WO2015079814A1

WO2015079814A1 - Active-light-sensitive or radiation-sensitive resin composition, resist film and pattern formation method in which same is used, method for manufacturing electronic device, and electronic device

Info

Publication number: WO2015079814A1
Application number: PCT/JP2014/077238
Authority: WO
Inventors: 北村　哲; 祥平片岡; 渋谷　明規; 啓太加藤
Original assignee: 富士フイルム株式会社
Priority date: 2013-11-26
Filing date: 2014-10-10
Publication date: 2015-06-04
Also published as: TW201520256A; JP6194236B2; JP2015102749A

Abstract

　Provided are an active-light-sensitive or radiation-sensitive resin composition allowing the formation of patterns with a wide exposure latitude and focus depth latitude and low LWR, a resist film and pattern formation method in which said composition is used, a method for manufacturing an electronic device, and an electronic device. The active-light-sensitive or radiation-sensitive resin composition contains the photoacid generator (A) represented by general formula (I), and a resin (B) having a group that is decomposed by the action of an acid and generates a polar group.

Description

Actinic ray-sensitive or radiation-sensitive resin composition, resist film and pattern forming method using the same, electronic device manufacturing method, and electronic device

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the same, and a pattern forming method. More specifically, the present invention relates to an actinic ray used for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a further photofabrication process, a lithographic printing plate, and an acid curable composition. The present invention relates to a photosensitive or radiation-sensitive resin composition, and a resist film and a pattern forming method using the same. The present invention also relates to an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by the method.

The chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and the acid-catalyzed reaction makes the active radiation irradiated and non-irradiated areas soluble in the developer. It is a pattern forming material that changes and forms a pattern on a substrate.

Various compounds have been developed for the photoacid generator that is the main constituent of the chemically amplified resist composition (for example, Patent Documents 1 and 2).

International Publication No. 2013/058250 Special table 2013-520458 gazette

Under these circumstances, the present inventors examined the composition containing the photoacid generator described in Patent Documents 1 and 2, and as a result, exposure latitude (EL) and depth of focus (DOF) latitude were studied. It has become clear that it does not meet the level required recently. Moreover, the pattern formed from the said composition has large LWR (Line Width Roughness), and it became clear that the level currently requested | required is not satisfy | filled.

Accordingly, in view of the above circumstances, the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a large exposure latitude and a depth of focus latitude and a small LWR, and a resist using the same. It is an object to provide a film and pattern forming method, an electronic device manufacturing method, and an electronic device.

As a result of intensive studies on the above problems, the present inventors have used a photoacid generator represented by the general formula (I) to be described later, so that a pattern with large exposure latitude and depth of focus latitude and small LWR is obtained. The inventors have found that can be formed, and have reached the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

1. Actinic ray-sensitive or radiation-sensitive containing a photoacid generator (A) represented by general formula (I) described later and a resin (B) having a group that decomposes by the action of an acid to generate a polar group Resin composition.
2. 2. The actinic ray-sensitive or radiation-sensitive resin composition as described in 1 above, wherein R ₁₅ in formula (I) described later is a substituted or unsubstituted adamantyl group.
3. 3. The actinic ray-sensitive or radiation-sensitive resin composition according to the above 1 or 2, wherein at least one of R ₁₁ to R ₁₄ in the general formula (I) described later is a substituted or unsubstituted alkyl group.
4). 4. The actinic ray-sensitive or radiation-sensitive resin according to any one of 1 to 3 above, wherein at least one of R ₁₁ to R ₁₄ in the general formula (I) described later is a substituted or unsubstituted cyclic alkyl group. Composition.
5. 5. The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 4 above, wherein the photoacid generator (A) is a compound represented by the general formula (ZI-4) described later.
6). 6. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 5 above, wherein the photoacid generator (A) is a compound represented by the general formula (ZI-3) described later.
7). The actinic ray-sensitive or radiation-sensitive material according to any one of 1 to 6 above, which comprises two or more photoacid generators, wherein at least one of the photoacid generators is the photoacid generator (A). Resin composition.
8). 8. The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of 1 to 7 above, which comprises two or more photoacid generators (A) having different A ⁺ in the general formula (I) .
9. 9. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 8 above, which is a negative resist composition for organic solvent development.
10. 10. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 9 above.
11.
(1) forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 9 above,
(2) exposing the film, and
(3) developing the exposed film,
A pattern forming method including:
12 12. The pattern forming method as described in 11 above, wherein the exposure is immersion exposure.
13. 13. The pattern forming method as described in 11 or 12 above, wherein the step (3) is a step of developing the exposed film using a developer containing an organic solvent.
14 14. An electronic device manufacturing method including the pattern forming method according to any one of 11 to 13 above.
15. 15. An electronic device manufactured by the method for manufacturing an electronic device according to 14 above.

As shown below, according to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a large exposure latitude and a focal depth latitude and a small LWR, and a resist using the same A film and pattern formation method, an electronic device manufacturing method, and an electronic device can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, 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) and the like. . In the present invention, light means actinic rays or radiation.
In addition, the term “exposure” in this specification means not only exposure with far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also electron beams, ion beams, etc. Drawing with particle beams is also included in the exposure.

In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, (meth) acrylate represents acrylate and methacrylate, and (meth) acryl represents acryl and methacryl.

[Actinic ray-sensitive or radiation-sensitive resin composition]
A feature of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as the composition of the present invention) is that it contains a photoacid generator containing a specific anion.
As shown in the general formula (I) described later, the anion in the photoacid generator contained in the composition of the present invention may have a carbon atom and a hetero atom to which a fluorine atom as an electron-withdrawing group is bonded. It has a structure in which a good alicyclic group is connected by a single bond or a carbon atom, and only in an oxygen atom such as an ether bond (—O—) in the main chain skeleton between the carbon atom and the alicyclic group. Has no bonds. For this reason, it is considered that the stability of the acid generated by light absorption is high, and as a result, the exposure latitude and the focal depth latitude are increased, and the LWR of the formed pattern is decreased. As shown in a comparative example to be described later, when the main chain skeleton between the carbon atom and the alicyclic group has a bond only with an oxygen atom (Comparative Examples 1 to 4), exposure latitude and This is also inferred from the fact that the depth of focus latitude decreases and the LWR of the pattern to be formed increases.

Hereinafter, the photoacid generator (A) and the resin (B) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and optional components that may be contained will be described.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably for ArF exposure, and more preferably for ArF immersion exposure.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may be a negative resist composition for organic solvent development or a positive resist composition for alkali development, but for organic solvent development. The negative resist composition is preferable. The composition according to the present invention is typically a chemically amplified resist composition.

<Photoacid generator (A)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a photoacid generator (A) represented by the following general formula (I).

(Anion)
In general formula (I), R ₁₁ to R ₁₄ each independently represents a hydrogen atom or a substituent.
For the reason that the exposure latitude becomes larger, at least one of R ₁₁ to R ₁₄ is preferably a substituent.

Although it is not particularly limited as a substituent, for example, a halogen atom, hydroxy group, nitro group, carboxy group, alkoxy group, amino group, mercapto group, acyl group, imide group, phosphino group, phosphinyl group, silyl group, heteroatom The hydrocarbon group etc. which may have are mentioned.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Examples of the hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
Examples of the hydrocarbon group of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
The aliphatic hydrocarbon group may be linear, branched, cyclic, or a group obtained by combining these. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly having 1 to 20 carbon atoms), a linear or branched alkenyl group (particularly having 2 to 20 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly having 2 to 20 carbon atoms).
Examples of the aromatic hydrocarbon group include an aryl group and a naphthyl group. Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group.

