TW201830136A - Active ray-sensitive or radiation-sensitive resin composition, method for forming pattern, method for manufacturing electronic device and method for manufacturing resin wherein the resin includes different resins having different repeating units - Google Patents

Abstract

The present invention provides an active ray-sensitive or radiation-sensitive resin composition containing a resin capable of controlling a composition ratio of a plurality of repeating units contained therein with a high precision. The present invention also provides a pattern forming method and an electronic device manufacturing method using the active ray-sensitive or radiation-sensitive resin composition. Further, a method for producing the above resin is also provided. The present invention provides an active ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound (B) which generates an acid by irradiation with actinic rays or radiation. In the present invention, the resin (A) contains N kinds of resins (a1) to (aN) satisfying the following requirement I, and there are N peaks derived from each of the N kinds of resins (a1) to (aN), and the peaks may be measured by HPLC. The requirement I includes: each of the N kinds of the resin (a1) to the resin (aN) is a resin containing two or more kinds of repeating units, and the two or more kinds of the above-mentioned repeating units are all the same and the ratio of the repeating units are different from each other. N represents an integer of 2 or more.

Description

Photosensitive ray- or radiation-sensitive resin composition, pattern forming method, method for producing electronic device, and method for producing resin

The present invention relates to a sensitized ray-sensitive or radiation-sensitive resin composition, a pattern forming method, a method for producing an electronic device, and a method for producing a resin. More specifically, the present invention relates to a sensitizing ray used in a semiconductor manufacturing process such as an IC, a circuit substrate such as a liquid crystal or a thermal head, and a lithography process such as another photolithography process. A radiation-sensitive resin composition, a pattern forming method, a method for producing an electronic device including the pattern forming method, and a method for producing a resin.

In the manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), fine processing is performed by using a lithography of a resist composition. In recent years, with the high integration of integrated circuits, ultrafine patterns of submicron regions or quarter micrometer regions are required to be formed. Accordingly, the exposure wavelength also tends to be shorter than that of the excimer laser light such as the g-ray to the i-ray and further to KrF (for example, refer to Patent Documents 1 and 2). Further, in addition to excimer laser light, lithography using an electron beam or X-ray or EUV light (Extreme Ultra Violet) has been developed (for example, see Patent Document 3).

The high functionality of various electronic devices is required, and it is required to further improve the characteristics of the resist pattern used in the microfabrication. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-275282.

In the future, with the further advancement of lithography technology and the expansion of application fields, as the pattern refinement progresses, chemically amplified resists are required to further improve lithography characteristics. Conventionally, as a base resin used in a chemically amplified resist, a resin containing a plurality of constituent units (repeating units) is used in order to improve properties such as lithographic properties. In order to obtain the desired excellent lithographic characteristics, the more the pattern is refined, the more important it is to control the composition ratio of the plurality of repeating units contained in the base resin with high precision.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a sensitized ray-sensitive or radiation-sensitive resin composition containing a resin capable of controlling a composition ratio of a plurality of types of repeating units contained with high precision. Moreover, an object of the present invention is to provide a pattern forming method using the sensitized ray-sensitive or radiation-sensitive resin composition and a method of manufacturing an electronic device. Further, an object of the present invention is to provide a method for producing a resin which can control the composition ratio of a plurality of types of repeating units contained with high precision.

The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, it has been found that a plurality of resins are blended by using a relationship in which the structures having the plural kinds of repeating units are all the same and the composition ratios of the respective repeating units are different from each other. The latter can solve the above problems as a base resin. In one form, the invention is as follows.

[1] A photosensitive ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound (B) which generates an acid by irradiation with actinic rays or radiation, wherein the resin (A) contains the following N kinds of resins (a ₁ ) to resin (a _N ) of the material I, and there are N peaks derived from each of the N kinds of the resins (a ₁ ) to (a _N ), and the peaks are subjected to high performance liquid chromatography. Determination. Requirement I: Each of the N kinds of the resins (a ₁ ) to (a _N ) is a resin containing two or more kinds of repeating units, and the above-mentioned repeating units having two or more kinds of the above-mentioned repeating units are all the same and two or more types are the same. The relationship between the content rates is different from each other. Here, N represents an integer of 2 or more.

[2] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [1], wherein each of the N kinds of the resins (a ₁ ) to (a _N ) contains three or more kinds of repeating units.

[3] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [1] or [2] wherein N is an integer of 3 or more.

[4] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3] wherein each of the N kinds of the resins (a ₁ ) to (a _N ) has an acid The repeating unit of the group that decomposes.

[5] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [4], wherein the above group decomposed by the action of an acid is a group which is decomposed by an action of an acid to produce a phenolic hydroxyl group.

[6] of [1] to [5] of the actinic ray or a radiation-sensitive resin composition, wherein N resins (a ₁₎ ~ resin (A _N) each having a phenolic hydroxyl group-containing Repeat unit.

[7] A pattern forming method comprising the following process: forming a film comprising the film of the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6]; exposing the film a process; and a process for developing the exposed film after exposure.

[8] The pattern forming method according to [7], wherein the developing process includes at least a process of developing using an alkali developing solution.

[9] The pattern forming method according to [7] or [8], wherein the developing process includes at least a process of developing using a developing solution containing an organic solvent.

[10] A method of producing an electronic device, comprising the pattern forming method according to any one of [7] to [9].

[11] A method for manufacturing a resin, which is a method for producing a photosensitive resin ray-sensitive or radiation-sensitive resin used in the composition, wherein the resins by mixing N satisfies the following requirements I (a ₁₎ ~ Resin (A _N) obtained from the presence of the resin (a ₁₎ ~ resin (A _N) of each of the N peak of resin, the peak was measured by high performance liquid chromatography. Requirement I: Each of the N kinds of resins (a ₁ ) to (a _N ) is a resin containing two or more kinds of repeating units, and the above-mentioned repeating units are all the same and the content ratio of the repeating units is different from each other. Here, N represents an integer of 2 or more. [Effect of the invention]

According to the present invention, it is possible to provide a sensitized ray-sensitive or radiation-sensitive resin composition containing a resin capable of controlling a composition ratio of a plurality of types of repeating units contained therein with high precision, and using the sensitizing ray-sensitive or radiation-sensitive resin A pattern forming method of a composition and a method of manufacturing an electronic device. Moreover, according to the present invention, it is possible to provide a method for producing a resin capable of controlling the composition ratio of a plurality of types of repeating units contained with high precision.

Hereinafter, an example of a mode for carrying out the present invention will be described. In the labeling of the group and the atomic group in the present specification, when neither substituted or unsubstituted is included, both the unsubstituted group and the substituted group are included. For example, it is not expressly stated that the substituted or unsubstituted "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

In addition, the "exposure" in the present specification includes not only the use of a mercury lamp, but also ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) represented by excimer lasers, and the like. A beam of particles, an ion beam, or the like is drawn.

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

In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method. GPC was able to use HLC-8120 (manufactured by TOSOH CORPORATION), and used TSK gel Multipore HXL-M (manufactured by TOSOH CORPORATION, 7.8 mm ID × 30.0 cm) as a column, and THF (tetrahydrofuran) as an eluent.

[Photosensitive ray-sensitive or radiation-sensitive resin composition] The sensitized ray-sensitive or radiation-sensitive resin composition of the embodiment of the present invention is typically a resist composition, preferably a chemically amplified resist composition. . The photosensitive ray-sensitive or radiation-sensitive resin composition is preferably a photosensitive ray-sensitive or radiation-sensitive resin composition for developing an organic solvent using a developing solution containing an organic solvent and/or for developing an alkali using an alkali developing solution. . Here, the organic solvent development means a use for at least a process for developing using a developer containing an organic solvent. The alkali development means a use for at least a process for developing using an alkali developer.

The photosensitive ray-sensitive or radiation-sensitive resin composition may be a positive resist composition or a negative resist composition. The actinic ray or radiation suitable for the sensitizing ray-sensitive or radiation-sensitive resin composition is not particularly limited, and for example, KrF excimer laser, ArF excimer laser, Extreme Ultra Violet (EUV), and electron can be used. Beam (EB, Electron Beam) or the like is preferably used for electron beam or extreme ultraviolet exposure. Hereinafter, each of the essential components and optional components contained in the sensitized ray-sensitive or radiation-sensitive resin composition will be described.

<Resin (A)> The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains the resin (A) as a base resin. In the embodiment of the present invention, the resin (A) is preferably a resin which has an increased solubility in an alkali developing solution by an action of an acid and which has reduced solubility in an organic solvent.

The resin (A) is a resin obtained by mixing N kinds of resins (a ₁ ) to (a _N ) satisfying the following requirements I. Here, N represents an integer of 2 or more. Requirement I: Each of the N kinds of the resins (a ₁ ) to (a _N ) is a resin containing two or more kinds of repeating units, and the above-mentioned repeating units having two or more kinds of the above-mentioned repeating units are all the same and two or more types are the same. The relationship between the content rates is different from each other.

The resin (A) obtained by blending the above N kinds of resins (a ₁ ) to (a _N ) has N peaks derived from each of the N kinds of resins (a ₁ ) to (a _N ), and the peak is efficiently The measurement was carried out by high performance liquid chromatography (HPLC). As described above, in order to improve properties such as lithographic properties, a resin containing a plurality of repeating units is used, and it is desired to form a desired fine pattern, and the composition ratio of a plurality of repeating units contained in the resin is controlled with high precision. important. However, in the case of producing a resin containing a plurality of types of repeating units, although the composition ratio of the repeating units contained can be controlled to some extent, it is difficult to control more than the manufacturing margin required to obtain a desired fine pattern.

In this case, the N kinds of resins (a ₁ ) to (a _N ) having the relationship of the above-mentioned requirement I are blended, that is, the two or more types of repeating units which are contained are all the same and two or more types are used. The N kinds of resins (a ₁ ) to (a _N ) in which the content of the repeating unit is different from each other can provide a resin which can control the composition ratio of the plurality of repeating units contained therein with high precision. Hereinafter, the N kinds of resins (a ₁ ) to (a _N ) having the relationship of the above-mentioned requirement I are collectively referred to as "resin (a)".

In the embodiment of the present invention, the resin (a) which satisfies the requirement I in the resin (A) may be two or more types (that is, N ≥ 2), but in one embodiment, three or more types are used (that is, , N ≥ 3) is preferred. The upper limit is not particularly limited, for example, resin (A) contained in the resin satisfying the requirements of I (a) may be the following 10 kinds of (i.e., N ≤ 10).

When the resin (A) is, for example, a resin obtained by blending three kinds of resins (a ₁ ), a resin (a ₂ ) and a resin (a ₃ ) satisfying the requirements I, the resin (A) has a property by HPLC. It originates from the three peaks of each of the three resins.

In the embodiment of the present invention, the resin (a) may be a resin containing two or more kinds of repeating units, but in one embodiment, it is preferable to contain three or more kinds of repeating units. The upper limit is not particularly limited. For example, the resin (a) may have 10 or more repeating units.

