TWI778180B - Photosensitive radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic element, compound - Google Patents

Abstract

The present invention provides a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of obtaining a pattern with excellent storage stability and excellent LWR performance. Furthermore, there are provided a resist film, a pattern forming method, a method for producing an electronic element, and a compound of the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition. The photosensitive radiation-sensitive or radiation-sensitive resin composition includes a resin having a repeating unit having a group whose polarity is increased by decomposition by the action of an acid, and a compound Q represented by the general formula (I).

Description

Photosensitive radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic element, compound

The present invention relates to a photosensitive radiation-sensitive or radiation-sensitive resin composition, a resist film, a method for forming a pattern, a method for producing an electronic component, and a compound.

Conventionally, in the manufacturing steps of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), micro-processing based on the use of photosensitive radiation or radiation sensitive resin compositions has been performed. The micro-processing of shadow art. For example, Japanese Patent Document 1 discloses a resist composition containing a compound represented by the following formula.

[先前技術文獻] [專利文獻][hua 1]

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2012-189977

As a result of a specific study of the compound disclosed in Japanese Patent Document 1, the present inventors found that the photosensitive radiation or radiation sensitive resin composition using the compound disclosed in Japanese Patent Document 1 may have poor storage stability. must be sufficient. In addition, it is found that the LWR (line width roughness) performance of the obtained pattern also has room for improvement.

An object of the present invention is to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent storage stability and excellent LWR performance.

Another object of the present invention is to provide a resist film, a method for forming a pattern, a method for producing an electronic device, and a compound for the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition.

The inventors of the present invention, as a result of intensive studies to accomplish the above-mentioned problems, found that the above-mentioned problems can be solved by using a compound Q of a specific structure, and completed the present invention.

That is, it was found that the above-mentioned problems can be solved by the following configuration.

[1] A photosensitive radiation-sensitive or radiation-sensitive resin composition comprising a resin and a compound Q represented by the general formula (I), the resin having a group having a group whose polarity is increased by decomposition by the action of an acid repeating unit.

[2] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1], wherein in the general formula (I), A represents a single bond.

[3] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein in the general formula (I), any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a group represented by the general formula (II).

[4] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], further comprising a photoacid generator other than the above-mentioned compound Q. [5] A resist film formed using the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4]. [6] A pattern forming method comprising the steps of forming a resist film on a support using the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], exposing the above The manufacturing process of the resist film, the process of developing the above-mentioned exposed resist film using a developing solution. [7] A method of manufacturing an electronic component, comprising the pattern formation method described in [6]. [8] A compound represented by the general formula (I-2). [9] The compound according to [8], wherein in the general formula (I-2), A represents a single bond. [10] The compound according to [8] or [9], wherein in the general formula (I-2), any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is represented by the general formula (II) the group. [Inventive effect]

According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of obtaining a pattern with excellent storage stability and excellent LWR performance. Another object of the present invention is to provide a resist film, a method for forming a pattern, a method for producing an electronic device, and a compound for the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail. The description of the constituent requirements described below may be completed based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the labels of groups (atomic groups) in this specification, labels that do not describe substitution and unsubstituted include those without a substituent and those with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In addition, the "organic group" in this specification means the group containing at least 1 carbon atom. In this specification, "actinic ray" or "radiation" means, for example, the bright-line spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) etc. "Light" in this specification means actinic rays or radiation. Unless otherwise specified, the term "exposure" in this specification includes not only exposure by bright-line spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also exposure by electron beams and depiction of particle beams such as ion beams. In this specification, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit.

In this specification, (meth)acrylate means acrylate and methacrylate. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution.) (Mw/Mn) of a resin are defined as those obtained by using GPC (gel permeation chromatography). GPC measurement by Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C , Flow rate: 1.0 mL/min, Detector: Polystyrene conversion value of a differential refractive index detector (Refractive Index Detector).

In this specification, pKa (acid dissociation constant pKa) means the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Handbook of Chemistry (II) (Revision 4, 1993, The Chemical Society of Japan, Maruzen Inc.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, Hammett's substituent constant and a value based on a database of known literature values can also be obtained by using the following package software 1. All the pKa values described in this specification represent the values obtained by calculation using this software package.

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

In this specification, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

[Photosensitive or radiation-sensitive resin composition] The photosensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as "composition" or "composition of the present invention") will be described. The composition of the present invention is a so-called resist composition, and may be a positive-type resist composition or a negative-type resist composition. Moreover, the resist composition for alkali image development may be sufficient, and the resist composition for organic solvent image development may be sufficient. The composition of the present invention is typically a chemically amplified resist composition.

Features of the composition of the present invention include a resin containing a repeating unit having a group whose polarity is increased by decomposing by the action of an acid, and a compound Q represented by the general formula (I) described later. The mechanism for solving the problems of the present invention with such a configuration is not clear, but the inventors of the present invention conjecture as follows. It is considered that compound Q has a high degree of anionic radical acidity and low nucleophilicity, and therefore, compared with the compound described in Japanese Patent Document 1, it is difficult to decompose other components (the above-mentioned resin, etc.) in the composition, and thereby the composition The storage stability is improved. Moreover, compound Q is a betaine compound, and since the electric charge is neutralized in a molecule|numerator, ionicity falls. As a result, it is considered that the compatibility with the resin is improved and the film can be uniformly dispersed in the film, whereby the LWR performance is improved.

Hereinafter, the components contained in the composition of the present invention will be described in detail.

<Resin having a repeating unit having a group whose polarity is increased by decomposition by the action of an acid> The photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention contains a resin (hereinafter, also referred to as "acid-decomposable resin" or "resin A"), which has a repeating unit having a group (hereinafter, also referred to as an "acid-decomposable group") that decomposes by the action of an acid to increase its polarity. In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed pattern.

(Repeating unit having an acid-decomposable group) It is preferable that the resin A has a repeating unit having an acid-decomposable group.

The acid-decomposable group preferably has a structure in which the polar group is protected by a group (leaving group) that is decomposed and detached 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 sulfonamido group, a sulfonimide group, (alkylsulfonyl) (alkylcarbonyl)methylene, ( Alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imido, bis(alkylsulfonyl)methylene, bis Acidic groups such as (alkylsulfonyl)imide, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene (dissociated in a 2.38 mass % aqueous tetramethylammonium hydroxide solution) group) and alcoholic hydroxyl groups.

In addition, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and an aliphatic group in which the α-position of the hydroxyl group is substituted with an electron withdrawing group such as a fluorine atom. Alcohols (for example, hexafluoroisopropanol, etc.) are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferable.

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

Preferred groups as acid-decomposable groups are groups in which hydrogen atoms of these groups are substituted with groups (leaving groups) that are released by the action of an acid. Examples of groups (leaving groups) to be released by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ) and - C(R ₀₁ )(R ₀₂ )(OR ₃₉ ) and the like. 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. R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

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

The acid-decomposable group preferably has a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group or an acetal ester group, and more preferably has an acetal group or a tertiary alkyl ester group.

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

[hua 2]

In the general formula (AI), T represents a single bond or a divalent linking group. As a divalent linking group of T, an alkylene group, an arylidene group, -COO-Rt-, -O-Rt-, etc. are mentioned. In the formula, Rt represents an alkylene group, a cycloalkylene group or an aryl group. Preferably, T is a single bond or -COO-Rt-. Rt is preferably a chain alkylene having 1 to 5 carbon atoms, more preferably -CH ₂ -, -(CH ₂ ) ₂ - or -(CH ₂ ) ₃ -. It is more preferable that T is a single bond.

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

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 be formed.

The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be straight chain or branched chain, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tertiary Butyl and the like are preferred. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. In the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-carbon bond may be a double bond.

The cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be monocyclic or polycyclic. As a monocyclic cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. As a polycyclic cycloalkyl group, a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, an adamantyl group, and the like can be mentioned.

The ring formed by two bonds of Rx ₁ , Rx ₂ and Rx ₃ may be a single ring or a polycyclic ring. Examples of the monocyclic ring include monocyclic cycloalkane rings such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. Examples of polycyclic rings include polycyclic cycloalkyl rings such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, and an adamantane ring. Among them, cyclopentane ring, cyclohexyl ring or adamantane ring is preferable.

In addition, as a ring formed by two bonds of Rx ₁ , Rx ₂ and Rx ₃ , the ring shown below is also preferable.

Specific examples of the monomers corresponding to the repeating units represented by the general formula (AI) are given below. The following specific example corresponds to the case where Xa1 in the general formula (AI) is a methyl group, and Xa1 can be optionally substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[hua 4]

Resin A preferably has repeating units described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1 as repeating units having an acid-decomposable group.

In addition, the resin A may have a repeating unit having a group described in paragraphs <0363> to <0364> of U.S. Patent Application Publication No. 2016/0070167A1 that decomposes by the action of an acid to generate an alcoholic hydroxyl group as having acid decomposability base repeating unit.

Resin A may have 1 type of repeating unit which has an acid-decomposable group independently, and may have 2 or more types.

The content of the repeating unit having an acid-decomposable group contained in the resin A (when there are plural repeating units having an acid-decomposable group, the total) is preferably 10 to 90 mol % with respect to all the repeating units of the resin A , 20-80 mol % is more preferable, and 30-70 mol % is further preferable.

(has at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure) Resin A has a repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure At least one type of repeating unit is preferred.

The lactone structure or sultone structure may be any one having a lactone ring or a sultone ring, and a lactone structure having a 5- to 7-membered ring or a sultone ring having a 5- to 7-membered ring The sultone structure is preferred. It is also preferable to condense a lactone structure with a ring other than a 5- to 7-membered lactone ring in the form of forming a bicyclic structure or a spirocyclic structure. A sultone structure in which a ring other than a 5- to 7-membered sultone ring is condensed in the form of a bicyclic structure or a spiro ring structure is also preferable.

Among them, resin A has a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-22), or has a lactone structure represented by the following general formulae (SL1-1) to (SL1-3). Any one of the repeating units of the sultone structure represented is preferred. In addition, the lactone structure or the sultone structure may be directly bonded to the main chain. Among them, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21), Or the lactone structure represented by the general formula (LC1-22) or the sultone structure represented by the general formula (SL1-1) is preferred.

[hua 5]

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 An atom, a hydroxyl group, a cyano group, an acid-decomposable group, etc. are preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is more preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) present may be the same or different. Moreover, a plurality of substituents (Rb ₂ ) present may be bonded to each other to form a ring.

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

[hua 6]

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

n is the repeating number of the structure represented by -R ₀ -Z-, and represents an integer of 0 to 5, preferably 0 or 1, and 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 _0s , the plural R _0s may be the same or different. The alkylene group or cycloalkylene group of R ₀ may have a substituent.

Z is a single bond, ether bond, ester bond, amide bond, urethane bond or urea bond. When there are plural Zs, the plural Zs may be the same or different, respectively. Among them, Z is preferably an ether bond or an ester bond, more preferably an ester bond.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure. However, one of the structures represented by the general formulae (LC1-1) to (LC1-22) and the general formulae (SL1-1) to (SL1-3) constitutes a lactone structure or a sultone structure. A group obtained by removing one hydrogen atom from the carbon atom of the ester structure is preferable. In addition, it is preferable that the carbon atom from which one hydrogen atom has been removed is not a carbon atom constituting the substituent (Rb ₂ ).

R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III-2) is also preferable.

[hua 7]

In the general formula (III-2), RIII each independently represents a hydrogen atom or a substituent. As a substituent, a halogen atom and a monovalent organic group (preferably a methyl group) are mentioned, for example. RIII is preferably a hydrogen atom. cyc represents a group having a lactone structure or a sultone structure. Specifically, in any one of the structures represented by the general formulae (LC1-1) to (LC1-22) and the general formulae (SL1-1) to (SL1-3), one of them constitutes a lactone structure or A group formed by removing two hydrogen atoms from the carbon atom of the sultone structure is preferred. In addition, it is preferable that the carbon atom from which two hydrogen atoms have been removed is not a carbon atom constituting the substituent (Rb ₂ ).

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

[hua 8]

In the general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or more. R _A ² represents a substituent. When n is 2 or more, the plurality of R _A ^2s present may be the same or different, respectively. A represents a single bond or a divalent linking group. Z represents an atomic group which forms a monocyclic structure or a polycyclic structure together with the group represented by -O-CO-O- in the formula.

Resin A has the repeating units described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016/0070167A1 as having at least one type selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure The repeating unit of is also preferred.

Resin A may have 1 type of repeating unit which has at least 1 type chosen from the group which consists of a lactone structure, a sultone structure, and a carbonate structure independently, and may have 2 or more types.

The monomers corresponding to the repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure are exemplified below. In the following examples, the methyl group bonded to the vinyl group may be substituted with a hydrogen atom, a halogen atom or a monovalent organic group.

[Chemical 9]

[Chemical 10]

When the resin A has at least one repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the resin A contains a repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. The content of at least one repeating unit in the group of structures (when there are plural repeating units having at least one type selected from the group including a lactone structure, a sultone structure, and a carbonate structure, the total is the total) relative to All repeating units in resin A are preferably 5-70 mol %, more preferably 10-65 mol %, and even more preferably 20-60 mol %.

(Repeating unit having a polar group) The resin A may have a repeating unit having a polar group other than the above-mentioned groups. As a polar group, a hydroxyl group, a cyano group, a carboxyl group, a fluorinated alcohol group, etc. are mentioned. As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid-decomposable group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group or a norbornyl group is preferable.

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

[Chemical 11]

In addition, specific examples of the repeating unit having a polar group include repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1. Resin A may have 1 type of repeating unit which has a polar group independently, and may have 2 or more types. When resin A has repeating units with polar groups, the content of repeating units with polar groups relative to all repeating units in resin A is preferably 5-40 mol %, more preferably 5-30 mol %, 10 -25 mol% is further preferred.

(A repeating unit which does not have any of an acid-decomposable group and a polar group) Resin A may have a repeating unit which does not have any of an acid-decomposable group and a polar group other than the above-mentioned groups. It is preferable that the repeating unit which does not have any of an acid-decomposable group and a polar group has an alicyclic hydrocarbon structure. The repeating unit described in paragraphs <0236> to <0237> of US Patent Application Publication No. 2016/0026083A1 as a repeating unit not having either an acid-decomposable group or a polar group, for example. Preferred examples of monomers corresponding to repeating units not having either an acid-decomposable group or a polar group are shown below.

[Chemical 12]

In addition, as a specific example of the repeating unit which does not have any of an acid-decomposable group and a polar group, the repeating unit disclosed in the paragraph <0433> of US Patent Application Publication No. 2016/0070167A1 can be mentioned. Resin A may have 1 type of repeating unit which does not have any one of an acid-decomposable group and a polar group independently, and may have 2 or more types. When resin A has a repeating unit that does not have either an acid-decomposable group or a polar group, the content of the repeating unit that does not have either an acid-decomposable group or a polar group is relative to all repeating units in resin A, 5 ∼40 mol% is preferable, 5∼30 mol% is more preferable, and 5∼25 mol% is further preferable.

