Compound, (co)polymer, composition, and pattern formation method

Abstract

The objective of the present invention is to provide a composition or the like capable of forming a film having high definition and high sensitivity. The objective is achieved by a halogen-containing polymerizable compound represented by general formula (A).

Description

Technical Field

[0001] The present invention relates to a compound, a (co)polymer, a composition, and a pattern forming method.

Background Art

[0002] In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, miniaturization of semiconductors (patterns) and pixels has been rapidly progressing due to the advancement of lithography technology. As a method for miniaturizing pixels, generally, the wavelength of the exposure light source is shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but currently, far-ultraviolet exposure such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) has become the center of mass production, and furthermore, the introduction of extreme ultraviolet (EUV) lithography (13.5 nm) has been progressing. In addition, an electron beam (EB) is also used for forming a fine pattern.

[0003] Conventional general resist materials are polymer-based resist materials capable of forming an amorphous film. For example, polymer-based resist materials such as polymethyl methacrylate, polyhydroxystyrene having an acid dissociable group, or polyalkyl methacrylate can be mentioned (see, for example, Non-Patent Document 1). Conventionally, a resist thin film produced by applying a solution of these resist materials onto a substrate is irradiated with ultraviolet rays, far-ultraviolet rays, electron beams, extreme ultraviolet rays, etc., to form a line pattern of about 10 to 100 nm.

[0004] In addition, lithography using an electron beam or extreme ultraviolet rays has a reaction mechanism different from that of ordinary optical lithography. Furthermore, in lithography using an electron beam or extreme ultraviolet rays, formation of a fine pattern of several nm to a dozen or so nm is targeted. When the resist pattern size becomes small in this way, a resist material having higher sensitivity to the exposure light source is required. In particular, in lithography using extreme ultraviolet rays, further improvement in sensitivity is required in terms of throughput. As a resist material for improving the above problems, inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium have been proposed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Non-Patent Documents

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, conventionally developed resist compositions having high-sensitivity characteristics have problems such as insufficient pattern quality, such as large pattern defects and roughness, insufficient improvement in sensitivity, and insufficient etching resistance. Furthermore, the stability of the resist solution is also insufficient, and there are difficulties in actual deployment for semiconductor manufacturing. In view of these situations, a resist that achieves both high resolution and high sensitivity is required.

[0008] In lithography targeting fine lines in the range of several nanometers to a dozen or so nanometers using extreme ultraviolet light in particular, for patterns formed by hydrophilic and hydrophobic resins after exposure and baking, positive pattern formation (PTI) using an alkaline developer and negative pattern formation (PTI) using an organic solvent developer have each been studied in terms of materials and processes. From the perspective of the solubility of the resist resin remaining as the resin pattern in the developer, the solubility of the hydrophilic resin pattern in NTI in the organic solvent developer is greater than the solubility of the hydrophobic resin pattern in PTI in the alkaline developer. Therefore, NTI is more difficult to form fine lines, and it is difficult to sufficiently ensure the resolution on the fine line side due to pattern collapse caused by resin swelling.

[0009] In view of the above circumstances, an object of the present invention is to provide a resin material capable of forming a film having high resolution and high sensitivity, a resist composition containing the same, and a method for forming a resist pattern and a method for forming an insulating film using the same.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that a (co)polymer containing a compound having a specific structure has high solubility in a safe solvent, and when these compounds etc. are used in a composition for forming a film for photolithography or a film for resist, a film having high resolution and high sensitivity can be formed, and thus the present invention has been completed. That is, the present invention is as follows.

[0011] [1] A compound having one or more halogens and two or more substituents having an unsaturated double bond. [2] The compound according to [1], represented by the following general formula (A).

Chemical formula

Chemical formula

[10] The resist composition according to [9], further comprising an acid generator, a photo-base generator, or a base compound.

[11] A step of forming a film of the resist composition according to [9] or

[10] on a wafer, A step of forming an optical image as a pattern on the resist film on the wafer by exposure, and A step of forming a resist pattern based on the optical image by development processing, A pattern forming method comprising the above steps.

[12] An insulating film forming method comprising the method according to

[11] .

[13] General formula (a):

Chemical formula

[14] A step of purifying the compound represented by general formula (1) obtained by the production method described in

[13] to remove metal impurities, The production method according to

[13] , comprising

[15] The method according to

[14] , wherein the purification comprises dissolving the compound in an organic solvent to obtain a solution and extracting metal impurities contained in the solution with an acidic aqueous solution.

[16] The method according to

[14] , wherein the purification comprises dissolving the compound in a solvent to obtain a solution and passing the solution through a filter.

[17] A step of polymerizing the compound represented by general formula (1) obtained by the production method according to any one of

[13] to

[16] to obtain a (co)polymer, and A step of purifying the (co)polymer to remove metal impurities, A method for producing a (co)polymer, comprising

[18] The method according to

[17] , wherein the purification comprises dissolving the (co)polymer in an organic solvent to obtain a solution and extracting metal impurities contained in the solution with an acidic aqueous solution.

[19] The method according to

[17] , wherein the purification includes dissolving the (co)polymer in a solvent to obtain a solution and passing the solution through a filter. [Advantages of the Invention]

[0012] The present invention can provide a compound, a composition capable of forming a film having high resolution and sensitivity, a method for forming a resist pattern using the same, and a method for forming an insulating film. [Embodiments for Carrying Out the Invention]

[0013] Hereinafter, embodiments of the present invention will be described (hereinafter sometimes referred to as "the present embodiment"). It should be noted that the present embodiment is an exemplification for explaining the present invention, and the present invention is not limited only to the present embodiment.

[0014] In the present specification, (meth)acrylate means acrylate and methacrylate. Other terms having the expression (meth) are also interpreted in the same manner as (meth)acrylate. In the present specification, (co)polymer means homopolymer and copolymer.

[0015] [Halogen-Containing Polymerizable Compound] One embodiment of the present embodiment relates to a compound having one or more halogens and two or more substituents having an unsaturated double bond, and more specifically, to a halogen-containing polymerizable compound represented by the general formula (A). [Chemical Formula] (In formula (A), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, a halogen, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, L represents a divalent linking group, A represents an organic group having 1 to 30 carbon atoms, X represents Cl, Br, or I, or contains a halogen atom selected from the group consisting of Cl, Br, and I, and is a hydrocarbon group having 1 to 30 carbon atoms bonded to A via a single bond, an ester group, an ether group, an amide group, an imide group, a urethane group, a urea group, a thioether group, a phosphine group, or a phosphate ester group. n 0 represents an integer from 2 to 5, n 2 represents an integer from 1 to 5.)

[0016] The compound of this embodiment preferably contains two or more ester moieties containing a polymerizable functional group in the compound. For example, by using a copolymer containing at least a structural unit derived from the compound of this embodiment and a structural unit having a functional group in which a hydrophilic-hydrophobic conversion reaction proceeds with an acid to improve solubility in an alkaline developer or reduce solubility in an organic solvent developer as a resin for lithography, it is possible to suppress the solubility of the resin pattern formed after the processes of exposure, baking (PEB, Post Exposure Bake), and development in the developer, and particularly in the formation of fine patterns, it is possible to suppress pattern collapse due to mechanisms such as swelling of the resin, and improve the resolution of fine line patterns. Further, particularly for monomers having a phenol structure, by introducing the ester structure into the phenolic hydroxyl group, it is possible to reduce the change over time of the resist resin derived from the pKa of the phenolic hydroxyl group, and as a result, it is also possible to secondarily have the effect of maintaining the pattern quality after aging. In addition, the compound in this embodiment is characterized by having a halogen element in the compound. By having a halogen element, the activity in the lithography process is improved, and by ensuring an improvement in efficiency in lithography or a margin for efficiency improvement in lithography, and making the performance in material design a more suitable distribution, it is possible to contribute to an improvement in lithography performance and an improvement in manufacturing stability. This effect is particularly remarkable in exposure processes using short wavelengths such as EUV and EB or electron beams.

[0017] The compound represented by the general formula (A) is preferably a compound represented by the general formula (1).

Chemical formula

[0018] R 4 may also be a combination of two or more selected from the group consisting of a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, and a cyclic organic group having 3 to 20 carbon atoms.

[0019] R 4 may have a substituent. As R 4 , for example, an alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms that may have a substituent; an alkenyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms that may have a substituent; an alkynyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms that may have a substituent; a cycloalkyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms that may have a substituent; a cycloalkenyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms that may have a substituent; a cycloalkynyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms that may have a substituent; an aryl group having 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms that may have a substituent; combinations thereof, etc. can be mentioned.

