TW201702743A - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern molding method, and electronic device production method - Google Patents

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) that includes a repeating unit (a) having an Si atom, a crosslinking agent (B), and a compound (C) that generates an acid upon irradiation with active light or radiation (with the caveat that a repeating unit having the Si atom has a structure in which a polar group is protected by a leaving group that is decomposed and removed by the action of the acid, and if the Si atom is only included in the leaving group, the repeating unit is not included in the repeating unit (a)); an actinic ray-sensitive or radiation-sensitive film that includes the actinic ray-sensitive or radiation-sensitive resin composition; a pattern molding method using the actinic ray-sensitive or radiation-sensitive resin composition; and an electronic device production method using the pattern molding method.

Description

Photosensitive ray- or radiation-sensitive resin composition, sensitized ray-sensitive or radiation-sensitive film, pattern forming method, and method of manufacturing electronic device

The present invention relates to a sensitized ray- or radiation-sensitive resin composition, a sensitized ray-sensitive or radiation-sensitive film, a pattern forming method, and a method of producing an electronic device. More specifically, the present invention relates to a lithography process suitable for semiconductor manufacturing processes such as IC (Integrated Circuit), manufacturing of circuit substrates such as liquid crystals and thermal heads, and other photofabrication processes. A sensitizing ray-sensitive or radiation-sensitive resin composition, a sensitizing ray-sensitive or radiation-sensitive film, a pattern forming method, and a method of producing an electronic device.

In order to compensate for the decrease in sensitivity caused by light absorption after the photoresist for KrF excimer laser (248 nm), an image forming method called chemical amplification is used as an image forming method of photoresist. When an image forming method of positive-type chemical amplification is exemplified, an image forming method is disclosed in which an acid generator in an exposed portion is decomposed to generate an acid by exposure, and in post-exposure baking (Post Exposure Bake: PEB) The generated acid was used as a reaction catalyst to change the alkali-insoluble group into an alkali-soluble group, and the exposed portion was removed by alkali development.

In order to miniaturize the semiconductor element, the short wavelength of the exposure light source and the high number of openings (high NA) of the projection lens are being developed, and an exposure machine using an ArF excimer laser as a light source having a wavelength of 193 nm has been developed. When an ArF excimer laser is used as an exposure light source, a compound having an aromatic group exhibits a large absorption in the 193 nm region in nature, and thus an ArF excimer laser photoresist containing a resin having an alicyclic hydrocarbon structure is being developed. Further, as a technique for further improving the resolution, a method of filling a liquid having a high refractive index (hereinafter also referred to as "liquid immersion liquid") between the projection lens and the sample (that is, a liquid immersion method) is proposed. Further, EUV (Extreme Ultra violet) lithography using a shorter wavelength (13.5 nm) of ultraviolet light is also advocated.

In recent years, a negative image forming method including an organic solvent developing program in which a developing solution containing an organic solvent (hereinafter also referred to as "organic solvent developing solution") is used for development is developed (in the organic solvent developing program) For example, refer to Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2011-13812 [Patent Document 2] JP-A-2011-100089

The integrated body of the integrated circuit is getting higher and higher, and the etching resistance of the photoresist pattern is further improved, and the width and pitch of the photoresist pattern are narrowed. If the circuit line width is reduced, the difference (optical contrast) between the exposure amount of the exposed area and the unexposed area is reduced, and the difference in the dissolution speed of the developer in the low exposure area, the intermediate exposure area, and the high exposure area becomes small, thereby Causes contrast to deteriorate. Such deterioration of the contrast causes line width Width (RWR) of the fine line pattern and the like.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sensitized ray-sensitive or radiation-sensitive resin which is excellent in etching resistance, has a high dissolution contrast in an exposed portion and an unexposed portion, and has excellent LWR performance. A composition and a sensitizing ray-sensitive or radiation-sensitive film. Further, an object of the present invention is to provide a pattern forming method using the above-described sensitized ray-sensitive or radiation-sensitive resin composition, and a method of manufacturing an electronic device including the pattern forming method.

In one aspect, the invention is as follows. [1] A photosensitive ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) comprising a repeating unit (a) having a Si atom; a crosslinking agent (B); and by actinic ray or radiation The compound (C) which produces an acid upon irradiation. Wherein, the repeating unit having a Si atom has a structure for protecting a polar group by a decomposing group which is decomposed by an action of an acid, and, when the Si atom is contained only in the above-mentioned leaving group, the repeating unit is not included in the above repeating unit (a).

[2] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin in the sensitized ray-sensitive or radiation-sensitive resin composition is based on the total solid content in the composition The content of (A) is 50% by mass or more.

[3] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [1] or [2] wherein the repeating unit (a) having the above Si atom has a decane structure.

[4] The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3] wherein the repeating unit (a) having the above Si atom has a sesquiterpene oxide structure.

[5] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4] wherein the content of Si atoms in the resin (A) is 10% by mass or more. In the above, the resin (A) is a repeating unit having a structure for protecting a polar group by a leaving group which is desorbed by an action of an acid, and when the leaving group includes a repeating unit having a Si atom, the Si contained in the leaving group The atom is not included in the above content ratio of the Si atom.

[6] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1], wherein the resin (A) comprises a reaction capable of reacting with the crosslinking agent (B). Repeat unit (d) of the reactive group. Among them, the repeating unit (d) having the above crosslinkable reactive group may have a structure for protecting the crosslinkable reactive group by a decomposing group which is decomposed and desorbed by the action of an acid.

[7] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6] wherein the crosslinking agent (B) comprises a melamine-based crosslinking agent and urea. At least one of a crosslinking agent, a phenol crosslinking agent, an epoxy crosslinking agent, a vinyl ether crosslinking agent, and a glycoluric crosslinking agent.

[8] The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7] wherein the resin (A) contains a repeating unit (c) having an acid-decomposable group.

[9] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8] wherein the resin (A) has a lactone structure, a sultone structure, and a cyclic carbonic acid a repeating unit (b) of at least any one of the ester structures.

[10] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9] which is used for development using a developing solution containing an organic solvent.

[11] A sensitizing ray-sensitive or radiation-sensitive linear composition according to any one of [1] to [10].

[12] A pattern forming method comprising: forming a photosensitive ray-sensitive or radiation-sensitive film comprising the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10]; The sensitizing ray-sensitive or radiation-sensitive film is exposed; and the exposed sensitizing ray-sensitive or radiation-sensitive film is developed using a developing solution containing an organic solvent to form a pattern.

[13] A method of producing an electronic device, comprising the pattern forming method according to [12]. [Effect of the invention]

According to the present invention, it is possible to provide a sensitized ray-sensitive or radiation-sensitive resin composition and a sensitizing ray property which are excellent in etching resistance, have high dissolution contrast in an exposed portion and an unexposed portion, and have excellent LWR performance. Radiation sensitive film. Moreover, according to the present invention, it is possible to provide a pattern forming method using the above-described sensitized ray-sensitive or radiation-sensitive resin composition, and a method of manufacturing an electronic device including the pattern forming method.

Hereinafter, preferred aspects of the invention will be described in detail. In the group of the present specification and the label of the atomic group, in the case where the substitution or the unsubstituted is not indicated, both the substituent-free group and the substituent-containing group are included. For example, it is not indicated that the substituted or unsubstituted "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present invention, "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam, or the like. . Further, in the present invention, "light" means actinic rays or radiation.

Further, the term "exposure" in the present specification means not only exposure by far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) represented by a mercury lamp or an excimer laser, but also including Drawing by a particle beam such as an electron beam or an ion beam.

In the present specification, "(meth) acrylate" means "at least one of acrylate and methyl acrylate". Further, “(meth)acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

[Photosensitive ray-sensitive or radiation-sensitive resin composition (photoresist composition)] The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention" or "the present invention" The photoresist composition") contains: a resin (A) comprising a repeating unit (a) having a Si atom (hereinafter also referred to as "repeating unit (a)"); a crosslinking agent (B); A compound (C) which produces an acid by irradiation of actinic rays or radiation.

In the present invention, a resin (A) (hereinafter, also referred to as "resin (A)") and a crosslinking agent (B) containing a repeating unit (a) having a Si atom is used in combination as a first feature.

Wherein the repeating unit having a Si atom contained in the resin (A) has a structure for protecting a polar group by a decomposing group which is decomposed and desorbed by an action of an acid, and the repeating unit is contained only when the Si atom is contained in the above-mentioned leaving group Not included in repeat unit (a).

That is, when the repeating unit having a Si atom is a repeating unit containing only Si atoms in the leaving group, the debonding group containing the Si atom is volatilized by exposure and subsequent heating (Post Exposure Bake: PEB), and the obtained pattern is obtained. The content of Si atoms is low. On the other hand, such a case does not occur in the repeating unit (a) having Si atoms, and therefore the content of Si atoms in the obtained pattern does not become low, and a pattern excellent in etching resistance can be obtained.

On the other hand, the organic molecule containing Si atoms is highly hydrophobic, and therefore, when a negative pattern is formed using a photoresist composition containing a resin (A) containing a repeating unit (a) having a Si atom, the unexposed portion is used in the unexposed portion. The hydrophobicity of the repeating unit (a) increases the dissolution rate of the organic solvent developing solution. On the other hand, since the composition of the present invention contains a crosslinking agent, a crosslinking reaction in which an acid is generated as a catalyst is carried out in the exposed portion, and the permeability of the organic solvent developing solution is lowered to lower the dissolution rate. As a result of the increase in the dissolution contrast between the exposed portion and the unexposed portion, it is estimated that a pattern excellent in LWR can be obtained.

Further, the composition of the present invention is a typical chemically amplified photoresist composition. Hereinafter, each component contained in the composition of the present invention will be described. [1] Resin (A) The resin (A) contains a repeating unit (a) having a Si atom. The content of Si atoms contained in the resin (A) is preferably 10% by mass or more, more preferably 12% by mass or more, even more preferably 15% by mass or more, and 18 masses, based on the total mass of the resin (A). More than % is especially good.

Furthermore, in the aspect of the invention, the content of Si atoms contained in the resin (A) is preferably 30% by mass or less, based on the total mass of the resin (A).

Here, the resin (A) is a repeating unit having a structure for protecting a polar group by using a leaving group which is desorbed by an action of an acid, and when the leaving group includes a repeating unit having a Si atom, the Si atom contained in the leaving group is not The above content ratio of Si atoms is included.

Further, in the present specification, a repeating unit having both a Si atom and an acid-decomposable group corresponds to a repeating unit (a) having a Si atom, and corresponds to a repeating unit having an acid-decomposable group. For example, a resin composed only of repeating units having both Si atoms and acid-decomposable groups corresponds to a resin containing a repeating unit (a) having a Si atom and a repeating unit having an acid-decomposable group. In addition, the "acid-decomposable group" will be described in the repeating unit (c) having an acid-decomposable group described later.

First, the repeating unit (a) having a Si atom will be described, and then the repeating unit which the resin (A) may contain will be described.

[1-1] Repeating unit having Si atom (a) The repeating unit (a) having a Si atom is not particularly limited as long as it has a Si atom. For example, a repeating unit having a decane structure (-SiR ₂ -: R ₂ is an organic group), a repeating unit having a decane structure (-SiR ₂ -O-: R ₂ is an organic group), and a Si atom are mentioned. A (meth) acrylate-based repeating unit, an ethylene-based repeating unit having a Si atom, or the like.

It is preferred that the repeating unit (a) having a Si atom does not have an acid-decomposable group.

In one embodiment of the present invention, the repeating unit (a) having a Si atom preferably has a decane structure, and more preferably has a sesquiterpene structure. In addition, it may have a decane structure or a sesquioxane structure in the main chain, or a decane structure or a sesquioxane structure in the side chain, but a decane structure or a sesquiterpene in the side chain. The oxyalkylene structure is preferred.

Examples of the sesquiterpene oxide structure include a cage sesquiterpene oxide structure, a stepped sesquiterpene alkane structure (a ladder type sesquiterpene oxide structure), and a random sesquiterpene alkane structure. Among them, a cage sesquiterpene structure is preferred.

Here, the cage sesquiterpene structure refers to a sesquiterpene structure having a cage skeleton. The cage sesquiterpene structure may be a completely caged sesquiterpene structure or an incomplete cage sesquiterpene structure, but a fully caged sesquiterpene structure is preferred.

Further, the ladder type sesquiterpene oxide structure means a sesquiterpene structure having a stepped skeleton.

Further, the random sesquioxane structure means that the skeleton is a random sesquiterpene structure.

The above cage sesquioxane structure is preferably a oxoxane structure represented by the following formula (S).

[Chemical Formula 1]

In the above formula (S), R represents a monovalent substituent. A plurality of Rs may be the same or different.

The substituent is not particularly limited, and specific examples thereof include a halogen atom, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an amine group, a fluorenyl group, and a blocked fluorenyl group (for example, a thiol group (protected)). Mercapto), fluorenyl, fluorenylene, phosphino, phosphinyl, germyl, vinyl, hydrocarbyl group having a hetero atom, a group containing a (meth)acryl group, and an epoxy group-containing group Wait.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hetero atom which may have a hydrocarbon group of a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

Examples of the hydrocarbon group which may have a hydrocarbon group having a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups.

