TW202340276A - Active light sensitive or radiation sensitive resin composition, resist film, method for forming pattern, and method for producing electronic device - Google Patents

Abstract

The present invention provides: an active light sensitive or radiation sensitive resin composition which contains a resin (A) that contains a group which is decomposed by the action of an acid, thereby increasing the polarity, wherein the resin (A) contains an acid-decomposable repeating unit which has a specific structure containing an aromatic heterocyclic group that contains a sulfur atom; a resist film which uses this active light sensitive or radiation sensitive resin composition; a method for forming a pattern; and a method for producing an electronic device.

Description

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

The present invention relates to photosensitive radiation or radiation-sensitive resin compositions, photoresist films, pattern forming methods and manufacturing methods of electronic devices. More specifically, the present invention relates to a manufacturing process that can be applied to ultra-LSI (Large Scale Integration, large-scale integrated circuit) and high-capacity microchips, a nanoimprint mold manufacturing process, and a manufacturing process of high-density information recording media, etc. Ultralithography process, as well as photosensitive radioactive or radiation-sensitive resin compositions, photosensitive radioactive or radiation-sensitive films, pattern forming methods and electronic device manufacturing methods that can be suitably used in other photosensitive etching processes.

In the past, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integration), microfabrication was performed by lithography using photoresist compositions. In recent years, with the high integration of integrated circuits, it is required to form ultra-fine patterns in the sub-micron area or the quarter-micron area. Along with this, the exposure wavelength has also shown a trend of shortening from g-rays to i-rays, and then to KrF excimer laser light. Currently, an exposure machine using ArF excimer laser with a wavelength of 193 nm as the light source has been developed. In addition, as a technology to further improve the resolution, the so-called liquid immersion method is being developed in which a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample.

In addition, in addition to excimer laser light, lithography using electron beam (EB), X-ray, extreme ultraviolet (EUV), etc. is currently under development. Along with this, photoresist compositions that effectively sense various actinic rays or radiation have been developed.

Various resins are known as resins used in photosensitive radiation or radiation-sensitive resin compositions. For example, Patent Document 1 and Patent Document 2 describe a photoresist composition containing a resin having an aromatic heterocyclic group containing a sulfur atom. [Prior technical literature] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2019-70677 Patent Document 2: Japanese Patent Application Publication No. 2021-33026

[Problem to be solved by the invention]

However, the photoresist compositions described in Patent Documents 1 and 2 have problems such as poor resolution, exposure latitude (EL) performance, and line width roughness (LWR) performance. The so-called LWR performance refers to the performance that can reduce the pattern LWR.

An object of the present invention is to provide a photosensitive radiation or radiation-sensitive resin composition that is excellent in resolution, EL performance, and LWR performance. Furthermore, an object of the present invention is to provide a photoresist film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned photosensitive radiation or radiation-sensitive resin composition. [Means to solve the problem]

The present inventors found that the above problems can be solved by the following configuration.

[1] A photosensitive radiation-sensitive or radiation-sensitive resin composition containing a resin (A) containing a group that is decomposed by the action of an acid and increases in polarity, wherein the resin (A) contains the following general formula (S1) The acid-decomposable repeating unit represented.

[Chemical formula 1]

In the general formula (S1), Ra ₁ to Ra ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. La ₁ represents a bivalent coupling group containing an aromatic group. Ra ₃ and La ₁ can be connected to form a ring. Ra ₄ to Ra ₆ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group or an alkenyl group. Among them, at least one of Ra ₄ to Ra ₆ represents an aromatic heterocyclic group containing a sulfur atom. Two of Ra ₄ to Ra ₆ may be bonded to each other to form a ring. [2] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1], wherein La ₁ in the general formula (S1) contains an aryl group. [3] The photosensitive radiation-sensitive or radiation-sensitive resin composition as described in [1] or [2], wherein La ₁ in the above general formula (S1) represents an aryl group or an aryl group and a carbonyl group. Bivalent linking base. [4] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein any one of Ra ₄ to Ra ₆ in the general formula (S1) represents Hydrogen atoms. [5] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the acid-decomposable repeating unit represented by the above-mentioned general formula (S1) is the following general formula (S1-1) or ( Acid-decomposable repeating unit represented by S1-2).

[Chemical formula 2]

In the general formulas (S1-1) and (S1-2), Ra ₁ to Ra ₃ have the same meanings as Ra ₁ to Ra ₃ in the general formula (S1). Ra ₄ to Ra ₆ have the same meanings as Ra ₄ to Ra ₆ in the above general formula (S1). La ₂ represents a single bond or -COO-. Ara ₁ represents an aryl group. Ra ₃ and Ara ₁ can be connected to form a ring. [6] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin (A) contains a substance that is decomposed by irradiation with electron beams or extreme ultraviolet rays. A repeating unit of an acid-producing group. [7] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], which contains an acidic salt with a pKa of -2.0 or more. [8] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], which contains an acidic salt having a pKa of -2.0 or more and 1.0 or less. [9] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the resin (A) further contains a repeating unit having a phenolic hydroxyl group and a lactone at least one of the repeating units of the base. [10] A photoresist film formed using the photosensitive radiation or radiation-sensitive resin composition described in any one of [1] to [9]. [11] A pattern forming method, which includes: a process of forming a photoresist film on a substrate using the photosensitive radiation or radiation-sensitive resin composition described in any one of [1] to [9]; The process of exposing the photoresist film; and the process of using a developer to develop the exposed photoresist film. [12] A method of manufacturing an electronic device, which includes the pattern forming method described in [11]. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive radiation or radiation-sensitive resin composition excellent in resolution, EL performance, and LWR performance. Furthermore, according to the present invention, it is possible to provide a photoresist film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

In this specification, "actinic rays" or "radiation" means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays and electron beams (EB: Electron Beam), etc. In this specification, "light" means actinic rays or radiation. In this manual, the so-called "exposure", unless otherwise specified, includes not only exposure using far ultraviolet, extreme ultraviolet, X-ray and EUV represented by the bright line spectrum of mercury lamps and excimer lasers, but also includes exposure using electrons Particle beams such as beams and ion beams. In this specification, "～" is used in the sense that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In this specification, (meth)acrylate means at least one kind of acrylate and methacrylate. Moreover, (meth)acrylic acid means at least one kind of acrylic acid and methacrylic acid.

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) are measured using a GPC (Gel Permeation Chromatography) device (Eastern HLC-8120GPC manufactured by Tosoh Corporation) measured by GPC (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C , flow rate: 1.0mL/min, detector: differential refractive index detector (Refractive Index Detector)) and the polystyrene conversion value is defined.

Regarding the expressions of groups (atomic groups) in this specification, as long as they do not violate the gist of the present invention, those that do not describe substituted or unsubstituted include both groups without substituents and groups containing substituents. For example, the so-called "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, the so-called "organic group" in this specification means a group containing at least one carbon atom. As the substituent, unless otherwise specified, a monovalent substituent is preferred. Examples of the substituent include monovalent non-metal atomic groups other than hydrogen atoms. For example, the substituent T can be selected from the following.

(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 group, ethoxy group and tert-butoxy group; cycloalkoxy group; phenoxy group and Aryloxy groups such as p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; acetyloxy, propyloxy and benzene Carboxylic acid groups such as formyloxy group; acetyl group, benzyl group, isobutyl group, acryl group, methacryl group and methyl oxalyl group; sulfanyl group; methylthio group and the third Alkylsulfanyl groups such as butylsulfanyl; arylthio groups such as phenylthio and p-tolylsulfanyl; alkyl; alkenyl; cycloalkyl; aryl; aromatic heterocyclic group; hydroxyl; Carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amine group; aminoformyl group; etc. Furthermore, when these substituents may further have one or more substituents, a group having one or more substituents selected from the above substituents as the further substituent (for example, a monoalkylamino group, a dialkylamino group, Arylamine group, trifluoromethyl, etc.) are also included in the examples of the substituent T.

In this specification, the bonding direction of the divalent group described is not particularly limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", when Y is -COO-, Y can be either -CO-O- or -O-CO-. The above compound may be "X-CO-O-Z" or "X-O-CO-Z".

In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution. Specifically, the following software package 1 is used to borrow the value from the database based on the Hammett substituent constant and the known literature value. The value obtained by calculation. All pKa values recorded in this manual represent values calculated using this software package. Software package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

In addition, pKa can also be obtained using the molecular orbital calculation method. A specific method is a method of calculating the H ⁺ dissociation free energy in an aqueous solution based on a thermodynamic cycle. Regarding the calculation method of H ⁺ dissociation free energy, for example, it can be calculated by DFT (density functional theory), but it is not limited to this, and various other methods are also reported in the literature. In addition, there are multiple types of software that can implement DFT. For example, Gaussian16 can be cited.

In this specification, pKa, as mentioned above, refers to a value obtained by calculation using the software package 1 based on the Hammett substituent constant and the value of the database of known literature values. However, it cannot be calculated using this method. For pKa, the value obtained by Gaussian16 based on DFT (density functional theory) is used. In this specification, pKa refers to "pKa in aqueous solution" as shown above. However, when the pKa in aqueous solution cannot be calculated, "pKa in dimethylstyrene (DMSO) solution" is used. ”.

In this specification, "solid content" means a component that forms a photosensitive radiation-sensitive film or a radiation-sensitive film, and does not contain a solvent. In addition, as long as it is a component that forms a photosensitive radiation or a radiation-sensitive film, it is regarded as a solid component even if its nature is liquid.

＜Photosensitive radiation or radiation-sensitive resin composition＞ The photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention (also referred to as the "composition of the present invention") contains at least a resin (A) containing a group that is decomposed by the action of an acid and increases its polarity, wherein , the resin (A) contains an acid-decomposable repeating unit represented by the following general formula (S1).

[Chemical formula 3]

In the general formula (S1), Ra ₁ to Ra ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. La ₁ represents a divalent linking group containing an aromatic group. Ra ₃ and La ₁ can be connected to form a ring. Ra ₄ to Ra ₆ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group or an alkenyl group. Among them, at least one of Ra ₄ to Ra ₆ represents an aromatic heterocyclic group containing a sulfur atom. Two of Ra ₄ to Ra ₆ may be bonded to each other to form a ring.

The reason why the composition of the present invention is excellent in resolution, EL performance, and LWR performance is not necessarily clear, but the inventors speculate as follows. The resin (A) containing a group whose polarity is increased by decomposition by the action of an acid contained in the composition of the present invention contains an aromatic heterocyclic group containing a sulfur atom (sulfur-containing aromatic heterocyclic group). An acid-decomposable repeating unit (acid-decomposable repeating unit represented by general formula (S1)) in which a divalent connecting group of an aromatic group is bonded to a main chain. Since the sulfur-containing aromatic heterocyclic group exhibits good reactivity, acid decomposition proceeds faster than causing diffusion of the acid. In addition, the diffusion of acid is suppressed by interaction with sulfur atoms. Furthermore, it is presumed that the acid-decomposable repeating unit of the resin (A) in the present invention is a sulfur-containing aromatic heterocyclic group bonded to the main chain via a divalent linking group containing an aromatic group. Compared with repeating units that are bonded to the main chain without using aromatic groups, the heterocyclic group has less polarity. The effect of the sulfur-containing aromatic heterocyclic group is more significant, and the resolution, EL performance and LWR performance are excellent.

