TWI898021B - Polymer, anti-corrosion agent composition containing the polymer, method for manufacturing a component using the anti-corrosion agent composition, method for forming a pattern, and method for forming a reverse pattern - Google Patents

Abstract

Provided are a polymer, an anti-etching agent composition containing the polymer, and a method for manufacturing a component utilizing the same. The polymer is used in an anti-etching agent composition having high absorption efficiency, excellent sensitivity, resolution, and pattern performance, and mitigates the effects of reduced sensitivity and deterioration of pattern roughness caused by a decrease in energy imparted density in patterns formed by irradiation with a particle beam or electromagnetic wave having high particle and photon energy. The polymer comprises a unit A and a unit B, wherein the unit A has an onium salt structure and generates an acid upon irradiation with a particle beam or electromagnetic wave, and the unit B has a structure in which a bond is catalyzed by an acid reaction, and the unit A is represented by the following general formula (1). [Chemistry 1] (1) (In the above general formula (1), ^R1 is any one selected from a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms, wherein R In ¹ , at least one hydrogen atom in the alkyl and alkenyl groups may be substituted with a substituent; L is any one selected from a direct bond, a carbonyloxy group, a carbonylamino group, a phenylenediyl group, a naphthalenediyl group, a phenylenedioxy group, a naphthalenedioxy group, a phenylenedicarbonyloxy group, a naphthalenedicarbonyloxy group, a phenylenedioxycarbonyl group, and a naphthalenedioxycarbonyl group; Sp is any one of a direct bond; a linear, branched, or cyclic alkylene group having 1 to 6 carbon atoms which may have a substituent; and a linear, branched, or cyclic alkenylene group having 1 to 6 carbon atoms which may have a substituent; at least one methylene group in Sp may be substituted with a divalent heteroatom-containing group; M ⁺ is a sulfonium ion or an iodine ion; and ^X- is a monovalent anion having an organic group, wherein the organic group includes at least one selected from a hydroxyl group and a sulfanyl group.

Description

Polymer, anti-corrosion agent composition containing the polymer, method for manufacturing a component using the anti-corrosion agent composition, method for forming a pattern, and method for forming a reverse pattern

Several aspects of the present invention relate to polymers used in anti-etching compositions. Furthermore, several aspects of the present invention relate to anti-etching compositions containing the polymers, methods for manufacturing parts using the anti-etching compositions, methods for forming patterns, and methods for forming reverse patterns.

In recent years, photolithography technology has been actively employed using photoresists to manufacture display devices such as liquid crystal displays (LCDs) and organic electroluminescent displays (OLEDs), as well as to form semiconductor devices. In these electronic components and electronic product packaging, active energy rays such as i-rays (365nm), and longer-wavelength h-rays (405nm), and g-rays (436nm) are widely used.

With the increasing integration of devices, the demand for miniaturization in photolithography is increasing. There is a trend toward using shorter-wavelength light, such as KrF excimer lasers (248nm wavelength), ArF excimer lasers (193nm wavelength), extreme ultraviolet (EUV, 13.5nm wavelength), and electron beams (EB), for exposure. The use of these shorter-wavelength light, particularly EUV or EB lithography, enables single-patterning fabrication. Consequently, there will be an increasing demand for resist compositions that exhibit high sensitivity to EUV and EB.

As exposure light sources become shorter in wavelength, resist compositions are required to improve their photolithographic properties, achieving high sensitivity to exposure light sources and reproducible resolution for fine-scale pattern formation. Chemically enhanced resists using photoacid generators are known as resist compositions that meet these requirements (Patent Document 1).

However, with conventional chemically enhanced resists, it has been difficult to sufficiently suppress resist pattern collapse and the reduction in line width roughness (LWR) of the line pattern as the resolution and line width of the resist decrease.

It is well known that in order to reduce the LWR of the resist and achieve high resolution, one method is to reduce the diffusion of the acid caused by heat by using an acid generator having a large molecular weight, a bulk acid anion, or an acid anion bound to a polymer. (Patent Documents 2, 3)

To prevent resist pattern collapse, it has been proposed to increase the crosslink density of negative chemically enhanced resists. However, this can lead to defects such as bridges due to swelling during development, making it difficult to increase crosslink density with high sensitivity while maintaining resolution and pattern performance.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Publication No. 9-90637

Patent Document 2: Japanese Patent Publication No. 2011-53622

Patent Document 3: Japanese Patent Publication No. 2010-276910

Several aspects of the present invention are directed to providing a polymer for use in resist compositions that significantly suppresses acid diffusion and exhibits excellent resolution and patterning properties. This polymer utilizes a reaction induced by irradiation with electron beams or EUV, in addition to acid generated from an acid generator by irradiation with particle beams or electromagnetic waves, particularly electron beams or EUV, directly utilizing a reaction induced by irradiation with electron beams or EUV, simultaneously with the acid-catalyzed reaction.

Several aspects of the present invention provide an anti-corrosion agent composition containing the aforementioned polymer, a method for manufacturing a component utilizing the anti-corrosion agent composition, a method for forming a pattern, and a method for forming a reversed pattern.

The inventors conducted intensive research to address the above-mentioned issues and discovered that using a polymer containing a unit A having a specific onium salt structure and a unit B having a specific structure as a polymer in an anti-etching agent composition can achieve high sensitivity and suppress line width roughness (LWR). This led to the completion of several aspects of the present invention. Unit A has a monovalent organic group in the anion, and the monovalent organic group has at least one selected from a hydroxyl group and a sulfanyl group.

More specifically, the following results were obtained by irradiating an anti-etching agent composition containing the above-mentioned polymer with a particle beam or electromagnetic wave. First, the above-mentioned unit A decomposes, undergoing a significant polar transition from ionic to non-ionic. Simultaneously, the acid generated by the decomposition of the above-mentioned unit A undergoes an intramolecular crosslinking reaction between the hydroxyl groups of the above-mentioned unit B and/or between the above-mentioned unit A and the above-mentioned unit B. When the onium salt-structured anion of the above-mentioned unit A is an anion having an organic group containing a hydroxyl group or a sulfanyl group, a portion of the anion is bonded to the above-mentioned unit B through an acid-catalyzed reaction via the hydroxyl or sulfanyl groups in the anion, thereby incorporating into the polymer to form the acid of the polymer anion. Therefore, the anti-etching agent composition containing the above polymer can inhibit acid diffusion, has high sensitivity, and can suppress line width roughness (LWR).

One approach to solving the above-mentioned problems of the present invention is a polymer comprising a unit A that generates an acid upon irradiation with a particle beam or electromagnetic wave, and a unit B having a structure in which a bond is formed by an acid-catalyzed reaction. The unit A has a specific onium salt structure having a monovalent organic group in the anion, the monovalent organic group having at least one selected from a hydroxyl group and a sulfanyl group.

It should be noted that the above-mentioned unit A is represented by the following general formula (1).

(In the above general formula (1), ^R1 is any one selected from a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms, wherein R In ¹ , at least one hydrogen atom in the alkyl and alkenyl groups may be substituted with a substituent; L is any one selected from a direct bond, a carbonyloxy group, a carbonylamino group, a phenylenediyl group, a naphthalenediyl group, a phenylenedioxy group, a naphthalenedioxy group, a phenylenedicarbonyloxy group, a naphthalenedicarbonyloxy group, a phenylenedioxycarbonyl group, and a naphthalenedioxycarbonyl group; Sp is any one of a direct bond; a linear, branched, or cyclic alkylene group having 1 to 6 carbon atoms which may have a substituent; and a linear, branched, or cyclic alkenylene group having 1 to 6 carbon atoms which may have a substituent; at least one methylene group in Sp may be substituted with a divalent heteroatom-containing group; M ⁺ is a sulfonium ion or an iodine ion; and ^X- is a monovalent anion having a monovalent organic group in the anion, wherein the monovalent organic group has at least one selected from a hydroxyl group and a sulfanyl group.

One embodiment of the present invention is an anti-corrosion agent composition containing the above-mentioned polymer.

In addition, one embodiment of the present invention provides a component manufacturing method comprising the following steps: an anti-corrosion film forming step of forming an anti-corrosion film on a substrate using the anti-corrosion composition; a photolithography step of exposing the anti-corrosion film using a particle beam or an electron beam; and a pattern forming step of developing the exposed anti-corrosion film to obtain a photolithographic anti-corrosion pattern.

One embodiment of the present invention provides a pattern forming method comprising the following steps: an anti-etching film forming step of forming an anti-etching film on a substrate using the aforementioned anti-etching agent composition; a photolithography step of exposing the anti-etching film using a particle beam or electromagnetic waves; and a pattern forming step of developing the exposed anti-etching film to obtain a photolithographic anti-etching pattern.

One embodiment of the present invention provides a method for forming a reverse pattern, comprising the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition; a photolithography step of exposing the resist film using a particle beam or electromagnetic waves; a pattern forming step of developing the exposed resist film to obtain a photolithographic resist pattern; a step of etching a coating obtained by coating a reverse pattern composition to cover at least the recessed portions of the photolithographic resist pattern, thereby exposing the surface of the photolithographic resist pattern; and a step of removing the resist film from the exposed resist pattern surface to obtain a reverse pattern.

When the polymers according to some embodiments of the present invention are used as anti-etching agent compositions, they undergo decomposition from ionic to non-ionic properties upon irradiation with particle beams or electromagnetic waves, resulting in a polarity transition and the generation of an acid. This acid generation causes intramolecular crosslinking reactions between hydroxyl groups in the unit B and/or between the unit A and the unit B. Furthermore, the anions in the generated acid, which contain at least one of a hydroxyl group and a sulfanyl group, react with the unit B in the polymer to form an acid of the polymer anion. Therefore, even without using bulky anions, the use of the acid of the polymer anion can suppress intramolecular crosslinking reactions of the polymer that are subject to acid diffusion.

Therefore, when using the polymers involved in several aspects of the present invention to form patterns, characteristics such as sensitivity and line width roughness (LWR) are excellent.

In the present invention, "particle beam or electromagnetic wave" refers not only to electron beam and extreme ultraviolet light, but also includes ultraviolet light, etc., but electron beam or extreme ultraviolet light is preferred.

In the present invention, "irradiation with a particle beam or electromagnetic wave" means irradiating at least a portion of a polymer with a particle beam or electromagnetic wave. Irradiating a portion of the polymer with the particle beam or electromagnetic wave excites or ionizes specific portions of the polymer, generating active species. These active species partially decompose the aforementioned unit, attach to the aforementioned unit, or induce hydrogen removal from the aforementioned unit by the active species, thereby generating free radicals or acids. Here, "active species" refers to free radicals such as cations, free radicals, and electrons.

The present invention is described in detail below, but the present invention is not limited thereto.

<1>Polymers

The polymer of some embodiments of the present invention is a polymer comprising an acid-generating unit A having a specific onium salt structure, and a unit B having a structure in which a bond is formed by an acid-catalyzed reaction.

A polymer comprising units A and B is irradiated with a particle beam or electromagnetic waves on at least a portion of the polymer. Unit A is reduced, generating anions and a first free radical from the unit A. Some of the generated anions form acids by bonding with protons. The acid acts as a catalyst, causing etherification or thioetherification between units B and/or between units A and B, thereby inducing a crosslinking reaction. Furthermore, when a unit other than unit B has at least one of a hydroxyl group and a sulfanyl group, a crosslinking reaction also occurs between at least one of the hydroxyl and sulfanyl groups of the unit and at least one of the hydroxyl and sulfanyl groups of the unit B and/or the unit A.

The generated acid anions or a portion of the anions of unit A can bond to the unit B via the acid and at least one of the hydroxyl and sulfanyl groups of the anions to form a polymer acid.

Furthermore, the first radicals generated from unit A form bonds with each other and/or with the second radical generated when the polymer contains a radical-generating unit, thereby causing intramolecular crosslinking between the units A and/or between unit A and a radical-generating unit (e.g., unit C, described below). The formation of a bond between at least one of the hydroxyl and sulfanyl groups of the anion from the acid and the unit B suppresses acid diffusion, resulting in excellent LWR properties for the polymer.

(Unit A)

The above-mentioned unit A has a specific onium salt structure. Specifically, the onium salt structure undergoes polarity conversion by irradiating at least a portion of the polymer with a particle beam or electromagnetic wave, and preferably has an organic group containing at least one of a hydroxyl group and a sulfanyl group in the anion portion of the onium salt. In other words, the onium salt structure is not particularly limited as long as it has at least one of a hydroxyl group and a sulfanyl group in the anion portion and generates an acid by reduction of the onium salt. Specifically, for example, the onium salt structure represented by the following general formula (1) can be cited.

In the present invention, "polarity conversion" refers to directly or indirectly changing the polarity from ionic to non-ionic by irradiation with particle beams or electromagnetic waves.

In the above general formula (1), M ⁺ is a sulfonium ion or an iodine ion, and X ⁻ is a monovalent anion having an organic group containing at least one selected from a hydroxyl group and a sulfanyl group.

L is not particularly limited as long as it can bond the main chain constituting the polymer to the above-mentioned onium salt structure. For example, it can be any one selected from direct bonding, carbonyloxy, carbonylamino, phenylenediyl, naphthalenediyl, phenylenedioxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl, and naphthalenedioxycarbonyl.

From the perspective of ease of synthesis, L is preferably a carbonyloxy group or the like.

There are no particular limitations on Sp as long as it can serve as a backing for the aforementioned L and the aforementioned onium salt. For example, it can be a direct bond; an optionally substituted linear, branched, or cyclic alkylene group having 1 to 6 carbon atoms; or an optionally substituted linear, branched, or cyclic alkenylene group having 1 to 6 carbon atoms. At least one methylene group in Sp may be substituted with a divalent heteroatom-containing group.

Examples of linear alkylene groups with 1 to 6 carbon atoms as Sp include methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene.

Examples of branched alkylene groups having 1 to 6 carbon atoms as Sp include isopropylene, isobutylene, tert-butylene, isopentylene, tert-pentylene, and 2-ethylhexenyl.

Examples of cyclic alkylene groups having 1 to 6 carbon atoms in Sp include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene.

At least one methylene group in Sp may be substituted with a divalent heteroatom-containing group. Examples of divalent heteroatom-containing groups include -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -N(R ^Sp )-, -N(Ar ^Sp )-, -S-, -SO-, and SO ₂ ^- . Examples of RSp include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms. Examples of ^ArSp include groups having 12 or fewer carbon atoms, such as phenyl and naphthyl, and aryl groups. The carbon number of the alkylene group in Sp does not include the carbon number of any substituents that Sp may have.

Examples of the substituent that Sp may have (hereinafter referred to as the "first substituent") include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxyl group; a linear or cyclic alkyl group having 1 to 12 carbon atoms; an alkyl group having at least one methylene group substituted for the alkyl group and containing a heteroatom-containing group selected from -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -N(R ^Sp )-, -N(Ar ^Sp )-, -S-, -SO-, and SO ₂ ^- in the backbone; an aryl group; and a heteroaryl group.

Examples of alkyl groups containing Sp as the first substituent in the skeleton and alkyl groups containing a heteroatom group include the above-mentioned alkylene groups in which Sp is a monovalent alkyl group.

As the aryl group as the first substituent of Sp, the same options as those for Ar ^Sp described above can be listed.

Examples of heteroaryl groups serving as the first substituent of Sp include groups having skeletons such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine.

Sp can be directly bonded, but from the perspective of free radical recombination between units A and cross-linking reactions between units B, a molecularly mobile backing structure is preferred. Preferred examples include alkylene, alkyleneoxy, and alkylenecarbonyloxy groups.

^R1 is any one selected from a hydrogen atom; a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched, or cyclic alkenyl group having 1 to 6 carbon atoms. At least one hydrogen atom in the alkyl or alkenyl group in R1 may be substituted with a substituent. Substituents ^{that R1} may have include the same options as those for the first substituent described above.

Examples of the linear alkyl group having 1 to 6 carbon atoms represented by R ¹ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl.

Examples of the branched alkyl group having 1 to 6 carbon atoms represented by R ¹ include isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, and 2-ethylhexyl.

Examples of the cycloalkyl group having 1 to 6 carbon atoms represented by R ¹ include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

Examples of linear, branched, or cyclic alkenyl groups having 1 to 6 carbon atoms for ^R1 include the linear, branched, and cyclic alkyl groups listed above, wherein at least one carbon-carbon single bond is replaced by a carbon-carbon double bond. Furthermore, fluorinated alkyl and fluorinated alkenyl groups for ^R1 may have at least one hydrogen atom replaced by a fluorine atom. All hydrogen atoms may be replaced by the first substituent described above. Preferred fluorinated alkyl groups include trifluoromethyl and the like.

Preferred examples of the above-mentioned unit A include: in the above-mentioned formula (1), R ¹ is a hydrogen atom or a linear alkyl group, and L is a carbonyloxy group, a carbonylamino group or a phenylenediyl group.

Furthermore, from the perspective of LWR, the unit A preferably comprises a unit in which L represents a carbonyloxy group or a carbonylamino group, ^Sp represents a direct bond, and R represents a methyl group, wherein the methyl group has at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as the first substituent. Particularly preferred examples of ^R as the first substituent include ethyl, isopropyl, butyl, halogenated methyl (e.g., fluoromethyl, chloromethyl, bromomethyl, iodomethyl), and benzyl.

Examples of M ⁺ include sulfur cations or iodine cations having a bonding hand to Sp, specifically those represented by the following general formulas (a1) and (a2).

In the above general formula, R ^6a is selected from a linear, branched, or cyclic alkylene group having 1 to 6 carbon atoms, which may have a substituent; a linear, branched, or cyclic alkenylene group having 1 to 6 carbon atoms, which may have a substituent; an arylene group having 6 to 14 carbon atoms, which may have a substituent; a heteroarylene group having 4 to 12 carbon atoms, which may have a substituent; and a direct bond.

Examples of the linear, branched, or cyclic alkylene group for R ^6a include the same options as those for the alkylene group for Sp described above.

Examples of the linear, branched, or cyclic alkenylene group for R ^6a include the same options as those for the alkenylene group for Sp described above.

Examples of the arylene group having 6 to 14 carbon atoms represented by R ^6a include phenylene and naphthylene.

Examples of the heteroarylene group having 4 to 12 carbon atoms represented by R ^6a include divalent groups having skeletons such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, chromene, thianthrene, dibenzothiophene, phenothiazine, phenoxazine, xanthenes, acridine, phenazine, and carbazole.