In one embodiment, when the resin (a) is a resin containing two kinds of repeating units (hereinafter also referred to as "two-membered resin" or the like), the resin (A) is a resin that satisfies two or more of the requirements I (a) The blended resin (i.e., N ≥ 2) is preferred. Similarly, when the resin (a) is a ternary resin, the resin (A) is preferably N ≥ 3, and when the resin (a) is a quaternary resin, the resin (A) is preferably N ≥ 4. When the resin (a) is a 5-membered resin, the resin (A) is preferably N ≥ 5.

Hereinafter, the repeating unit which can be contained in the N types of resin (a) contained in the resin (A) is demonstrated. <Acid-decomposable repeating unit> In the embodiment, the resin (a) is preferably a repeating unit (hereinafter also referred to as "acid-decomposable repeating unit") having a group decomposed by an action of an acid.

The group which is decomposed by the action of an acid (hereinafter, also referred to as "acid-decomposable group") may, for example, be a hydrogen atom of an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group. A group protected by a group that is detached by the action of an acid. Examples of the group which is detached by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(= O)-OC(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )-C(=O)-OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) 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 to R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

- Repeating unit (b) - In one embodiment, the resin (a) preferably contains a repeating unit (b) represented by the following formula (A1) as an acid-decomposable repeating unit.

[Chemical Formula 1]

In the general formula (A1), Xa ₁ represents a hydrogen atom, or an optionally substituted alkyl group of. T represents a single bond or a divalent linking group. Rx ₁ , Rx ₂ and Rx ₃ each independently represent an alkyl group (straight chain or branched), or a cycloalkyl group (monocyclic or polycyclic) or a phenyl group. However, when all of Rx ₁ , Rx ₂ and Rx ₃ are an alkyl group (straight chain or branched), it is preferred that at least two of Rx ₁ , Rx ₂ and Rx ₃ are a methyl group. _{Two of} Rx ₁ , Rx ₂ and Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic). Rx ₁ , Rx ₂ and Rx ₃ each consist of only a carbon atom and a hydrogen atom, and the total number of carbon atoms contained in Rx ₁ , Rx ₂ and Rx ₃ is 4 or more and 11 or less.

The alkyl group which may have a substituent represented by Xa ₁ may, for example, be a group represented by a methyl group or -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and a fluorenyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms. Further preferred is a methyl group. In one aspect, Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the divalent linking group of T include an alkylene group, a —COO—Rt— group, and an —O—Rt— group. In the formula, Rt represents an alkylene group or a cycloalkyl group. T is preferably a single bond, an extended aryl group or a -COO-Rt- group, and a single bond or an extended aryl group is more preferred. As the aryl group, a aryl group having 6 to 10 carbon atoms is preferred, and a phenyl group is more preferred. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably -CH ₂ - group, -(CH ₂ ) ₂ - group or -(CH ₂ ) ₃ - group.

The alkyl group of Rx ₁ to Rx ₃ is preferably a carbon number of 1 to 4 such as a methyl group, an ethyl group, an n-butyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group.

The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a polycyclic cycloalkyl group such as a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group or a fluorenyl group.

a cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a polycyclic ring such as a fluorenyl group, a tetracyclononyl group or an adamantyl group; An alkyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.

The repeating unit represented by the formula (A1) is preferably, for example, a state in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the above cycloalkyl group.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxycarbonyl group ( The carbon number is 2 to 6), and the carbon number is preferably 8 or less.

The repeating unit represented by the formula (A1) is preferably an acid-degradable (meth)acrylic acid 3-alkyl ester-based repeating unit (Xa ₁ represents a hydrogen atom or a methyl group and T represents a repeating unit of a single bond). More preferably, Rx ₁ to Rx ₃ each independently represent a repeating unit of a linear or branched alkyl group, and it is further preferred that Rx ₁ to Rx ₃ each independently represent a repeating unit of a linear alkyl group.

Specific examples of the repeating unit represented by the formula (A1) are shown below, but the present invention is not limited thereto.

[Chemical Formula 2]

- Repeating unit (c) - In one embodiment, the resin (a) is preferably an acid-decomposable repeating unit containing a repeating unit having a group in which an acid-decomposable group is decomposed by an action of an acid to form a phenolic hydroxyl group. As such an acid-decomposable repeating unit, for example, a repeating unit (c) represented by the following formula (A2) is preferred.

[Chemical Formula 3]

In the formula (A2), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R ₆₂ may be bonded to Ar ₆ or L ₆ to form a ring, and R _{62 in this case} represents a single bond or an alkylene group. X ₆ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₆ represents a single bond or a divalent linking group, and when R ₆₂ forms a ring, it represents a trivalent linking group. Ar ₆ represents an (n+1)-valent aromatic ring group, and when R _{62 is} bonded to form a ring, it represents an (n+2)-valent aromatic ring group. Y ₂ represents a hydrogen atom or a group which is detached by the action of an acid. When m ≥ 2, there are a plurality of Y _{2 which} may be the same or different. Among them, at least one of Y ₂ represents a group which is detached by the action of an acid. m represents an integer of 1 to 4.

The general formula (A2) will be described in further detail. The alkyl group of R ₆₁ , R ₆₂ and R ₆₃ in the formula (A2) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a second group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R ₆₁ , R ₆₂ and R ₆₃ .

The cycloalkyl group may be a monocyclic type or a polycyclic type, and preferably a monocyclic ring having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent. Type of cycloalkyl. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is more preferable.

When R ₆₂ represents an alkylene group, as the alkylene group, a carbon number such as a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group or a octyl group which may have a substituent may be mentioned. 1 to 8 people.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₆ may be the same as the alkyl group of R ₆₁ to R ₆₃ . As X ₆ , a single bond, -COO-, -CONH- is preferable, and a single bond or -COO- is more preferable.

As the divalent linking group in L ₆ , an alkyl group is preferred. The alkylene group in L ₆ preferably has a carbon number of 1 to 8 such as a methylene group which may have a substituent, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. . It is particularly preferable that the ring formed by the bonding of R ₆₂ and L ₆ is a 5- or 6-membered ring. As L ₆ , a single bond is preferred.

Ar ₆ represents an (m+1)-valent aromatic ring group, and when R _{62 is} bonded to form a ring, it represents an (m+2)-valent aromatic ring group. The aromatic ring group may have a substituent, and examples thereof include an aromatic hydrocarbon ring having a carbon number of 6 to 18 which may have a substituent such as a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring, or a thiophene ring. Aromatic ring of heterocyclic ring such as furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring Heterocyclic.

Examples of the substituent which the alkyl group, the cycloalkyl group, the alkoxycarbonyl group, the alkylene group and the divalent aromatic ring group may have include R ₁₁ , R ₁₂ and R in the above formula (1). each group of ₁₃ represents the same substituent may have a specific example of the group.

m is preferably 1 or 2, and 1 is more preferred. the m Y ₂ each independently represent a hydrogen atom or a group disengaged by the action of an acid. Among them, at least one of m represents a group which is detached by the action of an acid. Examples of the group Y ₂ which is liberated by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(=O)-OC(R ₃₆ )(R ₃₇ )( R ₃₈ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )-C(=O)-OC(R ₃₆ )(R ₃₇ )(R ₃₈ ), -CH(R ₃₆ )(Ar), etc.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group obtained by combining an alkylene group and a monovalent aromatic ring 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, a monovalent aromatic ring group, a group obtained by combining an alkylene group and a monovalent aromatic ring group, or an alkenyl group. Ar represents a monovalent aromatic ring group.

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

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a monocyclic type or a polycyclic type. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include adamantyl group, thiol group, isodecyl group, fluorenyl group, dicyclopentyl group, and α-nonenyl group (pinel group). ), tricyclodecyl, tetracyclododecyl, androstanyl group, and the like. Further, a part of the carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The monovalent aromatic ring group of R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a fluorenyl group and the like. An aryl group, a divalent aromatic ring group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole or thiazole.

The group obtained by combining an alkylene group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ and a monovalent aromatic ring group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group. , phenethyl, naphthylmethyl and the like.

The alkenyl group of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

R ₃₆ and R ₃₇ rings bonded to each other to form the ring may be a single type, it can also be polycyclic. As the monocyclic type, a cycloalkyl structure having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and cyclooctane. Structure, etc. As the polycyclic type, a cycloalkyl structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Wait. Further, a part of the carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.

Each of the above groups of R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, and a urea group. a base, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, etc., the carbon number of the substituent is 8 The following are preferred. As the group Y ₂ which is detached by the action of an acid, the structure represented by the following formula (VI-A) is more preferable.

[Chemical Formula 4]

Here, each of L ₁ and L ₂ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, or a group obtained by combining an alkylene group and a monovalent aromatic ring group. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, a monovalent aromatic ring group which may contain a hetero atom, an amine group, an ammonium group, a fluorenyl group, a cyano group or an aldehyde group. At least two of Q, M, and L ₁ may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

The alkyl group of L ₁ and L _{2 is} , for example, an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group or a hexyl group can be preferably used. , Xinji.

The cycloalkyl group of L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms. Specific examples thereof include a cyclopentyl group, a cyclohexyl group, a decyl group, and an adamantyl group. Wait.

The monovalent aromatic ring group of L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms. Specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, a decyl group, and the like. . The group obtained by combining the alkylene group of L ₁ and L ₂ and the monovalent aromatic ring group is, for example, a carbon number of 6 to 20, and examples thereof include an aralkyl group such as a benzyl group or a phenethyl group.

The divalent linking group of M is, for example, an alkylene group (for example, a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, etc.), a cycloalkyl group (for example, a ring). a pentyl group, a cyclohexylene group, an adamantyl group, etc., an alkenyl group (for example, a vinyl group, a propenyl group, a butenyl group, etc.), a divalent aromatic ring group (for example, a phenyl group, a methyl group) a phenyl group, an anthranyl group, etc.), -S-, -O-, -CO-, -SO ₂ -, -N(R ₀ )-, and a divalent linking group obtained by combining a plurality of these . R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, an octyl group, etc.).

The alkyl group as Q is the same as each of the above groups as L ₁ and L ₂ . The cycloalkyl group which may contain a hetero atom as Q and the aliphatic hydrocarbon ring group which does not contain a hetero atom among the monovalent aromatic ring group which may contain a hetero atom, and the monovalent aromatic ring group which does not contain a hetero atom can mention The cycloalkyl group as the L ₁ and L ₂ and the monovalent aromatic ring group are preferably 3 to 15 carbon atoms.

Examples of the cycloalkyl group containing a hetero atom and the monovalent aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, and benzo. a group of a heterocyclic structure such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole or pyrrolidone, but as long as it is generally referred to as a heterocyclic structure (A ring formed of carbon and a hetero atom or a ring formed of a hetero atom) is not limited thereto.

The ring formed by bonding at least two of Q, M, and L ₁ may be formed by, for example, forming at least two of Q, M, and L ₁ to form a propyl group and a butyl group. The case of a 5-member ring or a 6-member ring of an oxygen atom.

Each group represented by L ₁ , L ₂ , M, and Q in the formula (VI-A) may have a substituent. For example, R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ and Ar may be mentioned. In the case of the substituent, the carbon number of the substituent is preferably 8 or less. The group represented by -MQ is preferably a group having 1 to 30 carbon atoms, and more preferably a group having 5 to 20 carbon atoms.