The above substituent is preferably a substituted or unsubstituted alkyl group (particularly, having 1 to 20 carbon atoms). Among them, a substituted or unsubstituted cyclic alkyl group (particularly, for the reason that exposure latitude becomes larger) Preferably, it has 3 to 20 carbon atoms. Examples of the substituted or unsubstituted cyclic alkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an isobornyl group, an adamantyl group, and the like.

In the general formula (I), R ₁₅ represents an alicyclic group (alicyclic hydrocarbon group) which may have a substituted or unsubstituted heteroatom.
Specific examples of the hetero atom are as described above. Of these, an oxygen atom is preferable.
The alicyclic group which may have a hetero atom is not particularly limited, and may be a monocyclic (monocyclic alicyclic group) or a polycyclic (polycyclic alicyclic group).
The number of carbon atoms of the alicyclic group which may have a hetero atom is not particularly limited, but is preferably 3 to 20.
Specific examples of the structure of the ring portion of the alicyclic group are shown below.

Specific examples of the alicyclic group which may have a hetero atom include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, And polycyclic cycloalkyl groups such as a tetracyclododecanyl group and an adamantyl group. In addition, these groups may be substituted with a group represented by —O—, a group represented by —COO—, a group represented by —S—, or a group represented by —SO ₂ —. Specifically, for example, cyclohexyloxy group, adamantyloxy group, 1-adamantylmethyl group, 1-adamantylethyl group, 1-adamantylmethoxy group, 1-adamantylethoxy group, cyclohexylcarbonyloxy group, 1-adamantylcarbonyloxy Group, 1-adamantylmethyloxycarbonyl group, cyclohexyloxycarbonyl group, adamantanethio group, cyclohexylthio group, tetrahydrofurfuryl group and the like.
The alicyclic group which may have a hetero atom is preferably a polycyclic (polycyclic alicyclic group), and more preferably a substituted or unsubstituted adamantyl group.
The substituent in the case where the alicyclic group which may have a hetero atom has a substituent is not particularly limited, but specific examples thereof are the same as those of R ₁₁ to R ₁₄ described above.

R ₁₅ is preferably an alicyclic group having no hetero atom because the depth of focus latitude becomes larger.

In general formula (I), n1 and n2 each independently represents an integer of 0 to 5.
In general formula (I), n3 represents 0 or 1. Among these, 0 is preferable because the depth of focus latitude becomes larger.
When n1 is an integer of 2 or more, the plurality of R ₁₁ and the plurality of R ₁₂ may be the same or different. When n2 is an integer of 2 or more, the plurality of R ₁₃ and the plurality of R ₁₄ may be the same or different.

R ₁₁ to R ₁₄ may be bonded to each other to form a ring. When n1 is an integer of 2 or more, a plurality of R _{11 s} and a plurality of R _{12 s} may be bonded to each other to form a ring. When n2 is an integer of 2 or more, a plurality of R _{13 s} and a plurality of R _{14 s} may be bonded to each other to form a ring.

For the reason that the exposure latitude becomes larger, it is preferable that R ₁₁ and R ₁₂ are bonded to each other to form a ring and / or R ₁₃ and R ₁₄ are bonded to each other to form a ring. The ring formed is not particularly limited, but is preferably a cycloalkyl ring (particularly having 3 to 20 carbon atoms).

Specific examples of the anion of the photoacid generator (A) are shown below.

(Cation)
In the general formula (I), A ⁺ represents a monovalent cation.
A ⁺ is not particularly limited as long as it is a monovalent cation, and a preferable embodiment includes, for example, a cation (part other than Z ⁻ ) in the general formula (ZI) or (ZII) described later.

(Preferred embodiment)
As a suitable aspect of a photo-acid generator (A), the compound represented by the following general formula (ZI) or (ZII) is mentioned, for example.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Further, two members out of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). To 15 are preferred).
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl group, alkyl group and cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.
Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as Formulas (I-1) to (I-70) in Patent Application Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in US Patent Application Publication No. 2003 / 0077540A1 And cation structures such as compounds exemplified as formulas (IA-54) and formulas (IB-1) to (IB-24).

Z ⁻ represents an anion in the general formula (I), and specifically represents the following anion.

More preferred examples of the compound represented by the general formula (ZI) include compounds represented by the following general formula (ZI-3) or (ZI-4). First, the compound represented by formula (ZI-3) will be described.

In general formula (ZI-3),
R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₁ and R ₂ , R ₂ and R ₃ may be connected to each other to form a ring.
R _X and R _y 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. To express.
R _X and R _y may be connected to each other to form a ring. The ring formed may have an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
Z ⁻ represents an anion in the general formula (I), specifically as described above.

The alkyl group as R ₁ 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 branched alkyl groups such as a linear alkyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group. The alkyl group for R ₁ 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. Can be mentioned.

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, may contain 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 as R ₁ may have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.

The alkoxy group as R ₁ 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 as R ₁ may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

The cycloalkoxy group as R ₁ is preferably a cycloalkoxy group having 3 to 20 carbon atoms, and examples thereof include a cyclohexyloxy group, a norbornyloxy group, and an adamantyloxy group. The cycloalkoxy group as R ₁ may have a substituent, and examples of the substituent include an alkyl group and a cycloalkyl group.

The aryl group as R ₁ 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 of R ₁ 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. When the substituent is an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, the same groups as the alkyl group, cycloalkyl group, alkoxy group and cycloalkoxy group as R ₁ described above can be used.

Examples of the alkenyl group as R ₁ include a vinyl group and an allyl group.

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₂ and R ₃ may be connected to each other to form a ring. However, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₂ and R ₃ are the same as the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are connected to each other to form a ring, the total number of carbon atoms contributing to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, and 4 or 5 It is particularly preferred that

R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are connected to each other to form a ring, R ₁ is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ has 1 to 4 carbon atoms. An alkylene group (preferably a methylene group or an ethylene group) is preferable, and examples of the preferable substituent include the same substituents that the aryl group as R ₁ may have. As another form when R ₁ and R ₂ are connected to each other to form a ring, it is also preferable that R ₁ is a vinyl group and R ₂ is an alkylene group having 1 to 4 carbon atoms.

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

The alkenyl group represented by R _X and R _y 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 _X and R _y , 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 phenalenyl 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.

As the alkyl group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.

The cycloalkyl moiety of the 2-oxocycloalkyl group and alkoxycarbonyl cycloalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.

Preferred examples of the compound represented by the general formula (ZI-3) include compounds represented by the following general formulas (ZI-3a) and (ZI-3b).

In the general formulas (ZI-3a) and (ZI-3b), R ₁ , R ₂ and R ₃ are as defined in the general formula (ZI-3).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m, n, p and q 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 ₅ 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 ₅ 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. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R include those similar to the specific examples and preferred examples described above for R ₁ in formula (ZI-3).
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 (ZI-3a).

When Y is a nitrogen atom, R ₅ is particularly preferably a group represented by —SO ₂ —R ₄ . R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₄ include those similar to the specific examples and preferred examples described above for R ₁ .

Z ⁻ represents an anion in the general formula (I), specifically as described above.

The compound represented by the general formula (ZI-3) is particularly preferably a compound represented by the following general formulas (ZI-3a ′) and (ZI-3b ′).

In the general formulas (ZI-3a ′) and (ZI-3b ′), R ₁ , R ₂ , R ₃ , Y and R ₅ are as defined in the general formulas (ZI-3a) and (ZI-3b). It is.

Specific examples of the cation moiety of the compound represented by the general formula (ZI-3) are given below.