[0020] R4 Specific examples thereof include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an icosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclicosyl group, an adamantyl group, an ethylene group, a propylene group, a butylene group, a phenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a tetracene group, a chrysene group, a triphenylene group, a pyrene group, a benzopyrene group, an azulene group, a fluorene group, etc., which may have a substituent. These may contain an ether bond, a ketone bond, or an ester bond.

[0021] Here, the exemplified groups include isomers. For example, the propyl group includes an n-propyl group and an isopropyl group, and the butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.

[0022] R 4 The substituents of R are not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyroyloxy group, an aryroyloxy group, an alkylsilyl group, and various crosslinkable groups and acid dissociable groups.

[0023] The "crosslinkable group" is a group that crosslinks by an acid, an alkali, light, or heat, and refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, and examples thereof include a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a urethane(meth)acryloyl group, a group having a hydroxyl group, a group having a glycidyl group, a group having a vinylphenylmethyl group, a group having a styrene group, a group having an alkynyl group, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and a group containing these groups.

[0024] The "acid-dissociable group" is a group that cleaves in the presence of an acid to generate an alkali-soluble group (e.g., phenolic hydroxyl group, carboxyl group, sulfonic acid group, hexafluoroisopropanol group, etc.). The acid-dissociable group is not particularly limited, and for example, it can be appropriately selected from those proposed in, for example, hydroxystyrene resins, (meth)acrylic acid resins, etc. used in chemically amplified resist compositions for KrF or ArF. Specific examples of the acid-dissociable group can include, for example, those described in International Publication No. WO2016 / 158168.

[0025] A may have a substituent. Examples of the compound serving as the skeleton of A include alkanes having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms, which may have a substituent; alkenes having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; alkynes having 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms, which may have a substituent; cycloalkanes having 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have a substituent; cycloalkenes having 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have a substituent; cycloalkynes having 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have a substituent; arenes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent; and combinations thereof, etc.

[0026] Specific examples of the compound serving as the skeleton of A include, for example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, icosane, triacontane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclicosane, cyclotriacontane, adamantane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, icocene, triacontene, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, combinations thereof, and the like. These may contain an ether bond, a ketone bond, or an ester bond. Preferred skeletons of A include benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, and combinations thereof, which may have a substituent, and these can be appropriately used. More preferred skeletons of A include benzene and adamantane.

[0027] The substituents of the compound serving as the skeleton of A are not particularly limited, and examples thereof include a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyroyloxy group, an aryroyloxy group, an alkylsilyl group, various crosslinkable groups, and acid dissociable groups.

[0028] The "crosslinkable group" and "acid dissociable group" are not particularly limited, and for example, those described in the description of R 4 can be used.

[0029] At least one n 1 is 0, and at least one n 1 is preferably 1.

[0030] n 2 is an integer from 1 to 5, preferably an integer from 2 to 5, more preferably an integer from 2 to 3.

[0031] From the viewpoint of easy reactivity, the compound represented by the formula (1) is preferably a compound represented by the following formula (2).

Chemical formula

[0032] In formula (2), R 1 , A, n 0 , n 1 , n 2 are as defined in the formula (1) above.

[0033] From the viewpoint of etching resistance, the compound represented by the formula (1) is more preferably a compound represented by the following formula (3).

Chemical formula

[0034] In formula (3), B represents an organic group having 5 to 30 carbon atoms containing an aromatic ring, R 1 , n 0 , n 1 , n 2 are as defined in the formula (1) above.

[0035] B may have a substituent. Examples of the compound serving as the skeleton of B include arenes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent.

[0036] Specific examples of the compound that forms the backbone of B include, for example, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, combinations thereof, etc., which may have substituents. These may contain ether bonds, ketone bonds, or ester bonds. A more preferred backbone of B is benzene.

[0037] The substituents of the compound that forms the backbone of B are not particularly limited. For example, they include halogen atoms (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkyroyloxy groups, aryroyloxy groups, alkylsilyl groups, and various crosslinkable groups and acid-dissociable groups. Preferably, they are hydroxyl groups or acid-dissociable groups.

[0038] The "crosslinkable group" and "acid-dissociable group" are not particularly limited. For example, those described in the description of R 4 can be used. Although not particularly limited, the acid-dissociable group bonded to the aromatic ring of B is preferably a group that cleaves in the presence of an acid to generate a hydroxyl group.

[0039] From the perspective of etching resistance, the compound represented by the above formula (1) is more preferably a compound represented by the following formula (3').

Chemical formula

[0040] In formula (3'), B' represents an organic group having 5 to 30 carbon atoms containing an alicyclic ring, and R 1 , n 0 , n 1 , n 2 are as defined in the above formula (1).

[0041] B’ may have a substituent. Examples of the compound serving as the skeleton of B’ include, for example, a cycloalkane having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent; a cycloalkene having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent; a cycloalkyne having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have a substituent; combinations thereof, and the like.

[0042] Specific examples of the compound serving as the skeleton of B’ include, for example, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloeicosane, cyclotriacontane, adamantane, combinations thereof, and the like, which may have a substituent. These may contain an ether bond, a ketone bond, or an ester bond. A more preferable skeleton of B’ is adamantane.

[0043] The substituent of the compound serving as the skeleton of B’ is not particularly limited. Examples thereof include a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyroyloxy group, an aryroyloxy group, an alkylsilyl group, and various crosslinkable groups and acid dissociable groups.

[0044] The “crosslinkable group” and “acid dissociable group” are not particularly limited. For example, those described in the description of R 4 can be used.

[0045] Specific examples of the halogen-containing polymerizable compound of this embodiment are listed below, but are not limited thereto. In the following examples, R 1 represents a hydrogen atom or a methyl group.

[0046]

Chemical formula

[0047] [Method for producing halogen-containing polymerizable compound] As a method for synthesizing the halogen-containing polymerizable compound of the present embodiment, for example, after introducing a halogen group (for example, an iodine group) into an alcohol derivative containing a hydroxy group-containing aromatic, an esterification reaction is performed on the alcohol group. As one specific example of the method for introducing an iodine group, a method of reacting iodine chloride in an organic solvent by performing an iodination reaction on a hydroxybenzyl alcohol derivative (for example, Patent No. 5754842), a method of introducing an alkaline atmosphere, a method of dropping iodine into an alkaline aqueous solution of phenol in the presence of β-cyclodextrin (JP-A-63-101342, JP-A-2003-64012), etc. are known. When introducing a plurality of iodine atoms, it is preferable to use an iodination reaction via iodine chloride in an organic solvent. By esterifying the alcohol moiety of the prepared iodine-introduced hydroxybenzyl alcohol derivative by the method described below, the halogen-containing polymerizable compound of the present embodiment can be synthesized.

[0048] As a method for producing the halogen-containing polymerizable compound of the present embodiment, for example, a method of reacting an iodine-containing hydroxy compound represented by the general formula (a) with a (meth)acrylic acid compound represented by the general formula (b) can be mentioned, but it is not limited thereto.

[0049] [Chemical formula] (In formula (a), R 4 , A, n 0 , n 1 , n 2 are as defined in formula (1)) [Chemical formula] (In formula (b), R 1 is as defined in formula (1). Also, R B is selected from the group consisting of a hydroxyl group, a halogen atom, and a (meth)acryloyloxy group. R B is preferably a halogen atom such as a chlorine atom.)

[0050] The compound represented by the general formula (a) is preferably a compound represented by the general formula (a1).

Chemical formula

[0051] The compound represented by the general formula (a) is preferably a compound represented by the general formula (a2).

Chemical formula

[0052] The compound represented by the general formula (a) is preferably a compound represented by the general formula (a3).

Chemical formula

[0053] The (meth)acrylic acid compounds represented by the general formula (b) of the present invention are exemplified below. [Chemical formula] Among these (meth)acrylic acid compounds, (meth)acrylic acid chloride is preferable from the viewpoint of reactivity.

[0054] The usage amounts of the iodine-containing hydroxy compound represented by the general formula (a) and the (meth)acrylic acid compound represented by the general formula (b) may be appropriately adjusted according to the number of n 0 as appropriate.

[0055] As the solvent used in this reaction, generally available solvents can be used. For example, alcohol, ether, hydrocarbon, halogen-based solvents, etc. can be appropriately used within the range that does not inhibit the above reaction. Within the range that does not inhibit the above reaction, a plurality of solvents can also be mixed and used. Since water inhibits the reaction, it is preferable to use a dehydrated solvent.

[0056] The reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but generally, the reaction temperature is -20°C to 100°C, the reaction time is 1 hour to 10 hours, and the pressure can be carried out under normal pressure, reduced pressure or increased pressure. Also, the reaction can be appropriately selected from known methods such as batch, semi-batch, and continuous methods.