Examples of the alkyl, alkenyl, aryl, and heteroaryl groups for R ^6b include the alkylene, alkenylene, arylene, and heteroarylene groups mentioned above for R ^6a , and they are monovalent.

The substituents for R ^6a and R ^6b include the same substituents as the first substituent that may be possessed by Sp. In the above formula (a1), R ^6a and any two of the two R ^6b groups may form a ring structure with the sulfur atom to which they are bonded, directly or through a single bond selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

Examples of the divalent nitrogen atom-containing group include the divalent heteroatom-containing groups containing a nitrogen atom, and specific examples include -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -N(R ^Sp )-, and N(Ar ^Sp )-.

Examples of the sulfur cation M ⁺ include those having the structure shown below, which have a bonding hand with the aforementioned Sp at any position. The compound shown below may have the same substituent as the first substituent at the positions corresponding to R ^6a and R ^6b .

[Chemistry 4]

^X- is a monovalent anion having an organic group including at least one of a hydroxyl group and a sulfanyl group.

It is preferred that the hydroxyl group is derived from any one selected from primary alcohol, secondary alcohol, and tertiary alcohol, and the sulfanyl group is derived from any one selected from primary thiol, secondary thiol, and tertiary thiol.

From the perspective of the space between the hydroxyl group and the unit B, it is preferably derived from any one selected from primary alcohols, secondary alcohols, primary thiols, and secondary thiols.

From the perspective of reactivity with unit B via an acid catalyst, it is preferred that the hydroxyl group is not a phenolic hydroxyl group.

^X- is preferably any one selected from an alkyl sulfate anion having at least one hydroxyl group and a sulfanyl group; an aryl sulfate anion having at least one hydroxyl group and a sulfanyl group; an alkyl sulfonate anion having at least one hydroxyl group and a sulfanyl group; an aryl sulfonate anion having at least one hydroxyl group and a sulfanyl group; an alkyl carboxylate anion having at least one hydroxyl group and a sulfanyl group; an aryl carboxylate anion having at least one hydroxyl group and a sulfanyl group; a dialkylsulfonimide anion having at least one hydroxyl group and a sulfanyl group; a trialkylsulfonic acid methyl ester anion having at least one hydroxyl group and a sulfanyl group; and a tetraphenylborate anion having at least one hydroxyl group and a sulfanyl group.

In addition, at least one of the hydrogen atoms of the alkyl group and the aryl group in ^X- may be substituted with a fluorine atom and/or an iodine atom. From the viewpoint of the reactivity of the bonding with the above-mentioned unit B, it is preferred that the number of fluorine atoms and iodine atoms is small.

^X- is more preferably an alkylsulfonate anion having at least one hydroxyl group and a sulfanyl group, or an arylsulfonate anion having at least one hydroxyl group and a sulfanyl group. It should be noted that at least one hydrogen atom in the alkyl group of the alkylsulfonate anion and the aryl group of the arylsulfonate anion may be substituted with a fluorine atom.

The alkyl sulfate anion having at least one hydroxyl group preferably has 1 to 12 carbon atoms.

The alkyl sulfate anion having at least one sulfanyl group preferably has 1 to 12 carbon atoms.

Alkyl sulfate anions can have multiple hydroxyl and sulfanyl groups.

The aryl sulfate anion having at least one hydroxyl group preferably has 4 to 12 carbon atoms.

The aryl sulfate anion having at least one sulfanyl group preferably has 4 to 12 carbon atoms.

Aryl sulfate anions can have multiple hydroxyl and sulfanyl groups.

The alkylsulfonate anion having at least one hydroxyl group preferably has 1 to 12 carbon atoms.

The alkylsulfonate anion having at least one sulfanyl group preferably has 1 to 12 carbon atoms.

Alkylsulfonate anions can have multiple hydroxyl and sulfanyl groups.

The arylsulfonate anion having at least one hydroxyl group preferably has 4 to 12 carbon atoms.

The arylsulfonate anion having at least one sulfanyl group preferably has 4 to 12 carbon atoms.

Arylsulfonate anions can have multiple hydroxyl and sulfanyl groups.

The alkyl carboxylate anion having at least one hydroxyl group preferably has 2 to 12 carbon atoms.

The alkyl carboxylate anion having at least one sulfanyl group preferably has 2 to 12 carbon atoms.

Alkyl carboxylate anions can have multiple hydroxyl and sulfanyl groups.

The carbon number of the aryl carboxylate anion having at least one hydroxyl group is preferably 5 to 12.

The number of carbon atoms in the aryl carboxylate anion having at least one sulfanyl group is preferably 5 to 12.

Aryl carboxylate anions can have multiple hydroxyl and sulfanyl groups.

The dialkylsulfonimide anion having at least one hydroxyl group preferably has 1 to 12 carbon atoms.

The dialkylsulfonimide anion having at least one sulfanyl group preferably has 1 to 12 carbon atoms.

The dialkylsulfonimide anion can have multiple hydroxyl and sulfanyl groups.

The trialkylsulfonic acid methyl ester anion having at least one hydroxyl group preferably has 1 to 12 carbon atoms.

The trialkylsulfonic acid methyl ester anion having at least one sulfanyl group preferably has 1 to 12 carbon atoms.

The trialkylsulfonate methyl ester anion can have multiple hydroxyl and sulfanyl groups.

The tetraphenylborate anion having at least one hydroxyl group preferably has 25 to 30 carbon atoms.

The tetraphenylborate anion having at least one sulfanyl group preferably has 25 to 30 carbon atoms.

Tetraphenylborate anions can have multiple hydroxyl and sulfanyl groups.

Examples of the above-mentioned ^X- include the following.

The above-mentioned unit A is preferably a unit represented by the following general formula (3).

In the above general formula (IV), L, Sp and ^X- are respectively the same as L, Sp and X- in the above general formula (1 ⁾ , and ^R6a and ^R6b are respectively the same as ^R6a and ^R6b in the above general formula (a1).

In one embodiment of the present invention, the polymer preferably comprises a unit A, wherein M ⁺ X ^- in the general formula (1) is an onium salt structure represented by either the following general formula (11) or the following general formula (12). When the polymer having this structure is used in an anti-etching agent composition, it is preferably irradiated with the above-mentioned particle beam or electromagnetic wave (hereinafter also referred to as "first active energy ray") and then exposed to a second active energy ray having a lower energy than the first active energy ray. The second active energy ray is preferably ultraviolet light or visible light. A polymer comprising units A and B is used as the polymer of the anti-etching agent composition. When the anti-etching agent composition comprising the polymer is irradiated with the first active energy ray, the onium salt structure of the unit A decomposes to generate an acid. The unit A has a specific onium salt structure having an acetal site or a thioacetal site (hereinafter also referred to as a "(thio)acetal site"), and the unit B has a structure that undergoes a bonding reaction catalyzed by the acid. When the composition comprising the first active energy ray is irradiated with the acid as a catalyst, the onium salt structure of the unit A having a (thio)acetal site undergoes structural change due to the acid, converting the structure into a ketone derivative that absorbs the second active energy ray. By exposing the composition generated from the ketone derivative to the second active energy ray, acid is generated efficiently, which is called sensitization.

In the polymer unit A of one embodiment of the present invention, the onium salts of the general formulae (11) and (12) have a specific structure between the (thio)acetal site and the dibenzothiophene skeleton, thereby improving the decomposition efficiency of the first active energy ray and enhancing the absorption of the second active energy ray after the first active energy ray irradiation.

In addition, when the onium salt structure of unit A of the polymer of one embodiment of the present invention is represented by the above-mentioned general formulas (11) and (12), unit A does not have significant absorption of the above-mentioned second active energy ray, such as ultraviolet light or visible light. On the other hand, the acid generated by the above-mentioned first active energy ray deprotects the (thio)acetal site of the above-mentioned onium salt structure and converts it into a ketone derivative without impairing the function of the above-mentioned onium salt structure as a photoacid generator. The ketone derivative contains a dibenzothiophene structure having a fused ring structure, thereby increasing the conjugation length and absorbing the second active energy ray at a longer wavelength. Since the ketone derivative generates an exposed portion in the anti-etching film irradiated with the above-mentioned first active energy ray, the acid generation amount in the exposed portion of the above-mentioned first active energy ray can be increased by further irradiating the above-mentioned second active energy.

In the present invention, the second active energy ray is preferably ultraviolet light or visible light with a wavelength of 365 nm or longer. The second active energy ray is preferably 420 nm or shorter. Furthermore, the first active energy ray is preferably higher in energy than the second active energy ray. There are no particular limitations on the type of active energy ray as long as it can generate active species such as acid from the onium salt of unit A. Preferred examples include KrF excimer lasers, ArF excimer lasers, electron beams, and extreme ultraviolet (EUV) light.

[Chemistry 7]

In the above formulas (11) and (12), R ¹⁴ is selected from any one of an alkyl group, a hydroxyl group, a hydroxyl group, an alkoxy group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylsulfanylcarbonyl group, a heteroarylsulfanylcarbonyl group, an arylsulfanyl group, a heteroarylsulfanyl group, an alkylsulfanyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a (poly)alkyleneoxy group, an alkylamino group, and a dialkylamino group.

^R and ^R are each selected from an alkyl group, a hydroxyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylsulfanylcarbonyl group, a heteroarylsulfanylcarbonyl group, an arylsulfanyl group, a heteroarylsulfanyl group, an alkylsulfanyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkylsulfinyl group, an arylsulfinyl group, a heteroarylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, a heteroarylsulfonyl group, a (poly)alkyleneoxy group, an alkylamino group, a dialkylamino group, a nitro group, and a halogen atom.

When R ¹⁴ , R ¹⁷ and R ¹⁸ have carbon atoms, the number of carbon atoms is 1 to 12. When R ¹⁴ , R ¹⁷ and R ¹⁸ have hydrogen atoms, the hydrogen atoms may be substituted by a substituent (hereinafter also referred to as a "second substituent").

The alkyl group in R ¹⁴ , R ¹⁷ , and R ¹⁸ may be linear, branched, or cyclic. Specifically, the same alkyl groups as those in the alkyl group of the second substituent R e described below can be cited. Furthermore, the alkyl moiety of an alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, etc. in R ¹⁴ , R ¹⁷ , and R ¹⁸ can also be the same alkyl groups as those in R 1 .

Examples of the aryl and heteroaryl groups in R ¹⁴ , R ¹⁷ , and R ¹⁸ include the same aryl and heteroaryl groups as those in R ^19. Examples of the aryl moiety in R ¹⁷ and R ¹⁸ , such as the arylcarbonyl group and aryloxycarbonyl group, are the same as those in R ^19. Examples of the heteroaryl moiety in R ¹⁷ and R ¹⁸ , such as the heteroarylcarbonyl group and heteroaryloxycarbonyl group, are the same as those in R ^1. From a synthetic perspective, it is preferred that R ¹⁷ and R ¹⁸ not have a substituent having a heteroaryl moiety such as the heteroarylcarbonyl group and heteroaryloxycarbonyl group.

It should be noted that when there are two or more R ¹⁴ in the above formulae (11) and (12), two of R ¹⁴ may be linked to each other to form a ring structure.

Examples of the (poly)alkyleneoxy group in R ¹⁴ , R ¹⁷ and R ¹⁸ include polyoxyethylene and polypropylene.

Examples of the halogen atom in R ¹⁷ and R ¹⁸ include a fluorine atom, a chlorine atom, and an iodine atom.

When R ¹⁴ , R ¹⁷ , and R ¹⁸ have carbon atoms, the number of carbon atoms is preferably 1 to 12, and these may have a second substituent. In addition, the carbon-carbon single bond in the alkyl group of R ² , R ³ , and R ⁴ may be replaced by a carbon-carbon double bond.

The second substituent that R ¹⁴ , R ¹⁷ , and R ¹⁸ may have includes, but is not limited to, a hydroxyl group, a cyano group, a hydroxyl group, a carboxyl group, an alkyl group ( ^—Re ), an alkoxy group (—OR ^e ), an acyl group (—COR ^e ), an alkoxycarbonyl group (—COOR e ), an aryl group (—Ar), an aryloxy group (—OAr ⁾ , an amino group, an alkylamino group (—NHR e ), a dialkylamino group (—N(R ^e ) ₂ ), an arylamino group (—NHAr), a diarylamino group (—N(Ar) ₂ ), an N-alkyl N-arylamino group (—NR ^e Ar), a phosphino group, a silyl group, a halogen atom, a trialkylsilyl group (—Si-(R ^e ) ₃ ), a silyl group in which at least one alkyl group of the trialkylsilyl group is substituted with Ar, an alkylsulfanyl group (—SR ^e ), and an arylsulfanyl group (—SAr).

^Re and Ar are described below.

The Re in the second substituent is preferably an alkyl group having 1 or more carbon atoms, and more preferably 20 or less carbon atoms. Specific examples of the alkyl group having 1 or more carbon atoms include, for example, linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, and 2-ethylhexyl; alicyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane-1-yl, adamantane-2-yl, norbornane-1-yl, and norbornane-2-yl; silyl-substituted alkyl groups in which one hydrogen atom of these groups is substituted with a trialkylsilyl group such as trimethylsilyl, triethylsilyl, and dimethylethylsilyl; and alkyl groups in which at least one hydrogen atom of these groups is substituted with a cyano group, a fluoro group, or the like. The carbon-carbon single bonds in the above alkyl groups can be replaced by carbon-carbon double bonds.

Ar in the second substituent is preferably an aryl group or a heteroaryl group. A heteroaryl group is an aryl group containing one or more heteroatoms in the ring structure. Specific examples of Ar include preferably groups having 20 or less carbon atoms, such as phenyl, biphenyl, triphenyl, quaterphenyl, naphthyl, anthracenyl, phenanthrenyl, pentalenyl, indenyl, indacenyl, acenaphthyl, fluorenyl, heptalenyl, naphthacene, pyrenyl, chrysyl, tetraphenyl, furanyl, thienyl, pyranyl, sulfonylpyranyl, pyrrolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, isobenzofuranyl, benzofuranyl, isochromenyl, chromenyl, indolyl, isoindolyl, benzimidazolyl, xanthanol, aquadinyl, and carbazolyl.

When R ¹⁴ , R ¹⁷ and R ¹⁸ have the aforementioned second substituent, the number of carbon atoms in R ¹⁴ , R ¹⁷ and R ¹⁸ is preferably 1 to 12, including the number of carbon atoms in the second substituent.

The onium salt structure involved in the polymer of one embodiment of the present invention preferably has at least one R ¹⁴ . Furthermore, at least one R ¹⁴ is preferably a hydroxyl group or an alkoxy group. Furthermore, R ¹⁴ is preferably located in the ortho or para position relative to the bonding position of the (thio)acetal moiety. By having a hydroxyl group or an alkoxy group in the ortho or para ^position of the onium salt structure, the absorption of the second active energy ray tends to increase when the ketone derivative is formed. In particular, a hydroxyl group is more preferred because it increases affinity for alkaline developer solutions and improves the solubility of the onium salt during development.

Generally, adding substituents to the cations in an onium salt structure increases the structural space of the onium salt cations, increasing their hydrophobicity and inhibiting dissolution during development. Therefore, a preferred configuration is one that increases the absorption wavelength of the second active energy ray by the ketone derivative after deprotection of the (thio)acetal site, without requiring a hydrophobic substituent with a low affinity for alkaline developers. Furthermore, since alkaline substituents deactivate the generated acid and inhibit the decomposition of acid-dissociable groups, configurations that incorporate alkaline substituents are not preferred. As described above, the onium salt cations of the polymer according to one embodiment of the present invention preferably do not have substituents such as aromatic rings or alicyclic structures in ^R14 , ^R17 , and ^R18 , and do not have basic groups such as amino groups that react with the generated acid. Furthermore, the molecular weight of the onium salt cations is preferably 500 or less. The onium salt cations of the polymer according to one embodiment of the present invention more preferably do not have basic groups such as amino groups in ^R17 and ^R18 , including ^R14 .

When multiple ^R14s are present, it is preferred that at least one ^R14 is a hydroxyl group or an alkoxy group, and the bonding position is ortho or para to the (thio)acetal site. Furthermore, when multiple ^R14s are present, as long as at least one ^R14 is a hydroxyl group or an alkoxy group, the other ^R4s do not need to be hydroxyl or alkoxy groups. From the perspective of increasing the absorption wavelength of the acid-generated ketone derivative to a longer wavelength, it is more preferred to use a substituent that donates electrons to the aromatic ring to which two or more ^R14s are bonded. More preferably, ^R14s are present at two or more positions ortho or para to the bonding position of the (thio)acetal site.

^R19 is any one selected from a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent.

Specific examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms in R ¹⁹ include methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane-1-yl, adamantane-2-yl, norbornane-1-yl, and norbornane-2-yl alkyl groups.

In the alkyl group represented by R ¹⁹ , at least one methylene group may be substituted with a divalent heteroatom-containing group. The divalent heteroatom-containing group is selected from -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -N( ^Re )-, -N(Ar)-, -S-, -SO-, and _-SO2- . The sulfur atom (S ⁺ ) of the alkyl group is preferably bonded to the divalent alkyl group described above, rather than directly bonding to the heteroatom-containing group. ^Re and Ar will be described below.

Examples of the alkenyl group for R ¹⁹ include groups in which at least one carbon-carbon single bond of the above-mentioned alkyl group is replaced by a carbon-carbon double bond.

Specific examples of the aryl group having 6 to 14 carbon atoms and optionally having a substituent for R ¹⁹ include monocyclic aromatic hydrocarbon groups and condensed polycyclic aromatic hydrocarbon groups formed by condensing at least two rings of the monocyclic aromatic hydrocarbon groups. These aryl groups may have a substituent.

Examples of the monocyclic aromatic hydrocarbon group include groups having a skeleton such as benzene.

Examples of the condensed polycyclic aromatic hydrocarbon group include groups having skeletons such as indene, naphthalene, azulene, anthracene, and phenanthrene.

Examples of the heteroaryl group having 4 to 12 carbon atoms which may have a substituent in R ¹⁹ include groups containing at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom in the skeleton in place of at least one carbon atom of the above-mentioned aryl group.

Examples of the heteroaryl group include monocyclic aromatic heterocyclic groups and condensed polycyclic aromatic heterocyclic groups formed by condensing at least one of the monocyclic aromatic heterocyclic groups with the aromatic alkyl group or aliphatic heterocyclic group. These aromatic heterocyclic groups may have a substituent.