Specific examples of the repeating unit (c) represented by the formula (A2) are shown below, but the present invention is not limited thereto.

[Chemical Formula 5]

[Chemical Formula 6]

In one embodiment, the resin (a) may contain a repeating unit (d) represented by the following formula (A3) as an acid-decomposable repeating unit.

[Chemical Formula 7]

In the formula (A3), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R _{42 in this case} represents an alkylene group. X ₄ represents a single bond, -COO- or -CONR ₄₄ -, and R ₄₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or a divalent linking group, and when R ₄₂ forms a ring, it represents a trivalent linking group. R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a fluorenyl group or a heterocyclic group. M ₄ represents a single bond or a divalent linking group. Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q ₄ , M ₄ and R ₄₄ may be bonded to form a ring.

The general formula (A3) will be described in further detail. The alkyl group of R ₄₁ to R ₄₃ in the formula (A3) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a second butyl group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably an alkyl group having 3 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R ₄₁ to R ₄₃ .

The cycloalkyl group may be a monocyclic type or a polycyclic type. Preferably, a cycloalkyl group having 3 to 10 carbon atoms and a monocyclic ring type such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent may be mentioned. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is particularly preferred.

Preferred examples of the above-mentioned respective groups include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom. The alkoxy group, the thioether group, the decyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group, the nitro group and the like, and the carbon number of the substituent is preferably 8 or less.

And, when R ₄₂ is an alkylene group and form a ring with L _4, as alkylene, preferably methylene group may include, extending ethyl, propyl stretched, stretch-butyl, hexyl extension, extending octyl An alkyl group having 1 to 8 carbon atoms. The alkylene group having 1 to 4 carbon atoms is more preferably, and the alkylene group having 1 to 2 carbon atoms is particularly preferred. It is particularly preferable that the ring formed by the bonding of R ₄₂ and L ₄ is a 5-membered ring or a 6-membered ring.

As R ₄₁ and R _43, a hydrogen atom, an alkyl group, more preferably a halogen atom, a hydrogen atom, a methyl, ethyl, trifluoromethyl (-CF _3), hydroxymethyl (-CH ₂ -OH), chloro A methyl group (-CH ₂ -Cl) or a fluorine atom (-F) is particularly preferred. R ₄₂ is preferably a hydrogen atom, an alkyl group, a halogen atom or an alkyl group (forming a ring with L ₄ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ) or a hydroxymethyl group ( -CH ₂ -OH), chloromethyl (-CH ₂ -Cl), a fluorine atom (-F), a methylene group (forming a ring with L ₄ ), and an ethyl group (forming a ring with L ₄ ) are particularly preferred.

In one embodiment, it is preferred that X ₄ is a single bond. Examples of the divalent linking group represented by L ₄ include an alkylene group, a divalent aromatic ring group, -COO-L ₁ -, -OL ₁ -, and a combination of two or more of them. Group and so on. Wherein L ₁ represents an alkyl group, a cycloalkyl group, a divalent aromatic ring group, a group obtained by combining an alkyl group and a divalent aromatic ring group.

L ₄ is a single bond, a group represented by -COO-L ₁ - or a divalent aromatic ring group, and a single bond or a divalent aromatic ring group (aryl group) is more preferable. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or a propyl group. As the divalent aromatic ring group, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthyl is preferred, 1,4-phenylene For better.

3 when the divalent linking group of L ₄ and L as R ₄₂ bond to form a ring represented by the _4, can be appropriately removing one hydrogen include any of the above specific examples of the linking group represented by L ₄ from the divalent 2 A group made of atoms.

The meaning of the alkyl group or the cycloalkyl group represented by R ₄₄ and R _{45 is the same} as the alkyl group or the cycloalkyl group represented by the above R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ . The meaning of the aryl group represented by R ₄₄ and R ₄₅ is the same as the meaning of the aryl group represented by the above R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ , and the preferred range is also the same. The aralkyl group represented by R ₄₄ and R ₄₅ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. The alkyl moiety of the alkoxy group represented by R ₄₄ and R _{45 is the same} as the alkyl group represented by the above R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ , and the preferred range is also the same.

Examples of the fluorenyl group represented by R ₄₄ and R ₄₅ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, a neopentyl group, a benzamidine group, and a naphthyl group. It is preferred to use an aliphatic fluorenyl group having 1 to 10 carbon atoms, an ethyl fluorenyl group or a benzamidine group. _Examples of the heterocyclic group represented by R ₄₄ and R ₄₅ include a cycloalkyl group containing a hetero atom and an aryl group containing a hetero atom, and a pyridine ring group or a pyran ring group is preferred.

R ₄₄ and R ₄₅ are a linear or branched alkyl group having 1 to 8 carbon atoms (specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, and third butyl group). a cycloalkyl group having 3 to 15 carbon atoms (specifically, a cyclopentyl group, a cyclohexyl group, a decyl group, an adamantyl group, etc.) is a group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and the like. Preferably, a base having 2 or more carbon atoms is preferred. R ₄₄ and R ₄₅ are ethyl, isopropyl, t-butyl, t-butyl, neopentyl, cyclohexyl, adamantyl, cyclohexylmethyl or adamantylmethyl, more preferably, third Further, a second, a butyl group, a neopentyl group, a cyclohexylmethyl group or an adamantylmethyl group is further preferred.

The alkyl group, the cycloalkyl group, the aryl group, the arylalkyl group, the alkoxy group, the fluorenyl group or the heterocyclic group may further have a substituent, and as the substituent which may be contained, R ₃₆ to R ₃₉ and R may be mentioned. ₀₁ , R ₀₂ and Ar may have substituents and are described.

The meaning of the divalent linking group represented by M ₄ is the same as the meaning of M in the structure represented by the above formula (VI-A), and the preferred range is also the same. M ₄ may have a substituent, and as the substituent which M ₄ may have, the same group as the substituent which M in the group represented by the above formula (VI-A) may have may be mentioned.

The meaning of the alkyl group, the cycloalkyl group and the aryl group represented by Q ₄ is the same as that of the Q in the structure represented by the above formula (VI-A), and the preferred range is also the same. The heterocyclic group represented by Q ₄ may, for example, be a cycloalkyl group containing a hetero atom and a aryl group containing a hetero atom as Q in the structure represented by the above formula (VI-A), and further preferably The scope is also the same. Q ₄ may have a substituent, and as the substituent which Q ₄ may have, the same group as the substituent which Q in the group represented by the above formula (VI-A) may have may be mentioned.

A ring formed by bonding at least two of Q ₄ , M ₄ and R ₄₄ and a ring formed by bonding at least two of Q, M, and L ₁ in the above formula (VI-A) The meanings are the same, and the preferred range is the same.

Specific examples of the repeating unit (d) represented by the general formula (A3) are shown below, but the present invention is not limited thereto.

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

The content ratio of the repeating unit having an acid-decomposable group in the resin (a) (total when it contains a plurality of kinds) is 5 mol% or more and 90 mol% with respect to all the repeating units in the above resin (a) % or less is preferably 5 mol% or more and 80 mol% or less is more preferably 5 mol% or more and 75 mol% or less is further more preferable, and 10 mol% or more and 70 mol% or less are special. Preferably, 10 mol% or more and 65 mol% or less are optimal.

The resin (a) may contain one type of repeating unit (b) alone or two or more types. The content of the repeating unit (b) (which is a total when it is contained in a plurality of kinds) is, for example, 0 to 90 mol%, preferably 5 to 80 mol%, based on all the repeating units in the resin (a). Preferably, 5 to 75 mol% is further preferred.

The resin (a) may contain one type of repeating unit (c) alone or two or more types. The content of the repeating unit (c) (total when it is contained in a plurality of kinds) is, for example, 0 to 90 mol%, preferably 5 to 80 mol%, based on all the repeating units in the resin (a). Preferably, 5 to 75 mol% is further preferred.

The resin (a) may contain one type of repeating unit (d) alone or two or more types. The content of the repeating unit (d) (which is a total when it contains a plurality of kinds) is, for example, 0 to 40 mol%, preferably 0 to 30 mol%, based on all the repeating units in the resin (a). Preferably, 0 to 20 mol% is further preferred.

- Repeating unit (e) - In one embodiment, the resin (a) preferably contains a repeating unit (e) having a phenolic hydroxyl group. As the repeating unit (e) having a phenolic hydroxyl group, a repeating unit represented by the following formula (1) is preferred.

[Chemical Formula 11]

Formula (1), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. R ₁₃ represents a hydrogen atom, a halogen atom or a monovalent organic group, or is a single bond or an alkyl group and is bonded to L or Ar in the formula to form a ring. L represents a single bond or a divalent linking group. Ar represents an aromatic ring group. n represents an integer of 1 or more.

The halogen atom represented by R ₁₁ , R ₁₂ and R ₁₃ in the formula (1) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

Examples of the monovalent organic group represented by R ₁₁ , R ₁₂ and R ₁₃ include an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, and a cyano group. The alkyl group of R ₁₁ , R ₁₂ and R ₁₃ preferably includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a hexyl group, and a 2- which may have a substituent. An alkyl group having a carbon number of 20 or less, such as an ethylhexyl group, an octyl group or a dodecyl group. In one embodiment, the alkyl group represented by R ₁₁ , R ₁₂ and R ₁₃ is preferably an alkyl group having 8 or less carbon atoms, more preferably an alkyl group having 3 or less carbon atoms.

The cycloalkyl group as R ₁₁ , R ₁₂ and R ₁₃ may be a monocyclic type or a polycyclic type. Preferable examples thereof include a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent. As the alkyl group contained in R _11, R ₁₂ and R ₁₃ of the alkoxycarbonyl group is the above R _11, R _12, and R ₁₃ are the same alkyl groups are preferred.

Each of the above groups represented by R ₁₁ , R ₁₂ and R ₁₃ may have a substituent. Preferred examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and a sulfur. The ether group, the mercapto group, the decyloxy group, the alkoxycarbonyl group, the cyano group, the nitro group and the like have a carbon number of the substituent of 8 or less.

The alkyl group having a substituent may, for example, be a halogenated alkyl group, and a fluorinated alkyl group (for example, CF ₃ ) is preferred.

The divalent linking group represented by L may, for example, be an ester bond, -CONR ₆₄ (R ₆₄ represents a hydrogen atom or an alkyl group), an alkylene group or an extended aryl group, or any selected from the group consisting of More than 2 combinations.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a n-butyl group which may have a substituent. An alkyl group having a carbon number of 20 or less, such as a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms. In one form, -CONR ₆₄ - is -CONH- is preferred.

Examples of the alkylene group represented by L include those having 1 to 8 carbon atoms such as a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a octyl group. The alkylene group may have a substituent. The extended aryl group represented by L is preferably a aryl group having 6 to 10 carbon atoms, and specific examples thereof include a stretching phenyl group and the like.

In one embodiment of the invention, L is a single bond, an ester bond or -CONH- is preferred, a single bond or an ester bond is more preferred, and a single bond is particularly preferred.