[0057] In addition, a polymerization inhibitor may be added to the series of reactions, and commercially available products that are generally available can be used. For example, nitrosocompounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, N,N'-dimethyl-p-nitrosoaniline; sulfur-containing compounds such as phenothiazine, methylene blue, 2-mercaptobenzimidazole; amines such as N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, aminophenol; quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, hydroquinone monomethyl ether; phenols such as p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, 2,2-methylenebis-(6-t-butyl-4-methylphenol); imides such as N-hydroxyphthalimide; oximes such as cyclohexanone oxime, p-quinonedioxime; and dialkyl thiodipropionate. The addition amount is, for example, 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the (meth)acrylic acid compound represented by the general formula (b).

[0058] The halogen-containing polymerizable compound of the present embodiment obtained by the reaction can be isolated and purified as a desired high-purity monomer by known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation and purification methods using activated carbon, etc., or methods by combinations thereof.

[0059] [(Co)polymer] The (co)polymer of the present embodiment preferably has a structural unit derived from the above halogen-containing polymerizable compound. It has a repeating unit represented by the following formula (A). [Chemical formula] (In formula (A-1), R 1 , R 2 , R 3 , L, A, X, n 0 , n 2 are as defined in the above formula (A))

[0060] The compound represented by general formula (A-1) is preferably a compound represented by general formula (1-1). [Chemical formula] (In formula (1-1), R 1 , R 4 , A, n 0 , n 1 , n 2 are as defined in the above formula (1))

[0061] The (co) polymer according to this embodiment having a structural unit derived from a halogen-containing polymerizable compound can be obtained by polymerizing the halogen-containing polymerizable compound according to this embodiment or by copolymerizing the halogen-containing polymerizable compound according to this embodiment with another monomer. Examples of the other monomer include those having a functional group that improves solubility in an alkaline developer by the action of an acid or a base. The (co) polymer according to this embodiment can be used as a material for forming a film for lithography.

[0062] The structural units other than the structural unit derived from the halogen-containing polymerizable compound according to this embodiment are not particularly limited. For example, those described in International Publication WO2016 / 125782, International Publication WO2015 / 115613, Japanese Patent Application Laid-Open No. 2015 / 117305, International Publication WO2014 / 175275, Japanese Patent Application Laid-Open No. 2012 / 162498, or compounds represented by the following formulas (C1) and (C2) can be used. [Chemical formula] (In formula (C1), R C11 represents a hydrogen or methyl group, R C12 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R C13 is, together with the carbon atom to which R C13 is attached, a cycloalkyl group or heterocycloalkyl group having 4 to 20 carbon atoms, The dot * represents the bonding position with an adjacent repeating unit.) Preferably, R C12 represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and R C13 is, together with the carbon atom to which R C13 is attached, a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms. R 13 may have a substituent (for example, an oxo group).

Chemical formula

[0063] Examples of the monomer raw material of the repeating unit represented by the general formula (C2) include, but are not limited to, 2-methyl-2-(meth)acryloyloxyadamantane, 2-ethyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxycyclopentane, 1-methyl-1-(meth)acryloyloxycyclohexane, 1-ethyl-1-(meth)acryloyloxycyclohexane, 1-methyl-1-(meth)acryloyloxycycloheptane, 1-ethyl-1-(meth)acryloyloxycycloheptane, 1-methyl-1-(meth)acryloyloxycyclooctane, 1-ethyl-1-(meth)acryloyloxycyclooctane, 2-ethyl-2-(meth)acryloyloxidecahydro-1,4:5,8-dimethanonaphthalene, 2-ethyl-2-(meth)acryloyloxynorbornane, and the like. Commercially available products can be used as these monomers.

[0064] The (co)polymer having a structural unit derived from the halogen-containing polymerizable compound according to this embodiment is preferable for improving the performance of the film-forming material for lithography.

[0065] Next, a method for producing the (co)polymer according to this embodiment by a polymerization reaction will be described. The polymerization reaction is carried out by dissolving a monomer that becomes a repeating unit in a solvent, adding a catalyst, and heating or cooling. The reaction conditions can be arbitrarily set depending on the type of initiator, the initiation method such as heat or light, temperature, pressure, concentration, solvent, additive, and the like. The production of the (co)polymer according to this embodiment can be carried out by a known method such as radical polymerization using a radical generator such as azoisobutyronitrile or peroxide, or ionic polymerization using a catalyst such as alkyllithium or Grignard reagent.

[0066] As the solvent used in the polymerization reaction, commercially available products that are generally available can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, halogenated solvents, etc. can be appropriately used within the range that does not inhibit the reaction. Within the range that does not inhibit the above reaction, a plurality of solvents can also be mixed and used.

[0067] The (co)polymer obtained by the polymerization reaction can be purified by a known method. Specifically, ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction can be combined and carried out.

[0068] [Purification method] It is preferable to remove residual metal impurities by further purifying the compound in this embodiment after obtaining it as a crude product by the above-described reaction. That is, from the viewpoints of preventing the deterioration of the resin over time and storage stability, and further from the viewpoints of process suitability and manufacturing yield due to process suitability and defects when resinified and applied to the semiconductor manufacturing process, it is used as a reaction aid in the manufacturing process of the compound, or it is preferable to avoid the residual of metal impurity losses derived from the metal components mixed in from the reaction kettle for manufacturing and other manufacturing facilities.

[0069] The compound in this embodiment is characterized by improving the lithography performance by improving the exposure efficiency in the lithography process by having a halogen element as a substituent. However, when metal-containing impurities remain in the system, the halogen element characteristic of the compound in this embodiment becomes unstable, and the desired properties cannot be obtained, or unexpected secondary reactions such as decomposition of the resin and formation of bonds between resins are induced due to the elimination of the halogen element, resulting in concerns about performance deterioration in terms of sensitivity, resolution, roughness, exposure stability, and defects in lithography. Due to these factors, it is preferable to reduce metal-containing impurities. For the compound in this embodiment, there are concerns that the halogen element may be destabilized particularly by Fe, Al, Sb, Ru, W, etc.

[0070] As the residual amount of the above-mentioned metal impurities, it is preferably less than 1 ppm, more preferably less than 100 ppb, and even more preferably less than 50 ppb, respectively, with respect to the resin. In particular, for metal species such as Fe, Al, Sb, Ru, and W classified as transition metals, if the metal residual amount is 1 ppm or more, there is a concern that it may cause material modification or deterioration over time due to the interaction with the compound in this embodiment. Also, if it is 1 ppm or more, when preparing a resin for semiconductor processes using the prepared compound, the metal residue amount cannot be sufficiently reduced, and there is a concern that it may cause a decrease in yield due to defects and performance deterioration resulting from residual metals in the semiconductor manufacturing process.

[0071] The purification method is not particularly limited, but includes a step of dissolving the compound in this embodiment in a solvent to obtain a solution (S), and a step of bringing the obtained solution (S) into contact with an acidic aqueous solution to extract impurities in the compound in this embodiment (first extraction step). The solvent used in the step of obtaining the solution (S) includes an organic solvent that is not arbitrarily miscible with water. According to the above purification method, the contents of various metals that can be contained as impurities in the resin can be reduced. More specifically, the compound in this embodiment can be dissolved in an organic solvent that is not arbitrarily miscible with water to obtain a solution (S), and further, the solution (S) can be brought into contact with an acidic aqueous solution for extraction treatment. Thereby, after transferring the metal content contained in the above solution (S) to the aqueous phase, the organic phase and the aqueous phase can be separated to obtain a resin with a reduced metal content.

[0072] The organic solvent that is not arbitrarily miscible with water used in the above purification method is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferred. Specifically, it is an organic solvent with a solubility in water of less than 30% at room temperature, more preferably less than 20%, and particularly preferably less than 10%. The usage amount of the organic solvent is preferably 1 to 100 mass times the total amount of the resin used.

[0073] Specific examples of solvents that are immiscible with water include, but are not limited to, for example, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc. are preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are even more preferred. Methyl isobutyl ketone, ethyl acetate, etc. have a relatively high saturated solubility of the compounds in this embodiment and a relatively low boiling point, so it is possible to reduce the load in the process of distilling off the solvent industrially or removing it by drying. These solvents can be used alone or in combination of two or more.

