2011-13479, and JP2010-44374.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 1 below are dissolved in a solvent, and a solution having a solid content concentration of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.05 μm. A composition (hereinafter also referred to as a resist composition) was prepared. This resist composition was stored in a dark place at room temperature for 1 month and then evaluated by the following method. The results are shown in Table 1.
About the solvent in Table 1, the number in a table | surface is mass ratio.
In Table 1, when the resist composition contains a hydrophobic resin (HR), the usage form was marked as “addition”. When the resist composition does not contain a hydrophobic resin (HR) and a topcoat protective film containing a hydrophobic resin (HR) is formed on the upper layer after forming a film, the usage form is “TC”. Marked.

Various components used in Table 1 are summarized below.
For each of the following resins A to H, the composition ratio of the repeating units is a molar ratio.
Moreover, regarding the hydrophobic resin in Table 1, the numbers of the hydrophobic resins exemplified in the above specification are shown.

[Basic compounds]
DIA: 2,6-diisopropylaniline TEA: triethanolamine DBA: N, N-dibutylaniline PBI: 2-phenylbenzimidazole PEA: N-phenyldiethanolamine

[Low molecular compound having a group capable of leaving by the action of an acid]

[Surfactant]
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorine-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

〔solvent〕
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: Cyclohexanone A3: γ-Butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate

<Evaluation>
(Pattern formation)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. On top of that, the resist composition prepared above was applied and baked at 95 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. In the case of using a top coat, a 3% by mass solution obtained by further dissolving a top coat resin in decane / octanol (mass ratio 9/1) is applied on the resist film obtained above, and at 85 ° C., 60 ° C. Baking was performed for 2 seconds to form a top coat layer having a thickness of 50 nm.
In contrast, using an ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection manufactured by ASML), a 1: 1 line with a line width of 48 nm Exposure was through a 6% halftone mask with andspace pattern. Ultra pure water was used as the immersion liquid. Then, after heating at 90 ° C. for 60 seconds, paddle with butyl acetate for 30 seconds to develop, paddle with pure water, rinse, and spin dry to form a pattern.

(LWR evaluation)
The line pattern of the above obtained line / space = 1/1 (ArF immersion exposure: line width 48 nm) was observed with a scanning microscope (Hitachi S9380). The line width was measured at 50 points in the range of 2 μm edge in the longitudinal direction of the line pattern, the standard deviation was determined for the measurement variation, and 3σ was calculated. A smaller value indicates better performance.

(Development defect evaluation)
Using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Corporation, the pixel size of the defect inspection device is set to 0.16 μm, the threshold value is set to 20, and measurement is performed in a random mode. The number of development defects per unit area (1 cm ² ) was calculated by detecting image defects extracted from the differences caused by pixel-by-pixel overlapping, and evaluated in four stages according to the following criteria. A smaller value indicates better performance.
A: Less than 0.2 pieces / cm ² B: 0.2 pieces / cm ² or more and less than 0.5 pieces / cm ² C: 0.5 pieces / cm ² or more and less than 1.0 pieces / cm ² D: 1. 0 / cm ² or more

As shown in Table 1, when the composition of the present invention was used, the occurrence of development defects was suppressed even after long-term storage, and the deterioration of LWR was also suppressed.
In particular, all of the examples in which the anions in the two kinds of cations were represented by the general formula (B-1) had the development defect “A”.
Further, as can be seen from a comparison between Examples 9, 32 and 33 and other examples, the cation represented by the general formula (C-3) as the cation in the two photoacid generators, and the general formula When the cation represented by (C-1) or general formula (C-2) was used, LWR was smaller and excellent results were obtained.
Further, when “H” having a repeating unit represented by the general formula (nI) or (nII) is used as the resin (B), as can be seen from a comparison between Example 28 and Example 34, LWR Was smaller and excellent results were obtained.
On the other hand, in Comparative Example 1 described in the Example column of Patent Document 1, the development result was large and the LWR was large. Further, in Comparative Example 3 in which the kind of cation is the same and in Comparative Example 4 in which a predetermined photoacid generator is not used, as in Comparative Example 1, the development result was large and the LWR was large.

Claims (16)

Containing at least two photoacid generators (A) and a resin (B) that decomposes by the action of an acid to increase the solubility in an alkali developer,
The photoacid generator contains at least a photoacid generator represented by general formula (A-1) and a photoacid generator represented by general formula (A-2). Radiation resin composition.

