JP7015295B2 - A method for producing a sensitive light-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device. - Google Patents

Description

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

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), fine processing by lithography using a radiation-sensitive resin composition is performed. There is.
For example, Patent Document 1 discloses a radiation-sensitive composition containing a monosulfonic acid-type acid generator that cleaves when irradiated with radiation. The acid generated by the cleavage of the acid generator has a function of causing a deprotection reaction of the resin component in the composition or a cross-linking reaction of the resin component.

International Publication No. 2011/030737

When the present inventors examined a sensitive light-sensitive or radiation-sensitive resin composition containing an acid generator specifically described in Patent Document 1, the formed pattern has fluctuations in the pattern line width (the pattern line width fluctuates (). It was clarified that LWR (line width roughness)) is not always sufficient and there is room for further improvement.

Therefore, it is an object of the present invention to provide a sensitive light-sensitive or radiation-sensitive resin composition having a small fluctuation (LWR) of the pattern line width when a pattern is formed.
Another object of the present invention is to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by containing an acid generator having a specific structure in the sensitive light-sensitive or radiation-sensitive resin composition. The present invention has been completed.
That is, it was found that the above object can be achieved by the following configuration.

[1] A sensitive light-sensitive or radiation-sensitive resin composition containing a compound that generates an acid represented by the general formula (I) described later by irradiation with active light or radiation.
[2] The actinic light-sensitive or radiation-sensitive resin composition according to [1], wherein the acid represented by the general formula (I) is an acid represented by the general formula (II) described later.
[3] The actinic or radiation-sensitive resin according to [1] or [2], wherein the acid represented by the general formula (I) is an acid represented by the general formula (III) described later. Composition.
[4] The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein R ₁ is a hydrogen atom.
[5] The sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein X ₂ is -CO-O- or -CO-.
[6] The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein R ₂ is an aliphatic hydrocarbon group.
[7] The sensitive light-sensitive or radiation-sensitive resin composition according to [6], wherein at least one of R ₂ is an aliphatic hydrocarbon group containing an alicyclic structure.
[8] The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], further containing a resin having a group that decomposes due to the action of an acid and has an increased polarity.
[9] A resist film formed by using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].
[10] A resist film forming step of forming a resist film using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].
The exposure process for exposing the resist film and
A developing step of developing the exposed resist film using a developing solution, and
A pattern forming method including.
[11] A method for manufacturing an electronic device, which comprises the pattern forming method according to [10].

According to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin composition having a small fluctuation (LWR) of the pattern line width when a pattern is formed.
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

Hereinafter, the actinic or radiation-sensitive resin composition, the resist film, the pattern forming method, and the method for producing an electronic device of the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). : Electron Beam) and the like. As used herein, "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, etc., but also electron beams. Also includes drawing with particle beams such as ion beams.
In the present specification, "to" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

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

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

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, it can be selected from the following substituent group T.
(Substituent T)
The substituent T includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfonyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; Can be mentioned.

[Actinic cheilitis or radiation-sensitive resin composition]
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is an acid represented by the general formula (I) described later by irradiation with active light or radiation. It contains a generated compound (hereinafter, also simply referred to as "specific compound").
The characteristic feature of the compound that generates the acid represented by the general formula (I), which will be described later, is that the generated acid (that is, the acid represented by the general formula (I)) has a strong acid strength.
The acid represented by the general formula (I) has X ₁ and / or X ₂ which are specific electron-withdrawing groups on the carbon atom substituted by the sulfonic acid ion. Due to this structural factor, the acid represented by the above general formula (I) has a high acid strength. As a result, the sensitive light-sensitive or radiation-sensitive resin composition containing the above-mentioned specific compound has a pattern in which unevenness of deprotection during the deprotection reaction of the acid-decomposable resin caused by exposure is suppressed. It is presumed that LWR is excellent.
Further, as another feature of the present invention, the acid represented by the above general formula (I) is an acid by molecular design using a strong electron-withdrawing group (X ₁ and / or X ₂ ) instead of a fluorine atom. The point is that the improvement in strength has been achieved. That is, the acid represented by the above general formula (I) does not necessarily have to contain a fluorine atom. As a result, the sensitive light-sensitive or radiation-sensitive resin composition containing the above-mentioned specific compound has an advantage that the load on the environment is small.

Hereinafter, the components contained in the composition of the present invention will be described in detail. The composition of the present invention is a so-called resist composition, and may be a positive type resist composition or a negative type resist composition. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

<Compound that generates an acid represented by the formula (I) by irradiation with active light or radiation>
The composition of the present invention contains a compound that generates an acid represented by the formula (I) when irradiated with active light or radiation.
The specific compound may be in the form of a small molecule compound or in the form of a polymer.
When the specific compound is in the form of a small molecule compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less.
When the specific compound is in the form of a polymer, its structure is not particularly limited, and examples thereof include a structure incorporated in a part of <resin (A)> described later. When the specific compound is in the form of a polymer, its weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, in terms of polystyrene by the GPC method.
Hereinafter, the acid represented by the general formula (I) will be described in detail.
(Acid represented by the general formula (I))

（Ｉ）

(I)

In the above general formula (I),
R ₁ represents a hydrogen atom or an organic group.
R ₂ represents an organic group.
X ₁ represents a cyano group or a nitro group.
X ₂ is a divalent selected from -CO-O-, -CO-, -CO-S-, -CO-NR-, -SO _2- , -SO _3- , -O-, and -S-. Represents a linking group of. R represents a hydrogen atom or a hydrocarbon group.
l represents 0 or 1.
m and n each independently represent an integer of 0 to 2.
However, l + m + n = 3 and m + n = 2 or 3.
When a plurality of X ₁ , R ₂ , and X ₂ exist, they may be the same or different from each other.

In the general formula (I), the organic group represented by R ₁ is not particularly limited, and examples thereof include a hydrocarbon group. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be linear, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, Examples thereof include a heptadecyl group, an octadecyl group, a nonadecil group, an eicosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group and the like.
These groups may have substituents. The substituent can be selected from, for example, the above-mentioned substituent group T.

Among them, as the above R ₁ , a hydrogen atom is preferable because it is superior in LWR performance.

In the general formula (I), the organic group represented by R ₂ is not particularly limited, and examples thereof include a hydrocarbon group. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Among the above R ₂ , an aliphatic hydrocarbon group is preferable because it is more excellent in LWR performance, and an aliphatic hydrocarbon group containing an alicyclic structure (for example, a cyclic alkyl group having 1 to 20 carbon atoms) is more preferable. preferable.
The aliphatic hydrocarbon group may be linear, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, eicosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, and the following general Examples include groups represented by formula (IA).

* -L ₁ -L ₂ (IA)

In the above general formula (IA), L ₁ represents a linear alkylene group having 1 to 5 carbon atoms, L ₂ represents a cyclic alkyl group having 3 to 12 carbon atoms, and * represents a bond position.
As the above L ₁ , a linear alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
As the above L ₂ , a cyclic alkyl group having 6 to 12 carbon atoms is preferable, and a cyclic alkyl group having 8 to 10 carbon atoms (for example, an adamantyl group) is more preferable.

Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group and the like.

The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. The substituent can be selected from, for example, the above-mentioned substituent group T.

In the above general formula (I), X ₁ represents a cyano group or a nitro group, and among them, a cyano group is preferable in that it is more excellent in LWR performance.

In the above general formula (I), X ₂ is -CO-O-, -CO-, -CO-S-, -CO-NR-, -SO _2- , -SO _3- , -O-, and-. Represents a divalent linking group selected from S-. The bonding direction of the divalent linking group (for example, —CO—O—) described in the present specification is not particularly limited, and for example, X ₂ in the above general formula (I) is −CO—O—. In the case of, if the position bonded to the carbon atom side is * 1 and the position bonded to the _R2 side is * 2, X ₂ may be * 1-CO-O- * 2. * 1-O-CO- * 2 may be used.
Among the above X ₂ , -CO-O- or -CO- is preferable because it is superior in LWR performance.
Further, R represents a hydrogen atom or a hydrocarbon group. As the hydrocarbon group, for example, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is further preferable.

In the general formula (I), l represents 0 or 1, and 1 is preferable because it is more excellent in LWR performance.
In the above general formula (I), m and n each independently represent an integer of 0 to 2. As m, 1 or 2 is preferable, and 2 is more preferable, because it is more excellent in LWR performance. As n, 0 or 1 is preferable, and 0 is more preferable, because it is more excellent in LWR performance.
In the above general formula (I), l + m + n = 3 and m + n = 2 or 3. Among them, m + n = 2 is preferable because it is more excellent in LWR performance.

The acid represented by the general formula (I) is preferably an acid represented by the general formula (II) in that it is superior in LWR performance.

（ＩＩ）(Acid represented by the general formula (II))

(II)

In the general formula (II), R ₁ , R ₂ , X ₁ , and X ₂ are synonymous with R ₁ , R ₂ , X ₁ , and X ₂ in the general formula (I), and preferred embodiments are also included. It is the same.
When a plurality of X ₁ , R ₂ , and X ₂ exist, they may be the same or different from each other.
In the above general formula (II), m and n each independently represent an integer of 0 to 2, and m + n = 2. As m, 1 or 2 is preferable, and 2 is more preferable, because it is more excellent in LWR performance. As n, 0 or 1 is preferable, and 0 is more preferable, because it is more excellent in LWR performance.

The acid represented by the general formula (I) is preferably the acid represented by the general formula (III) in that it is superior in LWR performance.

（ＩＩＩ）
上記一般式（ＩＩＩ）中、Ｒ_１、Ｒ_２、及びＸ_２は、上記一般式（Ｉ）中のＲ_１、Ｒ_２、及びＸ_２と同義である。
一般式（ＩＩＩ）中、複数存在するＲ_２同士、及び複数存在するＸ_２同士は、それぞれ同一であっても、異なっていてもよい。なかでも、ＬＷＲ性能により優れる点で、複数存在するＲ_２のうち少なくとも１つが、脂環構造を含有する脂肪族炭化水素基であることが好ましく、炭素数１～２０の環状アルキル基、又は上記一般式（ＩＡ）で表される基であることがより好ましい。(Acid represented by the general formula (III))

(III)
In the general formula (III), R ₁ , R ₂ , and X ₂ are synonymous with R ₁ , R ₂ , and X ₂ in the general formula (I).
In the general formula (III), a plurality of R _2s and a plurality of X _2s may be the same or different from each other. Among them, at least one of the plurality of R _2s present is preferably an aliphatic hydrocarbon group containing an alicyclic structure, and is preferably a cyclic alkyl group having 1 to 20 carbon atoms or the above, because it is more excellent in LWR performance. It is more preferable that the group is represented by the general formula (IA).

Hereinafter, specific examples of the acid represented by the formula (I) will be shown, but the present invention is not limited thereto.

The structure of the compound that generates the acid represented by the formula (I) by irradiation with active light or radiation is not particularly limited, and the compound has an ionic structure such as an onium salt such as a sulfonium salt and an iodonium salt, or a compound having an ionic structure. Compounds having a nonionic compound structure such as oxime ester and imide ester are preferable. As the onium salt, a sulfonium salt is more preferable.

-A compound having an ionic structure As a compound that generates an acid represented by the general formula (I) by irradiation with active light rays or radiation, a compound represented by the following general formula (IX) is preferable.

（ＩＸ）

(IX)

In the above general formula (IX), R ₁ , R ₂ , X ₁ , X ₂ , l, m, and n are R ₁ , R ₂ , X ₁ , X ₂ , respectively in the above general formula (I). Synonymous with l, m, and n, M ⁺ represents a monovalent cation.

In the above formula (IX), examples of the monovalent cation represented by M ⁺ include cations represented by the following formulas (ZI) and (ZII).

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group) and -CH ₂ -CH ₂ --O-CH ₂ -CH _2- .

The specific compound may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) is single-bonded or single-bonded to at least one of R ₂₀₁ to R ₂₀₃ of the other compound represented by the general formula (ZI). It may be a compound having a structure bonded via a linking group.

The organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include aryl groups (preferably 6 to 15 carbon atoms), linear or branched alkyl groups (preferably 1 to 10 carbon atoms), and cycloalkyl groups. (Preferably, the number of carbon atoms is 3 to 15) and the like.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , it is preferable that at least one is an aryl group, and it is more preferable that all three are aryl groups. Examples of the aryl group include a heteroaryl group such as an indole residue and a pyrrole residue, in addition to a phenyl group and a naphthyl group.

These aryl groups, alkyl groups, and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group and a fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably 1 to 15 carbon atoms), and a cycloalkyl group (preferably 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), and an alkoxycarbonyloxy group (preferably 2 carbon atoms). ~ 7) and the like, but are not limited to these.

Further, 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, but are not limited to, an alkylene group (preferably 1 to 3 carbon atoms), -O-, -S-, -CO-, and -SO _2- .
Preferred structures in the case where at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 to 0047 of JP-A-2004-233661, paragraphs 0040-0046 of JP-A-2003-35948, and the United States. Compounds exemplified as general formulas (I-1) to (I-70) in Japanese Patent Application Publication No. 2003/0224288A1 and general formula (IA-1) in US Patent Application Publication No. 2003/0077540A1. )-(IA-54), and cation structures such as compounds exemplified by the general formulas (IB-1)-(IB-24).

Preferred examples of the cation represented by the general formula (ZI) include the cation represented by the general formula (ZI-3) or (ZI-4) described below. First, the cation represented by the general formula (ZI-3) will be described.

In the above 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring.
R ₁ and R ₂ may be connected to each other to form a ring.
R _x and R _y each independently have 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. Represented, R _x and R _y may be linked to each other to form a ring, the ring structure containing an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond. May be good.

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, and n-octadecyl. Examples thereof include a linear alkyl group such as a group, and a branched chain alkyl group such as an isopropyl group, an isobutyl group, a t-butyl group, a neopentyl group and a 2-ethylhexyl group. The alkyl group of 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, and may have an oxygen atom or a sulfur atom in the ring. Specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like. The cycloalkyl group of 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 thereof include a methoxy group, an ethoxy group, an isopropyloxy group, a t-butyloxy group, a t-amyloxy group, an n-butyloxy group and the like. The alkoxy group of 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 of 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 examples as the above-mentioned alkyl group as R ₁ , cycloalkyl group, alkoxy group and cycloalkoxy group can be mentioned.