The composition of the present invention is typically a photoresist composition, which may be a positive photoresist composition or a negative photoresist composition. The composition of the present invention may be a photoresist composition for alkali development or a photoresist composition for organic solvent development. The photoresist composition of the present invention may be a chemically amplified photoresist composition or a non-chemically amplified photoresist composition. The composition of the present invention is typically a chemically amplified photoresist composition. The composition of the present invention can be used to form a photosensitive radiation-sensitive or radiation-sensitive film. The photosensitive radiation-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a photoresist film. Next, various components of the composition of the present invention are first described in detail.

[Resin (A)] The resin (A) contained in the composition of the present invention is a resin containing a group (also called an "acid-decomposable group") that is decomposed by the action of an acid and increases its polarity. Resin (A) is an acid-decomposable resin. In the pattern forming method using the composition of the present invention, typically, when an alkaline developer is used as the developer, it is preferable to form a positive pattern. When an organic developer is used as the developer, it is preferable to form a negative pattern.

The acid-decomposable group is typically a group that is decomposed by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is released by the action of an acid. The resin (A) has a group that is decomposed by the action of an acid to generate a polar group. The polarity of the resin (A) increases due to the action of acid, the solubility in an alkaline developer increases, and the solubility in an organic solvent decreases.

(Acid-decomposable repeating unit represented by general formula (S1)) The resin (A) contains an acid-decomposable repeating unit represented by the general formula (S1). The acid-decomposable repeating unit refers to a repeating unit having an acid-decomposable group. That is, the repeating unit represented by general formula (S1) has an acid-decomposable group. The acid-decomposable group of the repeating unit represented by formula (S1) preferably has a structure in which a carboxyl group or a phenolic hydroxyl group is protected by a leaving group.

Ra ₁ to Ra ₃ in the general formula (S1) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The alkyl groups of Ra ₁ to Ra ₃ may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the cycloalkyl group of Ra ₁ to Ra ₃ is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkyl group of Ra ₁ to Ra ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, an adamantyl group, or the like. Ring cycloalkyl. Examples of the halogen atom of Ra ₁ to Ra ₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or an iodine atom is preferred. The alkyl group contained in the alkoxycarbonyl group of Ra ₁ to Ra ₃ may be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.

La ₁ in the general formula (S1) represents a bivalent linking group containing an aromatic group. La ₁ preferably contains an aryl group. La ₁ preferably represents an aryl group or a bivalent linking group including an aryl group and a divalent linking group other than the aryl group. Examples of the bivalent linking group other than the aryl group include carbonyl group (-CO-), -O-, -S-, -SO-, -SO ₂ -, amide group (-CONR-), A sulfonamide group (-SO ₂ NR-), an alkylene group, a cycloalkylene group, an alkenylene group, a connecting group in which a plurality of these are connected, etc. The above-mentioned R respectively represent a hydrogen atom or an organic group. As the organic group, an alkyl group, a cycloalkyl group, an aryl group, and a combination thereof are preferred. The divalent linking group other than the aryl group is preferably at least one of a carbonyl group and -O-, more preferably a carbonyl group. La ₁ particularly preferably represents an aryl group or a bivalent linking group composed of an aryl group and a carbonyl group. The aryl group contained in La ₁ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and particularly preferably a phenyl group.

Ra ₃ and La ₁ in the general formula (S1) may be connected to form a ring.

Ra ₄ to Ra ₆ in the general formula (S1) each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group or an alkenyl group. In Ra4 to Ra6 At least one of represents an aromatic heterocyclic group containing a sulfur atom.

The alkyl groups of Ra ₄ to Ra ₆ may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6. The methylene group contained in the alkyl group of Ra ₄ to Ra ₆ may be substituted with at least one of -CO- and -O-. The alkoxy groups of Ra ₄ to Ra ₆ may be linear or branched. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6. The number of carbon atoms in the cycloalkyl group of Ra ₄ to Ra ₆ is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. As the cycloalkyl group of Ra ₄ to Ra ₆ , preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl and the like. Ring cycloalkyl. The number of carbon atoms in the aryl group of Ra ₄ to Ra ₆ is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. The aryl group of Ra ₄ to Ra ₆ is preferably a phenyl group.

The aralkyl group of Ra ₄ to Ra ₆ is preferably a group in which one hydrogen atom of the alkyl group of Ra ₄ to Ra ₆ is substituted by an aryl group having 6 to 10 carbon atoms (preferably a phenyl group). For example, benzyl group etc. are mentioned. The number of carbon atoms in the alkenyl group of Ra ₄ to Ra ₆ is not particularly limited, but is preferably 2 to 5, more preferably 2 to 4. As the alkenyl group of Ra ₄ to Ra ₆ , vinyl group is preferred.

The aromatic heterocyclic group of Ra ₄ to Ra ₆ preferably contains at least one hetero atom selected from the group consisting of a sulfur atom, a nitrogen atom and an oxygen atom, and more preferably contains a sulfur atom. The number of heteroatoms contained in the aromatic heterocyclic group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15. The aromatic heterocyclic group may be monocyclic or polycyclic. Examples of the aromatic heterocyclic group of Ra ₄ to Ra ₆ include thienyl, furyl, benzothienyl, dibenzothienyl, benzofuryl, pyrrolyl, oxazolyl, thiazolyl, and pyridine base, isothiazolyl, thiadiazolyl, etc. The aromatic heterocyclic group of Ra ₄ to Ra ₆ may have a substituent. Examples of the substituent include the above-mentioned substituent T, and an alkyl group, an aryl group, an aromatic heterocyclic group and an alkoxy group are preferred. In addition, two or more substituents may be bonded to each other to form a ring.

Among them, at least one of Ra ₄ to Ra ₆ represents an aromatic heterocyclic group containing a sulfur atom. Examples of the aromatic heterocyclic group containing a sulfur atom include aromatic heterocyclic groups containing at least one sulfur atom among the above-mentioned aromatic heterocyclic groups. As the aromatic heterocyclic group containing a sulfur atom, a thienyl group, a benzothienyl group, a dibenzothienyl group, a thiazolyl group, an isothiazolyl group and a thiadiazolyl group are preferred. The aromatic heterocyclic group containing a sulfur atom may have a substituent. Examples of the substituent include the above-mentioned substituent T, and an alkyl group, an aryl group, an aromatic heterocyclic group and an alkoxy group are preferred. In addition, two or more substituents may be bonded to each other to form a ring. Specific examples of the aromatic heterocyclic group containing a sulfur atom are shown below, but are not limited thereto. The following groups may further have a substituent, and two or more substituents may be bonded to each other to form a ring. * indicates the bonding position.

[Chemical formula 4]

Two of Ra ₄ to Ra ₆ may be bonded to each other to form a ring.

A preferred aspect of the resin (A) is an aspect in which any one of Ra ₄ to Ra ₆ represents a hydrogen atom. It is preferable that any one of Ra ₄ to Ra ₆ be a hydrogen atom because appropriate reactivity can be provided.

The acid-decomposable repeating unit represented by the general formula (S1) is preferably an acid-decomposable repeating unit represented by the following general formula (S1-1) or (S1-2).

[Chemical formula 5]

In the general formulas (S1-1) and (S1-2), Ra ₁ to Ra ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. La ₂ represents a single bond or -COO-. Ara ₁ represents an aryl group. Ra ₃ and Ara ₁ can be connected to form a ring. Ra ₄ to Ra ₆ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group or an alkenyl group, and at least one of Ra ₄ to Ra ₆ represents a group containing Aromatic heterocyclic group of sulfur atom. Two of Ra ₄ to Ra ₆ may be bonded to each other to form a ring.

Ra ₁ to Ra ₃ in general formula (S1-1) and (S1-2) have the same meaning as Ra ₁ to Ra ₃ in general formula (S1), and specific examples and preferred ranges are also the same. Ra ₄ to Ra ₆ in general formulas (S1-1) and (S1-2) have the same meaning as Ra ₄ to Ra ₆ in general formula (S1), and specific examples and preferred ranges are also the same.

La ₂ in the general formulas (S1-1) and (S1-2) represents a single bond or -COO-, preferably a single bond.

Ara ₁ in the general formulas (S1-1) and (S1-2) represents an aryl group, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, Particularly preferred is a phenyl group.

Specific examples of the acid-decomposable repeating unit represented by general formula (S1) are shown below, but are not limited thereto.

[Chemical formula 6]

[Chemical Formula 7]

The acid-decomposable repeating unit represented by the general formula (S1) contained in the resin (A) may be one type or two or more types.

The content of the acid-decomposable repeating unit represented by the general formula (S1) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% based on all the repeating units in the resin (A). More than % of ears. Moreover, the content of the acid-decomposable repeating unit represented by the general formula (S1) is preferably 90 mol% or less, more preferably 80 mol% or less, based on all the repeating units in the resin (A), and still more preferably Below 70 mol%.

The resin (A) may further contain other acid-decomposable repeating units (repeating units having an acid-decomposable group) in addition to the acid-decomposable repeating unit represented by the general formula (S1).

The resin (A) may include at least one repeating unit selected from the group consisting of the following group A and/or at least one repeating unit selected from the group consisting of the following group B. Group A: A group consisting of the following repeating units (20) to (25). (20) Repeating unit having an acid group described below (21) The repeating unit described below that does not have any of an acid-decomposable group and an acid group and has a fluorine atom, a bromine atom, or an iodine atom (22) Repeating unit having a lactone group, a sultone group or a carbonate group described below (23) Repeating unit having a photoacid generating group described below (24) Repeating unit represented by the formula (V-1) or the following formula (V-2) described below (25) Repeating units used to reduce the mobility of the main chain In addition, the repeating units represented by the formulas (A) to (E) described below correspond to (25) the repeating unit for reducing the mobility of the main chain. Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below (31) Repeating unit described below that has an alicyclic hydrocarbon structure and does not show acid decomposability (32) The following unit represented by formula (III) does not have any repeating unit of either a hydroxyl group or a cyano group.

A preferred aspect of the resin (A) is an aspect in which the resin (A) contains at least one of a repeating unit having a phenolic hydroxyl group and a repeating unit having a lactone group. Therefore, the adhesion of the photoresist film formed from the composition of the present invention to the substrate is improved.

The resin (A) preferably has an acid group, and as will be described later, preferably contains a repeating unit having an acid group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated by the photoacid generator is more excellent. As a result, the diffusion of acid can be further suppressed, so that the cross-sectional shape of the formed pattern becomes closer to a rectangular shape.

The resin (A) may have at least one repeating unit selected from the group consisting of the above-mentioned A group. When the composition of the present invention is used as a photosensitive radiation-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned A group. Resin (A) may contain at least one of a fluorine atom and an iodine atom. When the composition of the present invention is used as a photosensitive radiation-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both fluorine atoms and iodine atoms, the resin (A) may have one repeating unit containing both the fluorine atom and the iodine atom, and the resin (A) may also contain a repeating unit containing the fluorine atom and the iodine atom. Repeating units of atoms These two types of repeating units. The resin (A) may have at least one repeating unit selected from the group consisting of the above-described B group. When the composition of the present invention is used as a photosensitive radiation-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned B group. Furthermore, when the composition of the present invention is used as a photosensitive radiation-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably does not contain either fluorine atoms or silicon atoms.