In addition to the repeating structural units described above, the resin A may have the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist distribution, and further properties generally required for resists, ie, resolution, heat resistance, and sensitivity. Various repeating structural units. As such a repeating structural unit, although the repeating structural unit corresponding to a predetermined monomer is mentioned, it is not limited to this.

As the predetermined monomer, for example, there may be mentioned a monomer having one selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. Compounds of addition polymerizable unsaturated bonds, etc. In addition to these, addition polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the various repeating structural units described above can also be used. In order to adjust various properties, in Resin A, the molar ratio of each repeating structural unit is appropriately set.

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

In Resin A, all repeating units may be constituted by (meth)acrylate-based repeating units. In this case, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, and all repeating units may be a combination of methacrylate repeating units and acrylate repeating units. Among them, the content of the acrylate-based repeating unit is preferably 50 mol % or less with respect to all the repeating units of the resin A.

In addition, as resin A, a well-known resin can be used suitably. For example, paragraphs <0055> to <0191> of US Patent Application Publication No. 2016/0274458A1, paragraphs <0035> to <0085> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0147150A1 As the resin A, well-known resins disclosed in paragraphs <0045> to <0090> of the specification are suitably used.

When the composition of the present invention is used for KrF exposure, EB exposure or EUV exposure, it is preferable that the resin A has a repeating unit having an aromatic hydrocarbon group, and it is more preferable that the resin A has a repeating unit including a phenolic hydroxyl group. As a repeating unit containing a phenolic hydroxyl group, a hydroxystyrene type repeating unit and a hydroxystyrene (meth)acrylate type repeating unit are mentioned. When the composition of the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin A preferably has a structure in which the hydrogen atom of the phenolic hydroxyl group is protected by a group (leaving group) that is decomposed and released by the action of an acid. . At this time, the content of the repeating unit having an aromatic hydrocarbon group contained in the resin A is preferably 30-100 mol %, more preferably 40-100 mol %, and 50-100 mol % relative to all the repeating units in the resin A. Molar % is further preferred.

The weight average molecular weight of resin A is preferably 1,000-200,000, more preferably 2,000-20,000, further preferably 3,000-15,000, and particularly preferably 3,000-12,000. The degree of dispersion (Mw/Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0.

Resin A may be used individually by 1 type, and may use 2 or more types. The content of the resin A in the composition is usually 20% by mass or more, more preferably 40% by mass or more, more preferably 60% by mass or more, and more preferably 75% by mass or more, relative to the total solid content in the composition. better. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. In addition, solid content means the component which removed the solvent in a composition.

<Compound Q> The composition of the present invention contains compound Q. Compound Q is a compound represented by the general formula (I).

[Chemical 13]

In the general formula (I), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent. However, any one of R ¹ to R ¹⁰ is a group represented by the general formula (II). In other words, among R ¹ to R ¹⁰ , there is one group represented by the general formula (II), and the remaining nine groups are substituents or hydrogen atoms other than the groups represented by the general formula (II).

* ^-AX- (II) In the general formula (II), A represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include -O-, -S-, ^-NRF- ( ^RF is a hydrogen atom or an alkyl group.), a divalent hydrocarbon group (for example, an alkylene group) , alkenylene (eg: -CH=CH-), alkynylene (eg: -C≡C-) and aryl (preferably phenylene)) or a combination of these. As the above-mentioned divalent linking group, an alkylene group (preferably having 1 to 3 carbon atoms) which may have a substituent, an ester group, or a group composed of a combination thereof are preferable. As the substituent which the above-mentioned alkylene group may have, a halogen atom is preferable, and a fluorine atom is more preferable. Among them, A is preferably a single bond.

X ^- represents -SO ₃ ^- , -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or - CO-N ^-- COR ¹⁴ . R ¹¹ to R ¹⁴ each independently represent an organic group. As the above-mentioned organic group, an optionally substituted alkyl group or an optionally substituted cycloalkyl group is preferable. The above-mentioned alkyl group may be linear or branched. The number of carbon atoms is preferably 1 to 6. Among them, as the alkyl group, methyl, ethyl, propyl, isopropyl, tertiary butyl or n-butyl are preferred. As said cycloalkyl group, a monocyclic ring may be sufficient as it, and a polycyclic ring may be sufficient as it. The number of carbon atoms is preferably 5 to 10. As a substituent which the said alkyl group and a cycloalkyl group may have, a halogen atom is preferable, and a fluorine atom is more preferable. For example, it is also preferable that a part or all of the hydrogen atoms of the above-mentioned alkyl group and cycloalkyl group are substituted by halogen atoms (preferably fluorine atoms). In other words, it is also preferable that the above-mentioned alkyl group is a fluoroalkyl group (including a perfluoroalkyl group. Preferably, it has 1 to 6 carbon atoms). wherein R ³ or R ⁸ is a group represented by the general formula (II), and when it is -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , R ¹¹ represents an organic group other than a trifluoromethyl group is better.

From the standpoint of obtaining a pattern having a composition with better storage stability and better LWR performance, among R ¹ to R ¹⁰ , any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is represented by the general formula (II ) is the preferred group.

Among the substituents represented by R ¹ to R ¹⁰ , other than one group represented by the general formula (II) is a substituent other than a hydrogen atom or a group represented by the general formula (II). As substituents other than the group represented by the general formula (II), groups other than anionic groups are preferred. Among the substituents represented by R ¹ to R ¹⁰ , examples of the substituents other than the groups represented by the general formula (II) include an alkyl group which may be substituted with a halogen atom (preferably a fluorine atom). The alkyl group may be linear or branched, or may have a cyclic structure. Also, the carbon atoms constituting the alkyl group may be substituted with one or more groups selected from the group consisting of ether groups, carbonyl groups, and ester groups (for example, the carbon atoms at the root of the alkyl group are substituted with ether groups, and the alkyl group may become alkoxy form). Among them, as the alkyl group, methyl, ethyl, propyl, isopropyl, tertiary butyl or n-butyl are preferable. A part or all of the hydrogen atoms possessed by these groups are substituted by halogen atoms (preferably fluorine atoms) are also preferred. In other words, it is also preferable that the above-mentioned alkyl group is a fluoroalkyl group (including a perfluoroalkyl group. Preferably, it has 1 to 6 carbon atoms). Among R ¹ to R ¹⁰ other than the group represented by the general formula (II), 0 to 3 preferably represent a substituent, and more preferably 0 to 1 represent a substituent.

The compound Q is preferably a compound represented by the general formula (I-2).

[Chemical 14]

In the general formula (I-2), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent. However, any one of R ¹ to R ¹⁰ is a group represented by the general formula (II). * ^-AX- (II) In the general formula (II), A represents a single bond or a divalent linking group. X ^- represents -SO ₃ ^- , -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or - CO-N ^-- COR ¹⁴ . R ¹¹ to R ¹⁴ each independently represent an organic group.

The groups represented by the respective symbols in the general formula (I-2) have the same meanings as those corresponding to the groups in the general formula (I), and the preferred ranges are also the same. Wherein, in the general formula (I-2), when R ³ or R ⁸ is a group represented by the general formula (II), and is -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , R ¹¹ Represents an organic group other than trifluoromethyl.

Compound Q is a molecule having both positive and negative charges in the molecule, and is a so-called zwitterion. Compound Q is preferably a compound that generates an acid by irradiation with actinic rays or radiation. In addition, it is preferable that the compound Q exhibits basicity in an unexposed state and functions as an acid diffusion control agent. The acid diffusion control agent captures the acid generated from the photoacid generator or the like by exposure, thereby suppressing the excess generation of acid by the acid-decomposable gene of the resin A in the unexposed portion and reacting.

