TWI862516B - Active light sensitive or radiation sensitive resin composition, resist film, method for forming pattern, method for manufacturing electronic device - Google Patents

Abstract

The subject of the present invention is to provide an anti-etching film having excellent film thickness uniformity in a plane and capable of forming a pattern with excellent LWR. Another subject of the present invention is to provide an anti-etching film, a pattern forming method and a manufacturing method of an electronic device using the above-mentioned anti-etching film having excellent film thickness uniformity in a plane and capable of forming a pattern with excellent LWR. The photosensitive or radiation-sensitive resin composition of the present invention comprises: an acid-decomposable resin; a photoacid generator A that generates an acid having a pKa of -1.40 or more by irradiation with actinic rays or radiation; a photoacid generator B or a nitrogen-containing compound C, wherein the photoacid generator B generates an acid having a pKa greater than 1.00 or more than that of the acid generated from the photoacid generator A by irradiation with actinic rays or radiation, and the pKa of the covalent acid in the nitrogen-containing compound C is greater than 1.00 or more than that of the acid generated from the photoacid generator A by irradiation with actinic rays or radiation; and a hydrophobic resin, wherein a film formed using the photosensitive or radiation-sensitive resin composition has a receding contact angle with respect to water of 80.0° or more.

Description

Photosensitive or radiation-sensitive resin composition, anti-etching agent film, pattern forming method, and manufacturing method of electronic device

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

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), micro-fabrication based on lithography using chemically amplified photoresist compositions is performed.

For example, in the Example column of Patent Document 1, a photosensitive or radiation-sensitive resin composition is disclosed, which includes: a photoacid generator that generates an acid with a pKa of -1.40 or more by irradiation with actinic rays or radiation; an alkaline compound for neutralizing the acid generated from the photoacid generator (hereinafter, also referred to as "acid A"); and a resin containing a repeating unit having an acid-decomposable group. In the Example column of Patent Document 1, as the alkaline compound, the photoacid generator that generates an acid weaker than the acid A by irradiation with actinic rays or radiation; or a nitrogen-containing compound is used. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2018/116916

As a result of studying the photosensitive or radiation-sensitive resin composition described in Patent Document 1, the inventors of the present invention have found that the thickness of the formed anti-etching film (film of the photosensitive or radiation-sensitive resin composition) is uneven within the surface. In other words, it has been found that there is room for improving the uniformity of the thickness of the formed anti-etching film within the surface. Furthermore, it has been found that the pattern formed using the above-mentioned photosensitive or radiation-sensitive resin composition has room for further improving the fluctuation of the pattern line width (LWR (line width roughness)).

Therefore, the subject of the present invention is to provide an anti-etching film having excellent in-plane uniformity of film thickness and an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR. In addition, the subject of the present invention is to provide an anti-etching film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition.

As a result of intensive research to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using a photosensitive or radiation-sensitive resin composition of a specified composition, thereby completing the present invention.

[1] An actinic ray or radiation-sensitive resin composition, comprising: an acid-decomposable resin; a photoacid generator A that generates an acid having a pKa of -1.40 or more by irradiation with actinic rays or radiation; at least one of a photoacid generator B and a nitrogen-containing compound C, wherein the photoacid generator B generates an acid having a pKa greater than 1.00 or more than that of the acid generated from the photoacid generator A by irradiation with actinic rays or radiation, and the pKa of the covalent acid in the nitrogen-containing compound C is greater than 1.00 or more than that of the acid generated from the photoacid generator A by irradiation with actinic rays or radiation; and a hydrophobic resin, wherein a film formed using the actinic ray or radiation-sensitive resin composition has a receding contact angle with respect to water of 80.0° or more. [2] The photosensitive or radiation-sensitive resin composition as described in [1], wherein the acid generated from the photoacid generator A is a sulfonic acid. [3] The photosensitive or radiation-sensitive resin composition as described in [1] or [2], wherein the acid generated from the photoacid generator A is a sulfonic acid represented by the general formula (1) described below or a sulfonic acid represented by the general formula (2) described below. [4] The actinic or radiation-sensitive resin composition as described in any one of [1] to [3], wherein the hydrophobic resin has one or more groups selected from the group consisting of fluorine atoms, groups having fluorine atoms, groups having silicon atoms, linear, branched or cyclic alkyl groups having 6 or more carbon atoms, aryl groups having 9 or more carbon atoms, arylalkyl groups having 10 or more carbon atoms, aryl groups substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and aryl groups substituted with at least one cyclic alkyl group having 5 or more carbon atoms. [5] The actinic or radiation-sensitive resin composition as described in any one of [1] to [4], wherein the hydrophobic resin contains repeating units having fluorine atoms or groups having fluorine atoms. [6] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [5], wherein the hydrophobic resin does not substantially contain repeating units having a group whose polarity increases when decomposed by the action of an acid. [7] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [6], wherein the hydrophobic resin contains repeating units having a group whose solubility in an alkaline developer increases when decomposed by the action of an alkaline developer. [8] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [7], wherein the repeating units having a group whose solubility in an alkaline developer increases when decomposed by the action of the alkaline developer include repeating units represented by the general formula (3) described below. [9] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [8], wherein the hydrophobic resin is a copolymer comprising the repeating units represented by the general formula (3) and other repeating units other than the repeating units represented by the general formula (3). [10] An actinic radiation-sensitive or radiation-sensitive resin composition as described in [8] or [9], wherein the hydrophobic resin comprises: a repeating unit represented by the general formula (3); and a repeating unit having a group which is decomposed by the action of the alkaline developer and has increased solubility in the alkaline developer, and the repeating unit comprises a repeating unit of at least one group selected from the group consisting of a linear, branched or cyclic alkyl group having 6 or more carbon atoms, an aryl group having 9 or more carbon atoms, an arylalkyl group having 10 or more carbon atoms, an aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and an aryl group substituted with at least one cyclic alkyl group having 5 or more carbon atoms, and, The hydrophobic resin is substantially a copolymer that does not contain repeating units having a group whose polarity increases when decomposed by the action of an acid. [11] An actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [10], wherein the number of fluorine atoms contained in the hydrophobic resin is greater than the number of fluorine atoms contained in the photoacid generator A. When the hydrophobic resin contains only one type of repeating unit containing fluorine atoms, the number of fluorine atoms contained in the hydrophobic resin is calculated by the following formula (1). When the hydrophobic resin contains two or more types of repeating units containing fluorine atoms, the number of fluorine atoms contained in the hydrophobic resin is calculated as the sum of the values of each repeating unit containing fluorine atoms calculated by the following formula (1). Formula (1): Y _A =a×b÷100 Y _A : the number of fluorine atoms contained in the hydrophobic resin a : the number of fluorine atoms in the repeating unit containing fluorine atoms b : the content of the repeating unit containing fluorine atoms relative to all the repeating units in the hydrophobic resin (molar %) [12] An anti-etching agent film formed using the photosensitive or radiation-sensitive resin composition described in any one of [1] to [11]. [13] A pattern forming method, comprising: an etching agent film forming step of forming an etching agent film using the photosensitive or radiation-sensitive resin composition described in any one of [1] to [11]; an exposure step of exposing the above-mentioned etching agent film; and a developing step of developing the exposed etching agent film using a developer. [14] The pattern forming method as described in [13], wherein the above-mentioned developer is an alkaline developer. [15] A method for manufacturing an electronic device, comprising the pattern forming method described in [13] or [14]. [Effect of the invention]

According to the present invention, it is possible to provide an anti-etching film having excellent in-plane uniformity of film thickness and an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR. In addition, according to the present invention, it is possible to provide an anti-etching film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition.

The present invention is described in detail below. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. The "actinic ray" or "radiation" in this specification refers to, for example, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam). The "light" in this specification refers to actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle rays such as electron beams and ion beams. In this specification, "～" is used to mean that the numerical values written before and after it are included as lower and upper limits.

In this specification, (meth)acrylate refers to acrylate and methacrylate. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined as polystyrene conversion values based on GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40℃, flow rate: 1.0mL/min, detector: differential refractive index detector) using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by TOSOH CORPORATION).

In this specification, pKa (acid dissociation constant pKa) refers to the acid dissociation constant pKa in aqueous solution, for example, as defined in Chemical Handbook (II) (Revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. The value of pKa can be calculated using the following software package 1, based on the database of Hammett's substituent constant and known literature values. The pKa values described in this specification are all values calculated using the software package.

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

In the marking of groups (atomic groups) in this specification, the marking without the marking of substituted and unsubstituted includes groups without substitution and groups with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

In addition, in this specification, when "may have a substituent", the type of substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of substituents can be, for example, 1, 2, 3, or more. As examples of substituents, monovalent non-metallic atomic groups other than hydrogen atoms can be cited, for example, and can be selected from the following substituent group T. (Substituent T) As the substituent T, there can be cited halogen atoms such as fluorine, chlorine, bromine and iodine; alkoxy groups such as methoxy, ethoxy and tert-butyloxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetyloxy, propionyloxy and benzyloxy; acyl groups such as acetyl, benzyl, isobutyl, acyl, methacryl and methoxythioyl; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; sulfanyl); alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; formyl; sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonamido; silyl; amino; monoalkylamino; dialkylamino; arylamino; and combinations thereof.

[Acticular radiation or radiation-sensitive resin composition] One of the characteristic points of the actinic radiation or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as "the composition of the present invention") is that it contains at least one of the photoacid generator A described below, the photoacid generator B described below, and the nitrogen-containing compound C described below. When the above composition is used to form an anti-etching film, ^{the photoacid generator A that generates a relatively weak acid} is not easily aggregated in the anti-etching film and has excellent dispersibility. Furthermore, since the composition contains at least one of the photoacid generator B and the nitrogen-containing compound C, the diffusion of the acid generated from the photoacid generator A is controlled. As a result, it is considered that the pattern formed by the composition of the present invention has excellent pattern line width fluctuation (LWR).

In addition, as other characteristic points of the composition of the present invention, it can be cited that it contains a hydrophobic resin and that the film formed by using the above composition and under the conditions described below has a receding contact angle of 80° or more to water. As a method of setting the receding contact angle of the above film to 80° or more, a method of setting the hydrophobic resin contained in the above composition to a higher hydrophobicity and/or increasing the content of the hydrophobic resin in the composition can be cited. By setting the composition of the present invention to the above structure, the obtained anti-corrosion agent film has excellent film thickness uniformity. Although its mechanism of action is still unclear, the inventors of the present invention speculate as follows. When an anti-etching agent composition is used to form an anti-etching agent film, usually, a hydrophobic resin is present in greater amounts near the outermost layer of the film due to its surface free energy. However, when the hydrophobicity of the hydrophobic resin is low and/or the content of the hydrophobic resin is low, the hydrophobic resin has the tendency to form aggregates with components such as a photoacid generator and an acid-decomposable resin present near the outermost layer, and as a result, it is believed that the uniformity of the film surface is deteriorated. In contrast, the inventors of the present invention have made it clear through intensive research that if the receding contact angle of the film relative to water is 80° or more, the formation of the aggregates is suppressed in the outermost layer of the anti-etching agent film, and the uniformity of the film surface is excellent. In addition, the photoacid generator A has a structure that generates a relatively weak acid, and since the interaction between the photoacid generator A and the hydrophobic resin is small, it is difficult to condense the hydrophobic resin. It is speculated that this is also one of the main reasons why the thickness uniformity of the obtained anti-etching agent film is excellent. Below, first, each component of the composition of the present invention is described in detail.

[Acid-decomposable resin (resin A)] The composition of the present invention includes an acid-decomposable resin (hereinafter, also referred to as "resin A"). The acid-decomposable resin generally includes a repeating unit having a group whose polarity increases by decomposition by the action of an acid (hereinafter, also referred to as "acid-decomposable group"). In the pattern forming method of the present invention, typically, when an alkaline developer is used as a developer, a positive pattern is appropriately formed, and when an organic developer is used as a developer, a negative pattern is appropriately formed.

<Repeating unit with acid-decomposable group> It is preferred that the resin A contains a repeating unit with an acid-decomposable group (hereinafter, also referred to as "repeating unit A"). It is preferred that the acid-decomposable group contains a structure in which a polar group is protected by a group (degrouping) that is decomposed and released by the action of an acid. Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tri(alkylcarbonyl)methylene group, and an acidic group such as a tri(alkylsulfonyl)methylene group (a group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), and an alcoholic hydroxyl group.

In addition, alcoholic hydroxyl groups refer to hydroxyl groups that are bonded to a alkyl group and are excluding hydroxyl groups that are directly bonded to an aromatic ring (phenolic hydroxyl groups), and as hydroxyl groups, aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) whose α-positions are substituted with electron-withdrawing groups such as fluorine atoms are excluded. As alcoholic hydroxyl groups, hydroxyl groups having a pKa (acid dissociation constant) of 12 to 20 are preferred.

As the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group is preferred.