Examples of the aromatic ring group represented by Ar include an aromatic hydrocarbon ring having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring, or a thiophene ring, a furan ring, and a pyrrole ring. a heterocyclic aromatic heterocyclic ring such as a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring or a thiazole ring. Among them, from the viewpoint of analytical properties, a benzene ring or a naphthalene ring is preferred, and a benzene ring is preferred.

These aromatic rings may have a substituent. Preferred examples of the substituent include the above-mentioned alkyl group represented by R ₁₁ , R ₁₂ and R ₁₃ ; methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group; An alkoxy group such as a butoxy group; an aryl group such as a phenyl group; and the like.

n represents an integer of 1 or more, preferably an integer of 2 or more and 5 or less, more preferably 2 or 3. Specific examples of the repeating unit (e) are shown below, but the present invention is not limited thereto. In the formula, R represents a hydrogen atom or a methyl group, and a represents 1 or 2.

[Chemical Formula 12]

The resin (a) may contain one type of repeating unit (e) alone or two or more types. The content of the repeating unit (e) (the total content when two or more kinds are contained) is relative to all of the resin (a) from the viewpoints of the reactivity of the resin (a) and the ability to inhibit the diffusion of the acid. The repeating unit is preferably from 5 to 90 mol%, more preferably from 10 to 70 mol%, even more preferably from 20 to 40 mol%.

- Repeating unit (f) - In one embodiment, the resin (a) further preferably contains a repeating unit (f) having a lactone structure. The sensitivity is further improved by including the repeating unit (f) having a lactone structure.

As the lactone group, any group can be used as long as it contains a lactone structure, preferably a group having a 5- to 7-membered ring lactone structure, and a double-ring structure and a snail in a 5- to 7-membered ring lactone structure. It is preferred that the form of the ring structure is fused with other ring structures. It is more preferable to have a repeating unit having a group having a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-17). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are those represented by the formulae (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14). group.

[Chemical Formula 13]

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

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

[Chemical Formula 14]

In the formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. ₀ of Rb as alkyl group may have a substituent, Rb ₀ may have as the preferred substituents may include a hydroxyl group, a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It is preferred that Rb ₀ is a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, a carbonyl group, a carboxyl group or a divalent group obtained by combining the same. A single bond, a link represented by -Ab ₁ -CO ₂ - is preferred. Ab ₁ is a linear or branched alkyl, monocyclic or polycyclic cycloalkyl group, preferably methylene, ethyl, cyclohexyl, an adamantyl, or Norbornylene group. .

V represents a group represented by any one of the above formulae (LC1-1) to (LC1-17). The repeating unit containing a group having a lactone structure usually has an optical isomer, and any one of the optical isomers may be used. Further, one type of optical isomer may be used alone, or a plurality of kinds of optical isomers may be used in combination. When one optical isomer is mainly used, the optical purity (ee) is preferably 90 or more, and more preferably 95 or more.

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

(wherein Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .)

(wherein Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .)

The content of the repeating unit (f) having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, based on all the repeating units in the resin (a), further preferably 5 to 20 mol%.

- Repeating unit containing an organic group having a polar group - The resin (a) can further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, substrate adhesion and developer affinity are improved. As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diadamantyl group or a norbornyl group is preferred. As the polar group, a hydroxyl group or a cyano group is preferred. Specific examples of the repeating unit having a polar group are given below, but the present invention is not limited thereto.

[Chemical Formula 17]

When the resin (a) has a repeating unit containing an organic group having a polar group, the content thereof is preferably from 1 to 30 mol%, more preferably from 5 to 25, based on all the repeating units in the resin (a). The molar % is further preferably 5 to 20 mol%.

- the repeating unit having a photoacid generating group - the resin (a) can further comprise a repeating unit having a group (photoacid generating group) which generates an acid by irradiation with actinic rays or radiation as a repeating unit other than the above . In this case, it is considered that the repeating unit having a photoacid generating group corresponds to a compound (B) which generates an acid by irradiation with actinic rays or radiation, which will be described later. As such a repeating unit, for example, a repeating unit represented by the following formula (4) can be given.

[Chemical Formula 18]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site in which an acid is generated in a side chain by decomposition of actinic rays or radiation.

Examples of the repeating unit represented by the formula (4) include repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, the contents of which are incorporated herein.

When the resin (a) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably from 1 to 40 mol% based on all the repeating units in the resin (a). More preferably, it is 5 to 35 mol%, and further preferably 5 to 30 mol%.

The resin (a) can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a polymerization method in which a monomer species and a starter are dissolved in a solvent and heated to carry out polymerization is added, and a monomer is added dropwise to the heating solvent for 1 to 10 hours. The dropwise addition polymerization method of the solution of the initiator is preferred, and the dropwise addition polymerization method is preferred. The resin (A) is obtained by blending N or more (N is an integer of 2 or more) resin (a).

Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and ester solvents such as ethyl acetate; a guanamine solvent such as methyl methamine or dimethyl acetamide; a sensitizing ray-sensitive or radiation-sensitive resin of the present invention dissolved in propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone described later Solvent of matter; etc. It is preferred to carry out polymerization using a solvent similar to the solvent used in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation of fine particles during storage can be suppressed.

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

The purification can be carried out by a usual method such as liquid-liquid extraction in which residual monomers and oligomer components are removed by washing with water and a suitable solvent; and extraction and removal of a solution such as ultrafiltration of a specific molecular weight or less is carried out. a purification method; a reprecipitation method for removing a residual monomer or the like by solidifying a resin in a poor solvent by dropping a resin solution into a poor solvent; and purifying the solidified state by filtration of the filtered resin slurry by using a poor solvent method.

The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15,000, as measured by a GPC method. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated.

Another preferred form of the weight average molecular weight of the resin (A) is a polystyrene equivalent value of 3,000 to 9,500 as measured by a GPC method. By setting the weight average molecular weight to 3,000 to 9,500, it is possible to particularly suppress the resist residue (hereinafter also referred to as "scum"), and it is possible to form a more favorable pattern.

The degree of dispersion (molecular weight distribution) of the resin (A) is usually from 1 to 5, and is preferably from 1 to 3, more preferably from 1.2 to 3.0, particularly preferably from 1.2 to 2.0. The smaller the degree of dispersion, the more excellent the resolution and the resist shape, and the smoothness of the side walls of the resist pattern and the excellent roughness.

The weight average molecular weight of the resin (a) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15,000, as a polystyrene equivalent value measured by a GPC method. The degree of dispersion (molecular weight distribution) of the resin (a) is usually from 1 to 5, and is preferably from 1 to 3, more preferably from 1.2 to 3.0, particularly preferably from 1.2 to 2.0.

In the sensitizing ray-sensitive or radiation-sensitive resin composition, the content of the resin (A) is preferably from 50 to 99.9% by mass, more preferably from 60 to 99.0% by mass, based on all the solid components. Further, in the sensitized ray-sensitive or radiation-sensitive resin composition, the resin (A) may be used alone or in combination of plural kinds.

Specific examples of the resin (a) and the resin (A) include, for example, the resins described in paragraphs [0656] to [0696] of JP-A-2014-167579 (Ab-). 1) ~ (Ab-311), these contents are incorporated in the present specification.

[Chemical Formula 19]

<(B) Compound which generates an acid by irradiation with actinic rays or radiation> The sensitized ray-sensitive or radiation-sensitive resin composition of the embodiment of the present invention contains an acid generated by irradiation with actinic rays or radiation. Compound (hereinafter also referred to as "photoacid generator "PAG: Photo Acid Generator" or "compound (B)").

The photoacid generator may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, it is also possible to use both the form of the low molecular compound and the form incorporated in a part of the polymer. When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or may be incorporated into a resin different from the resin (A).

For the purpose of adjusting the cross-sectional shape of the pattern, the number of fluorine atoms in the acid generator is appropriately adjusted. By adjusting the fluorine atoms, the surface bias of the acid generator in the resist film can be controlled. The more fluorine atoms the acid generator has, the more it deviates from the surface. In the present invention, the photoacid generator is preferably in the form of a low molecular compound.

The photoacid generator is not particularly limited as long as it is known, and an organic acid such as a sulfonic acid or a bis(alkyl sulfonate) is produced by irradiation with actinic rays or radiation, preferably an electron beam or extreme ultraviolet rays. A compound of at least any one of fluorenyl imide or tris(alkylsulfonyl)methide is preferred. More preferably, the compounds represented by the following formulae (ZI), (ZII), and (ZIII) can be mentioned.

[Chemical Formula 20]

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually from 1 to 30, preferably from 1 to 20. Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Group as R ₂₀₁ ~ R ₂₀₃ are bonded to form 2's can include alkylene (e.g., stretch-butyl, pentyl extension). Z ^- represents a non-nucleophilic anion (an anion having a significantly lower ability to cause a nucleophilic reaction).

Examples of the non-nucleophilic anion include a sulfonic acid anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion, etc.), a carboxylic acid anion (an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and the like). An aralkylcarboxylic acid anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion, or the like.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of 3 ～30 cycloalkyl.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group or a naphthyl group.

The alkyl group, the cycloalkyl group and the aryl group mentioned above may have a substituent. Specific examples thereof include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably a carbon number). 3 to 15), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyl group. An oxy group (preferably having a carbon number of 2 to 7), an alkylthio group (preferably having a carbon number of 1 to 15), an alkylsulfonyl group (preferably having a carbon number of 1 to 15), and an alkylimidosulfonyl group. a base (preferably having a carbon number of 1 to 15), an aryloxysulfonyl group (preferably having a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), and a cycloalkane. An aryloxysulfonyl group (preferably having a carbon number of 10 to 20), an alkoxyalkoxy group (preferably having a carbon number of 5 to 20), a cycloalkyl alkoxy alkoxy group (preferably a carbon number) 8 to 20) and so on. The aryl group and the ring structure of each group may further be an alkyl group (preferably having a carbon number of 1 to 15) as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group or a naphthyl group. Base. Examples of the sulfonyl quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxy group. A sulfonyl group or the like, a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Further, the alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases. Examples of the other non-nucleophilic anion include phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and cesium fluoride (for example, SbF ₆ ^- ).

As a non-nucleophilic anion, an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and a double substituted with an alkyl group via a fluorine atom A (alkylsulfonyl) quinone imine anion and a tri(alkylsulfonyl)methide anion having an alkyl group substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion (more preferably a carbon number of 4 to 8), a benzenesulfonic acid anion having a fluorine atom, and still more preferably a nonafluorobutanesulfonic acid anion. Perfluorooctanesulfonate anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

From the viewpoint of acid strength, in order to increase the sensitivity, it is preferred that the pKa of the generated acid is -1 or less.

Further, examples of the non-nucleophilic anion include an anion represented by the following formula (AN1).

[Chemical Formula 21]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when plural or plural, R ¹ and R ² may be the same or different. L represents a divalent linking group, and L may be the same or different when there are a plurality of plural. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in further detail.

The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 4. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , and CH. ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein a fluorine atom or CF ₃ is preferred. In particular, it is preferred that both of the Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferred. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C _{7 .} F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F _7. CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein CF ₃ is preferred.