(Formula ^(A-1) A 1 and the general formula in ^(A-2) A 2 in is represented by anionic and general formula represented by the general formula (B-1) (B- 2) It is selected from the group consisting of anions, and at least one of A ¹ and A ² represents an anion represented by the general formula (B-1).
In General Formula (A-1), Z ¹ is any one of the cations represented by General Formulas (C-1) to (C-3), and Z ^{2 in} General Formula (A-2) Is any one of the cations represented by formulas (C-1) to (C-3), and is different from Z ¹ . )

(In General Formula (B-1), Q ¹ and Q ² each independently represent a hydrogen atom, a fluorine atom or an organic group, at least one of which is a fluorine atom or an alkyl substituted with at least one fluorine atom. P represents an integer of 1 to 3. q represents an integer of 2 to 8. R ¹ and R ² each independently represents a hydrogen atom or an organic group, and L ¹ represents a single group. Represents a bond, —O—, —COO—, or OCO—, L ² represents a single bond or a divalent linking group, and Y represents a C 3-18 alicyclic ring which may have a substituent. Represents a hydrocarbon group.
In formula (B-2), Q ^{1 ′} and Q ^{2 ′} each independently represent a hydrogen atom, a fluorine atom or an organic group, and at least one of them is substituted with a fluorine atom or at least one fluorine atom. Represents an alkyl group. p ′ represents an integer of 1 or more. q ′ represents 0 or 1. R ^{1 ′} and R ^{2 ′} each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. L ′ represents a single bond, —O—, —COO—, or OCO—. L ″ represents a single bond or a divalent linking group. Y ′ represents an alicyclic hydrocarbon group or a non-aromatic heterocyclic group.

(In General Formula (C-1), R ^{3 to} R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. Note that at least one of R ^{3 to} R ⁹ is R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, a hydroxyl group, a carboxyl group, a halogen atom or an organic group. Represents an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and any two of R ^{3 to} R ⁷ may be bonded to each other to form a ring, and R ⁸ and R ⁹ , Or, R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.)

(In the general formula (C-2), R ¹² and R ¹³ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. R ¹⁴ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, or a cycloalkyl group. R ¹⁵ represents a group, an alkoxy group, an alkoxycarbonyl group, a group having a monocyclic or polycyclic cycloalkyl skeleton, or an alkylene oxide chain, R ¹⁵ represents a hydroxyl group, a carboxyl group, a halogen atom, or an organic group. And represents an integer of 0 to 2. m15 represents an integer of 0 to 8. R ¹² and R ¹³ may be bonded to each other to form a ring.

(In General Formula (C-3), R ^{16 to} R ¹⁸ each independently represent a hydroxyl group, a carboxyl group, a halogen atom or an organic group. M16 to m18 each independently represents an integer of 0 to 5. Any two of R ^{16 to} R ¹⁸ may be bonded to each other to form a ring.) One of Z ¹ and Z ² is a cation represented by the general formula (C-1) or (C-2), and the other is a cation represented by the general formula (C-3). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1. The general formula (A-1) A ¹ and the general formula in (A-2) A ² in both an anion represented by the formula (B-1), in claim 1 or 2 The actinic ray-sensitive or radiation-sensitive resin composition described.   The actinic ray-sensitive or radiation-sensitive of any one of Claims 1-3 whose total content of the said photoacid generator is 12-30 mass% with respect to the total solid in a composition. Resin composition.   Content of the photo-acid generator which has the cation represented by the said general formula (C-1) or (C-2) is 6-25 mass% with respect to the total solid in a composition, Item 5. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of Items 1 to 4.   The total mass W1 of the photoacid generator having a cation represented by the general formula (C-1) or (C-2), and the photoacid generator having a cation represented by the general formula (C-3) The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-5 whose mixing ratio (W1 / W2) with mass W2 of this is 1.0-9.0.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein p is 1.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein q is 2.   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein Y is a substituted or unsubstituted adamantyl group. L ² is * ¹ -OCO- * ² group (* ¹ in (CR ¹ R ²⁾ coupled with q, * ² bonds to Y in) is, according to any one of claims 1-9 An actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10, wherein L ¹ is a single bond. L ¹ is * ¹ -COO- * ² group (* in ¹ (CQ ¹ Q ²⁾ coupled with p, at * ² (CR ¹ R ²⁾ coupled to q) which is, one of the claims 1 to 10 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1. The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-12 in which the said resin (B) has a repeating unit represented by general formula (nI) or (nII).
(In the general formulas (nI) and (nII), R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, An alkoxycarbonyl group, an alkylcarbonyl group, a group having a lactone structure, or a group having an acid-decomposable group, and X ₁ and X ₂ each independently represents a methylene group, an ethylene group, an oxygen atom, or a sulfur atom; N represents an integer of 0 to 2.) A film forming step of forming a film containing the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 13;
An exposure step of irradiating the film with actinic rays or radiation;
A patterning method comprising: developing a film irradiated with the actinic ray or radiation using a developer.   The pattern forming method according to claim 14, wherein the developing step includes a step of developing with a developer containing an organic solvent. The actinic-ray sensitive or radiation sensitive resin composition of any one of Claims 1-13 used for the pattern formation method including the process of developing with the developing solution containing an organic solvent.