Composition for lithography and pattern formation method

Abstract

To provide a composition for lithography that enables pattern formation with excellent exposure sensitivity and that is capable of yielding a film in contact with a resist layer or an underlayer film.SOLUTION: The present invention provides a composition for lithography containing a compound having at least one element selected from the group consisting of iodine, tellurium, and fluorine, or a resin having a constituent unit derived from the compound, wherein the total mass of the atoms in the compound is 15 mass% or more and 75 mass% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition for lithography and a method for forming a pattern.

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: Extreme Ultraviolet) lithography (13.5 nm) has been progressing. In addition, an electron beam (EB: Electron Beam) is also used for forming a fine pattern. Among these, in particular, lithography using extreme ultraviolet rays has an increasing number of introduction examples due to recent technological advancements.

[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 (for example, see 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 electron beams or extreme ultraviolet light has a reaction mechanism different from that of ordinary optical lithography (Non-Patent Document 2, Non-Patent Document 3). Furthermore, in lithography using electron beams or extreme ultraviolet light, the formation of fine patterns with dimensions of several nanometers to a dozen or so nanometers is targeted. When the size of the resist pattern becomes smaller in this way, a resist composition with even higher sensitivity to the exposure light source is required. In particular, in lithography using extreme ultraviolet light, 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

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the resist compositions developed so far with highly sensitive characteristics have problems such as insufficient pattern quality, such as large pattern defects and roughness, or insufficient improvement in sensitivity, and insufficient etching resistance. Based on these situations, a lithography technique that achieves both high resolution and high sensitivity is required.

[0008] In addition, in lithography using extreme ultraviolet light, since a wavelength as short as 13.5 nm is used, compared with conventional exposure techniques, the photon permeability is high and the number of photons at the same exposure intensity is small. Therefore, it is necessary to efficiently convert extreme ultraviolet light into protons required for exposure. Furthermore, it is also necessary to supply protons from the layer adjacent to the resist.

[0009] In view of the above circumstances, an object of the present invention is to provide a composition for lithography and a pattern forming method capable of forming a pattern excellent in exposure sensitivity, which can obtain a film (hereinafter referred to as "resist layer contact film") in contact with the resist layer and an underlying film.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that by using a compound having a specific elemental composition or a resin containing the compound as a structural unit in the resist layer contact film or the underlying film, the exposure sensitivity in the lithography process can be increased, and thus the present invention has been completed. That is, the present invention is as follows.

[0011] [1] A composition for lithography comprising a compound having at least one element selected from the group consisting of iodine, tellurium, and fluorine, or a resin having a structural unit derived from the compound, wherein the total mass of the atoms in the compound is 15% by mass or more and 75% by mass or less, the composition for lithography. [2] The lithography composition according to [1], wherein the at least one element is at least one element selected from the group consisting of iodine and tellurium. [3] The lithography composition according to [1] or [2], wherein the at least one element is iodine, and the mass of the iodine in the compound is 15% by mass or more and 75% by mass or less. [4] The lithography composition according to any one of [1] to [3], wherein the compound is represented by formula (A-4a).

Chemical formula

Chemical formula

Chemical formula

[10] The lithography composition according to any one of [1] to [9-6], further containing a solvent.

[11] The lithography composition according to any one of [1] to

[10] , further containing an acid generator.

[12] The lithography composition according to any one of [1] to

[11] , further containing an acid diffusion accelerator.

[13] The lithography composition according to any one of [1] to

[12] , further containing an acid diffusion inhibitor.

[14] The lithography composition according to any one of [1] to

[13] , further containing a crosslinking agent.

[15] The lithography composition according to any one of [1] to

[14] , which is cured after film formation.

[16] The lithography composition according to any one of [1] to

[15] for forming a resist layer contact film.

[17] The lithography composition according to any one of [1] to

[15] for forming a lower layer film.

[18] A lower layer film forming step of forming a lower layer film on a substrate using the lithography composition according to

[17] , A photoresist film forming step of forming at least one layer of photoresist film on the lower layer film formed by the lower layer film forming step, A step of irradiating a predetermined region of the photoresist film formed by the photoresist film forming step with radiation and developing it. A resist pattern forming method including the above steps.

[19] A lower layer film forming step of forming a lower layer film on a substrate, A resist layer contact film forming step of forming a resist layer contact film on the lower layer film formed by the lower layer film forming step using the lithography composition according to

[16] , A photoresist film forming step of forming at least one layer of photoresist film on the resist layer contact film formed by the resist layer contact film forming step. A resist pattern forming step of irradiating a predetermined area of the photoresist film formed by the photoresist film forming step with radiation and developing to form a resist pattern; A pattern forming step of etching the resist layer contact film, or the resist layer contact film and the lower layer film using the resist pattern formed by the resist pattern forming step as a mask to form a pattern; A substrate pattern forming step of etching the substrate using the pattern formed by the pattern forming step as a mask to form a pattern on the substrate; A circuit pattern forming method including:

[20] A compound represented by formula (A-4a). [Chemical formula] (In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond or no crosslinking; Y is a divalent group having 1 to 60 carbon atoms or a single bond; Here, when X is no crosslinking, Y is the divalent group; R 0 Each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group; Here, at least one of R 0 is a hydroxyl group; m is each independently an integer from 1 to 9; Q represents iodine, tellurium, fluorine, or an alkyl group having 1 to 30 carbon atoms containing at least iodine or tellurium or fluorine, or an aryl group having 6 to 40 carbon atoms containing at least iodine or tellurium or fluorine; n is an integer from 1 to 4; p is each independently an integer from 0 to 3; Q, R 0, at least one of Y contains at least one element of iodine, tellurium, and fluorine, q is independently an integer from 0 to (4 + 2×p - m).) [20-1] The compound according to

[20] , wherein X is an oxygen atom or unbridged. [20-2] The compound according to

[20] or [20-1], wherein Q is iodine. [20-3] Q, R 0 The compound according to any one of

[20] to [20-2], wherein at least one of Y contains iodine. [20-4] The compound according to any one of

[20] to [20-3], wherein q is independently an integer from 1 to (4 + 2×p - m).

[21] The compound according to any one of

[20] to [20-4], wherein Y is a 2n-valent hydrocarbon group having an aryl group with 6 to 60 carbon atoms which may have a substituent. [21-1] The compound according to

[21] , wherein the 2n-valent hydrocarbon group is a methylene group. [21-2] The compound according to

[21] or [21-1], wherein the aryl group with 6 to 60 carbon atoms is a phenyl group or a biphenyl group. [21-3] The compound according to any one of

[21] to [21-2], wherein the substituent is iodine.

[22] The compound represented by formula (A-4c).

Chemical formula

[22] , wherein X is an oxygen atom or uncrosslinked.

[23] The compound according to

[22] or [22-1], wherein Y is a 2n-valent hydrocarbon group having an optionally substituted aryl group having 6 to 60 carbon atoms. [23-1] The compound according to

[23] , wherein the 2n-valent hydrocarbon group is a methylene group. [23-2] The compound according to

[23] or [23-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group. [23-3] The compound according to any one of

[23] to [23-2], wherein the substituent is iodine. [Advantages of the Invention]

[0012] According to the present invention, there can be provided a lithography composition capable of enhancing the exposure sensitivity in a lithography process, and a pattern forming method. [Embodiments for Carrying Out the Invention]

[0013] Hereinafter, embodiments of the present invention will be described (hereinafter, may be referred to as "the present embodiment"). Note 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] [Compound (A) and Resin (A)] The compound according to the present embodiment (hereinafter, also referred to as "compound (A)"), and a resin having a structural unit derived from the compound (hereinafter, also referred to as "resin (A)") have at least one element selected from the group consisting of iodine, tellurium, and fluorine (preferably, the group consisting of iodine and tellurium). Since iodine and tellurium have a high extreme ultraviolet absorption ability, they can absorb extreme ultraviolet rays to ionize compound (A) and efficiently generate protons.

[0015] The total content of iodine and tellurium atoms is 15% by mass or more and 75% by mass or less of the whole compound (A), preferably 20% by mass or more and 75% by mass or less. When the total content of iodine and tellurium is 15% by mass or less, the extreme ultraviolet absorption ability becomes low, so the proton generation efficiency becomes low. Also, when the total content of iodine and tellurium is 75% by mass or more, the stability of the compound becomes low and it is likely to decompose.