(Repeating unit having an acid group) The resin (A) preferably has a repeating unit having an acid group. As the acid group, an acid group having a pKa of 13 or less is preferred. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and still more preferably 5 to 10. When the resin (A) has an acid group with a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but in many cases it is 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferred, 1.2 to 5.0 mmol/g is more preferred, and 1.6 to 4.0 mmol/g is further preferred. When the content of the acid group is within the above range, development proceeds smoothly, the shape of the formed pattern is excellent, and the resolution is also excellent. As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group or an isopropanol group is preferred. In the above-mentioned hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with groups other than fluorine atoms (alkoxycarbonyl group, etc.). As the acid group, -C(CF ₃ )(OH)-CF ₂ - thus formed is also preferred. Furthermore, one or more fluorine atoms may be substituted with groups other than fluorine atoms to form a ring containing -C(CF ₃ )(OH)-CF ₂ -. The repeating unit having an acid group is preferably a repeating unit having a structure in which the above-mentioned polar group is protected by a group detached by the action of an acid, and a repeating unit having a lactone group, a sultone group or a carbonate group described below. different repeating units. The repeating unit having an acid group may also have a fluorine atom or an iodine atom.

Examples of the repeating unit having an acid group include the following repeating units.

[Chemical formula 8]

As the repeating unit having an acid group, a repeating unit represented by the following formula (1) is preferred.

[Chemical formula 9]

In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkoxycarbonyl group or aryloxycarbonyl group, with plural numbers The times can be the same or different. When there are multiple R's, they can bond with each other to form a ring. R is preferably a hydrogen atom. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

Hereinafter, repeating units having an acid group are exemplified. In the formula, a represents an integer from 1 to 3.

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

Among the above-mentioned repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 3.

[Chemical formula 14]

[Chemical formula 15]

When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 5 mol% or more, more preferably 10 mol% or more relative to all the repeating units in the resin (A). . Moreover, the upper limit value is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less based on all the repeating units in the resin (A).

(A repeating unit that does not have either an acid-decomposable group or an acid group and has a fluorine atom, a bromine atom, or an iodine atom) In addition to the acid-decomposable repeating unit and the repeating unit having an acid group, the resin (A) may have a repeating unit that does not have any of the acid-decomposable group and the acid group and has a fluorine atom, a bromine atom, or an iodine atom. (Hereinafter, also referred to as unit X.). Moreover, the <repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom or an iodine atom> mentioned here is preferably the same as the <having a lactone group, a sulfonate group> which will be described later. Other types of repeating units belonging to group A such as the repeating unit of a lactone group or a carbonate group and the <repeating unit having a photoacid generating group> are different.

As the unit X, a repeating unit represented by formula (C) is preferred.

[Chemical formula 16]

L ₅ represents a single bond or ester group. R ₉ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R ₁₀ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these.

Hereinafter, repeating units having a fluorine atom or an iodine atom are exemplified.

[Chemical formula 17]

The content of the unit Moreover, the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and still more preferably 40 mol% or less based on all the repeating units in the resin (A).

In the repeating units of the resin (A), the total content of the repeating units including at least one of a fluorine atom, a bromine atom, and an iodine atom is preferably 10 mol% or more relative to all the repeating units of the resin (A), and more preferably Preferably it is 20 mol% or more, further preferably it is 30 mol% or more, and particularly preferably it is 40 mol% or more. The upper limit is not particularly limited, but for example, it is 100 mol% or less based on all the repeating units of the resin (A). Furthermore, examples of the repeating unit including at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-decomposable group; atom or an iodine atom and has a repeating unit of an acid group and a repeating unit of a fluorine atom, a bromine atom or an iodine atom.

(Repeating unit with lactone group, sultone group or carbonate group) The resin (A) may have at least one repeating unit selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, also referred to as "unit Y"). It is also preferable that unit Y does not have acidic groups such as hydroxyl group and hexafluoropropanol group.

As the lactone group or the sultone group, any one having a lactone structure or a sultone structure may be used. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, more preferred ones are those in which the 5- to 7-membered ring lactone structure has other ring structures condensed to form a bicyclic structure or a spirocyclic structure, or a 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure. There are other ring structures in the condensed ring of sultone structure. Resin (A) preferably has a repeating unit containing a lactone group or a sultone group, and the lactone group or sultone group is any one of the following formulas (LC1-1) to (LC1-21) Lactone is formed by extracting one or more hydrogen atoms from the ring member atoms of the lactone structure represented by or the sultone structure represented by any of the following formulas (SL1-1) to (SL1-3). The group or sultone group can also be directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may also constitute the main chain of the resin (A).

[Chemical formula 18]

The above-mentioned lactone structure or sultone group structure may have a substituent (Rb ₂ ). Preferable substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and alkyl groups having 1 to 8 carbon atoms. Oxycarbonyl group, carboxyl group, halogen atom, cyano group and acid-decomposable group. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plural Rb _2's may be different, and the plural Rb _2's may be bonded to each other to form a ring.

As having a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone represented by any one of formulas (SL1-1) to (SL1-3) Examples of the repeating unit of the group of the structure include repeating units represented by the following formula (AI).

[Chemical formula 19]

In formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a bivalent connecting group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a bivalent connecting group combining these. . Among them, Ab ₁ is preferably a single bond or a linking group represented by -Ab ₁ -CO ₂ -. Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkyl group, preferably a methyl group, an ethyl group, a cyclohexyl group, an adamantyl group or an norbornene group. base. V represents a group obtained by extracting one hydrogen atom from a ring member atom of the lactone structure represented by any one of the formulas (LC1-1) to (LC1-21) or a group obtained from the formulas (SL1-1) to ( A group formed by extracting one hydrogen atom from the ring member atom of the sultone structure represented by any of SL1-3).

When an optical isomer exists in the repeating unit having a lactone group or a sultone group, any optical isomer can be used. In addition, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When mainly using one optical isomer, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

As the carbonate group, a cyclic carbonate group is preferred. As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following formula (A-1) is preferred.

[Chemical formula 20]

In formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group). n represents an integer above 0. R _A ² represents a substituent. When n is 2 or more, the plural _RA ² may be the same or different. A represents a single bond or a divalent linking group. The bivalent connecting group is preferably an alkylene group, a bivalent connecting group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof. bivalent linking base. Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

The following is an example of unit Y. In the formula, Rx represents a hydrogen atom, -CH ₃ , -CH ₂ OH, or -CF ₃ .

[Chemical formula 21]

[Chemical formula 22]

When the resin (A) contains the unit Y, the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more relative to all the repeating units in the resin (A). Moreover, the upper limit value is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, based on all the repeating units in the resin (A), and particularly preferably Below 60 mol%.

(Repeating unit with photoacid generating group) As a repeating unit other than the above, the resin (A) may have a repeating unit having a group that generates an acid when irradiated with actinic rays or radiation (preferably electron beams or extreme ultraviolet rays) (hereinafter also referred to as "photoacid"). Generating base"). A preferred aspect of the resin (A) is one in which the resin (A) contains a repeating unit having a group that is decomposed by irradiation with electron beams or extreme ultraviolet rays to generate an acid. Examples of the repeating unit having a photoacid-generating group include a repeating unit represented by formula (4).

[Chemical formula 23]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a bivalent linking group. R ⁴⁰ represents a structural portion that is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain. Repeating units having a photoacid generating group are exemplified below.

[Chemical formula 24]

[Chemical formula 25]

Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs [0094] to [0105] of Japanese Patent Application Laid-Open No. 2014-041327 and International Publication No. 2018/193954 The repeating units described in paragraph [0094].

When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol%, based on all the repeating units in the resin (A). More than mol%. Moreover, the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less based on all the repeating units in the resin (A).

(Repeating unit represented by formula (V-1) or the following formula (V-2)) Resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). The repeating unit represented by the following formula (V-1) and the following formula (V-2) is preferably a repeating unit different from the above-mentioned repeating unit.

[Chemical formula 26]

In the formula, R ₆ and R ₇ respectively independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a nitro group, an amine group, a halogen atom, an ester group (-OCOR or -COOR: R It is an alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms) or carboxyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. n ₃ represents an integer from 0 to 6. n ₄ represents an integer from 0 to 4. X ₄ is a methyl group, an oxygen atom or a sulfur atom. The following illustrates the repeating unit represented by formula (V-1) or (V-2). Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph [0100] of International Publication No. 2018/193954.

(Repeating unit used to reduce the mobility of the main chain) From the viewpoint of being able to suppress excessive diffusion of acid or pattern collapse during development, the resin (A) preferably has a high glass transition temperature (Tg). The Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, from the viewpoint of excellent dissolution rate in a developer, Tg is preferably 400°C or lower, more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of polymers such as resin (A) (hereinafter referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of the homopolymer consisting only of each repeating unit contained in the polymer was calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio was calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum was calculated as the Tg (°C) of the polymer. The Bicerano method is documented in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). When calculating Tg using the Bicerano method, the polymer physical property evaluation software MDL Polymer (MDL Information Systems, Inc.) can be used for calculation.

In order to increase the Tg of the resin (A) (preferably, the Tg exceeds 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A). Examples of methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e). (a) Introducing bulky substituents into the main chain (b) Introducing multiple substituents into the main chain (c) Introducing substituents inducing interaction between resins (A) into the vicinity of the main chain (d) Forming a main chain in a ring structure (e) Connect the cyclic structure to the main chain. Moreover, it is preferable that resin (A) has a repeating unit whose Tg of a homopolymer shows 130 degreeC or more. In addition, the type of the repeating unit whose Tg of the homopolymer shows 130°C or higher is not particularly limited as long as the Tg of the homopolymer calculated by the Bicerano method is 130°C or higher. In addition, the repeating units represented by the formulas (A) to (E) described below correspond to repeating units whose Tg of the homopolymer shows 130° C. or higher depending on the type of functional groups therein.

An example of a specific method for realizing the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).

[Chemical formula 27]

In formula (A), R _A represents a group containing a polycyclic structure. R _x represents a hydrogen atom, methyl group or ethyl group. The so-called group containing a polycyclic structure refers to a group containing a plurality of ring structures, and the plurality of ring structures may or may not be fused. Specific examples of the repeating unit represented by formula (A) include the repeating units described in paragraphs [0107] to [0119] of International Publication No. 2018/193954.

An example of a specific method for realizing the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).

[Chemical formula 28]

In the formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two of R _b1 to R _b4 represent an organic group. When at least one of the organic groups is a group having a ring structure directly connected to the main chain of the repeating unit, the types of other organic groups are not particularly limited. Furthermore, when any of the organic groups is a group in which a non-cyclic structure is directly connected to the main chain of the repeating unit, at least two of the organic groups are substituted with three or more constituent atoms other than hydrogen atoms. base. Specific examples of the repeating unit represented by formula (B) include the repeating units described in paragraphs [0113] to [0115] of International Publication No. 2018/193954.

An example of a specific method for realizing the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).

[Chemical formula 29]

In the formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, and at least one of R _c1 to R _c4 is a group containing a hydrogen atom with hydrogen bonding properties within 3 atoms from the main chain carbon. group. Among them, in order to induce interaction between the main chains of the resin (A), hydrogen atoms having hydrogen bonding properties within 2 atoms (closer to the main chain side) are preferred. Specific examples of the repeating unit represented by formula (C) include the repeating units described in paragraphs [0119] to [0121] of International Publication No. 2018/193954.