The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic chain. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly, a carbon number of 1 to 30), a linear or branched alkenyl group (especially 2 to 30 carbon atoms), A linear or branched alkynyl group (especially 2 to 30 carbon atoms).

The aromatic hydrocarbon group may, for example, be an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group.

The repeating unit (a) having a Si atom is preferably represented by the following formula (I).

[Chemical Formula 2]

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

Examples of the divalent linking group include an alkylene group, a -COO-Rt- group, and an -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

A L-based single bond or a -COO-Rt- group is preferred. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

In the above formula (I), X represents a hydrogen atom or an organic group.

The organic group may, for example, be an alkyl group which may have a substituent such as a fluorine atom or a hydroxyl group, and a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferred.

In the above formula (I), A represents a group containing Si. Among them, a group represented by the following formula (a) or (b) is preferred.

[Chemical Formula 3]

In the above formula (a), R represents a monovalent substituent. A plurality of Rs may be the same or different. Specific examples and preferred aspects of R are the same as those of the above formula (S). * indicates the bonding position with L in the above formula (I). Further, when A in the above formula (I) is a group represented by the above formula (a), the above formula (I) is represented by the following formula (I-a).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formula (b), R _b each independently represents a hydrocarbon group which may have a hetero atom. Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom are the same as those in the above formula (S). * indicates the bonding position with L in the above formula (I).

The repeating unit (a) having a Si atom contained in the resin (A) may be used alone or in combination of two or more.

The content ratio of the repeating unit (a) having a Si atom contained in the resin (A) with respect to the total repeating unit in the resin (A) (the total of the repeating units (a) having a plurality of Si atoms) is 1 to 70 mol% is preferred, and 3 to 50 mol% is more preferred.

[1-2] Repeating unit having an acid-decomposable group The resin (A) preferably contains a repeating unit having an acid-decomposable group (hereinafter also referred to as "repeating unit (c)"). It is preferred that the repeating unit (c) having an acid-decomposable group does not have a Si atom.

Here, the acid-decomposable group refers to a group which is decomposed by the action of an acid to form a polar group.

It is preferred that the acid-decomposable group has a structure in which a polar group is decomposed by a group which is decomposed and desorbed by the action of an acid to protect the polar group.

The polar group is not particularly limited as long as it is insoluble or insoluble in a developing solution containing an organic solvent, and examples thereof include a phenolic hydroxyl group, a carboxyl group, and a fluorinated alcohol group (hexafluoroisopropanol group). Preferred), sulfonic acid group, sulfonylamino group, sulfonyl sulfoximine, (alkylsulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene , bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indenylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)indolylene, tris(alkylcarbonyl) An acidic group such as a methylene group or a tris(alkylsulfonyl)methylene group (a group which has been used as a resist for developing a photoresist, a dissociated group in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide), or an alcoholic hydroxyl group Wait.

Further, the alcoholic hydroxyl group means a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and a fat which is substituted by an electron withdrawing group such as a fluorine atom as a hydroxyl group. Except for a group of alcohols (for example, a fluorinated alcohol group (hexafluoroisopropanol group, etc.)). As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferable.

Preferred examples of the polar group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A group which is preferably an acid-decomposable group is a group substituted by a group which desorbs a hydrogen atom of the group by an acid.

Examples of the group (debonding group) which utilizes acid detachment include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R). ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and so on.

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 are bonded 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 arylalkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group and a second butyl group. Hexyl, octyl, etc.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a monocyclic type or a polycyclic type. The monocyclic type 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. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl group, norbornyl group, isobornyl group, fluorenyl group, dicyclopentyl group, and α-decenyl group (α). -pinenyl), tricyclodecyl, tetracyclododecyl, androstanyl, and the like. Further, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group having 6 to 10 carbon atoms of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ is preferably an aryl group, for example, a phenyl group, a naphthyl group or an anthracenyl group.

The aralkyl group having 7 to 12 carbon atoms of R ₃₆ to R ₃₉ and 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 having 2 to 8 carbon atoms of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ is preferably an alkyl group, an allyl group, a butenyl group or a cyclohexenyl group.

As the ring formed by bonding R ₃₆ and R ₃₇ , a cycloalkyl group (monocyclic or polycyclic) is preferred. As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a cycloalkyl group, a tetracyclononyl group, a tetracyclododecyl group or an adamantyl group is preferably a polycyclic cycloalkyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

As the acid-decomposable group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like is preferable. A tertiary alkyl ester group is further preferred.

The resin (A) preferably has a repeating unit represented by the following formula (AI) as the repeating unit (c) having an acid-decomposable group. The repeating unit represented by the general formula (AI) is a carboxyl group which is a polar group by the action of an acid, and exhibits a high interaction based on a hydrogen bond in a plurality of carboxyl groups, so that it can be formed more reliably. The negative pattern is insoluble or poorly soluble with respect to the solvent in the composition of the present invention described above.

[Chemical Formula 6]

In the general formula (AI), Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.

Two of Rx ₁ to Rx ₃ may be bonded to form a ring structure.

Examples of the divalent linking group of T include an alkylene group, a -COO-Rt- group, a -O-Rt- group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkyl group.

A T-based single bond or a -COO-Rt- group is preferred. The Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group. A single T key is preferred.

The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (a fluorine atom is preferred).

The alkyl group having 1 to 4 carbon atoms of Xa ₁ is preferably an alkyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferred.

Xa ₁ is a hydrogen atom or a methyl group is preferred.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and preferably may be methyl, ethyl, n-propyl, isopropyl, n-butyl or the like. Butyl, tert-butyl, and the like. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5.

Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx _{3 ,} a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a sulfhydryl group, a tetracyclononyl group, a tetracyclododecyl group or an adamantyl group. A cycloalkyl group is preferred.

a ring structure formed by two bonds of Rx ₁ , Rx ₂ and Rx ₃ , a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, a norbornane ring, a tetracyclodecane ring, and a tetracyclic ring A polycyclic cycloalkyl group such as a dialkyl ring or an adamantane ring is preferred. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferred.

Rx ₁ , Rx ₂ and Rx ₃ are each independently an alkyl group, and a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), a halogen atom, and an alkoxy group (carbon number). 1 to 4), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, and preferably having 8 or less carbon atoms. Among them, from the viewpoint of further improving the dissolution contrast of the developer containing the organic solvent before and after the acid decomposition, the substituent having no hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom is more preferable (for example, it is not a hydroxyl group). Further, a substituted alkyl group or the like is more preferable, and a group consisting only of a hydrogen atom and a carbon atom is further preferable, and a linear or branched alkyl group or a cycloalkyl group is particularly preferable.

In the general formula (AI), Rx ₁ to Rx ₃ are each independently an alkyl group, and it is preferred that two of Rx ₁ to Rx ₃ are bonded without forming a ring structure. Therefore, there is a tendency that the volume of the group represented by -C(Rx ₁ )(Rx ₂ )(Rx ₃ ), which is a group decomposed and desorbed by the action of an acid, can be suppressed, and the exposure process and the exposure process can be suppressed. The volume shrinkage of the exposed portion can be suppressed in the post-exposure heating process performed after the exposure process.

Specific examples of the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples.

In a specific example, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each independently represent an alkyl group (preferably having 1 to 10 carbon atoms and more preferably an alkyl group having 1 to 5 carbon atoms). Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Z represents a substituent. When there are a plurality of substituents, a plurality of Zs may be the same or different. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituents which each group such as Rx ₁ to Rx ₃ can have.

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

Further, the resin (A) is preferably a repeating unit described in paragraphs <0057> to <0071> of JP-A-2014-202969, and is preferably a repeating unit (c) having an acid-decomposable group.

In addition, the resin (A) may have a repeating unit which forms an alcoholic hydroxyl group as described in paragraphs <0072> to <0073> of JP-A-2014-202969, as a repeating unit (c) having an acid-decomposable group.

The repeating unit (c) having an acid-decomposable group may be one type or two or more types may be used in combination.

When the resin (A) contains the repeating unit (c) having an acid-decomposable group, the content thereof (total when a plurality of repeating units (c) are present) is 20 to 90 with respect to the total repeating unit in the resin (A) Molar% is preferred, and 40 to 80 mol% is more preferred. Here, the resin (A) has a repeating unit represented by the above formula (AI), and the content of the repeating unit represented by the above formula (AI) with respect to the total repeating unit of the resin (A) is 40 mol% or more. Preferably.

[1-3] Recurring unit (d) having a crosslinkable reactive group capable of reacting with a crosslinking agent Resin (A) comprises a crosslinkable reactive group capable of reacting with a crosslinking agent contained in the composition of the present invention The repeating unit (hereinafter also referred to as "repeating unit (d)") is preferred.

Examples of the crosslinkable reactive group include an alcoholic hydroxyl group, a thiol group, an amine group, an epoxy group, an oxetanyl group, a vinyloxy group, a carboxyl group, and an ester group. From the viewpoints of crosslinking efficiency and ease of handling, the crosslinking unit (d) has a crosslinkable reactive group which is preferably an alcoholic hydroxyl group or a carboxyl group.

The resin (A) contains such a crosslinkable reactive group, whereby the crosslinkable reactive group reacts with the crosslinking agent by the action of an acid in the exposed portion, and the sensitized ray-sensitive or radiation-sensitive film is substantially insoluble in the organic solvent. Developer solution.

Further, in the present invention, the repeating unit (d) having a crosslinkable reactive group may have a structure which protects the crosslinkable reactive group by using a leaving group which is decomposed and desorbed by the action of an acid.

The structure which protects the crosslinkable reactive group by the cleavage group, for example, the carboxyl group which protects the crosslinkable reactive group by the specific example of the cleavage group in the repeating unit (c) which has the acid-decomposable group mentioned above. Acid-decomposable group.

Further, the structure of the alcoholic hydroxyl group which protects the crosslinkable reactive group by the leaving group includes a structure such as a carbonate group, an acetal group or a third ether group, and a carbonate group or an acetal group is preferred. When the alcoholic hydroxyl group has a 1,2-diol or a 1,3-diol structure, preferred examples thereof include a cyclic ester and a cyclic orthoester.

The repeating unit (d) having a crosslinkable reactive group which may be contained in the resin (A) may be used alone or in combination of two or more.

When the resin (A) contains the repeating unit (d) having a crosslinkable reactive group, the content of the total repeating unit in the resin (A) (the total number of repeating units (d) is present) is 1 ~80% by mole is preferred, and 5 to 80% by mole is more preferred.

[1-4] Repeating unit (b) having at least any one of a lactone structure, a sultone structure, and a cyclic carbonate structure (A) The resin (A) comprises a lactone structure, a sultone structure, and a cyclic carbonate A repeating unit of at least one of the structures (hereinafter also referred to as "repeating unit (b)") is preferred.

As the lactone structure or the sultone structure, any one may be used as long as it has a lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered cyclic sultone structure is preferable. Forming a bicyclic structure on a 5- to 7-membered ring lactone structure, a ring-ring structure in the form of a ring-ring structure having another ring structure, or forming a bicyclic structure or a spiro ring structure in a 5- to 7-membered cyclic sultone structure It is better to have other ring structures in the ring. The lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-21) or represented by any one of the following general formulae (SL1-1) to (SL1-3) The repeating unit of the sultone structure is further preferred. Also, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), A particularly preferred lactone structure is (LC1-4). By using this specific lactone structure, LWR and development defects become good.

[Chemical Formula 10]

The lactone moiety or the sultone moiety may have a substituent (Rb ₂ ) or may have no substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 2 carbon atoms. ～8 alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group, and the like. More preferably, an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid-decomposable group is used. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used. Further, one type of optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, the optical purity (ee) is preferably 90% or more, and more preferably 95% or more.

The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following formula (III).

[Chemical Formula 11]

In the above formula (III), A represents an ester bond (a group represented by -COO-) or a guanamine bond (a group represented by -CONH-).

When a plurality of R ₀ are present, each independently represents an alkylene group, a cycloalkyl group, or a combination thereof.

When there are a plurality of Z, they independently represent a single bond, an ether bond, an ester bond, a guanamine bond, or a urethane bond.

[Chemical Formula 12]

Urea bond

[Chemical Formula 13]

Wherein R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

n is a repeating number of the structure represented by -R ₀ -Z-, and represents an integer of 0 to 5, 0 or 1 is preferable, and 0 is more preferable. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and the cycloalkyl group of R ₀ may have a substituent.

Z-ether ether bonds and ester bonds are preferred, and ester bonds are particularly preferred.

