TW202136224A - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, method for forming pattern, and method for manufacturing electronic device - Google Patents

Abstract

The present invention provides: an actinic ray-sensitive or radiation-sensitive resin composition, represented by specific general formula (1), containing (A) a resin, and (B) a compound that produces an acid when irradiated with actinic rays or radiation; an actinic ray-sensitive or radiation-sensitive film formed by the actinic ray-sensitive or radiation-sensitive resin composition; a method for forming a pattern; and a method for manufacturing an electronic device.

Description

Sensitizing radiation or radiation sensitive resin composition, sensitizing radiation or radiation sensitive film, pattern forming method, and manufacturing method of electronic device

The present invention relates to a photosensitive ray-sensitive or radiation-sensitive resin composition, a photosensitive ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of an electronic device.

Since the resist for KrF excimer laser (248 nm), in order to compensate for the decrease in sensitivity caused by light absorption, a patterning method using chemical amplification has been used. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. Then, in a post-exposure baking (PEB: Post Exposure Bake) process or the like, the alkali-insoluble group contained in the photosensitive composition is changed into an alkali-soluble group by the catalytic action of the generated acid. After that, for example, an alkaline solution is used for development. Thereby, the exposure part is removed, and a desired pattern is obtained. In the method, as the alkaline developer, various alkaline developers have been proposed. For example, an aqueous alkaline developer of 2.38% by mass of TMAH (tetramethylammonium hydroxide aqueous solution) is generally used as the alkaline developer.

For the miniaturization of semiconductor elements, the short wavelength of the exposure light source and the high numerical aperture (high NA (Numerical Aperture)) of the projection lens have been developed. Currently, an ArF excimer laser with a wavelength of 193 nm is being developed as the light source. Exposure machine. As a technique for further improving the resolution, a method (that is, a liquid immersion method) of filling a liquid with a high refractive index (hereinafter, also referred to as a "liquid immersion liquid") between the projection lens and the sample is exemplified.

As a conventional resist composition, various types are known. For example, Patent Document 1 describes a sensitizing radiation or radiation sensitive resin composition, which contains: a specific general formula represented by actinic radiation or Radiation radiation produces acid compounds and resins. In addition, Patent Document 2 describes a positive resist material comprising a photoacid generator as a compound represented by a specific general formula and a base resin in which the hydrogen atom of the carboxyl group or the phenolic property The hydrogen atom of the hydroxyl group is replaced by an acid-labile group with alkali dissolution control ability, and the acid-labile group is dissociated and the solubility in the alkaline aqueous solution is increased by the action of the acid generated by exposure. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-6491 [Patent Document 2] Japanese Patent Laid-Open No. 2003-321466

[The problem to be solved by the invention] In addition, the resist composition is usually built into the storage state during the fixation period. However, due to such time-lapse storage, the performance of the resist composition tends to deteriorate. Therefore, there is a further demand for a resist composition that can achieve excellent stability over time. Composition (here, the “excellent stability with time” refers to the pattern obtained by using the composition after time storage when the resist composition before the formation of the resist film is stored with time Less impact). As a countermeasure, it is conceivable to change the composition of the resist composition to a composition that can improve the stability over time, but in fact, it is not easy to find a composition that can further improve the stability over time.

Therefore, an object of the present invention is to provide a sensitizing radiation-sensitive or radiation-sensitive resin composition that can achieve extremely excellent stability over time. The object of the present invention is to further provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of an electronic device using the sensitized ray-sensitive or radiation-sensitive resin composition. [Means to solve the problem]

At this time, the inventors of the present invention conducted diligent studies on the structure of a sulfonate compound which is a compound (photoacid generator) that generates an acid by irradiation with actinic rays or radiation, and found that it is used as a substituent. While shielding the structure of the alumium ring with heteroatoms as ring members and its vicinity, the arrangement position of the substituents is precisely controlled. Although the detailed reason is not clear, it is surprisingly excellent in stability over time. The present invention.

That is, the present invention has the following structure, whereby the above-mentioned problem of the present invention can be solved.

[1] A sensitized radiation or radiation-sensitive resin composition containing: (A) Resin, and (B) A compound represented by the following general formula (1) that generates an acid by irradiation with actinic rays or radiation.

[化1]

In the general formula (1), W ₁ represents a ring. Q represents a _{divalent linking group in which one or more ring members constituting ring W 1} are heteroatoms, carbonyl carbon atoms, or a combination of these. R _1A and R _1B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. Among them, _{at least one of R 1A} and R _1B represents an organic group, a halogen atom, or a cyano group. R _2A and R _2B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. Among them, _{at least one of R 2A} and R _2B represents an organic group, a halogen atom, or a cyano group. p represents 0 or 1, and q represents 0 or 1. Here, p+q represents 1 or 2. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Among them, _{at least one of R 1} and R ₂ represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. n represents 0 or 1. R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. m represents an integer of 0 or more. When m represents an integer greater than or equal to 1, n represents 1. L represents a carbonyl bond or an ester bond. l means 0 or 1. When l represents 1, n represents 1. When l represents 1, _{at least two of R 5} to R ₉ may be connected to each other to form a ring. When l represents 0, m represents 0, and n represents 0. R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an alkoxycarbonyl group, and a cycloalkyl group An oxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or a cycloalkylthio group. Z ^- represents an anion.

[2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein in the general formula (1), the ring W ₁ is a 6-membered ring to an 8-membered ring.

[3] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein in the general formula (1), Z ^- is the following general formula (3) to general formula (5) An anion represented by any one of.

[化2]

In the general formula (3), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. L ₁ represents a single bond or a divalent linking group. A represents a monovalent organic group. x represents an integer of 1-20.

[化3]

In the general formula (4), Xf ₁ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf ₁ can be connected to each other to form a ring structure.

[化4]

In the general formula (5), Xf ₂ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf ₂ can be connected to each other to form a ring structure.

[4] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein in the general formula (1), Q is any linking group selected from the following group.

[化5]

In the formula, R ₁₁ represents a hydrogen atom or a substituent. * Represents the bond to the group adjacent to Q _{forming W 1} in the general formula (1).

[5] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the compound represented by the general formula (1) is represented by the following general formula (2) Compound.

[化6]

In the general formula (2), Ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Among them, at least one of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Q has the same meaning as Q in the general formula (1). R _1, R ₍₁₎ R ₂ in the above general formula _1, R ₂ have the same meaning. _{R 5, R 6, R 7} , R 8, and R ₉ in the general formula R ₅ (1) _{of, R 6, R 7, R} 8, and R ₉ is the same meaning. At least two of R ₅ to R ₉ may be connected to each other to form a ring. The Z ^- in the general formula Z (1) ^- A is the same meaning.

[6] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein in the general formula (1) or (2), R ₅ to R _{At least one of 9} represents an alkoxy group, a cycloalkyloxy group, an alkylthio group, or a cycloalkylthio group. [7] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the solid content concentration of the composition is 10% by mass or more. [8] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (A) has a phenolic hydroxyl group. [9] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the resin (A) has a carboxyl group.

[10] A sensitizing radiation or radiation-sensitive film formed of the sensitizing radiation or radiation-sensitive resin composition as described in any one of [1] to [9]. [11] A pattern forming method, comprising: exposing the sensitizing radiation or radiation-sensitive film as described in [10], and developing the exposed sensitizing radiation or radiation-sensitive film using a developing solution A step of. [12] A manufacturing method of an electronic device includes the pattern forming method as described in [11]. [Effects of the invention]

According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition that can achieve extremely excellent stability over time. According to the present invention, it is further possible to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of an electronic device using the sensitized ray-sensitive or radiation-sensitive resin composition.

Hereinafter, the content of the present invention will be described in detail. The description of the structural elements described below may be based on representative embodiments of the present invention, and the present invention is not limited to such embodiments. Regarding the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) having a substituent together with a group (atomic group) that does not have a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom.

In addition, the type of substituent, the position of the substituent, and the number of substituents when it is referred to as "may have a substituent" in this specification are not particularly limited. The number of substituents can be, for example, one, two, three, or more. As an example of the substituent, a monovalent non-metal atomic group other than a hydrogen atom can be mentioned, for example, it can be selected from the following substituent T.

(Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-tolyloxy, etc. Aryloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acetyloxy groups such as acetoxy, propoxy and benzyloxy; acetoxy, benzyl Aphthyl, isobutyryl, acrylic, methacrylic and methoxalyl groups; alkyl mercapto groups such as methyl mercapto and tertiary butyl mercapto; phenyl mercapto and p-tolyl mercapto Alkyl; Cycloalkyl; Aryl; Heteroaryl; Hydroxyl; Carboxy; Carboxylate; Sulfo; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; Silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; nitro group; methanoyl group; and combinations of these.

The "actinic rays" or "radiation rays" in this specification refer to, for example, the bright-ray spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electrons. Beam (EB: Electron Beam) and so on. Unless otherwise specified, the "light" in this specification refers to actinic rays or radiation. The "exposure" in this manual, unless otherwise specified, includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by excimer lasers, etc. Including exposure using particle beams such as electron beams and ion beams. In this specification, the term "~" is used to include the numerical values described before and after it as the lower limit and the upper limit.

In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic means acrylic and methacrylic acid. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw/Mn) of the resin components are defined as the use of gel permeation chromatography (Gel Permeation Chromatography) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: Tosoh (stock) HLC-8120GPC manufactured by Tosoh Co., Ltd.) Manufactured TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector) obtained by polystyrene conversion value.

Regarding the amount of each component in the composition in this specification, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the corresponding multiple substances present in the composition. The term "step" in this specification includes not only independent steps, but even when it cannot be clearly distinguished from other steps, as long as the desired purpose of the step is achieved, it is also included in this term. The "total solid content" in this specification refers to the total mass of the components after removing the solvent from the total composition of the composition. In addition, the so-called "solid content" is a component after removing the solvent as described above, and for example, it may be a solid or a liquid at 25°C. In this manual, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. In addition, in this specification, a combination of two or more preferable aspects is a more preferable aspect.

(Acceptable radiation or radiation-sensitive resin composition) The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "composition") of the present invention is the following actinic ray-sensitive or radiation-sensitive resin composition, which contains: (A) Resin; and (B) A compound represented by the following general formula (1) that generates an acid by irradiation with actinic rays or radiation.

[化7]

In the general formula (1), W ₁ represents a ring. Q represents a _{divalent linking group in which one or more ring members constituting ring W 1} are heteroatoms, carbonyl carbon atoms, or a combination of these. R _1A and R _1B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. Among them, _{at least one of R 1A} and R _1B represents an organic group, a halogen atom, or a cyano group. R _2A and R _2B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. Among them, _{at least one of R 2A} and R _2B represents an organic group, a halogen atom, or a cyano group. p represents 0 or 1, and q represents 0 or 1. Here, p+q represents 1 or 2. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Among them, _{at least one of R 1} and R ₂ represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. n represents 0 or 1. R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. m represents an integer of 0 or more. When m represents an integer greater than or equal to 1, n represents 1. L represents a carbonyl bond or an ester bond. l means 0 or 1. When l represents 1, n represents 1. When l represents 1, _{at least two of R 5} to R ₉ may be connected to each other to form a ring. When l represents 0, m represents 0, and n represents 0. R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an alkoxycarbonyl group, and a cycloalkyl group An oxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or a cycloalkylthio group. Z ^- represents an anion.

By adopting the above structure, the present invention can achieve extremely excellent storage stability. The reason is not clear, but it can be estimated as follows. First, the compound (photoacid generator) represented by the general formula (1) satisfies "wherein, _{at least one of R 1A} and R _1B represents an organic group, a halogen atom, or a cyano group.", "wherein, R _2A and At least one of R _2B represents an organic group, a halogen atom, or a cyano group.” and “p represents 0 or 1, and q represents 0 or 1. Wherein, p+q represents 1 or 2. Three-dimensionally hinder at least one _{of R 1A} , R _1B , R _2A and R _{2B that function.} Furthermore, with regard to the bond between the benzene ring and the alumenium ring, in the case where l=m=n=0, the benzene ring and the alumenium ring are bonded by a single bond, and the benzene ring can be especially derived from the alumenium ring. When the steric hindrance on the cation side of alumium cation functions, and when the relationship of l, m, and n is other than the above, n=1, _{and at least one of R 1} and R ₂ is an alkyl group, a cycloalkyl group, and a halogen atom , Cyano, or aryl can also function as a steric hindrance from the amenium ring, especially on the amenium cation side.

In this way, the photoacid generator represented by the general formula (1) has a group capable of functioning as a steric hindrance on and near the ring, so it is compared with a photoacid generator that does not satisfy the general formula (1). Even when the resist composition is preserved over time, the ring (especially the ring members of the ring) is not easily attacked by other components (for example, nucleophilic attack, etc.). As a result, first, it is considered that the structure of the photoacid generator represented by the general formula (1) is easily maintained in the resist composition without changing. Furthermore, the configuration is such that the arrangement position of at least one of _{R 1A} , R _1B , R _2A and R _2B that can function as a steric hindrance on the ring is defined as the general formula (1), and is not substituted The carbon atom of is adjacent to the alumium cation in the alumium ring. Although the detailed reason is not clear, the inventors of the present invention found that, surprisingly, the stability of the photoacid generator in the resist composition is extremely improved. From this, it is estimated that the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention has very excellent stability over time.

The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention is preferably a so-called resist composition, and may be a positive type resist composition or a negative type resist composition. In addition, it may be a resist composition for alkali development or a resist composition for organic solvent development. Typically, the composition of the present invention is preferably a chemically amplified resist composition. Hereinafter, the details of each component contained in the sensitizing radiation-sensitive or radiation-sensitive resin composition (also simply referred to as "composition") of the present invention will be described.

<(B) A compound represented by the general formula (1) that generates acid by irradiation with actinic rays or radiation> The composition of the present invention contains (B) a flux that generates acid by irradiation with actinic rays or radiation The compound represented by formula (1) (hereinafter also referred to as "photoacid generator (B)" and "compound (B)"). In the general formula (1), Q represents a _{divalent linking group in which one or more ring members constituting ring W 1} are heteroatoms, carbonyl carbon atoms, or a combination of these.

In the general formula (1), Q represents a _{divalent linking group in which one or more ring members constituting ring W 1} are heteroatoms, carbonyl carbon atoms, or a combination of these. In the divalent linking group as Q, _{one or more ring members constituting ring W 1} are heteroatoms, carbonyl carbon atoms, or a combination of these. The hetero atom means an atom other than a carbon atom, and is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom. The carbonyl carbon atom means a carbon atom in a carbonyl bond.

Q is not particularly limited, but is preferably any linking group selected from the following group.

[化8]

In the group, R ₁₁ represents a hydrogen atom or a substituent. * Represents the bond to the group adjacent to Q _{forming the ring W 1} in the general formula (1).

The substituent of R ₁₁ is not particularly limited, and examples thereof include an alkylsulfonyl group, an alkylcarbonyl group, and an alkyl group. The alkyl group in the alkylsulfonyl group may be linear or branched, for example, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is preferred. The alkyl group in the alkylcarbonyl group may be linear or branched, for example, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is preferred. The alkyl group may be linear or branched, for example, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is preferred. The alkylsulfonyl group, alkylcarbonyl group, and alkyl group may further have a substituent.

* Represents the bond to the group adjacent to Q _{forming the ring W 1} in the general formula (1). In addition, * only needs to be bonded to any one of the two groups adjacent to Q _{forming the ring W 1 in the general formula (1).}

Q is preferably any linking group selected from the following group.

[化9]

In the formula, R ₁₁ represents a hydrogen atom or a substituent. * Represents the bond to the group adjacent to Q _{forming the ring W 1} in the general formula (1).

R ₁₁ and * are as described respectively.

R _1A and R _1B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. R _2A and R _2B each independently represent a hydrogen atom, an organic group, a halogen atom, or a cyano group. The organic group of R _1A , R _2A , R _1B , and R _2B is not particularly limited, and for example, it represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, and an alkylcarbonyl group.