An example of a specific method for realizing the above (d) is a method of introducing a repeating unit represented by the formula (D) into the resin (A).

[Chemical formula 30]

In formula (D), "Cyclic" represents a group forming a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited. Specific examples of the repeating unit represented by formula (D) include the repeating units described in paragraphs [0126] to [0127] of International Publication No. 2018/193954.

An example of a specific method for realizing the above (e) is a method of introducing a repeating unit represented by the formula (E) into the resin (A).

[Chemical formula 31]

In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group which may have a substituent. "Cyclic" is a cyclic group containing carbon atoms of the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include the repeating units described in paragraphs [0131] to [0133] of International Publication No. 2018/193954.

(Repeating unit having at least one group selected from lactone group, sultone group, carbonate group, hydroxyl group, cyano group and alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group or a carbonate group that the resin (A) has include those described in the above <Repeating unit having a lactone group, a sultone group or a carbonate group> of repeating units. The preferred content is also the content described in the above <Repeating unit having a lactone group, a sultone group or a carbonate group>.

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include the repeating units described in paragraphs [0081] to [0084] of Japanese Patent Application Laid-Open No. 2014-098921.

The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonimide group, a disulfonimide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the α-position (for example, a hexafluoroisopropanol group). Preferably it is a carboxyl group. By including the repeating unit having an alkali-soluble group in the resin (A), the resolution in contact hole applications can be increased. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs [0085] and [0086] of Japanese Patent Application Laid-Open No. 2014-098921.

(A repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposability) The resin (A) may have a repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability. This can reduce the dissolution of low molecular components from the photoresist film into the immersion liquid during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and do not show acid decomposability include 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, and triadamantyl (meth)acrylate. Repeating unit of cyclodecyl ester or cyclohexyl (meth)acrylate.

(Represented by formula (III), it does not have any one of hydroxyl group and cyano group and has a repeating unit) The resin (A) may have a repeating unit represented by the formula (III) that does not have any of a hydroxyl group and a cyano group.

[Chemical formula 32]

In formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and not having any of a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a hydroxyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include the repeating units described in paragraphs [0087] to [0094] of Japanese Patent Application Laid-Open No. 2014-098921.

＜Other repeating units＞ The resin (A) may further have other repeating units in addition to the above-mentioned repeating units. For example, the resin (A) may have a repeating unit selected from a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit in the group consisting of repeating units having a hydantoin ring group. Specific examples having repeating units other than the above-mentioned repeating units are shown below.

[Chemical formula 33]

In addition to the above-mentioned repeating units, the resin (A) may also have various repeating units in order to adjust dry etching resistance, standard developer compatibility, substrate adhesion, photoresist profile, resolution, heat resistance, sensitivity, etc.

As the resin (A), especially when the composition of the present invention is used as a photosensitive radiation-sensitive or radiation-sensitive resin composition for ArF, it is preferable that all repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. Unit composition. In particular, it is also preferred that all the repeating units are composed of (meth)acrylate repeating units. When all the repeating units are composed of (meth)acrylate repeating units, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, all repeating units may be used. The units are all derived from either methacrylate repeating units or acrylate repeating units, and the acrylate repeating units are preferably 50 mol% or less of all repeating units.

Resin (A) can be synthesized according to conventional methods (such as free radical polymerization). The weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000 in terms of polystyrene conversion value by GPC method . The dispersion degree (molecular weight distribution, Pd, Mw/Mn) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, further preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and photoresist shape. Moreover, the sidewalls of the photoresist pattern will be smoother and the roughness will be better.

The resin (A) contained in the composition of the present invention may be one type, or two or more types.

In the composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9 mass%, more preferably 60.0 to 90.0 mass%, based on the total solid content of the composition of the present invention. One type of resin (A) may be used, or a plurality of types may be used in combination.

[acid salt] The composition of the present invention preferably contains an acidic salt, more preferably has a pKa of -2.0 or more, and still more preferably contains an acidic salt with a pKa of -2.0 or more and 1.0 or less. The acidic salt is preferably a compound (photoacid generator) that generates acid by irradiation with actinic rays or radioactive rays.

＜Photoacid generator＞ The photoacid generator may be in the form of a low molecular compound or may be incorporated into a part of the polymer. Moreover, a form of a low molecular compound and a form of being incorporated into a part of the polymer may be used together. When the photoacid generator is in the form of a low molecular compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. The lower limit is not particularly limited, but is preferably 100 or more. When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or may be incorporated into a resin different from the resin (A). The photoacid generator is preferably in the form of a low molecular compound. The photoacid generator is preferably a compound that generates an acid with a pKa of -2.0 or more by irradiation with actinic rays or radiation, and more preferably a compound that generates an acid with a pKa of -2.0 or more and 1.0 or less.

Examples of the photoacid generator include compounds (onium salts) ^represented by "M ⁺ Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.) ), carbonyl sulfonyl imide acid, bis(alkyl sulfonyl) amide acid, and ginseng (alkyl sulfonyl) methylated acid.

In the compound represented by "M ⁺ X ^- ", M ⁺ represents an organic cation. The organic cation is not particularly limited. The valence of the organic cation may be monovalent or bivalent or higher. Among these, the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)"). )".).

[Chemical formula 34]

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

Suitable aspects of the organic cation in the formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the cation (ZaI-3b), and the cation (ZaI-4b) described below.

First, the cation (ZaI-1) is explained. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R ²⁰¹ to R ²⁰³ of the above formula (ZaI) is an aryl group. The aryl sulfonium cation can be an aryl group in which R ²⁰¹ to R ²⁰³ are all aryl groups, or a part of R ²⁰¹ to R ²⁰³ can be an aryl group, and the rest can be an alkyl group or a cycloalkyl group. One of R ²⁰¹ to R ²⁰³ can be an aryl group, and the remaining two bonds between R ²⁰¹ to R ²⁰³ can form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, and amide groups. or carbonyl. Examples of the group formed by bonding two of R ²⁰¹ to R ²⁰³ include an alkylene group (for example, butylene group, pentylene group, and -CH ₂ -CH ₂ -O-CH ₂ - CH ₂ -), wherein more than one methylene group may be substituted by an oxygen atom, a sulfur atom, an ester group, a amide group and/or a carbonyl group. Examples of aryl sulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and arylbicycloalkylsulfonium cations.

The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation has if necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or an alkyl group having 3 to 15 carbon atoms. Cycloalkyl, more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl or cyclohexyl.

As the substituent that the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ may have, an alkyl group (for example, carbon number 1 to 15), cycloalkyl group (for example, carbon number 3 to 15), Aryl group (for example, carbon number 6 to 14), alkoxy group (for example, carbon number 1 to 15), cycloalkylalkoxy group (for example, carbon number 1 to 15), halogen atom (for example, fluorine and iodine) , hydroxyl group, carboxyl group, ester group, sulfinyl group, sulfonyl group, alkylthio group, or phenylthio group. The above-mentioned substituent may further have a substituent if possible, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent and is a haloalkyl group such as trifluoromethyl. It is also preferred that the above substituents form an acid-decomposable group by arbitrary combinations. In addition, the acid-decomposable group means a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that is detached by the action of an acid. The polar group and leaving group are as described above.

Next, the cation (ZaI-2) is explained. R ²⁰¹ to R ²⁰³ in the cation (ZaI-2) formula (ZaI) each independently represent a cation having an organic group that does not have an aromatic ring. The so-called aromatic ring also includes aromatic rings containing heteroatoms. The carbon number of the organic group that does not have an aromatic ring as R ²⁰¹ to R ²⁰³ is preferably 1 to 30, more preferably 1 to 20. R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or a 2-oxocyclic group. The alkyl group or alkoxycarbonylmethyl group is more preferably a linear or branched 2-oxoalkyl group.

Examples of the alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl , propyl, butyl and pentyl), and cycloalkyl groups with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl). R ²⁰¹ to R ²⁰³ may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. It is also preferable that the substituents of R ²⁰¹ to R ²⁰³ independently form an acid-decomposable group by any combination of the substituents.

Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[Chemical formula 35]

In the formula (ZaI-3b), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a cycloalkyl group. Alkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (for example, tert-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group. It is also preferred that the substituents of R _1c to R _7c and R _x and R _y independently form an acid-decomposable group through any combination of substituents.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring, and the rings may be independent of each other. Ground contains oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring in which two or more of these rings are combined. Examples of the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of the group formed by bonding any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include alkylene groups such as butylene group and pentylene group. The methyl group in the alkylene group may be substituted by a heteroatom such as an oxygen atom. The group formed by bonding R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include methylethylene group and ethylidene group.

R _1c to R _5c , R _6c , R _7c , R _x , R _y , and any two or more of R 1c to R _{5c , R 5c and} R _6c , R _6c and _{R 7c ,} R _5c and R _x , and The ring formed by each of R _x and R _y being bonded to each other may have a substituent.

Next, the cation (ZaI-4b) is explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[Chemical formula 36]

In the formula (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. R ₁₃ represents a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cyclic The alkyl group itself may be a group partially containing a cycloalkyl group). These groups may have substituents. R ₁₄ represents a hydroxyl group, a halogen atom (for example, a fluorine atom and an iodine atom, etc.), an alkyl group, a haloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, Or a group containing a cycloalkyl group (it may be the cycloalkyl group itself, or it may be a group partially containing a cycloalkyl group). These groups may have substituents. When there are plural R _14s , each independently represents the above-mentioned group such as hydroxyl group. R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R _15's may bond to each other to form a ring. When two R _15's are bonded to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one aspect, it is preferable that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned naphthyl group, and the ring formed by two R _15s bonded to each other may have a substituent.

In the formula (ZaI-4b), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ may be linear or branched. The carbon number of the alkyl group is preferably 1 to 10. The alkyl group is preferably methyl, ethyl, n-butyl or tert-butyl. It is also preferred that each of the substituents of R ₁₃ to R ₁₅ and R _x and R _y independently form an acid-decomposable group through any combination of substituents.

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

The aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, having 3 to 15 carbon atoms). ), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Moreover, it is also preferable that the substituents of R ²⁰⁴ and R ²⁰⁵ independently form an acid-decomposable group by any combination of the substituents.

Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[Chemical formula 37]

[Chemical formula 38]

[Chemical formula 39]

In the compound represented by "M ⁺ X ^- ", X ^- represents an organic anion. The organic anion is not particularly limited, and examples thereof include organic anions having a monovalent, divalent or higher valence. As the organic anion, an anion having a very low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, etc.) anions, and aralkylcarboxylic acid anions, etc.), sulfonimide anions, bis(alkylsulfonyl)imide anions, and ginseng(alkylsulfonyl)methide anions.

The aliphatic moiety in the aliphatic sulfonic acid anion and aliphatic carboxylic acid anion can be a linear or branched alkyl group, or a cycloalkyl group, preferably a linear or branched chain having 1 to 30 carbon atoms. Chain alkyl group or cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom. It may also be a perfluoroalkyl group).

The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include phenyl, tolyl, and naphthyl.