[0016] From the viewpoint of high density, compound (A) preferably contains an aromatic ring. When the density is improved, the absorption rate per passing length of extreme ultraviolet rays is improved. Also, from the viewpoint of the adhesion to a substrate or a resist layer, compound (A) preferably contains a hydrophilic group such as a hydroxyl group.

[0017] The "hydrophilic group" means a group that, when bonded to an organic compound, improves the affinity between the organic compound and water. Examples of the hydrophilic group include a hydroxyl group, a nitro group, an amino group, a carboxyl group, a thiol group, a phosphine group, a phosphon group, a phosphate group, an ether group, a thioether group, a urethane group, a urea group, an amide group, and an imide group.

[0018] Compound (A) preferably has curability and solvent resistance after curing so as to form a film and be insoluble in the resist solution when the resist is applied. For this reason, for example, it is also preferable that compound (A) contains a crosslinkable group or a polymerizable group.

[0019] The "crosslinkable group" 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 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. The "polymerizable group" refers to a group that polymerizes in the presence or absence of a catalyst. The polymerizable group is not particularly limited, and examples thereof include a group having a (meth)acrylic group, a group having an unsaturated double bond such as a vinyl group, and a group having an unsaturated triple bond such as a propargyl group.

[0020] It is also preferable that compound (A) contains a dissociable group. The "dissociable group" refers to a group that dissociates in the presence or absence of a catalyst. Among the dissociable groups, the acid dissociable group refers to a characteristic group that cleaves in the presence of an acid and changes to an alkali-soluble group or the like. Specific examples of the acid dissociable group can include those described in International Publication No. 2016 / 158168. Preferable examples of the acid dissociable group include a group selected from the group consisting of a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group, which have the property of dissociating by an acid.

[0021] As the resin (A), in addition to the resin obtained by polymerizing compound (A) alone, a resin polymerized using a crosslinking agent, a resin copolymerized with other compounds, etc. can also be used, and it is not particularly limited.

[0022] The weight average molecular weight of the resin (A) is preferably from 300 to 20,000, more preferably from 300 to 10,000, and still more preferably from 300 to 8,000, from the viewpoints of reducing defects in the formed film and obtaining a good pattern shape. The weight average molecular weight can be a value measured by GPC in terms of polystyrene equivalent weight average molecular weight.

[0023] For the production of the resin (A), any known method can be used without limitation as long as it can produce a resin having the compound (A) as a structural unit. For example, methods of crosslinking with aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, etc., and methods of copolymerizing with unsaturated hydrocarbon group-containing compounds, etc. can be mentioned. Examples of the "unsaturated hydrocarbon group-containing compound" are not particularly limited, and examples include compounds having a (meth)acrylic group, compounds having an unsaturated double bond such as a vinyl group, and compounds having an unsaturated triple bond such as a propargyl group.

[0024] The resin (A) can also be obtained during the synthesis reaction of the compound (A). For example, when synthesizing the compound (A), a method of obtaining the resin (A) from the raw materials of the compound (A) may be adopted.

[0025] The compound (A) is preferably a compound (A-1) represented by the formula (A-1) containing at least one selected from the group consisting of iodine, tellurium, and fluorine in a predetermined amount.

Chemical formula

[0026] It is also preferable that the compound (A) is a compound (A-2) represented by the formula (A-2) containing one or more selected from the group consisting of iodine, tellurium and fluorine in a predetermined amount.

Chemical formula

[0027] Compound (A) is preferably a compound (A-3) represented by formula (A-3) containing one or more selected from the group consisting of a predetermined amount of iodine, tellurium, and fluorine. [Chemical formula] (In formula (A-3), each R is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 12 carbon atoms, Z is an n-valent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom, n is 2 or more, and at least one selected from Z or R is a group containing one or more selected from the group consisting of an iodine atom, a tellurium atom, and a fluorine atom.)

[0028] Compound (A) is preferably a compound (A-4a) or a compound (A-4b) represented by formula (A-4a) or formula (A-4b) containing one or more selected from the group consisting of a predetermined amount of iodine, tellurium, and fluorine. The resin having a structural unit derived from compound (A) of the present invention may be a polycyclic polyphenol resin having a structural unit derived from compound (A-4a) and / or compound (A-4b). The polycyclic polyphenol resin in this embodiment is a polycyclic polyphenol resin having a repeating unit derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds (A-4a) and (A-4b), and the repeating units are linked by direct bonding of aromatic rings to each other. Since the film-forming composition of this embodiment is configured in this way, it has excellent film-forming properties, heat resistance, and sublimation resistance. [Chemical formula] (In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. Y represents a 2n-valent group having 1 to 60 carbon atoms or a single bond. Here, when X has no crosslinking, Y is the 2n-valent group. Further, in formula (A-4b), A represents a benzene ring or a condensed ring. Furthermore, in formulas (A-4a) and (A-4b), R 0 each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group, or a hydroxyl group. Here, at least one of R 0 is a hydroxyl group, and m is each independently an integer from 1 to 9. Q represents iodine, tellurium, fluorine, or an alkyl group having 1 to 30 carbon atoms containing at least iodine or tellurium or fluorine, or an aryl group having 6 to 40 carbon atoms containing at least iodine or tellurium or fluorine. n is an integer from 1 to 4, and p is each independently an integer from 0 to 3. At least one of Q, R 0 contains at least one element of iodine, tellurium, or fluorine. In formula (A-4a), q is each independently an integer from 0 to (4 + 2×p - m). In formula (A-4b), q is each independently an integer from 0 to (2 + 2×p - m) (where p represents the number of condensed rings in the condensed ring structure in formula (A-4b).).)

[0029] X in formula (A-4a) is preferably an oxygen atom from the viewpoints of heat resistance and reactivity. Further, p in formula (A-4a) is preferably 1 from the viewpoints of heat resistance and solubility. Furthermore, formula (A-4a) preferably contains an iodine atom in at least one of R 0 from the viewpoint of reactivity, and more preferably does not contain an iodine atom in Y from the viewpoint of storage stability.

[0030] Formula (A-4a) is preferably formula (A-4c).

Chemical formula

[0031] (Polycyclic polyphenol resin) The polycyclic polyphenol resin in this embodiment is not limited to the following, but typically has the following characteristics (1) to (5). (1) The polycyclic polyphenol resin in this embodiment has excellent solubility in organic solvents (especially safe solvents). Therefore, for example, when the polycyclic polyphenol resin in this embodiment is used as a film-forming material for lithography, a film for lithography can be formed by a wet process such as spin coating or screen printing. (2) In the polycyclic polyphenol resin in this embodiment, the carbon concentration is relatively high and the oxygen concentration is relatively low. In addition, since it has phenolic hydroxyl groups in the molecule, it is useful for the formation of a cured product by reaction with a curing agent, but even alone, a cured product can be formed by the crosslinking reaction of phenolic hydroxyl groups during high-temperature baking. Due to these, the polycyclic polyphenol resin in this embodiment can exhibit high heat resistance, and when used as a film-forming material for lithography, deterioration of the film during high-temperature baking is suppressed, and a film for lithography excellent in etching resistance to oxygen plasma etching or the like can be formed. (3) As described above, the polycyclic polyphenol resin in this embodiment can exhibit high heat resistance and etching resistance, and also has excellent adhesion to a resist layer or a resist intermediate layer film material. Therefore, when used as a film-forming material for lithography, a lithography film excellent in resist pattern formability can be formed. Here, the "resist pattern formability" refers to a property in which no large defects are observed in the resist pattern shape, and both the resolution and sensitivity are excellent. (4) The polycyclic polyphenol resin in this embodiment has a high refractive index due to its high aromatic ring density, and is also excellent in transparency because coloring is suppressed even by heat treatment in a wide range from low temperature to high temperature. Therefore, it is also useful as a material for forming various optical components. (5) By having Q as a functional group, the polycyclic polyphenol resin in this embodiment can improve the absorption rate with respect to the EUV exposure light source, and can lead to an improvement in productivity by improving the sensitivity and suppressing pattern defects such as pattern collapse when used as a lower layer film for lithography.