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 linked to each other to form a ring. It is preferable that at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, and an aryl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group, and aryl group represented by R ₂ and R ₃ include the same specific examples and preferred examples as 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 contained in R ₂ and R ₃ that contribute to the formation of the ring is preferably 4 to 7, preferably 4 or 5. Is more preferable.

R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are linked 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. It is preferably an alkylene group (preferably a methylene group or an ethylene group), and examples of the preferred substituent include the same substituents that the above-mentioned aryl group as _R1 may have. As another form in the case where 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, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-. Butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group. , And an eikosyl group and the like.

The cycloalkyl group represented by R _x and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. ..

The alkenyl group represented by R _x and R _y is preferably an alkenyl group having 2 to 30 carbon atoms, and examples thereof include 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, and specifically, a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a penalenyl group and a phenyl group are preferable. Examples thereof include a nantrasenyl group, a fluorenyl group, an anthrasenyl group, a pyrenyl group, a benzopyrenyl group and the like. Of these, a phenyl group or a naphthyl group is more preferable, and a phenyl group is even more preferable.

Examples of the alkyl group portion of the 2-oxoalkyl group and the alkoxycarbonylalkyl group represented by R _x and R _y include those listed above as R _x and R _y .

Examples of the cycloalkyl group portion of the 2-oxocycloalkyl group and the alkoxycarbonylcycloalkyl group represented by R _x and R _y include those listed above as R _x and R _y .

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

In the general formulas (ZI-3a) and (ZI-3b), _R1 , _R2 and R3 are as defined in the above general formula (ZI- ₃ ).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and an oxygen atom or a nitrogen atom is preferable. m, n, p and q mean integers, preferably 0 to 3, more preferably 1 to 2, and even more preferably 1. The alkylene group connecting S ⁺ and Y may have a substituent, and preferred substituents include an alkyl group.

R ₅ represents a monovalent organic group when Y is a nitrogen atom and does not exist when Y is an oxygen atom or a sulfur atom. R5 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 general formulas (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group, or aryl group for R include the same specific examples and preferred examples as described above for R ₁ in the above general formula (ZI-3).
In the above general formulas (ZI-3a-1) to (ZI-3a-4), * represents a bond that connects 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 preferably a group represented by _−SO2 - _R4 . _R4 represents an alkyl group, a cycloalkyl group or an aryl group, and an alkyl group is preferable. Specific examples and preferred examples of the alkyl group, cycloalkyl group, or aryl group for R ₄ include the same examples as those described above for R ₁ and preferred examples.

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

In the general formulas (ZI-3a') and (ZI-3b'), _R1 , _R2 , R3 _, Y and R5 are as defined in the above general formulas ₍ ZI-3a) and (ZI-3b). Is.

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

In the general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have substituents.
When a plurality of R _14s are present, each of them independently has a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group. show. These groups may have substituents.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or an aryl group. The two _R15s may be bonded to each other to form a ring, or the atoms constituting the ring may contain a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have substituents.
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched chain, and those having 1 to 10 carbon atoms are preferable.
Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.
The alkoxy groups of R ₁₃ and R ₁₄ are linear or branched, and preferably have 1 to 10 carbon atoms.
The alkoxycarbonyl groups of R ₁₃ and R ₁₄ are linear or branched chain, and those having 2 to 11 carbon atoms are preferable.
Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have substituents.
Examples of the alkyl group of the alkylcarbonyl group of R ₁₄ include the same specific examples as the above-mentioned alkyl groups of R ₁₃ to R ₁₅ .
The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ may be linear, branched or cyclic, and those having 1 to 10 carbon atoms are preferable.

The substituents that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy. The group etc. can be mentioned.

Examples of the ring structure in which the two R _15s may be bonded to each other include a 5-membered or 6-membered ring formed by the two R _15s together with the sulfur atom in the general formula (ZI-4). , More preferably a 5-membered ring (ie, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring). The ring may be fused with an aryl group or a cycloalkyl group. These two R _15s may have a substituent, and examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, and an alkoxycarbonyl. Examples include a group and an alkoxycarbonyloxy group. A plurality of substituents for the above ring structure may be present, or they may be bonded to each other to form a ring.

As the R ₁₅ in the general formula (ZI-4), a methyl group, an ethyl group, an aryl group, and a divalent group in which two R _15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom are preferable. A divalent group in which two _R15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is more preferable.

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

Specific examples of the cation structure represented by the general formula (ZI-3) or (ZI-4) described above include JP-A-2004-233661, JP-A-2003-35948, and US patent applications described above. Cationic structures such as compounds exemplified in Publication No. 2003/0224288A1 and US Patent Application Publication No. 2003/0077540A1, paragraphs 0046, 0047, 0072-0077, and JP-A-2011-533360. Examples thereof include cation structures in the chemical structures exemplified in 0107 to 0110, and cation structures in the chemical structures exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of JP-A-2011-53430. Be done.

Next, the general formula (ZII) will be described.
In the general formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represent 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-mentioned compound (ZI).

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

Further, as the alkyl group and cycloalkyl group of R ₂₀₄ and R ₂₀₅ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) is preferable. And a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have a substituent. Substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ may have include the aryl group, alkyl group, and cycloalkyl of R ₂₀₁ to R ₂₀₃ in the above-mentioned compound (ZI). Examples of the group may have an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 15 carbon atoms), and an alkoxy. Examples include a group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like.
A specific example of the cation represented by the general formula (ZII) is shown.

Preferred examples of the cation represented by the general formula (ZI) include the cation represented by the general formula (7) described below.

In the formula, A represents a sulfur atom.
m represents 1 or 2 and n represents 1 or 2. However, m + n = 3.
R represents an aryl group.
_RN represents an aryl group substituted with a proton acceptor functional group.
A proton-accepting functional group is a functional group having a group or an electron that can electrostatically interact with a proton, and is, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. Means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza-crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.

A compound (PA) having a proton-accepting functional group is decomposed by irradiation with active light or radiation to generate a compound whose proton-accepting property is reduced or eliminated, or whose proton-accepting property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. This means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
The proton acceptor property can be confirmed by measuring the pH.
A specific example of the cation represented by the general formula (7) is shown. In the following formula, Et represents an ethyl group.

-Compound having a non-ionic compound structure The compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation may have a non-ionic compound structure, for example, the following. Examples thereof include compounds represented by the general formula (ZV) or (ZVI).

In the general formulas (ZV) and (ZVI),
R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, a cyano group or an aryl group. The aryl group, alkyl group, and cycloalkyl group of R ₂₀₉ and R ₂₁₀ are the same as those described as the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above-mentioned compound (ZI). be. The aryl group, alkyl group, and cycloalkyl group of R ₂₀₉ and R ₂₁₀ may have a substituent. Examples of this substituent include the same substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above-mentioned compound (ZI) may have.