The alkyl group is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms. As the alkyl group, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is still more preferable. The alkyl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

The cycloalkyl group may be monocyclic or polycyclic, and is not particularly limited, but a cycloalkyl group having 3 to 20 carbon atoms is preferred. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. As the cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkyl group having 3 to 10 carbon atoms is still more preferable. The cycloalkyl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and still more preferably an alkoxy group having 1 to 10 carbon atoms. The alkoxy group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

The cycloalkyl group in the cycloalkyloxy group may be monocyclic or polycyclic, and is not particularly limited, but is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. As the cycloalkyl group in the cycloalkyloxy group, a cycloalkyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkyl group having 3 to 10 carbon atoms is still more preferable. The cycloalkyloxy group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

The aryl group is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferred, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a fused tetraphenyl group, and a fluorenyl group. The aryl group is more preferably an aryl group having 6 to 15 carbons, and still more preferably an aryl group having 6 to 10 carbons. The aryl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

The alkyl group in the alkylcarbonyl group is not particularly limited, and it may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group in the alkylcarbonyl group is more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms. The alkylcarbonyl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

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

R _1A and R _1B preferably represent a hydrogen atom, an organic group or a halogen atom, and more preferably represent a hydrogen atom or an organic group. R _2A and R _2B preferably represent a hydrogen atom, an organic group or a halogen atom, and more preferably represent a hydrogen atom or an organic group. Among them, _{at least one of R 1A} and R _1B represents an organic group, a halogen atom, or a cyano group, _{and at least one of R 2A} and R _2B represents an organic group, a halogen atom, or a cyano group.

p represents 0 or 1, and q represents 0 or 1. Here, p+q represents 1 or 2. At least one carbon atom adjacent to Q in ring W ₁ has an organic group, a halogen atom, or a cyano group as a substituent. There is no case where R _1A , R _2A , R _1B and R _2B all represent hydrogen atoms.

W ₁ represents a ring. In the general formula (1), W ₁ represents a ring. W ₁ is a ring with more than 5 members. The upper limit of the ring member of the ring represented by W _{1 is not particularly limited, but W 1 is} preferably a 10-membered ring or less. W _{1 is} preferably a 6-membered ring to an 8-membered ring, preferably a 6-membered ring or a 7-membered ring, and more preferably a 6-membered ring.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Among them, _{at least one of R 1} and R ₂ represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

The alkyl group as R ₁ and R ₂ is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms. As the alkyl group, an alkyl group having 1 to 15 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is still more preferable. The alkyl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

Regarding the cycloalkyl group as R ₁ and R ₂ , it may be monocyclic or polycyclic, and is not particularly limited, but is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. As the cycloalkyl group, a cycloalkyl group having 3 to 15 carbon atoms is more preferable, and a cycloalkyl group having 3 to 10 carbon atoms is still more preferable. The cycloalkyl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

Regarding the aryl group as R ₁ and R ₂ , there are no particular limitations, but an aryl group having 6 to 20 carbon atoms is preferred. Specific examples include phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and fused tetraphenyl. Base, fluorene base. The aryl group is more preferably an aryl group having 6 to 15 carbons, and still more preferably an aryl group having 6 to 10 carbons. The aryl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned. The halogen atom as R ₁ and R ₂ includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

R ₁ and R _{2 are} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group. More preferably, R ₁ represents a hydrogen atom and R ₂ represents an alkyl group.

R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. The alkyl group as R ₃ and R _{4 is} the same as the alkyl group described as R ₁ and R ₂ . The cycloalkyl group as R ₃ and R _{4 is} the same as the cycloalkyl group described above as R ₁ and R ₂ . The aryl groups as R ₃ and R ₄ are the same as the aryl groups described as R ₁ and R ₂ . The halogen atom as R ₃ and R ₄ includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

R ₃ and R _{4 are} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group. More preferably, R ₃ and R ₄ represent a hydrogen atom.

m represents an integer of 0 or more. The upper limit of m is not particularly limited, but m is preferably an integer of 5 or less. m is preferably an integer of 0-3, more preferably 0 or 1. When m represents an integer greater than or equal to 1, n represents 1.

L represents a carbonyl bond or an ester bond. As L, a carbonyl bond is preferable. When l represents 1, n represents 1. When l represents 0, m represents 0, and n represents 0.

R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an alkoxycarbonyl group, and a cycloalkyl group An oxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or a cycloalkylthio group.

The alkyl group as R ₅ , R ₆ , R ₇ , R ₈ , and R _{9 is} the same as the alkyl group described above as R _1A , R _2A , R _1B , and R _2B . The cycloalkyl group as R ₅ , R ₆ , R ₇ , R ₈ , and R _{9 is} the same as the cycloalkyl group described above as R _1A , R _2A , R _1B , and R _2B . The aryl groups as R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ are the same as the aryl groups described above as R _1A , R _2A , R _1B , and R _2B . The alkoxy groups as R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ are the same as the alkoxy groups described above as R _1A , R _2A , R _1B , and R _2B . The cycloalkyloxy group as R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ is the same as the cycloalkyloxy group described as R _1A , R _2A , R _1B , and R _2B .

The alkoxy group in the alkoxycarbonyl group as R ₅ , R ₆ , R ₇ , R ₈ , and R _{9 is} the same as the alkoxy group described above as R _1A , R _2A , R _1B , and R _2B . The cycloalkyl group in the cycloalkyloxycarbonyl group of R ₅ , R ₆ , R ₇ , R ₈ , and R _{9 and the cycloalkyl group described as R 1A} , R _2A , R _1B , and R _2B same. The alkyl group in the alkylcarbonyloxy group as R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ is the same as the alkyl group described as R _1A , R _2A , R _1B , and R _2B . As the cycloalkyl group in the cycloalkylcarbonyloxy group of _{R 5} , R ₆ , R ₇ , R ₈ , and R _{9 and the cycloalkyl group described as R 1A} , R _2A , R _1B , and R _2B same. The alkyl group in the alkylthio group of R ₅ , R ₆ , R ₇ , R ₈ , and R _{9 is the same as the alkyl group described above as R 1A} , R _2A , R _1B , and R _2B . The cycloalkyl group in the cycloalkylthio group of R ₅ , R ₆ , R ₇ , R ₈ , and R _{9 is} the same as the cycloalkyl group described as R _1A , R _2A , R _1B , and R _2B .

The alkenyl group as R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ is not particularly limited, and may be linear or branched, and preferably an alkenyl group having 2 to 20 carbon atoms. As the alkenyl group, an alkenyl group having 2 to 15 carbon atoms is more preferable, and an alkenyl group having 2 to 10 carbon atoms is still more preferable. The alkenyl group may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned. The halogen atom as R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkyloxy group, and more preferably represent a cycloalkyl group or an alkoxy group , Cycloalkyloxy, more preferably represents an alkoxy group or a cycloalkyloxy group.

When l represents 1, _{at least two of R 5} to R ₉ may be connected to each other to form a ring. The ring formed by connecting at least two of R ₅ to R ₉ is not particularly limited, and examples include aromatic or non-aromatic (for example, aliphatic) hydrocarbon rings, aromatic or non-aromatic heterocycles, And a polycyclic condensed ring formed by combining two or more of these rings. As the ring structure (the ring structure of a monocyclic ring constituting it in a polycyclic condensed ring), a 3-membered ring to a 10-membered ring may be exemplified, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring ring.

Z ^- represents an anion. The anion of Z ^- is not particularly limited, but is preferably a non-nucleophilic anion, for example, sulfonate anion, carboxylate anion, sulfonylimide anion, bis(alkylsulfonylimide)imide Anion, tris(alkylsulfonyl)methyl anion, etc.

The so-called non-nucleophilic anion is an anion whose ability to cause a nucleophilic reaction is significantly low, and is an anion that can inhibit decomposition over time caused by an intramolecular nucleophilic reaction. This improves the stability of the composition over time. As a sulfonate anion, aliphatic sulfonate anion, aromatic sulfonate anion, camphorsulfonate anion, etc. are mentioned, for example. Examples of carboxylate anions include aliphatic carboxylate anions, aromatic carboxylate anions, aralkylcarboxylate anions, and the like.

The aliphatic part in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms The aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group. The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. As other non-nucleophilic anion, and examples thereof include: phosphorus pentafluoride (e.g., PF ₆ ^-), boron trifluoride (e.g., BF ₄ ^-), antimony fluoride and the like (e.g., SbF ₆ ^-).

The anion of Z ^- is preferably an aliphatic sulfonate anion substituted with a fluorine atom at at least the α position of a sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom Bis(alkylsulfonyl)imide anion, tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a C4-8 perfluoroaliphatic sulfonate anion, a benzenesulfonate anion having a fluorine atom, and still more preferably a nonafluorobutanesulfonate anion and a perfluorooctanesulfonate anion , Pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

In the general formula (1), Z ^-is preferably an anion represented by any of the following general formulas (3) to (5).

[化10]

In the general formula (3), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. L ₁ represents a single bond or a divalent linking group. A represents a monovalent organic group. x represents an integer of 1-20.

[化11]

In the general formula (4), Xf ₁ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf ₁ can be connected to each other to form a ring structure.

[化12]

In the general formula (5), Xf ₂ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Two Xf ₂ can be connected to each other to form a ring structure.

The number of carbon atoms of the alkyl group in the alkyl group substituted with at least one fluorine atom as Xf is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. The alkyl group substituted with at least one fluorine atom may have a substituent. It does not specifically limit as a substituent, For example, the said substituent T is mentioned.

Examples of the divalent linking group of L ₁ include: -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S -, -SO-, -SO ₂ -, alkylene group (preferably carbon number 1 to 6), cycloalkylene group (preferably carbon number 3 to 15), alkenylene group (preferably carbon number 2 ~6) and a divalent linking group formed by combining a plurality of these. Of these, alkylene, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -SO _{2 -alkylene-,-are preferred} COO-alkylene-, -alkylene-COO-, -OCO-alkylene-, -alkylene-OCO-, -CONH-alkylene- or -NHCO-alkylene-, more preferably Alkylene, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene- or -alkylene- OCO-. The alkylene group, cycloalkylene group, and alkenylene group may have a substituent. The substituent is not particularly limited. For example, the substituent T may be mentioned above, and a fluorine atom is preferred.

A represents an organic group. The carbon number of the organic group is not particularly limited, and is generally 1-30, preferably 1-20. It does not specifically limit as an organic group, For example, an alkyl group, an alkoxy group, etc. are mentioned. The alkyl group is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 10 carbons, more preferably an alkyl group having 1 to 6 carbons, and still more preferably an alkyl group having 1 to 4 carbons. base. The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms. The alkyl group and alkoxy group may have a substituent. May have substituents. The substituent is not particularly limited. For example, the substituent T may be mentioned above, and a fluorine atom is preferred.

In addition, A may represent an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group, are preferred.

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group are mentioned, for example. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), cycloalkyl (which may be any one of monocyclic, polycyclic, and spirocyclic rings, Preferably it is carbon number 3-20), aryl group (preferably carbon number 6-14), hydroxyl group, alkoxy group, ester group, amide group, urethane group, urea group, thioether group, Sulfonamide group and sulfonate group. Furthermore, the carbon (carbon that contributes to ring formation) constituting the cyclic organic group may be a carbonyl carbon.

The alkyl group substituted with at least one fluorine atom as Xf ₁ is the same as the alkyl group substituted with at least one fluorine atom described as Xf. The alkyl group substituted with at least one fluorine atom as Xf ₂ is the same as the alkyl group substituted with at least one fluorine atom described as Xf.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).

[化13]

In the general formula (2), Ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Among them, at least one of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. Q has the same meaning as Q in the general formula (1). R _1, R ₍₁₎ R ₂ in the above general formula _1, R ₂ have the same meaning. _{R 5, R 6, R 7} , R 8, and R ₉ in the general formula R ₅ (1) _{of, R 6, R 7, R} 8, and R ₉ is the same meaning. At least two of R ₅ to R ₉ may be connected to each other to form a ring. The Z ^- in the general formula Z (1) ^- A is the same meaning.

The alkyl group as Ra to Rd is the same as the alkyl group described above as R _1A , R _2A , R _1B , and R _2B . The cycloalkyl group as Ra to Rd is the same as the cycloalkyl group described above as R _1A , R _2A , R _1B , and R _2B . The aryl group as Ra to Rd is the same as the aryl group described above as R _1A , R _2A , R _1B , and R _2B . The halogen atoms as Ra to Rd are the same as the halogen atoms described above as R _1A , R _2A , R _1B , and R _2B .

Ra to Rd preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a halogen atom, and more preferably a hydrogen atom, an alkyl group, or a cycloalkyl group.

At least two of R ₅ to R ₉ may be connected to each other to form a ring. The ring formed by connecting at least two of R ₅ to R ₉ is not particularly limited, and examples include aromatic or non-aromatic (for example, aliphatic) hydrocarbon rings, aromatic or non-aromatic heterocycles, And a polycyclic condensed ring formed by combining two or more of these rings. As the ring structure (the ring structure of a monocyclic ring constituting it in a polycyclic condensed ring), a 3-membered ring to a 10-membered ring may be exemplified, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring ring.

As a preferred aspect, it is preferable that in the general formula (1) or the general formula (2), _{at least one of R 5} to R ₉ represents an alkoxy group, a cycloalkyloxy group, an alkylthio group or a ring The alkylthio group more preferably represents an alkoxy group or a cycloalkyloxy group.

The specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to these specific examples. ^t Bu represents the tertiary butyl group, Et represents the ethyl group, and ⁿ Bu represents the n-butyl group.

[化14]

[化15]

In a range that does not impair the effects of the present invention, other photoacid generators may be used in addition to the compound represented by the general formula (1).

The photoacid generator may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated into a part of the polymer may be used in combination. The photoacid generator is preferably in the form of a low molecular compound. When the photoacid generator is in the form of a low-molecular 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 a form incorporated in a part of a polymer, it may be incorporated in a part of the resin (A) described later, or may be incorporated in a resin different from the resin (A).

One type of photoacid generator may be used alone, or two or more types may be used in combination. The content of the photoacid generator in the composition (the total when there are multiple types) is based on the total solid content of the composition, and is preferably 0.1% by mass to 35% by mass, more preferably 0.5% by mass to 25% by mass % By mass, more preferably 1.0% by mass to 20% by mass, particularly preferably 1.0% by mass to 20% by mass.

＜(A) Resin＞ The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains resin (A). The resin (A) is typically a resin whose polarity is increased by the action of an acid, and is preferably a resin whose polarity is increased by the action of an acid and whose solubility in a developer is changed.

The resin (resin (A)) whose polarity is increased by the action of an acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound. The ethylenically unsaturated compound preferably has one to four ethylenically unsaturated bonds, more preferably one. Furthermore, the ethylenically unsaturated compound is preferably a monomer which is a monomer. In addition, the molecular weight of the ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, and particularly preferably 100 to 600.

In addition, the resin whose polarity is increased by the action of an acid is preferably a resin having an acid-decomposable group, and more preferably a resin containing a structural unit having an acid-decomposable group. In this case, in the pattern forming method of the present invention described later, when an alkaline developer is used as the developer, a positive pattern can be preferably formed, and when an organic developer is used as the developer, , Can preferably form a negative pattern.

〔Structural units with acid-decomposable groups〕 The resin (A) preferably contains a structural unit having an acid-decomposable group (also referred to as "repeating unit").

As the resin (A), a known resin can be suitably used. For example, paragraph 0055 to paragraph 0191 of U.S. Patent Application Publication No. 2016/0274458 Specification, Paragraph 0035 to Paragraph 0085 of U.S. Patent Application Publication No. 2015/0004544 Specification, and U.S. Patent Application Publication No. 2016/ The well-known resin disclosed in paragraph 0045 to paragraph 0090 of Specification No. 0147150 is referred to as resin (A).

The acid-decomposable group preferably has a structure in which a polar group is decomposed by the action of an acid to be decomposed (a leaving group) protected by a group. Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamido groups, sulfonamido groups, (alkylsulfonyl groups) (alkylcarbonyl) methylene groups, (alkylsulfonyl groups). (Alkyl)(alkylcarbonyl)amido, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)amido, bis(alkylsulfonyl)methylene, bis(alkyl) Acidic groups such as sulfonylimine, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene (groups dissociated in 2.38% by mass tetramethylammonium hydroxide aqueous solution) ), and alcoholic hydroxyl groups.

In addition, the alcoholic hydroxyl group refers to a hydroxyl group other than the hydroxyl group (phenolic hydroxyl group) that is directly bonded to the aromatic ring and is bonded to a hydrocarbon group. As a hydroxyl group, an aliphatic group substituted with an electron withdrawing group such as a fluorine atom at the α-position Except for group alcohol groups (for example, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

As a preferable polar group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group can be mentioned.

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

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, for example, methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, And octyl and so on. The cycloalkyl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, adamantyl group, norbornyl group, isobornyl group, camphenyl group, dicyclopentyl group, α-pinenyl group, tricyclic group Decyl, tetracyclododecyl, and androstanyl, etc. Furthermore, at least one carbon atom in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom. The aryl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably aryl groups having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl. The aralkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl. The alkenyl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably alkenyl groups having 2 to 8 carbon atoms, and examples thereof include vinyl groups, allyl groups, butenyl groups, and cyclohexenyl groups. The ring formed by bonding R ³⁶ and R ^{37 to} each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic ring such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. alkyl.