[0032] Due to such characteristics, the polycyclic polyphenol resin in this embodiment can be preferably applied as a film-forming material for lithography. Therefore, it is considered that the desired characteristics described above are imparted to the film-forming composition of this embodiment. The film-forming composition of this embodiment is not particularly limited in the remaining configuration as long as it contains the polycyclic polyphenol resin described above. That is, it may contain any optional component in any blending ratio, and can be appropriately adjusted according to the specific use of the film-forming composition.

[0033] Hereinafter, the aforementioned formulas (A-4a) and (A-4b) will be described in detail. In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. From the viewpoint of heat resistance, an oxygen atom is preferable as X.

[0034] In formula (A-4a), Y is a divalent group having 1 to 60 carbon atoms or a single bond. Here, when X has no crosslinking, Y is the divalent group. The divalent group having 1 to 60 carbon atoms is, for example, a divalent hydrocarbon group, and the hydrocarbon group may have various functional groups described below as substituents. Further, when n = 1, the divalent hydrocarbon group is an alkylene group having 1 to 60 carbon atoms, when n = 2, it is an alkanetetrayl group having 1 to 60 carbon atoms, when n = 3, it is an alkanhexylyl group having 2 to 60 carbon atoms, and when n = 4, it is an alkanoctylyl group having 3 to 60 carbon atoms. Examples of the divalent hydrocarbon group include a group in which a (2n + 1)-valent hydrocarbon group is bonded to a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. Examples of the (2n + 1)-valent hydrocarbon group include, but are not limited to, a trivalent methine group, an ethine group, etc. Further, the divalent hydrocarbon group may have a double bond, a heteroatom, and / or an aryl group having 6 to 59 carbon atoms. Note that Y may include a group derived from a compound having a fluorene skeleton such as fluorene or benzofluorene, but in this specification, the term "aryl group" is used to exclude a group derived from a compound having a fluorene skeleton such as fluorene or benzofluorene.

[0035] In the present embodiment, the divalent group may contain a halogen group, a nitro group, an amino group, a hydroxyl group, an alkoxy group, a thiol group, or an aryl group having 6 to 40 carbon atoms. Further, the divalent group may contain an ether bond, a ketone bond, an ester bond, or a double bond.

[0036] In the present embodiment, from the viewpoint of heat resistance, the divalent group preferably contains a branched hydrocarbon group or an alicyclic hydrocarbon group rather than a linear hydrocarbon group, and more preferably contains an alicyclic hydrocarbon group. Further, in the present embodiment, it is particularly preferable that the divalent group has an aryl group having 6 to 60 carbon atoms.

[0037] Substituents that may be included in the 2n-valent group. The linear hydrocarbon group and the branched hydrocarbon group are not particularly limited. For example, unsubstituted methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-dodecyl group, barrel group, etc. can be mentioned. Substituents that may be included in the 2n-valent group. The alicyclic hydrocarbon group and the aromatic group having 6 to 60 carbon atoms are not particularly limited. For example, unsubstituted phenyl group, naphthalene group, biphenyl group, anthracyl group, pyrenyl group, cyclohexyl group, cyclododecyl group, dicyclopentyl group, tricyclodecyl group, adamantyl group, phenylene group, naphthalenediyl group, biphenyldiyl group, anthracenediyl group, pyrenediyl group, cyclohexanediyl group, cyclododecanediyl group, dicyclopentanediyl group, tricyclodecanediyl group, adamantanediyl group, benzenetriyl group, naphthalenetriyl group, biphenyltriyl group, anthracenetriyl group, pyrenetriyl group, cyclohexanetriyl group, cyclododecanetriyl group, dicyclopentanetriyl group, tricyclodecanetriyl group, adamantanetriyl group, benzenetetrayl group, naphthalenetetrayl group, biphenyltetrayl group, anthracenetetrayl group, pyrenetetrayl group, cyclohexanetetrayl group, cyclododecanetetrayl group, dicyclopentanetetrayl group, tricyclodecanetetrayl group, adamantanetetrayl group, etc. can be mentioned.

[0038] R 0 Each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group. Here, the alkyl group may be linear, branched or cyclic. Here, R 0 At least one of them is a hydroxyl group.

[0039] Examples of the alkyl group having 1 to 40 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-dodecyl group, barrel group and the like. Examples of the aryl group having 6 to 40 carbon atoms include, but are not limited to, phenyl group, naphthalene group, biphenyl group, anthracyl group, pyrenyl group, perylene group and the like. Examples of the alkenyl group having 2 to 40 carbon atoms include, but are not limited to, ethynyl group, propenyl group, butynyl group, pentynyl group and the like. Examples of the alkynyl group having 2 to 40 carbon atoms include, but are not limited to, acetylene group, ethynyl group and the like. Examples of the alkoxy group having 1 to 40 carbon atoms include, but are not limited to, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy and the like.

[0040] m is each independently an integer of 1 to 9. From the viewpoint of solubility, 1 to 6 are preferable, 1 to 4 are more preferable, and from the viewpoint of raw material availability, 1 is even more preferable.

[0041] n is an integer of 1 to 4. From the viewpoint of solubility, 1 to 2 are preferable, and from the viewpoint of raw material availability, 1 is even more preferable.

[0042] p is each independently an integer of 0 to 3. From the viewpoint of heat resistance, 1 to 2 are preferable, and from the viewpoint of raw material availability, 1 is even more preferable.

[0043] In this embodiment, the aromatic hydroxy compound may be used alone or in combination of two or more of those represented by the above formulas (A-4a) and (A-4b). In this embodiment, from the viewpoint of achieving both solvent solubility and heat resistance, it is preferable to employ the one represented by the above formula (A-4a) as the aromatic hydroxy compound. Also, from the viewpoint of achieving both solvent solubility and heat resistance, it is preferable to employ the one represented by the above formula (A-4b) as the aromatic hydroxy compound.

[0044] The compound (A) of this embodiment may be an oligomer (A-5) having an aralkyl structure represented by the following formula (A-5) and containing one or more selected from a predetermined amount of iodine, tellurium, and fluorine.

Chemical formula

[0045] In the oligomer (A-5), Ar 0 represents a divalent group containing a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrylene group, a fluorylene group, a biphenylene group, or a terphenylene group, and a divalent group containing a phenylene group, a naphthylene group, an anthrylene group, or a pyrylene group is preferable. Ar 0 each independently may be the same group or different groups. Ar 0Specific examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, a 2,4'-biphenylene group, a 2,2'-biphenylene group, a 2,3'-biphenylene group, a 3,3'-biphenylene group, a 3,4'-biphenylene group, a 2,6-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,8-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group, an anthrylene group, a phenanthrylene group, a pyrylene group, a fluorene group, a terphenyl group, etc. Further, the Ar 0 includes a divalent group containing a diphenylmethyl structure, a bisphenol structure, or a bis(hydroxyphenyl)diisopropylphenyl structure, and also includes a divalent group in which a plurality of phenylene groups such as these are linked by an alkylene group or the like. R 0 is a substituent of Ar 0 and each independently represents an alkyl group having 1 to 30 carbon atoms which may be the same or different and may have a substituent, or an aryl group which may have a substituent. Specific examples of R 0 include specific examples of R a and R b described later.

[0046] In oligomer (A-5), n represents an integer of 1 to 50. From the viewpoint of the planarization performance of the film, n is preferably 3 to 40, more preferably 3 to 30, and particularly preferably 3 to 20.

[0047] In oligomer (A-5), r 0 each independently represents an integer of 0 to 3. However, all r 0 do not simultaneously become 0. From the viewpoints of curability and solubility improvement, r 0 is preferably 1 to 3.

[0048] In oligomer (A-5), p each independently represents an integer of 0 or more. However, all p do not simultaneously become 0. p appropriately changes according to the type of Ar 0 .

[0049] Compound (A) is preferably a compound (A-6) represented by formula (A-6) containing at least one selected from a predetermined amount of iodine, tellurium, and fluorine. [Chemical formula]

[0050] In formula (A-6), R 1 represents a hydrogen atom, a methyl group, or a halogen group, R 2 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, Q each independently represents iodine, tellurium, fluorine, or an alkyl group or aryl group having 1 to 30 carbon atoms containing at least iodine or tellurium or fluorine, preferably Q is iodine, n 1 represents 0 or 1, n 2 represents an integer from 1 to 20.