A'represents an alkylene group, an alkenylene group or an arylene group.
The alkylene group as A'may have a substituent and preferably has 1 to 8 carbon atoms, and for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group and the like can be used. Can be mentioned.
The alkenylene group as A'may have a substituent and preferably has 2 to 6 carbon atoms, and examples thereof include an ethenylene group, a propenylene group, and a butenylene group.
The arylene group as A'may have a substituent and preferably has 6 to 15 carbon atoms, and examples thereof include a phenylene group, a trilene group, and a naphthylene group.

Examples of the substituent that A'may have include those having active hydrogen such as a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, and a carboxy group, and further, a halogen. Atomic (fluorine atom, chlorine atom, bromine atom, and iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.) ), Asyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group and the like. Further, as the arylene group, an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.) can be further mentioned.

Rz represents a structure in which H of the acid represented by the general formula (I) is dissociated, and is represented by the following general formula (IY).

（ＩＹ）

(IY)

In the general formula (IY), R ₁ , R ₂ , X ₁ , X ₂ , l, m, and n are R ₁ , R ₂ , X ₁ , X ₂ , l in the general formula (I) described above, respectively. , M, and n. * Represents a bond with a compound residue represented by the general formula (ZV) or (ZVI).

Specific examples of residues other than Rz in the compound represented by the general formula (ZV) or (ZVI) are shown below. * In the specific example represents a joint portion with * in the above general formula (IY). Me represents a methyl group.

Hereinafter, specific examples of compounds that generate an acid represented by the general formula (I) by irradiation with active light or radiation will be given. The compound that generates the acid represented by the general formula (I) by irradiation with active light or radiation is not limited to the following specific examples.

The compound that generates the acid represented by the general formula (I) by irradiation with active light or radiation can be synthesized by a known synthesis method.

The compound that generates the acid represented by the general formula (I) by irradiation with the above-mentioned active light rays or radiation can be used alone or in combination of two or more. Further, a known acid generator other than the compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation may be used in combination.
When a known acid generator is used, for example, the activity used in a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for dyes, a photochromic agent, a microresist, and the like. A known compound that generates an acid by irradiation with light or radiation can be appropriately selected and used.

In the composition of the present invention, the total content of the acid generator containing the specific compound is preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, based on the total solid content of the composition. 5 to 20% by mass is more preferable.
When the composition of the present invention contains two or more kinds of acid generators, it is preferable that the total content of the acid generators is within the above range.
Further, as described above, when a compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation is used in combination with another acid generator, the general formula (general formula by irradiation with active light or radiation described above) The content of the acid-generating compound represented by I) is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 85% by mass or more, based on the total mass of the acid generator used. , 90% by mass or more is particularly preferable, and 95% by mass or more is most preferable.

<Resin (A)>
The composition of the present invention is a resin (hereinafter, "acid-degradable resin" or "resin (A)" having a group having a group (hereinafter, also referred to as "acid-decomposable group") which is decomposed by the action of an acid and whose polarity is increased. Also referred to as).
In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer. A negative pattern is preferably formed.

The resin (A) preferably has a repeating unit having an acid-degradable group.

As the resin (A), a known resin can be appropriately used. For example, paragraphs <0055> to <0191> of U.S. Patent Application Publication No. 2016/0274458A1, paragraphs <0035> to <0087> of U.S. Patent Application Publication No. 2015/0004544A1, and U.S. Patent Application Publication No. 2016/0147150A1. The known resin disclosed in paragraphs <0045> to <0090> of the specification can be suitably used as the resin (A).

The acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) that is decomposed and desorbed by the action of an acid.
The polar group includes a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (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) methylene group, etc. Examples thereof include an acidic group (a group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution) and an alcoholic hydroxyl group.

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

Preferred polar groups include a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A preferable group as an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group (leaving group) that is eliminated by the action of an acid.
Examples of the group desorbed by the action of an acid (leaving group) include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and-. Examples thereof include C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be coupled to each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkyl groups having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and hexyl. Groups, octyl groups and the like can be mentioned.
The cycloalkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable. Examples thereof include a tetracyclododecyl group and an androstanyl group. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.
The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by bonding R ₃₆ and R ₃₇ to each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. ..

As the acid-degradable group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group and the like are preferable, and an acetal group or a tertiary alkyl ester group is more preferable.

The resin (A) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.

In the general formula (AI)
Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ independently represent an alkyl group or a cycloalkyl group, respectively.
Any two of Rx ₁ to Rx ₃ may or may not be combined to form a ring structure.

Examples of the divalent linking group of T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group. In addition, -COO- is synonymous with -CO-O-.
T is preferably single bond or -COO-Rt-. As Rt, a chain alkylene group having 1 to 5 carbon atoms is preferable, and −CH _2- , − (CH ₂ ) ₂ −, or − (CH ₂ ) ₃ − is more preferable. It is more preferable that T is a single bond.

Xa ₁ is preferably a hydrogen atom or an alkyl group.
The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a trifluoromethyl group. The alkyl group of Xa ₁ is preferably a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group. An isobutyl group, a t-butyl group, or the like is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may have a part of the carbon-carbon bond as a double bond.
Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like. The polycyclic cycloalkyl group of is preferred.

The ring structure formed by combining Rx ₁ , Rx ₂ and Rx ₃ is a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornane ring or a tetracyclo. Polycyclic cycloalkyl rings such as decane rings, tetracyclododecane rings, and adamantane rings are preferred. Of these, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As the ring structure formed by combining Rx ₁ , Rx ₂ and Rx ₃ , the structure shown below is also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) will be given below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa ₁ in the general formula (AI) is a methyl group, but Xa ₁ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

It is also preferable that the resin (A) has the repeating unit described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1 as the repeating unit having an acid-degradable group.

Further, the resin (A) is decomposed by the action of the acid described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016/0070167A1 as a repeating unit having an acid-degradable group and is alcoholic. It may have a repeating unit containing a group that produces a hydroxyl group.

The resin (A) may contain a repeating unit having an acid-decomposable group alone or in combination of two or more.

The content of the repeating unit having an acid-degradable group contained in the resin (A) (the total if there are a plurality of repeating units having an acid-degradable group) is determined with respect to all the repeating units of the resin (A). It is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%.

The resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

The lactone structure or sultone structure may have a lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, a 5- to 7-membered ring lactone structure in which another ring structure is condensed in a form forming a bicyclo structure or a spiro structure, or a 5- to 7-membered ring in the form of forming a bicyclo structure or a spiro structure. A sultone structure in which another ring structure is fused is more preferable.
The resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3). It is more preferred to have a repeating unit with the represented sultone structure. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1). Examples thereof include a lactone structure represented by -21) and a sultone structure represented by the general formula (SL1-1).

The lactone-structured portion or the sultone-structured portion 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 carboxy group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group is preferable. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other to form a ring.

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

In the above general formula (III),
A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
n is the number of repetitions of the structure represented by −R ₀ −Z—, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and a single bond is formed.
_R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R _0s , each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z's, Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of _R0 may have a substituent.
As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

The resin (A) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In the general formula (A-1), _RA ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
_RA ² represents a substituent. When n is 2 or more, _RA ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with the group represented by —O—C (= O) —O— in the formula.

The resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, as paragraphs <0370> to <0414> of US Patent Application Publication No. 2016/0070167A1. It is also preferable to have the repeating unit described in 1.

The resin (A) may have one type of repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and may have two or more types in combination. May be.

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific example of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given. The present invention is not limited to these specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and RA 1 in the general formula ( _A - ¹ ) are methyl groups, but R ₇ and _RA ¹ are hydrogen atoms and halogen atoms. , Or can be optionally replaced with a monovalent organic group.

In addition to the above-mentioned monomers, the monomers shown below are also suitably used as raw materials for the resin (A).

The content of the repeating unit having at least one selected from the group consisting of the lactone structure, the sultone structure, and the carbonate structure contained in the resin (A) (selected from the group consisting of the lactone structure, the sultone structure, and the carbonate structure). If there are a plurality of repeating units having at least one kind, the total) is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, and 20 to 20 to all the repeating units in the resin (A). 60 mol% is more preferred.

The resin (A) preferably has a repeating unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a fluorinated alcohol group and the like.
As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Further, it is preferable that the repeating unit having a polar group does not have an acid-degradable group. In the alicyclic hydrocarbon structure substituted with the polar group, the adamantane group or the norbornane group is preferable as the alicyclic hydrocarbon structure.

Specific examples of the monomer corresponding to the repeating unit having a polar group will be given below, but the present invention is not limited to these specific examples.

In addition, specific examples of the repeating unit having a polar group include the repeating unit disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1.
The resin (A) may have one type of repeating unit having a polar group alone, or may have two or more types in combination.
The content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (A).

The resin (A) may further have a repeating unit having neither an acid-degradable group nor a polar group. The repeating unit having neither an acid-degradable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating units described in paragraphs <0236> to <0237> of US Patent Application Publication No. 2016/0026083A1. Preferred examples of monomers corresponding to repeating units having neither an acid-degradable group nor a polar group are shown below.

In addition, specific examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating unit disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167A1. ..
The resin (A) may have one type of repeating unit having neither an acid-decomposable group nor a polar group, or may have two or more types in combination.
The content of the repeating unit having neither an acid-degradable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin (A). 5 to 25 mol% is more preferred.

In addition to the above-mentioned repeating structural units, the resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or resolution, heat resistance, sensitivity, etc., which are generally necessary characteristics of resist. May have various repeating structural units for the purpose of regulating.
Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.

The predetermined monomer has one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Examples include compounds.
In addition, an addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the above-mentioned various repeating structural units may be used.
In the resin (A), the molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

When the composition of the present invention is for ArF exposure, it is preferable that the resin (A) has substantially no aromatic group from the viewpoint of the transparency of ArF light. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally, with respect to all the repeating units in the resin (A). Is more preferably 0 mol%, i.e. not having a repeating unit with an aromatic group. Further, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

It is preferable that all of the repeating units of the resin (A) are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol% or less with respect to all the repeating units of the resin (A).

When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) preferably has a repeating unit having an aromatic hydrocarbon ring group. It is more preferable that the resin (A) has a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit.
When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) is a group (leaving group) in which the hydrogen atom of the phenolic hydroxyl group is decomposed and desorbed by the action of an acid. It is preferable to have a structure protected by.
The content of the repeating unit having an aromatic hydrocarbon ring group contained in the resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, based on all the repeating units in the resin (A). It is preferable, 50 to 100 mol% is more preferable.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and 3,000 to 11,000. Especially preferable. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0. preferable.

The resin (A) may be used alone or in combination of two or more.
In the composition of the present invention, the content of the resin (A) is generally 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, based on the total solid content. , 75% by mass or more is more preferable, and 80% by mass or more is particularly preferable. The upper limit is not particularly limited, and is preferably 99.5% by mass or less, more preferably 99% by mass or less, and further preferably 97% by mass or less.

<Resin (B)>
When the composition of the present invention contains a cross-linking agent (G) described later, the composition of the present invention may contain an alkali-soluble resin (B) having a phenolic hydroxyl group (hereinafter, also referred to as “resin (B)”). preferable. The resin (B) preferably has a repeating unit having a phenolic hydroxyl group.
In this case, typically a negative pattern is preferably formed.
The cross-linking agent (G) may be supported on the resin (B).
The resin (B) may have the above-mentioned acid-decomposable group.

As the repeating unit having the phenolic hydroxyl group of the resin (B), the repeating unit represented by the following general formula (II) is preferable.

In general formula (II),
R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).
B'represents a single bond or a divalent linking group.
Ar'represents an aromatic ring group.
m represents an integer of 1 or more.
The resin (B) may be used alone or in combination of two or more.
The content of the resin (B) in the total solid content of the composition of the present invention is generally 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is not particularly limited, and is preferably 99% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.
Preferred examples of the resin (B) include the resins disclosed in paragraphs <0142> to <0347> of US Patent Application Publication No. 2016/0282720A1.

The composition of the present invention may contain both the resin (A) and the resin (B).

<Acid diffusion control agent (D)>
The composition of the present invention preferably contains an acid diffusion control agent (D). The acid diffusion control agent (D) acts as a quencher that traps the acid generated from the acid generator or the like at the time of exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, an onium salt (DC) which is a weak acid relative to an acid generator, and a nitrogen atom. A low molecular weight compound (DD) having a group having a group desorbed by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion control agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0995> to <0187> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/02744558A1 are suitable as the acid diffusion control agent (D). Can be used for.

As the basic compound (DA), a compound having a structure represented by the following formulas (A) to (E) is preferable.

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

The alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the above alkyl group, as the alkyl group having a substituent, 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 is preferable.
It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholin, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. A trialkylamine structure, a compound having an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like are more preferable.

A basic compound (DB) (hereinafter, also referred to as “compound (DB)”) whose basicity is reduced or disappears by irradiation with active light or radiation has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton acceptor property, or to change from proton acceptor property to acidity.

A proton-accepting functional group is a functional group having a group or an electron that can electrostatically interact with a proton, and is, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. Means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza-crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.

The compound (DB) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or disappears, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group, and is specific. Means that when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
The proton acceptor property can be confirmed by measuring the pH.

The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with active light or radiation preferably satisfies pKa <-1, more preferably -13 <pKa <-1, and-. It is more preferable to satisfy 13 <pKa <-3.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate Hammett's substituent constants and values based on a database of publicly known literature values. All pKa values described herein indicate values calculated using this software package.

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

In the composition of the present invention, an onium salt (DC), which is a weak acid relative to the acid generator, can be used as the acid diffusion control agent.
When an acid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the acid generator are mixed and used, the acid generator is generated by active light or irradiation with radiation. When the acid collides with an onium salt having an unreacted weak acid anion, salt exchange releases the weak acid to produce an onium salt with a strong acid anion. In this process, the strong acid is replaced with a weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

As the onium salt that is relatively weak acid with respect to the acid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, 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. It is a hydrocarbon group containing, and M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented as M ⁺ include the sulfonium cation exemplified by the general formula (ZI) and the iodonium cation exemplified by the general formula (ZII).