Examples of the monocyclic aromatic heterocyclic group include groups having skeletons such as furan, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine.

Examples of condensed polycyclic aromatic heterocyclic groups include groups with skeletons such as indole, purine, quinoline, isoquinoline, benzopyran, phenoxazine, xanthone, acridine, phenazine, and carbazole.

Examples of the substituent for R ¹⁹ (hereinafter also referred to as "the third substituent") include the same substituents as those for the second substituent described above.

When the alkyl group or the like represented by R ¹⁹ has the aforementioned third substituent and the onium salt is a low molecular weight compound, the number of carbon atoms in R ¹⁹ is preferably 1 to 20, including the number of carbon atoms of the third substituent.

Any of the benzene ring bonded to R ¹⁹ and R ² and the benzene ring bonded to R ³ may form a ring structure with the sulfur atom bonded thereto directly or through any one selected from an oxygen atom, a sulfur atom, a nitrogen-containing group and a methylene group via a single bond.

Examples of the "nitrogen-containing group" include divalent nitrogen-containing groups such as aminodiyl (-NH-), alkylaminodiyl (-NR ^e -), and arylaminodiyl (-NAr-). ^{R e} and Ar are the same as R ^e and Ar of the third substituent.

From the viewpoint of improving stability, R ¹⁹ is preferably an aryl group.

Any of the benzene rings bonded to R ¹⁹ and R ¹⁸ and the benzene ring bonded to R ¹⁷ may form a ring structure with the sulfur atom bonded thereto directly or through any one selected from an oxygen atom, a sulfur atom, a nitrogen atom-containing group, and a methylene group via a single bond.

When R ¹⁴ , R ¹⁷ , and R ¹⁸ above have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group. However, it is preferred that the methylene groups not contain consecutive heteroatoms such as -OO-, -SS-, and OS-. Examples of R ¹⁴ , R ¹⁷ , and R ¹⁸ in which at least one methylene group may be substituted with a divalent heteroatom-containing group include polyalkyleneoxy groups such as 2-methoxyethoxy, 2-ethoxyethoxy, 2-(2-methoxyethoxy)ethoxy, 2-(2-ethoxyethoxy)ethoxy, 2-methoxypropoxy, and 3-methoxypropoxy; polyalkylenethio groups such as 2-methylthioethylthio and 2-ethylthioethylthio; and polyalkyleneoxythio groups such as 2-methylthioethoxy and 2-ethoxyethylthio. However, embodiments of the present invention are not limited thereto.

R ¹⁵ and R ¹⁶ are preferably each an optionally substituted linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms. These are preferably selected from the same options as for each of R ¹⁹ above.

Examples of the substituent for R ¹⁵ and R ¹⁶ (hereinafter also referred to as the "fourth substituent") include the same substituents as those for the second substituent described above.

The above R ¹⁵ and R ¹⁶ may be bonded to form a ring structure directly or through any one selected from an oxygen atom, a sulfur atom, and a methylene group via a single bond. At least one methylene group among the above R ¹⁵ and R ¹⁶ may be substituted by a divalent heteroatom-containing group.

From the viewpoint of synthesis, R ¹⁵ and R ¹⁶ are preferably the same.

L ³ is any one selected from a direct bond; a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; an alkenylene group having 2 to 12 carbon atoms; a sulfinyl group, a sulfonyl group and a carbonyl group.

The hydrogen atom in any one of R ¹⁴ , R ¹⁸ and R ¹⁹ is replaced by a bond with Sp in the above general formula (1).

Y is an oxygen atom or a sulfur atom.

q is an integer from 0 to 4, f is an integer from 0 to 3, g is an integer from 1 to 5, j is an integer from 0 to 2, and k is an integer from 1 to 4.

However, when any one of the benzene rings bonded to R ¹⁹ and R ¹⁸ and the benzene ring bonded to R ¹⁷ forms a ring structure with the sulfur atom, q in the general formula (11) is 0-3 or j is 0-2, and q in the general formula (12) is 0-3 or j is 0-1.

At least one of the benzene rings in the general formulae (11) and (12) may be a six-membered heteroaromatic ring having a heteroatom in the ring. When the benzene ring bonded to R1 ^{to R4} in the general formulae (11) and (12) is the above heteroaromatic ring, k may be 0 to 4.

When there are two or more R ¹⁴ in the general formulae (11) and (12), two of the R ¹⁴ may be linked to each other to form a ring structure.

^X- is selected from the same options as ^X- in the above general formula (1).

In the polymers of some embodiments of the present invention, the onium salt structure contained in unit A can be exemplified by the following examples of the cobalt ion cation. The wavy lines in the cobalt ion cations shown below represent the bonding sites with Sp in the above formula (1). When there are multiple wavy lines in the same structure, the onium salt structure is bonded to any of the above Sp. However, some embodiments of the present invention are not limited to these.

The anions of the above-mentioned unit A are preferably highly hydrophilic anions from the perspective of improving contrast in photolithographic resist pattern formation. Specifically, they include alkyl sulfate anions, aryl sulfate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, and aryl carboxylate anions. These anions have at least one hydroxyl group and a sulfanyl group.

A polymer according to one embodiment of the present invention may contain two or more of the above-mentioned units A in the above-mentioned polymer. For example, it is preferred to use one photoacid generator unit A (hereinafter also referred to as "unit A1") and another photodegradable base unit A (hereinafter also referred to as "unit A2"). ^X- in the above-mentioned photodegradable base unit A2 is preferably an alkyl carboxylate anion or an aryl carboxylate anion. It is preferred to use the above-mentioned photodegradable base unit A2 in combination with the above-mentioned photoacid generator unit A1. It should be noted that when the above-mentioned polymer contains unit A2, it has the effect of reducing the LWR, which is very effective when high resolution is required.

When the polymer contains two or more types of the unit A, units having the same M ⁺ X ⁻ portion and different substituents such as R ¹ and L may be used.

The onium salt involved in the polymer of some embodiments of the present invention preferably has a molar extinction coefficient at 365 nm of less than 1.0×10 ⁵ cm ² /mol, more preferably less than 1.0×10 ⁴ cm ² /mol.

Furthermore, the ketone derivative of the onium salt having the (thio)acetal site unprotected according to some embodiments of the polymer of the present invention preferably has a molar extinction coefficient at 365 nm of 1.0×10 ⁵ cm ² /mol or more, more preferably 1.0×10 ⁶ cm ² /mol or more.

The molar extinction coefficient of the ketone derivative at 365 nm is preferably 5 times or more, more preferably 10 times or more, and even more preferably 20 times or more, relative to the molar extinction coefficient of the onium salt involved in the polymers of some embodiments of the present invention at 365 nm.

In order to obtain the above characteristics, an onium salt represented by the above formula (11) or (12) can be used.

(Method for synthesizing monomers for unit A)

A method for synthesizing a cobalt salt structure contained in unit A of a polymer according to one embodiment of the present invention will be described. The present invention is not limited thereto.

When the target coronium salt structure is a (meth)acrylate monomer without a (thio)acetal moiety, the following synthesis method can be used, for example. First, a diarylsulfene having an R ^6b group and a benzene having a hydroxyl group (R ^6a group) undergo a Friedel-Crafts reaction using Bronsted acid to obtain a hydroxyaryldiarylsulfene. Next, an alkaline catalyst and (meth)acrylic acid chloride are used to obtain the target coronium salt. In this case, even if R ¹ , R ^6a , and R ^6b are substituents not exemplified here, the target coronium salt can be obtained as long as they are within the ranges of R ¹ , R ^6a , and R ^6b described above.

When the target codon salt structure does not contain an ethylene or isopropylene monomer with a (thio)acetal site, the following synthesis method can be used, for example. First, a diarylsulfene having an R ^6b group and a vinyl or isopropylene Grignard reagent (R ^6a group) are used to react with the sulfene having an R ^6b group to form a codon salt structure. Salt exchange is then performed using a salt having a corresponding anion to obtain the target codon salt structure. In this case, even if R ¹ , R ^6a , and R ^6b are substituents not exemplified herein, the target codon salt can be obtained as long as they are within the ranges of R ¹ , R ^6a , and R ^6b described above.

[Chemistry 11]

When the target coronium salt structure contains a (thio)acetal site, the following synthesis method can be used, for example. First, a dibenzothiophene having either ^R17 or ^R18 groups and benzoyl chloride having ^R14 (i = 1 in the following general formula) undergo a Friedel-Crafts reaction using a Lewis acid to produce a benzophenone derivative. Next, the sulfide is oxidized to sulfoxide. Then, benzene having a hydroxyl group and Brønsted's acid undergo a Friedel-Crafts reaction to produce coronium. The carbonyl group is acetalized using an acid catalyst and an alcohol ( ^R15OH ). Next, a basic catalyst and (meth)acryloyl chloride are used to produce the target onium salt. In this case, even if R ¹⁴ , R ¹⁵ , R ¹⁷ and R ¹⁸ are substituents not exemplified herein, the same target cobalt salt can be obtained as long as they are within the ranges of R ¹⁴ , R ¹⁵ , R ¹⁷ and R ¹⁸ .

When the target codon salt structure contains a (thio)acetal site, the following synthesis method can be used, for example. First, a dibenzothiophene having either ^R17 or ^R18 groups and a benzoyl chloride having an ^R14 group (i = 1 in the following general formula) are subjected to a Friedel-Crafts reaction using a Lewis acid to produce a benzophenone derivative. Next, the sulfide is oxidized to sulfoxide, and then a hydroxyl group is reacted with Brønsted's acid to produce codon. The carbonyl group is then acetalized using an acid catalyst and an alcohol ( ^R15OH ). This is then converted to a codon salt structure using a Grignard reagent, and then salt exchange is performed using a salt having the corresponding anion to obtain the target codon salt structure.

[Chemistry 13]

(Unit B)

The unit B is not particularly limited as long as it has a structure in which two molecules are bonded by an acid-catalyzed reaction. However, it is preferably a unit in which the compound represented by the general formula (I) or (II) is bonded to the Sp group of the formula (1) at any position of the compound.

At least one compound represented by the following general formula (I) or (II) is bonded to the * portion of the following formula (2) at any position in the compound as a unit B in the polymer. By including the above unit B in the above polymer, the sensitivity to particle beams or electromagnetic waves can be improved.

In the above formula (2), R ¹ , L, and Sp are the same as those in the above general formula (1).

In the general formula (I), ^R2 and ^R3 are each independently selected from a hydrogen atom, an electron-donating group, and an electron-withdrawing group. It is preferred that at least one of ^R2 and ^R3 is an electron-donating group, as this enhances acid reactivity.

E is preferably selected from any one of a direct bond, an oxygen atom, a sulfur atom, and a methylene group.

n ¹ is an integer of 0 or 1, n ⁴ and n ⁵ are integers of 1 to 2 respectively, and n ⁴ +n ⁵ is 2 to 4.

When n ⁴ is 1, n ² is an integer from 0 to 4; when n ⁴ is 2, n ² is an integer from 0 to 6.

When n ⁵ is 1, n ³ is an integer from 0 to 4; when n ⁵ is 2, n ³ is an integer from 0 to 6.

When n2 ^is 2 or more and ^R2 is an electron-donating group or an electron-withdrawing group, the two ^R2s may form a ring structure with each other directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group via a single bond.

When n3 ^is 2 or more and ^R3 is an electron-donating group or an electron-withdrawing group, two R3 ^groups may form a ring structure with each other directly or through a single bond via any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

The divalent nitrogen atom-containing groups used to form the ring structure in the above formula (I) can be the same as the divalent nitrogen atom-containing groups in the above formula (a1).

In the above general formula (II), each R ⁴ is independently selected from a hydrogen atom, an electron-donating group, and an electron-withdrawing group. Preferably, at least one of the R ⁴ is an electron-donating group to enhance acid reactivity.

R ⁵ is any one selected from a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent. At least one methylene group in the above R ⁵ may be substituted by a divalent heteroatom-containing group.

In addition, R ⁵ may form a ring structure together with the benzene ring bonded to the hydroxymethylene group having R ⁵ .

Examples of the alkyl group for R ⁵ include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms. Specifically, examples include the same alkyl groups as for R ^6b .

Examples of the substituent possessed by R ⁵ include the same substituents as those possessed by the above-mentioned first substituent for Sp.

n ⁶ is an integer from 0 to 7, n ⁷ is 1 or 2. When n ⁷ is 1, n ⁶ is an integer from 0 to 5. When n ⁷ is 2, n ⁶ is an integer from 0 to 7.

When ⁿ⁶ is 2 or greater and ^R4 is an electron-donating group or an electron-withdrawing group, the two R4 ^groups may form a ring structure with each other directly or through a single bond via any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group. Examples of the divalent nitrogen atom-containing group forming a ring structure in the above formula (II) include the same as the divalent nitrogen atom-containing group in the above formula (a1).

Examples of electron-donating groups for R ² , R ³ , and R ⁴ include: alkyl groups (-R ¹³ ), alkenyl groups in which at least one carbon-carbon single bond of the alkyl group (-R ¹³ ) is replaced by a carbon-carbon double bond; and aromatic rings bonded to the methine carbon of the hydroxyl group, alkoxy groups (-OR ¹³ ) and alkylthio groups (-SR ¹³ ) bonded to the ortho or para position of the aromatic ring.

The above-mentioned ^R13 is preferably an alkyl group having 1 or more carbon atoms. Specific examples of the alkyl group having 1 or more carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, and 2-ethylhexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane-1-yl, adamantane-2-yl, norbornane-1-yl, and cyclohexyl. and alicyclic alkyl groups such as norbornan-2-yl; silyl-substituted alkyl groups in which one hydrogen atom is substituted by a trialkylsilyl group such as trimethylsilyl, triethylsilyl, and dimethylethylsilyl; and alkyl groups in which at least one hydrogen atom not directly bonded to a carbon atom of an aromatic ring in the above-mentioned compound (I) or (II) is substituted by a cyano group, a fluoro group, or the like. R ¹³ preferably has 4 or fewer carbon atoms.

Examples of the electron-withdrawing groups for R ² , R ³ , and R ⁴ include: -C(=O)R ^13a (R ^13a is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent); -C(=O)R ^13b (R ^13b is an aryl group having 6 to 14 carbon atoms which may have a substituent); -C(=O)OR ^13a ; -SO ₂ R ^13a ; -SO ₂ R ^13b ; a nitro group; -OR 13a substituted at the meta-position of a nitroso group, a trifluoromethyl group, or a hydroxy group; -OR ^13b substituted at the meta-position of a hydroxy group; -SR ^13a substituted at the meta-position of a hydroxy group; -SR ^13b substituted at the meta-position of a hydroxy group; and the above-mentioned -C(=O)R ^{13a .} At least one of the carbon-carbon single bonds in -C(=O)OR ^13a , -SO ₂ R ^13a , and SR ^13a is substituted by a carbon-carbon double bond or a carbon-carbon triple bond.

The substituents that R ^13a and R ^13b may have include the same options as those for the first substituent that Sp may have.

Specific examples of the compounds represented by the above general formula (I) or (II) include the following compounds.

One embodiment of the polymer of the present invention comprises any one of the compounds represented by the general formula (I) or (II) as a unit B bonded to the * portion of the formula (2) at any position in the compound. In this case, the position bonded to the * portion of the formula (2) is preferably any one of R ² , R ³ , and R ⁴ . For example, in the case of the compound represented by the general formula (I), it is preferred that a bonding hand be present that is bonded to the * portion of the formula (2) instead of one H in R ² .

Preferred examples of the above-mentioned unit B include: units in the above-mentioned formula (2) wherein R ¹ is a hydrogen atom or a linear alkyl group, a carbonyloxy group, a carbonylamino group or a phenylenediyl group.

From the perspective of LWR, the unit B preferably comprises a unit in which L is a carbonyloxy group or a carbonylamino group, ^Sp is a direct bond, and R is a methyl group, wherein the methyl group has at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as the first substituent. Particularly preferred ^R having the first substituent are ethyl, isopropyl, butyl, halogenated methyl (e.g., fluoromethyl, chloromethyl, bromomethyl, iodomethyl), and benzyl.

One embodiment of the present invention is a polymer that may contain two or more types of the aforementioned unit B.

(Unit C)

The unit C is a unit having a radical-generating structure containing at least one type of multiple bond selected from multiple bonds between carbon atoms and multiple bonds between carbon atoms and heteroatoms. The structure is not particularly limited as long as the second radical is generated by irradiating at least a portion of the polymer with a particle beam or electromagnetic wave.

By irradiating with particle beams or electromagnetic waves, an intramolecular cross-linking reaction can be induced between the above-mentioned unit A and the above-mentioned unit C.

The multiple bonds in the unit C are not particularly limited as long as they can generate radical cations under the influence of a particle beam or electromagnetic waves, and these radical cations decompose into second radicals and cations. However, they are not included in benzene aromatics and are preferably at least one of the bonds listed below. Benzene aromatics include, in addition to benzene, aromatics having a benzene skeleton such as naphthalene and azulene. "Multiple bonds not included in benzene aromatics" refers to multiple bonds not possessed by these aromatics.

Specifically, the radical-generating structure containing the above-mentioned multiple bonds is a unit having any one selected from an alkylphenone skeleton, an acyl oxime skeleton, and a benzyl ketal. These skeletons may have any substituents, and the unit having an alkylphenone skeleton includes an α-aminoacetophenone skeleton, etc. More specifically, a structure represented by at least one of the following general formulas (4) is preferred.

In the general formula (4), R ¹ , L, and Sp are each selected from the same group as L and Sp in the general formula (1). R ⁷ is each independently selected from a hydrogen atom; a hydroxyl group; ^-Ra ( ^Ra is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent); -OR ^a ; a group in which at least one carbon-carbon single bond in said ^Ra is replaced by a carbon-carbon double bond; and -R ^b (R ^b is an aryl group having 6 to 14 carbon atoms which may have a substituent). Two or more R ³ may form a ring structure via a single bond, directly or through a group selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

As R ^a , the same options as those for the alkyl group for R ^13a can be listed. As R ^b , the same options as those for the aryl group for R ^13b can be listed.

As substituents that Ra and Rb may have, the same options as those for the substituents that Sp may have are listed above.

However, in the above formula (4), the three R ⁷ are preferably non-hydrogen atoms. In addition, in the above formula (4), at least one of the three R ⁷ is preferably OH. By having OH as the above unit C, a cross-linking reaction can be induced between the unit B and the unit C.