The alkyl group, cycloalkyl group, and aryl group listed above may have a substituent. The substituent is not particularly limited, and examples thereof include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), and alkyl groups. group (preferably carbon number 1 to 10), cycloalkyl group (preferably carbon number 3 to 15), aryl group (preferably carbon number 6 to 14), alkoxycarbonyl group (preferably carbon number 2 ~7), acyl group (preferably carbon number 2 to 12), alkoxycarbonyloxy group (preferably carbon number 2 to 7), alkylthio group (preferably carbon number 1 to 15), alkyl group Sulfonyl group (preferably having 1 to 15 carbon atoms), alkyl iminosulfonyl group (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl group (preferably having 6 to 20 carbon atoms) .

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthyl butyl.

Examples of sulfonimide anions include saccharin anions.

As the alkyl group in the bis(alkylsulfonyl)imide anion and the alkyl(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferred. Examples of substituents for such alkyl groups include halogen atoms, alkyl groups substituted by halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryl groups. The oxysulfonyl group is preferably a fluorine atom or an alkyl group substituted by a fluorine atom. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. By this, the acid strength can be increased.

Examples of other non-nucleophilic anions include phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and antimony fluoride (for example, SbF ₆ ^- ).

As the non-nucleophilic anion, preferred are an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which a fluorine atom or a group having a fluorine atom is substituted, and an alkyl group in which the alkyl group is substituted by a fluorine atom. Substituted bis(alkylsulfonyl)imide anion, or paras(alkylsulfonyl)methide anion in which the alkyl group is substituted by fluorine atom. Among them, perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or benzene sulfonate anion having a fluorine atom is more preferred, and nonafluorobutane sulfonate anion and perfluorooctane sulfonate are further preferred. Acid anion, pentafluorobenzenesulfonate anion, or 3,5-bis(trifluoromethyl)benzenesulfonate anion.

As the non-nucleophilic anion, an anion represented by the following formula (AN1) is also preferred.

[Chemical formula 40]

In formula (AN1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably a non-electron-withdrawing group. Examples of the non-electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbyl group, an oxycarbonylhydrocarbyl group, an amine group, a hydrocarbon-substituted amine group, and a hydrocarbon-substituted amide group. As the non-electron-withdrawing group, each independently preferably is -R', -OH, -OR', -OCOR', -NH ₂ , -NR' ₂ , -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

Examples of the monovalent hydrocarbon group represented by R′ include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propenyl, and butenyl; ethynyl, Monovalent linear or branched hydrocarbon groups such as propynyl and butynyl and other alkynyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl and other rings Alkyl; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, norbornenyl and other cycloalkenyl groups; phenyl, tolyl, xylyl, mesityl, naphthyl , methylnaphthyl, anthracenyl, and methylanthracenyl and other aryl groups; benzyl, phenethyl, phenylpropyl, naphthylmethyl, anthracenyl and other aralkyl and other monovalent aromatic hydrocarbon groups. Among them, R ¹ and R ² are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

L represents a bivalent linking group. When there are multiple L's, L's may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, Alkyl group (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), and a combination of a plurality of these into a bivalent linking base. Among them, as the divalent linking group, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkane is preferred. -, -COO-alkylene-, or -CONH-alkylene-, more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH- , -SO ₂ -, or -COO-alkylene-.

As L, for example, a group represented by the following formula (AN1-1) is preferred. ＊ ^a -(CR ^2a ₂ ) _X -Q-(CR ^2b ₂ ) _Y -＊ ^b (AN1-1)

In the formula (AN1-1), * ^a represents the bonding position with R ³ in the formula (AN1). * ^b represents the bonding position with -C(R ¹ )(R ² )- in the formula (AN1). X and Y each independently represent an integer from 0 to 10, preferably an integer from 0 to 3. R ^2a and R ^2b each independently represent a hydrogen atom or a substituent. When there are plural R ^2a and R ^2b respectively, the plural R ^2a and R ^2b may be the same or different. When Y is 1 or more, R ^2b in CR ^2b ₂ directly bonded to -C(R ¹ )(R ² )- in formula (AN1) is other than a fluorine atom. Q represents＊ ^A -O-CO-O-＊ ^B ,＊ ^A -CO-＊ ^B ,＊ ^A -CO-O-＊ ^B ,＊ ^A -O-CO-＊ ^B ,＊ ^A -O-＊ ^B , ＊ ^A -S-＊ ^B , or ＊ ^A -SO ₂ -＊ ^B . Among them, when X+Y in the formula (AN1-1) is 1 or more, and R ^2a and R ^2b in the formula (AN1-1) are both hydrogen atoms, Q represents * ^A -O-CO-O- * ^B , * ^A -CO-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A - _SO2- * ^B . * ^A represents the bonding position on the R ³ side in the formula (AN1), and * ^B represents the bonding position on the -SO ₃ ^- side in the formula (AN1).

In formula (AN1), R ³ represents an organic group. The above-mentioned organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group) or a branched group (for example, a tertiary butyl group, etc. branched alkyl group) or a cyclic group. The above organic group may or may not have a substituent. The above-mentioned organic group may have heteroatoms (oxygen atom, sulfur atom and/or nitrogen atom, etc.), or may not have heteroatoms.

Among them, R ³ is preferably an organic group having a cyclic structure. The above-mentioned cyclic structure may be a monocyclic ring or a polycyclic ring, or may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having the above-mentioned cyclic structure may or may not contain heteroatoms (eg, oxygen atom, sulfur atom, and/or nitrogen atom, etc.). Heteroatoms can replace more than one carbon atom forming a cyclic structure. Examples of the organic group having the above-described cyclic structure are preferably a hydrocarbon group, a lactone ring group, and a sultone ring group with a cyclic structure. Among them, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group of the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above-mentioned cycloalkyl group may be monocyclic (cyclohexyl, etc.) or polycyclic (adamantyl, etc.), and the carbon number is preferably 5 to 12. As the lactone group and the sultone group, for example, any of the structures represented by the above formulas (LC1-1) to (LC1-21) and the structures represented by the formulas (SL1-1) to (SL1-3) Among the structures, a group obtained by removing one hydrogen atom from a ring member atom constituting the lactone structure or sultone structure is preferred.

The non-nucleophilic anion may be a benzene sulfonate anion, preferably a benzene sulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

As the non-nucleophilic anion, an anion represented by the following formula (AN2) is also preferred.

[Chemical formula 41]

In formula (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. As the alkyl group substituted by at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ , and further preferably both Xf are fluorine atoms.

R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted by at least one fluorine atom. When there are plural R ⁴ and R ⁵ , R ⁴ and R ⁵ may be the same or different. The alkyl group represented by R ⁴ and R ⁵ preferably has 1 to 4 carbon atoms. The above-mentioned alkyl group may have a substituent. R ⁴ and R ⁵ are preferably hydrogen atoms.

L represents a bivalent linking group. The definition of L is synonymous with L in formula (AN1).

W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group and a heterocyclic group. The alicyclic group may be 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, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a bulky structure having 7 or more carbon atoms, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred.

Aryl groups can be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl, and anthracenyl. Heterocyclyl groups may be monocyclic or polycyclic. Among them, when it is a polycyclic heterocyclic group, the diffusion of acid can be further suppressed. The heterocyclic group may or may not be aromatic. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the nonaromatic heterocyclic ring include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferred.

The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or Any of the spiro rings, preferably carbon number 3 to 20), aryl group (preferably carbon number 6 to 14), hydroxyl group, alkoxy group, ester group, amide group, urethane group, Urea group, thioether group, sulfonamide group, and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

As the anion represented by formula (AN2), preferred are SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L) _q' -W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L) _q' -W, SO ₃ ^- -CF ₂ -COO-(L) _q' -W, SO ₃ ^- -CF ₂ -CF ₂ -CH ₂ -CH ₂ -(L) _q -W, or SO ₃ ^- - CF ₂ -CH(CF ₃ )-OCO-(L) _q' -W. Here, L, q and W are the same as Formula (AN2). q' represents an integer from 0 to 10.

As the non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[Chemical formula 42]

In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have a substituent other than a sulfonate anion and a -(D-B) group. Examples of substituents that may further include a fluorine atom and a hydroxyl group. n represents an integer above 0. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is still more preferable.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a tritylene group, a tritylene group, a sulfonate group, an ester group, and a group consisting of a combination of two or more of these.

B represents a hydrocarbon group. As B, an aliphatic hydrocarbon group is preferable, and an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (tricyclohexylphenyl group, etc.) is more preferable.

As the non-nucleophilic anion, disulfonamide anion is also preferred. The disulfonamide anion is, for example, an anion represented by N ^- (SO ₂ -R ^q ) ₂ . Here, R ^q represents an alkyl group which may have a substituent, and is preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. Two R ^q can bond to each other to form a ring. The group formed by bonding two R ^q to each other is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and further preferably a perfluoroalkylene group. The carbon number of the above-mentioned alkylene group is preferably 2 to 4.

Furthermore, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[Chemical formula 43]

[Chemical formula 44]

In formula (d1-1), R ⁵¹ represents a hydrocarbon group (for example, an aryl group such as phenyl group) which may have a substituent (for example, hydroxyl group).

In the formula (d1-2), Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (where the carbon atom adjacent to S is not substituted by a fluorine atom). The above-mentioned hydrocarbon group in Z ^2c may be linear or branched, or may have a cyclic structure. Furthermore, the carbon atom in the above-mentioned hydrocarbon group (preferably the carbon atom that is a ring member atom when the above-mentioned hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. "Z ^2c -SO ₃ ^- " in the formula (d1-2) is preferably different from the anions represented by the above formulas (AN1) to (AN3). For example, Z ^2c is preferably other than an aryl group. For example, it is preferable that the atoms at the α-position and β-position of Z ^2c with respect to -SO ₃ ^- are atoms other than carbon atoms having a fluorine atom as a substituent. For example, relative to -SO ₃ ^- in Z ^2c , the atoms at the α position and/or the atoms at the β position are preferably ring member atoms in the cyclic group.

In formula (d1-3), R ⁵² represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ³ is a linear, branched or cyclic alkylene group, aryl group or carbonyl group, Rf Represents a hydrocarbon group.

In formula (d1-4), R ⁵³ and R ⁵⁴ each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring.

One type of organic anion may be used alone, or two or more types of organic anions may be used.

The photoacid generator is also preferably at least one selected from the group consisting of compounds (I) to (II).

(Compound (I)) Compound (I) is a compound having one or more structural parts X and one or more structural parts Y described below, and is produced by irradiation of actinic rays or radioactive rays including those derived from the following structural parts A compound of an acid derived from the following first acidic site of X and the following second acidic site of structural site Y below. Structural site X: A structural site that is composed of an anionic site A ₁ ^- and a cationic site M ₁ ⁺ and forms a first acidic site represented by HA ₁ by irradiation with actinic rays or radioactive rays. Structural site Y: A structural site that is composed of an anionic site A ₂ ^- and a cationic site M ₂ ⁺ and forms a second acidic site represented by HA ₂ by irradiation with actinic rays or radioactive rays. The above compound (I) satisfies the following condition I.

Condition I: In the above-mentioned compound (1), the compound PI obtained by replacing the above-mentioned cationic site M ₁ ⁺ in the above-mentioned structural site X and the above-mentioned cationic site M ₂ ⁺ in the above-mentioned structural site Y with H ⁺ has a The acid _{dissociation constant a1 of the acidic site represented by HA 1} ⁱⁿ _which the above-mentioned cationic site M ₁ ⁺ in the above ^- mentioned structural site The acid dissociation constant a2 of the acidic site represented by HA ₂ formed by H ⁺ is greater than the acid dissociation constant a1.