[0051] R 1 can be a hydrogen atom, a methyl group, or a halogen group. As the halogen group, known atoms can be used, and F, Cl, Br, I, etc. can be used as appropriate. R 1 is preferably a methyl group or a halogen group from the viewpoints of exposure sensitivity and material stability when the compound of the present invention is used as a constituent unit of a resist resin, and more preferably a halogen group from the viewpoint of exposure sensitivity, and even more preferably I.

[0052] R 2 may 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.

[0053] R 2It is preferably a hydrogen atom for the purpose of suppressing the increase in the Tg of the resin and improving the introduction effect of the iodine element. Also, for the purpose of controlling the solubility in the developer, it is preferably an organic group having 1 or more carbon atoms for the purpose of improving the acid decomposability. Further, for the purpose of suppressing the acid decomposability and particularly ensuring the solubility in an alkaline developer and suppressing the residue, it is preferably a hydrogen atom.

[0054] R 2 may have a substituent. R 2 Examples of R include an alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms which may have a substituent; an alkenyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms which may have a substituent; an alkynyl group having 2 to 20 carbon atoms, 2 to 10 carbon atoms, or 2 to 6 carbon atoms which may have a substituent: a cycloalkyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms which may have a substituent; a cycloalkenyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms which may have a substituent; a cycloalkynyl group having 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms which may have a substituent; an aryl group having 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.

[0055] R 2 Specific examples of R 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.

[0056] Here, the exemplified groups include isomers. For example, the propyl group includes the n-propyl group and the isopropyl group, and the butyl group includes the n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group.

[0057] R 2 The substituents of R are not particularly limited. For example, they 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.

[0058] 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. For example, it includes 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.

[0059] The "acid dissociable group" is a group that cleaves in the presence of an acid to generate an alkali-soluble group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group, etc.). The acid dissociable group is not particularly limited. For example, it can be appropriately selected from those proposed in a hydroxystyrene resin, a (meth)acrylic acid resin, etc. used in a chemically amplified resist composition for KrF or ArF. Specific examples of the acid dissociable group can include those described in International Publication No. 2016 / 158168.

[0060] A may have a substituent. Examples of the compound that forms the backbone of A include, for example, an alkane 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; an alkene 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; an alkyne 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; a cycloalkane 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; a cycloalkene 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; a cycloalkyne 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; an arene 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.

[0061] Specific examples of the compound that forms the backbone 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.

[0062] The substituents of the compound forming 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, and various crosslinkable groups and acid dissociable groups.

[0063] The "crosslinkable group" and "acid dissociable group" are not particularly limited, and for example, those described in the description of the above R 2 can be used.

[0064] n 1 represents 0 or 1, and is preferably 1.

[0065] n 2 is an integer of 1 to 20, preferably an integer of 2 to 20, more preferably an integer of 2 to 10, and still more preferably an integer of 2 to 5.

[0066] The compound (A) according to this embodiment may be a compound (A-7) represented by the following formula (A-7) containing one or more selected from a predetermined amount of iodine, tellurium, and fluorine. The compound (A-7) preferably contains a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base. It is preferable that any of the following Z, Y, and X contains a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base.

Chemical formula

[0067] In formula (A-7), X is each independently tellurium, I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having 1 or more and 5 or less substituents selected from the group consisting of tellurium, I, F, Cl, and Br. At least one of X is tellurium or I.

[0068] L 1 is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. Among these, L 1 is preferably a single bond.

[0069] m is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and still more preferably 2 or 3.

[0070] Y are each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, and phosphate group of the Y may have a substituent.

[0071] Y is preferably each independently a group represented by the following formula (Y-1).

Chemical formula

[0072] In formula (Y-1), L 2 is a group that is cleaved by the action of an acid. Examples of the group that is cleaved by the action of an acid include an ester group [* 1 -O-(C=O)-* 2 or * 1 -(C=O)-O-* 2 , an acetal group [* 1 -O-(C(R 21 ) 2 )-O-* 2 (R 21 is each independently H, or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [*1 -O-R 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms.)], and a carbonate group [* 1 -O-(C=O)-O-* 2 , and at least one divalent linking group selected from the group consisting of.] is exemplified. In the formula, * 1 is a bonding site with A, * 2 is R 2 is a bonding site with R. Among these, L 2 is preferably an acetal group, a carbonate group or a carboxyalkoxy group.

[0073] R 2 is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched or cyclic aliphatic group containing a heteroatom having 1 to 30 carbon atoms, or an aromatic group containing a heteroatom having 1 to 30 carbon atoms. The aliphatic group, aromatic group, aliphatic group containing a heteroatom, and aromatic group containing a heteroatom of the said R 2 may further have a substituent. Here, examples of the substituent include a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms and an aromatic group having 6 to 20 carbon atoms. R 2 Among these, an aliphatic group is preferable. The aliphatic group in R 2 is preferably a branched or cyclic aliphatic group. The number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and still more preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, and a methylcyclohexyl group. Among these, a tert-butyl group or a cyclohexyl group is preferable.

[0074] L 2 is * 1 -(C=O)-O-* 2When it is a carboxyalkoxy group and is cleaved by the action of an acid, a carboxylic acid group is formed, and the solubility difference and dissolution rate difference between the developed part and the undeveloped part in the development treatment are enlarged, so that the resolution is improved. In particular, the residue at the bottom of the pattern in the fine line pattern is suppressed, which is preferable.

[0075] Y is preferably a group represented by any one of the following formulas (Y-1-1) to (Y-1-7) independently of each other.

Chemical formula

[0076] n is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 1 or more and 5 or less, still more preferably an integer of 1 or more and 3 or less, and even more preferably 1 or 2.

[0077] R a 、R b 、and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent. The substituent of the organic group having 1 to 60 carbon atoms is not particularly limited, and examples thereof include I, F, Cl, Br, or other substituents. The other substituents are not particularly limited, and examples thereof include a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphonate group, a urethane group, a urea group, an amide group, an imide group, and a phosphate group. Among these, the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphonate group, urethane group, urea group, amide group, imide group, and phosphate group may further have a substituent. The substituents here include linear, branched or cyclic aliphatic groups having 1 to 20 carbon atoms and aromatic groups having 6 to 20 carbon atoms.

[0078] R a 、R b 、and R cIn this case, the number of carbon atoms of the organic group which may have a substituent is preferably 1 to 30.

[0079] The organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, and examples thereof include a linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms, an alicyclic hydrocarbon group having 4 to 60 carbon atoms, and an aromatic group which may contain a hetero atom and has 6 to 60 carbon atoms. The linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a valeryl group, and a 2-ethylhexyl group.

[0080] The alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, and an adamantyl group. Further, an aromatic group which may contain a hetero atom such as a benzodiazole group, a benzotriazole group, and a benzothiadiazole group can also be appropriately selected. In addition, a combination of these organic groups can be selected.

[0081] The aromatic group which may contain a hetero atom and has 6 to 60 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a benzodiazole group, a benzotriazole group, and a benzothiadiazole group.

[0082] Among these organic groups having 1 to 60 carbon atoms which may have a substituent, a methyl group is preferred.

[0083] A is an organic group having 1 to 30 carbon atoms. A may be a monocyclic organic group or a polycyclic organic group. A is preferably an aromatic ring. The number of carbon atoms of A is preferably 6 to 14, and more preferably 6 to 10. A is preferably a group represented by any one of the following formulas (A-1) to (A-4), and more preferably a group represented by the following formula (A-1).

[0084]

Chemical formula

[0085] p represents the number of vinyl groups, and p is an integer of 1 or more, preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and still more preferably 1.

[0086] Z are each independently an alkoxy group, an ester group, an acetal group, or a carbonate ester group. r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and still more preferably 0.

[0087] The resin having a structural unit derived from the compound (A) of the present embodiment may have a structural unit represented by the following formula (A-8). By using the resist composition containing this resin component, it is possible to achieve high sensitivity in the lithography process and high resolution by expanding the solubility contrast of the resin in development.