Next, the compound represented by formula (ZI-4) will be described.

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, or an optionally substituted hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, or cycloalkyl group.
R ₁₄ represents a hydroxyl group or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylsulfonyl group, cycloalkylsulfonyl group, or cycloalkyl group. To express.
R ₁₅ represents an alkyl group, a cycloalkyl group, or a naphthyl group, which may have a substituent. Two R ₁₅ may be the same or different. Two R ₁₅ may be bonded to each other to form a ring. The ring formed may have a heteroatom.
l represents an integer of 0-2.
r represents an integer of 0 to 8. When r is an integer of 2 or more, a plurality of R ₁₄ may be the same or different.
Z ⁻ represents an anion in the general formula (I), specifically as described above.

In general formula (ZI-4), the alkyl groups represented by R ₁₃ , R _14, and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.
Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy group of R ₁₃ and R _14, may be linear or branched, preferably from 1 to 10 carbon atoms.
The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms.
Examples of the group having a cycloalkyl group as R ₁₃ and R ₁₄ include groups having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
The alkyl group of the alkyl group of R _14, include the same specific examples and the alkyl group as R ₁₃ ~ R ₁₅ described above.
The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ 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.

As the ring structure formed by bonding two R ₁₅ to each other, for example, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4), particularly preferable Includes 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 divalent R ₁₅ 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. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. A divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
r is preferably from 0 to 2.

Specific examples of the cation structure possessed by the compound represented by the general formula (ZI-3) or (ZI-4) described above include the above-mentioned JP-A-2004-233661, JP-A-2003-35948, In addition to cationic structures such as compounds exemplified in US Patent Application Publication No. 2003 / 0224288A1 and US Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046 and 0047 of JP2011-53360A Cation structures in chemical structures and the like exemplified in 0072-0077 and 0107-0110, and cation structures in chemical structures exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of JP2011-53430, etc. Is mentioned.

Next, the compound represented by the general formula (ZII) will be described.
In the general formula (ZII),
_R204 and _R205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ are the same as the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above general formula (ZI).
Aryl groups R ₂₀₄ and R _205, an alkyl group, a cycloalkyl group may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ in the general formula (ZI) may have.

The aryl group for R ₂₀₄ and R ₂₀₅ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group for R ₂₀₄ and R ₂₀₅ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

As the alkyl group and cycloalkyl group represented by R ₂₀₄ and R ₂₀₅ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
Z ⁻ represents an anion in the general formula (I), specifically as described above.
Specific examples of the cation represented by the general formula (ZII) are shown below.

In the composition of the present invention, the content of the photoacid generator (A) is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 3 to 25% by mass, based on the total solid content of the composition. %, More preferably 7 to 20% by mass.

Moreover, the composition of this invention may contain 2 or more types of photo-acid generators (A), and in addition to a photo-acid generator (A), photo-acid generators other than a photo-acid generator (A) ( Hereinafter, it may also contain a photoacid generator (A ′). When the composition of this invention contains 2 or more types of photo-acid generators, it is preferable that the total content of a photo-acid generator exists in the said range.

As the photoacid generator (A ′), a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, an actinic ray used for a micro resist, etc. Alternatively, known compounds that generate an acid upon irradiation with radiation and a mixture thereof can be appropriately selected and used.

Examples of the photoacid generator (A ′) include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, The compounds described in JP-A-62-153853 and JP-A-63-146029 can be used.

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.

As a preferable photoacid generator (A ′), the description in paragraphs <0337> to <0400> of US2012 / 0076996A1 can be referred to, and the contents thereof are incorporated in the present specification.

The composition of the present invention preferably contains two or more photoacid generators. Here, it is preferable that at least one of the photoacid generators is the photoacid generator (A) described above, and two or more are the photoacid generators (A) described above.
The composition of the present invention preferably contains two or more photoacid generators (A) in which A ⁺ in the general formula (I) is different from each other because the LWR of the pattern to be formed is smaller. .

<Resin (B)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention can take the form of positive and negative actinic ray-sensitive or radiation-sensitive resin compositions. The resin (B) contained in the composition of the present invention is a resin having a group that decomposes by the action of an acid to generate a polar group (hereinafter sometimes referred to as “acid-decomposable resin”). In this case, the resin (B) is a group that decomposes into the main chain or side chain, or both of the main chain and side chain by the action of an acid to generate a polar group (hereinafter also referred to as “acid-decomposable group”). Have The resin (B) preferably contains a repeating unit having an acid-decomposable group.

(1) Repeating unit having an acid-decomposable group The acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid.
Preferred examples of the polar group include a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.
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 capable of 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, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
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).
At least two of Rx ₁ to Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

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 or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx ₁ to Rx ₃ is preferably a linear or branched group having 1 to 4 carbon atoms.
The cycloalkyl group represented by Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms.
The cycloalkyl group formed by combining at least two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-described cycloalkyl group is preferred.

The content of the repeating unit having an acid-decomposable group is preferably 10 to 70 mol%, more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%, most preferably based on all repeating units in the resin (B). Is 45 to 55 mol%.

Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this. In the formula, Xa ₁ represents any of H, CH ₃ , CF ₃ , and CH ₂ OH, and Rxa and Rxb each represents a linear or branched alkyl group having 1 to 4 carbon atoms.

The resin (B) is more preferably a resin having a repeating unit represented by the following general formula (1) as a repeating unit represented by the general formula (AI).

In general formula (1),
R ₃₁ represents a hydrogen atom, an alkyl group or a fluorinated alkyl group,
R ₃₂ represents a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group;
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded.
In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.

The alkyl group for R ₃₁ may have a substituent, and examples thereof include a fluorine atom and a hydroxyl group.
R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₃₂ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.
The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom that can substitute a part of the carbon atoms constituting the ring include an oxygen atom and a sulfur atom. Examples of the carbonyl group include a carbonyl group. However, the group having a hetero atom is preferably not an ester group (ester bond).
The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.

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

In general formula (1 ′), R ₃₁ and R ₃₂ have the same meanings as in general formula (1).

Specific examples of the repeating unit having the structure represented by the general formula (1) are listed below, but are not limited thereto.

The content of the repeating unit having an acid-decomposable group is preferably 10 to 80 mol%, more preferably 25 to 70 mol%, more preferably 30 to 30 mol% based on all repeating units in the resin (B). More preferably, it is 60 mol%.

The repeating unit having an acid-decomposable group contained in the resin (B) may be one type, or two or more types may be used in combination. As the combination in the case of using together, the following are preferable. As specific structures, the following combinations are preferable. In the following formula, each R independently represents a hydrogen atom or a methyl group.

(2) A repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group The resin (B) is further at least one selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group. It is preferable to have a repeating unit having a kind of group.

The repeating unit having a lactone group that can be contained in the resin (B) will be described.
Any lactone group can be used as long as it has a lactone structure, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is formed in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17). By using this lactone structure, development defects are improved.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. 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. .

Examples of the repeating unit having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AII).

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Preferably, it is a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

The content of the repeating unit having a lactone group is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from 30 to 50 mol%, based on all repeating units in the resin (B).

Specific examples of the repeating unit having a lactone group are listed below, but the present invention is not limited thereto.

Particularly preferred repeating units having a lactone group include the following repeating units. By selecting an optimal lactone group, the pattern profile and the density dependence become good.

The resin (B) preferably has a repeating unit other than the general formulas (AI) and (AII) having a hydroxyl group or a cyano group. 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. Examples of the repeating unit having these structures include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the 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 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. More preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 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 are listed below, but the present invention is not limited thereto.