The alkyl group of R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkyl group, the cycloalkyl group, and the alkyl group in R ₇ of R ₀ may be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a fluorenyl group, a hydroxyl group or a methoxy group. An alkoxy group such as an ethoxy group, an isopropoxy group, a tert-butoxy group or a benzyloxy group; an anthracene group such as an ethoxy group or a propyloxy group;

R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The chain alkyl group having 1 to 10 carbon atoms which is preferably a chain alkyl group in R ₀ is preferably a chain alkyl group having 1 to 5 carbon atoms, and more preferably, for example, a methylene group. Stretching ethyl, stretching propyl and the like. The ring-opening alkyl group having 3 to 20 carbon atoms is preferably a cyclohexylene group, a cyclopentylene group, a Norbornylene group, an adamantyl group or the like. In order to exhibit the effects of the present invention, a chain alkyl group is more preferable, and a methylene group is particularly preferable.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and specific examples thereof include a formula (LC1-1) to The lactone structure or the sultone structure represented by any of (LC1-21) and (SL1-1) to (SL1-3) is particularly preferable in the structure represented by (LC1-4). And (LC1-1) ~ (LC1-21) in the system n ₂ is more preferably an integer of 2 or less.

Further, R ₈ is a monovalent organic group having an unsubstituted lactone structure or a sultone structure, or a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent or a sultone structure. The valent organic group is preferably a monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent.

Specific examples of the repeating unit including a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

In order to enhance the effect of the present invention, two or more kinds of repeating units having a lactone structure or a sultone structure may be used in combination.

When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 with respect to the total repeating unit in the resin (A) Molar% is preferred, and 5 to 55 mol% is more preferably 10 to 50 mol%, further preferably.

Further, the resin (A) may contain a repeating unit having a carbonate structure (cyclic carbonate structure).

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

[Chemical Formula 17]

In the formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.

When n is 2 or more, R _A ² each independently represents a substituent.

A represents a single bond or a divalent linking group.

Z represents an atomic group which forms a monocyclic or polycyclic structure together with a group represented by -O-C(=O)-O- in the formula.

n represents an integer of 0 or more.

The general formula (A-1) will be described in detail.

The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and preferably a methyl group is more preferable.

The substituent represented by R _A ² is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amine group or an alkoxycarbonylamino group. The alkyl group having 1 to 5 carbon atoms is preferable, and examples thereof include a linear alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group; an isopropyl group and an isobutyl group; A branched alkyl group having 3 to 5 carbon atoms such as a third butyl group. The alkyl group may have a substituent such as a hydroxyl group.

n is an integer of 0 or more indicating the number of substituents. For example, 0 to 4 is preferable, and 0 is more preferable.

Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, a guanamine bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an exoethyl group, and a propyl group.

In one embodiment of the present invention, the A-line single bond and the alkylene group are preferred.

The monocyclic ring containing -OC(=O)-O- represented by Z, for example, 5 to 7 in which n _A = 2 to 4 in the cyclic carbonate represented by the following general formula (a) A member ring, a 5-member ring or a 6-member ring (n _A = 2 or 3) is preferred, and a 5-member ring (n _A = 2) is preferred.

The polycyclic ring containing -OC(=O)-O- represented by Z, for example, a cyclic carbonate represented by the following general formula (a) and a ring structure represented by 1 or 2 or more together form a condensed ring. The structure or the structure of the spiral ring. The "other ring structure" which can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hetero ring.

[Chemical Formula 18]

The monomer corresponding to the repeating unit represented by the above formula (A-1) can be, for example, by Tetrahedron Letters, Vol. 27, No. 32 p. 3741 (1986), Organic Letters, Vol. 4, No. 15. A conventionally known method described in p.2561 (2002) or the like is synthesized.

One type of the repeating unit represented by the formula (A-1) may be contained in the resin (A), and two or more types may be contained.

In the resin (A), the content of the repeating unit having a cyclic carbonate structure (the repeating unit represented by the general formula (A-1) is preferable) is higher than the total repeating unit 3 constituting the resin (A). 80% by mole is preferred, 3 to 60% by mole is further preferred, and 3 to 40% by mole is particularly preferred. By setting such a content ratio, it is possible to improve developability as a photoresist, low defect, low LWR (Line Width Roughness), low PEB (Post Exposure Bake) temperature dependency, contour, and the like.

Specific examples of the repeating unit represented by the general formula (A-1) (repeating units (A-1a) to (A-1w)) are given below, but the present invention is not limited thereto.

Further, the following specific examples are the same as R _A ¹ in the general formula (A-1) in the meaning of R _A ^1.

[Chemical Formula 19]

[Other Repeating Units] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group. Examples of such a repeating unit include the repeating unit described in paragraphs <0081> to <0084> of JP-A-2014-098921.

Further, the resin (A) may contain a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, a bis-sulfonyl fluorenylene group, and an aliphatic alcohol having an α-position substituted with an electron withdrawing group (for example, a hexafluoroisopropanol group). ). Examples of the repeating unit having an alkali-soluble group include the repeating unit described in paragraphs <0085> to <0086> of JP-A-2014-098921.

Further, the resin (A) further contains an alicyclic hydrocarbon structure which does not have a polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group or the like), and can have a repeating unit which does not exhibit acid decomposition property. Examples of the repeating unit include the repeating unit described in paragraphs <0114> to <0123> of JP-A-2014-106299.

Further, the resin (A) may include, for example, a repeating unit described in paragraphs <0045> to <0065> of JP-A-2009-258586.

In addition to the above-mentioned repeating structural unit, for the purpose of adjusting dry etching resistance or standard developer suitability, substrate adhesion, photoresist profile, and resolution, heat resistance, sensitivity, etc., which are generally required for photoresist In addition, the resin (A) used in the method of the present invention can also have various repeating structural units. Examples of such a repeating structural unit include repeating structural units corresponding to the following monomers, but are not limited thereto.

Thereby, the properties required for the resin (A) used in the composition of the present invention, in particular, (1) solubility with respect to a coating solvent, (2) film forming property (glass transition temperature), ( 3) alkali developability, (4) thin film formation (hydrophobicity, alkali-soluble base selection), (5) adhesion of the unexposed portion to the substrate, (6) dry etching resistance, and the like are finely adjusted.

Examples of such a monomer include acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. A compound having one addition polymerizable unsaturated bond or the like.

In addition to this, it is possible to copolymerize as long as it is an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to the above various repeating structural units.

In the resin (A), in order to adjust the dry etching resistance or the standard developer suitability of the photoresist, the substrate adhesion, the photoresist profile, and the resolution, heat resistance, sensitivity, etc., which are generally required for the photoresist, The molar ratio of each repeating structural unit is appropriately set.

When the composition of the present invention is used for ArF exposure, it is preferred that the resin (A) does not substantially have an aromatic group from the viewpoint of transparency to ArF light. More specifically, in the total repeating unit of the resin (A), the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and more preferably 0 mol%. Further, it is further preferred that the repeating unit having no aromatic group is contained. Further, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

As the resin (A), it is preferred that all of the repeating units are composed of a (meth) acrylate-based repeating unit. In this case, any of the repeating units may be a methyl acrylate-based repeating unit, all of the repeating units may be an acrylate-based repeating unit, and any of the repeating units may be based on any of a methyl acrylate-based repeating unit and an acrylate-based repeating unit. The acrylate-based repeating unit is preferably 50 mol% or less of the total repeating unit.

The resin (A) can be synthesized in accordance with a conventional method such as radical polymerization. For example, as a general synthesis method, a polymerization method in which a monomer type and an initiator are dissolved in a solvent and heated to carry out polymerization, and a solution in which a monomer type and an initiator are dropped over 1 to 10 hours are mentioned. The dropwise addition polymerization method or the like is added to the heating solvent, and the dropwise addition polymerization method is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone, such as ethyl acetate. An ester solvent such as ester solvent, guanamine solvent such as dimethylformamide or dimethylacetamide, and dissolution of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone as described later. A solvent for the composition of the present invention. More preferably, the polymerization is carried out using the same solvent as the solvent used in the composition of the present invention. Thereby, generation of particles during storage can be suppressed.

The polymerization is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate polymerization. As the radical initiator, an azo initiator is preferred, and an azo initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). The initiator is added in an additional or batchwise manner as needed, and after completion of the reaction, it is introduced into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The reaction concentration is preferably 5 to 50% by mass, and preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and further preferably from 60 to 100 ° C.

As described above, the content of Si atoms in the resin (A) is preferably 10% by mass or more.

In the above, the repeating unit having a Si atom has a structure in which a polar group is protected by a decomposing group which is decomposed and desorbed by an action of an acid, and when the exfoliating group has a Si atom, the content of the Si atom in the resin (A) The amount of Si atoms in the leaving group is not contained. That is, even if Si atoms are present in the leaving group, the amount of Si atoms is not included in the content of Si atoms in the resin (A).

For example, the repeating unit on the right side of the resin A-19 used in Comparative Example 4 to be described later has Si atoms derived from TMS (trimethylformamidine), but the above repeating unit has a leaving group (*: bond) The junction position) protects the structure of the polar group (-COOH), and therefore the amount of Si atoms derived from TMS in the leaving group is not contained in the content of Si atoms in the resin. Further, the above repeating unit contains only Si atoms in the leaving group, and thus does not conform to the repeating unit (a) of the present invention.

[Chemical Formula 20]

The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, still more preferably from 3,000 to 15,000, and particularly preferably from 3,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance or dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated.

The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0. The smaller the molecular weight distribution, the more excellent the resolution and the photoresist shape, and the side walls of the photoresist pattern are smooth and excellent in roughness.

In the present specification, the weight average molecular weight is a standard polystyrene equivalent value obtained by gel permeation chromatography (GPC) under the following conditions.・Type of column: TSK gel Multipore HXL-M (manufactured by TOSOH CORPORATION, 7.8mmID × 30.0cm) ・Expanding solvent: THF (Tetrahydrofuran: tetrahydrofuran) ・Temperature temperature: 40°C ・Flow rate: 1ml/min ・Sample injection amount: 10μl - Device name: HLC-8120 (manufactured by TOSOH CORPORATION) The content of the resin (A) in the total solid content of the composition of the present invention is preferably 50% by mass or more. The content of the resin (A) is preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content of the resin (A) is not particularly limited, but in one embodiment of the present invention, 95% by mass or less is preferable. In the present invention, the resin (A) may be used alone or in combination of plural kinds.

[2] Crosslinking agent The composition of the present invention contains a compound having an acid crosslinkable group (hereinafter also referred to as "crosslinking agent (B)" or "compound (B)"). In one embodiment of the present invention, the crosslinking agent (B) is selected from the group consisting of a melamine crosslinking agent, a urea crosslinking agent, a phenol crosslinking agent, an epoxy crosslinking agent, a vinyl ether crosslinking agent, and The compound of the urea-based crosslinking agent is preferably used, and one type of these may be used alone or two or more types may be used.

Further, in another embodiment of the present invention, the crosslinking agent (B) is preferably a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. Further, from the viewpoint of increasing the LWR, the compound (B) preferably contains a methylol group.

As the compound (B), a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound, and an alkoxy group are preferably mentioned. A urea compound. The particularly preferable compound (B) includes a phenol derivative and an alkoxy group having 3 to 5 benzene rings in the molecule and having 2 or more hydroxymethyl groups or alkoxymethyl groups in total, and having a molecular weight of 1200 or less. Methylglycolide derivative.

As the alkoxymethyl group, a methoxymethyl group or an ethoxymethyl group is preferred.

In the example of the above compound (B), a phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound having no corresponding hydroxymethyl group with formaldehyde under a base catalyst. Further, the phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol under an acid catalyst.

Further, examples of the other preferable compound (B) include, for example, an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound, and an alkoxymethylated urea compound. A compound of N-hydroxymethyl or N-alkoxymethyl.

Examples of such a compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, and 1,3-dimethoxymethyl-4,5-dimethoxy Ethyl urea, dimethoxymethyl urea, and the like are disclosed in EP 0,133,216 A, West German Patent No. 3,634,671, West German Patent No. 3,711,264, and EP 0,212,482 A.

Further, examples of other preferable compounds (B) include ethylene glycol ethylene ether, trimethylolpropane trivinyl ether, and 1,4-cyclohexane dimethanol divinyl ether. Alkyl ether crosslinking agent.

Further, examples of other preferable compounds (B) include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerin. Diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol An epoxy-based crosslinking agent such as erythritol polycondensation or diglycerin polyglycidyl ether.

The following is a particularly preferable example of the compound (B).

[Chemical Formula 21]

[Chemical Formula 22]

In the formula, L ₁ to L ₈ each independently represent a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or an alkyl group having 1 to 6 carbon atoms.

In one embodiment of the present invention, the compound (B) is preferably a phenol compound represented by the following formula (I).

[Chemical Formula 23]

In the formula (I), R ₁ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms.

R ₂ and R ₅ each independently represent an alkyl group, a cycloalkyl group, an aryl group or a fluorenyl group.

R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R ₃ and R ₄ may be bonded to each other to form a ring.

In one embodiment of the invention, R ₁ and R ₆ are preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, and particularly preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. .

The alkyl group represented by R ₂ and R ₅ is preferably an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms as an aryl group. For example, an aryl group having 6 to 12 carbon atoms is preferred, and as the fluorenyl group, for example, a fluorenyl group having 1 to 6 carbon atoms in the alkyl group is preferred.

In one embodiment of the present invention, R ₂ and R ₅ are preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.