[0074] As the acidic aqueous solution used in the above purification method, it is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water. Although not limited to the following, for example, mineral acid aqueous solutions in which mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are dissolved in water, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. Organic acid aqueous solutions in which organic acids are dissolved in water can be mentioned. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid It is preferably one or more organic acid aqueous solutions selected from the group consisting of, more preferably an aqueous solution of sulfuric acid, nitric acid, and a carboxylic acid such as acetic acid, oxalic acid, tartaric acid, citric acid, further preferably an aqueous solution of sulfuric acid, oxalic acid, tartaric acid, citric acid, and even more preferably an aqueous solution of oxalic acid. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions and produce a chelating effect, so it is considered that metals can be removed more effectively. In addition, the water used here is preferably water with a low metal content, such as ion-exchanged water, in accordance with the purpose of the purification method in this embodiment.

[0075] The pH of the acidic aqueous solution used in the above purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the resin. Usually, the pH range is about 0 to 5, preferably about pH 0 to 3.

[0076] The amount of the acidic aqueous solution used in the above purification method is not particularly limited, but it is preferably adjusted from the viewpoints of reducing the number of extraction times for metal removal and ensuring operability in consideration of the total liquid volume. From the above viewpoints, the amount of the acidic aqueous solution is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, based on 100% by mass of the above solution (S).

[0077] In the above purification method, by bringing the acidic aqueous solution into contact with the solution (S), the metal content can be extracted from the resin in the solution (S).

[0078] In the above purification method, the solution (S) may further contain an organic solvent that is optionally miscible with water. When an organic solvent that is optionally miscible with water is included, the charged amount of the resin can be increased, and the liquid separation property is improved, and there is a tendency that purification can be performed with high kettle efficiency. The method of adding an organic solvent that is optionally miscible with water is not particularly limited. For example, any of a method of adding it to a solution containing an organic solvent in advance, a method of adding it to water or an acidic aqueous solution in advance, and a method of adding it after bringing a solution containing an organic solvent into contact with water or an acidic aqueous solution may be used. Among these, the method of adding it to a solution containing an organic solvent in advance is preferable in terms of the workability of the operation and the ease of managing the charged amount.

[0079] The organic solvent that is optionally miscible with water used in the above purification method is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable. The amount of the organic solvent that is optionally miscible with water used is not particularly limited as long as the solution phase and the aqueous phase can be separated, but it is preferably 0.1 to 100 times by mass, more preferably 0.1 to 50 times by mass, and still more preferably 0.1 to 20 times by mass, based on the total amount of the resin used.

[0080] Specific examples of the organic solvent miscible with water used in the above purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and N-methylpyrrolidone; and aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether, etc. are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferred. These solvents can be used alone or in combination of two or more.

[0081] The temperature during the extraction treatment is usually 20 to 90 °C, preferably in the range of 30 to 80 °C. The extraction operation is performed, for example, by stirring well and then allowing to stand, whereby the metal content contained in the solution (S) migrates to the aqueous phase. Also, by this operation, the acidity of the solution is reduced, and the deterioration of the above resin can be suppressed.

[0082] Since the above mixed solution is separated into a solution phase containing resin and solvent and an aqueous phase by standing, the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of better separating the solution phase containing the solvent and the aqueous phase. Usually, the standing time is 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more. Also, the extraction treatment may be carried out only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.

[0083] In the above purification method, after the first extraction step, it is preferable to include a step of further bringing the solution phase containing the resin into contact with water to extract impurities in the resin (second extraction step). Specifically, for example, after performing the above extraction treatment using an acidic aqueous solution, it is preferable to further subject the solution phase containing the resin extracted and recovered from the aqueous solution and the solvent to an extraction treatment with water. The above extraction treatment with water is not particularly limited, but for example, it can be performed by well mixing the solution phase and water by stirring or the like and then allowing the obtained mixed solution to stand. Since the mixed solution after standing is separated into a solution phase containing the resin and the solvent and an aqueous phase, the solution phase can be recovered by decantation or the like. Also, the water used here is preferably water with a low metal content, such as ion-exchanged water, in accordance with the purpose of the present embodiment. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. Also, the usage ratio of both in the extraction treatment and conditions such as temperature and time are not particularly limited, and may be the same as in the case of the previous contact treatment with the acidic aqueous solution.

[0084] Regarding the moisture that may be mixed into the solution containing the resin and the solvent thus obtained, it can be easily removed by performing an operation such as vacuum distillation. Also, if necessary, a solvent can be added to the solution to adjust the concentration of the resin to an arbitrary concentration.

[0085] The purification method of the compound according to the present embodiment can also be purified by passing a solution in which the resin is dissolved in a solvent through a filter. According to the purification method of the substance according to the present embodiment, the contents of various metal components in the above resin can be effectively and significantly reduced. The amounts of these metal components can be measured by the method described in the examples below. Note that "liquid passage" in this embodiment means that the above solution passes from the outside of the filter through the inside of the filter and then moves back to the outside of the filter again. For example, modes such as simply contacting the above solution with the surface of the filter or moving the above solution while contacting it on the surface and moving it outside the ion exchange resin (that is, simply contacting mode) are excluded.

[0086] In the purification using a filter, a filter used for removing metal components in a solution containing the resin and a solvent can usually be a commercially available one for liquid filtration. The filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, still more preferably 0.1 μm or less, even more preferably less than 0.1 μm, and even more preferably 0.05 μm or less. Also, the lower limit value of the nominal pore size of the filter is not particularly limited, but is usually 0.005 μm. The nominal pore size mentioned here is a nominal pore size indicating the separation performance of the filter, and is, for example, the pore size determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury intrusion method test, a standard particle capture test, etc. When using a commercial product, it is the value described in the manufacturer's catalog data. By setting the nominal pore size to 0.2 μm or less, the content of metal components after passing the solution through the filter once can be effectively reduced. In this embodiment, in order to further reduce the content of each metal component in the solution, the filter liquid passage step may be performed two or more times.

[0087] As the form of the filter, a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, and a filter filled with a filter medium such as non-woven fabric, cellulose, and diatomaceous earth can be used. Among the above, it is preferable that the filter is one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter, and a pleated membrane filter. Also, particularly because of the high-precision filtration accuracy and the high filtration area height compared with other forms, it is particularly preferable to use a hollow fiber membrane filter.

[0088] Examples of the material of the filter include polyolefins such as polyethylene and polypropylene, polyethylene-based resins with functional groups having ion exchange ability by graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, and fluorine-containing resins such as polytetrafluoroethylene (PTFE). Among the above, it is preferable that the filter medium is one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin. Further, polyamide is particularly preferable from the viewpoint of the effect of reducing heavy metals such as chromium. In addition, from the viewpoint of avoiding metal elution from the filter medium, it is preferable to use a filter other than a sintered metal material.

[0089] Examples of polyamide-based filters (hereinafter, trademarks) include, but are not limited to, for example, the Polyfix Nylon series manufactured by Kitz Microfilter Co., Ltd., the Ultipleats P-Nylon 66, Ultipore N66 manufactured by Nippon Pall Co., Ltd., the Life Assure PSN series, and the Life Assure EF series manufactured by 3M Co., Ltd. Examples of polyolefin-based filters include, but are not limited to, for example, the Ultipleats PE Clean and Ion Clean manufactured by Nippon Pall Co., Ltd., the ProTego series, Microguard Plus HC10, Optimizer D, etc. manufactured by Nippon Integris Co., Ltd. Examples of polyester-based filters include, but are not limited to, for example, the Gelaflo DFE manufactured by Central Filter Industry Co., Ltd., the Breathtype PMC manufactured by Nippon Filter Co., Ltd., etc. Examples of polyacrylonitrile-based filters include, but are not limited to, for example, the Ultrafilter AIP-0013D, ACP-0013D, ACP-0053D, etc. manufactured by Advantec Toyo Co., Ltd. Examples of fluororesin-based filters include, but are not limited to, for example, the Enflon HTPFR manufactured by Nippon Pall Co., Ltd., the LifeShure FA series manufactured by 3M Co., Ltd., etc. These filters may be used alone or in combination of two or more.

[0090] In addition, the filter may contain an ion exchanger such as a cation exchange resin, a cation charge regulator that generates a zeta potential in the organic solvent solution to be filtered, and the like. Examples of the filter containing an ion exchanger include, but are not limited to, the Protego series manufactured by Nippon Integris Co., Ltd., the Clangraft manufactured by Kurashiki Fiber Processing Co., Ltd., and the like. Examples of the filter containing a substance having a positive zeta potential, such as a polyamide polyamine epichlorohydrin cation resin (hereinafter, trademarks), include, but are not limited to, Zeta Plus 40QSH and Zeta Plus 020GN manufactured by 3M Company, or the Life Assure EF series and the like.