Resin (B) preferably has a repeating unit having an acid group. Examples of the acid group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (for example, hexafluoroisopropanol group) substituted with an electron-withdrawing group at the α-position, and has a carboxy group. It is more preferable to have a repeating unit. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group 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 an acid group in the main chain of the resin through a linking group. Either a repeating unit bonded, or a polymerization initiator or chain transfer agent having an acid group is introduced at the end of the polymer chain at the time of polymerization, both of which are preferable, and the linking group is a monocyclic or polycyclic hydrocarbon structure You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The content of the repeating unit having an acid group is preferably from 0 to 20 mol%, more preferably from 3 to 15 mol%, still more preferably from 5 to 10 mol%, based on all repeating units in the resin (B).

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group and an acid group is more preferably a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group and an acid group. Preferably, it is a repeating unit having a cyano group and a lactone group. Particularly preferred is a repeating unit having a structure in which a cyano group is substituted on the lactone structure of (LC1-4).

(3) Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability The resin (B) may further have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. . This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. Examples of such repeating units include repeating units of 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and cyclohexyl (meth) acrylate.

(4) Repeating unit having neither a hydroxyl group nor a cyano group The resin (B) of the present invention further contains a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group. It is preferable.

In general formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. As the bridged cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic ring Examples include hydrocarbon rings. The bridged cyclic hydrocarbon ring also includes, for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5.2.1.0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferable acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The content of the repeating unit represented by the general formula (III) having neither a hydroxyl group nor a cyano group is preferably 0 to 40 mol%, more preferably based on all repeating units in the resin (B). 0 to 20 mol%.
Specific examples of the repeating unit represented by the general formula (III) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

Resin (B) may contain 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. A tertiary alkyl ester group represented by —C (═O) —O—R ₀ is preferred.
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, alkoxymethyl group such as 1-methoxymethyl group and 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- Examples thereof include an oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue, and the like.
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 represents a hydrogen atom or an organic group (preferably an acid-decomposable protective 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. Of these, repeating units represented by (II-f-16) to (II-f-19) are preferred.

Resin (B) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required properties 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), in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

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 for ArF exposure, the resin (B) preferably has no aromatic group from the viewpoint of transparency to ArF light. Moreover, 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.

Resin (B) 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. More preferably, 20-50 mol% of (meth) acrylate-based repeating units having an acid-decomposable group represented by general formula (AI), 20-50 mol% of (meth) acrylate-based repeating units having a lactone group, A copolymer having 5 to 30 mol% of (meth) acrylate repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and further containing 0 to 20 mol% of other (meth) acrylate repeating units. .

When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (B) is represented by the general formula (AI). In addition to the repeating unit, it is preferable to further have a hydroxystyrene-based repeating unit. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

Preferred examples of the repeating unit having an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester repeating units, and the like. 2-alkyl- More preferred are repeating units of 2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

The resin (B) 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 the polymerization is performed by heating, 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. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.

The weight average molecular weight of the resin (B) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, and even more preferably from 3,000 to 15 in terms of polystyrene by GPC method. 1,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin were measured by GPC (solvent: tetrahydrofuran, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40). (° C., flow rate: 1.0 mL / min, detector: RI).

The degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. The smaller the molecular weight distribution, the better the resolution and resist shape.

In the composition of the present invention, the blending amount of the resin (B) in the whole composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In the present invention, the resin (B) may be used alone or in combination.

Specific examples of the resin (B) are shown below, but the present invention is not limited thereto.

<Hydrophobic resin (HR)>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention, particularly when applied to immersion exposure, is a hydrophobic resin having at least one of a fluorine atom and a silicon atom (hereinafter referred to as “hydrophobic resin (HR)”). May also be included). As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, 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.
Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

The hydrophobic resin typically contains a fluorine atom and / or a silicon atom. The fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, it may be 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. preferable.
The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.
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 another substituent.
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 the aryl group may further have another substituent.
As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R ₅₇ to R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). Provided that 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 a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (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 a fluoroalkyl group (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. When R ₆₂ and R ₆₃ are perfluoroalkyl groups, R ₆₄ is preferably a hydrogen atom. 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 trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
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 can be mentioned, and —C (CF ₃ ) ₂ OH is preferable.
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.
Suitable examples of the repeating unit having a fluorine atom include those shown below.

In formulas (C-Ia) to (C-Id), R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
W ₃ to W ₆ each independently represents an organic group containing at least one fluorine atom. Specifically, the atomic groups of (F2) to (F4) are mentioned.
In addition to these, the hydrophobic resin may have a unit as shown below as a repeating unit having a fluorine atom.

In formulas (C-II) and (C-III), R ₄ to R ₇ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
However, at least one of R ₄ to R ₇ represents a fluorine atom. R ₄ and R _5, or R ₆ and R ₇ may form a ring.
W ₂ represents an organic group containing at least one fluorine atom. Specifically, the atomic groups of (F2) to (F4) are mentioned.
L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-(Wherein R represents a hydrogen atom or an alkyl group), —NHSO ₂ —, or a divalent linking group formed by combining a plurality of these.
Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and may be bridged in the case of polycyclic. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopentane structure, a cyclohexane structure, a cyclobutane structure, and a cyclooctane structure. Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkane structure having 6 to 20 carbon atoms is preferable. For example, an adamantane structure, norbornene structure, dicyclopentane A structure, a tricyclodecane structure, a tetracyclododecane structure, etc. can be mentioned. Note that at least one carbon atom in the cycloalkane structure may be substituted with a heteroatom such as an oxygen atom. Particularly preferable examples of Q include a norbornene structure, a tricyclodecane structure, a tetracyclododecane structure, and the like.
The hydrophobic resin may contain a silicon atom.
The partial structure having a silicon atom preferably has 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 to L _{5 each} represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, or a group of two or more groups selected from the group consisting of a ureylene bond. A combination is mentioned.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.
The repeating unit having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate-based repeating unit.
Hereinafter, although the specific example of the repeating unit which has at least any one of a fluorine atom and a silicon atom is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

The hydrophobic resin preferably has a repeating unit (b) having at least one group selected from the group consisting of the following (x) to (z).
(X) Alkali-soluble group (y) A group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (hereinafter also referred to as a polar conversion group).
(Z) A group that decomposes by the action of an acid to increase the solubility in an alkali developer. Examples of the repeating unit (b) include the following types.
A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of the above (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) and different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
It is more preferable that the hydrophobic resin has a repeating unit (b ′) as the repeating unit (b). That is, it is more preferable that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has at least one of a fluorine atom and a silicon atom.
When the hydrophobic resin has a repeating unit (b *), a repeating unit having at least one of a fluorine atom and a silicon atom (a repeating unit different from the above repeating units (b ′) and (b ″)) In addition, in the repeating unit (b ″), a side chain having at least one group selected from the group consisting of (x) to (z) above and at least one of a fluorine atom and a silicon atom Are preferably bonded to the same carbon atom in the main chain, that is, in a positional relationship as shown in the following formula (K1).
In the formula (K1), B1 represents a partial structure having at least one group selected from the group consisting of the above (x) to (z), and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