Preferred acid-decomposable groups are groups in which the hydrogen atoms of the groups are replaced by groups that are dissociated by the action of an acid (dissociated groups). Examples of the groups that are dissociated by the action of an acid (dissociated groups) include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ). In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. _R01 and _R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl and octyl. The cycloalkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. As a monocyclic cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferably a cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl. As the polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl, norbornyl, isobornyl, bornyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl, and androstanyl. In addition, one or more carbon atoms in the cycloalkyl group may be substituted by a heteroatom such as an oxygen atom. The aryl group of R ₃₆ to R ₃₉ , R ₀₁ , and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl. The aralkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, for example, benzyl, phenethyl and naphthylmethyl. The alkenyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, for example, vinyl, allyl, butenyl and cyclohexenyl. The ring formed by R ₃₆ and R ₃₇ bonding to each other is preferably a cycloalkyl group (monocyclic or polycyclic). The monocyclic cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group, and the polycyclic cycloalkyl group is preferably a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group.

As the acid-decomposable group, a tertiary alkyl ester group, an acetal ester group, an isopropyl ester group, an enol ester group or an acetal ester group is preferred, and an acetal ester group or a tertiary alkyl ester group is more preferred.

The resin A preferably contains, as the repeating unit A, a repeating unit represented by the following general formula (AI).

[Chemical formula 1]

In the general formula (AI), T represents a single bond or a divalent linking group. Examples of the divalent linking group of T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group. T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ - is more preferably. T is more preferably a single bond.

In the general formula (AI), _Xa1 represents a hydrogen atom, a halogen atom or a monovalent organic group. Preferably, _Xa1 is a hydrogen atom or an alkyl group. The alkyl group of _Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom). Preferably, the alkyl group of _Xa1 has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group. Preferably, the alkyl group of _Xa1 is a methyl group.

In the general formula (AI), Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Any two of Rx ₁ to Rx ₃ may be bonded to form a ring structure, or may not form a ring structure. The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be a linear or branched chain, and preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group and a tert-butyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. In the alkyl group of Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-carbon bonds may be double bonds. The cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be a monocyclic or polycyclic group. Examples of the monocyclic cycloalkyl group include cyclopentyl and cyclohexyl, and examples of the polycyclic cycloalkyl group include norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

The ring formed by two of _Rx1 , _Rx2 and _Rx3 being bonded may be a monocyclic ring or a polycyclic ring. Examples of monocyclic rings include monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctane ring. Examples of polycyclic rings include polycyclic cycloalkyl rings such as norbornane ring, tetracyclic decane ring, tetracyclic dodecane ring and adamantane ring. Among them, cyclopentyl ring, cyclohexyl ring or adamantane ring is preferred. Furthermore, as a ring formed by two bonds among Rx ₁ , Rx ₂ and Rx ₃ , the following rings are also preferred.

[Chemical formula 2]

Specific examples of monomers that conform to the repeating unit represented by the general formula (AI) are given below. The following specific examples conform to the case where _Xa1 in the general formula (AI) is a methyl group, and _Xa1 can be arbitrarily substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[Chemical formula 3]

It is also preferred that resin A has the repeating units described in paragraphs [0336] to [0369] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 as repeating unit A.

Furthermore, the resin A may have, as the repeating unit A, a repeating unit containing a group that generates an alcoholic hydroxyl group by decomposition by the action of an acid as described in paragraphs [0363] to [0364] of the specification of U.S. Patent Application Publication No. 2016/0070167A1.

The resin A may contain one type of repeating unit A alone, or may contain two or more types of repeating units A in combination.

The content of repeating unit A contained in resin A (the total of repeating units A when there are multiple repeating units) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and even more preferably 30 to 70 mol % relative to all repeating units in resin A.

<Repeating units having at least one selected from the group consisting of lactone structure, sultone structure and carbonate structure> Resin A preferably contains a repeating unit having at least one selected from the group consisting of lactone structure, sultone structure and carbonate structure (hereinafter, also referred to as "repeating unit B").

As the lactone structure or sultone structure, any structure having a lactone ring or a sultone ring is sufficient, and a lactone structure having a lactone ring of 5 to 7 members or a sultone structure having a sultone ring of 5 to 7 members is preferred. A lactone structure having another ring condensed on a 5 to 7 member lactone ring in the form of a bicyclic structure or a spirocyclic structure is also preferred. A sultone structure having another ring condensed on a 5 to 7 member sultone ring in the form of a bicyclic structure or a spirocyclic structure is also preferred.

Among them, the resin A preferably contains a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-22) or a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). In addition, the lactone structure or the sultone structure can be directly bonded to the main chain. Among them, the lactone structure represented by the general formula (LC1-1), the general formula (LC1-4), the general formula (LC1-5), the general formula (LC1-8), the general formula (LC1-16), the general formula (LC1-21), or the general formula (LC1-22) or the sultone structure represented by the general formula (SL1-1) is preferred.

[Chemical formula 4]

The lactone structure or the sultone structure may or may not have a substituent (Rb ₂ ). As the substituent (Rb _{2 )} , an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, or a cyano group is preferred, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferred. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, the substituents (Rb ₂ ) present in plurality may be the same or different. In addition, the substituents (Rb ₂ ) present in plurality may be bonded to each other to form a ring.

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

[Chemical formula 5]

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

n is the number of repetitions of the structure represented by -R ₀ -Z- and represents an integer of 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, (-R ₀ -Z-)n becomes a single bond.

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are plural R ₀ groups, the plural R ₀ groups may be the same or different. The alkylene group or cycloalkylene group of R ₀ may have a substituent.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are multiple Zs, the multiple Zs may be the same or different. Preferably, Z is an ether bond or an ester bond, and more preferably, an ester bond.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure. Among them, in any of the structures represented by general formulae (LC1-1) to (LC1-22) and the structures represented by general formulae (SL1-1) to (SL1-3), a group formed by removing one hydrogen atom from one carbon atom constituting the lactone structure or the sultone structure is preferred. Furthermore, the carbon atom from which the one hydrogen atom is removed is preferably not a carbon atom constituting the substituent (Rb ₂ ).

_R7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The following are examples of monomers that have at least one repeating unit selected from the group consisting of a lactone structure and a sultone structure. In the following examples, the methyl group bonded to the vinyl group may be substituted by a hydrogen atom, a halogen atom, or a monovalent organic group.

[Chemical formula 6]

[Chemical formula 7]

Resin A may contain repeating units having a carbonate structure. As the carbonate structure, a cyclic carbonate structure is preferred. As the repeating unit having a cyclic carbonate structure, a repeating unit represented by the following general formula (A-1) is preferred.

[Chemical formula 8]

In the general formula (A-1), _RA1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group). n represents an integer greater than or equal to 0. _RA2 represents a substituent. When ⁿ is greater than or equal to 2, _{the plural RA2s} ^may be the same or different. A represents a single bond or a divalent linking group. Z represents an atomic group ^that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

It is also preferred that resin A has the repeating units described in paragraphs [0370] to [0414] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 as the repeating units B.

The repeating unit B may be contained alone or in combination of two or more.

When resin A contains repeating units B, the content of repeating units B contained in resin A (the total of repeating units B when there are multiple repeating units B) is preferably 5 to 70 mol %, more preferably 10 to 65 mol %, and even more preferably 20 to 60 mol % relative to all repeating units in resin A.

<Repeating unit with polar group> It is preferable that the resin A contains a repeating unit with a polar group (hereinafter, also referred to as "repeating unit C"). As the polar group, hydroxyl group, cyano group, carboxyl group and fluorinated alcohol group (for example, hexafluoroisopropanol group) can be cited. As the repeating unit C, a repeating unit with an alicyclic hydrocarbon structure substituted with a polar group is preferable. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, a cyclohexyl group, an adamantyl group or a norbornyl group is preferable.

Specific examples of monomers that conform to the repeating unit C are given below, but the present invention is not limited to these specific examples.

[Chemical formula 9]

In addition, as a specific example of the repeating unit C, the repeating unit disclosed in paragraphs [0415] to [0433] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 can be cited. Resin A can have only one type of repeating unit C, or can contain two or more types of repeating units C in combination.

When resin A contains repeating units C, the content of repeating units C (the total of repeating units C when there are multiple repeating units C) is preferably 5 to 60 mol %, and more preferably 5 to 30 mol % relative to all repeating units in resin A.

<Repeating units that do not have either an acid-degradable group or a polar group> Resin A may further include a repeating unit that does not have either an acid-degradable group or a polar group (hereinafter, also referred to as "repeating unit D"). It is preferred that the repeating unit D has an alicyclic hydrocarbon structure. As repeating unit D, for example, the repeating units described in paragraphs [0236] to [0237] of the specification of U.S. Patent Application Publication No. 2016/0026083A1 can be cited. Preferred examples of monomers that meet the repeating unit D are shown below.

[Chemical formula 10]

In addition, as a specific example of repeating unit D, the repeating unit disclosed in paragraph [0433] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 can be cited. Resin A can contain one type of repeating unit D alone, or two or more types of repeating units D can be used in combination. When resin A contains repeating unit D, the content of repeating unit D (the total of repeating units D when there are multiple repeating units D) relative to all repeating units in resin A is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 5 to 25 mol%.

Furthermore, in order to adjust the etching resistance, standard developer compatibility, substrate adhesion, photoresist profile, or further adjust the generally necessary characteristics of the anti-etching agent, namely, resolution, heat resistance, and sensitivity, resin A may have various repetitive structure units as other repetitive structure units in addition to the above-mentioned repetitive structure units. As such repetitive structure units, repetitive structure units that meet the prescribed unit body can be cited, but are not limited to such.

As the specified monomer, for example, there can be cited a compound having an addition polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. In addition, an addition polymerizable unsaturated compound that can copolymerize with a monomer that conforms to the above-mentioned various repeating structural units can also be used. In resin A, the molar ratio of each repeating structural unit is appropriately set to adjust various properties.

When the composition of the present invention is a composition for ArF exposure, from the viewpoint of the transmittance of ArF light, the content of repeating units having an aromatic group is preferably 15 mol% or less, and more preferably 10 mol% or less, relative to all repeating units in resin A.

When the composition of the present invention is for ArF exposure, it is preferred that all the repeating units of resin A are composed of (meth)acrylate repeating units. In this case, all the repeating units are methacrylate repeating units, all the repeating units are acrylate repeating units, or all the repeating units are based on methacrylate repeating units and acrylate repeating units. It is preferred that the acrylate repeating units account for 50 mol% or less relative to all the repeating units of resin A.

When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, it is preferred that resin A contains repeating units having aromatic hydrocarbon groups, and it is more preferred that it contains repeating units containing phenolic hydroxyl groups or repeating units having a structure (acid-decomposable group) in which the phenolic hydroxyl groups are decomposed and released by the action of an acid. In addition, as repeating units containing phenolic hydroxyl groups, hydroxystyrene repeating units and hydroxystyrene (meth)acrylate repeating units can be cited. When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, it is preferred that the content of repeating units having aromatic hydrocarbon groups contained in resin A is 30 mol% or more relative to all repeating units in resin A. The upper limit is not particularly limited, and is, for example, 100 mol% or less, preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%.

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

Resin A may be used alone or in combination of two or more. In the composition of the present invention, the content of resin A relative to the total solid content is generally 20.0 mass % or more, 40.0 mass % or more is preferred, 60.0 mass % or more is more preferred, and 80.0 mass % or more is further preferred. There is no particular upper limit, 99.5 mass % or less is preferred, 99.0 mass % or less is more preferred, and 97.0 mass % or less is further preferred. In addition, the solid component refers to the component excluding the solvent in the composition, and as long as it is a component other than the solvent, even a liquid component is regarded as a solid component.

[Photoacid generator A] The composition of the present invention contains a photoacid generator A. The photoacid generator A is a compound that generates an acid by irradiation with actinic rays or radiation. In addition, the photoacid generator A mentioned here is equivalent to a photoacid generator commonly used to cause a deprotection reaction of a resin component (deprotection reaction of an acid-decomposable resin).

The pKa of the acid generated from the photoacid generator A is -1.40 or more. The upper limit of the pKa of the above acid is not particularly limited, and is, for example, 5.00 or less. As the pKa of the acid generated from the photoacid generator A, from the viewpoint of a better LWR of the formed pattern and/or a better film surface uniformity of the film, -1.38 or more is preferred. Furthermore, from the viewpoint of a better LWR of the formed pattern, the upper limit is preferably 2.00 or less, and more preferably 1.30 or less. As the acid generated from the photoacid generator A, there is no particular limitation as long as the above pKa is satisfied, and sulfonic acid is preferred, and sulfonic acid represented by the following general formula (1) or sulfonic acid represented by the following general formula (2) is more preferred.

The sulfonic acid represented by the general formula (1) and the sulfonic acid represented by the general formula (2) are described in detail below.

[Chemical formula 11]

In the general formula (1), R ₁₁ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms represented by R ₁₁ is not particularly limited, and for example, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms) (may be any of a linear, branched, and cyclic group) is preferred. In addition, the alkyl group represented by R ₁₁ may further have a substituent, and may be substituted by a fluorine atom, for example. As R ₁₁ , a hydrogen atom is preferred.