^{-R a ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​} ;-NHC(=O)R ^b ;-NR ^b C(=O)R ^b ;-NR ^a C(=O)R ^b ;-NR ^b C(=O)R ^a ;-N(R ^a ) ₂ ;-N(R ^b ) ₂ ;-N(R ^a )(R ^b );-SO ₃ R ^a ;-SO ₃ R ^b ;-SO ₂ R ^a ;-SO ₂ R ^b ;the-R ^a) wherein at least one of the carbon-carbon single bonds in the group a is replaced by a carbon-carbon double bond; and any one of the nitro groups.

In the above formula (4), when m ¹ is 2 or more, two R ⁸ groups may form a ring structure via a single bond, directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

^m2 is an integer from 1 to 3. When m2 is ¹ , ^m1 is an integer from 0 to 4. When m2 is ² , ^m1 is an integer from 0 to 6. When ^m2 is 3, ^m1 is an integer from 0 to 8.

The unit C is preferably a unit in which R ¹ in the above formula (4) is a hydrogen atom or a linear alkyl group, and L is a carbonyloxy group, a carbonylamino group or a phenylenediyl group.

From the perspective of LWR, the unit C preferably comprises a unit in which L represents a carbonyloxy group or a carbonylamino group, Sp represents a direct bond, and ^R1 represents a methyl group, wherein the methyl group comprises at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as the first substituent. Particularly preferred examples of ^R1 as the first substituent include ethyl, isopropyl, butyl, halogenated methyl groups (e.g., fluoromethyl, chloromethyl, bromomethyl, iodomethyl), and benzyl.

The polymer of one embodiment of the present invention may also contain two or more types of the above-mentioned unit C in the above-mentioned polymer.

(Unit D)

The polymer of one embodiment of the present invention preferably contains a unit having an aryloxy group (hereinafter referred to as "unit D") in addition to the above-mentioned units A to C. The above-mentioned unit D is preferably a unit having a phenol structure bonded to the * portion of the above-mentioned formula (2) at any position of the structure.

Unit D is not particularly limited as long as it can improve the efficiency of acid generation by the above-mentioned unit A. Specific examples include the following units.

Preferably, in the above general formula, R ¹¹ is independently selected from a hydrogen atom and an alkyl group. The alkyl group represented by R ¹¹ may have a substituent.

The above-mentioned alkyl groups include methyl, ethyl, isopropyl, n-isopropyl, sec-butyl, tert-butyl, n-butyl, pentyl and other linear or branched alkyl groups with 1 to 5 carbon atoms.

The substituents that the above-mentioned alkyl groups may have include hydroxyl, sulfonyloxy, alkylcarbonyloxy, alkoxycarbonyl, cyano, methoxy, ethoxy, etc.

The substituent that R ¹¹ may have is the same as the first substituent that Sp may have.

In the above formula, when two or more R ¹¹ are not hydrogen atoms, the two R ¹¹ that are not hydrogen atoms may form a ring structure via a single ^bond directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

n ⁸ is 4.

Specifically, examples of unit D include units composed of monomers such as 4-hydroxyphenyl (meth)acrylate.

By including the above-mentioned unit D in the above-mentioned polymer, the acid generation efficiency can be improved.

The unit D is preferably a unit in which R ¹ in the above formula (2) is a hydrogen atom or a linear alkyl group, and L is a carbonyloxy group or a phenylenediyl group.

From the perspective of LWR, the unit D preferably comprises a unit in which L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, and ^R is a methyl group, wherein the methyl group has at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as the first substituent described above. Particularly preferred ^R having the first substituent described above is an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (e.g., a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group), and a benzyl group.

The polymer of one embodiment of the present invention may also contain two or more types of the above-mentioned unit D in the above-mentioned polymer.

(Unit E)

The polymer of one embodiment of the present invention preferably contains, in addition to the above-mentioned units A to D, an organometallic compound unit E (hereinafter referred to as "unit E") having a metal atom selected from Sn, Sb, Ge, Bi, and Te.

The metal atoms contained in the above-mentioned unit E are not particularly limited as long as they have a high absorption capacity for EUV or electron beams, and may be atoms from Groups 10 to 16 of the periodic table other than the above-mentioned metal atoms.

The above-mentioned unit E is preferably a unit in which alkyltin and aryltin, alkylantimony and arylantimony, alkylgermanium and arylgermanium, or alkylbismuth and arylbismuth structures are bonded to the * portion of the above-mentioned formula (2) at any position.

Unit E has a high efficiency in generating secondary electrons from EUV irradiation, which can improve the decomposition efficiency of the aforementioned units A and B. Unit E is not particularly limited as long as it contains the aforementioned metal atoms with high EUV absorption. Specifically, the following units are exemplified.

Preferably, in the above general formula, R ^12a is independently selected from a hydrogen atom and an alkyl group. The alkyl group of ^{R 12a} may have a substituent.

The above-mentioned alkyl groups include methyl, ethyl, isopropyl, n-isopropyl, sec-butyl, tert-butyl, n-butyl, pentyl and other linear or branched alkyl groups with 1 to 5 carbon atoms.

The substituents that the above-mentioned alkyl groups may have include hydroxyl, sulfonyloxy, alkylcarbonyloxy, alkoxycarbonyl, cyano, methoxy, ethoxy, etc.

In the above formula, when two or more R ^12a are not hydrogen atoms, the two R ^12a which are not hydrogen atoms may form a ring structure via a single ^bond directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

In the above formula, two or more R ^12b may form a ring structure via a single bond, directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

n ⁹ is an integer between 0 and 4.

In the above general formula, R ^12b is any one selected from a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent; a linear, branched, or cyclic alkenyl group having 1 to 6 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; and a directly bonded group.

Examples of the linear, branched, or cyclic alkyl group for R ^12b include the same options as those for the alkyl group for R ^2b described above.

Examples of the linear, branched, or cyclic alkenyl group for R ^12b include the same options as those for the alkenyl group for R ^2b described above.

Examples of the aryl group having 6 to 14 carbon atoms for R ^12b include the same options as those for the aryl group for R ^2b above. Examples of the heteroaryl group having 4 to 12 carbon atoms for R ^12b include the same options as those for the heteroaryl group for R ^2b above.

Two or more R ^12a groups may form a ring structure by a single bond, either directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group. Furthermore, any two of the three R ^12b groups may be bonded to each other and to form a ring structure together with the metal atoms to which they are bonded.

The substituents that R ^12a and R ^12b may have include the same options as those for the first substituent that Sp may have.

Specifically, examples of unit E include 4-vinylphenyl-triphenyltin, 4-vinylphenyl-tributyltin, 4-isopropenylphenyl-triphenyltin, 4-isopropenylphenyl-trimethyltin, trimethyltin acrylate, tributyltin acrylate, triphenyltin acrylate, trimethyltin methacrylate, tributyltin methacrylate, triphenyltin methacrylate, 4-vinylphenyl-diphenylantimony, 4-isopropenylphenyl-diphenylantimony, 4-vinylphenyl-triphenylgermanium, 4-vinylphenyl-tributylgermanium, 4-isopropenylphenyl-triphenylgermanium, and 4-isopropenylphenyl-trimethylgermanium.

By containing the aforementioned unit E, the polymer can improve the efficiency of generating secondary electrons when irradiated with a particle beam or electromagnetic wave.

The above-mentioned unit E is preferably such that R ¹ in the above-mentioned formula (2) is a hydrogen atom or a linear alkyl group, L-carbonyloxy group or phenylenediyl group.

From the perspective of LWR, the unit E preferably comprises a unit in which L represents a carbonyloxy group or a carbonylamino group, Sp represents a direct bond, and ^R1 represents a methyl group, wherein the methyl group comprises at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as the first substituent. Particularly preferred examples of ^R1 as the first substituent include ethyl, isopropyl, butyl, halogenated methyl groups (e.g., fluoromethyl, chloromethyl, bromomethyl, iodomethyl), and benzyl.

One embodiment of the present invention is a polymer that may contain two or more of the above-mentioned units E.

(Unit F)

The polymer of one embodiment of the present invention preferably further has a unit F, and the unit F is represented by the following formula (7) having a halogen atom.

In the above general formula (7), R ¹ , L, and Sp are preferably selected from the same options as R ¹ , L, and Sp in the above general formula (2).

^Rh is any one selected from a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkyleneoxy group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyleneoxy group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent, and some or all of the hydrogen atoms substituted on the carbon atoms are substituted with fluorine atoms or iodine atoms.

Examples of the alkyl group, alkenyl group, alkylene group of an alkyleneoxy group, alkenylene group of an alkenyleneoxy group, aryl group, and heteroaryl group for R ^h include the same options as those for Sp above.

In addition, these substituents can also be listed with the same options as the substituents of Sp.

Specifically, unit F can be obtained from the following monomers.

[Chemistry 22]

The unit F is preferably such that in the formula (7), R ¹ is a hydrogen atom or a linear alkyl group, L-carbonyloxy group, carbonylamino group or phenylenediyl group.

From the perspective of LWR, the unit F preferably comprises a unit in which L represents a carbonyloxy group or a carbonylamino group, Sp represents a direct bond, and ^R1 represents a methyl group, wherein the methyl group comprises at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as the first substituent. Particularly preferred examples of ^R1 as the first substituent include ethyl, isopropyl, butyl, halogenated methyl groups (e.g., fluoromethyl, chloromethyl, bromomethyl, iodomethyl), and benzyl.

One embodiment of the present invention is a polymer that may contain two or more of the above-mentioned units F.

(Other units)

The polymer of one embodiment of the present invention may contain units commonly used as anti-corrosion agent components in addition to the above-mentioned units A to F, within the scope that does not impair the effects of the present invention.

For example, a unit can be cited, which has a skeleton containing an ether group, a lactone skeleton, an ester group, a hydroxyl group, an epoxy group, an epoxypropyl group, an oxycyclobutane group, etc. in the * part of the above formula (2) (hereinafter referred to as "unit G").

In addition, a unit having a skeleton with an alcoholic hydroxyl group in the * portion of the above formula (2) (hereinafter referred to as "unit H") can be cited. This unit H is different from the above units A to G. The above polymer contains the above unit H, which is preferred to increase the percentage of intramolecular cross-linking reactions.

Units having skeletons containing epoxy, epoxypropyl, and cyclohexane are preferred because they induce cationic polymerization when the acid generated by the above-mentioned unit A is a strong acid.

A polymer according to one embodiment of the present invention may have a unit I represented by the following general formula (8). Unit I is a unit different from the above-mentioned units A to H. When a polymer according to one embodiment of the present invention has unit I, the polymer main chain is easily cut by the action of free radicals generated by irradiation with a particle beam or electromagnetic wave, and the polymer chain at the exposure boundary can be shortened, which has the effect of reducing LWR.

[Chemistry 23]

In the general formula (8), ^each substituent is preferably selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched, or cyclic alkenyl group having 1 to 6 carbon atoms. At least one hydrogen atom in the alkyl group or alkenyl group in ^R1 may be substituted with a substituent. ^L10 is a direct bond, and ^Rc is an aryl group having 6 to 12 carbon atoms that may have the first substituent. The alkyl group or alkenyl group having 1 to 6 carbon atoms in ^R10 is selected from the same group as the alkyl group or alkenyl group having 1 to 6 carbon atoms in ^R1 .

Alternatively, R ¹⁰ is a methyl group and the methyl group has at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group as described above as the first substituent; L is a carbonyloxy group or a carbonylamino group; and R ^c is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom or the first substituent.

In addition, L is a carbonyloxy group or a carbonylamino group, ^R is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and R ^is a methyl group, wherein the methyl group contains at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group in the first substituent described above. Particularly preferred ^R in the first substituent described above is an ethyl group, an isopropyl group, a butyl group, a halogenated methyl group (e.g., a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group), and a benzyl group.

It should be noted that the above-mentioned unit I is different from the above-mentioned units A to H.

The above-mentioned unit I is, for example, a unit derived from the following monomers, which include α-methylstyrene derivatives, 2-ethylacrylic acid and its ester derivatives, 2-benzylacrylic acid and its ester derivatives, 2-propylacrylic acid and its ester derivatives, 2-isopropylacrylic acid and its ester derivatives, 2-butylacrylic acid and its ester derivatives, 2-sec-butylacrylic acid and its ester derivatives, 2-fluoromethylacrylic acid and its ester derivatives, 2-chloromethylacrylic acid and its ester derivatives, 2-bromomethylacrylic acid and its ester derivatives, 2-iodomethylacrylic acid and its ester derivatives, and the like.

Specifically, the above-mentioned unit I can be listed as a unit derived from the monomers shown below.

The polymer of one embodiment of the present invention may also have a unit J represented by the following general formula (9).

In the above formula (9), R ¹ , L, and Sp are respectively selected from the same options as R ¹ , L, and Sp in the above general formula (2).

^Rd is selected from an optionally substituted linear, branched, or cyclic alkylsilyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched, or cyclic alkoxysilyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched, or cyclic alkenylsilyl group having 1 to 12 carbon atoms; and an optionally substituted linear, branched, or cyclic alkenyloxysilyl group having 1 to 12 carbon atoms. Siloxane bonds may also be present, wherein some carbon atoms are replaced by silicon atoms and oxygen atoms, thereby replacing the hydrogen or carbon atoms in the bond with oxygen.

Unit J, by containing silicon, can improve its etch resistance against oxygenated plasma. Furthermore, when the polymer contains a silane structure as unit J, the unit B reacts with an acid catalyst to produce water. This water hydrolyzes unit J into silanol, forming siloxane bonds and crosslinking, which is preferred for improved sensitivity and substrate adhesion.

It should be noted that the above-mentioned unit J is a unit different from the above-mentioned units A to I.

Unit J may be a unit derived from the following monomers, which can be exemplified by: 4-trimethylsilylstyrene, 4-trimethoxysilylstyrene, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 3-(3,5,7,9,11,11,13,15 ^- heptadiisobutylpentacyclo[ ^{9,5,13,9,15,17,13 ]} ]octasiloxane-1-yl)propyl methacrylate, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 8-acryloyloxyoctyltrimethoxysilane, 3-(3,5,7,9,11,11,13,15 ^- heptaisobutylpentacyclo[ ^{9,5,13,9,15,17,13} ]octasiloxane-1-yl)propyl methacrylate, and ^the like.

The resist composition in one embodiment of the present invention is characterized by an intramolecular cross-linking reaction induced by irradiation with a particle beam or electromagnetic wave. Therefore, it may contain a unit K having an onium salt structure in addition to the unit A. An example of unit K is the anion ^X- in the unit A described above replaced by the following ^Y- anion. Note that ^Y- is a monovalent anion having an organic group that does not include a hydroxyl group or a sulfanyl group.

^Y- is preferably any one selected from alkyl sulfate anions, aryl sulfate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, aryl carboxylate anions, tetrafluoroborate anions, hexafluorophosphonate anions, dialkylsulfonylimide anions, trialkylsulfonic acid methyl ester anions, tetraphenylborate anions and hexafluoroantimonate anions.

In addition, ^Y- can be selected from any one of a monovalent metal oxonium anion and an acid anion containing a hydrogen atom of a monovalent metal oxonium anion. Furthermore, at least one of the hydrogen atoms of the alkyl and aryl groups in ^Y- may be substituted with a fluorine atom, and the first hydrogen atom may be substituted (but hydroxyl groups are excluded). ^Y- preferably has 1 to 6 carbon atoms, including substituents.

Examples of metal oxonium anions include NiO ₂ ^- and SbO ₃ ^- . Furthermore, to divalent or trivalent metal oxonium anions such as VO ₄ ^3- , SeO ₃ ^2- , SeO ₄ ^2- , MoO ₄ ^2- , SnO ₃ ^2- , TeO ₃ ^2- , TeO ₄ ^2- , TaO ₃ ^{2- ,} and WO ₄ ^2- , H ⁺ , sulfonium ions, iodine ions, and univalent or divalent metal cations may be appropriately added to achieve a univalent valence. The univalent or divalent metal cations may be general, such as Na ⁺ , Sn ²⁺ , and Ni ²⁺ .

When a strong acid (e.g., ^Y- is CF ₃ SO ₃ ^- ) is used as the acid generated by the unit K and an aqueous organic solvent solution is used as a developer, it is preferable that the other units in the polymer of the present invention do not include units having acid-dissociable groups. The reason for this is that when the other units in the polymer of the present invention include units having acid-dissociable groups, the acid generated by the decomposition of the unit K causes the polymer to become more soluble in the aqueous developer.

The unit K can be used as a photodegradable base (when used as a photodegradable base, the unit K is also referred to as "unit K2"). The anion of the unit K2 is preferably any one selected from alkyl carboxylate anions and aryl carboxylate anions, among which Y-. These are monovalent anions having an organic group that does not include a hydroxyl group or a sulfanyl group. At least one hydrogen atom in the alkyl group of the alkyl carboxylate anion and the aryl group of the aryl carboxylate anion may be substituted with a fluorine atom. The presence of the unit K2 in the polymer reduces the LWR, which is effective when high resolution is required.

The polymer of one embodiment of the present invention may contain two or more of the above-mentioned units K in the above-mentioned polymer.

When the unit A is 1, the molar ratios of the polymer in one embodiment of the present invention are as follows: the unit B is preferably 0.2 to 5, the unit C is preferably 0 to 3, the unit D is preferably 0 to 2, the unit E is preferably 0 to 2, the unit F is preferably 0 to 2, the unit G is preferably 0 to 2, the unit H is preferably 0 to 2, the unit I is preferably 0 to 0.5, the unit J is preferably 0 to 4, and the unit K is preferably 0 to 2. When the polymer contains at least one selected from the unit A1, unit A2, and unit K2 as a photodegradable base, and when unit A1 is 1, the total molar ratio of the units A2 and K2 is preferably 0.1 to 1.0, and more preferably 0.3 to 0.6.

The polymer according to one embodiment of the present invention can be obtained by using the monomer components constituting each of the above-mentioned units as raw materials and polymerizing them according to conventional methods to achieve the above-mentioned mixing ratio. Alternatively, a polymer containing units having an onium salt structure (referred to as a "precursor polymer") can be synthesized first, and the anions of the onium salt structure in the precursor polymer can be partially salt-exchanged to obtain a polymer containing units A having the desired anion.

The molecular weight of the polymer in one embodiment of the present invention is not particularly limited.

<2> Anti-corrosion Agent Composition

One embodiment of the anti-corrosion agent composition of the present invention is characterized by containing the above-mentioned polymer.