Condition I will be described in more detail below. When compound (I) is, for example, a compound generating an acid having the above-mentioned first acidic site derived from the above-mentioned structural site X and the above-mentioned second acidic site derived from the above-mentioned structural site Y, the compound PI corresponds to "having HA ₁ and HA ₂ compounds”. The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are, more specifically, when the acid dissociation constant of the compound PI is determined and the compound PI becomes a "compound having A ₁ ^- and HA ₂ " pKa is the acid dissociation constant a1, and the pKa when the above "compound having A ₁ ^- and HA ₂ " becomes "the compound having A ₁ ^- and A ₂ ^- " is the acid dissociation constant a2.

When compound (I) is, for example, a compound that generates an acid having two first acidic sites derived from the above structural site X and one second acidic site derived from the above structural site Y, the compound PI corresponds to "having two A compound of HA ₁ and HA _2. " When the acid dissociation constant of compound PI is found, the acid dissociation constant of compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " and "it has one A ₁ ^- and one HA ₁ The acid dissociation constant when "a compound having two A ₁ ^- and one HA ₂ " becomes "a compound having two A 1 - and one HA ₂ " is equivalent to the above-mentioned acid dissociation constant a1. The acid dissociation constant when "a compound having two A ₁ ^- and one HA ₂ " becomes "a compound having two A ₁ ^- and A ₂ ^- " is equivalent to the acid dissociation constant a2. That is, in the case of compound PI, when there are multiple acid dissociation constants of the acidic site represented by HA ₁ in which the cationic site M ₁ ⁺ in the structural site X is replaced by H ⁺ , the acid dissociation The value of constant a2 is greater than the maximum value among the plurality of acid dissociation constants a1. In addition, when the acid dissociation constant of compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " is aa, and "a compound having one A ₁ ^- , one HA ₁ and one HA _2" When the acid dissociation constant when "compound" becomes "a compound having two A ₁ ^- and one HA ₂ " is ab, the relationship between aa and ab satisfies aa<ab.

The acid dissociation constant a1 and the acid dissociation constant a2 can be determined by the above-described acid dissociation constant measuring method. The above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radioactive rays. When the compound (I) has two or more structural parts X, the structural parts X may be the same or different. In addition, two or more of the above-mentioned A ₁ ^- and two or more of the above-mentioned M ₁ ⁺ may be the same or different. In the compound (I), the above-mentioned A ₁ ^- and the above-mentioned A ₂ ^- , and the above-mentioned M ₁ ⁺ and the above-mentioned M ₂ ⁺ may be the same or different respectively, but the above-mentioned A ₁ ^- and the above-mentioned A ₂ ^- are preferably different.

In the above-mentioned compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably is above 1.0. In addition, the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when a plurality of acid dissociation constants a1 exists) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. In addition, the lower limit value of the acid dissociation constant a2 is preferably -4.0 or more.

In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less. In addition, the lower limit value of the acid dissociation constant a1 is preferably -20.0 or more.

The anionic site A ₁ ^- and the anionic site A ₂ ^- are structural sites containing negatively charged atoms or atomic groups. Examples thereof include the following formulas (AA-1) to (AA-3) and formula ( Structural parts in the group composed of BB-1) ~ (BB-6). The anionic site A ₁ ^- is preferably one that can form an acidic site with a small acid dissociation constant. Among them, any one of the formulas (AA-1) to (AA-3) is more preferred, and the formula (AA-3) is more preferred. Any one of AA-1) and (AA-3). Furthermore, the anionic site A ₂ ^- is preferably one capable of forming an acidic site with a larger acid dissociation constant than the anionic site A ₁ ^- , and is more preferably any one of the formulas (BB-1) to (BB-6). More preferred is either one of formulas (BB-1) and (BB-4). In addition, in the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R ^A represents a monovalent organic group. The monovalent organic group represented by ^RA is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[Chemical formula 45]

[Chemical formula 46]

The cationic site M ₁ ⁺ and the cationic site M ₂ ⁺ are structural sites containing positively charged atoms or atomic groups. Examples thereof include organic cations with a single charge. Examples of the organic cation include the organic cation represented by M ₁ ⁺ mentioned above.

(Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural parts X and one or more of the following structural parts Z, and is a compound containing two or more structural parts derived from the above-mentioned structural parts X produced by irradiation with actinic rays or radiation. The acid compound of the above-mentioned first acidic site and the above-mentioned structural site Z. Structural part Z: a non-ionic part that can neutralize acid

In the compound (II), _the definition of the structural part X and the definitions of A ₁ ^- and M ₁ ⁺ are synonymous with _the ^definitions of ^the structural part The same goes for good looks.

In the compound (II), the compound PII in which the cationic site M ₁ ⁺ in the structural site X is substituted with H ⁺ is derived from the substitution of the cationic site M ₁ ⁺ in the structural site X with The preferable range of the acid dissociation constant a1 of the acidic site represented by HA ₁ formed by H ⁺ is the same as the acid dissociation constant a1 of the above-mentioned compound PI. Furthermore, for example, when compound (II) is a compound that generates an acid having two first acidic sites derived from the above structural site X and the above structural site Z, the compound PII is equivalent to "a compound having two HA ₁ " . When the acid dissociation constant of compound PII is found, the acid dissociation constant when compound PII becomes "a compound having one A ₁ ^- and one HA ₁ " and "a compound having one A ₁ ^- and one HA ₁ " The acid dissociation constant when it becomes a "compound having two A ₁ ^- " is equivalent to the acid dissociation constant a1.

The acid dissociation constant a1 can be determined by the above-described acid dissociation constant measuring method. The above-mentioned compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radioactive rays. In addition, the above two or more structural parts X may be the same or different. Two or more of the above-mentioned A ₁ ^- and two or more of the above-mentioned M ₁ ⁺ may be the same or different.

The nonionic moiety capable of neutralizing the acid in the structural moiety Z is not particularly limited. For example, a moiety containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferred. Examples of the group capable of electrostatic interaction with protons or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers or nitrogen containing non-shared electron pairs that do not contribute to π conjugation. functional groups of atoms. The nitrogen atom having a non-shared electron pair that does not contribute to π conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical formula 47] non-shared electron pair

Examples of the partial structure of a group capable of electrostatically interacting with a proton or a functional group having electrons include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine. structure, among which the 1st to 3rd level amine structure is preferred.

Examples of possible sites other than cations that compound (I) and compound (II) may have.

[Chemical formula 48]

[Chemical formula 49]

Specific examples of the photoacid generator are shown below, but are not limited thereto.

[Chemical formula 50]

[Chemical formula 51]

The content of the photoacid generator is not particularly limited. However, since the cross-sectional shape of the formed pattern is closer to a rectangular shape, it is preferably 0.5% by mass or more and more preferably 1.0% by mass relative to the total solid content of the composition of the present invention. %above. The above content is preferably 50.0 mass% or less, more preferably 30.0 mass% or less, and further preferably 25.0 mass% or less based on the total solid content of the composition of the present invention. One type of photoacid generator may be used alone, or two or more types of photoacid generators may be used.

[Acid diffusion control agent] The compositions of the present invention may contain acid diffusion controlling agents. The acid diffusion control agent functions as a quencher that captures acid generated from a photoacid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to excessive generation of acid. The type of acid diffusion control agent is not particularly limited. Examples thereof include a basic compound (CA), a low molecular compound (CB) having a nitrogen atom and a group that is detached by the action of an acid, and a compound that can be controlled by light. Compounds (CC) whose ability to control acid diffusion is reduced or eliminated due to exposure to chemical rays or radioactive rays. Examples of the compound (CC) include an onium salt compound (CD) that is a relatively weak acid relative to the photoacid generator, and a basic compound (CE) whose alkalinity is reduced or eliminated by irradiation with actinic rays or radioactive rays. ). Specific examples of the basic compound (CA) include those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824. Specific examples of the reduced or eliminated basic compound (CE) include those described in paragraphs [0137] to [0155] of International Publication No. 2020/066824 and paragraph [0164] of International Publication No. 2020/066824. Specific examples of the low molecular compound (CB) having a nitrogen atom and a group that is detached by the action of an acid include paragraphs [0156] to [0163 of International Publication No. 2020/066824 ]. Specific examples of the onium salt compound (CD) that is a relatively weak acid relative to the photoacid generator include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337.

In addition to the above, for example, paragraphs [0627] to [0664] of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of U.S. Patent Application Publication No. 2015/0004544A1, and Paragraphs [0095] to [0187] of U.S. Patent Application Publication No. 2015/0004544A1 can be appropriately used. Well-known compounds disclosed in paragraphs [0403] to [0423] of Publication No. 2016/0237190A1 and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 serve as acid diffusion control agents.

When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (if there are plural species, the sum thereof) is preferably 0.1 to 15.0 mass based on the total solid content of the composition of the present invention. %, more preferably 1.0 to 15.0% by mass. In the composition of the present invention, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.

[Hydrophobic resin (D)] The composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (D)") that is different from resin (A). Hydrophobic resin (D) is preferably designed to exist preferentially on the surface of the photoresist film, but unlike surfactants, it does not necessarily have a hydrophilic group in its molecule, and it may not help polar and non-polar substances. Mix evenly. Examples of effects brought about by adding the hydrophobic resin (D) include controlling the static and dynamic contact angles of the photoresist film surface with respect to water and suppressing outgassing.

From the viewpoint of localizing the film surface layer, the hydrophobic resin (D) preferably has at least one of a fluorine atom, a silicon atom, and a CH ₃ partial structure included in the side chain part of the resin, and more preferably has Two or more types. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may exist in the main chain of the resin or may be substituted on the side chain. Examples of the hydrophobic resin (D) include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.

When the composition of the present invention contains the hydrophobic resin (D), the content of the hydrophobic resin (D) is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 15.0 mass% relative to the total solid content of the composition of the present invention. %.

[Surfactant] The composition of the present invention may contain surfactants. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and/or silicone-based surfactant. Examples of fluorine-based and/or silicone-based surfactants include those disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/193954.

One type of these surfactants may be used alone, or two or more types of surfactants may be used.

When the composition of the present invention contains a surfactant, the content of the surfactant, relative to the total solid content of the composition of the present invention, is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and further preferably Preferably, it is 0.1 to 1.0% by mass.

[Solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains at least one of (M1) and (M2), where (M1) is propylene glycol monoalkyl ether carboxylate, and (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, and ethyl ether. At least one of the group consisting of acid esters, alkoxypropionate esters, chain ketones, cyclic ketones, lactones and alkylene carbonates. In addition, the above-mentioned solvent may further contain components other than components (M1) and (M2).

From the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects of the pattern, it is preferable to combine the above-mentioned solvent and the above-mentioned resin. Since the resin has a good balance of solubility, boiling point and viscosity, the solvent can suppress uneven film thickness of the photoresist film and the generation of precipitates during the spin coating process. The details of the component (M1) and the component (M2) are described in paragraphs [0218] to [0226] of International Publication No. 2020/004306, and these contents are incorporated into this specification.

When the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

The content of the solvent in the composition of the present invention is preferably set so that the solid content concentration becomes 0.5 to 30% by mass, more preferably 1 to 20% by mass. In this way, the coatability of the composition of the present invention can be further improved.