Compound Q may be used alone or in two or more. The content of the compound Q in the total solid content of the composition of the present invention is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, and even more preferably 2.5 mass % or more. The upper limit is not particularly limited, but is preferably 15.0 mass % or less, more preferably 7.0 mass % or less, and even more preferably 5.0 mass % or less.

<Photoacid generator> It is preferable that the composition of this invention contains a compound other than compound Q, ie, a photoacid generator. In the present specification, the photoacid generator is a compound that generates an acid by irradiation with actinic rays or radiation, and is a compound other than compound Q. As the photoacid generator, a compound that generates an organic acid by irradiation with actinic rays or radiation is preferable. For example, periconium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodithiolate compounds, diazonium compounds, and o-nitrobenzyl groups can be mentioned. Sulfonate compounds. The photoacid generator may be a zwitterion, but it cannot be compound Q.

As the photoacid generator, a known compound that generates an acid by irradiation with actinic rays or radiation can be used alone, or a mixture of these can be appropriately selected and used. For example, paragraphs <0125> to <0319> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0086> to <0094> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0237190A1 The known compounds disclosed in the paragraphs <0323> to <0402> of the specification are preferably used as the photoacid generator.

As the photoacid generator, for example, compounds represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) are preferred.

[Chemical 15]

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

As a preferable aspect of the cation in the general formula (ZI), the corresponding ones of the compound (ZI-1), the compound (ZI-2), the compound (ZI-3), and the compound (ZI-4) described later can be mentioned. group. In addition, the photoacid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of the other compound represented by the general formula (ZI) may be a compound having a compound represented by a single bond. Or a compound with a structure where the linking group is bonded.

First, the compound (ZI-1) will be described. The compound (ZI-1) is an aryl perionium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the general formula (ZI) is an aryl group, that is, a compound in which the aryl perionium is a cation. In the aryl perionium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or some of R ₂₀₁ to R ₂₀₃ may be aryl groups, and the rest may be alkyl groups or cycloalkyl groups. Examples of the aryl perionium compound include triaryl perionium compounds, diarylalkyl perionium compounds, aryldialkyl perionium compounds, diarylcycloalkyl perionium compounds, and arylbicycloalkyl perionium compounds.

As the aryl group contained in the aryl perionium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, a benzothiophene residue, and the like. When the aryl perionate compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl or cycloalkyl group that the aryl perionate compound has according to needs is a straight-chain 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. Preferable examples include methyl, ethyl, propyl, n-butyl, tertiary butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

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

Next, the compound (ZI-2) will be described. In the compound (ZI-2), R ₂₀₁ to R ₂₀₃ in the formula (ZI) are each independently a compound representing an organic group without an aromatic ring. Aromatic rings here also include aromatic rings containing heteroatoms. The number of carbon atoms of the organic group which does not have an aromatic ring as R ₂₀₁ to R ₂₀₃ is usually 1 to 30, preferably 1 to 20 carbon atoms. R ₂₀₁ to R ₂₀₃ preferably each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkane group or alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

Preferred examples of the alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ include straight-chain alkyl groups having 1 to 10 carbon atoms or branched-chain alkyl groups having 3 to 10 carbon atoms (eg, methyl, ethyl, etc.). group, propyl group, butyl group and pentyl group) and cycloalkyl group with 3 to 10 carbon atoms (such as cyclopentyl group, cyclohexyl group and norbornyl group). R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (eg, carbon number 1 to 5), a hydroxyl group, a cyano group or a nitro group.

Next, the compound (ZI-3) will be described. Compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a benzalkonium methyl perionate structure.

[Chemical 16]

In the general formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a ring Alkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. _Rx and _Ry 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 each be bonded to form a ring structure, and the ring structures may be independent of each other. It contains oxygen atom, sulfur atom, ketone group, ester bond or amide bond. Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined. As the ring structure, a 3- to 10-membered ring is mentioned, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.

As a group formed by bonding any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y , a butylene group, a pentylene group, and the like can be mentioned. As a group formed by R _5c and R _6c , and R _5c and R _x are bonded together, a single bond or an alkylene group is preferable. As an alkylene group, a methylene group, an ethylene group, etc. are mentioned. Zc ^- represents an anion.

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

[Chemical 17]

In general formula (ZI-4), l represents an integer of 0-2. r represents an integer of 0 to 8. R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a cycloalkyl group. These groups may have substituents. R ₁₄ represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a cycloalkyl group. These groups may have substituents. When plural R ₁₄ are present, 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 substituents. Two R _15s may be bonded to each other to form a ring. When two R _15s are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, the two R ₁₅ are alkylene groups, which are preferably bonded to each other to form a ring structure. Z ^- represents an anion.

In the general formula (ZI-4), 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 tertiary butyl and the like are more preferable.

Next, the general formula (ZII) and the general formula (ZIII) will be described. In general formula (ZII) and general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group of R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As the alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butylene) and pentyl) or cycloalkyl groups having 3 to 10 carbon atoms (such as cyclopentyl, cyclohexyl and norbornyl) are preferred.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of substituents that the aryl, alkyl, and cycloalkyl groups of R ₂₀₄ to R ₂₀₇ may have include, for example, alkyl groups (for example, having 1 to 15 carbon atoms), cycloalkyl groups (for example, having 3 to 15 carbon atoms), and aryl groups. group (for example, carbon number 6-15), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group, phenylthio group, and the like. Z ^- represents an anion.

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4), the following general formulas The anion represented by the formula (3) is preferred.

[Chemical 18]

In the general formula (3), o represents an integer of 1 to 3. p represents an integer of 0-10. q represents an integer of 0-10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . Among them, it is more preferable that Xf of both is a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When there are plural R ₄ and R ₅ , the plural R ₄ and the plural R ₅ may be the same or different, respectively. The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms. Specific examples and preferable aspects of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferable aspects of Xf in the general formula (3).

L represents a divalent linking group. When there are plural Ls, the plural Ls may be the same or different, respectively. As a divalent linking group, for example, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a bivalent compound combining a plurality of these linking groups, etc. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH- Alkylene- or -NHCO-alkylene- is better, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene- is more good.

W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferable. As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms are preferred, and examples thereof include norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. .

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group are mentioned, for example. The heterocyclic group may be monocyclic or polycyclic. Polycycles are more capable of inhibiting the diffusion of acids. Moreover, the heterocyclic group may or may not have aromaticity. As an aromatic heterocyclic ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a heterocyclic ring which does not have aromaticity, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the aforementioned resins. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is preferable.

The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic (including spiro ring, etc.), preferably with 3 to 20 carbon atoms), aryl (preferably with 6 to 14 carbon atoms), hydroxyl, alkoxy, ester, amido, urethane group, urea group, thioether group, sulfonamide group and sulfonate group. Further, the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

As anions represented by the general formula (3), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L)q'-W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L)q' -W, SO3 _{-- CF2} -COO-(L)q'-W, SO3 ^-- _{CF2 - CF2} - _CH2 ^- CH2-(L)qW or SO3 _{-- CF2} ^- _CH ( CF ₃ )-OCO-(L)q'-W is preferred. Here, L, q and W are the same as the general formula (3). q' represents an integer of 0-10.

In one aspect, as Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4), An anion represented by the following general formula (4) is also preferable.

[Chemical 19]

In the general formula (4), X ^B1 and X ^B2 each independently represent a monovalent organic group that does not have a hydrogen atom or a fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms. X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. Preferably, at least one of X ^B3 and X ^B4 is a monovalent organic group having a hydrogen atom or a fluorine atom, and both X ^B3 and X ^B4 are a monovalent organic group having a hydrogen atom or a fluorine atom. better. It is further preferred that both X ^B3 and X ^B4 are alkyl groups substituted with fluorine. L, q and W are the same as the general formula (3).

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4), the following general formula The anion represented by (5) is also preferable.