Examples of the organic group having 2 or more carbon atoms represented by R ₃ and R ₄ include an alkyl group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, and the like, and R ₃ and R ₄ are bonded to each other to form a group. It is preferred to form a ring as detailed below.

Examples of the ring formed by bonding R ₃ and R _{4 to} each other include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic hetero ring, or a combination of two or more of these rings. Ring condensation ring.

These rings may have a substituent, and examples of the substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, a decyl group, an alkoxy group, and a nitro group. , halogen atom or hydroxyl group.

Hereinafter, specific examples in which R ₃ and R ₄ are bonded to each other to form a ring will be described. * in the formula indicates a linking site with a phenol nucleus.

[Chemical Formula 24]

In one embodiment of the present invention, it is preferred that R ₃ and R ₄ in the formula (I) are bonded to each other to form a polycyclic condensed ring containing a benzene ring, and it is more preferable to form a fluorene structure.

The compound (B) is preferably bonded to R ₃ and R ₄ in the formula (I) to form a fluorene structure represented by the following formula (Ia).

[Chemical Formula 25]

In the formula, R ₇ and R ₈ each independently represent a substituent. The substituent may, for example, be an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, a decyl group, an alkoxycarboxy group, a nitro group, a halogen atom or a hydroxyl group.

N1 and n2 each independently represent an integer of 0 to 4, indicating that 0 or 1 is preferable.

* indicates the site of attachment to the phenol nucleus.

Further, in one embodiment of the present invention, the compound (B) is preferably represented by the following formula (I-b).

[Chemical Formula 26]

In the formula, R _1b and R _6b each independently represent an alkyl group having 5 or less carbon atoms.

R _2b and R _5b each independently represent an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

Z represents an atomic group required to form a ring together with a carbon atom in the formula.

The ring formed by Z together with the carbon atom in the formula is the same as that described for the ring in which R ₃ and R ₄ are bonded to each other in the description of the above formula (I).

In one embodiment of the present invention, the compound (B) preferably has four or more aromatic rings in the molecule, and a total of two alkoxymethyl groups and/or hydroxymethyl groups.

Next, a method for producing the compound (B) represented by the formula (I) will be described.

The bisphenol compound which is a mother nucleus of the compound (B) represented by the formula (I) is generally synthesized by subjecting a corresponding two molecules of a phenol compound to a corresponding one molecule of a ketone in a dehydration condensation reaction in the presence of an acid catalyst. .

The obtained bisphenol is treated with paraformaldehyde and dimethylamine, and subjected to aminomethylation to obtain an intermediate represented by the following formula (I-C). Then, it is subjected to acetylation, deacetylation, and alkylation to obtain an intended acid crosslinking agent.

[Chemical Formula 27]

In the formula, R ₁ , R ₃ , R ₄ and R ₆ have the same meanings as the respective groups in the formula (I).

Compared with the conventional method of synthesizing a methylol group under a base condition (for example, JP-A-2008-273844), the present synthesis method is difficult to form an oligomer, and therefore has a particle formation suppressing effect.

Specific examples of the compound (B) represented by the formula (I) are shown below.

[Chemical Formula 28]

In the present invention, the compound (B) may be used singly or in combination of two or more. From the viewpoint of a good pattern shape, it is preferred to use two or more kinds in combination.

The compound (B) containing an acid crosslinkable group may be in the form of a resin (hereinafter, also referred to as a compound (B'')) containing a repeating unit having an acid crosslinkable group.

In the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition, the content of the crosslinking agent (B) in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is 0.5 to 30% by mass. Good, 1~15% by mass is better. [3] Compound which generates an acid by irradiation with actinic rays or radiation. The composition of the present invention contains a compound (C) which generates an acid by irradiation with actinic rays or radiation (hereinafter, also referred to as "acid generator" "or "Compound (C)"). The acid generator is not particularly limited, but a compound which generates an organic acid by irradiation with actinic rays or radiation is preferred. The acid generator may be a low molecular compound or may be contained in a resin (for example, the above-mentioned resin (A) or the like).

As the acid generator, a photoinitiator which is photocationically polymerized, a photoinitiator which is photoradically polymerized, a photodecolorizer of a dye, a photochromic agent, or a light resist used in a microphotoresist can be suitably selected and used. For example, a compound described in paragraphs <0039> to <0103> of JP-A-2010-61043, and JP-A-2013 The compound described in paragraphs <0284> to <0389> of the '4820 publication, but the present invention is not limited thereto.

For example, a diazonium salt, a sulfonium salt, a sulfonium salt, a sulfonium salt, a quinone imide sulfonate, an anthracene sulfonate, a diazodiazine, a diterpene, an o-nitrobenzyl sulfonate can be mentioned.

For the acid generator to be contained in the composition of the present invention, for example, a compound (specific acid generator) which generates an acid by irradiation with actinic rays or radiation, which is represented by the following general formula (3), can be suitably used.

[Chemical Formula 29]

(Anion) In the formula (3), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ are present in plural plural, they may be the same or different.

L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.

W represents an organic group containing a cyclic structure.

o represents an integer from 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Further, an alkyl-based perfluoroalkyl group substituted with at least one fluorine atom is preferred.

The Xf-based fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferred. The Xf-based fluorine atom or CF ₃ is more preferred. In particular, both of the Xf-based fluorine atoms are preferred.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ are present in plural plural, they may be the same or different.

The alkyl group of R ₄ and R ₅ may have a substituent, and an alkyl group having 1 to 4 carbon atoms is preferred. The R ₄ and R ₅ -based hydrogen atoms are preferred.

Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as those of the specific examples and preferred aspects of Xf in the formula (3).

L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.

Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, - SO-, -SO ₂ -, alkylene (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 3 to 10 carbon atoms), and alkenyl group (having 2 to 6 carbon atoms) Preferably, or a combination of the plurality of divalent linking groups or the like. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO-alkylene-preferably, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene - For better.

W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferred.

Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

The alicyclic group may be a single ring type or a polycyclic type. The monocyclic alicyclic group may, for example, be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a thiol group, a tricyclodecanyl group, a tetracyclononyl group, a tetracyclododecyl group, and an adamantyl group. Among them, from the viewpoint of suppressing the diffusibility in the film in the PEB (post-exposure heating) process and improving the MEEF (Mask Error Enhancement Factor), a thiol group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group An alicyclic group having a bulky structure having 7 or more carbon atoms such as adamantyl group is preferred.

The aryl group may be a single ring type or a polycyclic type. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group. Among them, a naphthalene group having a relatively low light absorbance in 193 nm is preferred.

The heterocyclic group may be a monocyclic ring or a polycyclic ring, and the polycyclic ring is more capable of inhibiting acid diffusion. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferred. Further, examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above resin (A).

The above cyclic organic group may have a substituent. The substituent may, for example, be an alkyl group (which may be either a straight chain or a branched group, preferably having 1 to 12 carbon atoms) or a cycloalkyl group (which may be monocyclic, polycyclic or spiro). Any one, preferably having 3 to 20 carbon atoms, an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, or a ureido group. , thioether group, sulfonamide group and sulfonate group. Further, the carbon constituting the cyclic organic group (carbon which contributes to ring formation) may be a carbonyl carbon.

o represents an integer from 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

In the one state, o in the formula (3) is an integer of 1 to 3, p is an integer of 1 to 10, and q is 0. The Xf-based fluorine atom is preferred, and both R ₄ and R ₅ are preferably a hydrogen atom, and a W-based polycyclic hydrocarbon group is preferred. o is 1 or 2 is more preferred, and 1 is further preferred. An integer of p to 1 to 3 is more preferable, 1 or 2 is further more preferable, and 1 is particularly preferable. The W-based polycyclic cycloalkyl group is more preferably, and an adamantyl group or a diadamantyl group is further preferred. (cation) In the formula (3), X ⁺ represents a cation.

X ⁺ is not particularly limited as long as it is a cation, and preferred examples thereof include a cation (a portion other than Z ^- ) in the above-described general formula (ZI), (ZII) or (ZIII). (Preferred aspect) As a preferable aspect of the specific acid generator, for example, a compound represented by the following formula (ZI), (ZII) or (ZIII) can be mentioned.

[Chemical Formula 30]

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has usually 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butenyl group and a pentyl group).

Z ^- represents an anion in the formula (3), and specifically represents the following anion.

[Chemical Formula 31]

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups of the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) which will be described later. .

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, it may also be represented by the general formula having a R (ZI) the compound in ₂₀₁ ~ R ₂₀₃ R via at least one linking group or a single bond with another of the compound represented by the general formula (ZI) ₂₀₁ ~ R ₂₀₃ A compound of at least one bonded structure.

Further preferred (ZI) components include the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

First, the compound (ZI-1) will be described.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the above formula (ZI) is an aryl group, that is, a compound having an aryl hydrazine as a cation.

In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound.

As the aryl group of the arylsulfonium compound, a phenyl group or a naphthyl group is preferred, and a phenyl group is further preferred. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an anthracene residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, two or more aryl groups may be the same or different.

The aryl hydrazine compound is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, which may be an alkyl group or a cycloalkyl group, and a methyl group having 3 to 15 carbon atoms. , ethyl, propyl, n-butyl, t-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ may have an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group (for example, a carbon number of 6). ～14), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.

The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. The aromatic ring means an aromatic ring containing a hetero atom.

The organic group which does not contain an aromatic ring of _R201 to _R203 is usually a carbon number of 1 to 30, and preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonyl group. A methyl group is further preferred, and a linear or branched 2-oxoalkyl group is particularly preferred.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably 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 or a pentyl group). a cycloalkyl group having a carbon number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

Next, the compound (ZI-3) will be described.

The compound (ZI-3) means a compound represented by the following formula (ZI-3), which is a compound having a benzamidine methyl phosphonium salt structure.

[Chemical Formula 32]

In the formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a ring. An alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring structure, and the ring structure may include An oxygen atom, a sulfur atom, a ketone group, an ester bond, or a guanamine bond.

Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic fused ring in which two or more such rings are combined. The ring structure may be a 3 to 10 member ring, a 4 to 8 member ring is preferred, and a 5 or 6 member ring is more preferred.

_Examples of the group formed by bonding any two or more of R _1c to R _5c and R _6c and R _7c and R _x and R _y include a butenyl group and a pentyl group.

The group formed by bonding R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an exoethyl group.

Zc ^- represents an anion in the formula (3), specifically as described above.

Specific examples of R _1c ~ R _5c alkoxycarbonyl group the alkoxy group of the above-described specific examples of R _1c ~ R _5c alkoxy same.

Specific examples of R _1c ~ R _5c alkylcarbonyloxy group and alkylthio group with a particular group of examples _1c ~ R _5c R is the same as the above-described alkyl group.

Specific examples of R _1c ~ R _5c cycloalkylcarbonyl group in the cycloalkyl group and the above-described specific examples of R _1c ~ R _5c cycloalkyl same.

As R _1c ~ R _5c and aryloxy Specific embodiments of aryl groups in the aryl group and specific examples of the R _1c ~ R _5c aryl group is the same.

Examples of the cation in the compound (ZI-2) or (ZI-3) of the present invention include the cations described later in the paragraph <0036> of the specification of the U.S. Patent Application Publication No. 2012/0076996.

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

The compound (ZI-4) is represented by the following formula (ZI-4).

[Chemical Formula 33]

In the 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 a substituent.

When a plurality of R ₁₄ are present, each independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Group. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R _{15 groups} may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one state, two R ₁₅ are an alkyl group and are bonded to each other to form a ring structure.

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Z ^- represents an anion in the formula (3), specifically as described above.

In the formula (ZI-4), the alkyl group as R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, and an alkyl group having 1 to 10 carbon atoms is preferred, and methyl group, ethyl group, and N-butyl, tert-butyl and the like are preferred.

Examples of the cation of the compound represented by the formula (ZI-4) of the present invention include paragraphs <0121>, <0123>, <0124> and JP-A-2011-76056 of JP-A-2010-256842. The cations described in paragraphs <0127>, <0129>, <0130>, and the like of the publication.

Next, the general formulae (ZII) and (ZIII) will be described.

In the general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

As the aryl group of R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferred, and a phenyl group is further preferred. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, anthracene, benzofuran, and benzothiophene.

The alkyl group and the cycloalkyl group in R ₂₀₄ to R ₂₀₇ are preferably 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 or a pentyl group). And a cycloalkyl group having a carbon number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent which the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ has may be an alkyl group (for example, a carbon number of 1 to 15) or a cycloalkyl group (for example, a carbon number of 3 to 15). An aryl group (for example, a carbon number of 6 to 15), an alkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group.

Z ^- represents an anion in the formula (3), specifically as described above.

The acid generator (including a specific acid generator. The same applies hereinafter) may be in the form of a low molecular compound or a form in which a part of the polymer is incorporated. Further, the form of the low molecular compound and the form of a part of the polymer may be used in combination.

When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 580 or more, more preferably 600 or more, further preferably 620 or more, and particularly preferably 640 or more. The upper limit is not particularly limited, but preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

When the acid generator is in a form of being incorporated into a part of the polymer, a part of the above-mentioned resin (A) may be incorporated, or a resin different from the resin (A) may be incorporated.