The group selected from the group consisting of (x) to (z) is preferably (x) an alkali-soluble group or (y) a polar conversion group, and more preferably (y) a polar conversion group.
Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.
Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonimide groups, and bis (carbonyl) methylene groups.
As the repeating unit (bx) having an alkali-soluble group (x), a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a linking group is used. Examples include a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain, Either case is preferred.
When the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (bx) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the above general formulas (CS-1) to (CS-3) can be exemplified.
The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 20 mol% based on all repeating units in the hydrophobic resin. %.
Specific examples of the repeating unit (bx) having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), Carboxylic acid thioester group (—COS—), carbonic acid ester group (—OC (O) O—), sulfuric acid ester group (—OSO ₂ O—), sulfonic acid ester group (—SO ₂ O—) and the like A lactone group is preferred.
The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.
Specific examples of the repeating unit (by) having a polarity converting group (y) include repeating units having a lactone structure represented by the following formulas (KA-1-1) to (KA-1-17). Can do.
Further, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′), (b ″) corresponds to the above repeating unit (b ′)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.
As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a group containing a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.
The polarity converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer as described above. The polar converting group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.
The repeating unit (by) has a group having a partial structure represented by the general formula (KA-1) or (KB-1), thereby increasing the solubility in a preferable alkaline developer. Are bonded to each other as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent When it does not have a hand, the group having the partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure.
The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the hydrophobic resin through a substituent at an arbitrary position.
The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure together with the group as X.
X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .
Z _ka1 independently represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group.
Z _ka1 may be linked to form a ring. Examples of the ring formed by linking Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (such as a cyclic ether ring and a lactone ring).
nka represents an integer of 0 to 10. It is preferably an integer of 0 to 8, more preferably an integer of 0 to 5, further preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.
The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described above. The electron withdrawing group may be substituted with another electron withdrawing group.
Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable.

As in the case of the resin (B) described above, the hydrophobic resin is naturally low in impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0. More preferably, it is ˜5% by mass and 0 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 3, more preferably 1 to 2, still more preferably 1 to 1, in terms of resolution, resist shape, resist pattern side walls, and the like. 1.8, most preferably in the range of 1 to 1.5.
As the hydrophobic resin, various commercially available products can be used, and 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 the polymerization is performed by heating, 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) described above.
Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of repeating units in each resin (the positional relationship of each repeating unit in each resin shown in the specific example corresponds to the positional relationship of the composition ratio numbers in Table 1), weight average Indicates molecular weight and degree of dispersion.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an actinic ray-sensitive or radiation-sensitive resin composition by containing a hydrophobic hydrophobic resin containing at least one of a fluorine atom and a silicon atom. When the hydrophobic resin is unevenly distributed in the surface layer of the film formed from the material and the immersion medium is water, the receding contact angle of the film surface after baking to water and before exposure is improved, and the immersion liquid followability is improved. Can be made.
After the coating film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is baked and before exposure, the receding contact angle of the film is the temperature at the time of exposure, usually room temperature 23 ± 3 ° C., humidity 45 ± 5%. The angle is preferably 60 ° to 90 °, more preferably 65 ° or more, further preferably 70 ° or more, and particularly preferably 75 ° or more.
The hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It does not have to be.
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 to form the exposure pattern. The contact angle of the immersion liquid with respect to the resist film in the resist film becomes important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
Hydrophobic resins are hydrophobic, so that development residues (scum) and BLOB defects are likely to deteriorate after alkali development, but they have three or more polymer chains via at least one branch, compared to linear resins. Further, since the alkali dissolution rate is improved, development residue (scum) and BLOB defect performance are improved.
When the hydrophobic resin has fluorine atoms, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the hydrophobic resin. Further, the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units in the hydrophobic resin.
When the hydrophobic resin has a silicon atom, the content of silicon atom is preferably 2 to 50% by mass, more preferably 2 to 30% by mass with respect to the molecular weight of the hydrophobic resin. Further, the repeating unit containing a silicon atom is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, based on all repeating units of the hydrophobic resin.
The weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).
The content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray or radiation-sensitive resin film falls within the above range. Is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the total solid content of the light-sensitive or radiation-sensitive resin composition. Particularly preferred is 0.2 to 8% by mass.
Hydrophobic resins can be used alone or in combination of two or more.

<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 during exposure and suppresses the reaction of the acid-decomposable resin (resin (B)) in the unexposed area due to excess generated acid. To do. 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 decreases or disappears upon irradiation with actinic rays or radiation, or An onium salt that is a weak acid relative to the photoacid generator can be used.

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

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

Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
Specific examples of preferred compounds include those exemplified in US2012 / 0219913A1 <0379>.
Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

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

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

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

As basic compounds, in addition to the above-mentioned compounds, JP2011-22560A [0180] to [0225], JP2012-137735A [0218] to [0219], International Publication Pamphlet WO2011 / 158687A1 [ [0416] to [0438] 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 0.001 to 10% by mass based on the solid content of the composition, The content is preferably 0.01 to 5% by mass.
The photoacid generator (in the case of containing the photoacid generator (A ′), the content of the photoacid generator (A ′) is included) and the basic compound in the composition of the photoacid generator It is preferable that the agent / basic compound (molar ratio) = 2.5 to 300. In other words, 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 the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

A low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (C)”) is an amine derivative having a group on the nitrogen atom that is leaving by the action of an acid. It is preferable that
As the group capable of leaving by the action of an acid, 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. .
The molecular weight of the compound (C) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
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),
R _b 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 having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b 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. May be. The same applies to the alkoxyalkyl group represented by R _b .

R _b 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 R _b 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 structures disclosed in US2012 / 0135348 A1 <0466>, but are not limited thereto.

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

In the general formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a 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.
R _b has the same meaning as R _b 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), an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group as R _a are groups in which the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b may be substituted. It may be substituted with a group similar to the group described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) , R _b includes the same groups as the specific examples described above.
A particularly preferred compound (C) in the present invention is specifically shown, but the present invention is not limited thereto.

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.
The content of the compound (C) in the composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, further based on the total solid content of the composition. Preferably, the content is 0.01 to 5% by mass.

A basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (PA)”) has a proton acceptor functional group and is irradiated with actinic rays or radiation. Is a compound whose proton acceptor properties are degraded, disappeared, or changed from proton acceptor properties to acidic properties.

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

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

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

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

In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

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

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

In general formula (PA-1),
Q represents —SO ₃ H, —CO ₂ H, or —W ₁ NHW ₂ R _f . Here, R _f represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and W ₁ and W ₂ each independently represents —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or —N (R _x ) R _y —. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or may be bonded to R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

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

The monovalent organic group for R _x is preferably an organic group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.
The alkyl group in R _x may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. It may be.
The cycloalkyl group in R _x may have a substituent, and is preferably a monocyclic cycloalkyl group or a polycyclic cycloalkyl group having 3 to 20 carbon atoms, and an oxygen atom, a sulfur atom, It may have a nitrogen atom.
The aryl group in R _x may have a substituent, and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
The aralkyl group in R _x may have a substituent, and preferably has 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
The alkenyl group for R _x may have a substituent, may be linear, or may be branched. The alkenyl group preferably has 3 to 20 carbon atoms. Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups.

Examples of the substituent when R _x further has a substituent include a halogen atom, a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, Examples include carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, nitro group, hydrazino group, and heterocyclic group.

Preferred _examples of the divalent organic group for R _y include an alkylene group.
Examples of the ring structure that R _x and R _y may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

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

An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group containing a proton acceptor functional group or an ammonium group in R are the above R _{The same} as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned as _x .

When B is —N (R _x ) R _y —, R and R _x are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures.

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

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

In the general formulas (4) to (6), A, X, n, B, R, R _f , W ₁ and W ₂ have the same meanings as in the general formula (PA-1).
C ⁺ represents a counter cation.
The counter cation is preferably an onium cation. More specifically, the sulfonium cation described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in the general formula (ZI) described above, I ⁺ (R ₂₀₄ ) (R ₂₀₅ ) in the general formula (ZII) As a preferable example, an iodonium cation described as
Specific examples of the compound (PA) include compounds exemplified in US2011 / 0269072A1 <0280>.