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

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

[化16]

In formula AI, Xa ¹ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group, T represents a single bond or a divalent linking group, Rx ¹ to Rx ³ each independently represent an alkyl group or a cycloalkyl group, and Rx ^{Any two of 1} to Rx ³ may be bonded to form a ring structure, or may not form a ring structure.

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

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

The alkyl groups of Rx ¹ , Rx ² and Rx ³ may be linear or branched, and preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl Butyl, tertiary butyl, etc. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and still more preferably 1-3. In ^{the alkyl group of Rx 1} , Rx ² and Rx ³ , a part of the inter-carbon bond may be a double bond. The cycloalkyl group of Rx ¹ , Rx ² and Rx ³ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl, adamantane Polycyclic cycloalkyl groups such as alkyl groups.

The ring structure formed by the two bonding of Rx ¹ , Rx ² and Rx ³ is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, Or polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring. More preferably, it is a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring. As ^{a ring structure formed by two bonding of Rx 1} , Rx ² and Rx ³ , the structure shown below is also preferable.

[化17]

Specific examples of monomers corresponding to the structural unit represented by formula AI are listed below, but the present invention is not limited to these specific examples. Corresponds to the following specific examples of AI of formula Xa ¹ is a methyl group, optionally substituted Xa ¹ represents a hydrogen atom, a halogen atom other than fluorine atom, or a monovalent organic group.

[化18]

It is also preferable that the resin (A) has the structural unit described in paragraph 0336 to paragraph 0369 of the specification of U.S. Patent Application Publication No. 2016/0070167 as the structural unit having an acid-decomposable group.

In addition, the resin (A) may have a structural unit described in paragraphs 0363 to 0364 of the specification of U.S. Patent Application Publication No. 2016/0070167, which includes a group that is decomposed by the action of an acid to generate an alcoholic hydroxyl group as a structural unit having acid decomposition. The structural unit of the sex base.

In addition, the resin (A) preferably contains a repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid as a repeating unit having an acid-decomposable group. In addition, in this specification, the phenolic hydroxyl group is a group in which the hydrogen atom of an aromatic hydrocarbon group is substituted with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

Examples of the leaving group decomposed and released by the action of an acid include groups represented by formula (Y1) to formula (Y4). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar)

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Among them, it is more preferred that Rx ₁ to Rx ₃ each independently represent a repeating unit of a linear or branched alkyl group, and it is more preferred that Rx ₁ to Rx ₃ each independently represent a repeating unit of a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring. The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl Such as polycyclic cycloalkyl. As _{the cycloalkyl formed by bonding two of Rx 1} to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, and tetracyclodecyl are preferred. Polycyclic cycloalkyl groups such as dialkyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. Among _{the cycloalkyl groups formed by bonding two of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. The group represented by the formula (Y1) and the formula (Y2) is preferably a state in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R _{36 is} preferably a hydrogen atom.

In formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar can bond with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As a repeating unit having a structure (acid decomposable group) protected by a leaving group that is decomposed by the action of an acid, the phenolic hydroxyl group preferably has a hydrogen atom in the phenolic hydroxyl group from formula (Y1) to formula ( Y4) The repeating unit of the structure protected by the group represented.

The repeating unit having a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed by the action of an acid is preferably a repeating unit represented by the following general formula (AII).

[化19]

In the general formula (AII), 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. Among them, R ₆₂ may bond with Ar ₆ to form a ring. In this case, R ₆₂ represents a single bond or an alkylene group. X ₆ represents a single bond, -COO-, or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group. L ₆ represents a single bond or an alkylene group. Ar ₆ represents an (n+1)-valent aromatic hydrocarbon group, and when it _{bonds with R 62} to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. In the case of n≧2, Y ₂ each independently represents a hydrogen atom or a group released by the action of an acid. Among them, _{at least one of Y 2} represents a group that is detached by the action of an acid. The group that is released _{by the action of acid as Y 2} is preferably formula (Y1) to formula (Y4). n represents an integer of 1-4.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (carbon number 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (carbon number 1 to 4), a carboxyl group, and an alkoxycarbonyl group. (C2-6), etc., preferably having a carbon number of 8 or less.

[化20]

[化21]

The resin (A) may contain one kind of structural unit having an acid-decomposable group alone, or two or more kinds.

The content of the acid-decomposable group-containing structural unit contained in the resin (A) relative to all the structural units of the resin (A) (the total when there are multiple structural units having acid-decomposable groups) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 15 mol% to 70 mol%. In addition, in the present invention, when the content of the "structural unit" is specified in molar ratio, the "structural unit" and the "monomer unit" have the same meaning. In addition, the "monomer unit" in the present invention can be modified after being polymerized by a polymer reaction or the like. The following is also the same.

[Having at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure] The resin (A) preferably contains a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

As the lactone structure or sultone structure, any one may be used as long as it has a lactone structure or a sultone structure, preferably a 5-membered to 7-membered cyclic lactone structure or a 5-membered to 7-membered cyclic sultone Ester structure, more preferably other ring structure in the form of a bicyclic structure, spiro ring structure and 5-membered to 7-membered cyclic lactone structure, or other ring structure in the form of a bicyclic structure, spiro ring structure It is formed by condensing ring with 5-member ring to 7-member ring sultone structure. More preferably, it contains a lactone structure represented by any one of the following formulas LC1-1 to LC1-21, or a sultone structure represented by any one of the following formulas SL1-1 to SL1-3 The structural unit. In addition, the lactone structure or sultone structure may be directly bonded to the main chain. As a preferable structure, it is LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, SL1-1.

[化22]

The lactone moiety or the sultone moiety may have a substituent (Rb ² ) or may not have a substituent (Rb ² ). Preferred substituents (Rb ² ) include: alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and alkyl groups having 2 to 8 carbons. An oxycarbonyl group, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, an acid-decomposable group, etc. More preferably, they are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0-4. When n2 is 2 or more, a plurality of substituents (Rb ² ) may be the same or different. In addition, a plurality of substituents (Rb ² ) may be bonded to each other to form a ring.

The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III. In addition, the resin containing a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.

[化23]

In the formula III, A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-). n is the ^{number of repetitions of the structure represented by -R 0} -Z-, and represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, -R ⁰ -Z- does not exist, and A and R ⁸ are bonded by a single bond. R ⁰ represents an alkylene group, a cycloalkylene group, or a combination thereof. When ^{there are a plurality of R 0} , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, ether bond, ester bond, amide bond, urethane bond, or urea bond. When there are a plurality of Z, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. R ⁸ represents a monovalent organic group having a lactone structure or a sultone structure. R ⁷ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of R ^{0 may have a substituent.} Z is preferably an ether bond or an ester bond, more preferably an ester bond.

Specific examples of monomers corresponding to the structural unit represented by formula III and specific examples of monomers corresponding to the structural unit represented by formula A-1 described below are listed below, but the present invention is not limited to these specific examples . Specific examples corresponds to the following formula III R ⁷ and described below in the formula A 1-R _A ¹ is a methyl group, R ⁷ and R _A ¹ is optionally substituted other than a hydrogen atom, a fluorine atom halogen Atom, or monovalent organic group.

[化24]

In addition to the above-mentioned monomers, the monomers shown below can also be preferably used as the raw material of the resin (A).

[化25]

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

[化26]

In Formula A-1, R _A ¹ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer of 0 or more, and R _A ² represents a substituent. R _A ² each independently represents a substituent when n is 2 or more, A represents a single bond or a divalent linking group, and Z represents a group formed with the group represented by -OC(=O)-O- in the formula A group of atoms in a monocyclic structure or a polycyclic structure.

The resin (A) preferably has the structural unit described in paragraphs 0370 to 0414 of the specification of US Patent Application Publication No. 2016/0070167 as having a structure selected from a lactone structure, a sultone structure, and a carbonate structure. At least one structural unit in the group.

The resin (A) preferably contains a structural unit (a) having at least two lactone structures (hereinafter, also referred to as "structural unit (a)"). The at least two lactone structures may be, for example, a structure in which at least two lactone structures are condensed, and may be a structure in which at least two lactone structures are connected by a single bond or a linking group. The lactone structure of the structural unit (a) is not particularly limited, and is preferably a 5-membered to 7-membered cyclic lactone structure, and preferably other ring structures to form a bicyclic structure, a spiro ring structure, and 5-membered ring structure. Ring ~ 7-membered ring lactone structure formed by condensing ring. As the lactone structure, for example, a lactone structure represented by any one of LC1-1 to LC1-21 is preferably mentioned.

The structural unit having at least two lactone structures (hereinafter also referred to as "structural unit (a)") is preferably a structural unit represented by the following formula L-1.

[化27]

In formula L-1, Ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having two or more lactone structures.

The alkyl group of Ra is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom, or an alkoxy group such as a mercapto group, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tertiary butoxy group, and a benzyloxy group. , Acetyl, Propyl and other acetoxy groups. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

Examples of the lactone structure possessed by the Rb partial structure include the aforementioned lactone structures. The partial structure of Rb having two or more lactone structures is preferably, for example, a structure in which at least two lactone structures are connected by a single bond or a linking group, and a structure in which at least two lactone structures are condensed. The structural unit (a1) having a structure in which at least two lactone structures are condensed and the structural unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group are each explained below.

-Structural unit (a1) having at least two lactone structure condensed rings- The structure in which at least two lactone structures are condensed is preferably a structure in which two or three lactone structures are condensed, and more preferably a structure in which two lactone structures are condensed. The structural unit (hereinafter, also referred to as "structural unit (a1)") having a structure in which at least two lactone structures have condensed rings may be, for example, a structural unit represented by the following formula L-2.

[化28]

In formula L-2, Ra has the same meaning as Ra in formula L-1, Re ₁ to Re ₈ each independently represent a hydrogen atom or an alkyl group, Me ₁ represents a single bond or a divalent linking group, Me ₂ and Me ₃ , respectively Independently represents a divalent linking group.

The alkyl group of Re ₁ to Re ₈ preferably has a carbon number of 5 or less, and more preferably has a carbon number of 1, for example. Examples of the alkyl groups having 5 or less carbon atoms of Re ₁ to Re ₈ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, and isopentyl. Group, the second pentyl group, the third pentyl group, etc. Among them, Re ₁ to Re _{8 are} preferably hydrogen atoms.

Examples of the divalent linking group of Me ₁ include: alkylene, cycloalkylene, -O-, -CO-, -COO-, -OCO-, and combinations of two or more of these groups. base. The alkylene group of Me ₁ preferably has 1 to 10 carbon atoms, for example. In addition, it is more preferably a carbon number of 1 or 2. As the alkylene group having a carbon number of 1 or 2, for example, a methylene group or an ethylene group is preferable. The alkylene group of Me ₁ may be linear or branched. Examples include: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group of Me ₁ preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms, for example. Examples of the cycloalkylene group of Me ₁ include cyclopentyl, cyclohexyl, heptyl, cyclooctyl, and cyclodecylene. As the _{divalent linking group of Me 1} , the group formed by combining two or more groups is preferably, for example, a group formed by combining an alkylene group and -COO-, and a combination of -OCO- and an alkylene group Formed base. In addition, the group formed by combining two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group.

Examples of the divalent linking group of Me ₂ and Me _{3 include alkylene and -O-.} The _{divalent linking group of Me 2} and Me ₃ is preferably methylene, ethylene, and -O-, and more preferably -O-.

The monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP 2015-160836 A.

Although the specific example of a structural unit (a1) is shown below, this invention is not limited to this. In the following formulae, R ₉ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and * represents a bonding position with other structural units.

[化29]

[化30]

[化31]

-A structural unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group-A structure in which at least two lactone structures are connected by a single bond or a linking group is preferably two to four A structure in which each lactone structure is connected by a single bond or a linking group, and more preferably a structure in which two lactone structures are connected by a single bond or a linking group. Examples of the linking group include the same groups as those exemplified in the linking group _{of M 2} in formula L-3 described later. The structural unit (hereinafter, also referred to as "structural unit (a2)") having a structure in which two or more lactone structures are connected by a single bond or a linking group (hereinafter, also referred to as "structural unit (a2)") includes, for example, a structural unit represented by the following formula L-3.

[化32]

In the formula L-3, Ra has the same meaning as the Ra in the formula L-1, M ₁ and M ₂ each independently represent a single bond or a linking group, and Lc ₁ and Lc ₂ each independently represent a group having a lactone structure. .

Examples of the linking group of M ₁ include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a combination of two or more of these groups. The alkylene group of M ₁ preferably has 1 to 10 carbon atoms, for example. The alkylene group of M ₁ may be linear or branched, for example: methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. The cycloalkylene group of M ₁ preferably has 5 to 10 carbon atoms, for example. Examples of the cycloalkylene group of M ₁ include cyclopentyl, cyclohexyl, heptyl, cyclooctyl, and cyclodecylene. As _{the linking group of M 1} , the group formed by combining two or more groups is preferably, for example, a group formed by combining an alkylene group and -COO-, and a group formed by combining -OCO- and an alkylene group.的基。 The base. In addition, the group formed by combining two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group. Examples of the linking group of M ₂ include the same groups as those listed for the linking group of _{M 1.}

The lactone structure of Lc ₁ is, for example, a 5-membered to 7-membered cyclic lactone structure, and other ring structures are preferably formed in the form of a bicyclic structure, a spiro structure, and a 5-membered to 7-membered cyclic lactone structure Those who condensed the ring. The lactone structure is more preferably a lactone structure represented by any one of LC1-1 to LC1-21. As a further preferable lactone structure, LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14, and LC1-17 can be mentioned. The lactone structure of Lc ₁ may include a substituent. Examples of the substituent that may be included in the lactone structure of Lc ₁ include the same substituents as the substituent ^{(Rb 2) of the lactone structure.} The lactone structure that Lc ₂ has, for example, the same structure as the lactone structure exemplified in the lactone structure that _{Lc 1 has.}

In the structural unit (a2), the structural unit represented by the above formula L-3 is preferably a structural unit represented by the following formula L-4.

[化33]

In the formula L-4, Ra has the same meaning as the Ra in the formula L-1, Mf ₁ and Mf ₂ each independently represent a single bond or a linking group, and Rf ₁ , Rf ₂ and Rf ₃ each independently represent a hydrogen atom or In the alkyl group, Mf ₁ and Rf ₁ may be bonded to each other to form a ring, and Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring.

The linking group of Mf _{1 has} the same meaning as the linking group _{of M 1} of the formula L-3. The linking group of Mf _{2 has} the same meaning as the linking group _{of M 2} in the formula L-3. Examples of the alkyl group of Rf ₁ include alkyl groups having 1 to 4 carbon atoms. The C1-C4 alkyl group of Rf ₁ is preferably methyl or ethyl, more preferably methyl. The alkyl group of Rf ₁ may have a substituent. Examples of the substituent that the alkyl group of Rf ₁ may have include alkoxy groups such as a hydroxyl group, a methoxy group, and an ethoxy group, and halogen atoms such as a cyano group and a fluorine atom. The alkyl group of Rf ₂ and Rf _{3 has} the same meaning as the alkyl group of Rf _1.

Mf ₁ and Rf ₁ may be bonded to each other to form a ring. Examples of the structure in which Mf ₁ and Rf ₁ are bonded to each other to form a ring include the lactone structure represented by LC1-13, LC1-14, or LC1-17 in the lactone structure. Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring. Examples of the structure in which Mf ₂ and Rf ₂ are bonded to each other to form a ring include the lactone structure represented by LC1-7, LC1-8, or LC1-15 in the lactone structure. Examples of the structure in which Mf ₂ and Rf ₃ are bonded to each other to form a ring include a lactone structure represented by any one of the aforementioned LC1-3 to LC1-6 among the aforementioned lactone structures. Although the specific example of a structural unit (a2) is shown below, this invention is not limited to this. * Indicates the bonding position with other structural units.

[化34]

The structural unit having at least two lactone structures usually has optical isomers, and any optical isomers can be used. In addition, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. In the case of mainly using one optical isomer, its optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

Relative to all the structural units in the resin (A), the content of structural units having at least two lactone structures is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol% , And more preferably 30 mol% to 50 mol%. In order to improve the effect of the present invention, two or more structural units having at least two lactone structures may be used in combination. When two or more repeating units having at least two lactone structures are contained, it is preferable that the total content of structural units having at least two lactone structures is the above-mentioned range.

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

Relative to all the structural units of the resin (A), the resin (A) contains at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure (in When there are a plurality of structural units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the total is preferably 5 mol% to 70 mol% , More preferably 10 mol% to 65 mol%, and still more preferably 20 mol% to 60 mol%.

〔Structural units with polar groups〕 The resin (A) preferably contains a structural unit having a polar group. As a polar group, a hydroxyl group, a cyano group, a carboxyl group, etc. are mentioned. The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. In addition, the structural unit having a polar group preferably does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornyl group. The resin (A) preferably has a carboxyl group.