The onium salt (DC), which is a relatively weak acid with respect to the acid generator, is a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond (hereinafter,). , Also referred to as "compound (DCA)").
As the compound (DCA), a compound represented by any of the following general formulas (C-1) to (C-3) is preferable.

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or single bond that links the cation site and the anion site.
_-X- represents an anion site selected from -COO- ^, -SO _3- ^, -SO ^{2- ,} and -N ^--- R ₄ . _R4 has a carbonyl group (-C (= O)-), a sulfonyl group (-S (= O) _2- ), and a sulfinyl group (-S (= O)-) at the linking site with the adjacent N atom. ) Represents a monovalent substituent having at least one of them.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be coupled to each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

Substituents having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two kinds thereof. A group obtained by combining the above can be mentioned. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

A small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
As the group desorbed by the action of the acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiaminol ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

In the general formula (d-1)
R _b is independently 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), and an aralkyl group. It represents (preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 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 _Rb are independently hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, or alkyl groups. It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group indicated by R _b .

As _Rb , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two R _bs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon and a derivative thereof.
Specific examples of the structure of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph <0466> of the US Patent Publication No. US2012 / 0135348A1.

The compound (DD) preferably has a structure represented by the following general formula (6).

In the general formula (6)
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents _a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When _l is 2, the two Ras may be the same or different, and the two Ras may be interconnected to form _a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the equation.
R _b has the same meaning as R _b in the above general formula (d-1), and the same applies to preferred examples.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _a are independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b , respectively. The group may be substituted with a group similar to the above-mentioned group.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above group _{) of Ra are the same groups as those of the above-mentioned specific example for R b .} Can be mentioned.
Specific examples of a particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of U.S. Patent Application Publication No. 2012/01335348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is even more preferred that all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly linked to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compound disclosed in paragraph <0203> of US Patent Application Publication 2015/0309408A1.

Preferred examples of the acid diffusion control agent (D) are shown below.

In the composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more.
The content of the acid diffusion control agent (D) in the composition (the total of a plurality of types if present) is preferably 0.1 to 10% by mass, preferably 0.1 to 10% by mass, based on the total solid content of the composition. 5% by mass is more preferable.

<Hydrophobic resin (E)>
The composition of the present invention may contain a hydrophobic resin (E). The hydrophobic resin (E) is preferably a resin different from the resin (A) and the resin (B).
By including the hydrophobic resin (E) in the composition of the present invention, the static / dynamic contact angle on the surface of the sensitive light-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgas, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and is a polar / non-polar substance. It does not have to contribute to uniform mixing.

The hydrophobic resin (E) is selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of uneven distribution on the surface layer of the film. It is preferable that the resin has a repeating unit having at least one kind.
When the hydrophobic resin (E) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, and the side may be contained. It may be contained in the chain.

When the hydrophobic resin (E) contains a fluorine atom, the partial structure having a fluorine atom 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. preferable.

The hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) A group that decomposes by the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity conversion group).
(Z) A group that decomposes by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl). A carbonyl) imide group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) group. ) Methylene group and the like can be mentioned.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfoneimide group, or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester group (-OSO ₂ O-), and Examples thereof include a sulfonic acid ester group (-SO ₂ O-), and a lactone group or a carboxylic acid ester group (-COO-) is preferable.
Examples of the repeating unit containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units made of acrylic acid ester and methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the terminal of the resin by using a polymerization initiator or a chain transfer agent having these groups at the time of polymerization.
Examples of the repeating unit having a lactone group include the same repeating units having the lactone structure described above in the section of the resin (A).

The content of the repeating unit having a group (y) that decomposes by the action of the alkaline developer and increases the solubility in the alkaline developer is 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin (E). Is preferable, 3 to 98 mol% is more preferable, and 5 to 95 mol% is further preferable.

Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the hydrophobic resin (E) include the same repeating units having an acid-degradable group mentioned in the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having the group (z) decomposed by the action of the acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (E). , 20-60 mol% is more preferred.
The hydrophobic resin (E) may further have a repeating unit different from the repeating unit described above.

The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all the repeating units in the hydrophobic resin (E). The repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all the repeating units in the hydrophobic resin (E).

On the other hand, particularly when the hydrophobic resin (E) contains a _CH3 partial structure in the side chain portion, a form in which the hydrophobic resin (E) does not substantially contain fluorine atoms and silicon atoms is also preferable. Further, it is preferable that the hydrophobic resin (E) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

The total content of the residual monomer and / or the oligomer component contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The dispersity (Mw / Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin (E), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of U.S. Patent Application Publication 2015/016883A1 and paragraphs <0340> to <0356> of U.S. Patent Application Publication 2016/0274458A1. Can be suitably used as the hydrophobic resin (E). Further, the repeating unit disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (E).

A preferred example of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) is shown below.

The hydrophobic resin (E) may be used alone or in combination of two or more.
It is preferable to mix and use two or more kinds of hydrophobic resins (E) having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and 0.1 to 0.1 to the total solid content in the composition. 5% by mass is more preferable.

<Solvent (F)>
The composition of the present invention may contain a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of the US Patent Application Publication No. 2016/02744558A1 can be preferably used.
Examples of the solvent that can be used when preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionic acid, and cyclic lactone (preferably having 4 to 10 carbon atoms). Examples thereof include organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used may be used.
As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-mentioned exemplary compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (propylene glycol monomethyl ether). PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, alkylene glycol monoalkyl ether acetate, alkyl acetate and the like are preferable. Propropylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate. , Cyclohexanone, cyclopentanone or 2-heptanone are even more preferred. Propylene carbonate is also preferable as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 20/80 to 60/40. More preferred. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)>
The composition of the present invention may contain a compound (hereinafter, also referred to as a cross-linking agent (G)) that cross-links the resin by the action of an acid. As the cross-linking agent (G), a known compound can be appropriately used. For example, known compounds disclosed in paragraphs <0379> to <0431> of U.S. Patent Application Publication 2016 / 0147154A1 and paragraphs <0064> to <0141> of U.S. Patent Application Publication 2016/0282720A1. Can be suitably used as the cross-linking agent (G).
The cross-linking agent (G) is a compound having a cross-linking group capable of cross-linking the resin, and examples of the cross-linking group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, and an oxylan ring. And the oxetane ring and the like.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxylan ring or an oxetane ring.
The cross-linking agent (G) is preferably a compound (including a resin) having two or more cross-linking groups.
The cross-linking agent (G) is more preferably a phenol derivative, a urea-based compound (compound having a urea structure) or a melamine-based compound (compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
The cross-linking agent may be used alone or in combination of two or more.
The content of the cross-linking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, still more preferably 5 to 30% by mass, based on the total solid content of the resist composition.

<Surfactant (H)>
The composition of the present invention may contain a surfactant. When a surfactant is contained, a fluorine-based and / or a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom). Is preferable.

When the composition of the present invention contains a surfactant, a pattern having good sensitivity and resolution and few adhesions and development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less is used.
Fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
Further, other surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of Japanese Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.
On the other hand, when the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased. Thereby, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability at the time of immersion exposure is improved.