Chemical formula

[0088] The (meth)acrylate (co)polymer represented by the above formula (A-8) can be obtained by polymerizing one or more (meth)acrylate compounds represented by the above formula (A-6), or by polymerizing one or more (meth)acrylate compounds represented by the above formula (A-6) together with other monomers. The (meth)acrylate (co)polymer can be used as a material for forming a film for lithography. When the compound (A) of the present embodiment and the resin derived from the compound (A) are used as an underlayer film of a resist in an exposure process, they are used as an underlayer film of a resist layer and laminated on a layer to be processed such as a dry etching process after pattern formation on the layer to be processed to form an underlayer film layer and process the layer to be processed. When using such a process, from the viewpoint of etching mask performance for improving pattern quality such as rectangularity and roughness after processing of the layer to be processed, it is preferable to have a high carbon content, a low hydrogen content, and a high ring structure introduction rate so that the etching rate can be suppressed, and it is preferable to use a resin having a monocyclic structure or a condensed ring structure in which two or more ring structures are condensed as the compound structure. At this time, the ring structure preferably has an aromatic structure or a heteroaromatic structure. Further, when the compound (A) of the present embodiment and the resin derived from the compound (A) are used as a resist underlayer film, and one or more other spin-on carbon (SOC) layers or inorganic hard mask layers are used as an etching mask layer, from the viewpoint of the processability of the etching mask layer which is the target for transferring the pattern shape of the resist layer by etching, and from the shape of the resist immediately after development, so as not to deteriorate the pattern shape by etching, a resist underlayer film made of the compound (A) of the present embodiment or a resin derived from the compound (A) which shows easy etchability with an etching rate faster than that of the resist is used, at least one or more etching mask layers are laminated on a substrate having a layer to be processed, and further a layer made of a resin containing the compound (A) of the present embodiment or the compound (A) is laminated on the upper layer side of the etching mask layer, it is also preferable to improve the quality of the pattern shape of the layer to be processed after processing. From these viewpoints, a resin having fewer aromatic ring structures or a structure having no novolak structure is preferable, and a resin having an aliphatic structure in the main chain such as a polyacrylic resin, a polyethylene resin, a polyalkylene ether resin, or a resin having a high content ratio of a carbon skeleton constituting the aliphatic structure is more preferable.

[0089] Specific examples of the compound (A) are exemplified below, but the compound (A) is not limited thereto.

[0090] [Chemical formula] [Chem.] [Chem.]

[0091] [Composition containing compound (A) or / and resin (A)] The composition of this embodiment contains compound (A) or / and resin (A).

[0092] (Solvent) In this embodiment, as long as the solvent can at least dissolve the above-described compound (A) or / and resin (A), known solvents can be appropriately used.Specific examples of the solvent are not particularly limited, and include, for example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and 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, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and 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, and 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, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and 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 still more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0093] 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, still 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.

[0094] (Acid generator) In the composition of the present embodiment, it is preferable to contain one or more acid generators that directly or indirectly generate an acid by irradiation with any radiation selected from visible light, ultraviolet rays, excimer lasers, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams, or by heating. The acid generator is not particularly limited, and either a nonionic or ionic type may be used. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), and the like. Representative examples of ionic acid generators include onium salts containing an onium cation (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, and the like. For example, compounds that generate an acid described in International Publication WO2013 / 024778, Japanese Patent Application Laid-Open No. 2009-134088, Japanese Patent Application Laid-Open No. 63-26653, Japanese Patent Application Laid-Open No. 55-164824, Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, and the like can be used. The acid generator can be used alone or in combination of two or more.

[0095] The usage amount of the acid generator is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, still more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass based on the total mass of the solid content. By using the acid generator within the above range, the curability tends to be improved. In the present embodiment, if an acid is generated in the system, the method of generating the acid is not particularly limited.

[0096] (Acid diffusion control agent) In addition, as other compounds that can be used in combination, compounds that can promote or suppress the diffusion of the generated acid can be included as acid diffusion control agents. <Acid diffusion accelerator> Preferred acid diffusion accelerators include compounds that have a low pKa value of 2.0 or less for the purpose of releasing acid in necessary situations while retaining the generated acid, and have a molecular weight of 1000 or less or a clogP value of 30 or less or a Tg of 250 °C or less, so that the thermal diffusibility in the resin matrix can be promoted, and also have heat resistance at least at 250 °C. As the structure of specific acid diffusion accelerators, either non-ionic or ionic ones can be used. Examples of non-ionic acid diffusion accelerators include sulfonate esters (such as 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone), sulfones (such as disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid diffusion accelerators include onium salts containing onium cations (such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, etc. As the cation in ionic compounds, any cation that satisfies any of the above molecular weight, clogP, Tg, and heat resistance in the state of forming a salt with an anion can be used without particular limitation. Specific examples of cations preferably include organic ammonium cations, organic iodonium cations, and organic sulfonium cations.

[0097] <Acid diffusion inhibitor> An acid diffusion inhibitor can be used for the purpose of suppressing the diffusion of acid generated from an acid generator or the like by exposure in the resist film and the underlying film during each process of exposure, PEB, and development, and suppressing the reaction of the resist resin or the underlying film resin due to the influence of acid generated in trace amounts or present by diffusion in the unexposed area. As other effects, it can lead to an improvement in the temporal stability of the resist resin composition or the underlying film resin composition, an improvement in resolution in lithography, and an improvement in process robustness by suppressing the time dependence required from after exposure to development for pattern quality, and a resist resin composition or an underlying film resin composition excellent in process stability can be provided. As the acid diffusion inhibitor, a low molecular compound, a form incorporated as a part of a polymer, or both forms may be used in combination.

[0098] In addition, as the acid diffusion inhibitor, a salt that forms an acid with weaker acid dissociability compared to the acid generated from the acid generator used can be used. The acidity as an index of acid dissociability is represented by the acid dissociation constant (pKa). When a salt that generates an acid with weaker acidity than the acid generated from the acid generator is used as the acid diffusion inhibitor, the acid dissociation constant of the acid generated from the acid diffusion inhibitor satisfies -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the acid diffusion inhibitor include nitrogen atom-containing compounds, photo-base generators that are photosensitive upon exposure and generate weak acids, and the like.

[0099] Examples of the nitrogen atom-containing compounds include amine compounds such as tripentylamine and trioctylamine, amide group-containing compounds such as formamide and N,N-dimethylacetamide, urea compounds such as urea and 1,1-dimethylurea, and nitrogen-containing heterocyclic compounds such as pyridine, N-(undecylcarbonyloxyethyl)morpholine, and N-t-pentyloxycarbonyl-4-hydroxypiperidine.

[0100] Examples of the photo-base generator include compounds containing an onium cation that decomposes upon exposure and an anion of a weak acid. In the exposed area, the photo-dissociable base generates a weak acid from the proton generated by the decomposition of the onium cation and the anion of the weak acid, resulting in a decrease in acid diffusion controllability. Examples of salts that generate an acid with a lower acidity than the acid generated from the acid generator include the salts represented by formula (D) described in JP-A-2015-147926, and the salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. Examples of other preferred acid diffusion inhibitors include, but are not limited to, the following.

Chemical formula

Chemical formula

[0101] When the lower layer film resin composition contains an acid diffusion controller, the lower limit of the content of the acid diffusion controller is preferably 0.1 part by mass, more preferably 0.5 part by mass, and still more preferably 1 part by mass with respect to 100 parts by mass of the polymer component (or resin component). The upper limit of the above content is preferably 20 parts by mass, more preferably 10 parts by mass, and still more preferably 5 parts by mass.

[0102] When the lower layer film resin composition contains an acid diffusion controller, the lower limit of the content of the acid diffusion controller is preferably 1 mol%, more preferably 5 mol%, and still more preferably 10 mol% with respect to 100 mol% of the acid generator. The upper limit of the above content is preferably 250 mol%, more preferably 150 mol%, and still more preferably 100 mol%.

[0103] By setting the content of the acid diffusion controller within the above range, the defect suppression property and LWR performance of the lower layer film resin composition can be further improved. The acid diffusion controller can contain one kind or two or more kinds.

[0104] (Crosslinking agent) In this embodiment, one or more crosslinking agents can be included in the composition. The crosslinking agent means a compound capable of crosslinking at least either the compound (A) or the resin (A). As the crosslinking agent, an acid crosslinking agent capable of crosslinking the compound (A) or the resin (A) intramolecularly or intermolecularly in the presence of an acid generated from an acid generator is preferable. Examples of such an acid crosslinking agent include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the compound (A) or the resin (A).

[0105] 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, glycidyl amino 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 this embodiment are preferably hydroxyalkyl groups and alkoxyalkyl groups, and particularly preferably alkoxymethyl groups.