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

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

Specific examples of the proton acceptor functional group R _N has the previously described formula (PA-1)
It is the same as the proton acceptor functional group described in 1.
Specific examples of the ionic compound having a proton acceptor site in the cation moiety include compounds exemplified in US2011 / 0269072A1 <0291>.
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.
The content of the compound (PA) is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content of the composition.

In the composition of the present invention, an onium salt that becomes a weak acid relative to the photoacid generator can be used as an acid diffusion control agent.
When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator are mixed and used, the photoacid generator is generated by irradiation with actinic rays or radiation. When the acid 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 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 (provided that the carbon adjacent to S R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently a sulfonium or iodonium cation.

Preferable examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation in the general formula (ZI) described above and the iodonium cation in the general formula (ZII) described above.

Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures 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 structures 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 (C) having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (Hereinafter also referred to as “onium salt (C)”).
The onium salt (C) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
-X ^- it is, ^-COO ^-, -SO ₃ - represents an anion portion selected from _{^{_{-R 4 -, -SO 2 -,}}} -N. R ₄ is a group having a carbonyl group: —C (═O) —, a sulfonyl group: —S (═O) ₂ —, and a sulfinyl group: —S (═O) — at the site of connection with the adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In (C-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.

The content of the onium salt that is a weak acid relative to the photoacid generator is preferably 0.5 to 10.0% by mass, based on the solid content of the composition, and preferably 0.5 to 8.0. The content is more preferably mass%, and further preferably 1.0 to 8.0 mass%.

<Solvent>
Solvents that can be used in preparing the composition of the present invention by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate. And organic solvents such as cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates. it can.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid Examples include -2- (2-ethoxyethoxy) ethyl and propylene carbonate.
In the present invention, the above solvents may be used alone or in combination of two or more.

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.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. 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, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are 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 is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate. A mixed solvent containing at least propylene glycol monomethyl ether acetate and cyclohexanone, or a mixed solvent containing at least propylene glycol monomethyl ether acetate and γ-butyrolactone is more preferable. A mixed solvent containing at least three kinds of propylene glycol monomethyl ether acetate, cyclohexanone and γ-butyrolactone is particularly preferable.

<Surfactant>
The composition of the present invention may further contain a surfactant. When it contains, it contains either fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, surfactant having both fluorine atom and silicon atom), or two or more kinds It is preferable to do.

When the composition of the present invention contains the above-described 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. It becomes.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in <0276> of US Patent Application Publication No. 2008/0248425, such as F-top EF301 and EF303 (Shin-Akita Kasei Co., Ltd.). ), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF 22B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G, 204G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), an acrylate having a C ₆ F ₁₃ group (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than the 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.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content (total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %, Particularly preferably 0.0005 to 1% by mass.

<Dissolution-inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer>
As a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution inhibiting compound”), which is decomposed by the action of an acid to increase the solubility in an alkaline developer, it does not decrease the permeability of 220 nm or less. Of these, alicyclic or aliphatic compounds containing an acid-decomposable group are preferred, such as cholic acid derivatives containing an acid-decomposable group described in OF SPIE, 2724, 355 (1996). Examples of the acid-decomposable group and alicyclic structure are the same as those described for the resin (B).

When the composition of the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the dissolution inhibiting compound contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. preferable. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the composition.

Specific examples of dissolution inhibiting compounds are shown below, but the present invention is not limited to these.

<Other additives>
If necessary, the composition of the present invention further contains a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, a carboxyl group). Alicyclic or aliphatic compound) or the like.

Such a phenol compound 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.

[Pattern formation method]
Next, the pattern forming method of the present invention will be described.
The pattern forming method of the present invention comprises:
(1) A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition (film formation),
(2) exposing the film, and
(3) developing the exposed film,
At least.

The exposure in the step (2) may be immersion exposure.
The pattern forming method of the present invention preferably includes (4) a heating step after (2) the exposure step.
The pattern formation method of this invention may include the (2) exposure process in multiple times.
The pattern formation method of this invention may include the (4) heating process in multiple times.

The resist film of the present invention is formed using the above-described actinic ray-sensitive or radiation-sensitive resin composition of the present invention. More specifically, the resist film of the present invention is applied to a substrate. Or it is preferable that it is a film | membrane formed by apply | coating a radiation sensitive resin composition. In the pattern forming method of the present invention, the step of forming a film (resist film) 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.

Also, 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.

In the case of performing immersion exposure, (A) after forming a film on the substrate, before the exposure step and / or (B) 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 which does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage 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 substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

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

The receding contact angle of the resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, and is passed through an immersion medium. And is preferably 75 ° or more, more preferably 75 to 85 °.

If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the above-described hydrophobic resin (HR) in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”) formed of the above-described hydrophobic resin (HR) may be provided on the upper layer of the resist film. The functions necessary for the top coat are suitability for application to the upper layer portion of the resist film and poor solubility of the immersion liquid. It is preferable that the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.
Specific examples of the topcoat include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, fluorine-containing polymers, and the like. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the film development processing step, it is preferable that the peeling step can be performed with a developer containing an organic solvent.
The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. When water is used as the immersion liquid, the top coat is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.
The top coat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this viewpoint, when the immersion liquid is water, it is preferable that the solvent used for the topcoat is a poorly water-soluble and water-insoluble medium in the solvent used for the composition of the present invention. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble. Hereinafter, the topcoat composition used for forming the topcoat layer will be described.

The solvent used in the top coat composition in the present invention is preferably an organic solvent. More preferred is an alcohol solvent.
When the solvent is an organic solvent, it is preferably a solvent that does not dissolve the resist film. As the solvent that can be used, an alcohol solvent, a fluorine solvent, or a hydrocarbon solvent is preferably used, and a non-fluorine alcohol solvent is more preferably used. As the alcohol solvent, a primary alcohol is preferable from the viewpoint of applicability, and a primary alcohol having 4 to 8 carbon atoms is more preferable. As the primary alcohol having 4 to 8 carbon atoms, a linear, branched, or cyclic alcohol can be used, and preferably, for example, 1-butanol, 1-hexanol, 1-pentanol and 3-methyl- Examples include 1-butanol, 2-ethylbutanol, and perfluorobutyltetrahydrofuran.
As the resin for the top coat composition, resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can also be preferably used.
The weight average molecular weight of the water-soluble resin is not particularly limited, but is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 100,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

The pH of the top coat composition is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and particularly preferably 1 to 7.

The concentration of the resin in the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass.
The topcoat material may contain components other than the resin, but the ratio of the resin to the solid content of the topcoat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably Is from 95 to 100% by weight.
The solid content concentration of the topcoat composition in the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 6% by mass, and 0.3 to 5% by mass. Is more preferable. By setting the solid content concentration within the above range, the topcoat composition can be uniformly applied onto the resist film.

In the pattern forming method of the present invention, a film (resist film) is formed on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and the top coat composition is used on the resist film. A topcoat layer may be formed. The thickness of the resist film is preferably 10 to 100 nm, and the thickness of the topcoat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
As a method for applying the actinic ray-sensitive or radiation-sensitive resin composition on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form a resist film. In addition, a known antireflection film can be applied in advance. Further, it is preferable to dry the resist film before forming the top coat layer.
Next, the top coat composition can be applied on the obtained resist film by the same means as the resist film forming method and dried to form a top coat layer.
The resist film having the top coat layer as an upper layer is usually irradiated with actinic rays or radiation through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

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 to form the exposure pattern. The contact angle of the immersion liquid with respect to the resist film is important. For this reason, the resist is required to have the capability of following the high-speed scanning of the exposure head without any 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 actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, but 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 developer is 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 to the above, examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetra Butylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Tetraalkylammonium hydroxide such as trimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, quaternary ammonium salts such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide An alkaline aqueous solution of cyclic amines such as pyrrole and piperidine can be used.