[0091] [Composition containing a halogen-containing polymerizable compound or its (co)polymer] The composition of the present embodiment contains a halogen-containing polymerizable compound or its (co)polymer, and is a composition particularly suitable for lithography technology. Although not particularly limited, the composition can be used for lithography film formation applications, for example, resist film formation applications (i.e., "resist composition"). Furthermore, the composition can be used for upper layer film formation applications (i.e., "composition for upper layer film formation"), intermediate layer formation applications (i.e., "composition for intermediate layer formation"), lower layer film formation applications (i.e., "composition for lower layer film formation"), and the like. According to the composition of the present embodiment, a film having high sensitivity can be formed, and it is also possible to impart a good resist pattern shape.

[0092] The composition of this embodiment can also be used as an optical component forming composition applying lithography technology. The optical components are used in the form of films or sheets, and are also useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast improvement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition is particularly suitable for use as an embedded film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, a planarizing film and a conformal film on a microlens, which are members of a solid-state imaging device that requires a particularly high refractive index.

[0093] The composition of this embodiment contains a halogen-containing polymerizable compound or its (co)polymer (B), and may contain other components such as a substrate (A), a solvent (S), an acid generator (C), an acid diffusion controller (E), etc. as required. Each component will be described below.

[0094] [Substrate (A)] In this embodiment, the "substrate (A)" refers to a compound other than a halogen-containing polymerizable compound or its (co)polymer (including resins), which is a substrate (for example, a substrate for lithography or a substrate for resist) applicable as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB). These substrates are not particularly limited and can be used as the substrate (A) in this embodiment. Examples of the substrate (A) include phenol novolak resin, cresol novolak resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium, and derivatives thereof. Among them, from the viewpoint of the shape of the obtained resist pattern, phenol novolak resin, cresol novolak resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, and inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium, and derivatives thereof are preferable.

[0095] The derivatives are not particularly limited, and examples thereof include those into which a dissociable group is introduced and those into which a crosslinkable group is introduced. Derivatives into which the dissociable group or the crosslinkable group is introduced can exhibit a dissociation reaction or a crosslinking reaction by the action of light, acid, or the like.

[0096] The "dissociable group" refers to a characteristic group that generates a functional group such as an alkali-soluble group that cleaves and changes solubility. The alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group, etc. A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable.

[0097] The "crosslinkable group" refers to a group that crosslinks in the presence of a catalyst or without a catalyst. The crosslinkable group is not particularly limited, and examples thereof include an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy(meth)acryloyl group, a group having a hydroxyl group, a group having a urethane(meth)acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group containing vinyl.

[0098] [Solvent (S)] In this embodiment, as long as the solvent can dissolve at least the halogen-containing polymerizable compound or its (co)polymer (B), known solvents can be appropriately used.Specific examples of the solvent are not particularly limited, and examples include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-lactone, etc., but are not particularly limited.The solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0099] In this embodiment, the amount of the solid component and the amount of the solvent are not particularly limited, but with respect to the total mass of the solid component and the solvent, it is preferably 1 to 80% by mass of the solid component and 20 to 99% by mass of the solvent, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, even more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component and 90 to 98% by mass of the solvent.

[0100] [Acid generator (C)] In the composition of this embodiment, it is preferable to contain one or more acid generators (C) that generate acid directly or indirectly by irradiation with any radiation selected from visible light, ultraviolet rays, excimer lasers, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams. The acid generator (C) is not particularly limited, and for example, those described in International Publication WO2013 / 024778 can be used. The acid generator (C) can be used alone or in combination of two or more.

[0101] The amount of the acid generator (C) used is preferably 0.001 to 49% by mass of the total mass of the solid component, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained. In this embodiment, if acid is generated in the system, the method of generating the acid is not particularly limited. If an excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if electron beams, extreme ultraviolet rays, X-rays, and ion beams are used as high-energy rays, further finer processing is possible.

[0102] [Acid diffusion control agent (E)] In this embodiment, an acid diffusion control agent (E) having an action of controlling the diffusion of the acid generated from the acid generator in the resist film by radiation irradiation and preventing an undesirable chemical reaction in the unexposed region may be blended in the composition. By using the acid diffusion control agent (E), the storage stability of the composition of this embodiment tends to be improved. Further, by using the acid diffusion control agent (E), the resolution of the film formed using the composition of this embodiment can be improved, and the line width change of the resist pattern due to the variation between the standing time before radiation irradiation and the standing time after radiation irradiation can be suppressed, and it tends to have excellent process stability. The acid diffusion control agent (E) is not particularly limited, and examples thereof include radiation-decomposable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0103] The acid diffusion control agent (E) is not particularly limited, and for example, those described in International Publication WO2013 / 024778 can be used. The acid diffusion control agent (E) can be used alone or in combination of two or more.

[0104] The blending amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass based on the total mass of the solid content. When the blending amount of the acid diffusion control agent (E) is within the above range, it tends to be possible to prevent a decrease in resolution, deterioration of the pattern shape, dimensional fidelity, etc. Further, even if the standing time from electron beam irradiation to post-radiation irradiation heating becomes long, deterioration of the shape of the upper layer of the pattern can be suppressed. Also, when the blending amount is 10% by mass or less, a decrease in sensitivity, developability of the unexposed portion, etc. can be prevented. Further, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the line width change of the resist pattern due to the variation between the standing time before radiation irradiation and the standing time after radiation irradiation can be suppressed, and it tends to have excellent process stability.

[0105] [Other component (F)] In the composition of the present embodiment, as the other component (F), if necessary, one or more of various additives such as a crosslinking agent, a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added.

[0106] [Crosslinking agent] In the present embodiment, one or more crosslinking agents can be included in the composition. The crosslinking agent means a compound capable of crosslinking at least one of the base material (A), the halogen-containing polymerizable compound, or its (co)polymer (B). As the crosslinking agent, an acid crosslinking agent capable of crosslinking the base material (A) intramolecularly or intermolecularly in the presence of an acid generated from the acid generator (C) is preferable. Examples of such an acid crosslinking agent include compounds having one or more groups capable of crosslinking the base material (A) (hereinafter referred to as "crosslinkable groups").

[0107] Examples of the crosslinkable group include (i) hydroxyalkyl groups such as hydroxy (alkyl group having 1 to 6 carbon atoms), alkoxy (alkyl group having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, acetoxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups such as formyl group, carboxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (iii) nitrogen-containing group-containing groups such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing groups such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) groups derived from aromatic groups such as allyloxy (alkyl group having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, aralkyloxy (alkyl group having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, such as benzyloxymethyl group, benzoyloxymethyl group; (vi) polymerizable multiple bond-containing groups such as vinyl group, isopropenyl group, etc. The crosslinkable groups of the crosslinking agent in the present embodiment are preferably hydroxyalkyl groups and alkoxyalkyl groups, and particularly preferably alkoxymethyl groups.

[0108] The crosslinking agent having the crosslinkable group is not particularly limited. For example, the acid crosslinking agent described in International Publication WO2013 / 024778 can be used. The crosslinking agent can be used alone or in combination of two or more.

[0109] In this embodiment, the blending amount of the crosslinking agent is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less of the total mass of the solid components.

[0110] (Dissolution accelerator) The dissolution accelerator is a component having an action of increasing the solubility of the solid component in the developer when the solubility is too low and moderately increasing the dissolution rate of the compound during development. As the dissolution accelerator, those having a low molecular weight are preferable, and for example, low molecular weight phenolic compounds can be mentioned. Examples of the low molecular weight phenolic compounds include bisphenols, tris(hydroxyphenyl)methane, and the like. These dissolution accelerators can be used alone or in combination of two or more.

[0111] The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid components.

[0112] (Dissolution controller) The dissolution controller is a component having an action of controlling the solubility when the solubility of the solid component in the developer is too high and moderately decreasing the dissolution rate during development. As such a dissolution controller, those that do not chemically change in processes such as baking, radiation irradiation, and development of the resist film are preferable.

[0113] The dissolution control agent is not particularly limited, and examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These dissolution control agents can be used alone or in combination of two or more.

[0114] The blending amount of the dissolution control agent is appropriately adjusted according to the type of the compound to be used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total solid content.

[0115] (Sensitizer) The sensitizer is a component that absorbs the energy of the irradiated radiation, transfers the energy to the acid generator (C), thereby increasing the amount of acid generated, and improving the apparent sensitivity of the resist. Examples of such sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes, etc., but are not particularly limited. These sensitizers can be used alone or in combination of two or more.

[0116] The blending amount of the sensitizer is appropriately adjusted according to the type of the compound to be used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total solid content.