Specific examples of monomers corresponding to the structural unit having a polar group are listed below, but the present invention is not limited to these specific examples. In addition, the following specific examples are described as methacrylate compounds, but they may also be acrylate compounds.

[化35]

In addition, as a specific example of the structural unit having a polar group, the structural unit disclosed in paragraph 0415 to paragraph 0433 of the specification of U.S. Patent Application Publication No. 2016/0070167 can also be cited. Resin (A) may contain the structural unit which has a polar group individually by 1 type, and may contain it using 2 or more types together. Relative to all the structural units in the resin (A), the content of the structural unit having a polar group is preferably 5 mol% to 40 mol%, more preferably 5 mol% to 30 mol%, and still more preferably 10 mol% Mole%～25mole%.

[Structural units that do not have any of acid-decomposable groups and polar groups] The resin (A) may further have a structural unit that does not have any of an acid-decomposable group and a polar group. The structural unit that does not have any of an acid-decomposable group and a polar group preferably has an alicyclic hydrocarbon structure. As a structural unit that does not have any of an acid-decomposable group and a polar group, for example, the structural unit described in paragraph 0236 to paragraph 0237 of the specification of U.S. Patent Application Publication No. 2016/0026083 can be cited. The preferable example of the monomer corresponding to the structural unit which does not have any of an acid-decomposable group and a polar group is shown below.

[化36]

In addition, as a specific example of a structural unit that does not have any of an acid-decomposable group and a polar group, the structural unit disclosed in paragraph 0433 of the specification of U.S. Patent Application Publication No. 2016/0070167 can also be cited. The resin (A) may contain one kind of structural unit that does not have any of an acid-decomposable group and a polar group alone, or may contain two or more kinds in combination. Relative to all the structural units in the resin (A), the content of the structural unit that does not have any of an acid-decomposable group and a polar group is preferably 5 mol% to 40 mol%, more preferably 5 mol% ~30 mol%, more preferably 5 mol% to 25 mol%.

[Repeat unit (a1)] The resin (A) may further have the following repeating unit (a1). The repeating unit (a1) is a repeating unit derived from a monomer (also referred to as "monomer a1") having a glass transition temperature of 50° C. or less when it is made into a homopolymer. In addition, the repeating unit (a1) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a1) does not have an acid-decomposable group.

(Method for measuring the glass transition temperature of homopolymers) Regarding the glass transition temperature of the homopolymer, the value is used when there is a catalog value or a literature value, and when there is no catalog value or a literature value, it is measured by the differential scanning calorimetry (DSC: Differential scanning calorimetry) method. . The weight average molecular weight (Mw) of the homopolymer used for the Tg measurement was set to 18000, and the degree of dispersion (Mw/Mn) was set to 1.7. As a DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. was used, and the measurement was performed at a temperature increase rate of 10° C./min. In addition, the homopolymer used for Tg measurement may be synthesized by a known method using a corresponding monomer, for example, it can be synthesized by a general dropping polymerization method or the like. An example is shown below. 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were heated to 80°C under a nitrogen stream. While stirring the liquid, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After the dropwise addition, it was further stirred at 80°C for 2 hours. After the reaction liquid was left to cool, it was re-precipitated and filtered with a large amount of methanol/water (mass ratio 9:1), and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw/Mn: 1.7). The obtained homopolymer was subjected to DSC measurement. The DSC device and the heating rate are as described above.

The monomer a1 is not particularly limited as long as the glass transition temperature (Tg) when it is made into a homopolymer is 50°C or less. It improves the resolution of the dot pattern and suppresses the roughness of the sidewall of the resist pattern that may occur during etching. From the viewpoint of the degree of temperature, the Tg when it is made into a homopolymer is preferably 30°C or less. The lower limit of Tg when the monomer a1 is made into a homopolymer is not particularly limited, but is preferably -80°C or higher, more preferably -70°C or higher, further preferably -60°C or higher, particularly preferably -50°C or higher . By setting the lower limit of the Tg when the monomer a1 is a homopolymer to the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, which is preferable.

As the repeating unit (a1), it is preferable that the repeating unit has a non-acid-decomposable alkyl group having a carbon number of 2 or more that can contain a hetero atom in the chain in terms of being able to more easily volatilize the residual solvent. The term "non-acid decomposability" in this specification refers to the property that does not cause a separation/decomposition reaction due to the acid generated by the photoacid generator. That is, the so-called "non-acid decomposable alkyl group" more specifically includes: an alkyl group that is not detached from the resin (A) by the action of an acid generated by a photoacid generator, or an alkyl group that is not decomposed by a photoacid generator An alkyl group that is decomposed by the action of the generated acid. The non-acid-decomposable alkyl group may be either linear or branched. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having a carbon number of 2 or more that can include a hetero atom in the chain will be described.

The non-acid-decomposable alkyl group with a carbon number of 2 or more that may contain a hetero atom in the chain is not particularly limited. Examples include an alkyl group with 2 to 20 carbon atoms and a chain with a heteroatom containing 2 carbon atoms. ~20 alkyl. Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or two or more -CH ₂ -via -O-, -S-, -CO-, -NR ₆ -, or the like These combine two or more to form a divalent organic-substituted alkyl group. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of non-acid-decomposable alkyl groups that can contain heteroatoms in the chain and have a carbon number of 2 or more include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and non-acid-decomposable alkyl groups. Base, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, and 2-ethylhexyl, and one or more of these -CH _2- -O- or -O-CO- substituted monovalent alkyl group.

The carbon number of the non-acid-decomposable alkyl group having a hetero atom and a carbon number of 2 or more is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 8 the following. The lower limit of the carbon number of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more. In addition, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, substituent T).

The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

[化37]

In the general formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ represents a non-acid-decomposable alkyl group having a carbon number of 2 or more that may contain a hetero atom in the chain.

The halogen atom represented by R ₁ is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R ₁ is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, and specific examples include methyl, ethyl, and tertiary butyl groups. Among them, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. The cycloalkyl group represented by R ₁ is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups and the like. Among them, R _{1 is} preferably a hydrogen atom or a methyl group.

The definition and preferred aspects of the non-acid-decomposable alkyl group having a carbon number of 2 or more and which may include a hetero atom in the chain represented by R _{2 are as described above.}

In addition, in terms of easier volatilization of the residual solvent, the repeating unit (a1) may be a non-acid-decomposable alkyl group that may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or may contain a heteroatom in the ring member. A repeating unit of non-acid-decomposable cycloalkyl having a carboxyl group or a hydroxyl group. Hereinafter, the repeating unit having a non-acid-decomposable alkyl group which can contain a hetero atom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which can contain a hetero atom in the ring member and has a carboxyl group or a hydroxyl group is carried out. illustrate.

The non-acid-decomposable alkyl group may be either linear or branched. The carbon number of the non-acid-decomposable alkyl group is preferably 2 or more. From the viewpoint that the Tg of the homopolymer is 50°C or less, the upper limit of the carbon number of the non-acid-decomposable alkyl group is preferably 20 or less, for example. .

The non-acid-decomposable alkyl group that can contain a hetero atom in the chain is not particularly limited, and examples include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms that contain a hetero atom in the chain. . Furthermore, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group. Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or two or more -CH ₂ -via -O-, -S-, -CO-, -NR ₆ -, or the like These combine two or more to form a divalent organic-substituted alkyl group. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As the carbon number of the non-acid-decomposable alkyl group which can contain a hetero atom in the chain, it is preferably 2-16, more preferably 2-10 in terms of more excellent crack resistance (less cracks are generated) , More preferably 2-8. Furthermore, the non-acid-decomposable alkyl group may have a substituent (for example, the substituent T). As a specific example of the repeating unit which has a non-acid-decomposable alkyl group which contains a hetero atom in a chain and has a carboxyl group, the repeating unit of the following structure is mentioned, for example.

[化38]

The carbon number of the non-acid-decomposable cycloalkyl group is preferably 5 or more. From the viewpoint that the Tg of the homopolymer is set to 50°C or less, the upper limit of the carbon number of the non-acid-decomposable cycloalkyl group is, for example, 20 or less, more preferably 16 or less, and still more preferably 10 or less.

The non-acid-decomposable cycloalkyl group that may contain a heteroatom in the ring member is not particularly limited. For example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and a ring member C5-20 cycloalkyl group containing heteroatoms. Furthermore, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group. Examples of the cycloalkyl group having 5 to 20 carbon atoms and containing a hetero atom in the ring member include one or two or more -CH ₂ -, -O-, -S-, -CO-, -NR ₆ -, Or a divalent organic-substituted cycloalkyl group formed by combining two or more of these. The R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Furthermore, the non-acid-decomposable cycloalkyl group may have a substituent (for example, the substituent T).

As a repeating unit having a non-acid-decomposable alkyl group that can contain a heteroatom in the chain and have a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group that can contain a heteroatom in the ring member and have a carboxyl group or a hydroxyl group, it is essential In terms of more excellent effects of the invention, the repeating unit represented by the following general formula (1-3) is particularly preferred.

[化39]

In the general formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ represents a non-acid-decomposable alkyl group which may include a hetero atom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may include a hetero atom in a ring member and has a carboxyl group or a hydroxyl group.

In the general formula (1-3), R ₃ and R _{1 have} the same meaning, and preferred aspects are also the same.

The definition of a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or hydroxyl group represented by R ₄ , or a non-acid-decomposable cycloalkyl group which may contain a hetero atom in the ring member and has a carboxyl group or hydroxyl group, and The preferred aspect is as described. Among them, R _{4 is} preferably a non-acid-decomposable cycloalkyl group which can include a hetero atom in the ring member and has a carboxyl group or a hydroxyl group. As this aspect, the repeating unit etc. of the following structure are mentioned, for example.

[化40]

Examples of monomer a1 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), methyl N-Butyl acrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (- 70℃), isononyl acrylate (-82℃), lauryl methacrylate (-65℃), 2-hydroxyethyl acrylate (-15℃), 2-hydroxypropyl methacrylate (26℃), 1-[2-(methacryloxy)ethyl] succinate (9°C), 2-ethylhexyl methacrylate (-10°C), second butyl acrylate (-26°C), Methoxy polyethylene glycol monomethacrylate (n=2) (-20°C), cetyl acrylate (35°C), etc. In addition, the Tg (°C) when it is made into a homopolymer is shown in parentheses.

In addition, methoxy polyethylene glycol monomethacrylate (n=2) is a compound of the following structure.

[化41]

Monomer a1 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, ten acrylate Hexaalkyl ester, 2-hydroxyethyl acrylate, and the compound represented by MA-5 below.

[化42]

The resin (A) may include only one type of repeating unit (a1), or two or more types. In the resin (A), the content of the repeating unit (a1) (the total when there are multiple repeating units (a1)) is preferably 5 mol% or more relative to all the repeating units of the resin (A) , More preferably 10 mol% or more, more preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less. Among them, the content of the repeating unit (a1) in the resin (A) (the total when there are multiple repeating units (a1)) is preferably 5 mol% relative to all repeating units of the resin (A) ~50 mol%, more preferably 5 mol% to 40 mol%, and still more preferably 5 mol% to 30 mol%.

[Repeating unit with phenolic hydroxyl group (a4)] The resin (A) may contain a repeating unit (a4) having a phenolic hydroxyl group. Since the resin (A) contains the repeating unit (a4), the dissolution rate during alkali development is more excellent, and the etching resistance is excellent.

It does not specifically limit as a repeating unit which has a phenolic hydroxyl group, A hydroxystyrene repeating unit, or a hydroxystyrene (meth)acrylate repeating unit is mentioned. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I).

[化43]

In the formula, 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. Among them, R ₄₂ may be _{bonded to Ar 4} to form a ring. In this case, R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or a divalent linking group. Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group, and when it _{bonds with R 42} to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1-5. For the purpose of highly polarizing the repeating unit represented by the general formula (I), it is also preferable that n is an integer of 2 or more, or X ₄ is -COO- or -CONR ₆₄ -.

_{As the alkyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I), preferably substituted methyl, ethyl, propyl, isopropyl, n-butyl, second The alkyl group having 20 or less carbon atoms, such as butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, is more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.

_{The cycloalkyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) may be a monocyclic ring or a polycyclic ring. It is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as optionally substituted cyclopropyl, cyclopentyl, and cyclohexyl. _{Examples of the halogen atom represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred. _{The alkyl group included in the alkoxycarbonyl group represented by R 41} , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in the above-mentioned R ₄₁ , R ₄₂ , and R ₄₃ By.

Examples of preferred substituents in each of the above groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, and halogen atoms. , Alkoxy, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc., the carbon number of the substituent is preferably 8 or less.

Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent. For example, phenylene, phenylene, naphthylene, and anthracenyl are preferably arylene groups having 6 to 18 carbon atoms, or include, for example, Heterocyclic aromatic hydrocarbon groups such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

As a specific example of the (n+1) valence aromatic hydrocarbon group when n is an integer of 2 or more, it is preferable to remove (n-1) arbitrary hydrogens from the specific examples of the divalent aromatic hydrocarbon group. A base made of atoms. The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include: R ₄₁ , R ₄₂ , and in the general formula (I) Alkyl groups listed in R ₄₃ ; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl, and the like. _{The alkyl group of R 64} in -CONR _64- (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, which may have a substituent, An alkyl group having 20 or less carbon atoms, such as n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, is more preferably an alkyl group having 8 or less carbon atoms. X _{4 is} preferably a single bond, -COO-, or -CONH-, and more preferably a single bond, or -COO-.

The _{divalent linking group of L 4} is preferably an alkylene group, and the alkylene group is preferably an optionally substituted methylene, ethylene, propylene, butylene, hexylene, and octylene group. Alkylene having 1 to 8 carbon atoms such as group. Ar _{4 is} preferably an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenyl ring group. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar _{4 is} preferably a benzene ring group.

Although the specific example of the repeating unit which has a phenolic hydroxyl group is shown below, this invention is not limited to this. In the formula, a represents 1 or 2.

[化44]

The resin (A) preferably has a phenolic hydroxyl group. The resin (A) may have one type of repeating unit (a4) alone, or two or more of them may be used in combination. Relative to all the repeating units in the resin (A), the content of the repeating unit (a4) in the resin (A) is preferably 40 mol% or more, more preferably 50 mol% or more, and still more preferably 60 mol% or more . In addition, the content of the repeating unit (a4) relative to all repeating units in the resin (A) is preferably 85 mol% or less, and more preferably 80 mol% or less.

Resin (A) has the above-mentioned structural units, and can be used to adjust dry etching resistance or standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics as a resist. It has various structural units for the purpose of heat resistance and sensitivity. As such a structural unit, the structural unit corresponding to other monomers can be mentioned, but it is not limited to these.

Examples of other monomers include those selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. The compound with an addition polymerizable unsaturated bond, etc. In addition to this, as long as it is an addition polymerizable unsaturated compound that can be copolymerized with a monomer corresponding to the various structural units described above, it may be copolymerized. In the resin (A), the molar ratio of each structural unit is appropriately set in order to adjust various properties.

When the sensitized radiation or radiation-sensitive resin composition of the present invention is used for fluorine-argon (ArF) laser exposure, from the viewpoint of the permeability of ArF light, the resin (A) is preferably substantially free of aroma. Family base. More specifically, among all the structural units of the resin (A), the structural unit having an aromatic group is preferably 5 mol% or less of the whole, more preferably 3 mol% or less, and ideally 0 mol%, That is, it is more preferable not to contain a structural unit having an aromatic group. In addition, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The resin (A) preferably has a (meth)acrylate-based structural unit in all structural units. In this case, resins whose structural units are all methacrylate-based structural units, resins whose structural units are all acrylate-based structural units, and whose structural units are all composed of methacrylate-based structural units and acrylate-based structural units can be used. Any of the resins to be formed, it is preferable that the acrylic structural unit is 50 mol% or less with respect to all the structural units of the resin (A).

When the sensitized radiation or radiation-sensitive resin composition of the present invention is used for exposure of krypton fluoride (KrF), electron beam (EB) or extreme ultraviolet (EUV) exposure, the resin (A) preferably contains Structural units with aromatic hydrocarbon groups. The resin (A) more preferably contains a structural unit having a phenolic hydroxyl group. As a structural unit which has a phenolic hydroxyl group, the said repeating unit (a4) is mentioned, for example. When the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a hydrogen atom having a phenolic hydroxyl group by the action of an acid. The structure protected by the decomposing group (departing group). Relative to all the structural units in the resin (A), the content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol% Mole%, more preferably 50 mole% to 100 mole%.

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

As specific examples of the resin (A), the resin A-1 to the resin A-12 used in the examples can be cited, but it is not limited to these.

The resin (A) may be used singly, or two or more of them may be used in combination. The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more with respect to the total solid content of the sensitized radiation or radiation-sensitive resin composition of the present invention , Particularly preferably above 80% by mass. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 97% by mass or less.