R ₁₂ represents a monovalent organic group having 1 to 20 carbon atoms and having no fluorine atom. The monovalent organic group having 1 to 20 carbon atoms and having no fluorine atom represented by R ₁₂ is not particularly limited, and examples thereof include a group represented by *-L ₁₁ -W _11. Here, L ₁₁ represents a divalent linking group, W ₁₁ represents an organic group including a cyclic structure, and * represents a bonding position.

Examples of the divalent linking group represented by _L11 include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, _-SO2- , linear or branched alkylene groups (preferably having 1 to 6 carbon atoms), cyclic alkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups obtained by combining a plurality of these groups. Specifically, there can be mentioned -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -AL-, -COO-AL-, -OCO-AL-, -CONH-AL-, -NHCO-AL-, -AL-OCO-, -AL-COO-, -CO-AL-, -AL-CO-, -O-AL-, -AL-O-, and -AL-O-CO-O-AL-. In addition, the above-mentioned AL represents a linear or branched alkylene group (preferably having 1 to 6 carbon atoms).

W ₁₁ represents an organic group including a cyclic structure. Among them, a cyclic organic group is preferred. As the cyclic organic group, for example, an alicyclic group, an aryl group and a heterocyclic group can be cited. The alicyclic group can be monocyclic or polycyclic. As the monocyclic alicyclic group, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl can be cited. As the polycyclic alicyclic group, for example, polycyclic cycloalkyl groups such as norbornyl, tricyclic decanyl, tetracyclic decanyl, tetracyclic dodecyl and adamantyl can be cited. Among them, alicyclic groups having a bulk structure of 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl and adamantyl, are preferred.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl, and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. Furthermore, the heterocyclic group may be aromatic or non-aromatic. Examples of the aromatic heterocyclic group include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of the non-aromatic heterocyclic group include tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferred.

The above-mentioned cyclic organic group may have a substituent. As the substituent, for example, an alkyl group (may be any of a linear chain and a branched chain, preferably having 1 to 12 carbon atoms), a cycloalkyl group (may be any of a monocyclic ring, a polycyclic ring, and a spirocyclic ring, 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, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group may be mentioned. In addition, the carbon (carbon that contributes to the formation of the ring) constituting the cyclic organic group may be a carbonyl carbon.

Rf ₁₁ represents a fluorine atom or a monovalent organic group containing a fluorine atom. The monovalent organic group containing a fluorine atom represented by Rf ₁₁ is not particularly limited, and for example, an alkyl group substituted with at least one fluorine atom (which may be a linear, branched, or cyclic group) can be cited. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4. In addition, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. As Rf ₁₁ , a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferred, and a fluorine atom or CF ₃ is more preferred.

Specific examples of the sulfonic acid represented by the above general formula (1) are shown below.

[Chemical formula 12]

In the above general formula (2), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ₂₁ , R ₂₂ and R ₂₃ is not particularly limited, and for example, the groups exemplified in the above substituent group T can be cited, among which a fluorine atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) (may be any of a linear, branched or cyclic type). In addition, the alkyl group represented by R ₂₁ , R ₂₂ and R ₂₃ may further have a substituent, for example, may be substituted by a fluorine atom. As R ₂₁ , R ₂₂ and R ₂₃ , a hydrogen atom or a fluorine atom is preferred. Furthermore, it is preferred that at least one of R ₂₁ and R ₂₂ represents a group other than a fluorine atom, and it is more preferred that both represent a hydrogen atom.

_R24 represents a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbon atoms represented by _R24 include monovalent organic groups having 1 to 20 carbon atoms not having a fluorine atom, and specifically, the same ones as the monovalent organic groups having 1 to 20 carbon atoms not having a fluorine atom represented by _R12 in the general formula (1) can be mentioned.

_Rf21 represents a fluorine atom or a monovalent organic group containing a fluorine atom. Examples of the monovalent organic group containing a fluorine atom represented by _Rf21 include the monovalent organic group containing a fluorine atom represented by _Rf11 in the general formula (1).

Specific examples of the sulfonic acid represented by the above general formula (2) are shown below.

[Chemical formula 13]

Regarding the photoacid generator A, there is no particular limitation as long as the acid generated satisfies the above-mentioned necessary conditions, and it can be an onium salt compound or a zwitterion. Among them, the photoacid generator A is preferably an onium salt compound having anions and cations. As the photoacid generator A, the compound represented by the general formula (ZaI) or the compound represented by the general formula (ZaII) is preferred. Among them, Z ₂₀₁ ^- in the compound represented by the general formula (ZaI) and Z ₂₀₂ ^- in the compound represented by the general formula (ZaII) independently represent a group represented by the following general formula (1-1) or a group represented by the following general formula (1-2). R ₁₁ , R ₁₂ and Rf ₁₁ in the general formula (1-1) have the same meanings as R ₁₁ , R ₁₂ and Rf ₁₁ in the general formula (1) above, respectively. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and Rf ₂₁ in the general formula (1-2) have the same meanings as R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and Rf ₂₁ in the general formula (1) above, respectively.

[Chemical formula 14]

In the general formula (ZaI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually 1 to 30, preferably 1 to 20. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group. Examples of the group formed by two of R ₂₀₁ to R ₂₀₃ being bonded include an alkylene group (e.g., a butylene group, a pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

As preferred embodiments of the cation in the general formula (ZaI), the corresponding groups in the compound (ZaI-1), compound (ZaI-2), compound represented by the general formula (ZaI-3b) (compound (ZaI-3b)), and compound represented by the general formula (ZaI-4b) (compound (ZaI-4b)) described later can be cited. In addition, the photoacid generator A may be a compound having a plurality of structures represented by the general formula (ZaI). For example, it may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by the general formula (ZaI) is bonded to at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by the general formula (ZaI) via a single bond or a linking group.

First, the compound (ZaI-1) will be described. The compound (ZaI-1) is an aryl coronium compound in which at least one of R ₂₀₁ to R ₂₀₃ in the general formula (ZaI) is an aryl coronium compound, that is, a compound in which the aryl coronium is a cation. In the aryl coronium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, a part of R ₂₀₁ to R ₂₀₃ may be aryl groups, and the remaining part may be an alkyl group or a cycloalkyl group. Furthermore, one of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remaining two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group may be contained in the ring. Examples of the group formed by two of R ₂₀₁ to R ₂₀₃ being bonded include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups (e.g., butylene groups, pentylene groups, or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -). Examples of the aryl coronium compound include triaryl coronium compounds, diaryl alkyl coronium compounds, aryl dialkyl coronium compounds, diaryl cycloalkyl coronium compounds, and aryl dicycloalkyl coronium compounds.

As the aryl group contained in the aryl coronium compound, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. As the heterocyclic structure, pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue and benzothiophene residue can be cited. When the aryl coronium compound has two or more aryl groups, the two or more aryl groups can be the same or different. The alkyl or cycloalkyl group that the aryl calcium compound has as required is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, for example, methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

The aryl group, alkyl group and cycloalkyl group for R ₂₀₁ to R ₂₀₃ may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group as a substituent.

Next, compound (ZaI-2) is described. Compound (ZaI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZaI) independently represent an organic group without an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. The organic group without an aromatic ring represented by R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ₂₀₁ to R ₂₀₃ independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group.

As the alkyl and cycloalkyl groups of R ₂₀₁ to R ₂₀₃ , linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl) are preferred. R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

Next, the compound (ZaI-3b) is described. The compound (ZaI-3b) is a compound having a benzoylmethyl sirconium salt structure represented by the following general formula (ZaI-3b).

[Chemical formula 15]

In the general formula (ZaI-3b), 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, a cycloalkylcarbonyloxy 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 (such as tert-butyl 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 form a ring, and the ring may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above-mentioned ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring include 3-10 membered rings, preferably 4-8 membered rings, and more preferably 5- or 6-membered rings.

As the group formed by any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y bonding, there can be mentioned alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted by a heteroatom such as an oxygen atom. As the group formed by the bonding of R _5c and R _6c , and R _5c and R _x , a single bond or an alkylene group is preferred. As the alkylene group, there can be mentioned methylene and ethylene. Zac ^- has the same meaning as the group represented by the above general formula (1-1) or the group represented by the above general formula (1-2).

Next, the compound (ZaI-4b) is described. The compound (ZaI-4b) is a compound represented by the following general formula (ZaI-4b).

[Chemical formula 16]

In the general formula (ZaI-4b), l represents an integer from 0 to 2. r represents an integer from 0 to 8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. R ₁₄ represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When R ₁₄ exists in plural, each independently represents the above-mentioned groups such as a hydroxyl group. 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 groups are bonded to each other to form a ring, a heteroatom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one embodiment, two R ₁₅ groups are preferably alkylene groups and are bonded to each other to form a ring structure. Za ^- has the same meaning as the group represented by the above general formula (1-1) or the group represented by the above general formula (1-2).

In the general formula (ZaI-4b), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. As the alkyl group, methyl, ethyl, n-butyl or t-butyl is more preferred.

Next, the general formula (ZaII) is described. In the general formula (ZaII), R ₂₀₄ and R ₂₀₅ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. As the aryl group of R ₂₀₄ and R ₂₀₅ , a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group of R ₂₀₄ and R ₂₀₅ may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the aryl group containing a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. The alkyl group and cycloalkyl group for R ₂₀₄ and R ₂₀₅ are preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl or norbornyl).

The aryl group, alkyl group and cycloalkyl group of R _{204 and R 205 may each independently have a substituent. Examples of the substituent that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have} include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group. Z ₂₀₂ ^- in the general formula (ZaII) represents a group represented by the general formula (1-1) or a group represented by the general formula (1-2).

Specific examples of the cationic structural part of the photoacid generator A are shown below.

[Chemical formula 17]

Specific examples of the photoacid generator A are shown below.

[Chemical formula 18]

The photoacid generator A may be in the form of a low molecular weight compound or in the form of being incorporated into a part of a polymer. In addition, the photoacid generator A may be used in the form of a low molecular weight compound and in the form of being incorporated into a part of a polymer. It is preferred that the photoacid generator A is in the form of a low molecular weight compound. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

One photoacid generator A may be used alone, or two or more photoacid generators A may be used. The content of the photoacid generator A (the total content when multiple photoacid generators are included) is preferably 0.1 to 35 mass %, more preferably 0.5 to 25 mass %, further preferably 3 to 20 mass %, particularly preferably 3 to 15 mass %, and most preferably 3 to 10 mass % relative to the total solid content of the composition.

[Photoacid generator B] The composition of the present invention further comprises at least one of a photoacid generator B and a nitrogen-containing compound C. The photoacid generator B is a compound that generates an acid by irradiation with actinic rays or radiation. The photoacid generator B is a compound that generates an acid whose pKa is 1.00 or more greater than that of the acid generated by the photoacid generator A. In addition, if it is a compound having a nitrogen atom and the pKa of the conjugated acid is 1.00 or more greater than that of the acid generated by the photoacid generator A, then even if it is a compound that generates an acid whose pKa is 1.00 or more greater than that of the acid generated by the photoacid generator A, the above compound also meets the nitrogen-containing compound C, but does not meet the photoacid generator B. The difference between the pKa of the acid generated from the photoacid generator B and the pKa of the acid generated from the photoacid generator A is preferably 1.00 to 10.00, more preferably 1.00 to 5.00, and further preferably 1.00 to 3.00. In addition, the pKa of the acid generated from the photoacid generator B varies depending on the type of the photoacid generator A used, for example, 0.00 to 10.00 is preferred, 0.50 to 5.00 is more preferred, and 1.00 to 5.00 is further preferred.

The photoacid generator B is preferably an onium salt compound containing anions and cations. As such onium salt compounds, compounds represented by general formulas (d1-1) to (d1-3) are preferred.

[Chemical formula 19]

In the formula, R ⁵¹ represents a alkyl group (e.g., an aryl group such as a phenyl group) which may have a substituent (e.g., a hydroxyl group). Z ^2c represents a alkyl group having 1 to 30 carbon atoms which may have a substituent (wherein the carbon atom adjacent to S is not substituted with a fluorine atom). The alkyl group in Z ^2c may be a straight chain, a branched chain, or a ring structure. In addition, the carbon atom in the alkyl group (preferably the carbon atom forming the ring structure when the alkyl group has a ring structure) may be a carbonyl carbon (-CO-). As the alkyl group, for example, a group containing a norbornyl group which may have a substituent can be cited. The carbon atom forming the norbornyl group may be a carbonyl carbon. R ⁵² represents an organic group, Y ³ represents a linear, branched or cyclic alkylene group or arylene group, and Rf represents a fluorine-containing alkylene group. In addition, "Z ^2c -SO ₃ ^- " in the general formula (d1-2) is preferably different from the group represented by the general formula (1-1) or the group represented by the general formula (1-2). M ⁺ is independently an ammonium cation, a coronium cation or an iodine cation. As the zirconia cations and iodine cations, for example, zirconia cations and iodine cations that can be included in the cations of the photoacid generator A (more specifically, cations in the compound represented by the general formula (ZaI) and the compound represented by the general formula (ZaII)) can be used in the same manner.