[hua 20]

In the general formula (5), Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb each independently represents an organic group having no hydrogen atom or fluorine atom. The definitions and preferable aspects of o, p, q, R ₄ , R ₅ , L and W are the same as those of the general formula (3).

Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3) and Z ^- in general formula (ZI ^- 4) can be benzenesulfonate anion, Benzenesulfonate anions substituted with branched alkyl or cycloalkyl groups are preferred.

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4), the following general formulas The aromatic sulfonate anion represented by formula (SA1) is also preferable.

[Chemical 21]

In formula (SA1), Ar represents an aryl group, and may further have a substituent other than a sulfonate anion and a -(D-B) group. As a substituent which may further have, a fluorine atom, a hydroxyl group, etc. are mentioned.

n represents an integer of 0 or more. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is still more preferable.

D represents a single bond or a divalent linking group. The divalent linking group includes an ether group, a thioether group, a carbonyl group, a sulfene group, a sulfonic acid group, a sulfonic acid ester group, an ester group, and a group including a combination of two or more of these.

B represents a hydrocarbon group.

Preferably, D is a single bond, and B is an aliphatic hydrocarbon structure. More preferably, B is isopropyl or cyclohexyl.

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI ^{-3), and Z - in} the general formula (ZI-4), trityl carbon may be used anion or disulfonamide anion. The triphenylcarbanion is, for example, an anion represented by C ^- (SO ₂ -R ^p ) ₃ . Here, R ^p represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group, and even more preferably a trifluoromethyl group. The disulfonamide anion is, for example, an anion represented by N- ⁽ SO ₂ -R ^q ) ₂ . Here, R ^q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. Two R ^qs may be bonded to each other to form a ring. The group formed by the bonding of two R ^q to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The number of carbon atoms in the alkylene group (preferably a fluoroalkylene group, more preferably a perfluoroalkylene group) is preferably 2 to 4.

Preferred examples of the periconium cation in the general formula (ZI) and the iodide cation in the general formula (ZII) are shown below.

[Chemical 22]

Preferred examples of the general formula (ZI), the anion Z ^- in the general formula (ZII), the Zc ^- in the general formula (ZI-3), and the Z ^- in the general formula (ZI-4) are shown below.

[Chemical 23]

The above-mentioned cations and anions can be used in any combination as a photoacid generator.

The photoacid generator may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low molecular weight compound and the form combined in a part of a polymer can be used together. The photoacid generator is preferably in the form of a low molecular 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. The lower limit is not particularly limited, but is usually 50 or more. When the photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the aforementioned resin A, or may be incorporated in a resin different from the resin A. A photoacid generator may be used individually by 1 type, and may use 2 or more types.

Based on the total solid content of the composition, the content of the photoacid generator in the composition (the total when there are plural kinds) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, and 3 to 3% by mass. 20 mass % is more preferable.

<Hydrophobic resin>

The composition of the present invention may contain a hydrophobic resin. In addition, it is preferable that the hydrophobic resin is different from the resin A.

The composition of the present invention can control the static and/or dynamic contact angle of the surface of the photosensitive radiation or radiation sensitive film by including the hydrophobic resin. Thereby, developing characteristics can be improved, outgassing can be suppressed, immersion liquid followability in liquid immersion exposure can be improved, and immersion defects can be reduced.

The hydrophobic resin is preferably designed to be biased on the surface of the resist film, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it can not be uniformly mixed with polar substances and non-polar substances. effect.

From the viewpoint of localization to the film surface layer, the hydrophobic resin has at least one selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ moiety structure contained in the side chain moiety of the resin" The resin of the repeating unit is preferred.

When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the above-mentioned fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chains.

When the hydrophobic resin contains a fluorine atom, as a partial structure having a fluorine atom, a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferable.

It is preferable that the hydrophobic resin has at least one group selected from the following groups (x) to (z). (x) Acid group (y) A group that decomposes by the action of an alkali developer to increase the solubility in an alkali developer (hereinafter, also referred to as a polarity conversion group.) (z) A group that decomposes by the action of an acid group

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamido group, a sulfonimide group, and (alkylsulfonyl)(alkylcarbonyl)methylene. base, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imido, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, etc. As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group or a bis(alkylcarbonyl)methylene group is preferable.

Examples of groups (y) that are decomposed by the action of an alkaline developing solution to increase the solubility in an alkaline developing solution include a lactone group, a carboxyester group (-COO-), an acid anhydride group (-CO-O- CO-), acid imide group (-NHCONH-), carboxythioester group (-COS-), carbonate ether group (-O-CO-O-), sulfate group (-OSO ₂ O-) and sulfonic acid An ester group (-SO ₂ O-), etc., a lactone group or a carboxyester group (-COO-) is preferable. The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units derived from acrylates and methacrylates. In the repeating unit, these groups can be bonded to the main chain of the resin through a linking group. Alternatively, the repeating unit is used when polymerizing a polymerization initiator or a chain transfer agent having these groups, and can be introduced into the terminal of the resin. As a repeating unit which has a lactone group, the thing similar to the repeating unit which has the lactone structure demonstrated in the item of the said resin A is mentioned, for example.

The content of the repeating unit having the group (y) which is decomposed by the action of the alkali developing solution and increases the solubility to the alkali developing solution is preferably 1 to 100 mol % relative to all repeating units in the hydrophobic resin, 3-98 mol% is more preferable, and 5-95 mol% is more preferable.

The repeating unit which has a group (z) decomposable by the action of an acid in the hydrophobic resin is the same as the repeating unit which has an acid-decomposable group mentioned in resin A. The repeating unit having the group (z) decomposed by the action of an acid may have at least any one of a fluorine atom and a silicon atom. The content of the repeating unit having the group (z) decomposed by the action of an acid is preferably 1 to 80 mol %, more preferably 10 to 80 mol %, with respect to all repeating units in the hydrophobic resin, and 20 -60 mol% is further preferred. The hydrophobic resin may further have repeating units different from the above-mentioned repeating units.

The repeating unit containing a fluorine atom is preferably 10-100 mol%, more preferably 30-100 mol%, relative to all repeating units in the hydrophobic resin. Moreover, 10-100 mol% of the repeating unit containing a silicon atom is preferable with respect to all repeating units in a hydrophobic resin, and 20-100 mol% is more preferable.

On the other hand, especially when the side chain part of the hydrophobic resin contains a CH ₃ moiety structure, the form in which the hydrophobic resin does not substantially contain fluorine atoms and silicon atoms is also preferable. Moreover, it is preferable that the hydrophobic resin consists essentially of only repeating units (which consist only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms).

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 the residual monomers and/or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5 mass %, more preferably 0.01 to 3 mass %. Further, the degree of dispersion (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 of these. For example, the known resins disclosed in paragraphs <0451> to <0704> of the specification of US Patent Application Publication No. 2015/0168830A1 and paragraphs <0340> to <0356> of the specification of US Patent Application Publication No. 2016/0274458A1 can be preferably used. Used as a hydrophobic resin. In addition, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 are also preferred as repeating units constituting the hydrophobic resin.

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

[Chemical 24]

[Chemical 25]

A hydrophobic resin may be used individually by 1 type, and may use 2 or more types. It is also preferable to mix and use two or more types of hydrophobic resins having different surface energies, from the viewpoint of both the followability of liquid immersion liquid and the developing characteristics in liquid immersion exposure. The content in the composition of the hydrophobic resin is preferably 0.01 to 10% by mass, more preferably 0.03 to 8% by mass, based on the total solid content in the composition of the present invention.