[0117] (Surfactant) The surfactant is a component having the effect of improving the coatability, striation, and resist developability of the composition of the present embodiment. The surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in the production of the composition of the present embodiment and can enhance the effect of the composition of the present embodiment more effectively. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, etc., but are not particularly limited. Commercially available products of these surfactants include, under the following trade names, EFtop (manufactured by Gemco), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), Pepole (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), etc.

[0118] The blending amount of the surfactant is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid component.

[0119] (organic carboxylic acid or oxo acid of phosphorus or its derivative) For the purpose of preventing sensitivity degradation or improving the resist pattern shape, standing stability, etc., an organic carboxylic acid, an oxo acid of phosphorus or a derivative thereof can be further contained as an optional component. The organic carboxylic acid, the oxo acid of phosphorus or a derivative thereof can be used in combination with an acid diffusion control agent or can be used alone. Examples of the organic carboxylic acid include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. which are suitable. Examples of the oxo acid of phosphorus or a derivative thereof include phosphoric acid such as phosphoric acid, dibutyl phosphate, diphenyl phosphate or derivatives such as their esters, phosphonic acid, dimethyl phosphonate, dibutyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and other phosphonic acids or derivatives such as their esters, phosphinic acid, phenylphosphinic acid and other phosphinic acids and derivatives such as their esters. Among these, phosphonic acid is particularly preferred.

[0120] The organic carboxylic acid, the oxo acid of phosphorus or a derivative thereof can be used alone or in combination of two or more. The blending amount of the organic carboxylic acid, the oxo acid of phosphorus or a derivative thereof is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid content.

[0121] [Other Additives] Furthermore, in the composition of the present embodiment, one or more additives other than the above-described components can be blended as necessary. Examples of such additives include dyes, pigments, adhesion aids, etc. For example, blending a dye or a pigment is preferable because it can visualize the latent image in the exposed area and mitigate the influence of halation during exposure. Also, blending an adhesion aid is preferable because it can improve the adhesion to the substrate. Furthermore, other additives include anti-halation agents, storage stabilizers, defoaming agents, shape improvers, etc., and specifically, 4-hydroxy-4'-methylchalcone and the like can be mentioned.

[0122] In the composition of the present embodiment, the total amount of the optional component (F) can be 0 to 99% by mass of the total solid content, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0123] To form a resist pattern from the composition of the present invention, the composition solution is applied onto a substrate such as a silicon wafer, metal, plastic, glass, or ceramic by an appropriate coating means such as a spin coater, dip coater, or roller coater to form a resist film. Optionally, after heat treatment at a temperature of about 50°C to 200°C in advance, exposure is performed through a predetermined mask pattern. The thickness of the coating film is, for example, 0.1 to 20 μm, preferably about 0.3 to 2 μm. For exposure, light rays of various wavelengths such as ultraviolet rays and X-rays can be used. For example, as the light source, far ultraviolet rays such as F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), and KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13 nm), X-rays, electron beams, etc. are appropriately selected and used. Also, the exposure conditions such as the exposure amount are appropriately selected according to the compounding composition of the above resin and / or compound, the type of each additive, etc.

[0124] In the present invention, in order to stably form a highly accurate fine pattern, it is preferable to perform heat treatment at a temperature of 50 to 200°C for 30 seconds or more after exposure. In this case, if the temperature is less than 50°C, the variation in sensitivity depending on the type of substrate may spread. Thereafter, development is carried out with an alkaline developer, usually at 10 to 50°C for 10 to 200 seconds, preferably at 20 to 25°C for 15 to 90 seconds, to form a predetermined resist pattern.

[0125] As the above-mentioned alkaline developer, for example, an alkaline aqueous solution in which an alkaline compound such as an alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene is dissolved to a concentration of usually 1 to 10% by weight, preferably 1 to 3% by weight is used. Further, a water-soluble organic solvent or a surfactant can be appropriately added to the developer composed of the above-mentioned alkaline aqueous solution.

[0126] In addition, the composition of this embodiment can be used as a patterning material for lithography applications. As applications of the lithography process, it can be used for various applications such as semiconductors, liquid display panels, display panels using OLEDs, power devices, CCDs, and other sensors. Particularly for integrated circuits of semiconductors and devices, in the process of forming device elements on a silicon wafer, based on a pattern formed using the composition of this embodiment on the upper surface side of an insulating layer such as a silicon oxide film or other oxide films, a pattern is formed on the insulating film on the substrate side by etching, and further, a metal film or semiconductor material is laminated based on the formed insulating film pattern to form a circuit pattern, and the composition of this embodiment can be suitably used for the purpose of constructing semiconductor elements and other devices.

Examples

[0127] Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by these examples in any way.

[0128] [Measurement method] (1) Structure of the compound The structure of the compound was confirmed by performing 1H-NMR measurement under the following conditions using an Advance600II spectrometer manufactured by Bruker. 1 1H-NMR measurement was performed and confirmed. Frequency: 400 MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measured temperature: 23°C

[0129] 〔Inorganic element content〕 The metal content contained in the compounds prepared in the examples and comparative examples was measured using the inorganic element analysis (ICP - AES / ICP - MS) apparatus "AG8900" (product name, manufactured by Agilent Technologies, Inc.).

[0130] (Synthesis Example 1 - 1) Synthesis of M1 128 g (0.78 mol) of calcium chloride and 91.3 g (2.4 mol) of NaBH4 were dissolved in 2.8 L of ethanol, and 410 g (1.1 mol) of 4 - hydroxy - 3,5 - diiodobenzaldehyde was added thereto under ice cooling. After stirring at 25°C for 18 hours to cause a reaction, 10 L of water was added, the pH was adjusted to 2.5 with hydrochloric acid, the precipitate was filtered, washed with water, and dried to obtain 401 g (yield 97%) of 4 - hydroxy - 3,5 - diiodobenzyl alcohol shown below.

Chemical formula

[0131] 400 g (1.06 mol) of the 4 - hydroxy - 3,5 - diiodobenzyl alcohol obtained above was dissolved in 2.8 L of toluene, 1832 g (21.2 mol) of methacrylic acid, 40 g (0.21 mol) of p - toluenesulfonic acid monohydrate, and 26 mg (0.02 mmol) of 4 - methoxyphenol were added, and the mixture was stirred under reflux at 110°C for 2 hours. After the reaction, 4 L of water was added, the organic layer was dried, and recrystallization purification was performed twice with hexane to obtain 158 g (yield 33%) of the target product M1 shown below.

Chemical formula

[0132] (Synthesis Example 2 - 1) Synthesis of M2 90 g (0.24 mol) of 3,5-diiodosalicylaldehyde was dissolved in 900 ml of methanol, and 22.8 g (0.60 mol) of NaBH4 was added at 10°C or lower. Subsequently, after stirring for 3 hours under ice cooling, the mixture was stirred at 25°C for 16 hours to cause a reaction, and methanol was distilled off under reduced pressure for concentration. Water and ethyl acetate were added to the concentrate, and the organic phase was extracted. Magnesium sulfate was added to this organic phase for drying, and the solvent was distilled off under reduced pressure to obtain a crude product of 2-hydroxy-3,5-diiodobenzyl alcohol. The obtained crude product of 2-hydroxy-3,5-diiodobenzyl alcohol was purified by column chromatography to obtain 82.5 g (yield 91%) of 2-hydroxy-3,5-diiodobenzyl alcohol shown below.

Chemical formula

[0133] 10 g (27 mmol) of 2-hydroxy-3,5-diiodobenzyl alcohol obtained above was dissolved in 100 mL of dichloromethane, 3.1 g (39 mmol) of pyridine was added under ice cooling, and 8.2 g (54 mmol) of methacrylic anhydride was added dropwise. Subsequently, the mixture was stirred at ice-cooled temperature for 4 hours and at room temperature for 24 hours to cause a reaction. After completion of the reaction, water was added to the reaction solution, washed with an aqueous sodium hydrogen carbonate solution, magnesium sulfate was added to the organic phase for drying, concentrated, and then purified by column chromatography to obtain 9 g (yield 88%) of the target product M2 shown below.

Chemical formula

[0134] The following compounds M3 to M5, MRA1, MRA3, and MRA5 were synthesized according to the method of Synthesis Example 1-1 using the corresponding raw materials. The following compounds MRB1, MRB3, MRB5, MRC1, MRC3, and MRC5 were synthesized according to the method of Synthesis Example 1-1 using the corresponding raw materials and appropriately reducing the amount of methacrylic acid used.