[Other additives] The composition of the present invention may further contain a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenolic compound with a molecular weight of 1000 or less, or alicyclic or aliphatic compounds containing carboxyl groups).

The above-mentioned "dissolution-inhibiting compound" refers to a compound with a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

The composition of the present invention is suitable for use as a photosensitive composition for EUV exposure. The wavelength of EUV light is 13.5nm. Compared with ArF (wavelength 193nm) light, etc., its wavelength is shorter, so the number of incident photons when exposed to the same sensitivity is smaller. Therefore, the "photon shot noise" with a deviation in the number of photons in probability has a greater impact, leading to deterioration of line edge roughness (LER) and bridging defects. In order to reduce photon shot noise, there is a method of increasing exposure to increase the number of incident photons, but this is weighed against the requirement for high sensitivity.

When the A value calculated from the following formula (1) is high, the absorption efficiency of EUV light and electron beams of the photoresist film formed of the photoresist composition becomes high, and photon shot noise can be effectively reduced. The A value represents the mass ratio of the photoresist film to the EUV light and electron beam absorption efficiency. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) /([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) The A value is preferably 0.120 or more. The upper limit is not particularly limited, but if the A value is too large, the EUV light and electron beam transmittance of the photoresist film will decrease, and the optical image profile in the photoresist film will deteriorate. As a result, it will be difficult to obtain a good pattern shape, so it is preferably 0.240 or less, more preferably 0.220 or less.

In the formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solid content of the photosensitive radiation or radiation-sensitive resin composition to all atoms of the total solid content, and [C] represents The molar ratio of carbon atoms derived from the total solid content of the photosensitive radiation-sensitive or radiation-sensitive resin composition to all atoms in the total solid content, [N] represents the molar ratio derived from the photosensitive radiation-sensitive or radiation-sensitive resin composition The molar ratio of nitrogen atoms in the total solid content in the composition to all atoms in the total solid content, [O] represents the molar ratio of oxygen atoms derived from the total solid content in the photosensitive radiation or radiation-sensitive resin composition to the total The molar ratio of all atoms in the solid content, [F], represents the molar ratio of fluorine atoms derived from the total solid content in the photosensitive radiation or radiation-sensitive resin composition to all the atoms in the total solid content, [S ] represents the molar ratio of sulfur atoms derived from the photosensitive radiation or the total solid content in the radiation-sensitive resin composition to all atoms in the total solid content, and [I] represents the molar ratio derived from the photosensitive radiation or radiation sensitivity. The molar ratio of iodine atoms in the total solid content in the resin composition to all atoms in the total solid content. For example, when the photoresist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion control agent, and a solvent, the acid-decomposable resin, the photoacid generator, and the acid diffusion control agent correspond to the solid content. That is, all atoms of the total solid content correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms in the total solid content. Based on the above example, [H] represents the hydrogen atoms derived from the acid-decomposable resin, the source The sum of hydrogen atoms derived from the photoacid generator and the hydrogen atoms derived from the acid diffusion control agent is relative to all atoms derived from the acid-decomposable resin, all atoms derived from the photoacid generator, and The molar ratio of the total atoms of the above acid diffusion control agent.

The A value can be calculated by calculating the ratio of the number of atoms contained in the photoresist composition when the structure and content of the total solid components are known. Furthermore, even when the constituent components are unknown, the constituent atomic number ratio of the photoresist film obtained by evaporating the solvent component of the resist composition can be calculated by analysis methods such as elemental analysis.

＜Photosensitive radiation or radiation-sensitive film and pattern forming method＞ The present invention also relates to a photosensitive radiation-sensitive or radiation-sensitive film formed by the composition of the present invention. The photosensitive radiation or radiation-sensitive film of the present invention is preferably a photoresist film. The sequence of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following processes. Process 1: A process of forming a photoresist film on a substrate using the composition of the present invention. Process 2: The process of exposing the photoresist film. Process 3: The process of developing the exposed photoresist film using a developer. Below, the steps of each of the above processes are described in detail.

(Process 1: Photoresist film formation process) Process 1 is a process for forming a photoresist film on a substrate using the composition of the present invention.

An example of a method for forming a photoresist film on a substrate using the composition of the present invention is a method of applying the composition of the present invention onto a substrate. In addition, it is preferable to filter the composition of the present invention with a filter if necessary before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, further preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The composition of the present invention can be coated onto a substrate (eg, silicon, silicon dioxide coating) used for manufacturing integrated circuit components by a suitable coating method such as a spinner or a coater. The coating method is preferably spin coating using a spinner. The rotation speed when using a spinner for spin coating is preferably 1000 to 3000 rpm (rotations per minute, revolutions per minute). After coating the composition of the present invention, the substrate can be dried and a photoresist film can be formed. In addition, if necessary, various base films (inorganic films, organic films, anti-reflection films) can be formed on the lower layer of the photoresist film.

An example of the drying method is a method of drying by heating. Heating can be implemented by devices provided with a common exposure machine and/or developing machine, or by using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and further preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, further preferably 60 to 600 seconds.

The film thickness of the photoresist film is not particularly limited, but from the viewpoint of forming a fine pattern with higher precision, it is preferably 10 to 120 nm. Among them, in the case of EUV exposure, the film thickness of the photoresist film is more preferably 10 to 65 nm, further preferably 15 to 50 nm. In the case of ArF immersion exposure, the film thickness of the photoresist film is more preferably 10 to 120 nm, further preferably 15 to 90 nm.

In addition, a top coat composition may be used to form a top coat layer on the upper layer of the photoresist film. The top coating composition is preferably not mixed with the photoresist film and can be evenly coated on the upper layer of the photoresist film. The top coat layer is not particularly limited, and a previously known top coat layer can be formed by a previously known method. For example, it can be formed according to the descriptions in paragraphs [0072] to [0082] of Japanese Patent Application Laid-Open No. 2014-059543. Top coat. For example, it is preferable to form a top coat layer containing a basic compound such as that described in Japanese Patent Application Laid-Open No. 2013-61648 on the photoresist film. Specific examples of the basic compounds that can be contained in the top coat include basic compounds that can be contained in the composition of the present invention. It is also preferred that the top coat layer contains a compound containing at least one group or bond selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond.

(Process 2: Exposure process) Process 2 is a process for exposing the photoresist film. An example of the exposure method is a method of irradiating the formed photoresist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. The ray is preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 10 nm. Far ultraviolet light with a wavelength of 200nm, specifically, KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), EUV (13.5nm), X rays, and electron beams.

It is preferable to bake (heat) after exposure and before development. Baking can promote the reaction of the exposed part, thereby improving the sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and further preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and further preferably 30 to 120 seconds. Heating can be performed by devices provided with a common exposure machine and/or developing machine, or by using a hot plate or the like. This process is also called post-exposure bake.

(Process 3: Development process) Process 3 is a process in which a developer is used to develop the exposed photoresist film to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

Examples of the development method include a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (immersion method), and a method in which the developer is deposited on the surface of the substrate by surface tension and left to stand for a certain period of time to develop. (puddle method), a method of spraying a developer onto a substrate surface (spray method), and a method of continuously spraying a developer from a nozzle while scanning at a certain speed on a substrate rotating at a certain speed (spray method) dynamic allocation method). In addition, after performing the development process, it is also possible to perform a process of stopping the development while replacing it with another solvent. The development time is not particularly limited as long as the resin in the unexposed portion is fully dissolved, but it is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

As an alkaline developer, an alkaline aqueous solution containing an alkali is preferably used. The type of alkaline aqueous solution is not particularly limited, and examples thereof include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcoholamines, or cyclic alkaline solutions. Alkaline aqueous solutions of amines, etc. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc. can be added to the alkaline developer. The alkali concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of an alkaline developer is generally preferably 10.0 to 15.0.

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.

A plurality of types of the above-mentioned solvents may be mixed, and they may be mixed with solvents other than those mentioned above or water. The moisture content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably contains substantially no water. The content of the organic solvent relative to the organic developer is preferably 50 mass% or more and 100 mass% or less, more preferably 80 mass% or more and 100 mass% or less, and further preferably 90 mass% relative to the total amount of the developer. It is 95 mass % or more and 100 mass % or less, especially preferably 95 mass % or more and 100 mass % or less.

(Other processes) The above pattern forming method preferably includes a process of cleaning with a rinse liquid after process 3.

Examples of the rinse liquid used in the rinse process after the development process with an alkaline developer include pure water. In addition, an appropriate amount of surfactant can be added to pure water. An appropriate amount of surfactant can also be added to the rinse solution.

The rinse liquid used in the rinse process after the development process using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid 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.

The method of the rinsing process is not particularly limited. Examples include a method of continuously spraying a rinsing liquid onto a substrate rotating at a certain speed (spin coating method), and a method of immersing the substrate in a tank filled with a rinsing liquid for a certain period of time ( dipping method), and the method of spraying rinsing liquid on the surface of the substrate (spraying method). In addition, the pattern forming method may include a heating process (Post Bake) after the rinse process. Through this process, the developer and rinse fluid remaining between and inside the patterns are removed by baking. In addition, this process also has the effect of annealing the photoresist pattern and improving the surface roughness of the pattern. The heating process after the rinsing process is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

Furthermore, the formed pattern can be used as a mask to perform etching of the substrate. That is, the pattern formed in process 3 can be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method of the substrate (or the underlying film and the substrate) is not particularly limited, but it is preferable to use the pattern formed in process 3 as a mask and dry-etch the substrate (or the underlying film and the substrate) to form a pattern on the substrate. method of forming patterns. Dry etching is preferably oxygen plasma etching.

Various materials used in the composition and pattern forming method of the present invention (for example, solvents, developers, rinse solutions, antireflection film forming compositions, top coat forming compositions, etc.) are preferably free of metal, etc. Impurities. The impurity content contained in these materials is preferably 1 mass ppm (parts per million, one part per million) or less, more preferably 10 mass ppb (parts per billion, one part per billion) or less, still more preferably It is less than 100 ppt by mass, the best is less than 10 ppt by mass, and the best is less than 1 ppt by mass. The lower limit is not particularly limited, but is preferably 0 mass ppt or more. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W and Zn.

An example of a method for removing impurities such as metals from various materials is filtration using a filter. Details of filtering using a filter are described in paragraph [0321] of International Publication No. 2020/004306.

Examples of methods for reducing impurities such as metals contained in various materials include selecting raw materials with low metal content as the raw materials constituting the various materials, filtering the raw materials constituting the various materials with a filter, and using TEFLON (Registered Trademark) A method of distilling under conditions that suppress contamination as much as possible by forming a lining in the device, etc.

In addition to filter filtration, adsorbent materials can also be used to remove impurities, or a combination of filter filtration and adsorbent materials can be used. As the adsorbent material, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be used. In order to reduce metal and other impurities contained in the various materials mentioned above, it is necessary to prevent the mixing of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning liquid used to clean the manufacturing equipment. The content of the metal component contained in the cleaning solution after use is preferably 100 ppt by mass (parts per trillion, one part per trillion) or less, more preferably 10 ppt by mass or less, and still more preferably 1 ppt by mass or less. The lower limit is not particularly limited, but is preferably 0 mass ppt or more.