The photoacid generator B may be a compound having a cationic part and an anionic part in the same molecule, and the cationic part and the anionic part are bonded to each other by a covalent bond. As the above-mentioned compound, a compound represented by the general formula (C-1) or a compound represented by the general formula (C-2) is preferred.

[Chemical formula 20]

In general formulae (C-1) to (C-3), R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms. L ₁ represents a divalent linking group or a single bond that bonds a cationic group (S ⁺ , I ⁺ , or N ⁺ ) to -X ^- . -X ^- represents -COO ^- , -SO ₃ ^- , -SO ₂ ^- or -N ^- -R ₄ . R ₄ represents a monovalent substituent having at least one of a carbonyl group (-CO-), a sulfonyl group (-SO ₂ -) and a sulfinyl group (-S(=O)-) at the bonding site to the adjacent N atom. R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may bond to each other to form a ring. In the general formula (C-3), two of R ₁ to R ₃ together represent a divalent substituent, and may be bonded to the N atom via a double bond.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl, cycloalkyl, aryl (preferably having 6 to 15 carbon atoms), alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl. Among them, alkyl, cycloalkyl, and aryl are preferred.

Examples of L ₁ as a divalent linking group include linear or branched alkylene groups, cycloalkylene groups, arylene groups (preferably having 6 to 15 carbon atoms), carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these groups. Among them, alkylene groups, arylene groups, ether bonds, ester bonds, and groups formed by combining two or more of these groups are preferred.

The acid generator B may be in the form of a low molecular weight compound or in the form of being incorporated into a part of a polymer. In addition, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used together. It is preferred that the photoacid generator B is in the form of a low molecular weight compound. When the photoacid generator B is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

One photoacid generator B may be used alone, or two or more photoacid generators B may be used. When the above composition contains a photoacid generator B, the content of the photoacid generator B (the total content when there are multiple photoacid generators) relative to the total solid content of the composition is preferably 0.1 to 15 mass %, 0.1 to 10 mass % is more preferably, 0.1 to 5.0 mass % is further preferably, and 0.1 to 3.0 mass % is particularly preferably.

[Nitrogen-containing compound C] The composition includes at least one of the photoacid generator B and the nitrogen-containing compound C. The nitrogen-containing compound C is a compound different from the photoacid generator A. The nitrogen-containing compound C has at least one nitrogen atom and is a compound whose pKa of the conjugated acid is greater than that of the acid generated by the photoacid generator A by 1.00 or more. As long as the necessary condition that the pKa of the conjugated acid is greater than that of the acid generated from the photoacid generator A by 1.00 or more is satisfied, the nitrogen-containing compound C may be a compound that generates an acid by irradiation with actinic rays or radiation. The difference between the pKa of the conjugated acid of the nitrogen-containing compound C and the pKa of the acid generated from the photoacid generator A is preferably 1.00 to 14.00, and more preferably 2.00 to 13.00. The pKa of the conjugated acid of the nitrogen-containing compound C varies depending on the type of the photoacid generator A used. For example, 0.00 to 14.00 is preferred, 3.00 to 13.00 is more preferred, and 3.50 to 12.50 is further preferred.

The nitrogen-containing compound C captures the acid generated from the photoacid generator A or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed portion caused by the excess generated acid. As the nitrogen-containing compound C, for example, there can be cited alkaline compounds (DA) having nitrogen atoms, alkaline compounds (DB) having nitrogen atoms and whose alkalinity decreases or disappears by irradiation with actinic rays or radiation, low molecular weight compounds (DD) having nitrogen atoms and having a group that is released by the action of an acid, and onium salt compounds (DE) having nitrogen atoms in the cationic portion.

<Alkaline compound (DA)> As the alkaline compound (DA), for example, compounds having structures represented by general formulae (A) to (E) can be cited.

[Chemical formula 21]

In general formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 20 carbon atoms). 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 independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl group in the general formula (A) and (E) may have a substituent or may be unsubstituted. Regarding the above-mentioned alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. It is more preferred that the alkyl group in the general formula (A) and (E) is unsubstituted.

As the alkaline compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperidine, aminopyrrolidine, aminoalkylpyrrolidine or piperidine are preferred, and compounds having an imidazole structure, a diazepine bicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl and/or ether group, or an aniline derivative having a hydroxyl and/or ether group are more preferred.

<Compound (DB)> The nitrogen-containing compound C may be an alkaline compound (DB) having a nitrogen atom and whose alkalinity is reduced or eliminated by irradiation with actinic rays or radiation (hereinafter, also referred to as "compound (DB)"). The compound (DB) is a compound having a proton acceptor functional group and whose proton acceptor is reduced or eliminated or changes from proton acceptor to acidic by decomposition by irradiation with actinic rays or radiation.

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

[Chemical formula 22]

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, nitrogen-doped crown ethers, mono- to tertiary amines, pyridine, imidazole, and pyridine-like structures.

Compound (DB) produces a compound whose proton acceptor property decreases, disappears, or changes from proton acceptor property to acidic property by decomposition due to irradiation with actinic rays or radiation. The decrease or disappearance of proton acceptor property, or the change from proton acceptor property to acidic property, refers to the change of proton acceptor property caused by the addition of proton to the proton acceptor functional group. Specifically, when a proton addition product is generated from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant under chemical equilibrium decreases. The proton acceptor property can be confirmed by pH measurement.

The pKa of the compound produced by decomposing the compound (DB) by irradiation with actinic rays or radiation is preferably pKa < -1, more preferably -13 < pKa < -1, and even more preferably -13 < pKa < -3. The compound produced in this way can be neutralized within the molecule and the pKa can be above -1.

The compound (DB) is preferably a compound represented by the general formula (c-1). RBXAW ₁ -N ^- -W ₂ -R _f [C ⁺ ] (c-1)

In the general formula (c-1), _W1 and _W2 each independently represent _-SO2- or -CO-. _Rf represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. A represents a single bond or a divalent linking group. X represents a single bond, _-SO2- or -CO-. B represents a single bond, an oxygen atom, or -N(Rx)Ry-. _Rx represents a hydrogen atom or an organic group. _Ry represents a single bond or a divalent organic group. R represents a monovalent organic group having a proton accepting functional group. _Rx may be bonded to _Ry to form a ring, or may be bonded to R to form a ring. [C ⁺ ] represents a relative ion.

It is preferred that at least one of _W1 and _W2 is -SO ₂ -, and it is more preferred that both of them are -SO ₂ -.

Rf is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

As the divalent linking group in A, a divalent linking group having 2 to 12 carbon atoms is preferred, for example, an alkylene group and a phenylene group. Among them, an alkylene group having at least one fluorine atom is preferred, and a carbon number of 2 to 6 is preferred, and 2 to 4 is more preferred. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. An alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted by fluorine atoms, and it is more preferred that the carbon atom bonded to the Q position has a fluorine atom. Among them, the divalent linking group in A is preferably a perfluoroalkylene group, and a perfluoroethylene group, a perfluoropropylene group or a perfluorobutylene group is more preferred.

As the monovalent organic group in Rx, preferably, the carbon number is 2 to 30, for example, alkyl, cycloalkyl which may have an oxygen atom in the ring, aryl, aralkyl and alkenyl etc. can be cited. As the alkyl group in Rx, it may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and the alkyl chain may have an oxygen atom, a sulfur atom and/or a nitrogen atom. In addition, as the alkyl group having a substituent, a group in which a cycloalkyl is substituted in a linear or branched alkyl group (for example, adamantylmethyl, adamantylethyl, cyclohexylethyl and camphor residue etc.) can be cited. As the cycloalkyl group in Rx, it may have a substituent, and preferably, a cycloalkyl group having 3 to 20 carbon atoms is preferred. In addition, the cycloalkyl group may have an oxygen atom in the ring. The aryl group in Rx may have a substituent, preferably an aryl group having 6 to 14 carbon atoms. The aralkyl group in Rx may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms. The alkenyl group in Rx may have a substituent, for example, a group having a double bond at any position of the alkyl group listed as Rx may be listed.

When B represents -N(Rx)Ry-, an alkylene group is preferably used as the divalent organic group in Ry. In this case, as the ring formed by Rx and Ry being bonded to each other, for example, a 5- to 8-membered ring containing a nitrogen atom can be mentioned, and a 6-membered ring is particularly preferred. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

When B represents -N(Rx)Ry-, it is preferred that R and Rx are bonded to each other to form a ring. If a ring is formed, the stability is improved, and the storage stability of the composition using the same is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and it can be a monocyclic ring or a polycyclic ring, and the ring can contain oxygen atoms, sulfur atoms and/or nitrogen atoms. The nitrogen atom contained in the ring can be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

Examples of monocyclic rings include 4-membered rings, 5-membered rings, 6-membered rings, 7-membered rings, and 8-membered rings containing nitrogen atoms. Examples of such ring structures include piperidine rings and piperidine rings. Examples of polycyclic rings include structures including a combination of 2 or 3 or more monocyclic structures. The monocyclic and polycyclic rings may each have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 15 carbon atoms), an acyloxy group (preferably having 2 to 15 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms), or an aminoacyl group (preferably having 2 to 20 carbon atoms) is preferred. If possible, the substituents may further have a substituent. As an example of an aryl group and a cycloalkyl group further having a substituent, an alkyl group (preferably having 1 to 15 carbon atoms) can be cited. Examples of the substituent that the aminoacyl group may further have include an alkyl group (preferably having 1 to 15 carbon atoms).

As the proton acceptor functional group in R, as described above, as a partial structure, for example, a structure having a crown ether, a mono-tertiary amine, and a nitrogen-containing heterocyclic group (pyridine, imidazole, pyridine, etc.) is preferred. In addition, as a proton acceptor functional group, a functional group having a nitrogen atom is preferred, and a group having a mono-tertiary amine group or a nitrogen-containing heterocyclic group is more preferred. In these structures, it is preferred that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. In addition, it is preferred that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom. The monovalent organic group in the monovalent organic group (group R) containing such a proton acceptor functional group preferably has 2 to 30 carbon atoms, and examples thereof include alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups, and each group may have a substituent.

The alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group containing a proton acceptor functional group in R can be exemplified by the same groups as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group exemplified as Rx.

Examples of substituents that the above groups may have include halogen atoms, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, cycloalkyl groups (preferably having 3 to 10 carbon atoms, which may be partially substituted with heteroatoms or groups having heteroatoms (ester groups, etc.)), aryl groups (preferably having 6 to 14 carbon atoms), alkoxy groups (preferably having 1 to 10 carbon atoms), acyl groups (preferably having 2 to 20 carbon atoms), acyloxy groups (preferably having 2 to 10 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms), and aminoacyl groups (preferably having 2 to 20 carbon atoms). Examples of substituents that the cyclic groups in the aryl group and the cycloalkyl group include alkyl groups (preferably having 1 to 20 carbon atoms). As the substituent which the aminoacyl group may have, for example, there can be mentioned 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

[C ⁺ ] As the counter ion, a zirconia cation or an iodine cation is preferred. As the zirconia cation and the iodine cation, for example, zirconia cations and iodine cations among the cations that the photoacid generator A may have (more specifically, cations in the compound represented by the general formula (ZaI) and cations in the compound represented by the general formula (ZaII) etc.) can be used in the same manner.

(Compound (DD)) The nitrogen-containing compound C may be a low molecular compound (DD) having a nitrogen atom and a group that is dissociated by the action of an acid (hereinafter, also referred to as "compound (DD)"). Compound (DD) is preferably an amine derivative having a group that is dissociated by the action of an acid on the nitrogen atom. As the group that is dissociated by the action of an acid, it is preferably an aldehyde ester group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemialdehyde ether group, and a carbamate group or a hemialdehyde ether group is more preferably. The molecular weight of compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500. Compound (DD) may also have a carbamate group having a protective group on the nitrogen atom. As the protecting group constituting the carbamate group, the group represented by the following general formula (d-1) is preferred.

[Chemical formula 23]

In the general formula (d-1), R _b independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may also be linked to each other to form a ring. The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b may be independently substituted by a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidinyl group, a piperidinyl group, a quinoline group, an oxo group, an alkoxy group or a halogen atom. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferred, and a linear or branched alkyl group or a cycloalkyl group is more preferred. As the ring formed by two R _bs linked to each other, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and their derivatives can be cited. As the specific structure of the group represented by the general formula (d-1), the structure disclosed in paragraph [0466] of the specification of U.S. Patent Gazette No. US2012/0135348A1 can be cited, but it is not limited thereto.

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

[Chemical formula 24]

In the general formula (6), l represents an integer from 0 to 2, and m represents an integer from 1 to 3, satisfying l+m=3. _Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra _groups may be the same or different, and the two Ra _groups may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain heteroatoms other than the nitrogen atom in the formula. _Rb has the same meaning as _Rb in the general formula (d-1) above, and preferred examples are also the same. In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as _Ra may be independently substituted by the same groups as the aforementioned groups, and the aforementioned groups are groups with which the alkyl group, cycloalkyl group, aryl group, and aralkyl group as _Rb may be substituted.