In addition to the above polymers, the composition may optionally contain components such as polysubstituted alcohol compounds, organometallic compounds, and organometallic mixtures. Each component is described below.

The mixing amount of the above polymer in the anti-corrosion agent composition is preferably 70-100% by mass of the total solid content.

(Polysubstituted alcohol compounds)

The anti-etching agent composition of one embodiment of the present invention may contain only the aforementioned polymer or may further contain other components in addition to the aforementioned polymer, such as ethylene glycol, triethylene glycol, erythritol, arabitol, 1,4-benzenedimethanol, and 2,3,5,6-tetrafluoro-1,4-benzenedimethanol, compounds having two or more hydroxyl groups in the molecule. Including these components in the anti-etching agent composition can improve the efficiency of the crosslinking reaction and the sensitivity to particle beams or electromagnetic waves.

(Organometallic compounds and organometallic mixtures)

The anti-corrosion agent composition of one embodiment of the present invention preferably further contains an organometallic compound or an organometallic mixture.

In order to enhance the sensitivity of the above-mentioned unit A and the above-mentioned unit B, the above-mentioned metal is preferably at least one selected from Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn, and Ra.

Examples of the above-mentioned organometallic compounds include tetraaryltin, tetraalkyltin, bis(alkylphosphine)platinum, etc.

Examples of organometallic compounds include bismuth (IV) acrylate, zirconium (IV) acrylate, bismuth (III) acrylate, bismuth (III) acetate, and tin (II) oxalate.

The mixing amount of the above-mentioned organometallic compound and organometallic mixture in the anti-corrosion agent composition is preferably 0 to 0.5 molar equivalent relative to unit A.

(Other ingredients)

The anti-corrosion agent composition of one embodiment of the present invention may contain other components in any embodiment, as long as the effects of the present invention are not impaired. The components that may be mixed are known additives, such as at least one selected from fluorinated water-repellent polymers, acid diffusion control agents, organic carboxylic acids, surfactants, fillers, pigments, antistatic agents, flame retardants, light stabilizers, antioxidants, ion scavengers, and organic solvents.

The fluorinated water-repellent polymer can be any of the polymers commonly used in immersion lithography processes, preferably one having a fluorine content greater than that of the aforementioned polymers. This allows the water-repellent properties of the fluorinated water-repellent polymer to be localized on the surface of the film when the anti-etching film is formed using the anti-etching composition.

The acid diffusion control agent inhibits the diffusion of acid generated by the photoacid generator within the resist film, suppressing undesirable chemical reactions in non-exposed areas. This further improves the storage stability of the resulting resist composition, further enhancing its resolution as a resist. It also suppresses variations in the line width of the resist pattern caused by changes in the holding time between exposure and development, resulting in a resist composition with excellent process stability.

Examples of acid diffusion control agents include compounds containing one nitrogen atom, two nitrogen atoms, and three nitrogen atoms in the same molecule; compounds containing amide groups; urea compounds; and nitrogen-containing heterocyclic compounds. These acid diffusion control agents are used as monomers constituting the polymer units and may be included in the polymer.

Alternatively, a photodegradable base that generates a weak acid upon exposure to light can be used as an acid diffusion control agent. Examples of photodegradable bases include onium salt compounds and iodonium salt compounds that exhibit acid diffusion control properties upon decomposition upon exposure.

Specific examples of acid diffusion control agents include Japanese Patent No. 3577743, Japanese Patent Publication No. 2001-215689, Japanese Patent Publication No. 2001-166476, Japanese Patent Publication No. 2008-102383, Japanese Patent Publication No. 2010-243773, Japanese Patent Publication No. 2011-37835, and Japanese Patent Publication No. 2012-173505.

The content of the acid diffusion controller is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polymer component.

The surfactant is preferably used to improve coating properties. Examples of surfactants include non-ionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyls, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fluorine-based surfactants, and organosilicone polymers.

The content of the surfactant is preferably 0.0001 to 12 parts by mass, more preferably 0.0005 to 1% by mass, relative to 100 parts by mass of the polymer component.

Preferred organic solvents include, for example, ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N,N-dimethylformamide, γ-butyrolactone, N,N-dimethylacetamide, propylene carbonate, and ethylene carbonate. These organic solvents may be used alone or in combination.

<3> Preparation method of anti-corrosion agent composition

The method for preparing the anti-corrosion agent composition of one embodiment of the present invention is not particularly limited, and the above-mentioned polymer and other optional components can be prepared by common methods such as mixing, dissolving, or kneading.

The above polymer can be synthesized by appropriately polymerizing monomers constituting unit A and unit B, and optionally, appropriately polymerizing monomers constituting other units by conventional methods. However, the method for producing the polymer involved in the present invention is not limited thereto.

The anti-corrosion agent composition components are dissolved in the organic solvent at a solid content concentration of preferably 1 to 40% by mass. More preferably, it is 1 to 30% by mass, and even more preferably, it is 3 to 20% by mass. By achieving the solid content concentration within this range, the aforementioned film thickness can be achieved.

The composition of one embodiment of the present invention can be obtained by mixing the components of the above-mentioned composition, and the mixing method is not particularly limited.

<4> Component Manufacturing Method

One embodiment of the present invention is a method for manufacturing a component, comprising the following steps: an anti-corrosion film forming step of forming an anti-corrosion film on a substrate using the anti-corrosion agent composition; a photolithography step of exposing the anti-corrosion film using a particle beam or an electron beam; and a pattern forming step of developing the exposed anti-corrosion film to obtain a photolithographic anti-corrosion pattern.

Examples of the above components include equipment and masks.

As particle beams or electromagnetic waves used for exposure in the photolithography step, electron beams and EUV can be listed respectively.

The amount of light irradiation varies depending on the type and mixing ratio of each component in the photocurable composition and the film thickness of the coating, but is preferably 1 J/ ^cm2 or less or 1000 μC/ ^cm2 or less.

When the above-mentioned resist composition is included in the polymer as a sensitizing unit (unit C) or as a sensitizing compound, it is preferable to perform a secondary exposure using ultraviolet light or the like after irradiation with a particle beam or electromagnetic wave.

In addition, one embodiment of the present invention is a method for manufacturing a component, wherein in the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having a lower energy than the particle beam or electromagnetic wave is irradiated.

The onium salts used in several embodiments of the present invention as the first and second active energy rays are not particularly limited, as long as they do not significantly absorb the second active energy ray. Preferably, the wavelength of the first active energy ray is shorter than that of the second active energy ray, or the energy of the photon or particle beam is higher than that of the second active energy ray. Examples of various active energy rays are given below, but are not limited to the examples provided that the wavelength of the first active energy ray is shorter than that of the second active energy ray, or the energy of the photon or particle beam is higher than that of the second active energy ray.

The first active energy ray is not particularly limited as long as it can generate active species such as acid in the resist film after irradiation. Preferred examples include KrF excimer lasers, ArF excimer lasers, electron beams, and extreme ultraviolet (EUV) rays.

The second active energy ray can be any of the following. Specifically, after irradiation with the first active energy ray, an acid is generated in the resist. This acid deprotects the (thio)acetal site of the onium salt in the polymers of the various embodiments of the present invention, generating a ketone derivative. This energy ray activates the ketone derivative to generate an acid or other active species. Examples include KrF excimer lasers, UV light, and visible light. UV light in the 365nm (i-ray) to 436nm (g-ray) range is particularly preferred.

The component manufacturing method according to one embodiment of the present invention preferably includes a heating step using a heating wire or laser between the first and second active energy ray irradiation steps. This step improves the decomposition efficiency of the onium salt in unit A, further enhancing sensitivity. The heating step can be performed on a hot plate, for example, and pre-baking in the component manufacturing method corresponds to this step.

The component manufacturing method according to one embodiment of the present invention preferably further comprises the steps of: etching a coating obtained by coating a composition for a reverse pattern so as to cover at least the recessed portions of the photoresist pattern, thereby exposing the surface of the photoresist pattern; and removing the resist film from the exposed resist pattern surface portion to obtain a reverse pattern.

As the reverse pattern composition, a known reverse pattern composition can be used, for example, a composition containing a siloxane polymer as described in International Publication No. WO2015/025665.

In addition, one aspect of the present invention is a method for forming a reverse pattern, comprising the following steps: an anti-etching film forming step of forming an anti-etching film on a substrate using the anti-etching agent composition; a photolithography step of exposing the anti-etching film using a particle beam or electromagnetic waves; and a pattern forming step of developing the exposed anti-etching film to obtain a photolithographic anti-etching pattern.

In addition, one embodiment of the present invention is a method for forming a reverse pattern, comprising the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition; a photolithography step of exposing the resist film using a particle beam or electromagnetic waves; a pattern forming step of developing the exposed resist film to obtain a photolithographic resist pattern; a step of etching a coating obtained by coating a reverse pattern composition so as to cover at least the recessed portions of the photolithographic resist pattern, thereby exposing the surface of the photolithographic resist pattern; and a step of removing the resist film from the exposed resist pattern surface to obtain a reverse pattern.

In addition to using the above-mentioned resist composition, conventional methods for forming inverse patterns can also be used.

The substrate is preferably an inorganic substrate such as Si, _SiO2 , SiN, SiON, TiN, WSi, or BPSG (Boron Phosphorus Silicon Glass). For example, in the case of a device manufacturing method, a coated inorganic substrate such as SOG (Spin on Glass) coated with an organic antireflection film is preferred.

Furthermore, in the mask manufacturing method, the substrate is preferably an inorganic substrate such as Cr, CrO, CrON, _MoSi2 , or _SiO2 , and more preferably, the inorganic substrate has an EUV absorbing layer such as TaO. The substrate used to manufacture the mask can have the same structure as that used for conventional masks. For example, in the case of a transmissive mask, it is preferably transparent to the target light being transmitted, while in the case of a reflective mask, it is preferably highly reflective to the target light (such as EUV and electromagnetic waves).

Common developers can be used for developing the pattern formation step. These include alkaline developers, neutral developers, and organic solvent developers.

In addition, it is preferred to use a water-soluble developer containing a water-soluble organic solvent other than the above-mentioned developer. The water-soluble organic solvent can be an organic compound with one or more carbon atoms mixed in water at any percentage. Specific examples include methanol, ethanol, isopropyl alcohol, diacetone alcohol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, triethylene glycol, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, acetonitrile, acetone, N,N-dimethylformamide, dimethyl sulfoxide, formic acid, acetic acid, propionic acid, and the like.

The water-soluble developer solution may be an aqueous solution containing one or more water-soluble organic solvents, and may further contain a water-insoluble organic solvent. Examples of such water-insoluble organic solvents include water-immiscible alcohols, water-immiscible ethers, water-immiscible nitriles, water-immiscible ketones, water-immiscible esters (e.g., ethyl acetate), and organic halogen compounds (e.g., dichloromethane).

The substrate is not particularly limited, and any known substrate can be used. Examples include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, palladium, copper, chromium, and aluminum; and glass substrates.

In one embodiment of the present invention, active energy rays used for exposure in a photolithography step for obtaining an interlayer insulating film, etc., used in the manufacture of LSIs, preferably include UV, KrF excimer laser, ArF excimer laser, electron beam, or extreme ultraviolet (EUV) rays.

The irradiation dose of the first active energy ray varies depending on the types and mixing ratios of the components in the photocurable composition, the coating thickness, etc., but is preferably 1 J/ ^cm2 or less or 1000 μC/ ^cm2 or less.

In one embodiment of the present invention, the anti-etching film formed from the anti-etching composition preferably has a thickness of 10 to 200 nm. The anti-etching composition is applied to the substrate using an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor blade coating, and pre-baked at 60 to 150°C for 1 to 20 minutes, preferably 80 to 120°C for 1 to 10 minutes, to form a thin film. The film has a thickness of 5 to 200 nm, preferably 10 to 100 nm.

[Example]

The following describes several aspects of the present invention based on embodiments, but the present invention is not limited to these embodiments.

<Synthesis of Compound A1 Constituting Unit A>

(Synthesis Example 1) Synthesis of dibenzothiophene 9-oxide

7.0 g of dibenzothiophene was dissolved in 21.0 g of formic acid and heated to 35°C. 4.1 g of a 35% by mass hydrogen peroxide solution was added dropwise and stirred at 25°C for 5 hours. After cooling, the reaction mixture was added dropwise to 50 g of pure water to precipitate a solid. The precipitated solid was filtered, washed twice with 20 g of pure water, and recrystallized using acetone. The solid was filtered and dried to yield 7.6 g of dibenzothiophene 9-oxide.

(Synthesis Example 2) Synthesis of 9-(4-hydroxyphenyl)dibenzothiophene iodide

4.0 g of dibenzothiophene 9-oxide and 2.8 g of phenol obtained in Synthesis Example 1 above were dissolved in 16 g of methanesulfonic acid and heated to 25°C. 1.5 g of phosphorus pentoxide was added and stirred at room temperature for 15 hours. Then, 60 g of pure water was added and stirred for 5 minutes. The mixture was washed twice with 20 g of ethyl acetate and separated. To the aqueous layer, 3.6 g of potassium iodide and 30 g of dichloromethane were added and stirred at room temperature for 2 hours. The organic layer obtained by separation was washed four times with 40 g of pure water. The recovered organic layer was concentrated and added dropwise to 100 g of diisopropyl ether to precipitate a solid. The precipitated solid was filtered and dried to yield 6.6 g of 9-(4-hydroxyphenyl)dibenzothiophene iodide.

(Synthesis Example 3) Synthesis of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate

6.0 g of 9-(4-hydroxyphenyl)dibenzothiophene iodide obtained in Synthesis Example 2 above and 2.3 g of dimethyl sulfate were dissolved in 15 g of methanol and the mixture was heated to 25°C. After stirring at room temperature for 4 hours, 45 g of ethyl acetate was added to precipitate a solid. The precipitated solid was filtered and dried to obtain 4.9 g of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate.

(Synthesis Example 4) Synthesis of 9-(4-methacryloyloxyphenyl)dibenzothiophene-methylsulfate (Compound a1)

[Chemistry 29]

4.0 g of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate and 1.9 g of methacrylic acid chloride obtained in Synthesis Example 3 above were dissolved in 25 g of dichloromethane and heated to 25°C. A solution of 1.4 g of triethylamine dissolved in 7 g of dichloromethane was added dropwise, and the mixture was stirred at 25°C for 2 hours. After stirring, 20 g of pure water was added, and stirring continued for 10 minutes before separation. The organic layer was washed twice with 20 g of pure water, and the recovered organic layer was concentrated and added dropwise to 60 g of diisopropyl ether to precipitate a solid. The precipitated solid was filtered and dried to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate (Compound a1).

(Synthesis Example 5) Synthesis of 9-(4-methacryloyloxyphenyl)dibenzothiophene 1,1-difluoro-2-hydroxyethylsulfonate (Compound A1)

4.0 g of 9-(4-methylacryloyloxyphenyl)dibenzothiophene methyl sulfate obtained in Synthesis Example 4 above and 3.2 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate were added to 25 g of dichloromethane and 20 g of pure water and stirred at 25°C for 1 hour. After stirring, the mixture was separated. 1.6 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate and 20 g of pure water were added and stirred at 25°C for 30 minutes. After stirring, the mixture was separated and the recovered organic layer was concentrated. The resulting organic layer was removed by distillation and then purified by column chromatography (dichloromethane/methanol = 90/10 (volume ratio)) to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)dibenzothiophene 1,1-difluoro-2-hydroxyethylsulfonate (Compound A1).

<Synthesis of Compound A2 Constituting Unit A>

(Synthesis Example 6) Synthesis of (4-Hydroxy)phenyldiphenylsulfonic Acid Iodide

The same procedures as in Synthesis Example 2 were followed, except that diphenylsulfone was used instead of dibenzothiophene 9-oxide, to obtain 5.9 g of (4-hydroxyphenyl)diphenylsulfonate iodide.

(Synthesis Example 7) Synthesis of (4-Methacryloyloxy)phenyldiphenylsulfonic acid trifluoromethanesulfonate (Compound a2)

[Chemistry 32]

The same procedures as in Synthesis Example 4 were followed, except that (4-hydroxyphenyl)diphenylsulfonic acid-methyl sulfate was used instead of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate, and solid precipitation was performed using silica gel column chromatography (dichloromethane/methanol = 9/1) instead of diisopropyl ether, to obtain 3.8 g of 9-(4-methacryloyloxyphenyl)dibenzothiophene trifluoromethanesulfonate (Compound a2).

(Synthesis Example 8) Synthesis of 9-(4-methacryloyloxyphenyl)diphenylphosphine 1,1-difluoro-2-hydroxyethylsulfonate (Compound A2)

The same procedures as in Synthesis Example 5 were followed, except that (4-methacryloyloxy)phenyldiphenylcoppermonium methyl sulfate was used instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate, to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)diphenylcoppermonium 1,1-difluoro-2-hydroxyethylsulfonate (Compound A2).

<Synthesis of Compound A3 Constituting Unit A>

(Synthesis Example 9) Synthesis of 9-(4-methacryloyloxyphenyl)diphenylphosphine 1,1,2-trifluoro-3-hydroxypropylsulfonate (Compound A3)

The same procedures as in Synthesis Example 5 were performed, except that (4-methacryloyloxy)phenyldiphenyluronium methyl sulfate was used instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate, and sodium 1,1,2-trifluoro-2-hydroxypropanesulfonate was used instead of sodium 1,1,2-trifluoro-2-hydroxypropanesulfonate, to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)diphenyluronium 1,1,2-trifluoro-3-hydroxypropanesulfonate (Compound A3).

<Synthesis of Compound A4 Constituting Unit A>

(Synthesis Example 10) Synthesis of 9-(4-methacryloyloxyphenyl)diphenylphosphine 3-allyloxy-2-hydroxypropylsulfonate (Compound A4)

[Chemistry 35]

The same procedures as in Synthesis Example 5 were followed, except that (4-methacryloyloxy)phenyldiphenyluronium methyl sulfate was used in place of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate, and sodium 3-allyloxy-2-hydroxypropanesulfonate was used in place of sodium 1,1-difluoro-2-hydroxyethanesulfonate, to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)diphenyluronium 3-allyloxy-2-hydroxypropanesulfonate (Compound A4).