R ¹ and R ^{2 are} preferably a fluorine atom or CF ₃ .

x is preferably from 1 to 10, more preferably from 1 to 5. y is preferably 0 to 4, and 0 is more preferred. z is preferably 0 to 5, and more preferably 0 to 3. The divalent linking group of L is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, and extens. A cycloalkyl group, an alkenyl group or a linking group obtained by linking a plurality of these groups, and the like, and a linking group having a total carbon number of 12 or less is preferred. Among them, -COO-, -OCO-, -CO-, -O- are preferred, and -COO- and -OCO- are more preferred.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only aromatic but also aromatic) Ethnicity) and so on.

As the alicyclic group, it may be a monocyclic ring or a polycyclic ring, a cyclopentyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, a cycloalkyl group, a decyl group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group or a tetracyclic decyl group. A polycyclic cycloalkyl group such as a dialkyl group or an adamantyl group is preferred. Among them, an alicyclic group having a large volume structure having a carbon number of 7 or more, such as a thiol group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group or an adamantyl group, can suppress the film in the post-exposure heating process. The diffusibility is preferable from the viewpoint of improving the MEEF (mask error enhancement factor).

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, those derived from a furan ring, a thiophene ring, and a pyridine ring are preferred.

In addition, as a cyclic organic group, a lactone structure is mentioned, and a lactone structure represented by the above-mentioned general formula (LC1-1) - (LC1-17) is mentioned as a specific example.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be any of a straight chain, a branch, and a ring, preferably a carbon number of 1 to 12), and a cycloalkyl group ( It may be any one of a monocyclic ring, a polycyclic ring and a spiro ring, preferably having a carbon number of 3 to 20, an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group or a decylamino group. A urethane group, a urea group, a thioether group, a sulfonylamino group, a sulfonate group or the like. Further, the carbon constituting the cyclic organic group (carbon which contributes to ring formation) may be a carbonyl carbon.

_Examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group. It is preferred that at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group, and all three are aryl groups. The aryl group may be a heteroaryl group such as a hydrazine residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group. The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, an isopropyl group or an n-butyl group. The cycloalkyl group is more preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. These groups may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably a carbon number). 3 to 15), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyl group. The oxy group (preferably having a carbon number of 2 to 7) or the like is not limited thereto.

Preferred examples of the anion represented by the formula (AN1) include the followings. In the following examples, A represents a cyclic organic group. SO ₃ -CF ₂ -CH ₂ -OCO-A, SO ₃ -CF ₂ -CHF-CH ₂ -OCO-A, SO ₃ -CF ₂ -COO-A, SO ₃ -CF ₂ -CF ₂ -CH ₂ - A, SO ₃ -CF ₂ -CH(CF ₃ )-OCO-A

In the general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group. The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R _{207 is the same} as the aryl group described as the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI).

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent, the aforementioned compounds also include (ZI) in the R ₂₀₁ ~ R ₂₀₃ is an aryl group, an alkyl group, a cycloalkyl group who may have.

Z ^- represents a non-nucleophilic anion, and may be the same as the non-nucleophilic anion of Z ^- in the general formula (ZI).

In the present invention, suppressing generation of acid during exposure to parse the diffusion of the non-exposed portion becomes good viewpoint of the photoacid generator is irradiated by an electron beam or extreme ultraviolet generated volume 130Å ³ A compound of (10 Å = 1 nm) or more of an acid (more preferably a sulfonic acid) is preferred, and a compound having a volume of 190 Å ³ or more (more preferably a sulfonic acid) is more preferable, and a volume of 270 Å ³ or more is produced. size acids (more preferably a sulfonic acid) is further preferred compound of the generated volume size than 400Å ³ acid (more preferably sulfonic acid) the compound is particularly preferred. Wherein, the sensitivity and the solubility in a coating solvent viewpoint of the volume is 2000Å ³ or less is preferred, 1500Å ³ or less is further preferred. The value of the above volume was determined using "WinMOPAC" manufactured by Fujitsu Limited. That is, the chemical structure of the acid of each example is first input, and then, the structure is taken as the initial structure, and the most stable stereo configuration of each acid is determined by using the molecular force field calculation of the MM3 method, and then, the most The stable stereo configuration is performed using the molecular orbital calculation of the PM3 method, whereby the "accessible volume" of each acid can be calculated.

Japanese Patent Application Publication No. 2014-41328 [0368] to [0377], and Japanese Patent Application Publication No. 2013-228681 [0240] to [0262] (corresponding U.S. Patent Application Publication No. 2015) [0339] of the specification of /004533, the contents of which are incorporated herein by reference. Moreover, as a preferable specific example, the following compounds are mentioned, but it is not limited to these.

[Chemical Formula 22]

[Chemical Formula 23]

[Chemical Formula 24]

[Chemical Formula 25]

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

The content of the photoacid generator in the sensitized ray-sensitive or radiation-sensitive resin composition is preferably from 0.1 to 50% by mass, more preferably from 5 to 50% by mass, based on the total solid content of the composition. Good is 8 to 40% by mass. In particular, in order to achieve high sensitivity and high resolution in electron beam or extreme ultraviolet light exposure, the content of the photoacid generator is preferably higher, more preferably 10 to 40% by mass, most preferably 10 to 35 mass. %.

<Solvent> The photosensitive ray-sensitive or radiation-sensitive resin composition used in the present invention preferably contains a solvent (also referred to as "resist solvent"). Isomers (compounds of the same atomic number and different structures) may be included in the solvent. Further, the isomer may be contained alone or in combination of plural kinds. The solvent comprises (M1) propylene glycol monoalkyl ether carboxylate and is selected from the group consisting of (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone At least one of at least one of the groups consisting of alkylene carbonates is preferred. Further, the solvent may further contain components other than the components (M1) and (M2).

As the component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred, and propylene glycol monomethyl ether acetate is preferred. Ester is especially good.

As the component (M2), the following are preferred. As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferred. As the lactate, ethyl lactate, butyl lactate or propyl lactate is preferred.

As acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetic acid 3- Methoxybutyl ester is preferred. Butyl butyrate is also preferred.

As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred. As a chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenyl Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetonyl acetone, ionone, diacetone alcohol, acetamethanol, acetophenone, methyl naphthyl ketone or methyl amyl Ketones are preferred. As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferred.

As the lactone, γ-butyrolactone is preferred. As the alkylene carbonate, propyl carbonate is preferred.

As component (M2), propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, γ-butyrolactone or Propyl carbonate is more preferred.

In addition to the above components, an ester solvent having 7 or more carbon atoms (preferably 7 to 14 and more preferably 7 to 12, more preferably 7 to 10) and having 2 or less carbon atoms is used.

Preferable examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, and hexyl acetate. Amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., are particularly preferably used with isoamyl acetate.

As the component (M2), it is preferred to use a flash point (hereinafter, also referred to as fp) of 37 ° C or higher. As such a component (M2), propylene glycol monomethyl ether (fp: 47 ° C), ethyl lactate (fp: 53 ° C), ethyl 3-ethoxypropionate (fp: 49 ° C), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), amyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone (fp: 101 ° C) or propyl carbonate (fp: 132 ° C) is preferred. Among these, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone is further preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. Here, the "flash point" means a value described in the catalogue of the reagent product of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

The solvent contains the component (M1) as a preferred one. The solvent includes substantially only the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is further preferred that both the solvent-containing component (M1) and the component (M2) are contained.

The mass ratio of the component (M1) to the component (M2) is preferably in the range of 100:0 to 15:85, more preferably in the range of 100:0 to 40:60, and in the range of 100:0 to 60:40. The scope is further preferred. That is, the solvent includes only the component (M1) or both the component (M1) and the component (M2), and the mass is preferably as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and still more preferably 60/40 or more. According to this configuration, the number of development defects can be further reduced.

Further, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.

As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably in the range of 5 mass% to 30 mass% with respect to the total amount of the solvent.

The content of the solvent in the sensitizing ray-sensitive or radiation-sensitive resin composition is preferably such that the solid content concentration of all the components is from 0.5 to 30% by mass, more preferably from 1 to 20% by mass. In this way, the coatability of the sensitizing ray-sensitive or radiation-sensitive resin composition can be further improved.

The solid content concentration of the sensitizing ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted for the purpose of adjusting the thickness of the resist film to be formed.

<Basic compound> The photosensitive ray-sensitive or radiation-sensitive resin composition of the embodiment of the present invention contains a basic compound in order to reduce the change in performance due to the elapse of time from exposure to heating. The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E).

[Chemical Formula 26]

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

The alkyl group is preferably an alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represent an alkyl group having 1 to 20 carbon atoms. The alkyl group in the above formulae (A) and (E) is preferably unsubstituted.

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

Further preferred examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

As the amine compound, an amine compound of a 1, 2, or 3 type can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The amine compound is preferably a tertiary amine compound. The amine compound is a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (preferably, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom. The carbon number 6 to 12) may also be bonded to a nitrogen atom.

Further, the amine compound preferably has an oxygen atom in the alkyl chain to form an oxyalkylene group. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred, and further preferably an oxygen-extended ethyl group.

As the ammonium salt compound, an ammonium salt compound of a 1, 2, 3, or 4 grade, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The ammonium salt compound is preferably a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom. It can also be bonded to a nitrogen atom for a carbon number of 6 to 12).

The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxygen-extended alkyl group. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, oxygen-extended ethyl (-CH ₂ CH ₂ O-) or oxygen-extended propyl (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) Preferably, it is further preferably an oxygen-extended ethyl group.

The anion of the ammonium salt compound may, for example, be a halogen atom, a sulfonate, a borate or a phosphate. Among them, a halogen atom or a sulfonate is preferred. As the halogen atom, a chloride, a bromide or an iodide is particularly preferable, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable.

The phenoxy-containing amine compound can be reacted by heating a phenoxy group-containing amine or a quaternary amine and a haloalkyl ether, and then adding sodium hydroxide, potassium hydroxide, tetraalkylammonium, or the like. After the strong alkali aqueous solution is extracted with an organic solvent such as ethyl acetate or chloroform. Alternatively, it may be added to a strong alkali aqueous solution such as sodium hydroxide, potassium hydroxide or tetraalkylammonium by heating a primary amine or a secondary amine and a halogenated alkyl ether having a phenoxy group at the terminal. After that, it is obtained by extraction with an organic solvent such as ethyl acetate or chloroform.

Specific examples of the basic compound described above can be referred to, for example, in paragraphs 0237 to 0294 of International Publication No. 2015/178375, the contents of which are incorporated herein by reference. (a compound (PA) having a proton-receptive functional group and decomposing by actinic radiation or radiation to cause a decrease in proton acceptor property or a compound which is changed from proton acceptor to acid) sensitized ray or The radiation sensitive linear resin composition may further comprise a compound having a proton-receptive functional group and decomposing by actinic radiation or radiation to cause a decrease in proton acceptor property, disappearance, or a compound which is changed from proton acceptor to acid. [hereinafter, also referred to as a compound (PA)] as a basic compound.