The acid generator can be synthesized by a known method, and can be synthesized, for example, according to the method described in JP-A-2007-161707.

The acid generator can be used alone or in combination of two or more.

The content of the composition of the acid generator (in total for a plurality of species) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, more preferably 3 to 20, based on the total solid content of the composition. The mass % is further preferably, and 3 to 15% by mass is particularly preferable.

When the compound represented by the above formula (ZI-3) or (ZI-4) is contained as the acid generator, the content of the acid generator contained in the composition (the total of the plurality of species is present) is composed of The total solid content of the material is preferably from 5 to 35% by mass, more preferably from 8 to 30% by mass, even more preferably from 9 to 30% by mass, even more preferably from 9 to 25% by mass.

[4] Hydrophobic Resin The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)"). Further, the hydrophobic resin (D) is preferably different from the resin (A).

The hydrophobic resin (D) is preferably designed to be biased at the interface, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it is not effective for uniformly mixing a polar/nonpolar substance.

The effect of adding a hydrophobic resin is control of the static/dynamic contact angle of the surface of the photoresist film with respect to water, improvement of the liquid immersion liquid followability, suppression of degassing, and the like.

The hydrophobic resin (D) has one or more of a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin" from the viewpoint of the surface layer of the film. Preferably, it is further preferable to have two or more types.

When the hydrophobic resin (D) contains a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin (D) may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, a resin having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferred as a partial structure having a fluorine atom.

An alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have a fluorine atom. Substituents other than the substituents.

The cycloalkyl group having a fluorine atom and the aryl group having a fluorine atom are each a cycloalkyl group in which one hydrogen atom is substituted by a fluorine atom and an aryl group having a fluorine atom, and may further have a substituent other than a fluorine atom.

The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom are preferably groups represented by the following general formulae (F2) to (F4), but the present invention It is not limited to this.

[Chemical Formula 34]

In the general formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched). Wherein at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ independently represent a fluorine atom or at least one hydrogen atom by a fluorine atom. A substituted alkyl group (having preferably 1 to 4 carbon atoms).

It is preferred that all of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom (preferably having 1 to 4 carbon atoms), and a perfluoroalkyl group having 1 to 4 carbon atoms is further preferred. good. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

The hydrophobic resin (D) may contain a ruthenium atom. As the partial structure having a ruthenium atom, a resin having an alkylformamidine structure (trialkylcarbenyl group is preferred) or a cyclic oxirane structure is preferred.

Examples of the repeating unit having a fluorine atom or a ruthenium atom are exemplified in the specification [0519] of U.S. Patent Application Publication No. 2012/0251948.

Further, as described above, it is also preferred that the hydrophobic resin (D) has a CH ₃ moiety structure in the side chain portion.

Wherein, in the side chain moiety (D) a hydrophobic resin having the partial structure ₃ CH (hereinafter, also referred to as "partial structure of side chain CH _3") contains the portion of the CH ₃ group, a propyl group or the like having structure.

On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) is affected by the main chain to the hydrophobic resin (D) The surface biasing is less helpful and therefore is not included in the CH ₃ partial structure of the present invention.

More specifically, in the case where the hydrophobic resin (D) contains, for example, a repeating unit represented by the following general formula (M), a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, When R ₁₁ to R ₁₄ are CH ₃ "by itself", CH _{3 is} not included in the CH ₃ moiety structure of the side chain moiety of the present invention.

On the other hand, via the presence of certain atoms from the backbone of CH ₃ CC partial structure corresponding to the partial structure CH ₃ of the present invention. For example, when R ₁₁ is ethyl (CH ₂ CH ₃ ), it has "one" structure of the CH ₃ moiety of the present invention.

[Chemical Formula 35]

In the above formula (M), R ₁₁ to R ₁₄ each independently represent a side chain moiety.

Examples of R ₁₁ to R ₁₄ which are side chain moieties include a hydrogen atom and a monovalent organic group.

The monovalent organic group for R ₁₁ to R ₁₄ may, for example, be an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group or a cycloalkylamine. The carbonyl group, the arylaminocarbonyl group and the like may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in a side chain portion, and as such a repeating unit, has a repeating unit represented by the following formula (II) and is passed through More than at least one repeating unit (x) of the repeating unit represented by the formula (III) is more preferable.

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

[Chemical Formula 36]

In the above formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an acid-stable organic group having one or more CH ₃ partial structures. Among them, more specifically, an organic group having no acid-decomposable group described in the resin (A) is preferred for the acid-stable organic group.

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

X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloaliphatic group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloaliphatic group, aryl group and aralkyl group may further have an alkyl group as a substituent.

R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ moiety structures.

The acid-stable organic group having one or more CH ₃ partial structures of R ₂ has two or more and ten or less CH ₃ partial structures, and more preferably two or more and eight or less.

Preferred specific examples of the repeating unit represented by the formula (II) are shown below. In addition, the invention is not limited to this.

[Chemical Formula 37]

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a repeat having no group which decomposes by the action of an acid and generates a polar group. The unit is preferred.

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

[Chemical Formula 38]

In the above formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ moiety structures, and n represents an integer of 1 to 5 .

The alkyl group of X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is preferred.

The X _{b 2} -based hydrogen atom is preferred.

R ₃ is an organic group which is stable to an acid, and therefore, more specifically, an organic group which does not have the "acid-decomposable group" described in the above resin (A) is preferred.

Examples of R ₃ include an alkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures of R ₃ has one or more and 10 or less CH ₃ partial structures, and preferably one or more and eight or less, more preferably One or more and four or less are further preferable.

n represents an integer of 1 to 5, and an integer of 1 to 3 is more preferable, and 1 or 2 is further preferable.

Preferred specific examples of the repeating unit represented by the formula (III) are shown below. In addition, the invention is not limited to this.

[Chemical Formula 39]

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a repeat having no group which decomposes by an action of an acid and generates a polar group. The unit is preferred.

When the hydrophobic resin (D) contains a CH ₃ partial structure in a side chain moiety, and particularly, does not have a fluorine atom and a ruthenium atom, the repeating unit represented by the general formula (II) and the general formula (III) The content of at least one repeating unit (x) in the repeating unit is preferably 90 mol% or more, more preferably 95 mol% or more, based on the total repeating unit of the hydrophobic resin (D). The content is usually 100 mol% or less based on the total repeating unit of the hydrophobic resin (D).

The hydrophobic resin (D) contains at least 90 mol% or more of the repeating unit represented by the general formula (II) and at least the repeating unit represented by the general formula (III) with respect to the total repeating unit of the hydrophobic resin (D) A repeating unit (x) whereby the surface free energy of the hydrophobic resin (D) is increased. As a result, the hydrophobic resin (D) is hardly biased on the surface of the photoresist film, and the static/dynamic contact angle of the photoresist film with respect to water can be reliably improved, and the liquid immersion liquid followability can be improved.

Further, the hydrophobic resin (D) may have at least one selected from the group consisting of (i) in the case where (i) contains a fluorine atom and/or a ruthenium atom, and (ii) in the case where the side chain portion contains a CH ₃ partial structure. The group in the group of (x) to (z) below.

(x) acid group, (y) a group having a lactone structure, an acid anhydride group or a hydrazide imine group, (z) a group decomposed by the action of an acid as an acid group (x), and phenol Hydroxyl, carboxylic acid, fluorinated alcohol, sulfonic acid, sulfonylamino, sulfonyl fluorenylene, (alkylsulfonyl) (alkylcarbonyl) methylene, (alkyl sulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)anthracene An imido group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, and the like.

Preferred examples of the acid group include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonium sulfonate group, and a bis(alkylcarbonyl)methylene group.

Examples of the repeating unit having an acid group (x) include a repeating unit in which an acid group is directly bonded to a main chain of a resin such as a repeating unit based on acrylic acid or methacrylic acid, or a resin in a resin via a linking group. A repeating unit having an acid group bonded to the main chain or the like can be introduced into the end of the polymer chain by using a polymerization initiator or a chain transfer agent having an acid group during polymerization, which is preferable in any case. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a halogen atom.

The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, more preferably from 5 to 20 mol%, based on the total repeating unit in the hydrophobic resin (D). % is further preferred.

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

[Chemical Formula 40]

[Chemical Formula 41]

As the group having a lactone structure, an acid anhydride group or an acid sulfonimide group (y), a group having a lactone structure is particularly preferable.

The repeating unit containing the groups is, for example, a repeating unit in which a group is directly bonded to a main chain of the resin based on a repeating unit of acrylate or methacrylate. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin by polymerization using a polymerization initiator or a chain transfer agent having the group.

The repeating unit having a group having a lactone structure may, for example, be the same as the repeating unit having a lactone structure described in the section of the resin (A).

The content of the group having a lactone structure, an acid anhydride group or a repeating unit having a hydrazide imine group is preferably from 1 to 100 mol% based on the total repeating unit in the hydrophobic resin (D), and is preferably 3 More preferably, ～98% by mole, and even more preferably 5 to 95% by mole.

The repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin (D) is the same as the repeating unit having an acid-decomposable group exemplified 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 ruthenium atom. The content of the repeating unit in the hydrophobic resin (D) having the group (z) decomposed by the action of an acid is preferably from 1 to 80 mol%, based on the total repeating unit in the resin (D), 10 More preferably, ～80 mol% is more preferably 20 to 60 mol%.

The hydrophobic resin (D) may further have a repeating unit different from the above repeating unit.

The repeating unit containing a fluorine atom is preferably from 10 to 100 mol%, more preferably from 30 to 100 mol%, based on the total repeating unit contained in the hydrophobic resin (D). Further, the repeating unit containing a halogen atom is preferably from 10 to 100 mol%, more preferably from 20 to 100 mol%, based on the total repeating unit contained in the hydrophobic resin (D).

On the other hand, in the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin (D) is preferably not substantially in the form of a fluorine atom or a ruthenium atom. Further, it is preferable that the hydrophobic resin (D) consists essentially only of a repeating unit composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.

The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin (D) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000.

Further, one type of the hydrophobic resin (D) may be used, or a plurality of types may be used in combination.

The content of the composition of the hydrophobic resin (D) is preferably from 0.01 to 10% by mass, more preferably from 0.05 to 8% by mass, based on the total solid content of the composition of the present invention.

The residual monomer or oligomer component of the hydrophobic resin (D) is preferably from 0.01 to 5% by mass, more preferably from 0.01 to 3% by mass. Further, the molecular weight distribution (Mw/Mn, also referred to as the degree of dispersion) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

The hydrophobic resin (D) can be synthesized by a conventional method (for example, radical polymerization) by using various commercially available products. [5] Acid Diffusion Control Agent The composition of the present invention preferably contains an acid diffusion controlling agent. The acid diffusion controlling agent functions as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excessive generation of acid, as an acid generated from an acid generator or the like during the capture exposure. As the acid diffusion controlling agent, a basic compound, a low molecular compound having a nitrogen atom and having a group desorbed by an action of an acid, and an alkalinity which is reduced or disappeared by irradiation with actinic rays or radiation can be used. A compound, or a phosphonium salt that is relatively weakly acidic relative to an acid generator.

[5-1] The basic compound may preferably be a compound having a structure represented by the following formulas (A) to (E).

[Chemical Formula 42]

In the general formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), or a cycloalkyl group (carbon atom). The number 3 to 20 is preferably a) or an aryl group (having 6 to 20 carbon atoms), wherein R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represent an alkyl group having 1 to 20 carbon atoms.

The alkyl group is preferably an 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. good.

The alkyl group in the above formulae (A) and (E) is preferably unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., and further preferred compounds are capable of A compound having an imidazole structure, a diazabicyclo structure, a ruthenium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, and an alkylamine derivative having a hydroxyl group and/or an ether bond An aniline derivative having a hydroxyl group and/or an ether bond.

Specific examples of preferred compounds include the compounds exemplified in the specification of US Patent Application Publication No. 2012/0219913 <0379>.

Further, as a preferred basic compound, an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group can be further exemplified.

These basic compounds may be used alone or in combination of two or more.

The composition of the present invention may or may not contain a basic compound. When a basic compound is contained, the content of the basic compound is usually 0.001 to 10% by mass based on the solid content of the composition. ～5% by mass is preferred.

The ratio of use of the acid generator to the basic compound in the composition is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300, more preferably 5.0 to 200, still more preferably 7.0 to 150.

[5-2] A low molecular compound having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter also referred to as "compound (F)") has a function of an acid on a nitrogen atom. Amine derivatives of the detached group are preferred.

As the group which is detached by the action of an acid, an acetal group, a carbonate group, a urethane group, a 3-stage ester group, a 3-stage hydroxyl group, a half-amine acetal group is preferable, and an aminocarboxylic acid is preferred. Ester groups and half amine acetal ether groups are particularly preferred.

The molecular weight of the compound (F) is preferably from 100 to 1,000, more preferably from 100 to 700, and particularly preferably from 100 to 500.