〔Hydrophobic resin〕 It is also preferable that the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (also referred to as "hydrophobic resin (E)"). The sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains at least a hydrophobic resin (E) other than a resin whose polarity is increased by the action of an acid, and a hydrophobic resin (E) whose polarity is increased by the action of an acid. Resin. When the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains the hydrophobic resin (E), the static/dynamic contact angle of the surface of the photosensitive ray-sensitive or radiation-sensitive film can be controlled. Thereby, the development characteristics can be improved, outgassing can be suppressed, the followability of the liquid immersion liquid in the liquid immersion exposure can be improved, and the liquid immersion defect can be reduced. The hydrophobic resin (E) is preferably designed to be biased toward the surface of the resist film. However, unlike surfactants, it does not necessarily have a hydrophilic group in the molecule, and it does not help remove polar/non-polar substances. Mix evenly. In addition, in the present invention, a resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. Moreover, it is preferable that the resin containing the structural unit which has the said acid-decomposable group does not have a fluorine atom.

From the viewpoint of being biased in the surface layer of the film, the hydrophobic resin (E) preferably has a structure selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain part of the resin" At least one kind of structural unit resin in the formed group. When the hydrophobic resin (E) contains fluorine atoms or silicon atoms, the fluorine atoms or silicon atoms in the hydrophobic resin (E) may be included in the main chain of the resin or may be included in the side chain.

The hydrophobic resin (E) preferably has at least one group selected from the group of (x) to (z) below. (X) Acid group (Y) A group that is decomposed by the action of an alkaline developer to increase its solubility in an alkaline developer (hereinafter, also referred to as a polarity conversion group) (Z) The base decomposed by the action of acid

Examples of the acid group (x) include: phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonamide group, (alkylsulfonyl group) (alkyl Carbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl) Group) methylene, bis(alkylsulfonyl)imino group, tri(alkylcarbonyl)methylene, tri(alkylsulfonyl)methylene, etc. As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfoximine group, or a bis(alkylcarbonyl)methylene group is preferable.

As the group (y) that is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer, for example, a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C (O)OC(O)-), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (- OSO ₂ O-), sulfonate group (-SO ₂ O-), etc., preferably a lactone group or a carboxylate group (-COO-). The structural unit including these groups is a structural unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include structural units formed of acrylate and methacrylate. These groups in the structural unit may be bonded to the main chain of the resin via the linking group. Alternatively, the structural unit may be introduced to the end of the resin using a polymerization initiator or chain transfer agent having these groups during polymerization. As a structural unit which has a lactone group, the structural unit which has a lactone structure demonstrated in the previous resin (A) section, for example, is the same.

The content of the structural unit having the group (y) that is decomposed by the action of the alkaline developer to increase the solubility of the alkaline developer is based on all the structural units in the hydrophobic resin (E), and is preferably 1 Mole% to 100 mol%, more preferably 3 mol% to 98 mol%, and still more preferably 5 mol% to 95 mol%.

In the hydrophobic resin (E), the structural unit having a group (z) that is decomposed by the action of an acid may be the same as the structural unit having an acid-decomposable group listed in the resin (A). The structural unit having a group (z) that is decomposed by the action of an acid may have at least any one of a fluorine atom and a silicon atom. Relative to all the structural units in the resin (E), the content of the structural unit having the group (z) decomposed by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% ~80 mol%, more preferably 20 mol% to 60 mol%.

The hydrophobic resin (E) may further have a structural unit different from the above-mentioned structural unit.

With respect to all the structural units contained in the hydrophobic resin (E), the structural unit containing a fluorine atom is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol%. In addition, with respect to all the structural units contained in the hydrophobic resin (E), the structural unit containing a silicon atom is preferably 10 mol% to 100 mol%, and more preferably 20 mol% to 100 mol%.

On the other hand, particularly when the hydrophobic resin (E) contains a CH ₃ partial structure in the side chain portion, the hydrophobic resin (E) is also preferably in a form that does not substantially contain fluorine atoms and silicon atoms. In addition, the hydrophobic resin (E) preferably contains substantially only structural units that only contain atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

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

The total content of the remaining monomer and oligomer components contained in the hydrophobic resin (E) is preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 3% by mass. In addition, the degree of dispersion (Mw/Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin (E), a known resin can be used alone, or a mixture of these can be appropriately selected and used. For example, the well-known resins disclosed in paragraphs 0451 to 0704 of the specification of U.S. Patent Application Publication No. 2015/0168830, and paragraphs 0340 to paragraph 0356 of the specification of U.S. Patent Application Publication No. 2016/0274458 can be preferably used as hydrophobic Resin (E). In addition, the structural unit disclosed in paragraph 0177 to paragraph 0258 of the specification of US Patent Application Publication No. 2016/0237190 is also preferable as a structural unit constituting the hydrophobic resin (E).

-Fluorine-containing resin- The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as "fluorine-containing resin"). When the hydrophobic resin (E) contains a fluorine atom, it is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom. As the aryl group having a fluorine atom, at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom.

As an alkyl group which has a fluorine atom, a cycloalkyl group which has a fluorine atom, and an aryl group which has a fluorine atom, the group represented by Formula F2-Formula F4 is preferable.

[化45]

In Formula F2 to Formula F4, R ⁵⁷ to R ⁶⁸ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched chain). Among them, ^{at least one of R 57} to R ⁶¹ , at least one of R ⁶² to R ⁶⁴ , and at least one of R ⁶⁵ to R ⁶⁸ each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Preferably, all of R ⁵⁷ to R ⁶¹ and R ⁶⁵ to R ⁶⁷ are fluorine atoms. R ⁶² , R ⁶³ and R ^{68 are} preferably alkyl groups in which at least one hydrogen atom is substituted with a fluorine atom (preferably carbon number 1 to 4), more preferably carbon number 1 to 4 perfluoroalkyl group. R ⁶² and R ⁶³ may be connected to each other to form a ring.

Among them, it is preferable that the fluorine-containing resin has alkali decomposability in terms of more excellent effects of the present invention. The so-called alkali decomposability of fluorine-containing resin means that 100 mg of fluorine-containing resin is added to a mixture of 2 mL of pH 10 buffer solution and 8 mL of THF. 30 mol% or more of the total amount of decomposable groups undergoes hydrolysis. In addition, the decomposition rate can be calculated from the ratio of the raw material to the decomposition product obtained by NMR analysis.

From the viewpoints of focus depth tolerance, pattern linearity, improvement of development characteristics, suppression of outgassing, improvement of liquid immersion liquid followability in liquid immersion exposure, and reduction of liquid immersion defects, the fluorine-containing resin is preferably one of formula X Represents the structural unit. In addition, from the viewpoints of the tolerance of the focal depth, the linearity of the pattern, the improvement of the development characteristics, the suppression of outgassing, the improvement of the followability of the liquid immersion in the liquid immersion exposure, and the reduction of the liquid immersion defect, the sensitizing radiation of the present invention may be The radiation-sensitive resin composition preferably further includes a fluorine-containing resin having a structural unit represented by formula X.

[化46]

In formula X, Z represents a halogen atom, ^{a group represented by R 11} OCH ₂ -, or a group represented by R ¹² OC(=O)CH ₂ -, R ¹¹ and R ¹² each independently represent a substituent, and X represents oxygen Atom, or sulfur atom. L represents a (n+1) valent linking group, R ¹⁰ represents a group having a group that increases the solubility of the fluororesin in the alkaline aqueous solution by decomposing by the action of the alkaline aqueous solution, n represents a positive integer, When n is 2 or more, a plurality of R ¹⁰ may be the same as or different from each other.

Examples of the halogen atom of Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Examples of the substituents of R ¹¹ and R ¹² include alkyl groups (preferably carbon number 1 to 4), cycloalkyl groups (preferably carbon number 6 to 10), and aryl groups (preferably carbon number 6～10). In addition, ^{the substituents of R 11} and R ¹² may further have substituents, and examples of such further substituents include alkyl groups (preferably with 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, and alkoxy groups ( Preferably, it is a carbon number of 1 to 4) and a carboxyl group. The linking group as L is preferably a divalent linking group or a trivalent linking group (in other words, n is preferably 1 or 2), and more preferably a divalent linking group (in other words, n is preferably 1). The linking group as L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination of these. For example, when n is 1, and the linking group as L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group. Among them, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred. The divalent aliphatic group can be a chain structure or a cyclic structure, but it is more preferably a chain structure than a cyclic structure, and a linear structure is more preferable for a branched chain structure . The divalent aliphatic group may have a substituent. Examples of the substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, carboxyl group, amino group, cyano group, aryl group, alkoxy group, Aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, arylamino, and diarylamino. As the divalent aromatic group, an aryl group can be mentioned. Among them, phenylene and naphthylene are preferred. The divalent aromatic group may have a substituent, and in addition to the examples of the substituent in the divalent aliphatic group, an alkyl group may also be mentioned. In addition, L may be a divalent group obtained by removing two hydrogen atoms at any positions from the structure represented by the above-mentioned formulas LC1-1 to LC1-21 or formulas SL1-1 to SL-3. When n is 2 or more, as a specific example of the (n+1)-valent linking group, a group obtained by removing arbitrary (n-1) hydrogen atoms from the specific example of the divalent linking group can be cited. As a specific example of L, the following linking group can be mentioned, for example.

[化47]

In addition, these linking groups may further have a substituent as described above.

As R ¹⁰ , a group represented by the following formula W is preferred. -YR ²⁰ type W

In the above-mentioned formula W, Y represents a group that is decomposed by the action of the alkaline aqueous solution to increase the solubility in the alkaline aqueous solution. R ²⁰ represents an electron withdrawing group.

Examples of Y include: carboxylic acid ester group (-COO- or OCO-), acid anhydride group (-C(O)OC(O)-), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-), and sulfonate group (-SO ₂ O-), preferably carboxylate group .

As the electron withdrawing group, a partial structure represented by the following formula EW is preferred. The * in the formula EW represents a bonding bond directly bonding to the group Y in the formula W.

[化48]

In the formula EW, n ^ew is the number of repetitions of the linking group represented by -C(R ^ew1 )(R ^ew2 )-, and represents an integer of 0 or 1. When n ^ew is 0, it represents a single bond, which means that Y ^{ew1 is} directly bonded. Y ^ew1 includes halogen atoms, cyano groups, nitro groups, ^{halogenated (cyclo)alkyl groups represented by -C(R f1} )(R ^f2 )-R ^f3 described later, halogenated aryl groups, oxy groups, carbonyl groups, A sulfonyl group, a sulfinyl group, and a combination of these (wherein, when ^Yew1 is a halogen atom, a cyano group, or a nitro group, n ^ew is 1). R ^ew1 and R ^{ew 2} each independently represent any group, for example, a hydrogen atom, an alkyl group (preferably carbon number 1-8), cycloalkyl (preferably carbon number 3-10) or an aryl group (more Preferably, the carbon number is 6-10). At least two of R ^ew1 , R ^{ew 2} and Y ^ew1 may be connected to each other to form a ring. In addition, the "halogenated (cyclo)alkyl group" means an alkyl group and a cycloalkyl group in which at least a part is halogenated, and the "halogenated aryl group" means an aryl group in which at least a part is halogenated.

Y ^{ew1 is} preferably a halogen atom, a halogenated (cyclo)alkyl group represented by ^{-C(R f1} )(R ^f2 )-R ^{f3, or a halogenated aryl group.}

R ^f1 represents a halogen atom, a perhalogenated alkyl group, a perhalogenated cycloalkyl group, or a perhalogenated aryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group base. R ^f2 and R ^f3 each independently represent a hydrogen atom, a halogen atom, or an organic group, and R ^f2 and R ^f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, and these may be substituted with a halogen atom (preferably a fluorine atom). R ^f2 and R ^{f3 are} preferably (halo)alkyl or (halo)cycloalkyl. More preferably, ^{R f2 represents the same group as R f1} , or is linked to R ^f3 to form a ring. Examples of the ring formed by linking R ^f2 and R ^f3 include a (halogenated) cycloalkyl ring.

The (halogenated) alkyl group in R ^f1 to R ^f3 may be linear or branched. The linear (halogenated) alkyl group preferably has 1 to 30 carbon atoms, more preferably It is 1～20.

The (halogenated) cycloalkyl group in the ring formed by connecting R ^f1 to R ^f3 or R ^f2 and R ^{f3 may be a monocyclic type or a polycyclic type.} In the case of a polycyclic type, the (halo)cycloalkyl group may be a bridged ring type. That is, in this case, the (halo)cycloalkyl group may have a bridge structure. Examples of these (halogenated) cycloalkyl groups include those represented by the following formulae and these halogenated groups. In addition, part of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[化49]

As the R ^f2 and R ^f3, R ^f2 and R ^f3, or formed by connecting ring (halo) cycloalkyl, preferably fluorine cycloalkyl _{-C (n) F (2n-} 2) H expressed by base. Here, the carbon number n is not particularly limited, but is preferably 5-13, more preferably 6.

^Examples of the (per)halogenated aryl group in Yew1 or R ^f1 include perfluoroaryl groups represented by _{-C (n)} F _(n-1). Here, the carbon number n is not particularly limited, but is preferably 5-13, more preferably 6.

^{At least two of Rew1} , ^Rew2, and ^Yew1 can be connected to each other to form a ring, preferably a cycloalkyl group or a heterocyclic group.

Each group and each ring constituting the partial structure represented by the formula EW may further have a substituent.

In the formula W, R ^{20 is} preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group, and more preferably an alkyl group substituted with a halogen atom (haloalkyl) , More preferably a fluoroalkyl group. The number of carbon atoms of the alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group is preferably 1-10, more preferably 1-5. More specifically, R ^{20 is} preferably an atomic group represented by -C(R' ¹ )(R' ^f1 )(R' ^f2 ) or -C(R' ¹ )(R' ² )(R' ^{f1 ).} R ^'1 and R' ² each independently represent a hydrogen atom, or a non-electron withdrawing group-substituted (preferably unsubstituted) alkyl group. ^R'f1 and ^R'f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group. As the R ^'1 and R' ² is alkyl may be linear chain may also be branched, preferably having 1 to 6 carbon atoms. As R ^'f1 and R' ^f2 is a perfluoroalkyl group may be linear chain may also be branched, preferably having 1 to 6 carbon atoms. Preferred specific examples of R ²⁰ _{include: -CF 3} , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -CF(CF ₃ ) ₂ , -CF(CF ₃ )C ₂ F ₅ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -C ₅ F ₁₁ , -C ₆ F ₁₃ , -C ₇ F ₁₅ , -C ₈ F ₁₇ , -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH (CF ₃ ) ₂ , -CH (CF ₃ ) C ₂ F ₅ , -CH ₂ CF (CF ₃ ) ₂ , and -CH ₂ CN. Among them, -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH (CF ₃ ) ₂ , or -CH ₂ CN, more preferably -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH(CF ₃ ) ₂ , or -CH ₂ CN , More preferably -CH ₂ C ₂ F ₅ , -CH(CF ₃ ) ₂ , or -CH ₂ CN, particularly preferably -CH ₂ C ₂ F ₅ , or -CH(CF ₃ ) ₂ .

The structural unit represented by the formula X is preferably a structural unit represented by the following formula X-1 or formula X-2, and more preferably a structural unit represented by the formula X-1.

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In formula X-1, R ²⁰ represents an electron withdrawing group, L ² represents a divalent linking group, X ² represents an oxygen atom or a sulfur atom, and Z ² represents a halogen atom. In formula X-2, R ²⁰ represents an electron withdrawing group, L ³ represents a divalent linking group, X ³ represents an oxygen atom or a sulfur atom, and Z ³ represents a halogen atom.

The specific examples and preferred examples of the divalent linking group as L ² and L ³ are the same as those described in the formula X as the divalent linking group L. The electron withdrawing group of R ² and R ³ is preferably a partial structure represented by the formula EW. Specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.

In the formula X-1, L ² and R ^{2 are} not bonded to each other to form a ring, and in the formula X-2, L ³ and R ^{3 are} not bonded to each other to form a ring.

As X ² and X ³ , an oxygen atom is preferred. As Z ² and Z ³ , a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

In addition, the structural unit represented by formula X is also preferably a structural unit represented by formula X-3.

[化51]

In formula X-3, R ²⁰ represents an electron withdrawing group, R ²¹ represents a hydrogen atom, an alkyl group, or an aryl group, L ⁴ represents a divalent linking group, X ⁴ represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

The specific examples and preferred examples of the divalent linking group as L ⁴ are the same as those described in the formula X as the divalent linking group. The electron withdrawing group as R ⁴ is preferably a partial structure represented by the formula EW, specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.

In addition, in the formula X-3, L ⁴ and R ^{4 are} not bonded to each other to form a ring. X ^{4 is} preferably an oxygen atom.