The proton acceptor functional group refers to a functional group having a group or an electron capable of electrostatically interacting with a proton, and for example, a functional group having a macrocyclic structure such as a cyclic polyether, or having a function of not contributing to π conjugate. The functional groups of the nitrogen atom of the electron pair are not shared. The nitrogen atom having an unshared electron pair which does not contribute to π conjugate means, for example, a nitrogen atom having a partial structure represented by the following general formula.

[Chemical Formula 27]

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

The compound (PA) is decomposed by irradiation with actinic rays or radiation to cause a decrease in proton acceptor property, disappearance, or a compound which is acidic by proton acceptability. Here, the decrease or disappearance of proton acceptor or the change from proton acceptor to acid refers to a change in proton acceptor caused by proton addition in a proton acceptor functional group, specifically, When a proton adduct is formed from a compound (PA) having a proton-receptive functional group and a proton, the equilibrium constant in the chemical equilibrium is reduced.

Specific examples of the compound (PA) include the following compounds. In addition, as a specific example of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP-A-2014-41328 and paragraphs 0108 to 0116 of JP-A-2014-134686 can be used. Into this specification.

[Chemical Formula 28]

[Chemical Formula 29]

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

The amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass based on the solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition.

The ratio of the acid generator to the basic compound used in the composition is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. In other words, from the viewpoint of the sensitivity and the resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution caused by the thickening of the resist pattern after the post-exposure heat treatment. 300 or less is preferred. The acid generator/basic compound (mole ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

As the basic compound, for example, a compound (an amine compound, a amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, or the like) described in paragraphs 0140 to 0144 of JP-A-2013-11833 can be used. The content is incorporated into this specification.

<Hydrophilic Resin> The sensitizing ray-sensitive or radiation-sensitive resin composition of the embodiment of the present invention may further contain a hydrophobic resin different from the resin (A).

The hydrophobic resin is preferably designed to be biased on the surface of the resist film, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it is not helpful to uniformly mix the polar/nonpolar substance.

Examples of the effect of adding the hydrophobic resin include control of the static/dynamic contact angle of the surface of the resist film with respect to water, suppression of degassing, and the like.

It is preferable that any one or more of the "perfluoro atom", the "deuterium atom", and the "CH ₃ partial structure contained in the side chain portion of the resin" of the hydrophobic resin is preferable from the viewpoint of the partiality of the film surface layer. It is further preferable to have two or more types. Further, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be provided in the main chain of the resin or may be substituted in the side chain.

When the hydrophobic resin contains a fluorine atom and/or a ruthenium atom, the above-mentioned fluorine atom and/or ruthenium atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

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

An alkyl group having a fluorine atom (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 4) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a fluorine atom Substituents.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may further have a substituent other than a fluorine atom.

The aryl group having a fluorine atom may be substituted with a fluorine atom by at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group, and may further have a substituent other than a fluorine atom.

Examples of the repeating unit having a fluorine atom or a ruthenium atom include those exemplified in paragraph 0519 of US2012/0251948A1.

Further, as described above, it is also preferred that the hydrophobic resin contains a CH ₃ moiety structure in the side chain portion. Wherein the side chain portion of the hydrophobic resin has a partial structure comprising the CH ₃ group, a propyl group or the like having the partial structure ₃ CH.

On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, α-methyl group having a repeating unit having a methacrylic acid structure) is biased against the surface of the hydrophobic resin due to the influence of the main chain. help small, and therefore deemed not included in the present invention, those portions of the structure CH _3.

For the hydrophobic resin, the descriptions of [0348] to [0415] of JP-A-2014-010245 can be referred to, and the contents are incorporated in the specification of the present application. In addition, as described in the above-mentioned Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei.

When the photosensitive ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin, the content of the hydrophobic resin is 0.01 to 20% by mass based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. Preferably, it is more preferably 0.01 to 10% by mass, further preferably 0.05 to 8% by mass, and particularly preferably 0.5 to 5% by mass.

<Interacting Agent> The sensitizing ray-sensitive or radiation-sensitive resin composition of the embodiment of the present invention may further contain a surfactant. When an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used by using a surfactant, a pattern having excellent adhesion and less development defects can be formed with good sensitivity and resolution.

As the surfactant, fluorine-based and/or lanthanoid surfactants are particularly preferred.

Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in [0276] of the specification of U.S. Patent Application Publication No. 2008/0248425. Further, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); Megafac F171, F173, F176, F189, F113, F110, F177, F120 can be used. Or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); Troy Sol S-366 (manufactured by Troy Chemical Industries Inc.); GF -300 or GF-150 (manufactured by TOAGOSEI CO., LTD.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the lanthanoid surfactant.

Further, in addition to the well-known ones as described above, the surfactant may be used by a telomerization method (also referred to as a telomer method) or an oligomerization method ( The fluoroaliphatic compound produced by the oligomer method is also synthesized. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

Further, a surfactant other than the fluorine-based and/or lanthanum-based surfactants described in [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 may be used. These surfactants may be used alone or in combination of two or more.

When the sensitizing ray-sensitive or radiation-sensitive resin composition contains a surfactant, the content thereof is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass based on the total solid content of the composition.

<Other Additives> The sensitizing ray-sensitive or radiation-sensitive resin composition of the embodiment of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorbing agent, and/or promote solubility in a developing solution. A compound (for example, a phenol compound having a molecular weight of 1,000 or less or an alicyclic or aliphatic compound containing a carboxyl group).

The photosensitive ray-sensitive or radiation-sensitive resin composition may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" means a compound having a molecular weight of 3,000 or less which is reduced in solubility in an organic developing solution by decomposition of an acid. Next, an embodiment of the pattern forming method of the present invention will be described.

[Pattern Forming Method] The pattern forming method of the present invention comprises the following processes: a sensitizing ray-sensitive or radiation-sensitive film forming process for forming a sensitizing ray property comprising the above-described sensitized ray-sensitive or radiation-sensitive resin composition of the present invention or a radiation sensitive linear film; an exposure process for exposing the sensitizing ray-sensitive or radiation-sensitive film; and a developing process for developing the exposed sensitized ray-sensitive or radiation-sensitive film by a developing solution.

<Photosensitizing ray-sensitive or radiation-sensitive film forming process> The sensitizing ray-sensitive or radiation-sensitive film forming process uses a sensitizing ray-sensitive or radiation-sensitive resin composition to form a sensitized ray-sensitive or radiation-sensitive film (typical) The process of the resist film can be carried out, for example, by the following method.

In order to form a sensitized ray-sensitive or radiation-sensitive film on a substrate by using a sensitizing ray-sensitive or radiation-sensitive resin composition, the above components are dissolved in a solvent to prepare a sensitized ray-sensitive or radiation-sensitive resin composition, according to After the filter is filtered, it is applied to the substrate. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less.

The sensitizing ray-sensitive or radiation-sensitive resin composition is applied to a substrate (for example, ruthenium or ruthenium dioxide coating) used in the production of an integrated circuit element by a suitable coating method such as a spinner. Then, it is dried to form a sensitizing ray-sensitive or radiation-sensitive film. Various base films (inorganic film, organic film, antireflection film) can be formed under the photosensitive ray or radiation sensitive film as needed.

As the drying method, a method of drying by heating is generally used. The heating can be performed by a mechanism provided in a general exposure/developer, or can be performed using a heating plate or the like. It is preferably carried out at a heating temperature of 80 to 150 ° C, more preferably at 80 to 140 ° C, and still more preferably at 80 to 130 ° C. The heating time is preferably from 30 to 1,000 seconds, more preferably from 60 to 800 seconds, and further preferably from 60 to 600 seconds.

The film thickness of the sensitizing ray-sensitive or radiation-sensitive film is generally 200 nm or less, preferably 100 nm or less.

In order to analyze, for example, a 1:1 line and a space pattern having a line width of 20 nm or less, the film thickness of the photosensitive ray-sensitive or radiation-sensitive film formed is preferably 50 nm or less. When the film thickness is 50 nm or less, it is more difficult to cause pattern collapse when a developing process to be described later is applied, and more excellent analytical performance can be obtained.

The range of the film thickness is more preferably in the range of 15 nm to 45 nm. When the film thickness is 15 nm or more, sufficient etching resistance can be obtained. The range of the film thickness is more preferably 15 nm to 40 nm. When the film thickness is within this range, it is possible to simultaneously satisfy the etching resistance and the more excellent analytical performance.

Further, in the pattern forming method of the present invention, an upper layer film (top coat layer) may be formed on the upper layer of the sensitized ray-sensitive or radiation-sensitive film. It is preferable that the top coat layer-forming composition is not uniformly mixed with the sensitizing ray-sensitive or radiation-sensitive film, and can be uniformly applied to the upper layer of the sensitizing ray-sensitive or radiation-sensitive film.

<Composition for forming an upper layer film> The composition for forming an upper layer film (a composition for forming a top coat layer) will be described. It is preferable that the top coat layer-forming composition is not uniformly mixed with the sensitizing ray-sensitive or radiation-sensitive film, and can be uniformly applied to the upper layer of the sensitizing ray-sensitive or radiation-sensitive film. The thickness of the top coat layer is preferably from 10 to 200 nm, further preferably from 20 to 100 nm, particularly preferably from 40 to 80 nm. The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method. For example, a top coat layer can be formed based on the description of paragraphs 0072 to 0082 of JP-A-2014-059543.

<Exposure Process> The exposure process is a process of exposing a resist film, and can be performed, for example, by the following method. The actinic radiation or radiation sensitive film formed in the above manner is irradiated with actinic rays or radiation through a predetermined mask. Further, in the irradiation of the electron beam, drawing (direct drawing) without passing through the mask is generally performed.

The actinic ray or radiation is not particularly limited, and is, for example, a KrF excimer laser, an ArF excimer laser, an extreme ultraviolet (EUV), an electron beam (EB, Electron Beam), or the like, an extreme ultraviolet ray or an electron beam. It is especially good. The exposure can be a liquid immersion exposure.

<Roasting> In the pattern forming method of the present invention, it is preferred to perform baking (PEB: Post Exposure Bake) after exposure and before development. The reaction of the exposed portion is promoted by baking, and the sensitivity and pattern shape are further improved. The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C. The heating time is preferably from 30 to 1,000 seconds, more preferably from 60 to 800 seconds, and further preferably from 60 to 600 seconds. The heating can be performed by a mechanism provided in a general exposure/developer, or can be performed using a heating plate or the like.

<Developing Process> The developing process is a process of developing an exposed photosensitive ray-sensitive or radiation-sensitive film using a developing solution. As the developing method, for example, a method of immersing the substrate in a tank filled with the developing solution for a certain period of time (dip method) can be applied, and the developer is deposited on the surface of the substrate by surface tension and static. a method of performing development for a certain period of time (puddle method); a method of spraying a developer onto a surface of a substrate (spray method); and developing at a constant speed on a substrate rotating at a constant speed A method in which a liquid ejecting nozzle performs scanning while continuously ejecting a developing solution (dynamic dispense method). Further, it is also possible to carry out a process of stopping development by replacing the solvent with another solvent after the development process.

The development time is not particularly limited as long as the resin of the exposed portion or the unexposed portion is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 10 to 120 seconds. The temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

(Developing Solution) The developing solution may be an alkali developing solution or a developing solution (organic developing solution) containing an organic solvent. - Alkali-developing solution - The alkali-developing liquid described in the paragraph [0407] of JP-A-2014-041327 is incorporated herein by reference.

Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution for use. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0. As the alkali developer, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide is particularly preferred.

- Organic developing solution - Specific examples of the organic solvent include, for example, the organic solvents described in paragraphs [0409] to [0411] of JP-A-2014-041327, the contents of which are incorporated herein by reference. .

The above organic solvent may be mixed in a plurality of kinds, or may be used in combination with a solvent or water other than the above. However, in order to fully exhibit the effects of the present invention, it is preferred that the water content of the entire developing solution is less than 10% by mass, and it is more preferable that the moisture content is substantially not contained. The concentration of the organic solvent in the developer (total of a plurality of kinds) is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90%. 100% by mass, particularly preferably 95 to 100% by mass. The best is the case where only organic solvents are substantially included. Further, the case where only an organic solvent is substantially included is considered to include a trace amount of a surfactant, an antioxidant, a stabilizer, an antifoaming agent, and the like.

It is also preferred that the developer contains an antioxidant. Thereby, the generation of the oxidizing agent can be suppressed, and the content of the oxidizing agent can be further reduced. As the antioxidant, a known one can be used, but when it is used for a semiconductor, an amine-based antioxidant or a phenol-based antioxidant is preferably used.

The content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and even more preferably 0.0001 to 0.01% by mass, based on the total mass of the developer. When it is 0.0001% by mass or more, a more excellent oxidation resistance effect can be obtained, and when it is 1% by mass or less, the development residue can be suppressed.

The developer may contain a basic compound, and specifically, the same as the basic compound which may be contained in the resist varnish.

The developer may contain a surfactant. When the developer contains a surfactant, the wettability of the sensitized ray-sensitive or radiation-sensitive film is improved, and development is performed more efficiently. As the surfactant, the same surfactant as that which can be contained in the resist composition can be used.

When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, still more preferably 0.01 to 0.5% by mass, based on the total mass of the developer. .

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 surface tension to deposit the developer on the surface of the substrate and allowing it to stand for a certain period of time can be applied. a method of developing (dipping method); a method of spraying a developer onto a surface of a substrate (spray method); and continuously ejecting a developing solution while ejecting a developing solution at a constant speed on a substrate rotating at a constant speed Method (dynamic allocation method).

Further, it is also possible to carry out a process of stopping development by replacing the solvent with another solvent after the development process. The development time is not particularly limited and is usually 10 to 300 seconds, preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

As the developing solution used in the developing process, both development using a developing solution containing an organic solvent and development using an alkali developing solution can be performed (so-called double development can be performed). In the pattern forming method of the present invention, the developer may include the above-described treatment liquid of the present invention, and in this case, the treatment liquid is preferably a developer.

<Roughing Process> The pattern forming method of the embodiment of the present invention may include a rinsing process after the developing process. In the rinsing process, the developed wafer is cleaned using a rinsing liquid. The method of the cleaning treatment is not particularly limited. For example, it can be applied to a method of continuously discharging a rinse liquid on a substrate rotating at a constant speed (rotary discharge method), and immersing the substrate in a tank filled with a rinse liquid for a certain period of time (dipping method) A method (spray method) or the like for spraying a rinse liquid onto the surface of the substrate, wherein the cleaning treatment is performed by a rotary discharge method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm to remove the rinse liquid from the substrate. The rinsing time is not particularly limited, and is preferably from 10 seconds to 300 seconds, more preferably from 10 seconds to 180 seconds, and most preferably from 20 seconds to 120 seconds. The temperature of the rinse liquid is preferably 0 to 50 ° C, and more preferably 15 to 35 ° C.

Further, the treatment for removing the developer or the rinse liquid adhering to the pattern by the supercritical fluid can be performed after the development treatment or the rinsing treatment. Further, after the development treatment or the rinsing treatment or the treatment using the supercritical fluid, the heat treatment may be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 to 160 °C. The heating temperature is preferably from 50 to 150 ° C, and most preferably from 50 to 110 ° C. The heating time is not particularly limited as long as a good resist pattern can be obtained, and is usually 15 to 300 seconds, preferably 15 to 180 seconds.

(Rinsing Liquid) The rinsing liquid used in the rinsing treatment performed after the developing process using the alkali developing solution can be used by using pure water and adding an appropriate amount of a surfactant.

As the rinsing liquid used in the rinsing treatment after the development process using the organic developing solution, a rinsing liquid containing an organic solvent is preferably used, and the organic solvent is selected from the group consisting of a hydrocarbon solvent, a ketone solvent, and an ester system. At least one organic solvent selected from the group consisting of a solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferred.

The organic solvent contained in the rinsing liquid is preferably at least one selected from the group consisting of a hydrocarbon solvent, an ether solvent, and a ketone solvent, and more preferably at least one selected from the group consisting of a hydrocarbon solvent and an ether solvent. As the organic solvent contained in the rinse liquid, an ether solvent can also be preferably used.

Examples of the ether solvent include, in addition to the glycol ether solvent containing a hydroxyl group, non-hydroxyl groups such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. A glycol ether solvent, an anionic ether solvent such as anisole or phenethyl ether, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, ring Cycloaliphatic ether of pentyl isopropyl ether, cyclopentyl second butyl ether, cyclopentyl third butyl ether, cyclohexyl isopropyl ether, cyclohexyl second butyl ether, cyclohexyl third butyl ether An ether solvent, or a non-cyclic aliphatic ether solvent having a linear alkyl group such as di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether or di-n-hexyl ether, diisohexyl ether, methyl Isoamyl ether, ethyl isoamyl ether, propyl isoamyl ether, diisoamyl ether, methyl isobutyl ether, ethyl isobutyl ether, propyl isobutyl ether, diisobutyl An acyclic aliphatic ether solvent having a branched alkyl group such as ether, diisopropyl ether, ethyl isopropyl ether, methyl isopropyl ether or diisohexyl ether. Among them, from the viewpoint of in-plane uniformity of the wafer, an acyclic aliphatic ether solvent having 8 to 12 carbon atoms is preferable, and an acyclic fat having a branched alkyl group having 8 to 12 carbon atoms is more preferable. A family ether solvent. Particularly preferred is diisobutyl ether or diisoamyl ether or diisohexyl ether.

Specific examples of the organic solvents are the same as those described in the organic solvent contained in the developer.

The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. When the rinse liquid is a mixed solvent of a plurality of solvents, the vapor pressure as a whole is preferably in the above range. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface can be improved, and the swelling due to the penetration of the rinse liquid can be suppressed, and the dimensional uniformity in the wafer surface can be changed. Good.

The organic solvent contained in the rinsing liquid may be one type or two or more types. When two or more types are contained, a mixed solvent of undecane and diisobutyl ketone, etc. are mentioned, for example.

The rinse solution may contain a surfactant. When the rinse liquid contains a surfactant, the wettability of the resist film is improved, and the rinsing property is improved, so that the generation of foreign matter tends to be suppressed.

As the surfactant, the same surfactant as that used in the sensitizing ray-sensitive or radiation-sensitive resin composition described later can be used.

When the rinse liquid contains a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, still more preferably 0.01 to 0.5% by mass, based on the total mass of the rinsing liquid. .

The rinse solution may contain an antioxidant. The antioxidant which may be contained in the rinsing liquid is the same as the antioxidant which the developing solution may contain. When the rinse liquid contains an antioxidant, the content of the antioxidant is not particularly limited, and is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0.01% by mass, based on the total mass of the rinse liquid. Further preferred.

The process of cleaning using a rinsing liquid may be included after the process of developing using a developing solution containing an organic solvent, but the process of cleaning using a rinsing liquid may not be included from the viewpoint of throughput.

For example, the method of [0014] to [0086] of JP-A-2015-216403 can be referred to as a processing method for the process of cleaning without using a rinsing liquid, and the content is incorporated in the specification of the present application. Further, as the rinse liquid, MIBC (methyl isobutylmethanol) and a liquid (especially butyl acetate) similar to the developer are preferably used.

<Storage container> An organic solvent (also referred to as an "organic treatment liquid") that can be used in a treatment liquid such as a developer or a rinse solution, and is used in a chemically amplified sensitizing ray or a radiation-sensitive linearity having a accommodating portion. It is preferred that the film is formed in a storage container for the organic treatment liquid. As the storage container, for example, the inner wall of the accommodating portion that is in contact with the organic treatment liquid is made of a resin different from any one of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust/metal is applied. It is preferable that the storage container for the organic processing liquid for pattern formation of the photosensitive ray-forming or radiation-sensitive film formed by the metal for elution prevention treatment is preferable. In the accommodating portion of the accommodating container, a predetermined organic solvent used as an organic processing liquid for pattern formation of a sensitizing ray or a radiation sensitive film is stored, and when a pattern of a sensitizing ray or a radiation sensitive film is formed, It is possible to use a person who is discharged from the above-described housing portion.

When the storage container further has a sealing portion for sealing the accommodating portion, the sealing portion is also one or more selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. A resin having a different resin or a metal having a rust preventive/metal elution prevention treatment is preferably formed.

Here, the sealing portion refers to a member capable of blocking the accommodating portion and the outside air, and a spacer, an O-ring, or the like can be preferably used.

A resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

Examples of the perfluoro resin include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), and tetrafluoroethylene. Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride copolymer resin (PCTFE), fluoroethylene resin ( PVF) and so on.

Examples of the particularly preferred perfluororesin include a tetrafluoroethylene resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, and a tetrafluoroethylene-hexafluoropropylene copolymer resin.

Examples of the metal in the metal subjected to the rust preventive/metal elution prevention treatment include carbon steel, alloy steel, nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, and manganese steel. As the rust preventive/metal elution prevention treatment, a film coating technique is preferred.

The film technology is roughly classified into three types: metal coating (various plating), inorganic coating (various passivation treatment, glass, concrete, ceramics, etc.) and organic coating (rustproof oil, paint, rubber, plastic).

As a preferable film technique, surface treatment using an rust preventive oil, a rust preventive, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent can be mentioned.

Among them, various chromate, nitrite, citrate, phosphate, oleic acid, dimer acid, naphthenic acid and other carboxylic acids, metal carboxylic acid soaps, sulfonates, amine salts, esters (higher fatty acid glycerin Corrosion inhibitors such as esters or phosphates, chelating compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and fluororesins The inner liner is preferred. Particularly preferred for phosphate treatment and fluororesin lining.

Moreover, compared with the direct coating treatment, it is not directly rust-proof, but as a treatment method relating to the extension of the rust-preventing period using the coating treatment, the "pretreatment" used as the stage before the rust-preventing treatment is also used. good.

As a specific example of such pretreatment, a treatment for removing various corrosion factors such as chloride or sulfate present on the metal surface by washing or polishing can be preferably used.

Specific examples of the storage container include the following.・FluoroPure PFA composite cylinder manufactured by Entegris, Inc. (liquid inner surface; PFA resin lining) ・Steel can (manufactured inner surface; zinc phosphate coating) manufactured by JFE CONTAINER CO., LTD. In addition, as a storage container which can be used, the container described in Unexamined-Japanese-Patent No. 11-021393 [0013] - [0030], and the container of [0012] - [0024].