Further, after the developing process or the rinsing process, it is possible to perform a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid.

When the pattern forming method of the present invention includes a step of developing using an organic developer, examples of the organic developer include ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and the like. Polar solvents and hydrocarbon solvents can be used.

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

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

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

Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used relative to 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-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

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

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the organic developer used in the present invention are the same as those in the basic compound that can be contained in the above-mentioned actinic ray-sensitive or radiation-sensitive resin 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 within the above range, it is possible to remarkably reduce pattern defects caused by resist residues after development.

The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer is reduced, and the resist film and the resist pattern are carelessly 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.

Further, after the step of developing using a developer containing an organic solvent, a step of stopping development may be performed while substituting with another solvent.

In the pattern forming method of the present invention, a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) are used in combination. Also good. 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, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 <0077). The same mechanism as>.
In the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.

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 rinse liquid, a rinse 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 is used. It is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.

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

Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Can.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

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

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

The pattern forming method of the present invention can also be suitably used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823).
The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method (preferably a negative type) 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.

<Synthesis of photoacid generator>
Photo acid generators of the following compounds 1 to 21 and comparative compounds 1 to 4 were synthesized. Specific synthesis methods for Compounds 1, 2, and 9 are shown below. Other photoacid generators were synthesized in the same manner.

(Compound 1)
4-Bromo-1,1,2-trifluoro-1-butene (51.0 g, 270 mmol), metallic magnesium (7.13 g, 297 mmol) and dehydrated tetrahydrofuran (500 mL) were mixed, and the mixture was stirred at 50 ° C. for 1 hour, Grignard Reagents were prepared. 84.3 g (270 mmol) of 1-[(trifluoromethylsulfonyloxy) ethyl] adamantane, 7.75 g (54 mmol) of copper (I) bromide, and 500 mL of dehydrated tetrahydrofuran were mixed. did. The prepared Grignard reagent was added to the mixture, and the mixture was stirred at −40 ° C. for 2 hours. The reaction solution was poured into 500 mL of hexane / 1 L of ammonium chloride aqueous solution to extract the organic layer, and then the organic layer was washed with brine. The organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography (developing solvent: hexane) to obtain 38.3 g of oily synthetic intermediate 1 (yield 52%).

30.0 g (110 mmol) of synthetic intermediate 1, 37.8 g (363 mmol) of sodium bisulfite, 16.6 g (132 mmol) of sodium sulfite, 500 mL of acetonitrile and 100 mL of water were mixed and stirred at 80 ° C. for 72 hours. . The solid content of the reaction solution was filtered off, and acetonitrile in the filtrate was distilled off under reduced pressure. Then, hexane / ethyl acetate (4/1) was added to remove the organic layer. A salt was added to the aqueous layer, followed by extraction five times with chloroform. The obtained organic layers were combined, concentrated under reduced pressure, and dried under vacuum to obtain 5.65 g of a solid intermediate 2 (yield 14%).

Synthetic intermediate 2 (3.76 g, 10.0 mmol), triphenylsulfonium bromide (3.43 g, 10.0 mmol), chloroform (30 mL), and water (30 mL) were mixed and stirred at room temperature for 1 hour. The organic layer was washed 5 times with water, concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 30: 1) to obtain Compound 1 as a 5.43 g solid (yield) 82%).

Compound 1 was identified by NMR measurement. The NMR data is shown below.
1H NMR (400 MHz, CDCl ₃ ); δ = 7.80-7.67 (m, 15H)
5.14-4.92 (m, 1H), 2.25-2.04 (m, 1H), 1.91-1.81 (m, 4H), 1.70-1.19 (m, 16H), 1.06-1.00 (m, 2H) ppm.
19F NMR (376 MHz, CDCl ₃ ); δ = −114.0 (d, 1F), −119.2 (d, 1F), −201.4 to −201.8 (m, 1F) ppm.

(Compound 2)
Compound 2 was synthesized in the same manner as Compound 1 except that triphenylsulfonium bromide was replaced with Synthesis Intermediate 3.

Compound 2 was identified by NMR measurement. The NMR data is shown below.
1H NMR (400 MHz, CDCl ₃ ); δ = 8.31 (s, 2H), 7.06 (d, 2H), 6.32 (s, 1H), 5.18-4.97 (m, 1H 4.42-4.27 (m, 2H), 4.02 (t, 1H), 3.91-3.79 (m, 7H), 3.17 (d, 1H), 2.24 1.86 (m, 5H), 1.70-1.25 (m, 25H), 1.09-1.03 (m, 2H) ppm.
19F NMR (376 MHz, CDCl ₃ ); δ = −115.3 (d, 1F), −117.8 (d, 1F), −200.8 to −201.1 ppm.

(Compound 9)
4-Bromo-1,1,2-trifluoro-1-butene (56.7 g, 300 mmol), metallic magnesium (7.92 g, 330 mmol) and dehydrated tetrahydrofuran (500 mL) were mixed and stirred at 50 ° C. for 1 hour, Grignard Reagents were prepared. 63.8 g (300 mmol) of 1-adamantanecarbonyl chloride, 2.40 g (18 mmol) of aluminum chloride, 3.56 g (36 mmol) of copper (I) chloride, and 500 mL of dehydrated tetrahydrofuran were mixed. did. The prepared Grignard reagent was added to the mixture, and the mixture was stirred at 0 ° C. for 2 hours. The reaction solution was poured into 500 mL of hexane / 1 L of ammonium chloride aqueous solution to extract the organic layer, and then the organic layer was washed with brine. The organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 100: 1) to obtain 45.5 g of oily synthetic intermediate 4 (yield 53%). .

Compound 9 was synthesized in the same manner as Compound 1, except that the synthetic intermediate 1 was replaced with the synthetic intermediate 4.

Compound 9 was identified by NMR measurement. The NMR data is shown below.
1H NMR (400 MHz, CDCl ₃ ); δ = 7.78-7.67 (m, 15H)
5.18-4.97 (m, 1H), 2.79-2.60 (m, 2H), 2.49-2.33 (m, 1H), 2.23-2.09 (m, 1H), 2.02 (s, 3H), 1.78-1.65 (m, 12H) ppm.
19F NMR (376 MHz, CDCl ₃ ); δ = −114.3 (d, 1F), −118.6 (d, 1F), −201.7 (s, 1F) ppm.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 2 below are dissolved in the solvent shown in Table 2 below to prepare a solution having a solid content concentration of 4% by mass, and this is filtered through a polyethylene filter having a pore size of 0.05 μm. Alternatively, a radiation sensitive resin composition (hereinafter also referred to as a resist composition) was prepared. The obtained resist compositions (compositions of examples and compositions of comparative examples) were evaluated as follows, and the results are shown in Table 2 below.

In Table 2 below, “addition” for the hydrophobic resin (HR) indicates that the resist composition contains the hydrophobic resin (HR), and is described as “TC”. The thing shows that the resist film was formed using the resist composition which does not contain hydrophobic resin (HR), and the topcoat (TC) containing hydrophobic resin (HR) was formed on it.