<Surfactant> The composition of the present invention may contain a surfactant. When a surfactant is included, 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) is preferred.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less (especially 220 nm or less) is used, it is possible to obtain a pattern with good sensitivity and resolution with few adhesion and development defects. As the fluorine-based and/or silicon-based surfactant, the surfactant described in the paragraph <0276> of the specification of US Patent Application Publication No. 2008/0248425 can be mentioned. In addition, other surfactants other than the fluorine-based and/or silicon-based surfactants described in the paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone, or two or more of them may be used. When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass % with respect to the total solid content of the composition. On the other hand, by setting the content of the surfactant with respect to the total solid content of the composition to 10 mass ppm or more, the surface localization of the hydrophobic resin is improved. Thereby, the surface of the photosensitive radiation-sensitive or radiation-sensitive film can be further made hydrophobic, and the water followability at the time of liquid immersion exposure can be improved.

<Solvent> The composition of the present invention may contain a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of the specification of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of the specification of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016 can be preferably used. Well-known solvents disclosed in paragraphs <0424> to <0426> of the specification /0237190A1 and paragraphs <0357> to <0366> of the specification of US Patent Application Publication No. 2016/0274458A1. Examples of solvents that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, and alkyl alkoxypropionate. Esters, cyclic lactones (preferably carbon number 4 to 10), monoketone compounds which may have a ring (preferably carbon number 4 to 10), alkylene carbonate, alkyl alkoxyacetate and acetone Organic solvents such as acid alkyl esters.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group and a solvent not having a hydroxyl group in the structure can be used. As the solvent with hydroxyl group and the solvent without hydroxyl group, the aforementioned exemplified compounds can be appropriately selected. As the solvent containing hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate is preferred, propylene glycol monomethyl ether (PGME) ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are better. In addition, as a solvent without a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone or alkyl acetate, etc. Preferably, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, Propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, cyclopentanone or 2-heptanone are further preferred. As a solvent which does not have a hydroxyl group, propylene carbonate is also preferable. The mixing ratio (mass ratio) of the solvent with hydroxyl group and the solvent without hydroxyl group is 1/99-99/1, preferably 10/90-90/10, more preferably 20/80-60/40. The mixed solvent containing 50 mass % or more of the solvent which does not have a hydroxyl group is preferable from a viewpoint of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate. In this case, the solvent may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more kinds including propylene glycol monomethyl ether acetate.

The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and even more preferably 2.0 to 5.3% by mass. That is, when the composition contains a solvent, the content of the solvent in the composition is preferably adjusted to satisfy the preferred range of the solid content concentration described above. In addition, the solid content concentration is the mass percentage of the mass of the resist components other than the solvent with respect to the total mass of the composition. By setting the solid content concentration in the composition in an appropriate range to have an appropriate viscosity, the coating properties or film-forming properties can be improved, whereby the resist film (photosensitive radiation resistance) composed of the composition of the present invention can be adjusted. or radiation-sensitive film).

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

<Preparation method> Regarding the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent (preferably, the above-mentioned mixed solvent), filtered through a filter, and then applied to a predetermined support (substrate) to be applied. It is better to use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667 ), circulatory filtration may be performed, or a plurality of filters may be connected in series or parallel to perform filtration. In addition, the composition can be filtered a plurality of times. Furthermore, the composition may be subjected to deaeration treatment or the like before and after the filter filtration.

<Usage> The composition of the present invention relates to a photosensitive radiation-sensitive or radiation-sensitive resin composition whose properties are changed by reacting with actinic radiation or radiation irradiation. More specifically, the composition of the present invention relates to a semiconductor manufacturing process such as IC (Integrated Circuit), the manufacture of a circuit board such as a liquid crystal or a thermal head, the manufacture of a mold structure for imprinting, and other photosensitive materials. Photosensitive radiation-sensitive or radiation-sensitive resin composition in etching process, lithographic printing plate, or acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern forming method and resist film] The present invention also relates to a pattern forming method using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. Moreover, the resist film (photosensitive radiation-sensitive or radiation-sensitive film) of this invention is demonstrated together with description of a pattern formation method.

The pattern forming method of the present invention includes: (i) a process (resist) for forming a resist film (photosensitive radiation or radiation sensitive film) on a support using the above-mentioned photosensitive radiation or radiation sensitive resin composition Film-forming process (film-forming process)), (ii) process (exposure process) of exposing the above-mentioned resist film (irradiation with actinic rays or radiation), and (iii) using a developing solution to conduct the above-mentioned exposed resist film The development process (development process).

The pattern forming method of the present invention is not particularly limited as long as it includes the processes (i) to (iii) above, and may further include the following processes. In the pattern forming method of the present invention, (ii) the exposure method in the exposure process may be liquid immersion exposure. The pattern forming method of the present invention preferably has (iv) a pre-bake (PB: PreBake) process before the (ii) exposure process. Preferably, the pattern forming method of the present invention has (v) a post-exposure heating (PEB: Post Exposure Bake) process after (ii) the exposure process and (iii) before the development process. The pattern forming method of the present invention may have a plurality of (ii) exposure processes. The pattern forming method of the present invention may have a plurality of (iv) pre-baking processes. The pattern forming method of the present invention may have a plurality of (v) post-exposure heating processes.

In the pattern forming method of the present invention, the above (i) resist film formation process (film formation process), (ii) exposure process, and (iii) development process can be performed by conventionally known methods.

From the viewpoint of improving the resolution, the thickness of the resist film is preferably 90 nm or less, and more preferably 85 nm or less. Also, as needed, a resist underlayer film (eg, SOG (Spin On Glass), SOC (Spin On Carbon), and an antireflection film) may be formed between the resist film and the support. ). As the material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used. A protective film (top coat) may be formed on the resist film. As a protective film, a well-known material can be used suitably. For example, the specification of US Patent Application Publication No. 2007/0178407, the specification of US Patent Application Publication No. 2008/0085466, the specification of US Patent Application Publication No. 2007/0275326, and the specification of US Patent Application Publication No. 2016/0299432 can be preferably used , the composition for forming a protective film disclosed in the specification of US Patent Application Publication No. 2013/0244438 and the specification of International Patent Application Publication No. 2016/157988A. As a composition for protective film formation, what contains the said acid diffusion control agent is preferable. A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

The support is not particularly limited, and substrates generally used in lithography processes such as photolithography processes other than semiconductor manufacturing processes such as ICs and circuit substrate manufacturing processes such as liquid crystals and thermal heads can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 150° C., and more preferably 80 to 120° C. in any one of the (iv) pre-baking process and (v) the post-exposure heating process. Regarding the heating time, in any one of the (iv) pre-baking process and (v) the post-exposure heating process, 30 to 300 seconds is preferred, 30 to 180 seconds is more preferred, and 30 to 90 seconds is further better. Heating can be performed by the member with which an exposure apparatus and a developing apparatus are equipped, and a hotplate etc. can also be used.

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Such medium and far ultraviolet light is preferred, and its wavelength is preferably below 250 nm, more preferably below 220 nm, and even more preferably from 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm) or electron beam are preferred, KrF excimer laser, ArF excimer laser, EUV or electron beam are more preferable.

In the (iii) development process, an alkali developer may be used, or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

As an alkali developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used, and other than this, an aqueous alkali solution such as an inorganic base, amines of 1st to 3rd grades, alcohol amines, and cyclic amines can be used. Furthermore, the above-mentioned alkaline developer may contain an appropriate amount of alcohols and/or surfactants. The alkali concentration of the alkali developing solution is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15. The time for developing using an alkali developing solution is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkali developing solution can be appropriately adjusted according to the pattern to be formed.

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

Examples of the ketone-based 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, methyl cyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetone, acetonyl acetone, ionone (ionone) , Diacetone alcohol, acetone methanol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate, etc.

Examples of the ether-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, and 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, 2- Methyl hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate, etc.