Chemical formula

[0135] (Synthesis Example 3-1) Synthesis of MAD1 To a 200 mL flask, 1.84 g (10 mmol) of adamantyltriol, 3.0 g (20 mmol) of NaI, 2.18 g (20 mmol) of chlorotrimethylsilane, and 15.7 g of acetonitrile were added, and reflux was carried out at 80 °C for 5 hours. After cooling to room temperature, 21.2 mL of a 6 mass% aqueous Na2S2O3 solution was added. Further, extraction of the organic phase was carried out 5 times with 80 mL of diethyl ether, and the obtained organic phase was concentrated under reduced pressure to obtain 1.68 g (yield 57%) of a pale yellow solid.

Chemical Structure

[0136] In a 200 mL flask, 1.68 g (5.7 mmol) of the monoiodoadamantanediol obtained above was dissolved in 150 mL of dichloromethane, and 1.56 g (15 mmol) of methacrylic acid chloride and 0.61 g (6 mmol) of triethylamine were added under temperature conditions of 0 °C, and stirring was carried out at 0 °C for 5 hours. After the reaction, liquid separation and washing were carried out with 50 mL of a 1% aqueous hydrochloric acid solution, and then 50 mL of water was added for liquid separation treatment. Magnesium sulfate was added to the organic layer for drying, and then the filtrate obtained by filtration was collected and concentrated under reduced pressure to obtain 1.96 g (yield 79%) of the target product MAD1 shown below.

Chemical Structure

[0137] (Synthesis Example 1) Synthesis of M1 Resin 1.5 g of M1, 3.0 g of 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was dropped into 2 L of n-heptane. The precipitated resin was filtered off and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-MAC-0I). The molecular weight (Mw) of this resin was 12,000, and the dispersity (Mw / Mn) was 1.90. Also, 13 As a result of measuring 13C-NMR, the composition ratio (molar ratio) in the following chemical formula (P-MAC-0I) was a:b:c:d = 40:30:15:15. The following chemical formula (P-MAC-0I) is described simply to show the ratio of each structural unit, but P-MAC-0I is not a block copolymer in which each structural unit forms an independent block.

[0138]

Chemical formula

[0139] (Synthesis Examples 2 to 6, Synthesis Comparative Examples 1 to 9) Various resins were prepared in the same manner as in Synthesis Example 1, except that M2 to 5, MRA1, MRA3, MRA5, MRB1, MRB3, MRB5, MRC1, MRC3, MRC5, and MAD1 were used instead of M1.

[0140] (EUV Sensitivity Evaluation) A resin solution containing the resin prepared in the synthesis example or synthesis comparative example was applied onto a silicon wafer and baked at 110 °C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. Here, the resin solution was prepared by blending 5 parts by mass of the resin prepared in the synthesis example or synthesis comparative example, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.2 part by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME. Subsequently, maskless shot exposure was performed using an EUV exposure apparatus (manufactured by Resotec Japan; EUVES-7000) with the exposure dose increased stepwise from 1 mJ / cm2 to 80 mJ / cm2 in increments of 1 mJ / cm2. After that, baking (PEB) was carried out at 110 °C for 90 seconds, followed by development for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), to obtain a wafer on which shot exposure for 80 shots was performed. For each shot exposure area obtained, the film thickness was measured using an interference film thickness meter to acquire profile data of the film thickness with respect to the exposure dose. The exposure dose at which the slope of the film thickness variation with respect to the exposure dose was the largest was calculated as the sensitivity value (mJ / cm2) and used as an index for the EUV sensitivity of the resist.

[0141] (EB Pattern Evaluation) A resin solution containing the resin prepared in the synthesis example or synthesis comparative example was applied onto a silicon wafer and baked at 110 - 130 °C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. Here, the resin solution was prepared by blending 5 parts by mass of the resin prepared in the synthesis example or synthesis comparative example, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.1 part by mass of tributylamine, and 92 parts by mass of PGMEA. Subsequently, exposure was carried out using an electron beam lithography apparatus (manufactured by Elionix; ELS-7500, 50 keV), followed by baking (PEB) at 115 °C for 90 seconds and development for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) to obtain a positive pattern. The exposure dose was adjusted so as to obtain a line and space with a half pitch of 20 nm. For the obtained pattern, 80 pattern images were acquired using S-4800 (manufactured by Hitachi, Ltd.) at a magnification of 100,000 times, and the number of pattern collapses was counted to perform an evaluation based on the total amount of pattern collapses.

[0142] (Sensitivity Evaluation over Time) The prepared resin solution was subjected to forced aging treatment under light-shielded conditions at 40 °C for 240 hours. Subsequently, EUV sensitivity evaluation was similarly performed on the aged solution, and an assessment was carried out according to the amount of sensitivity change.

[0143] (Evaluation of roughness over time) The prepared resin solution was subjected to forced aging treatment under light-shielded conditions at 40 °C for 240 hours. After the aging treatment, EB pattern evaluation was performed on the solution in the same manner, and pattern images were obtained by SEM in the same manner. Roughness and residue (scum) count between patterns were performed. Note that as the developer, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was used as an alkaline developer to form a PTI (positive) pattern for PTI roughness evaluation. Also, organic solvent development was performed using butyl acetate as the developer to form an NTI (negative) pattern for NTI scum evaluation. [Table 1]

[0144] As described above, it was found that a resin solution for lithography with excellent defects and aging performance can be prepared by using the halogen-containing polymerizable compound or its polymer of the present embodiment.

[0145] <Evaluation of etching defects in the laminated film> Quality evaluation before and after purification treatment was performed on the resin prepared using the compound of the present invention obtained in the synthesis example. That is, after the resin film formed on the wafer using the resin prepared using the compound of the present invention was transferred to the substrate side by etching, evaluation was performed by performing defect evaluation. A 12-inch silicon wafer was subjected to thermal oxidation treatment to obtain a substrate having a silicon oxide film with a thickness of 100 nm. On the substrate, after adjusting the spin coating conditions so that the resin solution of the resin prepared using the compound of the present invention has a thickness of 100 nm and forming a film, baking at 150 °C for 1 minute and then baking at 350 °C for 1 minute were performed to laminate the resin prepared using the compound of the present invention on silicon with a thermal oxide film. A laminated substrate was produced. Using TELIUS (manufactured by Tokyo Electron Limited) as the etching apparatus, the resin film was etched under the conditions of CF4 / O2 / Ar to expose the substrate on the surface of the oxide film. Further, etching treatment was performed under the condition of etching the oxide film by 100 nm with the gas composition ratio of CF4 / Ar, and an etched wafer was produced. The fabricated etched wafer was inspected for defects with a defect inspection apparatus SP5 (manufactured by KLA-Tencor) to measure the number of defects of 19 nm or more, and this was carried out as a defect evaluation by the etching process in the laminated film.

[0146] (Example E01) Purification of M1 resin with acid A 1000 mL four-necked flask (bottom-drained type) was charged with 150 g of a solution (10% by mass) in which the M1 resin obtained in Synthesis Example 1 was dissolved in PGMEA, and heated to 80 °C while stirring. Next, 37.5 g of an oxalic acid aqueous solution (pH 1.3) was added, and after stirring for 5 minutes, it was allowed to stand for 30 minutes. As a result, it separated into an oil phase and an aqueous phase, so the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was charged into the obtained oil phase, stirred for 5 minutes, allowed to stand for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, while heating to 80 °C, the pressure inside the flask was reduced to 200 hPa or less to concentrate and distill off the residual moisture and PGMEA. Then, it was diluted with EL grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of M1 resin with reduced metal content. After preparing a solution sample by filtering a solution containing the resin prepared using the obtained compound of the present invention through a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. under the condition of 0.5 MPa, an etching defect evaluation of the laminated film was carried out.

[0147] (Example E02) Purification of M2 resin with acid A four-necked flask (bottom-drained type) with a capacity of 1000 mL was charged with 140 g of a solution (10% by mass) in which the M2 resin obtained in Synthesis Example 2 was dissolved in PGMEA, and the mixture was heated to 60 °C while stirring. Next, 37.5 g of an oxalic acid aqueous solution (pH 1.3) was added, and after stirring for 5 minutes, the mixture was allowed to stand for 30 minutes. As a result, it was separated into an oil phase and an aqueous phase, so the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was charged into the obtained oil phase, and after stirring for 5 minutes, the mixture was allowed to stand for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, while heating to 80 °C, the pressure inside the flask was reduced to 200 hPa or less to concentrate and distill off the residual moisture and PGMEA. Thereafter, it was diluted with EL-grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of the M2 resin with a reduced metal content. After preparing a solution sample by filtering a solution containing a resin prepared using the obtained compound of the present invention through a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. under the condition of 0.5 MPa, an etching defect evaluation on the laminated film was carried out.