The compound (F) may have a urethane group having a protective group on a nitrogen atom. The protective group constituting the urethane group can be represented by the following formula (d-1).

[Chemical Formula 43]

In the formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), and an aryl group ( The number of carbon atoms is preferably from 3 to 30, the aralkyl group (preferably having 1 to 10 carbon atoms), or the alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by R _b may be a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group or an oxo group, or an alkoxy group. , halogen atom substitution. The alkoxyalkyl group represented by R _b is also the same.

As R _b , a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferred. A linear or branched alkyl group or a cycloalkyl group is more preferred.

Examples of the ring in which two R _b are bonded to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

The specific structure of the group represented by the formula (d-1) is exemplified by the structure disclosed in the specification of the US Patent Application Publication No. 2012/0135348, which is not limited thereto.

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

[Chemical Formula 44]

In the formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be bonded to each other to form a hetero ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

R _b same as in the general formula (d-1) of the definition of R _b, preferred embodiments are also the same.

l represents an integer of 0 to 2, and m represents an integer of 1 to 3, and satisfies l+m=3.

In the formula (6), the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group as R _a may be substituted with the same group as the aforementioned group of the group which may be substituted as R _b a group of an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

Specific examples of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group of the above R _a (the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group may be substituted by the above group) may be mentioned as follows. R _{b The} same group as the above specific examples.

Specific examples of the compound (F) which is particularly preferred in the present invention include the compounds disclosed in the specification of the U.S. Patent Application Publication No. 2012/0135348, which is incorporated herein by reference.

The compound represented by the formula (6) can be synthesized in accordance with JP-A-2007-298569, JP-A-2009-199021, and the like.

In the present invention, the low molecular compound (F) having a group which is detached by the action of an acid on the nitrogen atom may be used alone or in combination of two or more.

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

[5-3] A basic compound (hereinafter, also referred to as "compound (PA)") which is reduced or disappeared by alkali by irradiation with actinic rays or radiation. It is a proton-receptive functional group and is light-receiving. A compound which decomposes by irradiation of radiation or radiation and which has reduced proton acceptor properties, disappears, or changes from proton acceptor to acidity.

The proton acceptor functional group means a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or having a π-conjugated Functional groups that act as nitrogen atoms of a shared electron pair. The nitrogen atom having an unshared electron pair which does not contribute to π conjugate means, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical Formula 45]

Preferred examples of the structure of the proton acceptor functional group include a crown ether, an azacrown ether, a 1-3 amine, a pyridine, an imidazole, and a pyrazine structure.

The compound (PA) is a compound which is decomposed by irradiation with actinic rays or radiation to reduce or disappear the proton acceptor property or change from proton acceptor to acidity. The decrease or disappearance of proton acceptor or the change from proton acceptor to acid refers to the change of proton acceptor induced by proton acceptor functional group. Specifically, it refers to having When a proton acceptor functional group compound (PA) and a proton form a proton adduct, the equilibrium constant in the chemical equilibrium is reduced.

Proton acceptability can be confirmed by pH measurement.

In the present invention, the acid dissociation constant pKa of the compound produced by decomposition of the compound (PA) by the irradiation of actinic rays or radiation is preferably pKa < -1, and -13 < pKa < -1 is more preferable, - 13 < pKa < - 3 is further preferred.

In the present invention, the acid dissociation constant pKa represents an acid dissociation constant pKa in an aqueous solution, which is described, for example, in Chemical Fact (II) (Revision 4, 1993, edited by the Chemical Society of Japan, MARUZEN Co., Ltd.). The lower the value, the greater the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution, and can also be calculated by using the following software package 1 by Hammett. The value of the database of substituent constants and well-known literature values. The values of pKa described in the present specification all indicate values obtained by calculation using the software package.

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

The compound (PA), for example, produces a compound represented by the following formula (PA-1) as a proton adduct which is decomposed and produced by irradiation with actinic rays or radiation. The compound represented by the formula (PA-1) has an acidic group at the same time as having a proton-receptive functional group, and thus the proton acceptor is reduced, disappeared, or acidic from proton acceptor to the compound (PA). Compound of change.

[Chemical Formula 46]

In the formula (PA-1), Q represents -SO ₃ H, -CO ₂ H, or -W ₁ NHW ₂ R _f . Wherein R _f represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having preferably 6 to 30 carbon atoms), W ₁ And W ₂ independently represent -SO ₂ - or -CO-.

A represents a single bond or a divalent linking group.

X represents -SO ₂ - or -CO-.

n represents 0 or 1.

B represents a single bond, an oxygen atom or -N(R _x )R _y -. Wherein R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or may be bonded to R to form a ring.

R represents a monovalent organic group having a proton acceptor functional group.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in any one of the anion portion and the cation portion, and is preferably contained in the anion site.

Further, in the present invention, a compound (PA) other than the compound which produces the compound represented by the general formula (PA-1) can be appropriately selected. For example, a compound which is an ionic compound and has a proton acceptor moiety in the cation portion can be used. More specifically, a compound represented by the following formula (7) and the like can be given.

[Chemical Formula 47]

In the formula, A represents a sulfur atom or an iodine atom.

m represents 1 or 2, and n represents 1 or 2. Wherein, when A is a sulfur atom, m+n=3, and when A is an iodine atom, m+n=2.

R represents an aryl group.

R _N represents an aryl group substituted by a proton acceptor functional group. X ^- represents a counter anion.

Specific examples of X ^- may be the same as those of the above-mentioned acid generator.

A specific example of the aryl group of R and R _N is preferably a phenyl group.

Specific examples of the proton acceptor functional group possessed by R _N are the same as the proton acceptor functional group described in the above formula (PA-1).

In the following, as a specific example of the ionic compound having a proton acceptor moiety in the cation portion, a compound exemplified in the specification of US Patent Application Publication No. 2011/0269072, <0291> can be mentioned.

In addition, such a compound can be synthesized by referring to the methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

The compound (PA) may be used alone or in combination of two or more.

The content of the compound (PA) is preferably from 0.1 to 10% by mass, more preferably from 1 to 8% by mass based on the total solid content of the composition.

[5-4] In the composition of the present invention, an onium salt which is a relatively weak acid with respect to an acid generator can be used as an acid diffusion controlling agent.

When an acid generator is used in combination and a cerium salt which is a relatively weak acid acid with respect to an acid generated by an acid generator, an acid produced by an acid generator by irradiation with actinic radiation or radiation has When the unreacted weak acid anion is collided with a salt, a weak acid is released by salt exchange to form a phosphonium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid having a lower catalytic performance, so that the acid is deactivated in appearance and the acid diffusion can be controlled.

The onium salt which is a relatively weak acid with respect to the acid generator is preferably a compound represented by the following formulas (d1-1) to (d1-3).

[Chemical Formula 48]

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 (wherein a fluorine atom adjacent to the S atom is not substituted) R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkyl or aryl group, Rf is a hydrocarbon group containing a fluorine atom, and M ^{+ is} independently a phosphonium cation or a phosphonium cation.

Preferable examples of the phosphonium cation or the phosphonium cation represented by M ⁺ include a phosphonium cation exemplified by the general formula (ZI) and a phosphonium cation exemplified by the general formula (ZII).

A preferred example of the anion moiety of the compound represented by the formula (d1-1) is a structure exemplified in paragraph [0198] of JP-A-2012-242799.

A preferred example of the anion portion of the compound represented by the formula (d1 - 2) is a structure exemplified in paragraph [0201] of JP-A-2012-242799.

A preferred example of the anion portion of the compound represented by the formula (d1 - 3) is a structure exemplified in paragraphs [0209] and [0210] of JP-A-2012-242799.

The onium salt which becomes a relatively weak acid with respect to the acid generator may be (C) a compound having a cationic moiety and an anionic moiety in the same molecule and a cationic moiety and an anionic moiety linked by a covalent bond (hereinafter, also referred to as "a compound" (CA)".).

The compound (CA) is preferably a compound represented by any one of the following formulae (C-1) to (C-3).

[Chemical Formula 49]

In the general formulae (C-1) to (C-3), R ₁ , R ₂ and R _{3 each} represent a substituent having 1 or more carbon atoms.

L ₁ represents a divalent linking group or a single bond linking the cation moiety to the anion site.

-X ^- represents an anion moiety selected from the group consisting of -COO ^- , -SO ₃ ^- , -SO ₂ ^- , -N ^- -R ₄ . R ₄ represents a carbonyl group at a point of attachment to an adjacent N atom: -C(=O)-, sulfonyl group: -S(=O) ₂ -, sulfinyl group: -S(=O)- A monovalent substituent.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, and an alkylaminocarbonyl group. And a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, or the like. Alkyl groups, cycloalkyl groups, and aryl groups are preferred.

The L ₁ which is a divalent linking group may, for example, be a linear or branched alkyl group, a cycloalkyl group, an extended aryl group, a carbonyl group, an ether bond, an ester bond, a guanamine bond, a urethane bond, or a urea. A bond or a group obtained by combining these two or more types. More preferably, L ₁ is an alkyl group, an aryl group, an ether bond, an ester bond, or a combination of two or more of them.

Preferred examples of the compound represented by the formula (C-1) include paragraphs [0037] to [0039] of JP-A-2013-6827 and JP-A-2013-8020. The compound exemplified in 0027] to [0029].

Preferred examples of the compound represented by the formula (C-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP-A-2012-189977.

A preferred example of the compound represented by the formula (C-3) is a compound exemplified in paragraphs [0029] to [0031] of JP-A-2012-252124.

The content of the onium salt which is a relatively weak acid with respect to the acid generator is preferably from 0.5 to 10.0% by mass, more preferably from 0.5 to 8.0% by mass, even more preferably from 1.0 to 8.0% by mass, based on the solid content of the composition. good. [6] Solvent The composition of the present invention usually contains a solvent.

Examples of the solvent which can be used in the preparation of the composition include an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate, and an alkoxypropionic acid alkyl group. An ester or a cyclic lactone (preferably having 4 to 10 carbon atoms), a monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), an alkyl carbonate, an alkyl alkoxyacetate. An organic solvent such as an alkyl pyruvate.

Specific examples of such a solvent are described in the specification of U.S. Patent Application Publication No. 2008/0187860, <0441> to <0455>.

In the present invention, 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 in the structure are mixed may be used.

The solvent containing a hydroxyl group and the solvent containing no hydroxyl group can be suitably selected from the above-exemplified compounds, and as the solvent containing a hydroxyl group, an alkyl glycol monoalkyl ether, an alkyl lactate or the like is preferable, and propylene glycol monomethyl ether is preferable. (Propylene glycol monomethyl ether: PGME, alias 1-methoxy-2-propanol), ethyl lactate, methyl 2-hydroxyisobutyrate is more preferred. Further, as a solvent containing no hydroxyl group, an alkylene glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a monoketone compound which may contain a ring, a cyclic lactone, an alkyl acetate, etc. Preferably, among these, Propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-ethoxypropane propane), ethyl ethoxypropionate, 2 - Heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone are most preferred.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing no hydroxyl group is preferably 1/99 to 99/1, 10/90 to 90/10, and more preferably 20/80 to 60/40. In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable.

The solvent is preferably propylene glycol monomethyl ether acetate, and a mixed solvent of two or more kinds of propylene glycol monomethyl ether acetate alone solvent or propylene glycol monomethyl ether acetate is preferred. [7] Surfactant The composition of the present invention may further contain a surfactant or may not contain a surfactant, and when it contains a surfactant, it contains a fluorine-based and/or a lanthanoid surfactant (fluorine-based surfactant). Any one or two or more of a lanthanoid surfactant and a surfactant having both a fluorine atom and a ruthenium atom are more preferable.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a photoresist pattern having less adhesion and development defects can be provided with good sensitivity and resolution.

The surfactant described in the paragraph <0276> of the specification of U.S. Patent Application Publication No. 2008/0248425 is exemplified as the fluorine-based and/or lanthanide-based surfactant.

Further, in the present invention, other surfactants other than the fluorine-based and/or lanthanoid-based surfactants described in paragraph <0280> of the specification of U.S. Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used singly or in combination of several kinds.

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

On the other hand, when the amount of the surfactant added is 10 ppm or less based on the total amount of the composition (excluding the solvent), the surface bias of the hydrophobic resin is improved, whereby the surface of the photoresist film can be made more It is hydrophobic and can improve water followability during immersion exposure. [8] Other Additives The composition of the present invention may or may not contain a ruthenium carboxylate salt. The carboxylic acid cerium salt can be described in the specification of the US Patent Application Publication No. 2008/0187860, <0605> to <0606>.

These carboxylic acid cerium salts can be synthesized by reacting cerium hydroxide, cerium hydroxide, ammonium hydroxide and a carboxylic acid with silver oxide in a suitable solvent.

When the composition of the present invention contains a cerium carboxylate salt, the content thereof is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the total solid content of the composition. .

The composition of the present invention can further contain an acid sputum agent, a dye, a plasticizer, a photosensitizer, a light absorbing agent, an alkali-soluble resin, a dissolution inhibitor, and a compound which promotes solubility with respect to a developing solution (for example, a molecular weight of 1,000). The following phenol compound, alicyclic group having a carboxyl group or an aliphatic compound).