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

A plurality of the above-mentioned solvents may be mixed, and a solvent other than the above or water may be mixed. The moisture content of the whole developer is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably not containing water substantially.

The content of the organic solvent relative to the organic developing solution is preferably 50 to 100 mass % relative to the total amount of the developing solution, more preferably 80 to 100 mass %, further preferably 90 to 100 mass %, and 95 to 100 mass %. Mass % is particularly good.

The developer may contain a known surfactant in an appropriate amount as required.

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

The organic-based developer may contain an acid diffusion control agent.

As the developing method, for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dipping method), and a method of raising the developing solution by surface tension and allowing it to stand on the surface of the substrate for a certain period of time (liquid coating method) ), the method of spraying the developer on the surface of the substrate (spraying method), and the method of continuously ejecting the developer onto the substrate rotating at a certain speed while scanning the developer ejection nozzle at a certain speed (dynamic distribution method).

A process of developing using an aqueous alkaline solution (alkali development process) and a process of developing using a developer containing an organic solvent (organic solvent development process) may be combined. Thereby, a pattern can be formed without dissolving only a region of an exposure intensity of an intermediate level, so that a finer pattern can be formed.

It is preferable to have a process (rinsing process) for cleaning with a rinsing solution after the (iii) developing process.

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

The rinsing solution used in the rinsing process after the developing process using the organic solvent-containing developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent are the same as those described in the developer containing organic solvent. As the rinsing liquid used in the rinsing process at this time, a rinsing liquid containing a monovalent alcohol is more preferable.

As the monovalent alcohol used in the rinsing process, linear, branched or cyclic monovalent alcohols can be mentioned. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl alcohol can be mentioned. yl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol , 4-octanol and methyl isobutyl methanol. Preferably, the monovalent alcohol has 5 or more carbon atoms, and examples thereof include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl alcohol. -1-Butanol and methyl isobutyl methanol, etc.

Each component may be mixed with a plurality of types, and may be used by mixing with an organic solvent other than the above. The water content in the rinse solution used in the rinse process after the development process using the developer containing an organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to be 10 mass % or less, favorable developing characteristics can be obtained. The rinse solution after the development process using the organic solvent-containing developer may contain an appropriate amount of surfactant.

In the rinsing process, the developed substrate is cleaned with a rinsing solution. The cleaning treatment method is not particularly limited. For example, a method of continuously spraying a rinsing solution on a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with a developer solution for a certain period of time (dipping method) ) or the method of spraying the developer on the surface of the substrate (spraying method), etc. Among them, the cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a rotational speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. In addition, it is also preferable to have a heating process (post bake: Post Bake) after the rinsing process. The developing solution and the rinse solution remaining between the patterns and inside the patterns are removed by the heating process. In the heating process after the rinsing process, the heating temperature is usually 40-160°C, preferably 70-95°C, and the heating time is usually 10 seconds-3 minutes, preferably 30 seconds-90 seconds.

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

As a method of removing impurities, such as a metal, from the said various materials, the filtration using a filter is mentioned, for example. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. Filters can also be cleaned with organic solvents in advance. In the filter filtration process, a plurality of filters can be connected in series or in parallel for use. When using multiple 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 process of performing multiple filtrations can also be a cyclic filtering process. As the filter, the one with reduced eluates as disclosed in Japanese Patent Application Laid-Open No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426) is preferable. In addition to filter filtration, adsorbent materials can be used to remove impurities, and filter filtration and adsorbent materials can be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Laid-Open No. 2016-206500 (Japanese Patent Application Laid-Open No. 2016-206500). In addition, as a method for reducing impurities such as metals contained in the above-mentioned various materials, it is possible to select a raw material with a small metal content as a raw material constituting the various materials, filter the raw materials constituting the various materials, or use Teflon ( registered trademark) in the device, such as lining and other methods to conduct distillation under conditions that suppress contamination as much as possible. The preferable conditions in the filter filtration of the raw materials constituting the various materials are the same as those described above.

In order to prevent contamination of impurities, it is preferable to store the above-mentioned various materials in containers described in US Patent Application Publication No. 2015/0227049 and Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351). .

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

THE MANUFACTURING METHOD OF AN ELECTRONIC COMPONENT The present invention also relates to a manufacturing method of an electronic component including the above-described pattern forming method. The electronic component manufactured by the manufacturing method of the electronic component of the present invention can be preferably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.) .

[Compound] The present invention also includes the invention of a compound. The compound of the present invention is the same as the compound represented by the general formula (II-2), and the preferable conditions are also the same. [Example]

Hereinafter, the present invention will be described in more detail based on examples. Materials, usage amounts, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the examples shown below.

[Photosensitive or radiation-sensitive resin composition] [Ingredients] The photosensitive or radiation-sensitive resin compositions (hereinafter, also referred to as "compositions") used in Examples and Comparative Examples are shown below. ingredients contained.

<Acid-decomposable resin> The acid-decomposable resin used for manufacture of a composition is shown below. In the following formulas, * represents a bonding position. The numerical value attached to each repeating unit represents the molar ratio (mol %) of each repeating unit in each resin.

[Chemical 26]

<Compound Q> (Synthesis of Q-1) Compound Q-1 was synthesized according to the following method.

[Chemical 27]

After dissolving the compound HBI (5 g) shown in the above method in a 2,2,2-trifluoroethanol/dichloromethane mixed solution (volume ratio: 2/1) (84 ml), benzene (2.6 g), and the obtained solution was stirred at room temperature for 12 hours. After the solvent was distilled off from the above solution, the compound Q-1 (2.4 g) was obtained by crystallization using methanol (yield: 40%).

Compounds Q-2 to Q-8 were synthesized in the same manner. The compound Q used in the preparation of the composition is shown below. In addition, in the comparative example, compounds Q-9 and Q-10 were used as the compounds for comparison.

[Chemical 28]

<Photoacid generator> The photoacid generator used for the preparation of a composition is shown below.

[Chemical 29]

<Hydrophobic resin> The hydrophobic resin used for preparation of a composition is shown below. In the following formulas, * represents a bonding position. The numerical value attached to each repeating unit represents the molar ratio (mol %) of each repeating unit in each resin.

[Chemical 30]

<Surfactant> Surfactant used for preparation of a composition is shown below. W-1: MEGAFACE F176 (manufactured by DIC Corporation; fluorine-based) W-2: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

<Solvent> The solvent used for preparation of a composition is shown below. SL-1: Propylene Glycol Methyl Ether Acetate (PGMEA) SL-2: Propylene Glycol Monomethyl Ether (PGME) SL-3: Cyclohexanone SL-4: γ-Butyrolactone

[Preparation of a composition] Each component was dissolved in a solvent by blending as described in the table below to prepare a solution having a solid content concentration of 3.8% by mass, respectively. Next, the obtained solution was filtered with a polyethylene filter having a pore size of 0.1 μm, whereby a photosensitive radiation-sensitive or radiation-sensitive resin composition (composition) was prepared.

[Evaluation] <Formation of pattern> (Formation of resist film) ARC29SR (manufactured by Brewer Co., Ltd.) for organic antireflection film formation was applied on a silicon wafer, and the film thickness was formed by baking at 205° C. for 60 seconds. 98 nm anti-reflection coating. In addition, each composition prepared by blending described in the table shown below was applied and baked at 100° C. for 60 seconds to form a resist film having a thickness of 90 nm.

(Exposure to development) 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), and through a line width of 44 nm 1 : 1 line and space pattern 6% halftone mask to expose the resist film on the silicon wafer obtained in the above steps. Ultrapure water was used as the liquid immersion liquid. After that, after heating at 120° C. for 60 seconds, and developing with butyl acetate for 30 seconds, spin drying was performed to obtain a pattern.