[0148] (Example E03) Purification by Filter Passing Inside a clean booth of Class 1000, 500 g of a 10% by mass solution in which the M1 resin obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) was charged into a four-necked flask (bottom-drain type) with a capacity of 1000 mL. Subsequently, after evacuating the air inside the kettle, nitrogen gas was introduced to return to atmospheric pressure. While introducing nitrogen gas at 100 mL per minute and adjusting the internal oxygen concentration to less than 1%, the mixture was heated to 30 °C with stirring. The above solution was withdrawn from the bottom drain valve and passed through a nylon hollow fiber membrane filter with a nominal pore diameter of 0.01 μm (manufactured by Kitz Microfilter Co., Ltd., trade name: Polyfix Nylon Series) at a flow rate of 100 mL per minute by a diaphragm pump via a fluororesin pressure-resistant tube under a pressure filtration condition with a filtration pressure of 0.5 MPa. The filtered resin solution was diluted with EL-grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and adjusted to a concentration of 10% by mass to obtain a PGMEA solution of the M1 resin with a reduced metal content. After preparing a solution sample by filtering a solution containing the resin prepared using the compound of the present invention obtained above through a UPE filter with a nominal pore diameter of 3 nm manufactured by Nippon Integris Co., Ltd. under a condition of 0.5 MPa, an etching defect evaluation on the laminated film was carried out. The oxygen concentration was measured by an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies hereinafter).

[0149] (Example E04) As a purification process using filters, IONKLEEN manufactured by Nippon Paul Co., Ltd., a nylon filter manufactured by Nippon Paul Co., Ltd., and a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. were connected in series in this order to construct a filter line. Except for using the fabricated filter line instead of a 0.1 μm nylon hollow fiber membrane filter, liquid was passed through by pressure filtration under the condition that the filtration pressure was 0.5 MPa in the same manner as in Example E03. It was diluted with EL grade PGMEA (reagent manufactured by Kanto Chemical Co., Inc.) and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of M1 resin with a reduced metal content. After creating a solution sample containing the resin created using the compound of the present invention and filtering it under pressure through a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. so that the filtration pressure was 0.5 MPa, an etching defect evaluation on the laminated film was carried out.

[0150] (Example E05) The solution sample created in Example E01 was further filtered under pressure using the filter line created in Example E04 so that the filtration pressure was 0.5 MPa to create a solution sample, and then an etching defect evaluation on the laminated film was carried out.

[0151] (Example E06) Regarding the M3 resin created in (Synthesis Example 3), after creating a solution sample purified in the same manner as in Example E05, an etching defect evaluation on the laminated film was carried out.

[0152] (Example E07) Regarding the M4 resin created in (Synthesis Example 4), after creating a solution sample purified in the same manner as in Example E05, an etching defect evaluation on the laminated film was carried out.

[0153] (Example E08) Regarding the M5 resin created in (Synthesis Example 5), after creating a solution sample purified in the same manner as in Example E05, an etching defect evaluation on the laminated film was carried out.

[0154] (Example E09) For the MAD1 resin prepared in (Synthesis Example 6), after preparing a solution sample purified by the same method as in Example E01, an etching defect evaluation on a laminated film was performed.

[0155] (Example E10) For the MAD1 resin prepared in (Synthesis Example 6), after preparing a solution sample purified by the same method as in Example E01, an etching defect evaluation on a laminated film was performed.

[0156]

Table 2

[0157] (Synthesis Example F01) Regarding the synthesized compound M1, before the synthesis of the polymer, purification treatment of each raw material was additionally carried out. Ethyl acetate (PrimePure, manufactured by Kanto Chemical Co., Inc.) was used as the solvent, and a 10% by mass ethyl acetate solution of compound M1 in which compound M1 was dissolved was prepared. For the purpose of removing metal impurities, the ion exchange resin "AMBERLYST MSPS2-1·DRY" (product name, manufactured by Organo Corporation) was immersed in ethyl acetate (manufactured by Kanto Chemical Co., Inc., PrimePure), and after stirring for 1 hour, washing by a method of removing the solvent was repeated 10 times to wash the ion exchange resin. For the above-mentioned ethyl acetate solution of compound M1, the washed ion exchange resin was added so as to have the same mass as the resin solid content, stirred at room temperature for one day, and then ion exchange treatment was carried out by a method of filtering off the ion exchange resin, and washing was repeated 3 times to prepare an ion-exchanged ethyl acetate solution of compound M1. Further, the same treatment was carried out for other monomers to prepare an ion-exchanged monomer-containing ethyl acetate solution. Using the obtained ion-exchanged monomer-containing ethyl acetate solution, and using Pruimepure manufactured by Kanto Chemical Co., Inc. of electronic grade as solvents such as n-heptane and tetrahydrofuran, and further using all reaction vessels such as flasks that had been immersed in nitric acid for 1 day and then washed with ultrapure water, a compound represented by the above chemical formula (P-MAC-0I) was obtained by the same scheme as in Synthesis Example 1. Further, in the post-treatment after synthesis, purification treatment was carried out using a 5 nm nylon filter (manufactured by Pall Corporation) and a 15 nm PTFE filter (manufactured by Entegris, Inc.) in this order, and then a white powdery polymer (M1-CL resin) (the chemical structure is a polymer represented by the formula (P-MAC-0I).) was obtained by drying under reduced pressure. The results of measuring the inorganic element content of the polymer by the above method are shown in Table 3.

[0158] (Synthesis Examples F02 to F06) Various polymers (M2-CL resin to M5-CL resin, MDA1-CL resin) were prepared in the same manner as in Synthesis Example 1, except that M2 to 5 and MAD1 were used instead of M1, respectively.

[0159] Regarding the prepared polymers, the metal content and the PE-CVD defect evaluation were carried out in the same manner as in Example E01.

[0160]

Table 3

[0161] According to the present invention, it is possible to provide a compound and a composition capable of forming a film having high resolution and sensitivity, a method for forming a resist pattern using the same, and a method for forming an insulating film.

Claims

1. A (co)polymer having a structural unit derived from a compound having one or more halogens and two or more substituents having an unsaturated double bond, A composition for forming a resist film, comprising: The composition, wherein the (co)polymer further has a structural unit having a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base.

2. The composition according to claim 1, wherein the compound is represented by the following general formula (A). 【Chemical 1】 (In formula (A), R １ , R ２ , and R ３ each independently represents a hydrogen atom, a halogen, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms. L represents a divalent linking group, A represents an organic group having 1 to 30 carbon atoms, X represents Cl, Br or I, or represents a hydrocarbon group having 1 to 30 carbon atoms containing a halogen atom selected from the group consisting of Cl, Br and I and bonded to A via a single bond, an ester group, an ether group, an amide group, an imide group, a urethane group, a urea group, a thioether group, a phosphine group or a phosphate ester group.) n ０ represents an integer from 2 to 5, n ２ represents an integer from 1 to 5.)

3. The composition according to claim 2, wherein the general formula (A) is represented by the general formula (1). 【Chemical Formula 2】 (In formula (1), R １ represents a hydrogen atom, a halogen or a methyl group, R ４ each independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms, A represents an organic group having 1 to 30 carbon atoms.) n ０ represents an integer from 2 to 5, n １ represents 0 or 1, n ２ represents an integer from 1 to 5.)

4. The composition according to claim 2 or 3, wherein A contains an aromatic ring.

5. The composition according to any one of claims 1 to 4, wherein the contents of Fe, Al, Sb, Ru and W in the (co)polymer are less than 1 ppm.

6. A composition for forming a resist film, comprising a compound having one or more halogens and two or more substituents having an unsaturated double bond, and / or a (co)polymer having a structural unit derived from the compound, The composition further comprising an acid generator, a photo base generator, or a base compound.

7. A step of forming a film on a wafer of a composition for forming a resist film, comprising a compound having one or more halogens and two or more substituents having an unsaturated double bond, and / or a (co)polymer having a structural unit derived from the compound, A step of forming an optical image as a pattern on the resist film on the wafer by exposure, and A step of forming a resist pattern based on the optical image by development processing, A pattern forming method comprising:

8. A method for forming an insulating film, comprising the method according to claim 7.

9. A structural unit derived from a compound having one or more halogens and two or more substituents having an unsaturated double bond, and A structural unit having a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base, A copolymer having:

10. A compound having one or more halogens and two or more substituents having an unsaturated double bond, and / or a (co)polymer having a structural unit derived from the compound, and an acid generator, a photo-base generator, or a base compound, A resist composition containing the same.

11. A step of forming a film of the resist composition according to Claim 10 on a wafer, A step of forming an optical image as a pattern on the resist film on the wafer by exposure, and A step of forming a resist pattern based on the optical image by development processing, A pattern forming method including the same.

12. A method for forming an insulating film including the method according to Claim 11.

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