As specific examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group (these groups may be substituted by the above groups) for the above-mentioned _Ra , the same groups as the specific examples mentioned above for _Rb can be cited.

(Compound (DE)) The nitrogen-containing compound C may be an onium salt compound (DE) having a nitrogen atom in the cationic part (hereinafter, also referred to as "compound (DE)"). When compound (DE) generates an acid by irradiation with actinic rays or radiation, the pKa of the generated acid is smaller than the value obtained by adding 1.00 to the pKa of the acid generated by the photoacid generator A. Compound (DE) is preferably a compound having a basic part containing a nitrogen atom in the cationic part. The basic part is preferably an amine group, and more preferably an aliphatic amine group. Furthermore, it is preferred that all atoms adjacent to the nitrogen atom in the basic part are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving alkalinity, it is preferred that electron-withdrawing functional groups (carbonyl, sulfonyl, cyano, and halogen atoms, etc.) do not directly bond to nitrogen atoms.

One nitrogen-containing compound C may be used alone, or two or more nitrogen-containing compounds C may be used. When the composition contains nitrogen-containing compound C, the content of nitrogen-containing compound C in the composition (the total content when multiple nitrogen-containing compounds are included) is preferably 0.1 to 15 mass %, more preferably 0.1 to 10 mass %, further preferably 0.1 to 8.0 mass %, and particularly preferably 0.1 to 3.0 mass % relative to the total solid content of the composition.

The composition only needs to contain one or more selected from the group consisting of the photoacid generator B and the nitrogen-containing compound C, and may contain only one or both.

<Hydrophobic resin> The composition of the present invention includes a hydrophobic resin. In addition, the hydrophobic resin is a resin different from the resin A, and from the viewpoint of better uniformity of the film thickness, it is preferred that the hydrophobic resin does not substantially contain repeating units having a group (acid-decomposable group) whose polarity increases by decomposition by the action of an acid. In addition, the "substantially does not contain" mentioned here means that the content of the repeating units containing the above-mentioned acid-decomposable group in the hydrophobic resin is 0 mol% or more and 5 mol% or less relative to all the repeating units of the hydrophobic resin, and the upper limit is preferably 3 mol% or less, and 1 mol% or less is more preferred. Since the composition of the present invention includes a hydrophobic resin, it is easy to control the static and/or dynamic contact angle on the surface of the anti-etching agent film (photosensitive or radiation-sensitive film). This can improve the development characteristics, suppress degassing, improve the immersion liquid tracking performance in immersion exposure, and reduce immersion defects. The hydrophobic resin is preferably designed to be biased on the surface of the anti-etching agent film, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and may not contribute to the uniform mixing of polar and non-polar substances.

From the viewpoint of partial localization to the membrane surface, the hydrophobic resin is preferably a resin having at least one group selected from the group including fluorine atoms, groups having fluorine atoms, groups having silicon atoms, linear, branched or cyclic alkyl groups with 6 or more carbon atoms, aryl groups with 9 or more carbon atoms, arylalkyl groups with 10 or more carbon atoms, aryl groups substituted with at least one linear or branched alkyl group with 3 or more carbon atoms, and aryl groups substituted with at least one cyclic alkyl group with 5 or more carbon atoms (hereinafter also referred to as "hydrophobic groups"). Among them, it is more preferred that the hydrophobic resin contains repeating units containing the above hydrophobic groups. In addition, when the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

As the above-mentioned group having fluorine atoms, a linear, branched or cyclic alkyl group having fluorine atoms or an aryl group having fluorine atoms is preferred. As the above-mentioned linear, branched or cyclic alkyl group having fluorine atoms, a perfluoroalkyl group having 1 to 4 carbon atoms is preferred, and _CF3 is more preferred. As the aryl group having fluorine atoms, for example, a phenyl group substituted with a fluorine atom can be cited.

As the above-mentioned group having a silicon atom, for example, an alkylsilyl group can be cited. As the above-mentioned alkylsilyl group, for example, a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group can be cited.

Examples of the linear, branched or cyclic alkyl group having 6 or more carbon atoms include linear, branched or cyclic alkyl groups having 6 to 20 carbon atoms, such as 2-ethylhexyl, norbornyl and adamantyl.

Examples of the aryl group having 9 or more carbon atoms include a polycyclic aryl group in which two or more 5-membered or 6-membered monocyclic aromatic hydrocarbon rings are combined.

The aralkyl group having 10 or more carbon atoms is preferably an aralkyl group having 10 to 20 carbon atoms, and specific examples thereof include 1-naphthylmethyl, 1-(1-naphthyl)ethyl, triphenylmethyl, and thienylmethyl.

Examples of the aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms include a phenyl group substituted with a linear or branched alkyl group having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms).

Examples of the aryl group substituted with at least one cyclic alkyl group having 5 or more carbon atoms include a phenyl group substituted with a cyclic alkyl group having 5 to 20 carbon atoms (preferably 5 to 10 carbon atoms).

Regarding the hydrophobic resin, it is preferred that the hydrophobic resin contains a repeating unit containing a fluorine atom or a group having a fluorine atom. Furthermore, from the viewpoint of better uniformity of film thickness, it is preferred that the number of fluorine atoms contained in the hydrophobic resin is greater than the number of fluorine atoms contained in the above-mentioned photoacid generator A. Among them, when the above-mentioned hydrophobic resin contains only one repeating unit containing a fluorine atom, the number of fluorine atoms contained in the hydrophobic resin can be calculated by the following formula (1). Furthermore, when the above-mentioned hydrophobic resin contains two or more repeating units containing fluorine atoms, the number of fluorine atoms contained in the hydrophobic resin is calculated as the sum of the values of each repeating unit containing a fluorine atom calculated by the following formula (1). Formula (1): Y _A = a × b ÷ 100 Y _A : The number of fluorine atoms contained in the hydrophobic resin a: The number of fluorine atoms in the repeating unit containing fluorine atoms b: The content of the repeating unit containing fluorine atoms relative to all repeating units in the hydrophobic resin (mol %)

The hydrophobic resin preferably contains at least one of the groups selected from (x) and (y) shown below, and more preferably contains a repeating unit containing a group selected from (y). In addition, (x) and (y) shown below may contain the above-mentioned hydrophobic group. (x) Acid group (y) A group that is decomposed by the action of an alkaline developer and increases the solubility in the alkaline developer (hereinafter, also referred to as a polarity conversion group)

As the acid group (x), there can be cited a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tri(alkylcarbonyl)methylene group, and a tri(alkylsulfonyl)methylene group. As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group, or a bis(alkylcarbonyl)methylene group is preferred.

Examples of the group (y) that is decomposed by the action of an alkaline developer and has increased solubility in an alkaline developer include a lactone group, a carboxylate group (-COO- or -OCO-), an anhydride group (-CO-O-CO-), an acid imide group (-NHCONH-), a carboxylate thioester group (-COS- or -SCO-), a carbonate group (-O-CO-O-), a sulfate group (-OSO ₂ O-) and a sulfonate group (-SO ₂ O- or -OSO ₂ -). A lactone group or a carboxylate group (-COO- or -OCO-) is preferred, and a carboxylate group (-COO- or -OCO-) is more preferred.

As repeating units containing a group selected from the above (y), for example, the following can be cited: (1) a repeating unit in which a group selected from the above (y) is directly bonded to the main chain of the resin (for example, repeating units based on acrylate and methacrylate, etc.); and (2) a repeating unit in which a group selected from the above (y) is bonded to the main chain of the resin via a linking group. In addition, as repeating units having a lactone group, for example, the same repeating units as the repeating units having a lactone structure described previously in the section of Resin A can be cited.

As the repeating unit comprising a group selected from the above-mentioned (y), the form of the above-mentioned (2) is preferred, and the repeating unit represented by the following general formula (3) is more preferred.

[Chemical formula 25]

In the general formula (3), _Z1 represents a halogen atom, a hydrogen atom or an alkyl group. Examples of the halogen atom represented by _Z1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, among which a fluorine atom is preferred. Examples of the alkyl group represented by _Z1 include an alkyl group having 1 to 12 carbon atoms. The alkyl group may be any of a linear chain, a branched chain and a cyclic chain. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

_L1 represents an (n+1)-valent linking group. The (n+1)-valent linking group represented by _L1 is not particularly limited, and examples thereof include a divalent or higher aliphatic hydrocarbon group having 1 to 20 carbon atoms which may include a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroatom may be included in the form of, for example, -O-, -S-, _-SO2- , ^-NRA- , -CO-, or a combination of two or more of these linking groups. In addition, the above-mentioned ^RA represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Examples of the divalent or higher aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom include a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms which may contain a heteroatom, and a linear or branched alkylene group having 1 to 10 carbon atoms is preferred.

_X1 represents a group represented by * _-Y1 - _R1 . The above _Y1 represents -CO-O- or -O-CO-. The above * represents a bonding position.

The above R ₁ represents an electron-withdrawing group. There is no particular limitation on the electron-withdrawing group, and examples thereof include an alkyl group having 1 to 10 carbon atoms substituted with at least one fluorine atom (which may be a linear, branched, or cyclic alkyl group). Specifically, examples thereof include -CF ₃ , -CF ₂ CF ₃ , -CH ₂ CF ₃ , -CHFCF ₃ , and -CH(CF ₃ ) ₂ . From the perspective of better film thickness uniformity, -CH(CF ₃ ) ₂ is preferred as the electron-withdrawing group.

n represents a positive integer. There is no particular limitation as long as n is greater than 1, and its upper limit is, for example, 10. In addition, when n is greater than 2, the plurality of _X1s may be the same as or different from each other.

When the hydrophobic resin contains a repeating unit comprising a group selected from the above (y), the content thereof is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and even more preferably 5 to 95 mol % relative to all the repeating units in the hydrophobic resin.

When the hydrophobic resin contains repeating units containing fluorine atoms, the content thereof is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, and further preferably 30 to 95 mol % relative to all repeating units in the hydrophobic resin. In addition, when the hydrophobic resin contains repeating units containing silicon atoms, the content thereof is preferably 10 to 100 mol %, and more preferably 20 to 100 mol % relative to all repeating units in the hydrophobic resin.

From the perspective of achieving better uniformity of the membrane surface, it is preferred that the hydrophobic resin contains the repeating units represented by the above general formula (3) and other repeating units other than the repeating units represented by the general formula (3). As repeating units other than the repeating units represented by the general formula (3), it is preferred that the repeating unit comprises a group selected from the above (y) and comprises the above hydrophobic group (in other words, it is a repeating unit having the above group which decomposes by the action of the alkaline developer and increases the solubility in the alkaline developer and comprises the above hydrophobic group). It is preferred that the repeating unit comprises a group selected from the above (y) and comprises at least one group selected from the group consisting of a linear, branched or cyclic alkyl group having 6 or more carbon atoms, an aryl group having 9 or more carbon atoms, an arylalkyl group having 10 or more carbon atoms, an aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and an aryl group substituted with at least one cyclic alkyl group having 5 or more carbon atoms. In addition, as other repeating units other than the repeating units represented by the above general formula (3), it is preferred that no fluorine atoms are included. When the hydrophobic resin contains the repeating units represented by the general formula (3) and other repeating units other than the repeating units represented by the general formula (3), the content of the repeating units represented by the above general formula (3) relative to all the repeating units of the hydrophobic resin is preferably 95 mol% or less, 90 mol% or less is more preferably, and 85 mol% or less is further preferably. In addition, there is no particular restriction on the lower limit, for example, it is 10 mol% or more, and 30 mol% or more is more preferably.

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

The total content of residual monomers and/or oligomers contained in the hydrophobic resin is preferably 0.01 to 5 mass %, more preferably 0.01 to 3 mass %. Furthermore, the dispersion degree (Mw/Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

As the hydrophobic resin, a known resin can be appropriately selected and used alone or as a mixture thereof. For example, the known resins disclosed in paragraphs [0451] to [0704] of the specification of U.S. Patent Application Publication No. 2015/0168830A1 and paragraphs [0340] to [0356] of the specification of U.S. Patent Application Publication No. 2016/0274458A1 can be preferably used as the hydrophobic resin. In addition, the repeating units disclosed in paragraphs [0177] to [0258] of the specification of U.S. Patent Application Publication No. 2016/0237190A1 are also preferably used as the repeating units constituting the hydrophobic resin.

Preferred examples of monomers that correspond to the repeating units constituting the hydrophobic resin are shown below.

[Chemical formula 26]

[Chemical formula 27]

The hydrophobic resin may be used alone or in combination of two or more. From the perspective of taking both the immersion liquid tracking property and the developing property into consideration in the immersion exposure, it is preferable to use a mixture of two or more hydrophobic resins having different surface energies. The content of the hydrophobic resin in the above composition (the total content when multiple hydrophobic resins are included) is preferably 3.0 to 12.0 mass %, more preferably 5.0 to 10.0 mass %, and more preferably 6.0 to 10.0 mass % relative to the total solid content in the composition of the present invention.