In order to prevent malfunction of the liquid chemical pipe and various components (filters, O-rings, hoses, and the like) accompanying the charging of the static electricity and the subsequent electrostatic discharge, a conductive compound may be added to the organic processing liquid. The conductive compound is not particularly limited, and examples thereof include methanol. The amount of addition is not particularly limited, and from the viewpoint of maintaining preferable development characteristics, 10% by mass or less is preferable, and further preferably 5% by mass or less. As the member of the chemical liquid pipe, various pipes made of SUS (stainless steel) or a polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) film subjected to antistatic treatment can be used. As for the filter or the O-ring, polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) which is subjected to antistatic treatment can also be used.

Further, the developer and the rinsing liquid are generally stored in a waste liquid tank through a pipe after use. In this case, when a hydrocarbon-based solvent is used as the rinsing liquid, in order to prevent the resist dissolved in the developing solution from being deposited on the back surface of the wafer or the side surface of the pipe, the solvent in which the resist is dissolved again passes through the pipe. As a method of passing through the piping, a method of cleaning the back surface or the side surface of the substrate by using a solvent dissolved in the resist after washing with the rinse liquid, and discharging it by a resist without contacting the resist may be mentioned. A method in which a solvent is circulated in a pipe.

The solvent in the piping is not particularly limited as long as it can dissolve the resist, and examples thereof include the above organic solvent, and propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monoethyl ether acetate can be used. Propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone Wait. Among them, PGMEA, PGME, and cyclohexanone are preferably used.

The pattern obtained by the pattern forming method of the present invention is used as a mask, and an etching process, ion implantation, or the like is appropriately performed, and a semiconductor fine circuit, a die structure for imprint, a mask, and the like can be manufactured.

The pattern formed by the above method can also be used for guiding pattern formation in DSA (Directed Self-Assembly) (for example, see ACS Nano Vol. 4 No. 8 page 4815 - page 4823). Moreover, the pattern formed by the above-described method can be used as a core material (core) of a spacer process disclosed in Japanese Laid-Open Patent Publication No. Hei No. 3-270227 and No. 2013-164509.

In addition, the procedure for producing a stamping die using the pattern forming method of the present invention is disclosed in, for example, Japanese Patent No. 4109085, JP-A-2008-162101, and "N. Application unfolding - nanoimprinted substrate technology and the latest technology development - edit: Frontier Publishing.

The photomask manufactured by the pattern forming method of the present invention may be a light transmissive mask used in an ArF excimer laser or the like, or may be a light reflective type used in a reflection system lithography using EUV light as a light source. Mask.

Further, the present invention relates to a method of manufacturing an electronic device comprising the above-described pattern forming method of the present invention. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is preferably mounted on an electric and electronic device (home appliance, OA (office appliance), media-related device, optical device, communication device, etc.). [Examples]

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto. [Comparative Examples 1-1 to 1-3: Synthesis of Resin (ab-151)]

[Chemical Formula 30]

15.7 g of the compound (1), 10.6 g of the compound (2), 27.5 g of the compound (3), 19.1 g of the compound (4), and 2.76 g of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 268.9 g of cyclohexanone. 144.8 g of cyclohexanone was placed in a reaction container, and dropwise addition was carried out in a system at 80 ° C for 6 hours under a nitrogen atmosphere. After the reaction solution was stirred with heating for 2 hours, it was naturally cooled to room temperature. The above reaction solution was added dropwise to 3406 g of a mixed solution of methanol and distilled water (methanol/distilled water = 9/1 (mass ratio)), and the polymer was precipitated and filtered. The rinsing of the filtered solid was carried out using a mixed solution of 487 g of methanol and distilled water (methanol/distilled water = 9/1 (mass ratio)). Then, the washed solid was dried under reduced pressure to obtain 56.2 g of a resin (Ab-151). The synthetic resin (ab-151) was synthesized three times in total using the above synthesis method.

The average composition ratio of the obtained three resins (ab-151) (in order from the repeating unit on the left side) is 22/14/30/34, 22/14/28/36, and 18/16/32/34, respectively. At an average target composition ratio of 20/15/30/35, it is difficult to control the average composition ratio with good precision.

The weight average molecular weight (Mw: polystyrene conversion) and the number average molecular weight (Mn: calculated for each resin obtained by GPC (Gel Permeation Chromatography) (carrier: tetrahydrofuran (THF)). Polystyrene conversion) and dispersion (Mw/Mn). For the GPC, HLC-8120 (manufactured by TOSOH CORPORATION) was used, and as a column, TSK gel Multipore HXL-M (manufactured by TOSOH CORPORATION, 7.8 mm ID × 30.0 cm) was used. Further, the composition ratio (Morby ratio) was calculated by ¹ H-NMR (Nuclear Magnetic Resonance) and ¹³ C-NMR measurement. For the other resins shown below, the weight average molecular weight (Mw), the degree of dispersion (Mw/Mn), and the composition ratio were also calculated by the same method.

Further, each of the obtained resins was measured by high performance liquid chromatography (HPLC), and as a result, as shown in Table 1 below, the peaks were all one.

<HPLC measurement conditions> A sample diluted with THF (tetrahydrofuran) so that the resin was 0.2% by mass was used as a sample for HPCL measurement, and the measurement was carried out under the following conditions.

Detection: UV (277 nm) Column: CapcellPack C18 (particle size 5 μm, inner diameter 4.6 mm, length 150 mm) Injection amount: 5 μL Temperature: 40 ° C Flow rate: 1.0 mL/min Eluent: [A] MeOH/H ₂ O =65/35 (addition of 0.1% acetic acid) [B]THF (addition of 0.1% acetic acid) [B] Concentration: 0% (0 min) ⇒ 100% (120 min) ⇒ 100% (150 min) [Example 1: Resin (Ab Synthesis of -151) Resin (ab-151), 22/14/28/36 resin having an average composition ratio of 22/14/30/34 obtained by mixing the same synthesis method as in Comparative Example 1 ( Ab-151) and 18/16/32/34 resin (ab-151), which can produce 20/15/30/35 resin with the same average composition ratio and target average composition ratio with high precision (Ab-151) ). The obtained resin (Ab-151) was subjected to HPLC measurement, and as a result, as shown in Table 1 below, three peaks were confirmed.

[Comparative Example 2-1, 2-2: Synthesis of Resin (ab-275)]

[Chemical Formula 31]

10.0 g of poly(p-hydroxystyrene) (VP-2500, manufactured by NIPPON SODA CO., LTD.) as a polyhydroxystyrene compound was dissolved in 50 g of tetrahydrofuran (THF), and 9.66 g of triethylamine was added thereto, and ice was added thereto. Stirring was carried out in a water bath. To the reaction liquid, 13.84 g of a compound (5) (50 mass% THF solution) was added dropwise, and the mixture was stirred for 4 hours. Distilled water was added and the reaction was stopped. The THF was distilled off under reduced pressure, and the reaction was dissolved in ethyl acetate. After washing the obtained organic layer 5 times with distilled water, the organic layer was added dropwise to 800 mL of heptane. The obtained precipitate was filtered off, washed with a small amount of heptane, and dissolved in 40 g of PGMEA. By removing the low boiling point solvent from the obtained solution under reduced pressure, 51.67 g of a PGMEA solution of resin Ab-275 (30.0% by mass) was obtained. The synthetic resin (ab-275) was synthesized twice in total using the above synthesis method.

The average composition ratio of the obtained two kinds of resins was (in order from the repeating unit on the left side) 63/37, 60/40, and it was difficult to control the average composition ratio with good precision with respect to the target average composition ratio of 62/38. Each of the obtained resins was measured by high performance liquid chromatography (HPLC). As a result, as shown in Table 1 below, the peaks were all one.

[Example 2: Synthesis of Resin (Ab-275)] Resin (ab-275) and 60/40 resin having an average composition ratio of 63/37 obtained by mixing the same synthesis method as in Comparative Example 2 ( Ab-275), a resin (Ab-275) having an average composition ratio of 62/38 which is the same as the target average composition ratio can be produced with high precision. The obtained resin (Ab-275) was subjected to HPLC measurement, and as a result, as shown in Table 1 below, two peaks were confirmed.

The other resins shown below were also synthesized by the same method.

[Chemical Formula 32]

[Table 1]

As is apparent from the results shown in Table 1, it is difficult to synthesize a resin having a desired average composition ratio without any deviation, and it is preferable to blend two or more kinds of resins satisfying the requirements I, that is, two or more kinds of resins are satisfied. Two or more kinds of resins in which the repeating units are all the same and the content ratios of the repeating units are different from each other can obtain a resin having a desired average composition ratio without any deviation.

no

Fig. 1 is a view showing an HPLC chart of a resin (Ab-275) synthesized in Example 2.

Claims (11)

A photosensitive ray-sensitive or radiation-sensitive resin composition containing a resin (A) and a compound (B) which generates an acid by irradiation with actinic rays or radiation, wherein the aforementioned resin (A) contains the following requirements I N kinds of resins (a ₁ ) to resin (a _N ), and there are N peaks derived from the respective N kinds of resins (a ₁ ) to (a _N ), and the peaks are determined by high performance liquid chromatography. In the above-mentioned N kinds of the resin (a ₁ ) to the resin (a _N ), each of which is a resin containing two or more kinds of repeating units, and the two or more kinds of the repeating units contained therein are all the same and two or more kinds of the above-mentioned The content ratio of the repeating units is different from each other, wherein N represents an integer of 2 or more. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the N kinds of the resins (a ₁ ) to (a _N ) each contain three or more kinds of repeating units. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein N is an integer of 3 or more. The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the N kinds of the resins (a ₁ ) to (a _N ) each have a A repeating unit of a group which is decomposed by the action of an acid. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the group decomposed by the action of an acid is a group which generates a phenolic hydroxyl group by decomposition of an acid. The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the preceding claims, wherein the N kinds of the resins (a ₁ ) to (a _N ) each have a phenolic property. A repeating unit of a hydroxyl group. A pattern forming method comprising the steps of: forming a film comprising a photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6; a process for exposing; and a process for developing the film after exposure. The pattern forming method according to claim 7, wherein the developing process comprises at least a process of developing using an alkali developing solution. The pattern forming method according to claim 7 or 8, wherein the developing process comprises at least a process of developing using a developing solution containing an organic solvent. A method of manufacturing an electronic device, comprising the pattern forming method according to any one of claims 7 to 9. A method for producing a resin, which is a method for producing a resin used in a sensitizing ray-sensitive or radiation-sensitive resin composition, wherein N kinds of resins (a ₁ ) to resins (a _N satisfying the following requirement I) are mixed by mixing The resin having N peaks derived from the respective resins (a ₁ ) to (a _N ) is obtained, and the peak is measured by high performance liquid chromatography, and the material I: the above N kinds of resins (a ₁ ) to Each of the resins (a _N ) is a resin containing two or more kinds of repeating units, and all of the repeating units contained therein are the same as each other, and the content ratio of the repeating units is different from each other, wherein N represents an integer of 2 or more.