In addition, the structural unit represented by formula X is also preferably a structural unit represented by formula Y-1 or a structural unit represented by formula Y-2.

[化52]

In Formula Y-1 and Formula Y-2, Z represents a halogen atom, ^{a group represented by R 11} OCH ₂ -, or a group represented by R ¹² OC(=O)CH ₂ -, and R ¹¹ and R ¹² are each independently Represents a substituent, and R ²⁰ represents an electron withdrawing group.

The electron withdrawing group as R ²⁰ is preferably a partial structure represented by the formula EW, and specific examples and preferred examples are also as described above, and more preferably a halogenated (cyclo)alkyl group.

Specific examples and preferred examples of the halogen atom as Z, ^{the group represented by R 11} OCH ₂ -, and the group represented by R ¹² OC(=O)CH ₂ -are the same as those described in Formula 1.

Relative to all the structural units of the fluorine-containing resin, the content of the structural unit represented by formula X is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, and further preferably 30 mol% Ear%～100mol%.

The preferable example of the structural unit which comprises hydrophobic resin (E) is shown below. As a hydrophobic resin (E), the resin which combined these structural units arbitrarily can be mentioned suitably, but it is not limited to this.

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[化54]

The hydrophobic resin (E) may be used singly, or two or more of them may be used in combination. From the viewpoint of reconciliation of liquid immersion liquid followability and development characteristics in liquid immersion exposure, it is preferable to mix and use two or more hydrophobic resins (E) having different surface energies. The content of the hydrophobic resin (E) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass relative to the total solid content of the sensitized radiation or radiation-sensitive resin composition of the present invention ～8% by mass.

＜(D) Acid diffusion control agent＞ The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains an acid diffusion control agent (also referred to as "acid diffusion control agent (D)"). As a preferable aspect, the acid diffusion control agent (D) is preferably an amine compound. The acid diffusion control agent (D) functions as a quenching agent that captures acid generated by an acid generator during exposure, and suppresses the acid-decomposable resin in the unexposed portion caused by excess acid generation Reaction. For example, basic compounds (DA), basic compounds (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, onium salts (DC) which are relatively weak acids for acid generators, and A low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation part, etc. are used as the acid diffusion control agent (D). Among them, from the viewpoint of the linearity of the pattern obtained over time, the sensitizing or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing compound as the acid diffusion control agent (D), and more preferably Contains nitrogen-containing basic compounds. In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, a known acid diffusion control agent can be suitably used. For example, paragraphs 0627 to 0664 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0095 to 0187 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016 The well-known compounds disclosed in paragraphs 0403 to 0423 of the specification /0237190 and paragraphs 0259 to 0328 of the specification of U.S. Patent Application Publication No. 2016/0274458 are used as the acid diffusion control agent (D).

〔Basic Compound (DA)〕 As the basic compound (DA), preferably, a compound having a structure represented by the following formula A to formula E is mentioned.

[化55]

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

The alkyl group in the formula A and the formula E may have a substituent or may be unsubstituted. As for the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. The alkyl group in formula A and formula E is more preferably unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. are preferred, and imidazole is more preferred. Structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative with hydroxyl group and/or ether bond, or hydroxyl group And/or aniline derivatives of ether linkages, etc.

[Basic compound (DB) whose alkalinity decreases or disappears by irradiation with actinic rays or radiation] The basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity decreases or disappears by irradiation with actinic rays or radiation is a compound that has a proton-accepting functional group and is Irradiation of actinic rays or radiation decomposes and the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity.

The so-called proton-accepting functional group is a functional group having a group or electrons that can interact with protons electrostatically. The non-covalent electron pair is the functional group of the nitrogen atom. The nitrogen atom having a non-covalent electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[化56]

Examples of preferable partial structures of the proton-accepting functional group include a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (DB) is decomposed by irradiation with actinic rays or radiation to produce a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity. Here, the decrease or disappearance of proton acceptor, or the change from proton acceptor to acidity, is the change in proton acceptor caused by the addition of protons to the proton acceptor functional group. Specifically, it is It means that when a compound having a proton-accepting functional group (DB) and a proton generate a proton adduct, the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by performing a pH measurement.

The acid dissociation constant pKa of the compound produced by the decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and more preferably -13< pKa<-3.

The so-called acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by the Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can also be used to obtain values from a database based on Hammett's substituent constants and well-known literature values through calculations. The values of pKa described in this manual all indicate the values obtained by calculation using this software package.

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

〔Onium salt (DC) which is relatively weak acid for photoacid generator〕 In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, an onium salt (DC), which is a relatively weak acid with respect to the photoacid generator, can be used as the acid diffusion control agent (D). When a photoacid generator is used in combination with an onium salt that generates an acid that is relatively weak to the acid generated by the photoacid generator, if the photoacid generator is irradiated with actinic rays or radiation, the photoacid generator generates The acid collides with an unreacted onium salt with a weak acid radical anion, and the weak acid is released by the salt exchange and an onium salt with a strong acid radical anion is produced. In this process, the strong acid is exchanged for the weak acid with lower catalytic ability. Therefore, apparently, the acid is deactivated and the acid diffusion can be controlled.

From the viewpoints of the tolerance of the focal depth and the linearity of the pattern, the sensitizing radiation or radiation-sensitive resin composition of the present invention preferably further includes one selected from the group consisting of formula d1-1 to formula d1-3 At least one compound in the group consisting of compounds.

[化57]

In formulas d1-1 to d1-3, R ⁵¹ represents an optionally substituted hydrocarbon group, and Z ^2c represents an optionally substituted hydrocarbon group of 1 to 30 carbon atoms, which is not bonded to the carbon atom adjacent to the S atom It has a fluorine atom, R ⁵² represents an organic group, Y ³ represents a linear, branched or cyclic alkylene or arylene group, Rf represents a hydrocarbon group containing a fluorine atom, and M ⁺ each independently represents an ammonium cation, Sulfur cation or iodo cation.

As for ^{the preferable example of the amenium cation or the iodonium cation represented as M +} , the amenium cation exemplified in the formula ZI and the iodonium cation exemplified in the formula ZII can be cited.

The onium salt (DC) which is a relatively weak acid for the photoacid generator may also be a compound having a cation site and an anion site in the same molecule, and the cation site and anion site are linked by a covalent bond (hereinafter, Also known as "Compound (DCA)"). The compound (DCA) is preferably a compound represented by any one of the following formula C-1 to formula C-3.

[化58]

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

Examples of substituents having 1 or more carbon atoms in R ¹ to R ³ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, and alkylamines. Carbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, etc. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

^{Examples of L 1} as the divalent linking group include linear or branched alkylene, cycloalkylene, arylene, carbonyl, ether bond, ester bond, amide bond, urethane bond, urea A bond, and a base formed by combining two or more of these. L ^{1 is} preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more of these.

[Low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid] The low-molecular compound (DD) having a nitrogen atom and a group that is released by the action of an acid (hereinafter, also referred to as "compound (DD)") preferably has a nitrogen atom that is released by the action of an acid -Based amine derivatives. The group to be released by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a semiamine acetal ether group, and more preferably a urethane group Ester group, or semiamine acetal ether group. The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The compound (DD) may have a urethane group containing a protective group on the nitrogen atom. The protecting group constituting the urethane group can be represented by the following formula d-1.

[化59]

In formula d-1, R ^b each independently represents a hydrogen atom, an alkyl group (preferably carbon number 1-10), cycloalkyl group (preferably carbon number 3-30), aryl group (preferably carbon number 3-30), aralkyl (preferably carbon number 1-10), or alkoxyalkyl (preferably carbon number 1-10). R ^b may be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R ^b can be independently passed through functional groups such as hydroxyl, cyano, amino, pyrrolidinyl, piperidinyl, morpholinyl, and pendant oxy groups. Alkoxy or halogen atom substitution. The same applies to the alkoxyalkyl group represented by ^{R b.}

As R ^b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. Examples of the ring formed by linking two R ^b with each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. As a specific structure of the group represented by formula d-1, the structure disclosed in paragraph 0466 of the specification of U.S. Patent Application Publication No. 2012/0135348 can be cited, but it is not limited to this.

The compound (DD) preferably has a structure represented by Formula 6 below.

[化60]

In Formula 6, l represents an integer from 0 to 2, and m represents an integer from 1 to 3, and satisfies l+m=3. R ^a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When 1 is 2, two ^Ras may be the same or different, and two ^Ras may be connected to each other and form a heterocyclic ring together with the nitrogen atom in the formula. Heteroatoms other than the nitrogen atom in the formula may be included in the heterocyclic ring. R ^b in the formula 1 d-R ^b in the same sense, the preferred embodiments are also the same. In Formula 6, the alkyl group, cycloalkyl group, aryl group, and aralkyl group ^{as R a} may be independently substituted with a group that is the same as the alkyl group, cycloalkyl group, aryl group, and aryl group ^{as R b.} And the aralkyl group which may be substituted are the same as those mentioned above.

Specific examples of the above R ^a is alkyl, cycloalkyl, aryl, and aralkyl groups (the group may be substituted with those of the group) include the specific examples of R ^b and on the same base . As the specific structure of the particularly preferred compound (DD) in the present invention, the compound disclosed in paragraph 0475 of the specification of U.S. Patent Application Publication No. 2012/0135348 can be cited, but it is not limited to this.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic part including a nitrogen atom in the cation part. The basic part is preferably an amine group, and more preferably an aliphatic amine group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom. As a preferable specific structure of the compound (DE), the compound disclosed in paragraph 0203 of the specification of U.S. Patent Application Publication No. 2015/0309408 can be cited, but it is not limited to this.

The following shows a preferable example of the acid diffusion control agent (D), but it is not limited to this.

[化61]

[化62]

[化63]

[化64]

[化65]

[化66]

In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more kinds. The content of the acid diffusion control agent (D) in the composition (the total when there are multiple types) is based on the total solid content of the composition, and is preferably 0.01% by mass to 10% by mass, more preferably 0.02% by mass %～5 mass%.

＜Solvent＞ The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent (also referred to as "solvent (F)"), and more preferably contains an organic solvent. In the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention, a known resist solvent can be suitably used. For example, paragraphs 0665 to 0670 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0210 to 0235 of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication No. 2016/ Paragraph 0424 to Paragraph 0426 of Specification No. 0237190, and Paragraph 0357 to Paragraph 0366 of Specification No. 2016/0274458 of U.S. Patent Application Publication are known solvents. Examples of solvents that can be used when preparing the composition include: alkanediol monoalkyl ether carboxylate, alkanediol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic internal Esters (preferably with 4 to 10 carbons), monoketone compounds that may have a ring (preferably with 4 to 10 carbons), alkylene carbonate, alkyl alkoxy acetate, and alkyl pyruvate And other organic solvents.

As the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group in the structure can also be used. As a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, the exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, an alkanediol monoalkyl ether, an alkyl lactate, etc. are preferred, and propylene glycol is more preferred. Monomethyl ether (PGME (propylene glycol monomethyl ether): 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate. In addition, as a solvent that does not contain a hydroxyl group, an alkanediol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, or an alkyl acetate is preferred. Etc. Among these, more preferred are propylene glycol monomethyl ether acetate (PGMEA (propylene glycol monomethyl ether acetate): 1-methoxy-2-acetoxypropane), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate, more preferably propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclic Hexanone, cyclopentanone or 2-heptanone. As the solvent not containing a hydroxyl group, propylene carbonate is also preferred. Among these, from the viewpoint of the uniformity of the formed layer, the solvent particularly preferably contains γ-butyrolactone. The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is preferable. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate.

The solid content concentration of the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, and is preferably 0.5% by mass to 50% by mass, more preferably 1.0% by mass to 45% by mass, and still more preferably 1.0% by mass %～40% by mass. As a preferable aspect, the solid content concentration of the sensitized radiation-sensitive or radiation-sensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more. The so-called solid content concentration is the mass percentage of the mass of the resist components other than the solvent relative to the total mass of the composition.

＜(H) Surfactant＞ The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant (also referred to as "surfactant (H)"). As a preferable aspect, the sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention further contains a surfactant (H). When a surfactant is contained, it is preferably a fluorine-based and silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or those having both fluorine atoms and silicon atoms). Surfactant) at least one of them.

The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, and when an exposure light source with a wavelength of 250 nm or less, especially a wavelength of 220 nm or less, is used, adhesion can be obtained with good sensitivity and resolution And a resist pattern with less development defects. Examples of the fluorine-based or silicone-based surfactant include the surfactants described in paragraph 0276 of the specification of U.S. Patent Application Publication No. 2008/0248425. In addition, other surfactants other than the fluorine-based or silicone-based surfactants described in paragraph 0280 of the specification of U.S. Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used singly, or two or more of them may be used in combination. When the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.0001% by mass to 2% by mass, and more preferably It is 0.0005 mass% to 1 mass%. On the other hand, when the content of the surfactant is set to 0.0001% by mass or more with respect to the total solid content of the composition, the surface deflection existence of the hydrophobic resin improves. Thereby, the surface of the sensitized radiation-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during liquid immersion exposure can be improved.

＜Other additives＞ The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention may further contain other well-known additives. Examples of other additives include acid multiplying agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution promoters, and the like.

The sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention preferably dissolves the components in a predetermined organic solvent, preferably the mixed solvent, and filters it, for example, coating on a predetermined organic solvent. On the support (substrate). The pore size (pore size) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, when the solid content of the sensitized radiation or radiation-sensitive resin composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, and more It is preferably 0.5 μm or less, and more preferably 0.3 μm or less. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, as disclosed in Japanese Patent Laid-Open No. 2002-62667, for example, cyclic filtration may be performed, and multiple filters may be connected in series or in parallel to perform filtration. In addition, the composition may be filtered multiple times. Furthermore, the composition may be degassed before and after filtration by the filter.

＜Use＞ The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is a sensitizing ray-sensitive or radiation-sensitive resin composition whose properties are changed by reaction with light irradiation. In more detail, the photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention relates to a semiconductor manufacturing process such as an integrated circuit (IC), the manufacturing of a circuit board such as a liquid crystal or a thermal head, etc. A photosensitive ray-sensitive or radiation-sensitive resin composition used in the production of a mold structure for imprinting, other photosensitive etching processing steps, or the production of a lithographic printing plate or an acid-curable composition. The resist pattern formed by the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention can be used in an etching step, an ion implantation step, a bump electrode formation step, a rewiring formation step, and a microelectromechanical system (Micro Electro Mechanical System). Systems, MEMS) etc.

(Sensitized radiation or radiation-sensitive linear film) The actinic radiation or radiation-sensitive film (preferably a resist film) of the present invention is a film formed from the actinic radiation or radiation-sensitive resin composition of the present invention. The actinic radiation or radiation-sensitive film of the present invention is a cured product of the actinic radiation or radiation-sensitive resin composition of the present invention. The cured product in the present invention may be any one having at least a part of the solvent removed from the sensitizing radiation or radiation-sensitive resin composition of the present invention. Specifically, the actinic radiation or radiation-sensitive film of the present invention can be obtained, for example, by coating the actinic radiation or radiation-sensitive resin composition of the present invention on a support such as a substrate and then drying. The "drying" refers to removing at least a part of the solvent contained in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention. The drying method is not particularly limited, and a known method can be used, and examples thereof include drying by heating (for example, 70° C. to 130° C., 30 seconds to 300 seconds). It does not specifically limit as a heating method, A well-known heating mechanism can be used, For example, a heater, an oven, a hotplate, an infrared lamp, an infrared laser, etc. are mentioned.

The components contained in the sensitizing radiation or radiation-sensitive film of the present invention are the same as the components included in the sensitizing radiation or radiation-sensitive resin composition of the present invention after removing the solvent, and preferred aspects are also the same. The content of each component contained in the sensitizing radiation or radiation-sensitive film of the present invention corresponds to the "total content" in the description of the content of each component other than the solvent of the sensitizing radiation or radiation-sensitive resin composition of the present invention. The description of "solid content" is replaced with "total mass of sensitizing radiation or radiation sensitive film".

The thickness of the sensitized radiation-sensitive or radiation-sensitive film of the present invention is not particularly limited, and is preferably 50 nm to 3000 nm, more preferably 80 nm to 2500 nm. In addition, when a thick sensitizing or radiation-sensitive film is to be formed as the memory device becomes three-dimensional, it is preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and still more preferably 2 μm or more. μm or more and 20 μm or less. In general, in order to form a thick actinic ray-sensitive or radiation-sensitive film, there is a tendency to increase the solid content concentration in the actinic ray-sensitive or radiation-sensitive composition. Since such a composition can contain a large amount of components such as a resin and a photoacid generator, there is a tendency that more excellent stability over time is required. The sensitizing radiation or radiation-sensitive resin composition of the present invention is very excellent in stability over time, and therefore can be suitably used in the case of forming such a thick sensitizing radiation or radiation-sensitive film.