(Other additives)
The composition of the present invention may further contain an acid growth agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator and the like.

<Preparation method>
The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, still more preferably 2.0 to 5.3% by mass. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

The film thickness of the sensitive light-sensitive or radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving the resolving power. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coatability or the film forming property.

In the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtered through a filter, and then applied onto a predetermined support (substrate) for use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Unexamined Patent Publication No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be connected in series. Alternatively, they may be connected in parallel for filtration. Also, the composition may be filtered multiple times. Further, the composition may be degassed before and after the filter filtration.

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

[Pattern formation method]
The present invention also relates to a pattern forming method using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition to the description of the pattern forming method, the sensitive light-sensitive or radiation-sensitive film of the present invention will also be described.

The pattern forming method of the present invention is
(I) A step of forming a resist film (sensitive light-sensitive or radiation-sensitive film) on a support by the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition (resist film forming step).
(Ii) A step (exposure step) of exposing the resist film (irradiating with active light rays or radiation), and
(Iii) A step of developing the exposed resist film using a developing solution (development step).
Have.

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.
The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after (ii) exposure step and before (iii) development step.
The pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/805466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

The support is not particularly limited, and a substrate generally used in a semiconductor manufacturing process such as an IC, a circuit board manufacturing process such as a liquid crystal or a thermal head, and other photolithography lithography processes is used. be able to. Specific examples of the support include an inorganic substrate such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. in both the (iv) preheating step and (v) post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, still more preferably 30 to 90 seconds in both the (iv) pre-heating step and (v) post-exposure heating step.
The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed by using a hot plate or the like.

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, polar ultraviolet light (EUV), X-ray, and electron beam. Of these, far-ultraviolet light is preferable. The wavelength is preferably 250 nm or less, more preferably 220 nm or less, still more preferably 1 to 200 nm. Specifically, it is a KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV (13 nm), electron beam, etc., and is a KrF excimer laser, ArF excimer laser, etc. EUV or electron beam is preferred.

(Iii) In the developing step, it may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines are also used. It can be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkaline concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

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

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone. Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formic acid, ethyl forerate, butyl forerate, propyl forerate, ethyl lactate, butyl lactate, propyl lactate, butane Examples thereof include butyl acetate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like.

As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based solvent, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167A1 can be used.

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

The organic developer may contain an appropriate amount of a known surfactant, if necessary.

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution.

The organic developer may contain the above-mentioned acid diffusion control agent.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate. A method of spraying the developer on the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic discharge method) can be mentioned. Be done.

A step of developing with an alkaline aqueous solution (alkaline developing step) and a step of developing with a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, the pattern can be formed without dissolving only the region of the intermediate exposure intensity, so that a finer pattern can be formed.

(Iii) It is preferable to include a step of washing with a rinsing solution (rinsing step) after the developing step.

As the rinsing solution used in the rinsing step after the developing step using the alkaline developer, for example, pure water can be used. Pure water may contain an appropriate amount of a surfactant. In this case, after the developing step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added. Further, after the rinsing treatment or the treatment with the supercritical fluid, a heat treatment may be performed to remove the water remaining in the pattern.

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent shall be used. Is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include the same as those described for the developing solution containing the organic solvent.
As the rinsing liquid used in the rinsing step in this case, a rinsing liquid containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 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 methylisobutylcarbinol can be mentioned. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, methyl isobutylcarbinol and the like. ..

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

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, and for example, a method of continuously discharging a rinse liquid onto a substrate rotating at a constant speed (rotational coating method), or a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method). Above all, it is preferable to perform a cleaning treatment by a rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The sensitive light-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developing solution, a rinsing solution, an antireflection film forming composition, or The composition for forming a top coat, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). Is particularly preferable.

Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. The filter preferably has a reduced amount of eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Unexamined Patent Publication No. 2016-201426).
In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Unexamined Patent Publication No. 2016-206500).
Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method such as lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as the above-mentioned conditions.

In order to prevent impurities from being mixed in, the above various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351) and the like. It is preferably stored in the described container.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating the pattern with plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/010497. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 832883280N-1 “EUV Resist Curing Technology for LWR Redox and Etch Sensitivity Enhancement” may be applied.
Further, the pattern formed by the above method is disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. It can be used as a core material (Core) for the spacer process.

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

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limitedly construed by the examples shown below.

[Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition]
The various components contained in the actinic cheilitis or radiation-sensitive resin composition are shown below.
<Resin>
The structures of the resins (polymers (1) to polymer (7)) shown in Table 1 are shown below.
The weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the polymers (1) to polymer (7) were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene conversion value). The composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance).

<Compound that generates an acid represented by the general formula (I) by irradiation with active light or radiation>
The structures of the compounds (also referred to as "acid generators", PAG-1 to PAG-8) that generate an acid represented by the general formula (I) by irradiation with active light or radiation shown in Table 1 are as follows. show. In addition, an example of PAG-1 synthesis is shown as an example.
In addition, PAG-9 to PAG-11 shown in Table 1 do not correspond to the compound that generates an acid represented by the general formula (I).

(Synthesis of PAG-1)

15.74 g (95 mmol) of adamantane methanol and 11.1 g (110 mmol) of triethylamine were dissolved in 250 mL of dichloromethane. After cooling the obtained solution to 0 ° C., 15 g (100 mmol) of ethylmalonyl chloride was added dropwise to this solution. After the dropping, the temperature of the reaction solution was raised to room temperature, and the mixture was further stirred for 2 hours. 250 g of water was added to the obtained reaction solution, and the mixture was transferred to a separating funnel. The aqueous layer was extracted twice with 100 mL of dichloromethane, and the organic layer was washed twice with 100 mL of saturated brine. Dichloromethane was distilled off under reduced pressure, and then the crude product was purified by column chromatography to obtain 25.3 g of compound (1-1) as a colorless oily product (yield: 95%).
¹ H NMR (CDCl _3,300MHz ): δ = 1.27 (t, J = 5.37Hz, 3H), 1.54 (m, 6H), 1.69 (m, 6H), 1.99 (m, 3H), 3.38 (s, 2H) ), 3.75 (s, 2H), 4.21 (q, J = 5.37Hz, 2H).

6.0 g (21 mmol) of compound (1-1) was dissolved in 21 mL of dichloromethane. After cooling the obtained solution to 0 ° C., 2.5 g (21 mmol) of chlorosulfonic acid was added dropwise to this solution. After the dropping, the reaction solution was heated to 40 ° C., refluxed for another 3 hours, and then the reaction solution was slowly added to 50 mL of a cooled saturated aqueous sodium hydrogen carbonate solution. After transferring to a separating funnel and separating the organic layer, the aqueous layer was extracted 3 times with 50 mL of ethyl acetate. After distilling off the solvent under reduced pressure, the crude product was reslurried with diisopropyl ether to give 7.2 g of compound (1-2) as a white solid (yield: 90%).
¹ H NMR (CDCl _3,300MHz ): δ = 1.36 (t, J = 5.37Hz, 3H), 1.54 (m, 6H), 1.69 (m, 6H), 1.99 (m, 3H), 3.91 (d, J) = 2.82Hz, 2H), 4.38 (q, J = 5.37Hz, 2H), 5.02 (s, 1H).