[0106] The crosslinking agent having the crosslinkable group is not particularly limited, but 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.

[0107] In this embodiment, the usage amount of the crosslinking agent is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass of the total solid content. When the blending ratio of the crosslinking agent is 0.5% by mass or more, the solvent resistance can be improved, and the dissolution in the resist solvent applied after curing can be suppressed. On the other hand, when it is 50% by mass or less, the decrease in heat resistance after curing can be suppressed.

[0108] (Other components) In the composition of this embodiment, as other components, if necessary, various additives such as a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid or an oxo acid of phosphorus or its derivative can be added singly or in combination of two or more.

[0109] (Dissolution accelerator) The dissolution accelerator is a component having an action of increasing the solubility when the solubility of the solid content in the developer 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.

[0110] The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the solid content 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.

[0111] (Dissolution controller) The dissolution controller is a component having an action of controlling the solubility when the solubility of the solid content in the developer is too high and moderately decreasing the dissolution rate during development. As such a dissolution controller, those that do not undergo chemical changes in processes such as film baking, radiation irradiation, and coating of the upper layer are preferable.

[0112] The dissolution control agent is not particularly limited. For example, it can include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone, etc. These dissolution control agents can be used alone or in combination of two or more. The blending amount of the dissolution control agent is appropriately adjusted according to the type of the compound to be used. Preferably, it is 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 based on the total mass of the solid content.

[0113] (Sensitizer) The sensitizer is a component that absorbs the energy of the irradiated radiation, transfers the energy to the acid generator, thereby increasing the amount of acid generated, and has the effect of improving the curability. 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.

[0114] The blending amount of the sensitizer is appropriately adjusted according to the type of the compound to be used. Preferably, it is 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 based on the total mass of the solid content.

[0115] (Surfactant) The surfactant is a component having the effect of improving the coatability, striation, coatability of the upper layer film, etc. 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. The nonionic surfactant has 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. 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, Saffron (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.

[0116] The blending amount of the surfactant is appropriately adjusted according to the type of the solid component used, but 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 is preferred.

[0117] (Other Additives) Furthermore, one or more additives other than the above-described components can be blended in the composition of the present embodiment as needed. Examples of such additives include dyes, pigments, and adhesion aids. 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 between the substrate and the contacting layer. Furthermore, other additives include anti-halation agents, storage stabilizers, defoaming agents, shape improvers, etc., and specifically, 4-hydroxy-4'-methylchalcone, etc. can be mentioned.

[0118] In the composition of the present embodiment, the total amount of optional components can be 0 to 99% by mass of the total mass of the solid components, 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.

[0119] The composition of the present embodiment is usually prepared by dissolving each component in a solvent to form a uniform solution during use, and then, if necessary, filtering, for example, with a filter having a pore size of about 0.2 μm.

[0120] The composition of the present embodiment is used for lithography applications. It is preferable that the composition is cured after forming a thin film to form a lower layer film or a film in contact with a resist layer (resist layer contact film).

[0121] (Physical properties of the composition, etc.) The composition of the present embodiment can form an amorphous film by spin coating. Further, the composition of the present embodiment can be applied to a general semiconductor manufacturing process. After curing, the composition of the present embodiment can generate protons by irradiation with extreme ultraviolet light and supply the protons to an adjacent layer, thereby improving the sensitivity of the adjacent layer. The composition of the present embodiment is preferably used after curing. After curing, it is preferably solvent-resistant because it does not dissolve in the composition of the adjacent layer.

[0122] [Method for manufacturing an amorphous film] It is possible to form an amorphous film on a substrate using the composition of the present embodiment.

[0123] [Method for forming a resist pattern using the composition] The method for forming a resist pattern using the composition of the present embodiment includes a lower layer film forming step of forming a lower layer film on a substrate using the composition, a photoresist film forming step of forming at least one layer of a photoresist film on the lower layer film formed by the lower layer film forming step, and a step of irradiating a predetermined region of the photoresist film formed by the photoresist film forming step with radiation and developing.

[0124] [Method for Forming Circuit Pattern Using Composition] The method for forming a circuit pattern using the composition of the present embodiment includes a lower layer film forming step of forming a lower layer film on a substrate, a resist layer contact film forming step of forming a resist layer contact film using the composition on the lower layer film formed by the lower layer film forming step, a photoresist film forming step of forming at least one layer of photoresist film on the resist layer contact film formed by the resist layer contact film forming step, a resist pattern forming step of irradiating a predetermined region of the photoresist film formed by the photoresist film forming step with radiation and developing to form a resist pattern, a pattern forming step of etching the resist layer contact film or the resist layer contact film and the lower layer film using the resist pattern formed by the resist pattern forming step as a mask to form a pattern, and a substrate pattern forming step of etching the substrate using the pattern formed by the pattern forming step as a mask to form a pattern on the substrate.

Example

[0125] Hereinafter, the present embodiment will be described in more detail by synthesis examples and examples, but the present embodiment is not limited by these examples.

[0126] [Measurement Method] (1) Structure of Compound The structure of the compound was confirmed by performing 1H-NMR measurement under the following conditions using AdvanceIII 500 manufactured by Bruker. Frequency: 500 MHz Solvent: d6-DMSO Internal Standard: TMS Measurement Temperature: 23 °C

[0127] [Evaluation Method] (Adjustment of Lower Layer Film Composition) 10 parts by mass of the compound or polymer obtained in the following synthesis example, 0.2 parts by mass of the thermal acid generator TAG-2689 (manufactured by King Industries, quaternary ammonium salt of trifluoromethanesulfonic acid), 1 part by mass of TMOM-BP (manufactured by Honshu Chemical), 76.8 parts by mass of PGMEA, and 12 parts by mass of PGME were blended to prepare a lower layer film composition solution containing the compound of the present invention. Regarding the compound of Example 4, WPBG300 (0.2 parts by mass) was added instead of TAG-2689, and BPN01S (1 part by mass) was added instead of TMOM-BP.

[0128] (1) Safety Solvent Solubility Test of Compound The solubility of the compound in PGMEA was evaluated according to the following criteria using the amount of dissolution in each solvent. The measurement of the dissolution amount was carried out at 23 °C. The compound was precisely weighed into a test tube, and the target solvent was added to a predetermined concentration. Ultrasonic waves were applied for 30 minutes using an ultrasonic cleaner, and then the state of the liquid was observed visually for measurement. A: 5.0 mass% ≤ dissolution amount B: 2.0 mass% ≤ dissolution amount < 5.0 mass% C: dissolution amount < 2.0 mass%

[0129] (2) Storage Stability and Thin Film Formability of Composition The storage stability of the composition containing the compound and resin was evaluated by observing the presence or absence of precipitation visually after allowing the above lower layer film composition to stand at 23 °C for 3 days after preparation. Also, after spin-coating the composition on a clean silicon wafer, it was baked on a hot plate at 250 °C to form an amorphous film with a thickness of 100 nm. The prepared composition was evaluated as ○ when it was a uniform solution and had good thin film formation, △ when it was a uniform solution but had defects in the thin film, and × when there was precipitation.

[0130] (3) Sensitivity Evaluation (EUV Sensitivity - TMAH Aqueous Solution Development) 5 parts by mass of the polymer MAR1 obtained in the following resist polymer synthesis 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 were blended to prepare a resist solution for sensitivity evaluation and pattern evaluation. The above lower layer film composition was applied onto a silicon wafer and baked at 240 °C for 60 seconds to form a lower layer film with a film thickness of 100 nm on the silicon wafer. Furthermore, a resist solution was applied onto the lower layer film of the present invention formed on the silicon wafer and baked at 110 °C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. Next, using an extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.), shot exposure without a mask was performed while increasing the exposure dose from 1 mJ / cm 2 to 1 mJ / cm 2 in increments of 80 mJ / cm 2 up to. After baking (PEB) at 110 °C for 90 seconds and developing with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, a wafer on which shot exposure for 80 shots was performed on the wafer was obtained. For each shot exposure area obtained, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness with respect to the exposure dose was acquired, and the exposure dose at which the slope of the film thickness variation amount with respect to the exposure dose was the largest was calculated as the sensitivity value (mJ / cm 2 ) and used as an index for the EUV sensitivity of the resist.