<Synthesis of Compound A5 Constituting Unit A>

(Synthesis Example 11) Synthesis of 9-(4-methacryloyloxyphenyl)diphenylphosphine-3-hydroxypropylsulfonate (Compound A5)

The same procedures as in Synthesis Example 5 were followed, except that (4-methacryloyloxy)phenyldiphenylphosphine methyl sulfate was used in place of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate and sodium 3-hydroxypropanesulfonate was used in place of sodium 1,1-difluoro-2-hydroxyethanesulfonate, to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)diphenylphosphine-3-hydroxypropanesulfonate (Compound A5).

<Synthesis of Compound A6 Constituting Unit A>

(Synthesis Example 12) Synthesis of 5-(4-hydroxynaphthyl)tetramethylenetrium p-toluenesulfonate

The same procedures as in Synthesis Example 2 were followed, except that tetramethylenesulfonium was used in place of dibenzothiophene-9-oxide, 1-naphthol was used in place of phenol, and sodium p-toluenesulfonate was used in place of potassium iodide. 3.5 g of 5-(4-hydroxynaphthyl)tetramethylenecopperium p-toluenesulfonate was obtained.

(Synthesis Example 13) Synthesis of 5-(4-methylacryloyloxynaphthyl)tetramethylenecopperium-p-toluenecopperium

[Chemistry 38]

The same procedures as in Synthesis Example 4 were followed, except that 5-(4-hydroxynaphthyl)tetramethylenecopperium trifluoromethanesulfonate was used instead of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate to obtain 5.1 g of (5-(4-methylacryloyloxynaphthyl)tetramethylenecopperium-p-toluenecopperium).

(Synthesis Example 14) Synthesis of 5-(4-methylacryloyloxynaphthyl)tetramethylenetrium-1,1-difluoro-2-hydroxyethylsulfonate (Compound A6)

Using (4-methacryloyloxy)phenyldiphenylcathionium methyl sulfate instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate, the same procedures as in Synthesis Example 5 were performed to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)diphenylcathionium 1,1-difluoro-2-hydroxyethylsulfonate (Compound A6).

<Synthesis of Compound A7 Constituent Unit A>

(Synthesis Example 15) Synthesis of 2-(4-methoxybenzoyl)dibenzothiophene

5.0 g of aluminum chloride was added to 50 g of dichloromethane and the mixture was heated to 0°C. After adding 5 g of dibenzothiophene, 4.6 g of 4-methoxybenzyl chloride was dissolved in 9.2 g of dichloromethane and added dropwise over 30 minutes. After stirring at 25°C for 1 hour, 60 g of pure water was added and stirred for another 5 minutes. The mixture was then washed twice with 20 g of toluene. The resulting organic layer was removed by solvent distillation. The resulting residue was purified by recrystallization from 30 g of acetone to yield 6.1 g of 2-(4-methoxybenzyl)dibenzothiophene.

(Synthesis Example 16) Synthesis of 2-(4-methoxybenzoyl)dibenzothiophene 5-oxide

6.0 g of 2-(4-methoxybenzyl)dibenzothiophene obtained in Synthesis Example 15 above was dissolved in 30 g of formic acid. 3.5 g of a 35% by mass hydrogen peroxide solution was added dropwise under ice cooling. The mixture was then heated to room temperature and stirred for 5 hours. After stirring, 80 g of pure water was added dropwise to the reaction mixture to precipitate a solid. The precipitated solid was filtered, washed three times with 10 g of pure water, and dried to obtain crude crystals. The crude crystals were recrystallized from 100 g of acetone and 200 g of ethanol to obtain 4.3 g of 2-(4-methoxybenzyl)dibenzothiophene 5-oxide.

(Synthesis Example 17) Synthesis of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide]

5.0 g of 2-(4-methoxybenzyl)dibenzothiophene 5-oxide obtained in Synthesis Example 16 was added to 20 g of methanol. 5.0 g of trimethyl orthoformate and 20 mg of concentrated sulfuric acid were added to the mixture and stirred at 60°C for 3 hours. After stirring, the reaction solution was added to a mixed solution of 60 g of dichloromethane and 10 g of a 3% by mass aqueous sodium bicarbonate solution and stirred for 10 minutes. The organic layer was then recovered. The resulting organic layer was washed three times with water, and the dichloromethane was then distilled off to obtain 4.6 g of 2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-5-oxide.

(Synthesis Example 18) Synthesis of 4-vinylphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A7)

To a solution of 4.0 g of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide] obtained in Synthesis Example 17 above, 1.1 g of trimethylsilyl chloride, and 1.8 g of triethylamine dissolved in 15.5 g of dichloromethane, 15 ml of a 1.0 mol/L THF solution of 4-vinylphenylmagnesium bromide was added dropwise at below 10°C, followed by stirring at 25°C for 1 hour. After stirring, 30 g of a 10% by mass aqueous solution of ammonium chloride was added at below 5°C, followed by stirring for an additional 10 minutes. Then, 40 g of dichloromethane and 2.7 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate were added, and the mixture was stirred at 25°C for approximately 2 hours. The resulting fraction was washed three times with water, and the dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol = 90/10 (volume ratio)) to obtain 2.6 g of 4-vinylphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A7).

<Synthesis of Compound A8 Constituent Unit A>

(Synthesis Example 19) Synthesis of 4-hydroxyphenyl-2-[(4-methoxy)benzoyl]dibenzothiophene iodide

The same procedures as in Synthesis Example 2 were followed, except that 2-(4-methoxybenzoyl)dibenzothiophene 5-oxide was used instead of dibenzothiophene 9-oxide, to obtain 3.0 g of 4-hydroxyphenyl-2-[(4-methoxybenzoyl)dibenzothiophene iodide.

(Synthesis Example 20) Synthesis of 4-hydroxyphenyl-2-[(4-methoxy)benzoyl]dibenzothiophene-methylsulfate

The same procedures as in Synthesis Example 3 were followed, except that 4-hydroxyphenyl-2-[(4-methoxy)benzoyl]dibenzothiophene iodide obtained in Synthesis Example 19 was used instead of 9-(4-hydroxyphenyl)dibenzothiophene iodide to obtain 3.0 g of 4-hydroxyphenyl-2-[(4-methoxy)benzoyl]dibenzothiophene monomethyl sulfate.

(Synthesis Example 21) Synthesis of 4-hydroxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-methylsulfate

The same procedures as in Synthesis Example 17 were followed, except that 4-hydroxyphenyl-2-[(4-methoxy)benzoyl]dibenzothiophene-methyl sulfate obtained in Synthesis Example 20 was used instead of 2-(4-methoxybenzoyl)dibenzothiophene-5-oxide to obtain 3.0 g of 4-hydroxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-methyl sulfate.

(Synthesis Example 22) Synthesis of 4-Methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-methylsulfate

The same procedures as in Synthesis Example 4 were followed, except that 4-hydroxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene methyl sulfate obtained in Synthesis Example 21 was used instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate to obtain 3.0 g of 4-methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene methyl sulfate.

(Synthesis Example 23) Synthesis of 4-methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A8)

[Chemistry 48]

The same procedures as in Synthesis Example 5 were followed, except that 4-methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene methyl sulfate obtained in Synthesis Example 22 was used instead of 9-(4-methacryloyloxyphenyl)dibenzothiophene methyl sulfate to obtain 3.0 g of 4-methacryloyloxyphenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A8).

<Synthesis of Compound A9 Constituting Unit A>

(Synthesis Example 24) Synthesis of 2-[Methoxyphenyl-[1,3]dioxacycloheptane-2-yl]dibenzothiophene 5-oxide

The same procedures as in Synthesis Example 17 were followed, except that 1,4-butanediol was used instead of methanol, to obtain 3.0 g of 2-[methoxyphenyl-[1,3]dioxacycloheptane-2-yl]dibenzothiophene 5-oxide.

(Synthesis Example 25) Synthesis of 4-vinylphenyl-2-[methoxyphenyl-[1,3]dioxacycloheptane-2-yl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A9)

The same procedures as in Synthesis Example 18 were followed, except that 2-[methoxyphenyl-[1,3]dioxacycloheptan-2-yl]dibenzothiophene 5-oxide obtained in Synthesis Example 24 was used instead of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide methanol to obtain 3.0 g of 4-vinylphenyl-2-[methoxyphenyl-[1,3]dioxacycloheptan-2-yl]dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A9).

<Synthesis of Compound A10 Constituent Unit A>

(Synthesis Example 26) Synthesis of Phenyl-2-[Dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene Bromide

4.0 g of 2-[dimethoxy-(4-methoxyphenyl)methyldibenzothiophene-5-oxide] obtained in Synthesis Example 17 above, 1.1 g of trimethylsilyl chloride, and 1.8 g of triethylamine were dissolved in 15.5 g of dichloromethane. 15 ml of a 1.0 mol/L THF solution of 4-vinylphenylmagnesium bromide was added dropwise at below 10°C, and the mixture was stirred at 25°C for 1 hour. After stirring, 30 g of a 10% by mass aqueous solution of ammonium chloride was added at below 5°C. After stirring for an additional 10 minutes, 40 g of dichloromethane was added and stirred at 25°C for approximately 2 hours. The separated liquid was washed with water three times, and the dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol = 90/10 (volume ratio)) to obtain 3.0 g of phenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene bromide.

(Synthesis Example 27) Synthesis of Phenyl-2-(4-hydroxybenzoyl)dibenzothiophene Bromide

3.0 g of phenyl-2-[dimethoxy-(4-methoxyphenyl)methyl]dibenzothiophene bromide obtained in Synthesis Example 26 above was added to 30 ml of acetic acid and heated to 110°C. 2.2 g of a 48% aqueous hydrobromic acid solution was then added dropwise and stirred for 18 hours. The mixture was then cooled to 25°C, and 60 ml of purified water and 40 g of dichloromethane were added and stirred. The mixture was separated and washed three times with water. The dichloromethane was then distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol = 80/20 (volume ratio)) to obtain 1.4 g of phenyl-2-[4-hydroxybenzoyl]dibenzothiophene bromide.

(Synthesis Example 28) Synthesis of Phenyl-2-[Dimethoxy-(4-hydroxyphenyl)]methyldibenzothiophene Bromide

The same procedures as in Synthesis Example 17 were performed, except that phenyl-2-(4-hydroxybenzoyl)dibenzothiophene bromide obtained in Synthesis Example 27 was used instead of 2-(4-methoxybenzoyl)dibenzothiophene 5-oxide to obtain 1.5 g of phenyl-2-[dimethoxy-(4-hydroxyphenyl)]methyldibenzothiophene monobromide.

(Synthesis Example 29) Synthesis of Phenyl-2-{dimethoxy-[4-(3-methacryloyloxy)propyloxyphenyl]methyl}dibenzothiophene-1,1-difluoro-2-hydroxyethanesulfonate (Compound A10)

1.5 g of phenyl-2-[dimethoxy-(4-hydroxyphenyl)]methyldibenzothiophene bromide and 1.10 g of 3-trifluoromethanesulfonylpropane methacrylate obtained in Synthesis Example 28 were dissolved in 10 ml of acetonitrile. 2.1 g of potassium carbonate was added and stirred at 70°C for 3 hours. Subsequently, 30 ml of dichloromethane, 15 ml of pure water, and 1.3 g of sodium 1,1-difluoro-2-hydroxyethanesulfonate were added and stirred. The resulting fraction was washed with water three times, and the dichloromethane was distilled off to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (dichloromethane/methanol = 80/20 (volume ratio)) to obtain 1.0 g of phenyl-2-{dimethoxy-[4-(1-ethoxyethyl)oxyphenyl]methyl}dibenzothiophene-nonafluorobutanesulfonate (Compound A10).

<Synthesis of Compound B1 Constituting Unit B>

(Synthesis Example 30) Synthesis of 2,4-dimethoxy-2-hydroxybenzhydrol

6.0 g of 2,4-dimethoxy-4'-hydroxybenzophenone was dissolved in 32 g of THF, and 2.2 g of aluminum lithium hydroxide was added. The mixture was stirred at room temperature for 3 hours. After adding 6 g of pure water and confirming the generation of hydrogen atoms, the mixture was stirred for an additional 10 minutes. A 5% by mass aqueous sodium oxalate solution was added, stirred for 10 minutes, and then 30 g of ethyl acetate was added for separation. The mixture was washed three times with 10 g of water, and the organic layer was concentrated and recovered to yield 5.9 g of 2,4-dimethoxy-2-hydroxybenzhydrol.

(Synthesis Example 31) Synthesis of 2,4-dimethoxy-2'-methacryloyloxyhydroxybenzhydrol (Compound B1)

[Chemistry 56]

4.0 g of 2,4-dimethoxy-2'-hydroxybenzhydrol obtained in Synthesis Example 30 and 4.2 g of methacrylic anhydride were dissolved in 40 g of dichloromethane and the mixture was heated to 25°C. A solution of 2.8 g of triethylamine dissolved in 7 g of dichloromethane was added dropwise. After stirring at 25°C for 2 hours, 20 g of pure water was added and stirring continued for 10 minutes before separation. The organic layer was washed twice with 20 g of pure water, the recovered organic layer was concentrated, the solvent was distilled off, and the resulting organic layer was purified by column chromatography (ethyl acetate/hexane = 15/85 (volume ratio)) to obtain 2.6 g of 2,4-dimethoxy-2'-methacryloyloxyhydroxybenzhydrol (Compound B1).

<Synthesis of Compound B2 Constituting Unit B>

(Synthesis Example 32) Synthesis of 2-hydroxybenzhydrol

The same procedures as in Synthesis Example 30 were followed, except that 2-hydroxybenzophenone was used instead of 2,4-dimethoxy-4'-hydroxybenzophenone, to obtain 3.5 g of 2-hydroxybenzhydrol.

(Synthesis Example 33) Synthesis of 2-Methacryloyloxyhydroxybenzhydrol (Compound B2)

The same procedures as in Synthesis Example 31 were followed, except that 2-hydroxybenzhydrol obtained in Synthesis Example 32 was used instead of 2,4-dimethoxy-2'-hydroxybenzhydrol. The concentrated residue was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)). 3.5 g of 2-methacryloyloxyhydroxybenzhydrol (Compound B2) was obtained.

<Synthesis of Compound B3 Constituting Unit B>

(Synthesis Example 34) Synthesis of 1-(4-hydroxyphenyl)ethanol

The same procedures as in Synthesis Example 30 were followed, except that 4-hydroxyacetophenone was used instead of 2,4-dimethoxy-4'-hydroxybenzophenone, to obtain 2.7 g of 1-(4-hydroxyphenyl)ethanol.

(Synthesis Example 35) Synthesis of 1-(4-methacryloyloxyphenyl)ethanol (Compound B3)

[Chemistry 60]

The same procedures as in Synthesis Example 31 were followed, except that 2-hydroxybenzhydrol obtained in Synthesis Example 34 was used instead of 2,4-dimethoxy-2'-hydroxybenzhydrol. The concentrated residue was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 3.5 g of 2-methacryloyloxyhydroxybenzhydrol (Compound B3).

<Synthesis of Compound B4 Constituting Unit B>

(Synthesis Example 36) Synthesis of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone

4.0 g of 2,4-dimethoxy-4'-hydroxy-benzophenone, 4.8 g of 2-chloroethyl vinyl ether, and 6.4 g of potassium carbonate were dissolved in 24 g of dimethylformamide, and the mixture was stirred at 110°C for 15 hours. The mixture was then cooled to 25°C, 60 g of water was added, and stirring continued. The mixture was then extracted with 24 g of toluene. The organic layer, which was washed three times with 10 g of water, was concentrated, the solvent removed by distillation, and then purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 5.4 g of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone.

(Synthesis Example 37) Synthesis of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone

5.4 g of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone obtained in Synthesis Example 36, 0.42 g of pyridinium-p-toluenesulfonic acid, and 4.2 g of pure water were dissolved in 36 g of acetone. The mixture was stirred at 35°C for 12 hours, and then a 3% by mass aqueous sodium carbonate solution was added. The mixture was further stirred and extracted with 42 g of ethyl acetate. The organic layer, which was washed three times with 10 g of water, was recovered and concentrated to obtain 4.3 g of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone.

(Synthesis Example 38) Synthesis of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzhydrol

The same procedures as in Synthesis Example 30 were followed, except that 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone obtained in Synthesis Example 37 was used instead of 2,4-dimethoxy-2'-hydroxybenzhydrol to obtain 2.7 g of 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzhydrol.

(Synthesis Example 39) Synthesis of 2,4-dimethoxy-4'-(2-methylacryloyloxy)ethoxybenzhydrol (Compound B4)

The same procedures as in Synthesis Example 31 were followed, except that 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzhydrol obtained in Synthesis Example 38 was used instead of 2,4-dimethoxy-2'-hydroxybenzhydrol. The concentrated residue was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 3.5 g of 2,4-dimethoxy-4'-(2-methacryloyloxy)ethoxybenzhydrol (Compound B4).

<Synthesis of Compound B5 Constituting Unit B>

(Synthesis Example 40) Synthesis of 1-(3-hydroxy-4-methoxyphenyl)methanol

The same procedures as in Synthesis Example 30 were followed, except that 3-hydroxy-4-methoxybenzaldehyde was used instead of 2,4-dimethoxy-2'-hydroxybenzhydrol, to obtain 2.7 g of 1-(4-hydroxyphenyl)methanol.

(Synthesis Example 41) Synthesis of 1-(3-methacryloyloxy-4-methoxyphenyl)methanol (Compound B5)

The concentrated residue was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) using 1-(4-hydroxyphenyl)methanol obtained in Synthesis Example 40 instead of 2,4-dimethoxy-2'-hydroxybenzhydrol. The same procedures as in Synthesis Example 31 were followed to obtain 2.1 g of 1-(3-methacryloyloxy-4-methoxyphenyl)methanol (Compound B5).

<Synthesis of Compound B6 Constituting Unit B>

(Synthesis Example 42) Synthesis of 4-hydroxy-4'-methoxybenzhydrol

The same procedures as in Synthesis Example 30 were followed, except that 4-hydroxy-4'-methoxybenzophenone was used instead of 2,4-dimethoxy-4'-hydroxybenzophenone, to obtain 3.5 g of 4-hydroxy-4'-methoxybenzhydrol.

(Synthesis Example 43) Synthesis of 4-Methacryloyloxy-4'-methoxybenzophenone (Compound B6)

The same procedures as in Synthesis Example 31 were followed, except that 4-hydroxy-4'-methoxybenzhydrol obtained in Synthesis Example 42 was used instead of 4-hydroxybenzophenone to obtain 3.5 g of 4-methacryloyloxy-4'-methoxybenzophenone (Compound B6).