Conductive compounds can be added to organic treatment fluids such as flushing fluids to prevent breakdown of chemical piping and various components (filters, O-rings, tubes, etc.) caused by electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, and examples thereof include methanol. The addition amount is not particularly limited, but from the viewpoint of maintaining better development characteristics or flushing characteristics, it is preferably 10 mass% or less, and more preferably 5 mass% or less. The lower limit is not particularly limited, but is preferably 0.01 mass% or more. As the chemical liquid piping, for example, SUS (stainless steel) or various piping coated with polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been subjected to antistatic treatment can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been treated with antistatic treatment can be used.

＜Manufacturing method of electronic devices＞ This specification also relates to a manufacturing method of an electronic device including the above pattern forming method, and an electronic device manufactured by the manufacturing method. A preferable aspect of the electronic device described in this specification is one that is mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.). [Example]

The present invention will be described in more detail below based on examples. The materials, usage amounts, proportions, processing contents and processing steps shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed restrictively by the embodiments shown below.

Various components used in the photoresist compositions of Examples and Comparative Examples are shown below.

<Resin (A)> As the resin (A), AP-1 to AP-13 were used. In addition, in the comparative example, AX-1 to AX-3 were used as resins other than resin (A). For convenience, in Table 1 below, AX-1 to AX-3 are also listed in the resin (A) column. The structures of AP-1 to AP-13 and AX-1 to AX-3 are shown below. The content ratio of the following repeating units (relative to the content of all repeating units in the resin) is a molar ratio. The weight average molecular weight (Mw) and dispersion (Pd=Mw/Mn) of the resin are measured by GPC (carrier: tetrahydrofuran (THF)) (based on polystyrene conversion). In addition, the content of repeating units is measured by ¹³ C-NMR (nuclear magnetic resonance, nuclear magnetic resonance).

[Chemical formula 52]

[Chemical formula 53]

[Chemical formula 54]

[Chemical formula 55]

The synthesis example of AP-1 is shown below. Other resins (A) are synthesized in the same manner.

(Synthesis of AS-1)

[Chemical formula 56]

Dissolve 15.7g of thiophene-2-carboxylic acid in 100g of tetrahydrofuran (THF) in a three-neck flask and cool to -10°C. 125 ml of methylmagnesium bromide (MeMgBr) (1.0 mol/l THF solution) was added dropwise and stirred for 1 hour. After that, 4-vinylbenzoyl chloride was added and stirred at 40°C for 6 hours. Thereafter, 100 g of saturated aqueous ammonium chloride solution was added at room temperature, and after stirring for 1 hour, 100 g of ethyl acetate was added, the organic phase was separated, and the organic phase was washed with 150 g of water and concentrated to obtain AS-1 crude product. The obtained crude product was purified by column chromatography to obtain 14.2 g of AS-1.

[Chemical formula 57]

(Synthesis of AP-1) Cyclohexanone (57g) was heated to 85°C under a stream of nitrogen. While stirring the solution, AS-1 (51.6g), 4-vinylphenol (36.1g), cyclohexanone (105.8g) and 2,2'-azobisisobutyric acid were added dropwise to the solution. A mixed solution of dimethyl ester [V-601, manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.] (6.2 g) was prepared for 3 hours to obtain a reaction liquid. After completion of the dropwise addition, the reaction solution was further stirred at 85° C. for 3 hours. After the obtained reaction liquid was allowed to cool, it was reprecipitated with 4000 g of ethyl acetate/heptane (mass ratio 1:9), and then filtered. The obtained solid was vacuum dried to obtain AP-1 (79 g).

＜Acidic salt＞ As acidic salts, B-1 to B-6 were used. B-1 to B-6 are photoacid generators. The structures of B-1 to B-6 and the pKa of the acid generated from B-1 to B-6 are shown below. The pKa value of the acid produced from B-6 is an approximate value calculated using partial structures.

[Chemical formula 58]

＜Acid diffusion control agent＞ As acid diffusion control agents, D-1 to D-4 were used.

[Chemical formula 59]

＜Surface active agent＞ The surfactants used are shown below. W-1: MEGAFAC F176 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., fluorine-based) W-2: MEGAFAC R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., fluorine and silicon based) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.; silicone-based) W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) W-5: KH-20 (AGC (stock) system) W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

＜Solvent＞ The solvents used are shown below. SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: Ethyl lactate SL-5: Propylene glycol monomethyl ether (PGME) SL-6: cyclohexanone SL-7: γ-butyrolactone SL-8: Propylene carbonate

<Preparation of photoresist composition> The components shown in Table 1 were dissolved in the solvent shown in Table 1 using the mass (g) shown in Table 1 to prepare a solution with a solid content concentration of 2.5% by mass, and filtered through polyethylene having a pore size of 0.02 μm. Filter it with a device to obtain photoresist compositions R-1 to R-19 and R-x1 to R-x3. Regarding solvents, Table 1 describes the types of compounds used and their mass ratios. In Table 1, when two or more types of each component are used, the type and usage amount of each component are separated by "/". For example, "AP-1/AP-3" in the photoresist composition R-14 means that AP-1 and AP-3 are used as resin (A), and "5/5" means AP-1 and AP-3 Each used 5g.

[Table 1]

<Coating of photoresist composition> The prepared photoresist composition was coated on a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark8, and placed on a hot plate. Dry at 130°C for 300 seconds to obtain a photoresist film with a film thickness of 100 nm. Here, 1 inch is 0.0254m. In addition, even if the above-mentioned Si wafer is changed to a chromium substrate, the same result can be obtained.

<Pattern formation method (1): EB exposure, alkali development (positive)> The wafer coated with the photoresist film obtained above was pattern-irradiated using an electron beam drawing device (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50keV). At this time, draw to form a 1:1 line and space. After electron beam drawing, it was heated on a hot plate at 100° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds, and then baked and dried at 95° C. for 60 seconds.

[evaluation] 〔Sensitivity〕 The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The exposure amount when analyzing a 1:1 line-to-space photoresist pattern with a line width of 50 nm is defined as the sensitivity (Eop). The smaller the value, the higher the sensitivity.

[Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). When analyzing a 1:1 line and space photoresist pattern with a line width of 50 nm, the ultimate resolution power (the minimum line width that can be analyzed separately for line and space (line:space = 1:1)) at the exposure is set to the analysis Degree (nm). The smaller the value, the higher the resolution.

[LWR performance] Using a length-measuring scanning electron microscope (SEM (S-9380II manufactured by Hitachi, Ltd.)), a 50 nm (1:1) line and space pattern analyzed at an exposure amount indicating the above sensitivity (Eop) was viewed from above the pattern. Observations were made. Observe the line width of the pattern at any point, calculate its standard deviation (σ), and evaluate the measurement deviation of the line width in terms of 3σ (nm). Smaller values indicate better performance.

[EL performance] Based on the above sensitivity (Eop), determine the exposure amount that will be ±10% of the target value of 50nm (that is, 45nm and 55nm). Then, the exposure latitude (EL, unit: %) defined by the following formula is calculated. The larger the EL value, the smaller the performance change caused by changes in exposure, that is, the better it is. EL (%) = [[(Exposure amount when the line width is 55nm)-(Exposure amount when the line width is 45nm)]/Eop]×100

Table 2 below shows the photoresist composition used and the results.

[Table 2]

<Pattern formation method (2): EUV exposure, alkali development (positive)> An EUV exposure device (made by Exitech, Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma (σ) 0.68, inner sigma (σ) 0.36) was used, and an exposure mask (line/space=1/1) was used. , pattern exposure is performed on the wafer coated with the photoresist film obtained above. After exposure, it was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds, and then baked and dried at 95° C. for 60 seconds.

[evaluation] The sensitivity, resolution, LWR performance, and EL performance were evaluated in the same manner as above.

Table 3 below shows the photoresist composition used and the results.

[table 3]

<Pattern formation method (3): EUV exposure, organic solvent development (negative)> An EUV exposure device (made by Exitech, Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma (σ) 0.68, inner sigma (σ) 0.36) was used, and an exposure mask (line/space=1/1) was used. , pattern exposure is performed on the wafer coated with the photoresist film obtained above. After exposure, it was heated on a hot plate at 100° C. for 90 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

[evaluation] The sensitivity, resolution, LWR performance, and EL performance were evaluated in the same manner as above.

Table 4 below shows the photoresist composition used and the results.

[Table 4]

From the results in Tables 2 to 4, it can be seen that the photoresist composition used in the examples has excellent resolution, EL performance, and LWR performance. [Industrial availability]

According to the present invention, it is possible to provide a photosensitive radiation or radiation-sensitive resin composition excellent in resolution, EL performance, and LWR performance. Furthermore, according to the present invention, it is possible to provide a photoresist film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned photosensitive radiation-sensitive or radiation-sensitive resin composition.

The present invention has been described in detail with reference to specific embodiments. However, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2022-011974) filed on January 28, 2022, the contents of which are incorporated herein by reference.

without

without

Claims (12)

A photosensitive radiation-sensitive or radiation-sensitive resin composition, which contains a resin (A) containing a group that is decomposed by the action of an acid and whose polarity is increased, wherein the resin (A) contains the following general formula (S1) ), the acid-decomposable repeating unit represented by In the general formula (S1), Ra ₁ to Ra ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, and La ₁ represents a bivalent connecting group containing an aromatic group. , Ra ₃ and La ₁ can be connected to form a ring, Ra ₄ to Ra ₆ independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group or an alkenyl group, Among them, at least one of Ra ₄ to Ra ₆ represents an aromatic heterocyclic group containing a sulfur atom, and two of Ra ₄ to Ra ₆ may be bonded to each other to form a ring. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein La ₁ in the general formula (S1) contains an aryl group. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein La ₁ in the general formula (S1) represents an aryl group or a bivalent linking group consisting of an aryl group and a carbonyl group. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein any one of Ra ₄ to Ra ₆ in the general formula (S1) represents a hydrogen atom. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the acid-decomposable repeating unit represented by the general formula (S1) is the following general formula (S1-1) or (S1- 2) The acid-decomposable repeating unit represented, In general formulas (S1-1) and (S1-2), Ra ₁ to Ra ₃ have the same meanings as Ra ₁ to Ra 3 in the general formula (S1), and Ra ₄ to _{Ra 6 have} the same meanings as those in the general formula (S1). Ra ₄ to Ra ₆ in (S1) have the same meaning, La ₂ represents a single bond or -COO-, Ara ₁ represents an aryl group, and Ra ₃ and Ara ₁ may be connected to form a ring. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin (A) contains an acid that is decomposed by irradiation with electron beams or extreme ultraviolet rays to generate acid. The repeating unit of the group. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, which contains an acidic salt with a pKa of -2.0 or more. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, which contains an acidic salt with a pKa of -2.0 or more and 1.0 or less. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin (A) further contains a repeating unit having a phenolic hydroxyl group and a lactone group. at least one of the repeating units. A photoresist film formed using the photosensitive radiation or radiation-sensitive resin composition described in any one of claims 1 to 9. A pattern forming method, which includes: a process of forming a photoresist film on a substrate using the photosensitive radiation or radiation-sensitive resin composition described in any one of claims 1 to 9; and exposing the photoresist film The process; and the process of developing the exposed photoresist film using a developer. A method of manufacturing an electronic device, which includes the pattern forming method described in claim 11.