[0131] (4) Etching resistance Etching apparatus: RIE-10NR manufactured by Samco International Output: 50 W Pressure: 20 Pa Time: 2 min Etching gas Ar gas flow rate: CF 4 Gas flow rate: O 2 Gas flow rate = 50:5:5 (sccm)

[0132] For the films formed on silicon wafers using the lower layer film solutions made of the materials of the present invention created in each of the examples and comparative examples, an etching test was conducted under the above-mentioned conditions, and the etching rate at that time was measured. Then, based on the etching rate of the lower layer film made using novolak ("PSM4357" manufactured by Gunei Chemical Industry Co., Ltd.), the etching resistance was evaluated according to the following evaluation criteria. Evaluation Criteria A: The difference in etching rate compared to the novolak lower layer film is less than 10% in terms of the ratio to novolak. B: The difference in etching rate compared to the novolak lower layer film is within ±10% in terms of the ratio to novolak. C: The difference in etching rate compared to the novolak lower layer film is greater than 10% in terms of the ratio to novolak.

[0133] Synthesis Example 1: Synthesis of BisB-1 Into a 200 mL container equipped with a stirrer, a condenser, and a burette, 25.0 g (204.7 mmol) of 2,6-dimethylphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 25.0 g (107.7 mmol) of 4-iodobenzaldehyde (reagent manufactured by Tokyo Chemical Industry), and 20 mL of 1-methoxy-2-propanol were charged, and 5.3 g (53.9 mmol) of sulfuric acid was added to prepare a reaction solution. This reaction solution was stirred at 90 °C for 6 hours to conduct the reaction. After the reaction was completed, 1 L of pure water was added to the reaction solution, and sodium bicarbonate was added while ice-cooling to adjust the pH to 7-8. The solution was extracted with ethyl acetate and concentrated to obtain a solution. The obtained solution was separated and purified by column chromatography to obtain 24.9 g of the target compound (BisB-1) represented by the following formula. When NMR measurement was performed on the obtained compound (BisB-1) under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the following formula (BisB-1). δ (ppm) 8.1 (2H, -O-H), 6.5 - 7.7 (8H, Ph-H), 5.2 (1H, C-H), 2.1 (12H, CH3)

[0134]

Chemical Formula

[0135] Synthesis Example 2: Synthesis of BisB-2 Into a 500 mL container equipped with a stirrer, a cooling tube, and a burette, 42.8 g (230 mmol) of 4,4'-biphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 21.5 g (57.5 mmol) of 3,5-diiodosalicylaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and 428 mL of γ-butyrolactone were charged, and 5.8 g (58 mmol) of sulfuric acid was added to prepare a reaction solution. This reaction solution was stirred at 90 °C for 56 hours to conduct the reaction. After completion of the reaction, 1 L of pure water was added to the reaction solution, neutralized with sodium hydroxide, extracted with ethyl acetate, and concentrated to obtain a solution. By subjecting the obtained solution to separation and purification by column chromatography, 10 g of the target compound (BisB-2) represented by the following formula was obtained. When NMR measurement was performed on the obtained compound (BisB-2) under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the following formula (BisB-2). δ (ppm) 9.4 (4H, -O-H), 8.9 (1H, -O-H), 6.2 to 7.8 (16H, Ph-H), 6.3 (1H, C-H)

[0136]

Chemical formula

[0137] Synthesis Example 3: Synthesis of XbisN-1 Into a 300 ml container equipped with a stirrer, a cooling tube, and a burette, 7.0 g (40 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich Co., LLC) and 4.6 g (20 mmol) of 3-iodobenzaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into 100 ml of γ-butyrolactone, 0.5 g of p-toluenesulfonic acid was added, and the mixture was stirred at 90 °C for 23 hours to conduct the reaction to obtain a reaction solution. Next, the reaction solution was added to 1000 g of pure water, and then extracted and concentrated with ethyl acetate to obtain a solution. The obtained solution was subjected to chloroform washing after separation by column chromatography, and 4.2 g of the target compound (XbisN-1) represented by the following formula (XbisN-1) was obtained. As a result of measuring the molecular weight of the obtained compound (XbisN-1) by the above method, it was 516. When NMR measurement was performed on the obtained compound (XbisN-1) under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the following formula (XbisN-1). δ (ppm) 9.7 (2H, O-H), 7.0 to 8.5 (14H, Ph-H), 6.5 (1H, C-H)

[0138]

Chemical formula

[0139] Synthesis Example 4: Synthesis of BMI-1 Using a 200 mL glass flask as a reaction vessel, 5.73 g (20 mmol) of neopentyl glycol bis(4-aminophenyl) ether (product name: DANPG, manufactured by Wakayama Seika Kogyo Co., Ltd.) was dissolved using butanol as a solvent, and then a 20% by mass aqueous iodine chloride solution (81.2 g, 100 mmol) was added dropwise at 50 °C over 60 minutes, followed by stirring at 50 °C for 2 hours to react salicyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered off, washed, and dried to obtain 9.5 g of a brown solid. As a result of analyzing a sample of the brown solid by liquid chromatography-mass spectrometry (LC-MS), the compound (X) represented by the following formula (X) was confirmed.

Chemical formula

[0140] Next, the compound (X) obtained above was transferred to a 200-ml container equipped with a stirrer, a condenser, and a burette. 2.54 g (26.0 mmol) of maleic anhydride (manufactured by Kanto Chemical Co., Inc.), 50 ml of dimethylformamide, and 50 ml of m-xylene were charged, and 0.5 g (2.9 mmol) of p-toluenesulfonic acid was added to prepare a reaction solution. This reaction solution was stirred at 130 °C for 4.0 hours to conduct the reaction, and the water generated by azeotropic dehydration was recovered with a Dean-Stark trap. Next, after cooling the reaction solution to 40 °C, it was dropped into a beaker containing 500 ml of distilled water to precipitate the product. After filtering the obtained slurry solution, the residue was washed with methanol and separated and purified by column chromatography to obtain 1.5 g of the target compound (BMI-1) represented by the following formula.

Chemical formula

[0141] Synthesis Example 5: Synthesis of XBisN-2 Into a 500-mL container equipped with a stirrer, a condenser, and a burette, 32.0 g (20 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich), 29.9 g (80 mmol) of 3,5-diiodosalicylaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and 200 mL of 1,4-dioxane were charged, 10 mL of 95% sulfuric acid was added, and the mixture was stirred at 100 °C for 6 hours to conduct the reaction. Next, the reaction solution was neutralized with a 24% aqueous sodium hydroxide solution, 100 g of pure water was added to precipitate the reaction product, and after cooling to room temperature, filtration was performed for separation. After drying the obtained solid, separation and purification by column chromatography was performed to obtain 2.6 g of the target compound (XBisN-2) represented by the following formula. In addition, the following peaks were found by 500 MHz - 1H - NMR, and it was confirmed that it has the chemical structure of the following formula. 1H - NMR: (d - DMSO, internal standard TMS) δ (ppm) 9.6 - 9.7 (3H, O - H), 6.7 - 8.5 (12H, Ph - H), 6.2 (1H, C - H)

[0142]

Chemical formula

[0143] Synthesis Example 5 - 1: Synthesis of RXBisN - 2 2.6 g (7.0 mmol) of XBisN - 2 and 1.0 g (2 mmol) of monobutyl phthalate copper were charged into a 100 - mL container equipped with a stirrer, a condenser tube, and a burette. 20 mL of 1 - butanol was added as a solvent, and the reaction solution was stirred at 100 °C for 6 hours to carry out the reaction. After cooling, the precipitate was filtered, and the obtained crude product was dissolved in 20 mL of ethyl acetate. Next, 1 mL of hydrochloric acid was added, and after stirring at room temperature, neutralization treatment was carried out with sodium hydrogen carbonate. The ethyl acetate solution was concentrated, 40 mL of methanol was added to precipitate the reaction product, and after cooling to room temperature, filtration was carried out for separation. By drying the obtained solid, 1.0 g of the target resin (RXBisN - 2) having the structure represented by the following formula was obtained. Regarding the obtained resin, as a result of measuring the polystyrene - equivalent molecular weight by the above - mentioned method, Mn: 4300, Mw: 5500, Mw / Mn: 1.28. Regarding the obtained resin, when NMR measurement was carried out under the above - mentioned measurement conditions, the following peaks were found, and it was confirmed that it has the chemical structure of the following formula. δ (ppm) 9.5 - 9.7 (3H, O - H), 6.7 - 8.5 (12H, Ph - H), 6.0 - 6.3 (1H, C - H)

[0144]

Chemical formula

[0145] Synthesis Example 6: Synthesis of NAFP - AL Under nitrogen, 1,4-bis(chloromethyl)benzene (28.8 g, 0.148 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-naphthol (30.0 g, 0.1368 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (5.7 g, 0.029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 300 mL four-necked flask, and further 150.4 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) was charged. The mixture was stirred and heated to dissolve until reflux was confirmed, and polymerization was started. After 16 hours, the mixture was allowed to cool to 60 °C and then reprecipitated into 1600 g of methanol. The obtained precipitate was filtered and dried in a vacuum dryer at 60 °C for 16 hours to obtain 38.6 g of the target oligomer having a structural unit represented by the following formula (NAFP-AL). The weight average molecular weight measured by GPC of the obtained oligomer in terms of polystyrene was 2020, and the dispersity was 1.86.