<Synthesis of Compound C1 Constituting Unit C>

(Synthesis Example 44) Synthesis of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (Compound C1)

4.0 g of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959) and 4.6 g of methacrylic anhydride were dissolved in 40 g of dichloromethane and the mixture was heated to 25°C. A solution of 3.0 g of triethylamine dissolved in 7 g of dichloromethane was added dropwise, and the mixture was stirred at 25°C for 2 hours. 20 g of pure water was then added, and stirring was continued for 10 minutes before separation. The organic layer recovered after washing twice with 20 g of pure water was concentrated, the solvent was distilled off, and the resulting organic layer was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 4.9 g of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (Compound C1).

<Synthesis of Compound C2 Constituting Unit C>

(Synthesis Example 45) Synthesis of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone

2.0 g of magnesium and 10 g of THF were added to a pre-dehydrated flask. A solution of 10.0 g of 4-(2-ethoxy)ethoxyphenyl bromide dissolved in 50.0 g of THF was added dropwise over 1 hour at room temperature. After the addition, the mixture was stirred at room temperature for 1 hour. The resulting 4-(2-ethoxy)ethoxyphenyl magnesium bromide solution was then added dropwise over 30 minutes at 5°C to a flask containing 9.8 g of pivalic acid chloride and 40 g of THF. After the addition, the mixture was stirred for 30 minutes, followed by the addition of 150 g of 3% by mass hydrochloric acid and continued stirring for 10 minutes. The THF was then distilled off, and the mixture was extracted with 150 g of ethyl acetate. The resulting organic layer was then washed three times with 60 g of pure water. Afterwards, the organic layer obtained by solvent distillation was removed and then purified by column chromatography (ethyl acetate/hexane = 20/80 (volume ratio)) to obtain 5.8 g of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone.

(Synthesis Example 46) Synthesis of 1-(4-methacryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C2)

4.0 g of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone obtained in Synthesis Example 45 above and 4.1 g of methacrylic anhydride were dissolved in 32 g of dichloromethane. The mixture was heated to 25°C, and a solution of 2.7 g of triethylamine dissolved in 7 g of dichloromethane was added dropwise. After stirring at 25°C for 2 hours, 20 g of pure water was added and stirring continued for 10 minutes before separation. The organic layer was concentrated and washed twice with 20 g of pure water. The solvent was distilled off and the resulting organic layer was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 4.6 g of 1-(4-methacryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C2).

<Synthesis of Compound C3 Constituting Unit C>

(Synthesis Example 47) Synthesis of 1-(4-acryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C3)

The same procedures as in Synthesis Example 46 were followed, except that methacrylic anhydride was replaced with acrylyl chloride, to obtain 5.3 g of 1-(4-acryloyloxyphenyl)-2,2-dimethyl-1-propanone (Compound C3).

<Synthesis of Compound C4 Constituting Unit C>

(Synthesis Example 48) Synthesis of 1-(6-hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone

The same procedures as in Synthesis Example 45 were followed, except that 2-bromo-6-(2-ethoxy)ethoxynaphthalene was used instead of 4-(2-ethoxy)ethoxyphenyl bromide to obtain 6.9 g of 1-(6-hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone.

(Synthesis Example 49) Synthesis of 1-(6-methylacryloyloxynaphthalen-2-yl)-2,2-dimethyl-1-propanone (Compound C4)

The same procedures as in Synthesis Example 46 were followed, except that 1-(6-hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone was used instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, to obtain 5.3 g of 1-(6-methylacryloyloxynaphthalen-2-yl)-2,2-dimethyl-1-propanone (Compound C4).

<Synthesis of Compound C5 Constituting Unit C>

(Synthesis Example 50) Synthesis of 1-[4-(2-hydroxyethoxy)phenyl]-2,2-dimethyl-1-propanone

The same procedures as in Synthesis Example 45 were followed, except that 4-(2-vinyloxy)ethoxyphenyl bromide was used instead of 4-(2-ethoxy)ethoxyphenyl bromide to obtain 6.3 g of 1-[4-(2-hydroxyethoxy)phenyl]-2,2-dimethyl-1-propanone.

(Synthesis Example 51) Synthesis of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2,2-dimethyl-1-propanone (Compound C5)

The same procedures as in Synthesis Example 46 were followed, except that 1-(2-hydroxyethoxyphenyl)-2,2-dimethyl-1-propanone was used instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, to obtain 5.6 g of 1-[4-(2-methacryloyloxy)ethoxyphenyl]-2,2-dimethyl-1-propanone (Compound C5).

<Synthesis of Compound C6 Constituting Unit C>

(Synthesis Example 52) Synthesis of Phenylglyoxylic Acid Chloride

5.0 g of phenylglyoxylic acid was dissolved in 35 g of anisole and the mixture was heated to 50°C. 5.1 g of oxalyl chloride was added dropwise over 10 minutes, and the mixture was stirred at 50°C for 2 hours. Excess oxalyl chloride was removed by distillation at 70°C, and the anisole was removed by distillation under reduced pressure. The mixture was then concentrated to obtain 26.3 g of a solution of phenylglyoxylic acid chloride in anisole.

(Synthesis Example 53) Synthesis of 1-(4-methoxyphenyl)-2-phenylethanedione

25.0 g of the anisole solution of phenylglyoxylic acid chloride obtained in Synthesis Example 52 was dissolved in 35 g of dichloromethane and heated to 0°C. 4.3 g of aluminum chloride was added and stirred at 0°C for 2 hours. 35 g of pure water was added and stirred for 10 minutes before separation. The organic layer was concentrated and washed twice with 30 g of pure water. The solvent was distilled off and the resulting organic layer was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 5.6 g of 1-(4-methoxyphenyl)-2-phenylethanedione.

(Synthesis Example 54) Synthesis of 1-(4-hydroxyphenyl)-2-phenylethanedione

5.0 g of 1-(4-methoxyphenyl)-2-phenylethanedione was dissolved in 95 ml of acetic acid. 33.2 g of a 48% by mass aqueous HBr solution was added dropwise over 10 minutes at 70°C, and the mixture was stirred at 110°C for 70 hours. Then, 150 g of water was added for crystallization. The resulting solution was filtered, washed with 250 g of water, and dried to yield 4.1 g of 1-(4-hydroxyphenyl)-2-phenylethanedione.

(Synthesis Example 55) Synthesis of 2,2-dimethoxy-1-(4-methylacryloyloxyphenyl)ethan-1-one (Compound C6)

Dissolve 4.0 g of 1-(4-hydroxyphenyl)-2-phenylethanedione and 0.10 g of sulfuric acid in 12 g of methanol, heat to 25°C, and add 2.2 g of trimethyl orthoformate dropwise, stirring for 3 hours. Add 0.6 g of triethylamine at 30°C, stir for 5 minutes, and then distill off the solvent. Add 25 g of acetonitrile, 4.5 g of triethylamine, and 0.11 g of dimethylaminopyridine to the resulting residue, and then add 6.8 g of methacrylic anhydride diluted with 5.0 g of acetonitrile dropwise at room temperature. After the addition, stir at 25°C for 2 hours, then add 64 g of a 3% by mass aqueous solution of NaHCO₃, stirring for 5 minutes. The organic layer was then extracted with 32 g of ethyl acetate, concentrated, and washed three times with 10 g of water. The solvent was distilled off and the resulting organic layer was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 4.3 g of 2,2-dimethoxy-1-(4-methylacryloyloxyphenyl)ethan-1-one (Compound C6).

<Synthesis of Compound E1 Constituting Unit E>

(Synthesis Example 56) Synthesis of 4-vinylphenyl-triphenyltin (Compound E1)

1.2g of magnesium and 6g of THF were placed in a pre-dehydrated flask. A solution of 6.0g of 4-vinylbromobenzene dissolved in 12.0g of THF was added dropwise over 1 hour. After the addition, the mixture was stirred for 1 hour. The resulting 4-vinylphenylmagnesium bromide solution was then added dropwise over 30 minutes at 5°C to a flask containing 7.3g of triphenyltin chloride and 36g of THF. After the addition, the mixture was stirred for 30 minutes, followed by the addition of 600g of a 1% by mass aqueous solution of ammonium chloride. Stirring was continued for 10 minutes. The THF was then distilled off, and the mixture was extracted with 60g of toluene. The resulting organic layer was then washed three times with 60g of pure water. The organic layer obtained by solvent distillation was then purified by column chromatography (ethyl acetate/hexane = 5/95 (volume ratio)) to obtain 5.6 g of 4-vinylphenyl-triphenyltin (Compound E1).

<Synthesis of Compound E2 Constituting Unit E>

(Synthesis Example 57) Synthesis of 4-Isopropenylphenyl-triphenyltin (Compound E2)

The same procedures as in Synthesis Example 56 were followed, except that 4-isopropenylbromobenzene was used instead of 4-vinylbromobenzene, to obtain 7.1 g of 4-isopropenylphenyl-triphenyltin (Compound E2).

<Synthesis of Compound E3 Constituting Unit E>

(Synthesis Example 58) Synthesis of 4-vinylphenyl-tributyltin (Compound E3)

The same procedures as in Synthesis Example 56 were performed except that tributyltin chloride was used instead of triphenyltin chloride to obtain 5.1 g of 4-vinylphenyl-tributyltin (Compound E3).

<Synthesis of Compound E4 Constituting Unit E>

(Synthesis Example 59) Synthesis of 4-vinylphenyl-triphenylgermanium (Compound E4)

The same procedures as in Synthesis Example 56 were performed except that triphenylgermanium chloride was used instead of triphenyltin chloride to obtain 3.1 g of 4-vinylphenyl-tributylgermanium (Compound E4).

<Synthesis of Compound F1 Constituting Unit F>

(Synthesis Example 60) Synthesis of 1-trifluoromethyl-2-bromoethanol

Dissolve 6.0 g of 1-bromo-3,3,3-trifluoroacetone in 28 g of THF, add 0.3 g of lithium aluminum hydroxide, and stir at room temperature for 3 hours. Once hydrogen production is confirmed, add 6 g of pure water and continue stirring for 10 minutes. Add 5% sodium oxalate solution. After stirring the solution for 10 minutes, add 30 g of ethyl acetate and separate the layers. The organic layer is concentrated and washed three times with 10 g of water to yield 5.9 g of 1-trifluoromethyl-2-bromoethanol.

(Synthesis Example 61) Synthesis of 1-trifluoromethyl-2-methylacryloyloxyethanol (Compound F1)

5.0 g of 1-trifluoromethyl-2-bromoethanol was dissolved in 20 g of DMF. 3.9 g of potassium carbonate and 3.3 g of methacrylic acid were added and stirred at 80°C for 3 hours. 20 g of pure water was then added and stirred for 10 minutes. After adding 30 g of ethyl acetate, the mixture was separated and washed with 10 g of a 1% by mass aqueous hydrochloric acid solution. The recovered organic layer was washed three times with 10 g of concentrated water and purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 4.2 g of 1-trifluoromethyl-2-methylacryloyloxyethanol (Compound F1).

<Synthesis of Compound F2 Constituting Unit F>

(Synthesis Example 62) Synthesis of 1,3,5-triiodo-phenyl methacrylate (Compound F2)

The same procedures as in Synthesis Example 46 were followed, except that 1,3,5-triiodophenol was used instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, to obtain 4.3 g of 1,3,5-triiodo-phenyl methacrylate (Compound F2).

<Synthesis of Polymer 1>

(Synthesis Example 63) Synthesis of Polymer a1

3.0 g of compound a1 (Unit A), 1.8 g of compound B1 (Unit B), and 2.1 g of compound E1 (Unit E), along with 0.71 g of dimethyl-2,2'-azobis(2-methylpropionate) as a polymerization initiator and 0.15 g of α-thioglycerol, were dissolved in a mixture of 9 g of cyclohexanone and 13 g of γ-butyrolactone for deoxygenation. This solution was then added dropwise over 4 hours to a mixture of 4 g of γ-butyrolactone and 4 g of cyclohexanone preheated to 80°C, stirred for 2 hours, and then cooled. After cooling, the mixture was added dropwise to 90 g of ethyl acetate for reprecipitation. After filtration, the product was stirred in 40 g of 20% by mass methanol for 10 minutes, filtered again, and vacuum dried to obtain 5.3 g of the target polymer 1.

The unit ratios of the polymers are disclosed above and below, but the polymers of several embodiments of the present invention are not limited thereto.

(Synthesis Example 64) Synthesis of Polymer 1

2.0 g of polymer a1 obtained in Synthesis Example 63 above and 1.0 g of sodium 2-hydroxysulfonate were added to a mixed solution of 30 g of dichloromethane and 10 g of pure water and stirred at 25°C for 1 hour. After stirring, the mixture was separated, and 1.0 g of sodium 2-hydroxysulfonate and 10 g of pure water were added and stirred at 25°C for 30 minutes. This operation was repeated three times, followed by separation and concentration of the recovered organic layer. The resulting organic layer was removed by solvent distillation and then dispersed and washed with isopropyl alcohol to obtain 11.5 g of polymer.

(Synthesis Example 65) Synthesis of Polymer 2

[Chemistry 90]

The same procedures as in Synthesis Example 64 were followed, except that 2,3-dihydroxypropanesulfonic acid was used instead of 2-hydroxysulfonic acid, to obtain 21.4 g of a polymer.

(Synthesis Example 66) Synthesis of Polymer 3

[Chemistry 91]

The same procedures as in Synthesis Example 48 were followed, except that 3-[N,N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid was used instead of 2-hydroxysulfonic acid, to obtain 1.6 g of polymer 3.

<Synthesis of Polymers 4-13 and Comparative Polymers 1 and 2>

(Synthesis Example 67) Synthesis of Polymers 4-13 and Comparative Polymers 1 and 2

Following Synthesis Example 46, polymers 4 to 13 and comparative polymers 1 and 2 were synthesized by appropriately combining the aforementioned compounds A1 to A5, a1, and a2 as unit A, the aforementioned compounds B1, B2, and B4 as unit B, the aforementioned compounds C1, C2, and C6 as unit C, the following compound D as unit D, the aforementioned compounds E1 to E3 as unit E, and the aforementioned compounds F1 to F2 as unit F. Details of the synthesized polymers are shown in Table 1.

Compound D: 4-Hydroxyphenyl methacrylate

<Preparation of anti-corrosion agent composition>

Of the above polymers, polymers 1, 4-6, and 8, and 50 mg of comparative polymer 1 or 2 were dissolved in a solvent containing cyclohexanone, ethyl lactate, and γ-butyrolactone in a ratio of 5:5:1 to prepare anti-corrosion agent composition samples 1-7 for Examples 1-5 and Comparative Examples 1-2. The polymers used are shown in Tables 2 and 3.

<Developer Preparation>

Prepare the developer solution as follows.

(1) Using the anti-etching agent composition samples 1 to 7 in which the above-mentioned polymers 1, 4 to 6, and 8 and the comparative polymers 1 to 2 were dissolved, the composition was applied to a film having a thickness of 100 nm by spin coating to prepare a thin film.

(2) Prepare an acetonitrile aqueous solution with an acetonitrile concentration of 0-80% by mass.

(3) Each film obtained in (1) above was immersed in each acetonitrile aqueous solution, and the minimum acetonitrile concentration of the acetonitrile aqueous solution at which the composition applied to the film was completely dissolved within 30 seconds was determined.

(4) The acetonitrile aqueous solution obtained in (3) above was used as the developer for each resist composition sample.

<Electron beam sensitivity evaluation>

The resist composition sample 1 described above was spin-coated on a silicon wafer. This was pre-baked on a 110°C hotplate for one minute to obtain a substrate with a 30nm-thick coating. This substrate was patterned with a 50nm line pattern with a 160nm pitch using an electron beam patterning system (Elionix Inc. ELS-F100T) using a 125keV electron beam. The electron beam-irradiated substrate was post-exposure baked (PEB) on a 90°C hotplate for one minute. Subsequently, the substrate was developed for one minute using a patterning developer optimized for each polymer, with the acetonitrile concentration increased by 5% by mass. The resulting pattern was then rinsed with pure water to obtain a 50nm line pattern. The irradiation dose at this point was set to Emax [μC/ ^cm² ], and the sensitivity to electron beam irradiation was determined. The LWR was measured using a scanning electron microscope (SEM) (S-5500, manufactured by Hitachi High-Technologies Corporation) observing a 50 nm line pattern.

Samples 2-7 were also evaluated for sensitivity and LWR in the same manner as above. Using the sensitivity and LWR of resist composition sample 1 (Comparative Example 1) as a reference, the sensitivity and LWR of each resist composition sample 2-7 were compared. The resulting relative sensitivity and relative LWR are shown in Table 2.

[Table 2]

The results of Examples 1 and 2 demonstrate that because the polymers in both cases contain hydroxyl groups in the anions of Unit A, the hydroxyl groups in these anions can react with Unit B. Consequently, Examples 1 and 2 exhibit improved reaction efficiency, achieving a sensitivity that is over 15% higher than that of Comparative Example 1. Furthermore, the polymers in which the anions of Unit A contain hydroxyl groups react with Unit B to form acid anions that become part of the polymer, significantly improving acid diffusion control and achieving a low LWR of over 30% compared to Comparative Example 1.

Examples 3 and 4 share the same cationic structure as Comparative Example 2 and achieve a sensitivity increase of over 15% compared to Comparative Example 2. Comparative Example 2 exhibits improved sensitivity compared to Comparative Example 1, with a LWR 20% greater than that of Comparative Example 1. However, Examples 3 and 4 utilize polymers with hydroxyl groups in the anions of Unit A, demonstrating superior sensitivity compared to Comparative Example 1 and achieving a LWR reduction of over 30%.

The results of Example 5 show that anions with thiol groups and anions with hydroxyl groups can achieve improved sensitivity and lower LWR compared to the reference example.

<Synthesis of Polymers 14-20>

(Synthesis Example 68) Synthesis of Polymers 14-21

According to Synthesis Example 46, polymers 14 to 21 were synthesized using compounds A7 to A10 as unit A, compounds B1, B2, and B4 as unit B, compounds C1, C2, and C6 as unit C, compound E1 as unit E, and compound K as unit K. Details of the synthesized polymers are shown in Table 3.

Compound K: 9-(4-methacryloyloxyphenyl)dibenzothiophene 2,4,6-trifluorobenzoate

[Examples 6-13]

<Preparation of anti-corrosion agent composition>

50 mg of any of the above polymers 4, 14-21 was dissolved in a solvent containing cyclohexanone, ethyl lactate, and γ-butyrolactone in a ratio of 5:5:1 to prepare anti-corrosion agent composition samples 8-16 of Examples 6-14. The polymers used are shown in Table 4.