A reaction solution was obtained by dissolving 3.2 g (8.4 mmol) of compound (1-2) and 2.9 g (8.4 mmol) of triphenylsulfonium bromide in 100 mL of chloroform, and further adding 100 mL of water. After vigorously stirring the obtained reaction solution for 1 hour, the stirred reaction solution was transferred to a separating funnel, and the organic layer was washed 3 times with 100 mL of water. By distilling off the solvent under reduced pressure, 5 g of PAG-1 was obtained (yield: 95%).
¹ H NMR (CDCl _3,300MHz ): δ = 1.27 (t, J = 5.34Hz, 3H), 1.54 (m, 6H), 1.65 (m, 6H), 1.93 (m, 3H), 3.72 (s, 2H) ), 4.15-4.27 (m, 2H), 4.90 (s, 1H), 7.63-7.73 (m, 9H), 7.83-7.86 (m, 6H).

<Basic compound>
The structures of the basic compounds (N-1 to N-6) shown in Table 1 are shown below.

<Hydrophobic resin>
The structures of the hydrophobic resins (1b and 2b) shown in Table 1 are shown below. The weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the hydrophobic resins 1b and 2b were measured by GPC (carrier: THF) (polystyrene conversion value). The composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR.

<Solvent>
The solvents shown in Table 1 are as follows.

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: Cyclohexanone SL-4: γ-Butyrolactone

<Surfactant>
The surfactants shown in Table 1 are as follows.
W-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)
W-2: Megafuck F176 (manufactured by Dainippon Ink and Chemicals Co., Ltd .; fluorine-based)

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition>
Each component shown in Table 1 was mixed so that the solid content concentration was 4% by mass. Then, the obtained mixed solution is first filtered with a polyethylene filter having a pore diameter of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 5 nm, thereby causing sensitive light or radiation. A sex resin composition (hereinafter, also referred to as a resin composition) was prepared. In the resin composition, the solid content means all components other than the solvent. The obtained resin composition was evaluated by the following method. The results are shown in Table 1.

〔evaluation〕
<Method of forming resist pattern>
The composition for forming an organic antireflection film ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm. The resin composition shown in Table 1 was applied onto the resin composition and baked at 100 ° C. for 60 seconds to form an actinic or radiation-sensitive film having a film thickness of 90 nm.
ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection) for sensitive light or radiation sensitive film. It was exposed through a 6% halftone mask with a 1: 1 line and space pattern with a line width of 75 nm. Ultrapure water was used as the immersion liquid.
The exposed light-sensitive or radiation-sensitive film was baked at 120 ° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. Then, this was spin-dried to obtain a negative pattern.

<Evaluation of line with sloughness (LWR)>
For a 75 nm (1: 1) line-and-space resist pattern resolved at the optimum exposure, a length-measuring scanning electron microscope (SEM (Hitachi Co., Ltd. S-9380II)) was used to the upper part of the pattern. When observing from, the line width was observed at an arbitrary point, and the measurement variation was evaluated by 3σ. The smaller the value, the better the performance.
The results are shown in Table 1.

In Table 1, the numerical values in parentheses in the acid generator column and the basic compound column represent the content (g).
In Table 1, the numerical values in parentheses in the solvent column represent the mass ratio.
In Table 1, the contents of the resin, the hydrophobic resin, and the surfactant are as described in each column in the table (unit: g).

From the results in Table 1, it can be seen that the sensitive light-sensitive or radiation-sensitive resin composition of the example is excellent in LWR of the formed pattern. On the other hand, according to the sensitive light-sensitive or radiation-sensitive resin composition of the comparative example, the LWR of the formed pattern cannot achieve the desired level.
By comparison with Examples 1 and 5, it was confirmed that the LWR is more excellent when the acid represented by the general formula (I) is the acid represented by the general formula (III).
By comparison of Examples 1 to 3 and 6, the acid represented by the general formula (I) is the acid represented by the general formula (III), and X ₂ is -CO-O- or -CO-. In some cases, it was confirmed that the LWR was superior.
By comparison of Examples 1 to 3 and 4, the acid represented by the general formula (I) is the acid represented by the general formula (III), and at least one of R ₂ is a fat containing an alicyclic structure. It was confirmed that the LWR is superior when it is a group hydrocarbon group.

Claims (11)

A sensitive light-sensitive or radiation-sensitive resin composition containing a compound that generates an acid represented by the following general formula (I) when irradiated with active light or radiation.

(I)
In general formula (I),
R ₁ represents a hydrogen atom or an organic group.
R ₂ represents an organic group.
X ₁ represents a cyano group or a nitro group.
X ₂ is a divalent selected from -CO-O-, -CO-, -CO-S-, -CO-NR-, -SO _2- , -SO _3- , -O-, and -S-. Represents a linking group of. R represents a hydrogen atom or a hydrocarbon group.
l represents 0 or 1.
m represents 1 or 2.
n represents 1 .
However, l + m + n = 3 and m + n = 2 or 3.
When a plurality of X ₁ , R ₂ , and X ₂ exist, they may be the same or different from each other . The actinic or radiation-sensitive resin composition according to claim 1, wherein the acid represented by the general formula (I) is an acid represented by the following general formula (II).

(II)
In general formula (II),
R ₁ , R ₂ , X ₁ , and X ₂ are synonymous with R ₁ , R ₂ , X ₁ , and X ₂ in the general formula (I).
m represents 1 and n represents 1 . The actinic or radiation-sensitive resin composition according to claim 1 or 2, wherein R ₁ is a hydrogen atom. A sensitive light-sensitive or radiation-sensitive resin composition containing a compound that generates an acid represented by the following general formula (I) when irradiated with active light or radiation.

(I)
In general formula (I),
R ₁ represents a hydrogen atom.
R ₂ represents an organic group.
X ₁ represents a cyano group or a nitro group.
X ₂ is a divalent selected from -CO-O-, -CO-, -CO-S-, -CO-NR-, -SO _2- , -SO _3- , -O-, and -S-. Represents a linking group of. R represents a hydrogen atom or a hydrocarbon group.
l represents 0 or 1.
m represents an integer of 0 to 2.
n represents 1 or 2.
However, l + m + n = 3 and m + n = 2 or 3.
When a plurality of X ₁ , R ₂ , and X ₂ exist, they may be the same or different from each other . The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein X ₂ is -CO-O- or -CO-. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein R ₂ is an aliphatic hydrocarbon group. The actinic light-sensitive or radiation-sensitive resin composition according to claim 6, wherein at least one of R ₂ is an aliphatic hydrocarbon group containing an alicyclic structure. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 , further comprising a resin having a group that decomposes due to the action of an acid and has an increasing polarity. A resist film formed by using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8 . A resist film forming step of forming a resist film using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8 .
The exposure process for exposing the resist film and
A developing step of developing the exposed resist film with a developing solution, and
A pattern forming method including. A method for manufacturing an electronic device, including the pattern forming method according to claim 10 .