<Solvent> The composition of the present invention may contain a solvent. In the composition of the present invention, a known anti-etching agent solvent can be appropriately used. For example, the known solvents disclosed in paragraphs [0665] to [0670] of the specification of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs [0210] to [0235] of the specification of U.S. Patent Application Publication No. 2015/0004544A1, paragraphs [0424] to [0426] of the specification of U.S. Patent Application Publication No. 2016/0237190A1, and paragraphs [0357] to [0366] of the specification of U.S. Patent Application Publication No. 2016/0274458A1 can be preferably used. Examples of the solvent that can be used in preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

As an organic solvent, a mixed solvent of a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group can be used. As a solvent having a hydroxyl group and a solvent not having a hydroxyl group, the aforementioned exemplary compounds can be appropriately selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl ester is preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate is more preferred. Furthermore, as a solvent without a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compounds that may have a ring, cyclic lactone, or alkyl acetate are preferred, among which propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, cyclopentanone, or 2-heptanone are further preferred. As a solvent without a hydroxyl group, propylene carbonate is also preferred. The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and further preferably 20/80 to 60/40. From the perspective of coating uniformity, a mixed solvent containing more than 50% by mass of a solvent not having a hydroxyl group is preferred. The solvent preferably contains propylene glycol monomethyl ether acetate. At this time, the solvent may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more kinds of propylene glycol monomethyl ether acetate.

The solid content concentration of the composition of the present invention is preferably 1.0 to 10 mass %, more preferably 2.0 to 5.7 mass %, and further preferably 2.0 to 5.3 mass %. That is, when the composition contains a solvent, it is preferred to adjust the content of the solvent in the composition to meet the preferred range of the above solid content concentration. In addition, the solid content concentration refers to the mass percentage of the mass of other anti-corrosion agent components other than the solvent relative to the total mass of the composition. By setting the solid component concentration in the composition to an appropriate range, the composition has an appropriate viscosity to improve coating properties or film forming properties, thereby adjusting the film thickness of the anti-etching agent film (actinic radiation or radiation-sensitive film) including the composition of the present invention.

<Surfactant> The composition of the present invention may contain a surfactant. The surfactant is preferably a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both fluorine atoms and silicon atoms).

When the composition of the present invention includes a surfactant, it is easy to obtain a pattern with good sensitivity and resolution and few adhesion and development defects when using an exposure light source below 250nm, especially below 220nm. As fluorine-based and/or silicon-based surfactants, the surfactants described in paragraph [0276] of the specification of U.S. Patent Application Publication No. 2008/0248425 can be cited. In addition, other surfactants other than fluorine-based and/or silicon-based surfactants described in paragraph [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 can be used.

The surfactant may be used alone or in combination of two or more. When the composition of the present invention contains a surfactant, the content of the surfactant (when it contains multiple surfactants, the total content) is preferably 0.0001 to 2 mass % relative to the total solid content of the composition, and 0.0005 to 1 mass % is more preferably. On the other hand, when the content of the surfactant is set to 10 mass ppm or more relative to the total solid content of the composition, the surface localization of the hydrophobic resin is improved. As a result, the surface of the anti-etching agent film can be made more hydrophobic and the water tracking property during immersion exposure can be improved.

<Other additives> The composition of the present invention may further contain resins, crosslinking agents, acid proliferation agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors or dissolution promoters, etc. other than the above.

<Preparation method> The composition of the present invention is preferably used in the following manner, that is, the above-mentioned components are dissolved in a predetermined organic solvent (preferably the above-mentioned mixed solvent), and after filtering it through a filter, it is applied to a predetermined support (substrate). The pore size of the filter used in the filter filtering is preferably 0.1μm or less, more preferably 0.05μm or less, and further preferably 0.03μm or less. In addition, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for the filter filtering is preferably 3μm or less, more preferably 0.5μm or less, and further preferably 0.3μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, as disclosed in the specification of Japanese Patent Application Publication No. 2002-062667 (Japanese Patent Application Publication No. 2002-062667), cyclic filtration can be performed, and multiple filters can be connected in series or in parallel for filtration. In addition, the composition can be filtered multiple times. Furthermore, before and after the filter filtration, the composition can be degassed.

<Physical properties> The receding contact angle (RCA) of the film formed from the composition of the present invention relative to water is 80.0° or more, preferably 82.0° or more, and more preferably 83.0° or more. In addition, in this specification, "the receding contact angle of the film relative to water" refers to the receding contact angle of the film formed under the following conditions. (Film forming conditions) The composition of the present invention was applied to a silicon wafer by spin coating and then baked at 100°C for 60 seconds to form a film with a thickness of 90 nm. Next, the receding contact angle of a water droplet on the above film is measured using a dynamic contact angle meter (e.g., manufactured by Kyowa Interface Science Co., Ltd.) using an expansion-contraction method at room temperature of 23° C. and a relative humidity of 45%.

<Application> The composition of the present invention is related to an actinic or radiation-sensitive resin composition whose properties change by reacting to irradiation with actinic rays or radiation. More specifically, the composition of the present invention is related to an actinic or radiation-sensitive resin composition used in the manufacturing steps of semiconductors such as IC (Integrated Circuit), the manufacturing of circuit substrates such as liquid crystals or thermal heads, the manufacturing of mold structures for imprinting, other photosensitive etching processing steps or lithographic printing plates, or the manufacturing of acid-curable compositions. In the present invention, the formed pattern can be used in etching steps, ion implantation steps, bump electrode formation steps, redistribution formation steps, and MEMS (Micro Electro Mechanical Systems).

[Pattern forming method, anti-etching agent film] The present invention also relates to a pattern forming method using the above-mentioned photosensitive or radiation-sensitive resin composition. The pattern forming method of the present invention is described below. In addition, the anti-etching agent film (photosensitive or radiation-sensitive film) of the present invention is described together with the description of the pattern forming method.

The pattern forming method of the present invention has the following steps: (i) a step of forming an anti-etching agent film (actinic ray or radiation-sensitive film) on a support using the above-mentioned photosensitive ray or radiation-sensitive resin composition (anti-etching agent film forming step (film forming step)); (ii) a step of exposing the above-mentioned anti-etching agent film (irradiating with photochemical rays or radiation) (exposure step); and (iii) a step of developing the above-mentioned exposed anti-etching agent film using a developer (development step).

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

In the pattern forming method of the present invention, the above-mentioned (i) resist film forming step (film forming step), (ii) exposure step and (iii) development step can be performed by a generally known method.

From the perspective of improving resolution, the thickness of the anti-etching agent film is preferably 110 nm or less, and more preferably 95 nm or less. In addition, if necessary, an anti-etching agent underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon) and an anti-reflection film) can be formed between the anti-etching agent film and the support. As a material constituting the anti-etching agent underlayer film, a known organic or inorganic material can be appropriately used. A protective film (top coating) can be formed on the upper layer of the anti-etching agent film. As a protective film, a known material can be appropriately used. For example, the protective film forming composition disclosed in U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, U.S. Patent Application Publication No. 2013/0244438, and International Patent Application Publication No. 2016/157988A can be preferably used. As the protective film forming composition, it is preferred to include the above-mentioned acid diffusion control agent. The protective film can be formed on the upper layer of the anti-etching agent film including the above-mentioned hydrophobic resin.

The support is not particularly limited, and a substrate commonly used in a lithography step of a photosensitive etching process, in addition to a manufacturing step of a semiconductor such as an IC, or a manufacturing step of a circuit substrate such as a liquid crystal or a thermal head, can be used. Specific examples of the support include inorganic substrates such as silicon, _SiO2 , and SiN.

Regarding the heating temperature, it is preferably 70 to 130°C, and more preferably 80 to 120°C, in either the (iv) preheating step or the (v) post-exposure heating step. Regarding the heating time, it is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds, in either the (iv) preheating step or the (v) post-exposure heating step. The heating is performed by a mechanism provided in the exposure device and the developing device, and a heating plate or the like may be used.

The wavelength of the light source used in the exposure step is not particularly limited, and for example, infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams can be cited. Among them, far ultraviolet light is preferred, and its wavelength is preferably below 250nm, more preferably below 220nm, and further preferably 1 to 200nm. Specifically, KrF excimer laser (248nm), ArF excimer laser (193nm), _F2 excimer laser (157nm), X-rays, EUV (13nm), or electron beams are preferred, and KrF excimer laser, ArF excimer laser, EUV, or electron beams are more preferred.

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

As an alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide can be generally used. In addition, an alkaline aqueous solution such as an inorganic base, a mono-tertiary amine, an alcohol amine, and a cyclic amine can also be used. Furthermore, the alkaline developer may contain an appropriate amount of alcohol and/or a surfactant. The alkaline concentration of the alkaline developer is generally 0.1 to 20% by mass. The pH of the alkaline developer is generally 10 to 15. The development time using the alkaline developer is generally 10 to 300 seconds. The alkaline concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

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

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methylnaphthyl ketone, isophorone, and propyl carbonate.

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

As the alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent, the solvents disclosed in paragraphs [0715] to [0718] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 can be used.

The above solvents may be mixed in multiple types, or may be mixed with solvents other than the above or water. As for the water content of the developer as a whole, it is preferably less than 50% by mass, more preferably less than 20% by mass, more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent relative to the total amount of the developer is preferably 50-100% by mass, more preferably 80-100% by mass, more preferably 90-100% by mass, and particularly preferably 95-100% by mass.

The developer may contain an appropriate amount of a known surfactant as needed.

The content of the surfactant is generally 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the developer.

The organic developer may contain an acid diffusion control agent.

As developing methods, for example, there can be cited: a method of immersing a substrate in a tank filled with developer for a certain period of time (immersion method); a method of raising the developer by surface tension and leaving it on the substrate surface for a certain period of time (immersion method); a method of spraying the developer on the substrate surface (spraying method); and a method of continuously spraying the developer onto a substrate rotating at a certain speed while scanning a developer spray nozzle at a certain speed (dynamic dispensing method), etc.

The step of developing with an alkaline aqueous solution (alkaline developing step) and the step of developing with a developer containing an organic solvent (organic solvent developing step) can be combined. This allows only the area with the exposure intensity at the middle level to be insoluble and form a pattern, thereby enabling the formation of a finer pattern.

After the (iii) developing step, a step of washing with a washing solution (washing step) is preferably included.

The rinse solution used in the rinse step after the development step using an alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of a surfactant. In addition, after the development step or the rinse step, a supercritical fluid may be used to remove the developer or rinse solution attached to the pattern. Furthermore, in order to remove the water remaining in the pattern, a heat treatment may be performed after the rinse treatment or the supercritical fluid treatment.

The rinsing solution used in the rinsing step after the development step using the developer containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is preferably used. As specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, the same solvents as those described in the developer containing an organic solvent can be cited. As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing monohydric alcohol is more preferred.

As the monohydric alcohol used in the rinsing step, linear, branched or cyclic monohydric alcohols can be cited. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-hexanol, 2-octanol, 3-hexanol, 3-hexanol, 3-octanol, 4-octanol and methyl isobutyl carbinol can be cited. The monohydric alcohol may have more than 5 carbon atoms, and as examples thereof, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and methyl isobutyl carbinol can be cited.

The components may be mixed in plural types, and may be mixed with organic solvents other than the above. The water content in the rinse solution used in the rinse step after the development step using the developer containing an organic solvent is preferably 10% by mass or less, 5% by mass or less is more preferably, and 3% by mass or less is further preferably. When the water content is set to 10% by mass or less, good development characteristics can be obtained. The rinse solution after the development step using the developer containing an organic solvent may contain an appropriate amount of a surfactant.

In the rinsing step, the substrate to be developed is cleaned using a rinsing liquid. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously spraying the rinsing liquid on a substrate rotating at a certain speed (spin coating method), a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time (immersion method), or a method of spraying the rinsing liquid on the surface of the substrate (spraying method) can be cited. Among them, the method of using the spin coating method for cleaning treatment and rotating the substrate at a speed of 2,000 to 4,000 rpm after cleaning to remove the rinsing liquid from the substrate is preferred. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and rinse solution remaining between and inside the patterns are removed by the heating step. In the heating step after the rinse step, the heating temperature is usually 40 to 160°C, preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

It is preferred that the various materials used in the photosensitive or radiation-sensitive resin composition and the pattern forming method of the present invention (e.g., anti-etching agent solvent, developer, rinser, anti-reflection film forming composition or top coating forming composition, etc.) do not contain impurities such as metal components, isomers, and residual monomers. The content of such impurities contained in the above-mentioned various materials is preferably 1 mass ppm or less, 100 mass ppt or less is more preferred, 10 mass ppt or less is further preferred, and substantially no impurities (below the detection limit of the measuring device) are particularly preferred.