(Pattern forming method) The pattern forming method of the present invention includes: A step (exposure step) of exposing the sensitized ray-sensitive or radiation-sensitive film (preferably a resist film) of the present invention with actinic rays or radiation; and A step of developing the sensitized radiation-sensitive or radiation-sensitive film after the exposure step using a developing solution (developing step). In addition, the pattern forming method of the present invention may also be a method including the steps of forming a photosensitive ray-sensitive or radiation-sensitive film on a support using the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention (Film forming step); A step of exposing the sensitized ray-sensitive or radiation-sensitive film with actinic rays or radiation (exposure step); and A step of developing the sensitized radiation-sensitive or radiation-sensitive film after the exposure step using a developing solution (developing step).

＜Film forming step＞ The pattern forming method of the present invention may include a film forming step. As a method of forming the sensitizing radiation or radiation sensitive film in the film forming step, for example, the drying described in the item of the sensitizing radiation or radiation sensitive film can be used to form the sensitizing radiation or radiation sensitive film. Sexual film method.

[Support] The support is not particularly limited. In addition to semiconductor manufacturing steps such as ICs, or circuit substrate manufacturing steps such as liquid crystals or thermal heads, it can be used in other photolithography steps generally used in photosensitive etching processing. Substrate. Specific examples of the support include inorganic substrates such as _{silicon, SiO 2, and SiN.}

<Exposure step> The exposure step is a step of exposing the sensitizing radiation or radiation-sensitive film with light. The exposure method may be liquid immersion exposure. The pattern forming method of the present invention may include multiple exposure steps. The type of light (actinic rays or radiation) used in the exposure can be selected in consideration of the characteristics of the photoacid generator and the shape of the pattern to be obtained. Examples include infrared light, visible light, ultraviolet light, far ultraviolet light, Extreme ultraviolet light (EUV), X-ray, electron beam, etc. are preferably extreme ultraviolet light. For example, it is preferably an actinic ray with a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 nm to 200 nm. Specifically, the light used is KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm) , Or electron beam, etc., preferably ArF excimer laser, EUV or electron beam. Among them, the exposure in the exposure step is preferably performed by liquid immersion exposure using ArF excimer laser. The exposure amount is preferably 5 mJ/cm ² to 200 mJ/cm ² , and more preferably 10 mJ/cm ² to 100 mJ/cm ² .

<Development step> The developer used in the development step may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer), and is preferably an alkaline aqueous solution.

〔Alkaline developer〕 As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide can be preferably used. In addition, inorganic bases, primary to tertiary amines, alkanolamines, and cyclic amines can also be used. Alkaline aqueous solutions such as amines. Furthermore, the alkaline developer may contain an appropriate amount of at least one of alcohols and surfactants. The alkali concentration of the alkaline developer is preferably 0.1% by mass to 20% by mass. The pH of the alkaline developer is preferably 10-15. The time for developing using an alkaline developer is preferably 10 seconds to 300 seconds. The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the formed pattern.

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

-Ketone solvent- Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, Ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate, etc.

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

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

The said solvent may mix multiple types, and may mix with the solvent or water other than the said. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably contains substantially no water. Relative to the total amount of the developer, the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass Above and 100% by mass or less, particularly preferably 95% by mass or more and 100% by mass or less.

-Surfactant- The organic developer may contain a known surfactant in an appropriate amount as necessary. The content of the surfactant relative to the total mass of the developer is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and still more preferably 0.01% by mass to 0.5% by mass.

-Acid diffusion control agent- The organic developer may also contain the acid diffusion control agent described above.

〔Development method〕 As the development method, for example, a method of immersing the substrate in a tank filled with developer for a fixed period of time (dipping method); a method of depositing developer on the surface of the substrate using surface tension and leaving it to stand for a fixed period of time (puddle) Method); the method of spraying the developer on the surface of the substrate (spray method); or the method of continuously spraying the developer on the substrate rotating at a fixed speed while scanning the developer ejection nozzle at a fixed speed (dynamic distribution method), etc.

It is also possible to combine the step of developing using an alkaline aqueous solution (alkaline development step) and the step of developing using a developer containing an organic solvent (organic solvent development step). By this, it is possible to perform pattern formation not only by dissolving the intermediate exposure intensity area, and therefore it is possible to form a finer pattern.

<Pre-heating step, post-exposure heating step> The pattern forming method of the present invention preferably includes a pre-heating (PB: PreBake) step before the exposure step. The pattern forming method of the present invention may include multiple pre-heating steps. The pattern forming method of the present invention preferably includes a post-exposure heating (PEB: Post Exposure Bake) step after the exposure step and before the development step. The pattern forming method of the present invention may include a heating step after multiple exposures. The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C in any of the pre-heating step and the post-exposure heating step. The heating time in any of the pre-heating step and the post-exposure heating step is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and still more preferably 30 seconds to 90 seconds. Heating can be performed by the mechanism included in the exposure device and the developing device, or by using a heating plate or the like.

<Resist base film formation step> The pattern forming method of the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) before the film forming step. The step of forming a resist underlayer film is to form a resist underlayer film (for example, Spin On Glass (SOG), Spin On Carbon (SOC), SOC), between the resist film and the support. Anti-reflective film, etc.) steps. As the resist underlayer film, a known organic or inorganic material can be suitably used.

＜Protection film formation procedure＞ The pattern forming method of the present invention may further include a step of forming a protective film (protective film forming step) before the development step. The protective film forming step is a step of forming a protective film (top coat layer) on the upper layer of the resist film. As a protective film, a well-known material can be used suitably. For example, U.S. Patent Application Publication No. 2007/0178407 Specification, U.S. Patent Application Publication No. 2008/0085466 Specification, U.S. Patent Application Publication No. 2007/0275326 Specification, U.S. Patent Application Publication No. 2016/ The protective film forming composition disclosed in specification 0299432, specification of U.S. Patent Application Publication No. 2013/0244438, and International Publication No. 2016/157988. The composition for forming a protective film is preferably one containing the acid diffusion control agent. You may form a protective film on the upper layer of the resist film containing the said hydrophobic resin.

＜Rinse step＞ The pattern forming method of the present invention preferably includes a step of washing with a rinse solution (rinsing step) after the development step.

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

[In the case of a development step using an organic developer] The rinsing liquid used in the rinsing step after the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the eluent, it is preferable to use an eluent containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Lotion. Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same ones as those described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing a monohydric alcohol is more preferable.

Examples of monohydric alcohols used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specific examples include: 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2 -Pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4- Octanol, and methyl isobutyl methanol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl Isobutyl methanol and so on.

Each component may mix multiple types, and may mix and use with organic solvents other than the said. The water content in the rinsing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the moisture content to 10% by mass or less, good development characteristics can be obtained.

The eluent may contain an appropriate amount of surfactant. In the rinsing step, a rinsing liquid containing an organic solvent is used to clean the substrate that has been developed with an organic developer. The method of cleaning treatment is not particularly limited. For example, it can be applied: a method of continuously spraying rinsing liquid on a substrate rotating at a fixed speed (spin coating method), and a method of immersing the substrate in a tank filled with rinsing liquid for a fixed period of time (Dipping method), or a method of spraying rinsing liquid on the surface of the substrate (spray method), etc. Among them, it is preferable to use a spin coating method for cleaning treatment, after cleaning, the substrate is rotated at a rotation speed of 2,000 rpm to 4,000 rpm (revolutions per minute) to remove the eluent from the substrate. In addition, it is also preferable to include a heating step (Post Bake) after the rinsing step. Through the heating step, the developer and rinsing liquid remaining between and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is preferably 40°C to 160°C, more preferably 70°C to 95°C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.

＜Improvement of surface roughness＞ For the pattern formed by the pattern forming method of the present invention, a method of improving the surface roughness of the pattern can be applied. As a method of improving the surface roughness of the pattern, for example, a method of processing a resist pattern by a plasma containing hydrogen-containing gas disclosed in the specification of U.S. Patent Application Publication No. 2015/0104957 can be cited. In addition to this, Japanese Patent Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, "Proc. of SPIE (The International Society for Optical Engineering)) "(Vol. 8328 83280N-1) "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" is a well-known method described in "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement." In addition, the resist pattern formed by the method can be used, for example, as a core material for the spacer process disclosed in Japanese Patent Laid-Open No. 3-270227 and U.S. Patent Application Publication No. 2013/0209941 ( Core).

(Method of manufacturing electronic devices) The manufacturing method of the electronic device of this invention includes the pattern formation method of this invention. The electronic device manufactured by the manufacturing method of the electronic device of the present invention can be preferably mounted on electrical and electronic equipment (for example, home appliances, office automation (OA) related equipment, media related equipment, optical equipment, and communication equipment, etc.) )middle. [Example]

Examples are listed below to more specifically describe the embodiments of the present invention. The materials, usage amount, ratio, processing content, and processing order shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are quality standards.

<Resin (A)> The structure of the resin (A-1 to A-12) used is shown below. Furthermore, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) as described above. Styrene conversion amount). In addition, the composition ratio (mole% ratio) of the resin ^{was measured by 13} C-nuclear magnetic resonance (NMR).

[化67]

[化68]

[化69]

In addition, the unit of the content ratio of each repeating unit of the resin is mole %. ^t Bu represents the tertiary butyl group, Et represents the ethyl group, and ⁿ Bu represents the n-butyl group.

For the value of the glass transition temperature (Tg) when the monomer a1 is made into a homopolymer, please refer to the description of PCT/JP2018/018239. It corresponds to the repeating unit (a1) of the monomer (monomer a1) whose glass transition temperature (Tg) is below 50°C.

<Photo acid generator (B)> The structure of the photo acid generator (B-1 to B-16) used is shown below. ⁿ Bu represents n-butyl, and ^t Bu represents tertiary butyl. In addition, the photoacid generator (BX-1 to BX-3) is not a photoacid generator (B), but it is easy to understand, and is described below.

[化70]

[化71]

＜Acid diffusion control agent (D)＞ The structure of the acid diffusion control agent (D) used is shown below.

[化72]

The following shows the surfactants used.

[化73]

E-2: Megafac R-41 (manufactured by DIC (stock)) E-3: KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.) E-4: Megafac F176 (manufactured by DIC (stock)) E-5: Megafac R08 (manufactured by DIC (Stock))

The following shows the additives used.

[化74]

The following shows the solvents used. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Ethyl lactate S-4: Ethyl 3-ethoxypropionate S-5: 2-Heptanone S-6: Methyl 3-methoxypropionate S-7: 3-methoxybutyl acetate S-8: Butyl acetate

(Example 1 to Example 35, and Comparative Example 1 to Comparative Example 3) <Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition> (KrF exposure) (Example 1 to Example 7, Example 10 to Example 16, Example 19 to Example 31, Example 35, Comparative Example 1 to Comparative Example 3) Each component shown in Table 1 was mixed with the content (mass %) shown in Table 1, and the solution of the solid content concentration (mass %) shown in Table 1 was obtained. Then, the obtained solution was filtered with a polyethylene filter having a pore size of 3 μm, thereby preparing a sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition). In addition, in the resist composition, the so-called solid content refers to all components other than the solvent. The obtained resist composition was used in Examples and Comparative Examples. In addition, the content (mass %) of each component other than the solvent in Table 1 refers to the content ratio with respect to the total solid content. In addition, the usage amount (parts by mass) of the solvent used is described in the table.

<Pattern formation method (1): KrF exposure, alkaline aqueous solution development> Using the spin coater "ACT-8" manufactured by Tokyo Electronics Co., Ltd., applied to the Si substrate (advanced material) treated with hexamethyldisilazane No anti-reflective layer is provided on the product made by Advanced Materials Technology (hereinafter also referred to as "substrate"), and the prepared resist composition is coated, and heated and dried at 150°C for 60 seconds (PB ), thereby forming a resist film with a thickness of 5 μm. For this resist film, there is a mask with a line and space pattern with a space pattern of 250 nm and a pitch of 1000 nm after performing reduced projection exposure and positive development. A KrF excimer laser scanner (Ace Manufactured by ASML, PAS5500/850C, wavelength 248 nm), pattern exposure was performed under the exposure conditions of NA=0.68 and σ=0.60. After irradiation, it is baked at 130°C for 60 seconds (PEB), immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried to form Line and space patterns with a spatial dimension of 250 nm and a pitch of 1000 nm. Expose through the mask, set the line and space pattern formed to have a spatial size of 250 nm and a pitch of 1000 nm as the optimal exposure, and the optimal exposure as the sensitivity (mJ/ cm ² ). The measurement of the space pattern width is using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Co., Ltd.). Through the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

<Performance evaluation> [Stability with time] After the resist composition was stored at 40°C for 4 weeks, line and space patterns were formed in the same manner as described above. In the obtained pattern, the sensitivity was determined in the same manner as described above, and the sensitivity of the pattern formed by using the resist composition before preservation with time was evaluated in accordance with the following criteria. The difference in the sensitivity of the pattern formed by the resist composition after the week), that is, the degree of sensitivity variation. (Criteria) A: The observed sensitivity fluctuation is less than 1 mJ/cm ² B: The observed sensitivity fluctuation is 1 mJ/cm ² or more and less than 2 mJ/cm ² C: The observed sensitivity fluctuation is 2 mJ /cm ² or more and less than 3 mJ/cm ² D: The observed sensitivity variation is 3 mJ/cm ² or more and less than 4 mJ/cm ² E: The observed sensitivity variation is 4 mJ/cm ² or more

<Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition> (ArF exposure) (Example 8 to Example 9, Example 17 to Example 18, Example 32) Each component shown in Table 1 was mixed with the content (mass %) shown in Table 1, and the solution of the solid content concentration (mass %) shown in Table 1 was obtained. Then, the obtained solution was filtered with a polyethylene filter having a pore size of 0.1 μm, thereby preparing a sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition). In addition, in the resist composition, the so-called solid content refers to all components other than the solvent. The obtained resist composition was used in the examples. The content (mass %) of each component other than the solvent in Table 1 refers to the content ratio with respect to the total solid content. In addition, the amount (parts by mass) of the solvent used is described in Table 1.

<Pattern formation method (2): ArF exposure, alkaline aqueous solution development (positive)> No anti-reflection is provided on the Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane Layer, the resist composition prepared as described above is applied at a rotation speed that becomes the target film thickness, and baked at a temperature of 120° C. for 60 seconds to form a sensitizing radiation or sensitivity with a film thickness of 700 nm Radial film (resist film). For the wafer on which the resist film is formed, use an ArF excimer laser scanner (manufactured by ASML, PAS5500/1500, wavelength 193 nm, NA 0.50), and pattern exposure through an exposure mask . Then, after baking for 60 seconds at a temperature of 115°C, developing with a 2.38% by mass Tetramethyl Ammonium Hydroxide aqueous solution (TMAHaq) for 30 seconds, and rinsing with pure water, Perform spin drying. In this way, a line and space pattern with a spatial size of 250 nm and a pitch of 1500 nm is obtained. The line and space pattern formed has a spatial size of 250 nm and an exposure of 1500 nm as the optimal exposure, and the optimal exposure is the sensitivity (mJ/cm ² ). The measurement of the space pattern width is using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Co., Ltd.). Through the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

<Pattern formation method (3): ArF exposure, organic solvent development (negative)> Exposure using the light-transmitting part and light-shielding part of the exposure mask used in the pattern formation method (2) (positive development) inverted Mask, and use butyl acetate (organic developer) instead of 2.38% by mass tetramethylammonium hydroxide aqueous solution (TMAHaq), and use methyl isobutyl carbinol (MIBC) instead of pure water. The same operation as the pattern forming method (2) is used to obtain a line and space pattern with a space size of 250 nm and a pitch of 1500 nm. The line and space pattern formed has a spatial size of 250 nm and an exposure of 1500 nm as the optimal exposure, and the optimal exposure is the sensitivity (mJ/cm ² ). The measurement of the space pattern width is using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Co., Ltd.).

<Performance evaluation> [Stability with time] After the resist composition was stored at 40°C for 4 weeks, line and space patterns were formed in the same manner as described above. In the obtained pattern, the sensitivity was determined in the same manner as described above, and the sensitivity of the pattern formed by using the resist composition before preservation with time was evaluated in accordance with the following criteria. The difference in the sensitivity of the pattern formed by the resist composition after the week), that is, the degree of sensitivity variation. (Criteria) A: The observed sensitivity fluctuation is less than 1 mJ/cm ² B: The observed sensitivity fluctuation is 1 mJ/cm ² or more and less than 2 mJ/cm ² C: The observed sensitivity fluctuation is 2 mJ /cm ² or more and less than 3 mJ/cm ² D: The observed sensitivity variation is 3 mJ/cm ² or more and less than 4 mJ/cm ² E: The observed sensitivity variation is 4 mJ/cm ² or more

<Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition> (EUV exposure) (Example 34) Each component shown in Table 1 was mixed with the content (mass %) shown in Table 1, and the solution of the solid content concentration (mass %) shown in Table 1 was obtained. Then, the obtained solution was filtered in the order of a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 5 nm, thereby preparing Sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition). In addition, in the resist composition, the so-called solid content refers to all components other than the solvent. The obtained resist composition was used in the examples. The content (mass %) of each component other than the solvent in Table 1 refers to the content ratio with respect to the total solid content. In addition, the amount (parts by mass) of the solvent used is described in Table 1.