<Developer Preparation>

Prepare the developer solution as follows.

(1) Using the above-mentioned polymers 4, 14 to 20 and the anti-etching agent composition samples 8 to 15 dissolved, the composition was applied to a film with a thickness of 100 nm by spin coating to prepare a thin film.

(2) Prepare an acetonitrile aqueous solution with an acetonitrile concentration of 0-80% by mass.

(3) Each film obtained in (1) above was immersed in each acetonitrile aqueous solution, and the minimum acetonitrile concentration of the acetonitrile aqueous solution at which the composition applied to the film was completely dissolved within 30 seconds was determined.

(4) The acetonitrile aqueous solution obtained in (3) above was used as the developer for each resist composition sample.

<Electron beam-UV sensitivity evaluation>

The above-mentioned resist composition sample 8 was spin-coated on a silicon wafer. It was pre-baked on a hot plate at 110°C for 1 minute to obtain a substrate with a coating having a thickness of 30nm. The coating on the substrate was patterned with a 50nm line pattern with a 160nm pitch using an electron beam patterning device (Elionix Inc ELS-F100T) using a 125keV electron beam. The substrate after electron beam irradiation was post-exposure baked (PEB) on a hot plate at 90°C for 1 minute. Next, the entire surface was irradiated with a 395nm UV-LED at an exposure dose of 1000mJ/ ^cm2 . After that, the developer optimized for each polymer was used for patterning, in which the acetonitrile concentration was increased by 5% by mass, and then rinsed with pure water to obtain a 50nm line pattern. The irradiation dose at this time was defined as Emax [μC/cm ² ], and the sensitivity to electron beam irradiation was determined. LWR was measured using a 50 nm line pattern observed using a scanning electron microscope (SEM) (S-5500, manufactured by Hitachi High-Technologies Corporation).

Samples 9-16 were also evaluated for sensitivity and LWR in the same manner as above. Using the sensitivity and LWR of resist composition sample 8 as a reference, the sensitivity and LWR of each resist composition sample 9-16 were compared. The resulting relative sensitivity and relative LWR are shown in Table 4.

A comparison was made between Example 6 and Examples 7-10, which had the same composition ratio of units A, B, and E. The hydroxyl groups in the anions of compounds A7-A10 in Examples 7-10 generated acid upon electron beam irradiation, which then bonded to unit B via an acid-catalyzed reaction. Furthermore, identical units B also bonded to each other via an acid-catalyzed reaction. Furthermore, the water generated by this acid-catalyzed reaction hydrolyzed the acetal sites of the onium salts in unit A into ketone derivatives, shifting the light absorption to longer wavelengths and converting the polymers to UV absorption at 395 nm. Consequently, further acid was generated by full-scale UV exposure following EB irradiation, resulting in improved sensitivity in Examples 7-10, even with the same composition as Example 6.

Comparing Example 6 with Examples 7-13, it can be inferred that even with increased sensitivity to UV irradiation, the excellent LWR effectively negates the impact of acid diffusion caused by UV irradiation. Because patterning was performed at the same level of LWR in Examples 6 and 7-13, there is no trade-off between sensitivity and LWR.

Comparing Examples 8 and 14, it can be seen that while the addition of unit K suppresses the effect of acid generated by unit A, the sensitivity decreases, and the LWR decreases by suppressing acid diffusion. This is very effective when high resolution is required.

[Industrial Availability]

According to several aspects of the present invention, a polymer and an anti-etching agent composition containing the polymer can be provided. The polymer has high absorption efficiency for EUV and other particle beams or electromagnetic waves, and has excellent sensitivity, resolution, and patterning performance.

Claims (25)

A polymer comprising a unit A and a unit B, wherein the unit A has an onium salt structure and generates an acid by irradiation with a particle beam or an electromagnetic wave, and the unit B has a structure in which a bond is formed by an acid-catalyzed reaction, wherein the unit A is represented by the following general formula (1): (1) (In the general formula (1), ^R1 is any one selected from a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms, wherein R At least one hydrogen atom in the alkyl and alkenyl groups described in ¹ may be substituted by a substituent, L is any one selected from direct bond, carbonyloxy, carbonylamino, phenylenediyl, naphthalenediyl, phenylenedioxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl, and naphthalenedioxycarbonyl, Sp is a direct bond; a linear, branched, or cyclic alkylene group having 1 to 6 carbon atoms which may have a substituent; and any one of a linear, branched, or cyclic alkenylene group having 1 to 6 carbon atoms which may have a substituent, at least one methylene group in Sp may be substituted by a divalent heteroatom-containing group, M ⁺ is a sulfonium ion or an iodine ion, and X ^- is a monovalent anion having an organic group, the organic group including a hydroxyl group, wherein X ^- is any one selected from an alkyl sulfate anion having at least one hydroxyl group; an aryl sulfate anion having at least one hydroxyl group; an alkyl sulfonate anion having at least one hydroxyl group; an aryl sulfonate anion having at least one hydroxyl group; an alkyl carboxylate anion having at least one hydroxyl group; an aryl carboxylate anion having at least one hydroxyl group; a dialkylsulfonylimide anion having at least one hydroxyl group; a trialkylsulfonic acid methyl ester anion having at least one hydroxyl group; and a tetraphenylborate anion having at least one hydroxyl group, X ^-, at least one of the hydrogen atoms of the alkyl group and the aryl group in the compound may be substituted by a fluorine atom, wherein the unit B is a unit in which the compound represented by the following general formula (I) or (II) is bonded to the Sp group of the following general formula (2) at any position of the compound, [Chemical 2] (I) (II) (in the general formula (I), R ² and R ³ are each independently selected from a hydrogen atom; an electron donating group; and an electron withdrawing group, E is selected from a direct bond; an oxygen atom; a sulfur atom; and a methylene group, n ¹ is an integer of 0 or 1, n ⁴ and n ⁵ are each an integer of 1 to 2, n ⁴ + n ⁵ are 2 to 4, when n ⁴ is 1, n ² is an integer of 0 to 4, when n ⁴ is 2, n ² is an integer of 0 to 6, when n ⁵ is 1, n ³ is an integer of 0 to 4, when n ⁵ is 2, n ³ is an integer of 0 to 6, when n ² is 2 or more and R ² is an electron donating group or an electron withdrawing group, two R ² can form a ring structure with each other directly or through a single bond selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group, when n ³ is 2 or more and R ³ is an electron-donating group or an electron-withdrawing group, the two R ³ can form a ring structure with each other directly or through a single bond selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group, in the general formula (II), R ⁴ are each independently selected from a hydrogen atom; an electron-donating group; and an electron-withdrawing group, at least one of R ⁴ is the electron-donating group, R ⁵ is selected from a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent, at least one methylene group in the R ⁵ may be substituted by a divalent heteroatom-containing group, and the R ⁵ may be substituted with the R ⁵ hydroxymethylene bonded to the benzene ring to form a ring structure, ⁿ⁶ is an integer of 0 to 7, ⁿ⁷ is 1 or 2, when ⁿ⁷ is 1, ⁿ⁶ is an integer of 0 to 5, when ⁿ⁷ is 2, ⁿ⁶ is an integer of 0 to 7, when ⁿ⁶ is 2 or more and ^R4 is an electron donating group or an electron withdrawing group, the two ^R4 can form a ring structure with each other directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group by a single bond,) [Chemical 3] (2) (In the formula (2), R ¹ , L, and Sp are selected from the same options as R ¹ , L, and Sp in the general formula (1), and * represents the bonding site of the compound represented by the general formula (I) or (II)). The polymer according to claim 1, wherein X- ^is any one of an alkylsulfonate anion having at least one hydroxyl group and an arylsulfonate anion having at least one hydroxyl group, and at least one of the hydrogen atoms of the alkyl group and the aryl group in ^X- may be substituted with a fluorine atom. The polymer according to claim 1, wherein the polymer further comprises a unit C, the unit C having a free radical generating structure containing at least one multiple bond selected from multiple bonds between carbon atoms and multiple bonds between carbon atoms and heteroatoms, the unit C generating a second free radical by irradiation with a particle beam or an electromagnetic wave, wherein the multiple bonds in the free radical generating structure are not multiple bonds contained in a benzene aromatic group. The polymer according to claim 3, wherein the multiple bonds are at least any one of the following bonds: . The polymer according to claim 3, wherein the unit C has any one selected from an alkylphenone skeleton, an acyloxime skeleton, and a benzyl ketal. The polymer according to claim 1, wherein the unit A is represented by the following general formula (3): (3) (In the general formula (3), R ¹ , L, Sp and X ^- are selected from the same options as R ¹ , L, Sp and X ^- in the general formula (1), R ^6a is selected from a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms which may have a substituent; a linear, branched or cyclic alkenylene group having 1 to 6 carbon atoms which may have a substituent; an arylene group having 6 to 14 carbon atoms which may have a substituent; a heteroarylene group having 4 to 12 carbon atoms which may have a substituent; and any one of the direct bonds; at least one methylene group in the R ^6a may be substituted by a divalent heteroatom-containing group, R ^{R 6b} is selected from any one of a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; at least one methylene group in R ^6b may be substituted by a divalent heteroatom-containing group, and R ^6a and two of the two R ^6b may form a ring structure directly or through a single bond with any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group and the sulfur atom to which these groups are bonded. The polymer according to claim 1, wherein M ^{+ X-} is represented by either the following general formula (11) or the following general formula (12), [Chemical 6] [Chemistry 7] (In the formulae (11) and (12), R ¹⁴ is independently selected from any one of an alkyl group, a hydroxyl group, a hydroxyl group, an alkoxy group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylsulfanylcarbonyl group, a heteroarylsulfanylcarbonyl group, an arylsulfanyl group, a heteroarylsulfanyl group, an alkylsulfanyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, a (poly)alkyleneoxy group, an alkylamino group, and a dialkylcyano group, R ¹⁷ and R R ¹⁸ is independently selected from any one of an alkyl group, a hydroxyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylsulfanylcarbonyl group, a heteroarylsulfanylcarbonyl group, an arylsulfanyl group, a heteroarylsulfanyl group, an alkylsulfanyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkylsulfinyl group, an arylsulfinyl group, a heteroarylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, a heteroarylsulfonyl group, a (poly)alkyleneoxy group, an alkylamino group, a dialkylamino group, a nitro group, and a halogen atom; when R ¹⁴ , R ¹⁷ , and R ¹⁸ have carbon atoms, the number of carbon atoms is 1 to 12, and R ¹⁴ When R ¹⁷ and R ¹⁸ have a hydrogen atom, the hydrogen atom may be substituted by a substituent; R ¹⁹ is any one selected from a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; the benzene ring to which R ¹⁹ is bonded to R ¹⁸ and the benzene ring to which R ¹⁷ is bonded may form a ring structure together directly or through a single bond through any one selected from an oxygen atom, a sulfur atom, a nitrogen atom-containing group and a methylene group and the sulfur atom to which it is bonded; R ¹⁴ , R ¹⁷ and R When ^R18 has a methylene group, at least one of the methylene groups may be substituted by a divalent heteroatom-containing group, and ^R15 and ^R16 are each selected from a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms that may have a substituent; a linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms that may have a substituent; an aryl group having 6 to 14 carbon atoms that may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms that may have a substituent. ^R15 and ^R16 may be bonded to each other directly or through any one selected from an oxygen atom, a sulfur atom, and an alkylene group to form a ring structure. At least one of the methylene groups of ^R15 and ^R16 may be substituted by a divalent heteroatom-containing group. L ³ is a direct bond; a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; an alkenylene group having 2 to 12 carbon atoms; any one of a sulfinyl group, a sulfonyl group and a carbonyl group; any hydrogen atom in R ¹⁴ , R ¹⁸ and R ¹⁹ may be substituted by a bond with Sp in the formula (1); Y is an oxygen atom or a sulfur atom; q is an integer of 0 to 4, f is an integer of 0 to 3, g is an integer of 1 to 5, j is an integer of 0 to 2, and k is an integer of 1 to 4; (However, the benzene ring to which R ¹⁹ and R ¹⁸ are bonded and the R (When any one of the benzene rings bonded to ^{R 14} in the formulas (11) and (12) forms a ring structure together with the sulfur atom, q in the formula (11) is 0 to 3 or j is 0 to 2, and q in the formula (12) is 0 to 3 or j is 0 to 1) At least one of the benzene rings in the formulas (11) and (12) may be a six-membered heteroaromatic ring having a heteroatom in the ring, or k may be 0 to 4 when the benzene ring bonded to R ¹⁴ in the formulas (11) and (12) is the heteroaromatic ring; when there are two or more R ¹⁴ in the formulas (11) and (12), two of the R ¹⁴ may be linked to each other to form a ring structure, and ^X- is selected from the same options as ^X- in the formula (1)). The polymer according to claim 3, wherein the unit C is represented by at least one of the following general formula (4): (4) (In the general formula (4), R ¹ , L, Sp and X ^- are selected from the same options as R ¹ , L, Sp and X ^- in the general formula (1), and R ⁷ is selected from a hydrogen atom; a hydroxyl ^group ; -Ra ( ^Ra is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, and at least one methylene group in ^Ra may be substituted by a divalent heteroatom-containing group); -OR ^a ; and a group in which at least one carbon-carbon single bond in ^Ra is replaced by a carbon-carbon double bond; and -R ^b (R ^b is an aryl group having 6 to 14 carbon atoms which may have a substituent or a heteroaryl group having 4 to 12 carbon atoms which may have a substituent), two R ⁷ can form a ring structure with each other directly or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group via a single bond, and R ⁸ is selected from -R ^a ; -R ^b ; -OR ^a ; -SR ^a ; -OR ^b ; -SR ^b ; -OC(═O) ^{R a ;} -OC(═O) ^{R b} ; -C(═O)OR ^a ; -C(═O)OR ^b ; -OC(═O)OR ^a ; -OC(═O)OR ^b ; -NHC(═O)R ^a ; -NR ^a C(═O)R ^a ; -NHC(═O)R ^b ; -NR ^b C(═O)R ^b ; -NR ^a C(═O)R ^b ; -NR ^b C(═O)R a ; -N(R ^a ) ₂ ; -N(R ^b ) ₂ ; -N(R ^a )(R ^b ); -SO ₃ R ^a ; -SO ₃ R ^b ; -SO ₂ R ^a ; -SO ₂ R ^b ; a group in which at least one of the carbon-carbon single bonds in said -R ^a is replaced by a carbon-carbon double bond; and any one of the nitro groups, m ² is an integer of 1 to 3, when m ² is 1, m ¹ is an integer of 0 to 4, when m ² is 2, m ¹ is an integer of 0 to 6, when m ² is 3, m ¹ is an integer of 0 to 8, when m ¹ is 2 or more, two R ^8s may form a ring structure with each other directly through a single bond or through any one selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group). The polymer according to claim 8, wherein the unit C is represented by the general formula (4), and at least one of R ⁷ in the general formula (4) is a hydroxyl group. The polymer according to claim 1, wherein the polymer further comprises a unit D having an aryloxy group. The polymer according to claim 1, wherein the polymer further comprises an organometallic compound unit E, wherein the unit E has a metal atom selected from Sn, Sb, Ge, Bi and Te. The polymer according to claim 1, wherein the polymer further comprises a unit F, wherein the unit F is represented by the following general formula (7) having a halogen atom: (7) (In the general formula (7), R ¹ , L and Sp are respectively selected from the same options as R ¹ , L and Sp in the general formula (1), and R ^h is selected from any one of a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; a linear, branched or cyclic alkyleneoxy group having 1 to 12 carbon atoms which may have a substituent; an linear, branched or cyclic alkenyloxy group having 1 to 12 carbon atoms which may have a substituent; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent, and part or all of the hydrogen atoms substituted by carbon atoms are substituted by fluorine atoms or iodine atoms). An anti-corrosion agent composition comprising the polymer according to claim 1. The anti-etching agent composition according to claim 13, wherein the anti-etching agent composition further contains any one of an organic metal compound and an organic metal mixture, and the metal is at least one selected from Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn, and Ra. A method for manufacturing a component comprises the following steps: an anti-corrosion film forming step of forming an anti-corrosion film on a substrate using the anti-corrosion agent composition described in claim 13; a photolithography step of exposing the anti-corrosion film using a particle beam or electromagnetic waves; and a pattern forming step of developing the exposed anti-corrosion film to obtain a photolithographic anti-corrosion pattern. The method for manufacturing a component according to claim 15, wherein the development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. The method for manufacturing a component according to claim 15, wherein, in the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having lower energy than the particle beam or electromagnetic wave is irradiated. The method for manufacturing a component according to claim 15 further comprises the following steps: etching a coating obtained by coating a composition for a reverse pattern to cover at least the concave portion of the photolithographic anti-etching pattern, thereby exposing the surface of the photolithographic anti-etching pattern; and removing the anti-etching film from the exposed surface portion of the anti-etching pattern to obtain a reverse pattern. The method for manufacturing a component according to claim 15, wherein the particle beam is an electron beam and the electromagnetic wave is extreme ultraviolet light. A pattern forming method comprises the following steps: an anti-etching film forming step of forming an anti-etching film on a substrate using the anti-etching agent composition described in claim 13; a photolithography step of exposing the anti-etching film using a particle beam or electromagnetic waves; and a pattern forming step of developing the exposed anti-etching film to obtain a photolithographic anti-etching pattern. The pattern forming method according to claim 20, wherein the development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. The pattern forming method according to claim 20, wherein, in the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having lower energy than the particle beam or electromagnetic wave is irradiated. A method for forming a reverse pattern comprises the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition of claim 13; a photolithography step of exposing the resist film using a particle beam or electromagnetic waves; a pattern forming step of developing the exposed resist film to obtain a photoresist pattern; a step of etching a coating obtained by coating a reverse pattern composition so as to cover at least the recessed portions of the photoresist pattern, thereby exposing the surface of the photoresist pattern; and a step of removing the resist film from the exposed surface portion of the photoresist pattern to obtain a reverse pattern. The method for forming a reverse pattern according to claim 23, wherein the development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. The method for forming an inversion pattern according to claim 23, wherein, in the photolithography step, after exposing the particle beam or electromagnetic wave, a second active energy ray having lower energy than the particle beam or electromagnetic wave is irradiated.