As a method for removing impurities such as metal from the above-mentioned various materials, for example, filtering using a filter can be cited. As for the pore size of the filter, a pore size of 10 nm or less is preferably, 5 nm or less is more preferably, and 3 nm or less is further preferably. As for the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferably used. The filter can be a filter that has been pre-cleaned with an organic solvent. In the filter filtering step, a plurality of filters can be connected in series or in parallel for use. When using a plurality of filters, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can be filtered multiple times, and the multiple filtering steps can be a cyclic filtering step. As a filter, a filter with reduced dissolution as disclosed in the specification of Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Publication No. 2016-201426) is preferred. In addition to filter filtration, impurities can be removed using an adsorbent, and filter filtration and adsorbent can be used in combination. As an adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel or zeolite or an organic adsorbent such as activated carbon can be used. As metal adsorbing materials, for example, materials disclosed in the specification of Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Application Publication No. 2016-206500) can be cited. In addition, as a method for reducing impurities such as metals contained in the above-mentioned various materials, a method such as selecting raw materials with low metal content as raw materials constituting various materials, filtering the raw materials constituting various materials with a filter, or lining the inside of the device with Teflon (registered trademark) to perform distillation under conditions that suppress contamination as much as possible can be cited. In order to reduce metal to ppt level, it is preferred to implement glass lining treatment in all steps of the manufacturing equipment for various materials (binder and photoacid generator, etc.) used to synthesize the anti-corrosion agent components. The preferred conditions in the filter filtration performed on the raw materials constituting the various materials are the same as the above conditions.

In order to prevent the mixing of impurities, it is preferable to store the above-mentioned various materials in the container described in U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Publication No. 2015-123351), and Japanese Patent Application Publication No. 2017-013804 (Japanese Patent Application Publication No. 2017-013804).

A method for improving the surface roughness of a pattern formed by the pattern forming method of the present invention can be applied. As a method for improving the surface roughness of a pattern, for example, a method for treating a pattern by plasma of a hydrogen-containing gas disclosed in the specification of U.S. Patent Application Publication No. 2015/0104957 can be cited. In addition, the known methods described in the specification of Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), the specification of U.S. Patent Application Publication No. 2010/0020297, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" can be applied. Furthermore, the pattern formed by the above method can be used as a core material (Core) of the spacer manufacturing process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Publication No. 3-270227) and US Patent Application Publication No. 2013/0209941.

[Method for manufacturing electronic devices] In addition, the present invention also relates to a method for manufacturing electronic devices including the above-mentioned pattern forming method. The electronic devices manufactured by the method for manufacturing electronic devices of the present invention are appropriately mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment and communication equipment, etc.). [Example]

The present invention is further described in detail below based on the embodiments. The materials, usage amounts, ratios, processing contents and processing steps shown in the following embodiments can be appropriately changed as long as they do not deviate from the main purpose of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the embodiments shown below.

[Preparation of an Actinic Radiation or Radiation-sensitive Resin Composition] [Various Components] <Acid-degradable resin> The structures of the acid-degradable resins (resins D-1 to D-5) shown in Table 1 are shown below. The weight average molecular weight (Mw) and the dispersion (Mw/Mn) of the acid-degradable resins were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene conversion). The composition ratio (molar % ratio) of the resins was measured by ¹³ C-NMR (Nuclear Magnetic Resonance).

[Chemical formula 28]

<Hydrophobic resin> The structures of the hydrophobic resins (resins E-1 to E-9) shown in Table 1 are shown below. The weight average molecular weight (Mw) and the dispersion (Mw/Mn) of the hydrophobic resins were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene conversion). The composition ratio (molar % ratio) of the resins was measured by ¹³ C-NMR.

[Chemical formula 29]

<Photoacid generator A> The structures of the photoacid generators (PAG-1 to PAG-23) shown in Table 1 are shown below.

[Chemical formula 30]

[Chemical formula 31]

<Acid diffusion control agent> The structures of the acid diffusion control agents (B-1 to B-2, C-1 to C-3) shown in Table 1 are shown below. In addition, B-1 to B-2 are equivalent to the photoacid generator B, and C-1 to C-3 are equivalent to the nitrogen-containing compound C.

[Chemical formula 32]

<Surfactant> The following are the surfactants shown in Table 1. W-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

<Solvent> The following are the solvents shown in Table 1. SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether (PGME) SL-3: Cyclohexanone SL-4: γ-butyrolactone SL-5: Ethyl lactate

[Preparation of an actinic radiation or radiation-sensitive resin composition] The components shown in Table 1 were mixed to a solid content concentration of 4% by mass. Then, the obtained mixed solution was filtered using a polyethylene filter with a pore size of 50 nm to prepare an actinic radiation or radiation-sensitive resin composition (hereinafter also referred to as an anti-corrosion agent composition). In addition, in the anti-corrosion agent composition, the solid component refers to all components except the solvent. The obtained anti-corrosion agent composition was used in the examples and comparative examples. In addition, in Table 1, the content (mass %) of the hydrophobic resin refers to the content relative to the total solid content. In Table 1, the pKa in the column "Photoacid generator A" indicates the pKa of the acid generated from the photoacid generator A. The pKa in the column "Acid diffusion control agent (photoacid generator B or nitrogen-containing compound C)" indicates either the pKa of the acid generated from the photoacid generator B or the pKa of the conjugated acid of the nitrogen-containing compound C.

[Table 1] Table 1 Anticorrosive agent composition performance Acid decomposable resin (2g) Solvent (mass ratio) Photoacid generator A Acid diffusion control agent (photoacid generator B or nitrogen-containing compound C) Hydrophobic resin Surfactant (mg) Recessed contact angle (°) LWR (3σ) Film thickness uniformity within the surface (3σ) Type (mg) pKa Number of fluorine atoms Type (mg) pKa Type (mass %) Number of fluorine atoms The presence or absence of repeating units represented by general formula (3) The structure of ^R1 in the general formula (3) Presence of acid-degradable repeating units Embodiment 1 D-1 SL-1/SL-3/SL-4 PAG-1 -1.40 1 B-1 3.01 E-7 3.0 without - without - 84.2 B C 60/30/10 100 7 10.0 Embodiment 2 D-2 SL-1/SL-2 PAG-1/PAG-2 (PAG-1)-1.40 (PAG-1)1 B-1/C-1 (B-1) 3.01 E-4 3.6 have *-CH(CF ₃ ) ₂ without W-1 83.1 A A 80/20 50/50 (PAG-2) -0.81 (PAG-2)1 3/4 (C-1) 4.20 5.0 2 Embodiment 3 D-3 SL-1/SL-2 PAG-2 -0.81 1 B-2 1.17 E-3 4.2 have *-CH(CF ₃ ) ₂ without - 85.4 A A 70/30 100 7 8.0 Embodiment 4 D-5 SL-1/SL-3 PAG-2 -0.81 1 C-2 11.72 E-6 0.9 without - have - 80.9 A D 80/20 100 7 8.0 Embodiment 5 D-1 SL-1/SL-2 PAG-3 -0.66 0 C-3 10.08 E-1 1.2 have _{* -CF2CF3} have - 80.5 A C 80/20 100 7 8.0 Embodiment 6 D-2 SL-1/SL-2 PAG-4 -0.05 1 C-1 4.20 E-8 5.0 have _{* -CF2CF3} without - 81.2 A B 80/20 100 7 7.0 Embodiment 7 D-5 SL-1 PAG-5 -0.02 1 C-2 11.72 E-1 1.2 have _{* -CF2CF3} have - 81.9 A C 100 125 6 8.0 Embodiment 8 D-1 SL-1/SL-2 PAG-5 -0.02 1 C-3 10.08 E-2 2.4 without - without - 80.2 A B 70/30 125 8 8.0 Embodiment 9 D-2 SL-1/SL-5 PAG-6 1.87 0 B-1 3.01 E-8 5.0 have _{* -CF2CF3} without W-1 82.2 B B 80/20 100 7 5.0 2 Embodiment 10 D-2 SL-1/SL-3 PAG-7 0.77 2 B-1/C-2 (B-1) 3.01 E-3 4.2 have *-CH(CF ₃ ) ₂ without - 83.7 A A 80/20 100 7 (C-2) 11.72 8.0

[Table 2] Table 1 Continued Anticorrosive composition performance Acid decomposable resin (2g) Solvent (mass ratio) Photoacid generator A Acid diffusion control agent (photoacid generator B or nitrogen-containing compound C) Hydrophobic resin Surfactant (mg) Recessed contact angle (°) LWR (3σ) Film thickness uniformity within the surface (3σ) Type (mg) pKa Number of fluorine atoms Type (mg) pKa Type (mass %) The number of fluorine atoms The presence or absence of repeating units represented by general formula (3) The structure of ^R1 in the general formula (3) Presence of acid-degradable repeating units Embodiment 11 D-5 SL-1/SL-4 PAG-7 0.77 2 B-1 3.01 E-5 5.0 5.6 have *-CH(CF ₃ ) ₂ without - 84.2 A A 80/20 100 7 Embodiment 12 D-3 SL-1/SL-2 PAG-8 1.05 2 B-1 3.01 E-3 8.0 4.2 have *-CH(CF ₃ ) ₂ without - 82.1 A A 80/20 100 7 Embodiment 13 D-2 SL-1 PAG-8 1.05 2 C-2 11.72 E-5 5.0 5.6 have *-CH(CF ₃ ) ₂ without - 82.2 A A 100 100 7 Embodiment 14 D-3 SL-1/SL-2 PAG-9 -0.81 1 B-2 1.17 E-9 6.0 6.0 without - without - 80.6 A B 70/30 100 7 Embodiment 15 D-5 SL-1/SL-2 PAG-10 0.09 0 C-3 10.08 E-3/E-4 E-3:4.2 have *-CH(CF ₃ ) ₂ without W-1 85.2 A A 80/20 100 7 3.0/3.0 E-4:3.6 have *-CH(CF ₃ ) ₂ 2 Embodiment 16 D-3 SL-1/SL-2 PAG-11 -1.29 3 C-1/C-2 (C-1) 4.20 E-9 8.0 6.0 without - without - 81.0 A B 80/20 100 4/3 (C-2) 11.72 Embodiment 17 D-5 SL-1/SL-3 PAG-12 -1.38 1 B-1 3.01 E-1 8.0 1.2 have _{* -CH2CF3} have - 82.0 A C 80/20 100 7 Embodiment 18 D-3 SL-1/SL-2 PAG-12/PAG-6 (PAG-12) -1.38 (PAG-12)1 C-3 10.08 E-6 7.0 0.9 without - have - 80.3 A D 80/20 80/20 (PAG-6) 1.87 (PAG-6) 0 7 Embodiment 19 D-2 SL-1/SL-2 PAG-13 1.54 2 C-2 11.72 E-7 7.0 3.0 without - without - 81.0 B B 80/20 100 6 Embodiment 20 D-3 SL-1/SL-2 PAG-13 1.54 2 C-1/C-2 (C-1) 4.20 E-5 5.0 5.6 have *-CH(CF ₃ ) ₂ without - 85.3 B A 70/30 100 4/3 (C-2) 11.72

[Table 3] Table 1 Continued Anticorrosive composition performance Acid decomposable resin (2g) Solvent (mass ratio) Photoacid generator A Acid diffusion control agent (photoacid generator B or nitrogen-containing compound C) Hydrophobic resin Surfactant (mg) Recessed contact angle (°) LWR (3σ) Film thickness uniformity within the surface (3σ) Type (mg) pKa Number of fluorine atoms Type (mg) pKa Type (mass %) Number of fluorine atoms The presence or absence of repeating units represented by general formula (3) The structure of ^R1 in the general formula (3) Presence of acid-degradable repeating units Embodiment 21 D-5 SL-1/SL-2 PAG-14 0.49 0 B-1 3.01 E-3 4.2 have *-CH(CF ₃ ) ₂ without - 82.9 A A 80/20 100 7 8.0 Embodiment 22 D-4 SL-1/SL-2 PAG-15 -0.52 1 B-1 3.01 E-8 5.0 have _{* -CH2CF3} without - 81.1 A B 80/20 100 7 7.0 Embodiment 23 D-3 SL-1/SL-4 PAG-16 -0.81 1 C-1/C-2 (C-1) 4.20 E-3/E-4 E-3:4.2 have *-CH(CF ₃ ) ₂ without W-1 83.8 A A 80/20 100 4/3 (C-2) 11.72 3.0/3.0 E-4:3.6 have *-CH(CF ₃ ) ₂ 2 Embodiment 24 D-2 SL-1/SL-2 PAG-16 -0.81 1 C-1 4.20 E-5 5.6 have *-CH(CF ₃ ) ₂ without - 84.5 A A 80/20 100 7 5.0 Embodiment 25 D-5 SL-1/SL-2 PAG-17 0.16 6 C-1/C-2 (C-1) 4.20 E-9 6.0 without - without - 82.4 A B 70/30 100 4/3 (C-2) 11.72 6.0 Embodiment 26 D-2 SL-1/SL-2 PAG-18 0.86 3 C-2 11.72 E-4 3.6 have *-CH(CF ₃ ) ₂ without - 88.0 A A 80/20 100 7 7.0 Embodiment 27 D-5 SL-1/SL-3 PAG-19 0.49 2 B-1 3.01 E-3 4.2 have *-CH(CF ₃ ) ₂ without - 80.6 A A 80/20 100 7 8.0 Embodiment 28 D-3 SL-1/SL-2 PAG-20 0.67 3 C-1 4.20 E-9 6.0 without - without - 81.3 A B 80/20 100 7 6.0 Embodiment 29 D-4 SL-1/SL-2 PAG-21 0.08 0 C-2 11.72 E-2 2.4 without - without - 80.3 A B 80/20 100 7 8.0 Comparison Example 1 D-2 SL-1/SL-2 PAG-22 -3.27 6 C-1 4.20 E-3 4.2 - - - - 75.0 C E 80/20 100 7 5.0 Comparison Example 2 D-3 SL-1/SL-2 PAG-23 -2.70 2 C-2 11.72 E-7 3.0 - - - - 72.0 C E 80/20 100 7 5.0 Comparison Example 3 D-4 SL-1/SL-3/SL-4 PAG-1 -1.40 1 B-1 3.01 E-6 0.9 - - - - 70.0 C E 60/30/10 100 7 5.0

[Pattern formation and evaluation] [Evaluation of receding contact angle (RCA)] After applying each anti-etching agent composition shown in Table 1 on a silicon wafer by spin coating, it was baked at 100°C for 60 seconds to form a film with a thickness of 90 nm. Then, the receding contact angle (RCA) of the water droplet was measured for the obtained film using a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) and the expansion-contraction method. Specifically, a droplet (initial droplet size 35μL) was dripped onto the above film and absorbed at a rate of 6μL/second for 5 seconds, and the receding contact angle when the dynamic contact angle during the absorption process was stable was calculated. The measurement environment was room temperature 23°C and relative humidity 45%. The results are shown in Table 1.