<LWR performance> The exposure amount (mJ/cm ² ) at the time of forming a pattern of a 1:1 line and space pattern with a line width of 44 nm was set as the optimum exposure amount. A 1:1 line-and-space pattern with a line width of 44 nm obtained by exposure and development at the optimum exposure amount was observed. In pattern observation, a length measurement scanning electron microscope (SEM (Hitachi, Ltd. S-8840)) was used to observe from the upper part of the pattern, and the line width was observed at any point (160 points), and the measurement deviation was evaluated as 3σ. The results are described in the table below. The smaller the value shown in the "LWR (nm)" column in the table, the better the LWR performance. In addition, in this evaluation, the composition used for formation of a pattern is the composition immediately after preparation.

<Storage stability (sensitivity ratio)> In the obtained resist film, the exposure amount (mJ/cm ² ) at the time of forming a pattern of a 1:1 line and space pattern with a line width of 44 nm was taken as the optimum exposure quantity. Sensitivity was evaluated by the sensitivity ratio (S1/S2) of the optimum exposure amount S1 obtained when the composition immediately after preparation was used to the optimum exposure amount S2 obtained when the composition left at 4°C for 1 week after preparation was used Variety. The closer the value of S1/S2 is to 1, the smaller the change in sensitivity and the better the storage stability. The results are described in the table below.

<Storage stability (contamination)> The number of contaminants in the composition immediately after preparation (original value of contaminants) and the composition after being left at 4°C for 3 months were measured using a contamination counter manufactured by RION Co., Ltd. The number of pollutants in the material (the number of pollutants after time) was counted, and the number of pollutant increases calculated by "(number of pollutants after time) - (original value of pollutants)" was evaluated according to the following criteria Storage stability of the composition. The composition having a smaller increase in the number of contaminants has better storage stability. In addition, here, the thing with a particle diameter of 0.25 micrometer or more contained in 1.0 ml of a composition is counted as a contaminant. The results are described in the table below.

A: The increased number of pollutants is less than 0.2/ml B: The increased number of pollutants is more than 0.2/ml and less than 1.0/ml C: The increased number of pollutants is more than 1.0/ml and less than 5.0/ml D : The increased number of pollutants exceeds 5.0/ml

[Results] The results of evaluation performed using blending of the compositions and these compositions are shown in the following table. In addition, in each composition, 10 g, 0.05 g, and 0.03 g of resin, hydrophobic resin, and surfactant were blended, respectively. About compound Q and a photoacid generator, the mass (g) shown in parenthesis together with each component name was blended. The blending solvent was adjusted so that the internal fraction ratio (mass ratio) of each solvent was the ratio shown in each column, and the solid content concentration of the composition was 3.8 mass %.

[Table 1]

From the results shown in the table, it was confirmed that the composition of the present invention can obtain a pattern having excellent storage stability and excellent LWR performance. In addition, with regard to compound Q, it was confirmed that when any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a group represented by the general formula (II), it was confirmed that the composition has better storage stability and better LWR performance. Excellent pattern (comparison of Examples 1, 2 and 5). Regarding compound Q, it was confirmed that when A represents a single bond, a pattern with more excellent storage stability of the composition and more excellent LWR performance can be obtained (comparison of Examples 3, 7 and 11). It was confirmed that when the composition further contains a photoacid generator, which is a compound other than the compound Q, a pattern with more excellent LWR performance can be obtained (comparison of Examples 9 and 19).

Claims (19)

A photosensitive radiation-sensitive or radiation-sensitive resin composition comprising a resin and a compound Q represented by the general formula (I), the resin having a repeating unit having a group whose polarity is increased by decomposition by the action of an acid,

In the general formula (I), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent, wherein any one of R ² , R ⁴ , R ⁷ , and R ⁹ is a group represented by the general formula (II) group, * ^-AX- (II) In general formula (II), A represents a single bond or a divalent linking group, X- represents -SO ₃ ^- , ^- (SO ₂ )-N ^- -(SO ₂ ) R ¹¹ , -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ , and R ¹¹ to R ¹⁴ each independently represent an organic group. The photosensitive radiation-sensitive or radiation-sensitive resin composition as described in claim 1, wherein A represents a single bond. The photosensitive radiation-sensitive or radiation-sensitive resin composition described in item 1 of the patent application scope, wherein X ^- represents -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ . The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of items 1 to 3 of the claimed scope, wherein any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is composed of the A group represented by formula (II). The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of items 1 to 3 of the patent application scope, further comprising a photoacid generator other than the compound Q. A photosensitive radiation-sensitive or radiation-sensitive resin composition comprising a resin and a compound Q represented by the general formula (I), the resin having a repeating unit having a group whose polarity is increased by decomposition by the action of an acid,

In the general formula (I), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent, wherein any one of R ¹ to R ¹⁰ is a group represented by the general formula (II), *-AX ^- (II) In general formula (II), A represents a divalent linking group, X ^- represents -SO ₃ ^- , -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , -(SO ₂ )- N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ , R ¹¹ to R ¹⁴ each independently represent an organic group. The photosensitive radiation-sensitive or radiation-sensitive resin composition as described in claim 6, wherein X ^- represents -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ . The photosensitive radiation-sensitive or radiation-sensitive resin composition as described in item 6 or item 7 of the claimed scope, wherein any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is represented by the general formula (II) represented group. The photosensitive radiation-sensitive or radiation-sensitive resin composition as described in item 6 or 7 of the claimed scope further comprises a photoacid generator other than the compound Q. A resist film formed using the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of the claims 1 to 9 of the patent application. A pattern forming method comprising: a process of forming a resist film on a support using the photosensitive radiation-sensitive or radiation-sensitive resin composition as described in any one of items 1 to 9 of the patent application scope; A process of exposing the resist film; and a process of developing the exposed resist film with a developer. A manufacturing method of an electronic component, which includes the pattern forming method described in item 11 of the patent application scope. A compound represented by the general formula (I-2),

In general formula (I-2), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent, wherein any one of R ² , R ⁴ , R ⁷ , and R ⁹ is represented by general formula (II) group, *-AX ^- (II) In general formula (II), A represents a single bond or a divalent linking group, X ^- represents -SO ₃ ^- , -(SO ₂ )-N ^- -(SO ₂ ) R ¹¹ , -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ , R ¹¹ to R ¹⁴ each independently represent an organic group group, wherein R ³ or R ⁸ is a group represented by the general formula (II), and when it is -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , R ¹¹ represents a group other than trifluoromethyl organic group. The compound described in claim 13, wherein A represents a single bond. The compound described in item 13 of the claimed scope, wherein X ^- represents -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ . The compound according to any one of the claims 13 to 15, wherein any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a group represented by the general formula (II). A compound represented by the general formula (I-2),

In the general formula (I-2), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent, wherein any one of R ¹ to R ¹⁰ is a group represented by the general formula (II), *- AX ^- (II) In general formula (II), A represents a divalent linking group, X ^- represents -SO ₃ ^- , -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ , R ¹¹ to R ¹⁴ each independently represent an organic group, wherein R ³ or R ⁸ is a group represented by the general formula (II), and when it is -(SO ₂ )-N ^- -(SO ₂ )R ¹¹ , R ¹¹ represents an organic group other than a trifluoromethyl group. The compound described in item 17 of the claimed scope, wherein X ^- represents -(SO ₂ )-N ^- -COR ¹² , -CO-N ^- -(SO ₂ )R ¹³ or -CO-N ^- -COR ¹⁴ . The photosensitive radiation-sensitive or radiation-sensitive resin composition according to the claim 17 or 18 of the claimed scope, wherein any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is represented by the general formula (II) represented group.