<Pattern formation method (4): EUV exposure, alkali development (positive)> Coating AL412 (manufactured by Brewer Science) on a silicon wafer, and baking at 205°C for 60 seconds. The underlying film with a thickness of 30 nm. The resist composition shown in the table was coated thereon, and baked (PB) was performed at 120° C. for 60 seconds to form a positive resist film with a film thickness of 30 nm. For this resist film, use EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, 0.68 for outer sigma, 0.36 for inner sigma) Perform pattern illumination. Furthermore, as a reticle, a mask with line size=40 nm and line:space=1:1 is used. After the exposed resist film is baked (PEB) for 60 seconds at 120°C, it is developed with a tetramethylammonium hydroxide aqueous solution (TMAH, 2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Seconds. The silicon wafer is rotated at a speed of 4000 rpm for 30 seconds, and then baked at 90°C for 60 seconds to obtain a line and space pattern with a pitch of 80 nm and a line width of 40 nm (space width 40 nm). ^{In addition, set the optimal exposure (sensitivity) (mJ/cm 2} ) for forming a line-to-space (LS) pattern with a pitch of 80 nm and a line width of 40 nm. In the determination of the sensitivity, the spatial width of the pattern is measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Tech Co., Ltd.). Through the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

<Performance evaluation> [Stability with time] After the resist composition was stored at 40°C for 4 weeks, line and space patterns were formed in the same manner as described above. In the obtained pattern, the sensitivity was determined in the same manner as described above, and the sensitivity of the pattern formed by using the resist composition before preservation with time was evaluated in accordance with the following criteria. The difference in the sensitivity of the pattern formed by the resist composition after the week), that is, the degree of sensitivity variation. (Criteria) A: The observed sensitivity fluctuation is less than 1 mJ/cm ² B: The observed sensitivity fluctuation is 1 mJ/cm ² or more and less than 2 mJ/cm ² C: The observed sensitivity fluctuation is 2 mJ /cm ² or more and less than 3 mJ/cm ² D: The observed sensitivity variation is 3 mJ/cm ² or more and less than 4 mJ/cm ² E: The observed sensitivity variation is 4 mJ/cm ² or more

<Preparation of sensitizing radiation-sensitive or radiation-sensitive resin composition> (EB exposure) (Example 33) The various components shown in Table 1 were mixed, and the solid content concentration (mass %) described in Table 1 was mixed to obtain a solution. The obtained liquid was filtered with a polytetrafluoroethylene filter having a pore size of 0.03 μm, thereby obtaining a sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition). In addition, in the resist composition, the so-called solid content refers to all components other than the solvent. The obtained resist composition was used in the examples. The content (mass %) of each component other than the solvent in Table 1 refers to the content ratio with respect to the total solid content. In addition, the amount (parts by mass) of the solvent used is described in Table 1.

<Pattern formation method (5): EB exposure, alkali development (positive)> The resist composition shown in Table 1 was coated on a 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Co., Ltd., at 110 Bake (PB) on a hot plate at ℃ for 90 seconds to obtain a resist film with a film thickness of 80 nm. The resist film was patterned using an electron beam drawing device (manufactured by Elionix Co., Ltd.; ELS-7500, acceleration voltage 50 KeV). Furthermore, as a mask, a mask with line size=100 nm and line:space=1:1 is used. After irradiation, bake on a hot plate (PEB) at 110°C for 90 seconds, immerse in a 2.38% by mass tetramethylammonium hydroxide aqueous solution as a developer for 60 seconds, and rinse with pure water for 30 seconds. It is dried in seconds to obtain a line and space pattern with a pitch of 200 nm and a line width of 100 nm (space width of 100 nm). ^{In addition, set the optimal exposure (sensitivity) (μC/cm 2} ) for forming a line-to-space (LS) pattern with a pitch of 200 nm and a line width of 100 nm. In the determination of the sensitivity, the spatial width of the pattern is measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Tech Co., Ltd.). Through the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

<Performance evaluation> [Stability with time] After the resist composition was stored at 40°C for 4 weeks, line and space patterns were formed in the same manner as described above. In the obtained pattern, the sensitivity was determined in the same manner as described above, and the sensitivity of the pattern formed by using the resist composition before preservation with time was evaluated in accordance with the following criteria. The difference in the sensitivity of the pattern formed by the resist composition after the week), that is, the degree of sensitivity variation. (Criteria) A: The observed sensitivity fluctuation is less than 1 μC/cm ² B: The observed sensitivity fluctuation is 1 μC/cm ² or more and less than 2 μC/cm ² C: The observed sensitivity fluctuation is 2 μC /cm ² or more and less than 3 μC/cm ² D: The observed sensitivity variation is 3 μC/cm ² or more and less than 4 μC/cm ² E: The observed sensitivity variation is 4 μC/cm ² or more

Table 2 shows the obtained evaluation results.

[Table 1] Table 1 Resist composition Resin (A) Photo acid generator (B) Acid diffusion control agent Surfactant additive Solvent Solid content concentration (mass%) Pattern formation method type Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) Solvent 1 Mass ratio Solvent 2 Mass ratio Example 1 res-1 Al 97.90 B-1 2.0 D-1 0.05 E-1 0.05 - S-1 100 - 0 27 KrF Example 2 res-2 A-2 98.45 B-2 1.5 D-2 0.03 E-2 0.02 - S-1 60 S-2 40 30 KrF Example 3 res-3 A-3 97.90 B-3 2.0 D-3 0.05 E-3 0.05 - S-1 80 S-2 20 29 KrF Example 4 res-4 A-4 92.61 B-4 2.3 D-4 0.04 E-4 0.05 F-1 5.0 S-1 60 S-3 40 25 KrF Example 5 res-5 A-5 94.93 B-5 2.0 D-5 0.06 E-5 0.01 F-2 3.0 S-1 30 S-4 70 26 KrF Example 6 res-6 A-6 90.79 B-6 1.2 D-6 0.01 - F-3 8.0 S-1 80 S-2 20 26 KrF Example 7 res-7 A-7 97.75 B-7 2.2 D-7 0.05 - - S-1 70 S-3 30 29 KrF Example 8 res-8 A-8 92.94 B-8 2.0 D-8 0.05 E-1 0.01 F-5 5.0 S-1 40 S-4 60 14 ArF-positive Example 9 res-9 A-9 96.80 B-9 2.1 D-9 0.05 E-2 0.05 F-6 1.0 S-1 80 S-5 20 15 ArF-positive Example 10 res-10 Al 97.42 B-10 2.0 D-10 0.05 E-3 0.03 F-7 0.5 S-1 80 S-6 20 31 KrF Example 11 res-11 A-2 97.34 B-11 2.0 D-11 0.11 E-4 0.05 F-8 0.5 S-1 60 S-7 40 twenty three KrF Example 12 res-12 A-3 97.00 B-12 1.9 D-1 0.05 E-5 0.05 F-9 1.0 S-1 60 S-8 40 32 KrF Example 13 res-13 A-4 97.97 B-1 2.0 D-2 0.03 - - S-1 90 S-2 10 27 KrF Example 14 res-14 A-5 92.95 B-2 2.0 D-3 0.05 - F-1 5.0 S-1 90 S-2 10 28 KrF Example 15 res-15 A-6 94.30 B-3 2.6 D-4 0.05 E-1 0.05 F-2 3.0 S-1 90 S-2 10 29 KrF Example 16 res-16 A-7 89.95 B-4 2.0 D-5 0.04 E-2 0.01 F-3 8.0 S-1 60 S-3 40 27 KrF Example 17 res-17 A-8 93.72 B-5 2.2 D-6 0.05 E-3 0.03 F-4 4.0 S-1 70 S-4 30 14 ArF-positive Example 18 res-18 A-9 97.90 B-6 2.0 D-7 0.05 E-4 0.05 - S-1 80 S-5 20 16 ArF-positive Example 19 res-19 Al 98.50 B-7 1.4 D-8 0.05 E-5 0.05 - S-1 80 S-6 20 27 KrF Example 20 res-20 A-2 97.96 B-8 2.0 D-9 0.04 - - S-1 80 S-7 20 29 KrF

[Table 2] Table 1 (continued) Resist composition Resin (A) Photo acid generator (B) Acid diffusion control agent Surfactant additive Solvent Solid content concentration (mass%) Pattern formation method type Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) type Content (mass%) Solvent 1 Mass ratio Solvent 2 Mass ratio Example 21 res-21 A-3 98.37 B-9 1.5 D-10 0.03 - F-8 0.1 S-1 60 S-8 40 twenty four KrF Example 22 res-22 A-4 97.80 B-10 2.0 D-11 0.05 El 0.05 F-9 0.1 S-2 60 S-4 40 30 KrF Example 23 res-23 A-5 97.90 B-11 2.0 D-1 0.05 E-2 0.05 - S-2 60 S-5 40 29 KrF Example 24 res-24 A-6 98.43 B-12 1.4 D-2 0.04 E-5 0.03 F-6 0.1 S-1 80 S-6 20 27 KrF Example 25 res-25 A-4 97.90 B-8 2.0 D-5 0.05 E-2 0.05 - S-1 80 S-2 20 28 KrF Example 26 res-26 A-5 92.64 B-6 2.3 D-10 0.05 E-4 0.01 F-2 5.0 S-1 60 S-2 40 31 KrF Example 27 res-27 Al 97.90 B-3/B-8 1.0/1.0 D-1 0.05 El 0.05 - S-1 100 - 0 27 KrF Example 28 res-28 A-2 98.43 B-2 1.5 D-2/D-4 0.02/0.02 E-2 0.03 - S-1 60 S-2 40 30 KrF Example 29 res-29 A-3 97.90 B-13 2.0 D-3 0.05 E-3 0.05 - S-1 80 S-2 20 29 KrF Example 30 res-30 A-2 97.90 B-14 2.0 D-11 0.03 E-4 0.01 F-8 0.5 S-1 60 S-7 40 twenty three KrF Example 31 res-31 Al 97.90 B-15 2.0 D-1 0.05 El 0.05 - S-1 100 - 0 27 KrF Example 32 res-32 A-10 92.94 B-8 2.0 D-8 0.05 El 0.01 F-5 5.0 S-1 40 S-4 60 5 ArF-organic solvent development Example 33 res-33 A-11 94.30 B-3 2.6 D-4 0.05 El 0.05 F-2 3.0 S-1 90 S-2 10 4 EB Example 34 res-34 A-12 97.75 B-7 2.2 D-7 0.05 - - S-1 70 S-3 30 4 EUV Example 35 res-35 A-4 98.79 B-16 1.2 D-10 0.01 - - S-1 70 S-2 30 26 KrF Comparative example 1 res-Rl Al 97.90 BX-1 2.0 D-1 0.05 El 0.05 - S-1 100 - 0 27 KrF Comparative example 2 res-R2 A-2 98.39 BX-2 1.5 D-2 0.07 E-2 0.04 - S-1 60 S-2 40 30 KrF Comparative example 3 res-R3 A-3 97.89 BX-3 2.0 D-3 0.09 E-3 0.02 - S-1 80 S-2 20 29 KrF

[Table 3] Table 2 Pattern formation method Stability over time Example 1 KrF C Example 2 KrF D Example 3 KrF B Example 4 KrF C Example 5 KrF A Example 6 KrF A Example 7 KrF B Example 8 ArF-positive A Example 9 ArF-positive B Example 10 KrF C Example 11 KrF B Example 12 KrF C Example 13 KrF C Example 14 KrF D Example 15 KrF B Example 16 KrF C Example 17 ArF-positive A Example 18 ArF-positive A Example 19 KrF B Example 20 KrF A Example 21 KrF B Example 22 KrF C Example 23 KrF B Example 24 KrF C Example 25 KrF A Example 26 KrF A Example 27 KrF A Example 28 KrF D Example 29 KrF D Example 30 KrF D Example 31 KrF C Example 32 ArF-organic solvent development C Example 33 EB C Example 34 EUV C Example 35 KrF A Comparative example 1 KrF E Comparative example 2 KrF E Comparative example 3 KrF E

From the results of Table 2, it can be seen that the composition of the present invention has very excellent stability over time. [Industrial availability]

According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition that can achieve extremely excellent stability over time. According to the present invention, it is further possible to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of an electronic device using the sensitized ray-sensitive or radiation-sensitive resin composition.

Although the present invention has been described in detail with reference to specific embodiments, it is clear to those skilled in the art that various changes or modifications can be added without departing from the spirit and scope of the present invention. In addition, this application is based on a Japanese patent application (Japanese Patent Application No. 2020-32446) filed on February 27, 2020, and the content is incorporated into this application as a reference.

Claims (12)

A photosensitive ray-sensitive or radiation-sensitive resin composition containing: (A) resin, and (B) a compound represented by the following general formula (1) that generates acid by irradiation with actinic rays or radiation,

In the general formula (1), W ₁ represents a ring; Q represents a _{divalent linking group in which one or more ring members constituting ring W 1} are heteroatoms, carbonyl carbon atoms, or a combination of these; R _1A and R _1B are each independent Ground represents a hydrogen atom, an organic group, a halogen atom, or a cyano group; wherein _{at least one of R 1A} and R _1B represents an organic group, a halogen atom, or a cyano group; R _2A and R _2B each independently represent a hydrogen atom, an organic group , A halogen atom, or a cyano group; wherein _{at least one of R 2A} and R _2B represents an organic group, a halogen atom, or a cyano group; p represents 0 or 1, q represents 0 or 1; wherein, p+q represents 1 or 2 ; R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group; wherein _{at least one of R 1} and R ₂ represents an alkyl group, a cycloalkyl group, or a halogen atom , Cyano, or aryl; n represents 0 or 1; R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group; m represents 0 or 1 or more Integer; when m represents an integer greater than or equal to 1, n represents 1; L represents a carbonyl bond or an ester bond; l represents 0 or 1; when l represents 1, n represents 1; when l represents 1 Below, _{at least two of R 5} to R ₉ may be connected to each other to form a ring; when l represents 0, m represents 0 and n represents 0; R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ are each Independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group , Alkenyl, halogen atom, hydroxyl, nitro, alkylthio or cycloalkylthio; Z ^- represents an anion. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein in the general formula (1), the ring W ₁ is a 6-membered ring to an 8-membered ring. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein in the general formula (1), Z ^- is any one of the following general formulas (3) to (5) Represents the anion,

In the general formula (3), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom; L ₁ represents a single bond or a divalent linking group; A represents a monovalent organic group; x represents 1-20 Integer

In the general formula (4), Xf ₁ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom; two Xf ₁ may be connected to each other to form a ring structure;

In the general formula (5), Xf ₂ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom; two Xf ₂ may be connected to each other to form a ring structure. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein in the general formula (1), Q is any linking group selected from the following group,

In the formula, R ₁₁ represents a hydrogen atom or a substituent; * represents a bond to the group adjacent to Q _{forming W 1 in the general formula (1).} The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2),

In the general formula (2), Ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group; wherein, at least one of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group; Q (. 1) Q in the formula have the same meaning; R _1, R ₍₁₎ R ₂ in the above general formula _1, R ₂ have the same meaning; _{R 5, R 6, R 7} , R 8, and R ₉ in the general formula R (1) is _{5, R 6, R 7,} R 8, and R ₉ are the same meanings; R ₅ ~ R ₉ is at least two may be linked together to form a ring; the Z ^- in the general formula Z (1) ^- a is the same meaning. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein in the general formula (1) or (2), at least one of _{R 5} to R _{9 represents} Alkoxy, cycloalkyloxy, alkylthio, or cycloalkylthio. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the solid content of the composition is 10% by mass or more. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the resin (A) has a phenolic hydroxyl group. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein the resin (A) has a carboxyl group. A sensitizing radiation or radiation-sensitive film formed of the sensitizing radiation or radiation-sensitive resin composition according to any one of claims 1 to 9. A pattern forming method, comprising: exposing the sensitizing radiation or radiation-sensitive film as described in claim 10, and developing the exposed sensitizing radiation or radiation-sensitive film using a developing solution A step of. A manufacturing method of an electronic device includes the pattern forming method as described in claim 11.