[Formation of anti-corrosion agent film and evaluation of anti-corrosion agent film] <Formation of anti-corrosion agent film> An organic anti-reflection film ARC29SR (manufactured by Brewer Science, Inc.) was applied on a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflection film with a thickness of 98 nm. The anti-corrosion agent composition shown in Table 1 was applied thereon and baked at 100°C for 60 seconds to form an anti-corrosion agent film with a thickness of 90 nm.

<Evaluation of film thickness in-plane uniformity> The film thickness of the anti-etching film formed on the silicon wafer in the above manner was measured at 96 points on the outer periphery of the silicon wafer (on a circumference of 0.3 cm from the wafer end) using VM-3110 (manufactured by Dainippon Screen Mfg. Co., Ltd.), and the standard deviation (3σ) was calculated. The value of less than 0.5nm was set as A, the value of 0.5nm or more and less than 0.8nm was set as B, the value of 0.8nm or more and less than 1.0nm was set as C, the value of 1.0nm or more and less than 1.2nm was set as D, and the value of 1.2nm or more was set as E. The smaller the value, the better the film thickness uniformity. The values evaluated as A and B were judged to have good film thickness in-plane uniformity. The results are shown in Table 1.

[ArF exposure and development, LWR evaluation] <ArF exposure and development> The above-mentioned anti-etching agent film formed on the silicon wafer was exposed using an ArF excimer laser liquid immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection) with a 6% half-tone mask of a 1:1 line and space pattern with a line width of 75nm. Ultrapure water was used as the immersion liquid. Then, after heating at 120°C for 60 seconds, it was developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 30 seconds, and after rinsing with pure water, the pattern was formed by spin drying.

＜LWR evaluation＞ The obtained 1:1 line and space pattern with a line width of 75nm was observed from the top of the pattern using a line width measurement scanning electron microscope (SEM (Hitachi, Ltd. S-8840)). The line width at 50 points within the range of 2μm at the edge in the length direction of the line pattern was measured, and the standard deviation of the measurement fluctuation was calculated, and 3σ was calculated. A value less than 3.0nm, B value greater than 3.0nm and less than 3.5nm, and C value greater than 3.5nm. The smaller the value, the better the performance. Those evaluated as A and B were judged to have good LWR. The results are shown in Table 1.

From the results in Table 1, it can be seen that the anti-etching agent composition of the embodiment can form an anti-etching agent film with excellent in-plane uniformity of film thickness, and can form a pattern with excellent LWR. In addition, from the results in Table 1, it can be seen that when the pKa of the acid generated from the photoacid generator A is -1.38 to 1.30, the formed pattern tends to have a more excellent LWR. In addition, in Example 1 in which the pKa of the acid generated from the photoacid generator A is less than -1.38, it is confirmed that the film formed by the above composition has poor in-plane uniformity of film thickness. From the results in Table 1, it can be seen that when the pKa of the acid generated from the photoacid generator A is set to -1.38 or higher, the film thickness in-plane uniformity of the film formed from the above composition tends to be more excellent (becoming "B" evaluation or higher).

Furthermore, from the results in Table 1, it can be seen that when the hydrophobic resin contains a repeating unit (acid-decomposable repeating unit) having a group (acid-decomposable group) whose polarity increases by decomposition by the action of an acid, the film formed by the above composition may have poor in-plane uniformity of film thickness (see the results of Examples 4, 5, 7, 17, and 18). In other words, it is clear that when the hydrophobic resin does not substantially contain an acid-decomposable repeating unit, the film formed by the above composition tends to have a better in-plane uniformity of film thickness (becoming "B" evaluation or above). Furthermore, from the results in Table 1, it can be seen that when the hydrophobic resin is a copolymer comprising a repeating unit represented by the general formula (3) and a repeating unit comprising a group selected from the above (y) and comprising the above hydrophobic group (preferably a repeating unit comprising a group selected from the above (y) and comprising one or more groups selected from the group consisting of a linear, branched or cyclic alkyl group having 6 or more carbon atoms, an aryl group having 9 or more carbon atoms, an arylalkyl group having 10 or more carbon atoms, an aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and an aryl group substituted with at least one cyclic alkyl group having 5 or more carbon atoms), there is a tendency that the uniformity of the film thickness in the surface is more excellent (see the results of Examples 6, 9 and 22). Furthermore, from the results in Table 1, it can be seen that when the number of fluorine atoms contained in the hydrophobic resin is greater than the number of fluorine atoms contained in the photoacid generator A, there is a tendency for the film thickness in-plane uniformity to be more excellent (see the results of Examples 4 and 18). Furthermore, from the results in Table 1, it can be seen that when the hydrophobic resin contains a repeating unit represented by the general formula (3) (preferably, R ₁ in the general formula (3) is -CH(CF ₃ ) _2. ) and a repeating unit comprising a group selected from the above (y) and comprising the above hydrophobic group (preferably a repeating unit comprising a group selected from the above (y) and comprising one or more groups selected from the group consisting of a linear, branched or cyclic alkyl group having 6 or more carbon atoms, an aryl group having 9 or more carbon atoms, an arylalkyl group having 10 or more carbon atoms, an aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and an aryl group substituted with at least one cyclic alkyl group having 5 or more carbon atoms), and a copolymer having substantially no acid-decomposable repeating unit, the film formed by the above composition tends to have a more excellent in-plane uniformity of film thickness (becoming "A" evaluation).

without

without

without.

Claims (10)

A photosensitive resin composition comprising: an acid-decomposable resin; a photoacid generator A which generates an acid with a pKa of -1.40 or more by irradiation with actinic rays or radiation; a photoacid generator B or the photoacid generator B and a nitrogen-containing compound C, wherein the photoacid generator B generates an acid with a pKa greater than 1.00 or more than the acid generated from the photoacid generator A by irradiation with actinic rays or radiation, and the pKa of the covalent acid in the nitrogen-containing compound C is greater than the pKa of the covalent acid generated from the photoacid generator A by irradiation with actinic rays or radiation. The acid generated by the photoacid generator A is greater than 1.00; and a hydrophobic resin, the hydrophobic resin comprising a repeating unit having a group that is decomposed by an alkaline developer and has increased solubility in the alkaline developer, the receding contact angle of a film formed using the photosensitive radiation or radiation-sensitive resin composition relative to water is greater than 80.0°, and the repeating unit having a group that is decomposed by an alkaline developer and has increased solubility in the alkaline developer comprises a repeating unit represented by the following general formula (3):

In the general formula (3), Z ₁ represents a halogen atom, a hydrogen atom or an alkyl group, L ₁ represents a (n+1)-valent linking group, X ₁ represents a group represented by *-Y ₁ -R ₁ , the Y ₁ represents -CO-O- or -O-CO-, the * represents a bonding position, the R ₁ represents an electron-withdrawing group, and n represents a positive integer. In addition, when n is 2 or more, a plurality of X _1s may be the same as or different from each other. As described in item 1 of the patent application scope, the photosensitive or radiation-sensitive resin composition, wherein the acid generated from the photoacid generator A is sulfonic acid. The photosensitive or radiation-sensitive resin composition as described in item 1 or 2 of the patent application, wherein the acid generated from the photoacid generator A is a sulfonic acid represented by the following general formula (1) or a sulfonic acid represented by the following general formula (2),

In the general formula (1), R ₁₁ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R ₁₂ represents a monovalent organic group having 1 to 20 carbon atoms without a fluorine atom, and Rf ₁₁ represents a fluorine atom or a monovalent organic group containing a fluorine atom. In the general formula (2), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom or a monovalent substituent, R ₂₄ represents a monovalent organic group having 1 to 20 carbon atoms, and Rf ₂₁ represents a fluorine atom or a monovalent organic group containing a fluorine atom. A photosensitive resin composition comprising: an acid-decomposable resin; a photoacid generator A that generates an acid with a pKa of -1.40 or more by irradiation with actinic rays or radiation; a nitrogen-containing compound C or a photoacid generator B and the nitrogen-containing compound C, wherein the photoacid generator B generates an acid with a pKa greater than 1.00 or more than that of the acid generated from the photoacid generator A by irradiation with actinic rays or radiation, and the pKa of the covalent acid in the nitrogen-containing compound C is greater than 1.00 or more than that of the acid generated from the photoacid generator A by irradiation with actinic rays or radiation, wherein the acid generated from the photoacid generator A is A sulfonic acid represented by the following general formula (1) or a sulfonic acid represented by the following general formula (2); and a hydrophobic resin comprising repeating units having a group which is decomposed by an alkaline developer and has increased solubility in the alkaline developer, wherein the repeating units having a group which is decomposed by the alkaline developer and has increased solubility in the alkaline developer comprises repeating units represented by the following general formula (3), wherein a film formed using the actinic radiation or radiation-sensitive resin composition has a receding contact angle with respect to water of 80.0° or more,

In the general formula (1), R ₁₁ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R ₁₂ represents a monovalent organic group having 1 to 20 carbon atoms without a fluorine atom, and Rf ₁₁ represents a fluorine atom or a monovalent organic group containing a fluorine atom. In the general formula (2), R ₂₁ , R ₂₂ , and R ₂₃ each independently represent a hydrogen atom or a monovalent substituent, R ₂₄ represents a monovalent organic group having 1 to 20 carbon atoms, and Rf ₂₁ represents a fluorine atom or a monovalent organic group containing a fluorine atom.

In the general formula (3), Z ₁ represents a halogen atom, a hydrogen atom or an alkyl group, L ₁ represents a (n+1)-valent linking group, X ₁ represents a group represented by *-Y ₁ -R ₁ , the Y ₁ represents -CO-O- or -O-CO-, the * represents a bonding position, the R ₁ represents an electron-withdrawing group, and n represents a positive integer. In addition, when n is 2 or more, a plurality of X _1s may be the same as or different from each other. The photosensitive or radiation-sensitive resin composition as described in item 1 or item 4 of the patent application, wherein the hydrophobic resin is a copolymer comprising the repeating unit represented by the general formula (3) and other repeating units except the repeating unit represented by the general formula (3). The photosensitive or radiation-sensitive resin composition as described in item 1 or item 4 of the scope of the patent application, wherein the hydrophobic resin comprises: the repeating unit represented by the general formula (3); and the repeating unit having a group whose solubility in the alkaline developer is increased by decomposition by the action of the alkaline developer, comprising one or more groups selected from the group including a linear, branched or cyclic alkyl group with 6 or more carbon atoms, an aryl group with 9 or more carbon atoms, an arylalkyl group with 10 or more carbon atoms, an aryl group substituted by at least one linear or branched alkyl group with 3 or more carbon atoms, and an aryl group substituted by at least one cyclic alkyl group with 5 or more carbon atoms, and the hydrophobic resin is substantially a copolymer that does not contain the repeating unit having a group whose polarity is increased by decomposition by the action of an acid. An anti-etching agent film formed using an actinic radiation-sensitive or radiation-sensitive resin composition described in any one of items 1 to 6 of the patent application scope. A pattern forming method, comprising: an anti-etching film forming step of using the photosensitive or radiation-sensitive resin composition described in any one of items 1 to 6 of the patent application scope to form an anti-etching film; an exposure step of exposing the anti-etching film; and a developing step of using a developer to develop the exposed anti-etching film. A pattern forming method as described in Item 8 of the patent application, wherein the developer is an alkaline developer. A method for manufacturing an electronic device, which includes the pattern forming method described in item 8 or item 9 of the patent application scope.