In Table 2 below, for the photoacid generator and the acid diffusion controller, the numerical values in parentheses represent the blending amount (g). In Table 2 below, the numerical values for the solvents represent mass ratios.
In Example 19, the blending amount of the resin (B) is 5 g for each of P-1 and P-2. In all Examples and Comparative Examples other than Example 19, the blending amount of the resin (B) is 10 g. It is. In Example 18, the blending amount of the hydrophobic resin (HR) was 10 mg for B-14 and 25 mg for B-16. In all Examples and Comparative Examples other than Example 18, the hydrophobic resin The amount of (HR) is 35 mg. Moreover, in all the Examples and Comparative Examples, the compounding amount of the surfactant is 10 mg (however, Examples 7, 8 and 18 do not contain the surfactant).

<Evaluation>
(Pattern formation)
An organic antireflection coating material ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on 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 actinic ray-sensitive or radiation-sensitive resin 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 contrast, an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection), 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. Thereafter, the film was heated at 90 ° C. for 60 seconds, developed with paddle with butyl acetate for 30 seconds, and then spin-dried 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. Practically, it is preferably 6.0 nm or less.

(Exposure latitude (EL) evaluation)
An exposure amount that reproduces a 1: 1 line and space resist pattern with a line width of 48 nm is an optimal exposure amount, and an exposure amount width (exposure latitude) that allows a pattern size of 48 nm ± 10% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, which is desirable.

(Depth of focus (DOF) latitude evaluation)
The exposure amount and depth of focus for reproducing a 1: 1 line-and-space resist pattern with a line width of 48 nm are set as the optimum exposure amount and the optimum depth of focus, respectively. When changing (defocusing), a depth of focus allowing a line width of ± 10% (ie, 48 nm ± 10%) of the line width was observed. A larger value is desirable because the tolerance for defocus is large.

In Table 2, the structure of the photoacid generator is as follows. Comparative compound 1 is a compound described in Examples of International Publication No. 2013/058250, and Comparative Compound 4 is described in Examples of International Publication No. 2013/058250 and Examples of JP 2013-520458 A. It is a compound of this.

In Table 2, the structure of the resin (B) is as follows. Here, the composition ratio of the repeating units is a molar ratio.

In Table 2, the acid diffusion control agents are as follows.
DIA: 2,6-diisopropylaniline TEA: triethanolamine DBA: N, N-dibutylaniline PBI: 2-phenylbenzimidazole PEA: N-phenyldiethanolamine Q1 (the following structure)

・ Q2 (the following structure)

・ Q3 (the following structure)

In Table 2, the hydrophobic resin (HR) corresponds to the above specific example. For example, B-2 used in Example 1 corresponds to (B-2) in the specific example of the hydrophobic resin (HR).

In Table 2, the solvents are as follows.
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: cyclohexanone A3: γ-butyrolactone B1: propylene glycol monomethyl ether (PGME)
・ B2: Ethyl lactate

In Table 2, the surfactants are as follows.
・ 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.)

As can be seen from Table 2, the photoacid generator (A) represented by the general formula (I) is not contained, and a photoacid other than the photoacid generator (A) represented by the general formula (I) is used. Compared with Comparative Examples 1 to 4 containing a generator, Examples 1 to 21 containing the photoacid generator (A) represented by the above general formula (I) all have exposure latitude and depth of focus latitude. It was large and the LWR of the pattern formed was small.
From the comparison of Examples 1 to 20, Examples 1 to 15 in which n3 in the general formula (I) is 0 had a larger depth of focus latitude.
Moreover, from the comparison with Example 1 and 2, and the comparison with Example 7 and 8, the Example which uses "onium salt which becomes a weak acid relatively with respect to a photo-acid generator" as an acid diffusion control agent 2 and 8 had a larger depth of focus latitude and a smaller LWR of the pattern formed.
Further, in comparison with Examples 9 and 10, Example 10 using a “low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid” as an acid diffusion control agent shows a pattern to be formed. LWR was smaller.
Further, in comparison with Examples 12 and 13, Example 13 using a mixed solvent containing at least three kinds of propylene glycol monomethyl ether acetate, cyclohexanone and γ-butyrolactone as the solvent had a smaller LWR of the pattern formed. .

Claims

Actinic ray-sensitive or radiation-sensitive resin containing a photoacid generator (A) represented by the following general formula (I) and a resin (B) having a group that decomposes by the action of an acid to generate a polar group Composition.

In the general formula (I), A + represents a monovalent cation.
R 11 to R 14 each independently represents a hydrogen atom or a substituent. R 15 represents an alicyclic group which may have a substituted or unsubstituted heteroatom.
n1 and n2 each independently represents an integer of 0 to 5. n3 represents 0 or 1.
When n1 is an integer of 2 or more, the plurality of R 11 and the plurality of R 12 may be the same or different. When n2 is an integer of 2 or more, the plurality of R 13 and the plurality of R 14 may be the same or different.
R 11 to R 14 may be bonded to each other to form a ring. When n1 is an integer of 2 or more, a plurality of R 11 s and a plurality of R 12 s may be bonded to each other to form a ring. When n2 is an integer of 2 or more, a plurality of R 13 s and a plurality of R 14 s may be bonded to each other to form a ring.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein R 15 in the general formula (I) is a substituted or unsubstituted adamantyl group.
3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein at least one of R 11 to R 14 in the general formula (I) is a substituted or unsubstituted alkyl group.
The actinic ray-sensitive or radiation-sensitive substance according to any one of claims 1 to 3, wherein at least one of R 11 to R 14 in the general formula (I) is a substituted or unsubstituted cyclic alkyl group. Resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the photoacid generator (A) is a compound represented by the following general formula (ZI-4): .

In general formula (ZI-4),
R 13 represents a hydrogen atom, a fluorine atom, or an optionally substituted hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, or cycloalkyl group.
R 14 represents a hydroxyl group or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylsulfonyl group, cycloalkylsulfonyl group, or cycloalkyl group. To express.
R 15 represents an alkyl group, a cycloalkyl group, or a naphthyl group, which may have a substituent. Two R 15 may be the same or different. Two R 15 may be bonded to each other to form a ring. The ring formed may have a heteroatom.
l represents an integer of 0-2.
r represents an integer of 0 to 8. When r is an integer of 2 or more, a plurality of R 14 may be the same or different.
Z − represents an anion in the general formula (I).
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the photoacid generator (A) is a compound represented by the following general formula (ZI-3): .

In general formula (ZI-3),
R 1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or an alkenyl group.
R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R 1 and R 2 , R 2 and R 3 may be bonded to each other to form a ring.
R X and R y 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. To express.
R X and R y may combine with each other to form a ring. The ring formed may have an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
Z − represents an anion in the general formula (I).
The actinic ray-sensitive property according to any one of claims 1 to 6, comprising two or more photoacid generators, wherein at least one of the photoacid generators is the photoacid generator (A). Or a radiation sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive property according to any one of claims 1 to 7, comprising two or more photoacid generators (A) in which A + in the general formula (I) is different from each other. Resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, which is a negative resist composition for organic solvent development.
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9.
(1) forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9,
(2) exposing the film; and
(3) developing the exposed film;
A pattern forming method including:
The pattern formation method according to claim 11, wherein the exposure is immersion exposure.
The pattern formation method according to claim 11 or 12, wherein the step (3) is a step of developing the exposed film using a developer containing an organic solvent.
An electronic device manufacturing method comprising the pattern forming method according to any one of claims 11 to 13.
An electronic device manufactured by the method for manufacturing an electronic device according to claim 14.