For the phenolic compound having a molecular weight of 1,000 or less, for example, the method described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent No. 219294 can be used. See, synthesis by one skilled in the art with ease.

Specific examples of the alicyclic or aliphatic compound having a carboxyl group include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid or lithocholic acid, an adamantanecarboxylic acid derivative, and an adamantane dicarboxylic acid. And cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, etc., but it is not limited to these.

The solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7 % by mass, more preferably 2.0 to 5.3 % by mass. By setting the solid content concentration to the above range, the photoresist solution can be uniformly applied onto the substrate, and a photoresist pattern having excellent line width roughness can be formed. The reason for this is not clear, but it is considered that the solid content concentration is preferably 10% by mass or less and 5.7% by mass or less, whereby the raw material, particularly the photoacid generator, can be suppressed in the photoresist solution. Coagulation results in the formation of a uniform photoresist film.

The solid content concentration means the mass percentage of the mass of the other photoresist component other than the solvent with respect to the total mass of the composition.

The method for producing the composition of the present invention is not particularly limited, and it is preferred that the above components are dissolved in a predetermined organic solvent, dissolved in the mixed solvent, and filtered by a filter. The pore size of the filter for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and more preferably 0.03 μm or less. More preferably, it is made of polytetrafluoroethylene, polyethylene or nylon. In the case of performing filter filtration, for example, it is possible to carry out cyclic filtration by connecting a plurality of types of filters in series or in parallel, or to perform filtration, as in JP-A-2002-62667. Also, the composition may be filtered several times. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered.

The composition of the present invention relates to a sensitized ray-sensitive or radiation-sensitive resin composition in which the properties are changed by irradiation with actinic rays or radiation. More specifically, the present invention relates to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal induction head, a die structure for imprinting, and other photosensitive etching processes, a lithographic printing plate, and acid hardenability. A sensitizing ray-sensitive or radiation-sensitive resin composition used in the composition.

Further, the present invention relates to a pattern forming method using such a sensitizing ray-sensitive or radiation-sensitive resin composition. Hereinafter, a process which can be included in the pattern forming method of the present invention will be described. [Step of Process (1)] The step of the process (1) is not particularly limited, and a method of applying the composition of the present invention to a substrate and performing a curing treatment as needed (coating method), or A method of forming a sensitized ray-sensitive or radiation-sensitive film on a pseudo support and transferring a sensitized ray-sensitive or radiation-sensitive film onto a substrate. Among them, a coating method is preferred in terms of excellent productivity.

The substrate is not particularly limited, and a substrate which is generally used in a semiconductor manufacturing process such as an IC, a manufacturing process of a circuit substrate such as a liquid crystal or a thermal induction head, and a photolithography process such as enamel, SiN, and SiO can be used. ₂ or an inorganic substrate such as TiN or a coated inorganic substrate such as SOG (Spin on Glass). Further, an antireflection film can be formed between the photoresist film and the substrate as needed. As the antireflection film, a known organic or inorganic antireflection film can be suitably used. Further, the pattern forming method of the present invention can be combined with, for example, a two-layer photoresist program as disclosed in Japanese Laid-Open Patent Publication No. 2008-083384, or a plurality of exposures as disclosed in the pamphlet of International Publication No. 2011/122336. And the development process is combined. When the procedure disclosed in the pamphlet of the present invention and the International Publication No. 2011/122336 is incorporated, the second negative pattern forming method in the first application of the International Patent Publication No. 2011/122336 is applicable to the pattern of the present invention. The formation method is preferred. [Photosensitive ray-sensitive or radiation-sensitive film] The thickness of the sensitizing ray-sensitive or radiation-sensitive film is not particularly limited. However, from the viewpoint of forming a fine pattern having a higher precision, 1 to 500 nm is preferable, and 1 to 500 nm is preferable. 100nm is better. By setting the solid content concentration in the composition to an appropriate range and having an appropriate viscosity, and improving coatability and film formability, the film thickness can be set. [Process (2): Exposure Process] The process (2) is a process for irradiating (exposing) actinic rays or radiation to a film (photosensitive ray or radiation sensitive film) formed in the process (1).

The light used for exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, and the like. The far ultraviolet light of 250 nm or less is preferable, 220 nm or less is more preferable, and 1-200 nm is a further preferable wavelength.

More specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer lasers, ArF excimer lasers, EUVs or electron beams are preferred, and ArF excimer lasers are preferred.

The immersion exposure method can be applied in the exposure process. The liquid immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a deformation illumination method. The immersion exposure can be carried out, for example, according to the method described in paragraphs <0594> to <0601> of JP-A-2013-242397.

In addition, when the receding contact angle of the sensitizing ray-sensitive or radiation-sensitive film formed using the composition of the present invention is too small, it cannot be suitably used when exposed through a liquid immersion medium, and the water residue (watermark) defect cannot be sufficiently exhibited. Effect. In order to achieve a preferable receding contact angle, it is preferred to include the above hydrophobic resin (D) in the composition. Alternatively, a liquid immersion liquid poorly soluble film (hereinafter also referred to as a "top coat film") formed of the above hydrophobic resin (D) may be provided on the upper layer of the sensitizing ray-sensitive or radiation sensitive film. A top coat film may also be provided on the sensitized ray-sensitive or radiation-sensitive film containing the hydrophobic resin (D). The function required for the top coating film is to apply the coating to the upper portion of the sensitizing ray or the radiation sensitive film, and the liquid immersion liquid is poorly soluble. It is preferable that the top coating film is not mixed with the composition film, and it can be further uniformly applied to the upper layer of the composition film.

The top coating film is not particularly limited, and a conventionally known top coating film can be formed by a conventionally known method. For example, the top layer can be formed in accordance with the description of paragraphs <0072> to <0082> of JP-A-2014-059543. Coating film.

It is preferable to form a top coat film containing a basic compound on the resist film as described in JP-A-2013-61648.

Further, even when exposure is performed by a method other than the liquid immersion exposure method, a top coat film can be formed on the sensitized ray-sensitive or radiation-sensitive film.

In the liquid immersion exposure process, the liquid immersion liquid needs to follow the exposure head to scan at a high speed on the wafer to form a movement of the exposure pattern to move on the wafer, so that the liquid immersion liquid phase is sensitive to sensitizing ray or radiation in a dynamic state. The contact angle of the film becomes important, the droplets do not remain, and the sensitizing ray-sensitive or radiation-sensitive resin composition is required to follow the high-speed scanning performance of the exposure head.

The film irradiated with actinic rays or radiation in the process (2) may be subjected to heat treatment (PEB: Post Exposure Bake) after the process (2) and before the process (3) described later. The reaction of the exposure section is promoted by the process. Heat treatment (PEB) can be performed multiple times.

The temperature of the heat treatment is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.

The heat treatment time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.

The heat treatment can be performed by a mechanism provided in a general exposure/developer, or can be performed using a hot plate or the like. [Process (3): Developing Process] The pattern forming process of the present invention has a developing process. The developer is not particularly limited, and examples thereof include an alkali developer and a developer containing an organic solvent.

The alkali developer is preferably an aqueous alkali solution containing an alkali. The type of the aqueous alkali solution is not particularly limited, and examples thereof include a quaternary ammonium salt represented by tetramethylammonium hydroxide, an inorganic base, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, a cyclic amine, and the like. An aqueous alkali solution or the like. Among them, an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH) is preferred. An appropriate amount of an alcohol, a surfactant, or the like may be added to the alkali developer. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. Further, the pH of the alkali developer is usually from 10.0 to 15.0.

The process (3) is a process of developing a film irradiated with actinic rays or radiation in the process (2) using a developing solution containing an organic solvent (hereinafter also referred to as "organic solvent developing solution"). It is preferable to carry out development using a developing solution containing an organic solvent in order to simultaneously perform peeling and development of the top coating film.

As the organic developing solution, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, or an ether solvent, or a hydrocarbon solvent can be used. Specifically, for example, in addition to the Japanese Patent Publication No. 2014-048500 Other than those described in paragraphs <0461> to <0463> of the publication, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate, butyl butyrate, and isoamyl acetate are exemplified.

The above solvent may be mixed in plural, or may be used by mixing with a solvent other than the above or water. However, in order to fully exhibit the effects of the present invention, it is preferable that the water content of the entire developing solution is less than 10% by mass, and it is more preferable that the moisture content is substantially not contained.

In other words, the amount of the organic solvent to be used in the organic solvent developing solution is preferably 90% by mass or more and 100% by mass or less based on the total amount of the developing solution, and preferably 95% by mass or more and 100% by mass or less.

In particular, the organic solvent developing solution is preferably a developing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic solvent developing solution is preferably 5 kPa or less at 20 ° C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic solvent developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is optimized.

An appropriate amount of the surfactant can be added to the organic solvent developer as needed.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or lanthanoid surfactant can be used. For example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-61-226745 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 5, 405, 520, U.S. Patent No. 5, 560, 520, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5, 296, 730, U.S. Patent No. 5, 436, 830, U.S. Patent No. 5,576, 143, U.S. Patent No. 5,294,411 The surfactant described in the specification and the specification of U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a lanthanoid surfactant is more preferably used.

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

The organic solvent developer may contain a basic compound. Specific examples and preferred examples of the basic compound which may be contained in the organic solvent developing solution used in the present invention are the same as those defined as the basic compound which can be contained in the composition as the acid diffusion controlling agent.

As a developing method, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dipping method), and a method of developing the liquid on the surface of the substrate by a surface tension and standing still for a certain period of time can be applied (liquid coating) Paddle method, a method of spraying a developer on a surface of a substrate (spraying method), a method of continuously ejecting a developer while scanning a developing solution discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) . In addition, the preferred range of the discharge pressure of the developer to be discharged and the method of adjusting the discharge pressure of the developer are not particularly limited. For example, the paragraph <0631> of JP-A-2013-242397 can be used. The range and method described in <0636>.

In the pattern forming method of the present invention, a process for developing by an organic solvent developing solution (organic solvent developing process) and a process for developing by an alkali aqueous solution (alkali developing process) can be used in combination. Thereby, a finer pattern can be formed.

As the rinsing liquid in the rinsing treatment after the alkali development, pure water may be used, and an appropriate amount of the surfactant may be added and used.

In the present invention, the portion having a weak exposure intensity is removed by an organic solvent developing process, and the portion having a higher exposure intensity is removed by performing an alkali developing process. By performing the multiple development process for the plurality of developments in a plurality of times, the pattern can be formed only by the region in which the intermediate exposure intensity is not dissolved. Therefore, it is possible to form a pattern which is finer than usual (the same as the above-described Japanese Patent Laid-Open Publication No. 2008-292975-A. mechanism).

In the pattern forming method of the present invention, the order of the alkali developing process and the organic solvent developing process is not particularly limited, and alkali development is more preferably performed before the organic solvent developing process.

After the process of developing using a developing solution containing an organic solvent, a process including washing using a rinsing liquid is preferred.

The rinsing liquid used in the rinsing process after the process of developing using a developing solution containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferably used.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent may be the same as those described for the developer containing the organic solvent.

After the process of developing using a developing solution containing an organic solvent, a rinsing liquid containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and a hydrocarbon solvent is used. The process for cleaning is more preferable, and the process of washing with a washing liquid containing an alcohol solvent or an ester solvent is further preferable, and a process of washing with a rinse liquid containing a monovalent alcohol is particularly preferable. It is preferred to carry out a cleaning process using a rinse liquid containing a monovalent alcohol having 5 or more carbon atoms.

As the rinse liquid containing a hydrocarbon solvent, a hydrocarbon compound having 6 to 30 carbon atoms is preferable, a hydrocarbon compound having 8 to 30 carbon atoms is more preferable, and a hydrocarbon compound having 10 to 30 carbon atoms is particularly preferable. Among them, pattern collapse is suppressed by using a rinse liquid containing decane and/or undecane.

When an ester solvent is used as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (one or two or more). Specific examples of the present invention include an ester solvent (preferable as butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME) as a subcomponent. . Thereby, residue defects are more suppressed.

In the above, the monovalent alcohol used in the rinsing process may be a linear, branched or cyclic monovalent alcohol. Specifically, 1-butanol, 2-butanol or 3-methyl can be used. 1-butanol, tert-butanol, 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, etc., as a particularly preferred monovalent alcohol having 5 or more carbon atoms. 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol or the like can be used.

Each component may be mixed in a plurality of types, or may be used in combination with an organic solvent other than the above.

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

The vapor pressure of the rinse liquid used after the development process using the developer containing the organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and further preferably 0.12 kPa. Above and below 3 kPa is the best. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the rinse liquid is further suppressed, and the dimensional uniformity in the wafer surface is optimized.

An appropriate amount of surfactant can be added to the rinse solution for use.

In the rinsing process, a wafer containing a developing solution containing an organic solvent is used for cleaning using a rinsing liquid containing the above organic solvent. The method of the cleaning treatment is not particularly limited. For example, it can be applied to a method of continuously discharging a rinse liquid on a substrate that is rotated at a constant speed (a spin coating method), and a method of immersing the substrate in a tank filled with a rinse liquid for a certain period of time (impregnation) a method of spraying a rinsing liquid onto a surface of a substrate (spraying method), etc., wherein a cleaning treatment is performed by a spin coating method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm, and the rinse liquid is preferably removed from the substrate. . Also, it is preferred to include a post process after the rinsing process. The developer and the rinse liquid remaining between the patterns and the inside of the pattern are removed by baking. The heating process after the rinsing process is usually 40 to 160 ° C, preferably 70 to 95 ° C, usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The photosensitive ray-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 photoresist solvent, a developing solution, a rinsing liquid, an antireflection film forming composition, and a top coating film) It is preferable that the composition for formation or the like does not contain an impurity such as a metal. The content of the impurities contained in the materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, and particularly preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). optimal.

As a method of removing impurities such as metals from the above various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material that combines these materials with an ion exchange medium. The filter can also be cleaned with an organic solvent in advance. In the filter filtration process, a plurality of filters can be connected in series or in parallel. When a plurality of filters are used, a filter having a different aperture and/or material can be used in combination. Moreover, various materials can be subjected to multiple filtrations, and the process of performing multiple filtrations can also be a cyclic filtration process.

In addition, as a method of reducing impurities such as metals contained in the above various materials, a method of selecting a raw material having a small metal content as a raw material constituting each material, a method of filtering a raw material constituting each material, and A method of performing distillation under conditions such as suppression of contamination as much as possible by using Teflon (registered trademark) in a device. The preferred conditions for filter filtration of the materials constituting the various materials are the same as those described above.

In addition to filter filtration, impurities can be removed by the adsorbent material, and a filter can be used in combination to filter and adsorb the material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be used.

In order to prevent malfunction of sputum piping or various parts (filters, O-rings, hoses, etc.) caused by static electricity and static electricity discharge, conductive compounds may be added to organic processing liquids such as developing solution and rinsing liquid. . The conductive compound is not particularly limited, and examples thereof include methanol. The amount of addition is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics and rinsing characteristics. As the member of the sputum pipe, various pipes which are coated with SUS (stainless steel) or polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) which have been subjected to antistatic treatment can be used. Regarding the filter or the O-ring, polyethylene, polypropylene, or a fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) which has been subjected to an antistatic treatment can also be used.

For the pattern formed by the method of the present invention, a method of improving the surface roughness of the pattern can be applied. As a method of improving the surface roughness of the pattern, for example, a method of treating a photoresist pattern by a plasma containing a gas of hydrogen disclosed in the pamphlet of International Publication No. 2014/002808 can be mentioned. In addition, the EUV can be applied as disclosed in Japanese Laid-Open Patent Publication No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, Japanese Patent Application Publication No. 2008-83384, and Proc. of SPIE Vol. 8328 83280N-1. A well-known method described in Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement.

The pattern forming method of the present invention can also be used in the formation of a guide pattern in DSA (Directed Self-Assembly) (for example, see ACS Nano Vol. 4 No. 8 Page 4815-4823).

Further, the photoresist pattern formed by the above method can be used as a core of a spacer process disclosed in Japanese Laid-Open Patent Publication No. Hei No. 3-270227 and No. 2013-164509.

Further, the present invention relates to a method of manufacturing an electronic device comprising the above-described pattern forming method of the present invention and an electronic device manufactured by the method.

The electronic device of the present invention is suitably mounted on an electric and electronic device (home appliance, OA (Office Automation)/media related device, optical device, communication device, etc.). [Examples]

<Synthesis Example 1: Synthesis of Resin A-1> 214 g of cyclohexanone was placed in a three-necked flask under a nitrogen stream, and heated to 80 °C. In the above, 67.3 g, 4.81 g, and 35.33 g of a monomer corresponding to each repeating unit of the resin A-1 to be described later, and a polymerization initiator V-601 (Wako Pure Chemical Industries, A solution obtained by dissolving 396 g of cyclohexanone, manufactured by Ltd., 2.28 g). After completion of the dropwise addition, the obtained reaction liquid was further reacted at 80 ° C for 2 hours. After the reaction solution was allowed to stand for cooling, it was added dropwise to a mixed liquid of methanol:water (9:1) over 20 minutes, and the precipitated powder was filtered and dried to obtain the following resin A-1 as an acid-decomposable resin. (76g). The composition ratio (mol ratio) of the repeating unit determined by NMR (Nuclear Magnetic Resonance) method was 30/10/60. The weight average molecular weight of the obtained resin A-1 was 12,000 in terms of standard polystyrene under the above conditions, and the degree of dispersion (Mw/Mn) was 1.7.

[Chemical Formula 50]

The same operation as in the above Synthesis Example 1 was carried out to synthesize the resins A-2 to A-19 described later. <Preparation of Photoresist Composition> The components shown in the following Table 1 were dissolved in the solvent shown in Table 1 so as to have a content ratio (content ratio in the total solid content) shown in Table 1, and were separately prepared. A solution having a solid concentration of 4.9% by mass. Next, the obtained solution was filtered with a polyethylene filter having a pore size of 0.1 μm to prepare a sensitized ray-sensitive or radiation-sensitive resin composition (photoresist composition).

<Evaluation> [Formation of Photoresist Film] A spin coating of Tokyo Electron Limited was used on an 8-inch Si wafer (Si wafer having a diameter of 200 mm) coated with an organic anti-reflection film (ARC29A manufactured by Brewer Science, Inc.). The photoresist composition prepared by coating the Act 8 was dried on a hot plate at 90 ° C for 60 seconds to obtain a sensitized ray-sensitive or radiation-sensitive film (photoresist film) having a film thickness of 140 nm.

[Formation of a photoresist pattern using an organic solvent developing solution] (ArF immersion exposure) An organic anti-reflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was coated on a ruthenium wafer, and baked at 205 ° C for 60 seconds. Bake to form an antireflection film having a film thickness of 95 nm. The obtained photoresist composition was applied thereon, and baked at 100 ° C for 60 seconds (PB: Prebake) to form a photoresist film having a film thickness of 100 nm.

For the obtained wafer, an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, Nesigma 0.812, XY deflection) was used, and the line spacing was 90 nm. A line of 35 nm width and a 6% halftone mask of the spatial pattern were exposed. As the liquid immersion liquid, ultrapure water is used.

Then, it was heated at 105 ° C (PEB: Post Exposure Bake) for 60 seconds. Subsequently, development was carried out by coating with an organic solvent developing solution (butyl acetate) for 30 seconds, and rinsing with a rinse liquid [Methyl isobutyl carbinol (MIBC)] for 30 seconds. Next, the wafer was rotated at a number of revolutions of 4000 rpm for 30 seconds, thereby forming a pattern of lines and spaces having a pitch of 90 nm and a space width of 35 nm.

[Evaluation of Dissolution Rate of Exposure Section] Regarding the evaluation of the dissolution rate of the exposed portion, the photoresist composition was applied onto a 8-inch Si wafer so as to have a film thickness of 100 nm, and baked at 90 ° C for 60 seconds. This was subjected to excess exposure (30 mJ) and baked at 85 ° C for 60 seconds to sufficiently carry out the deprotection reaction, and after immersing the developer for 30 seconds, the film thickness of the residual film was measured. The value (nm/sec) obtained by (100 nm-residual film) / 30 seconds was the exposure part dissolution rate.

[LWR evaluation] The pattern of the line and space with a distance of 90 nm and a space width of 35 nm was observed by a scanning microscope (Hitachi, Ltd. S9380), and 50 points were measured for the edge of the line pattern in the longitudinal direction of 2 μm. The line width is determined by measuring the standard deviation and calculating 3σ. A smaller value indicates better performance.

[Evaluation of Etching Resistance] Using a plasma etching apparatus (Hitachi ECR plasma etching apparatus U-621), a pattern of lines and spaces having a distance of 90 nm and a space width of 35 nm was obtained, and the etching rate was determined ( Plasma conditions: Ar 500 ml/min, N ₂ 500 ml/min, O ₂ 10 ml/min). Further, in view of the stabilization of the plasma, as described below, the etching rate was determined from the difference between the film thickness which was etched 10 seconds after the start of etching and the film thickness which was etched after 5 seconds from the start of etching. The results are shown in Table 1.

Further, practically, the etching rate is preferably 7 nm/sec or less, more preferably 5 nm/sec or less, and still more preferably 2 nm/sec or less.

(etching speed)={(film thickness etched by 10 seconds)-(film thickness etched by 5 seconds)}/5 [formation of photoresist pattern using alkali developer] And, for Example 1 The above evaluation was carried out under the same conditions except that the developer was changed to a 2.38 mass% tetramethylammonium hydroxide aqueous solution. In this case, it was confirmed that a good photoresist pattern was formed.

[Table 1]

In Table 1, the structure of the resin (A) is as follows. Wherein, the composition ratio of the repeating unit is a molar ratio. Further, Me represents a methyl group, Et represents an ethyl group, and iBu represents an isobutyl group. Further, the composition ratio of the repeating unit, the weight average molecular weight (Mw) of the resin, and the degree of dispersion (Mw/Mn) were determined by the same method as the above-mentioned resin A-1.

[Chemical Formula 51]

[Chemical Formula 52]

In Table 1, the structure of the acid generator (C) is as follows.

[Chemical Formula 53]

In Table 1, the structure of the crosslinking agent (B) is as follows.

[Chemical Formula 54]

In Table 1, the structure of the acid diffusion inhibitor (E) is as follows.

[Chemical Formula 55]

In Table 1, the structure of the hydrophobic resin (D) is as follows.

[Chemical Formula 56]

With respect to each of the hydrophobic resins, the composition ratio (molar ratio; corresponding from the left), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) of each repeating unit are shown in Table 2 below. These were determined by the same method as the above-mentioned resin A-1.

[Table 2]

In Table 1, the solvent is as follows.

A1: propylene glycol monomethyl ether acetate (PGMEA) A2: cyclohexanone A3: γ-butyrolactone B1: propylene glycol monomethyl ether (PGME) B2: ethyl lactate In Table 1, the surfactant is as follows .

W-1: Megafac F176 (manufactured by DIC Corporation) (fluorine-based) W-2: Megafac R08 (manufactured by DIC Corporation) (fluorine-based and antimony-based) W-3: PF6320 (manufactured by OMNOVA Solutions Inc.) (fluorine-based)

no

no

Claims (13)

A photosensitive ray-sensitive or radiation-sensitive resin composition comprising: a resin (A) comprising a repeating unit (a) having Si atoms; a crosslinking agent (B); and irradiation by actinic rays or radiation An acid-producing compound (C) in which a repeating unit having a Si atom has a structure for protecting a polar group by a decomposing group which is decomposed by an action of an acid, and, when the Si atom is contained only in the above-mentioned leaving group, the repeat The unit is not included in the aforementioned repeating unit (a). The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin in the sensitized ray-sensitive or radiation-sensitive resin composition is based on the total solid content in the composition. The content of (A) is 50% by mass or more. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (a) having the Si atom has a decane structure. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the repeating unit (a) having the Si atom has a sesquiterpene structure. The photosensitive ray-sensitive or radiation-sensitive resin composition according to the first or second aspect of the invention, wherein the content of Si atoms in the resin (A) is 10% by mass or more, wherein the resin ( A) is a repeating unit having a structure for protecting a polar group by using a leaving group which is detached by the action of an acid, and when the above-mentioned leaving group contains a repeating unit having a Si atom, the Si atom contained in the above-mentioned leaving group is not included in The aforementioned content ratio of Si atoms. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) comprises a crosslinkable reactive group capable of reacting with the crosslinking agent (B) The repeating unit (d) in which the repeating unit (d) having the aforementioned crosslinkable reactive group may have a structure which protects the aforementioned crosslinkable reactive group by using a leaving group which is decomposed and desorbed by the action of an acid. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the crosslinking agent (B) comprises a melamine-based crosslinking agent and a urea-based crosslinking agent. At least one of a phenol-based crosslinking agent, an epoxy crosslinking agent, a vinyl ether crosslinking agent, and a glycoluric crosslinking agent. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) contains a repeating unit (c) having an acid-decomposable group. The photosensitive ray-sensitive or radiation-sensitive resin composition according to the first or second aspect of the invention, wherein the resin (A) has a lactone structure, a sultone structure, and a cyclic carbonate structure. Repeating unit (b) of at least any one of them. A photosensitive ray-sensitive or radiation-sensitive resin composition as described in claim 1 or 2, which is used for development using a developer containing an organic solvent. A sensitized ray-sensitive or radiation-sensitive linear composition comprising the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10. A pattern forming method comprising: forming a sensitized ray-sensitive or radiation-sensitive film comprising the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10; The photosensitive ray-sensitive or radiation-sensitive film is exposed; and the exposed sensitizing ray-sensitive or radiation-sensitive film is developed using a developing solution containing an organic solvent to form a pattern. A method of manufacturing an electronic device, comprising the pattern forming method according to claim 12 of the patent application.