[0146]

Chemical formula

[0147] Synthesis Example 6-1: Synthesis of I-NAFP-AL Using a 200 mL glass flask as a reaction vessel, 8 g (20 mmol) of NAFP-AL obtained above was dissolved using butanol as a solvent, and then a 20% by mass aqueous solution of iodine chloride (81.2 g, 100 mmol) was added dropwise at 50 °C over 60 minutes. After that, the mixture was stirred at 50 °C for 2 hours to react salicyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous solution of sodium thiosulfate was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate precipitated by cooling was filtered off, washed, and dried to obtain 11.5 g of a brown solid.

Chemical formula

[0148] Synthesis Example 7: Synthesis of 2I-PHS A 200 mL glass flask was used as the reaction vessel. After dissolving 4.96 g (40 mmol) of salicyl alcohol in butanol as the solvent, a 20 wt% aqueous iodine chloride solution (81.2 g, 100 mmol) was added dropwise at 50 °C over 60 minutes, followed by stirring at 50 °C for 2 hours to react salicyl alcohol with iodine chloride. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the liquid temperature was cooled to 10 °C. The precipitate deposited by cooling was filtered off, washed, and dried to obtain 12.1 g of a white solid. As a result of analyzing a sample of the white solid by liquid chromatography - mass spectrometry (LC - MS), 4 - hydroxy - 3,5 - diiodobenzyl alcohol was confirmed.

[0149] After adding MnO₂ (3.4 g, 40 mmol) in a methylene chloride solvent and stirring, a 50 wt% solution prepared by dissolving the total amount of the synthesized 4 - hydroxy - 3,5 - diiodobenzyl alcohol in methylene chloride was added dropwise while stirring for 1 hour, followed by stirring at room temperature for 4 hours. Then, the reaction solution was filtered off, and the solvent was distilled off to obtain 4 - hydroxy - 3,5 - diiodobenzaldehyde.

[0150] In a DMF solvent, a solution was prepared by dissolving dimethyl malonate (5.3 g, 40 mmol) and the total amount of the 4 - hydroxy - 3,5 - diiodobenzaldehyde synthesized above. After that, a solution prepared by dissolving ethylenediamine (0.3 g) in DMF was added dropwise while stirring for 1 hour, and then the reaction was carried out by stirring for 6 hours while controlling the liquid temperature to 150 °C using an oil bath. Then, after adding ethyl acetate and water, a 2 mol / L aqueous HCl solution was added to control the pH to 4 or less, and then the organic phase was separated by liquid - liquid separation. The obtained organic phase was further washed by liquid - liquid separation in the order of a 2 mol / L aqueous sodium carbonate solution, water, and brine, followed by filtration purification and distilling off the solvent from the organic phase to obtain 8.1 g of a compound 2I - PHS (4 - hydroxy - 3,5 - diiodostyrene) represented by the following formula (2I - PHS).

[0151]

Chemical formula

[0152] Synthesis Example 7-1: Synthesis of P-2I-PHS-MMA 3.0 g of compound 2I-PHS and 1.2 g of methyl 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 polymer was filtered off and dried under reduced pressure to obtain a polymer P-2I-PHS-MMA in the form of a white powder represented by the following formula (P-2I-PHS-MMA). The weight average molecular weight (Mw) of this polymer was 8000, and the dispersity (Mw / Mn) was 1.50. Further, as a result of measuring 13C-NMR, the composition ratio (molar ratio) in the following formula (P-2I-PHS-MMA) was a:b = 1:1. The following formula (P-2I-PHS-MMA) is described simply to show the ratio of each structural unit, but the sequence order of each structural unit is random, and it is not a block copolymer in which each structural unit forms an independent block.

[0153] [Chemical formula]

[0154] Synthesis Example 8: Synthesis of XBisN-3 Into a 3 L container equipped with a stirrer, a condenser tube and a burette, 100 g (0.214 mol) of a compound (XBisN-C1) represented by the following formula described in International Publication No. 2013 / 024779 and 71.2 g (0.429 mol) of potassium iodide were charged, 1 L of methanol was added as a solvent, and 146 g (1.5 mol) of sulfuric acid was further dropped under ice cooling, followed by stirring at 10 °C for 4 hours to carry out the reaction. After completion of the reaction, extraction was carried out with butyl acetate, followed by washing with water, neutralization, and then filtration and drying to obtain 87.8 g of the target compound (RBisN-3) represented by the following formula (XBisN-3). When NMR measurement was carried out on the obtained compound under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the following formula. δ (ppm) 10.6 (2H, O-H), 7.2 - 8.6 (17H, Ph-H), 6.7 (1H, C-H)

[0155]

Chem.

Chem.

[0156] Synthesis Example 9-1: Synthesis of MAC-ADI 16.8 g (0.1 mol) of 1,3-adamantanediol (manufactured by Mitsubishi Gas Chemical) was dissolved in 200 mL of toluene, 89.8 g (0.4 mol) of 57% aqueous hydrogen iodide solution was added, and the mixture was stirred at 80 °C for 8 hours for reaction. After the reaction, water was added, and the mixture was washed with sodium hydrogen carbonate. The organic layer was concentrated and then separated and purified by column chromatography to obtain 12 g of 3-iodo-1-hydroxyadamantane represented by the following formula.

Chem.

[0157] 2.78 g (10 mmol) of the 3-iodo-1-hydroxyadamantane obtained above was dissolved in chloroform, 0.96 g (12 mmol) of pyridine was added under ice-cooling, and 1.25 g (12 mmol) of methacrylic acid chloride was added dropwise. Subsequently, the mixture was stirred and reacted for 1 hour under ice-cooling and 3 hours at room temperature. After the reaction was completed, water was added to the reaction solution, and the mixture was washed with a saturated aqueous sodium hydrogen carbonate solution. Sodium sulfate was added to the organic phase for drying, and after concentration, it was purified by column chromatography to obtain 2.7 g of the target product (MAC-ADI) shown below.

[0158] When NMR measurement was performed on the obtained compound (MAC-ADI) under the above measurement conditions, the following peaks were found, and it was confirmed that it has the chemical structure of the following formula (MAC-ADI). δ (ppm) (d-DMSO): 6.4 - 6.5 (2H, =CH2), 1.3 - 3.2 (17H, Ad-H, -C(CH3)=C) [Chemical formula]

[0159] Synthesis Example 10-1: Synthesis of MAC-ADI2 Dissolve 2.3 g (12.5 mmol) of 1,3,5-adamantanetriol (manufactured by Mitsubishi Gas Chemical) in 100 mL of toluene, add 28.1 g (125 mmol) of 57% aqueous hydrogen iodide solution, and stir at 80 °C for 13 hours to react. After the reaction, add water, wash with sodium hydrogen carbonate, concentrate the organic layer, and perform separation and purification by column chromatography to obtain 0.9 g of 3,5-diiodo-1-hydroxyadamantane represented by the following formula. [Chemical formula]

[0160] Except for using 4.04 g (10 mmol) of 3,5-diiodo-1-hydroxyadamantane obtained above instead of 2.78 g of 3-iodo-1-hydroxyadamantane, in the same manner as in Synthesis Example 9-1, 3.5 g of the target compound (MAC-ADI2) represented by the following formula (MAC-ADI2) was obtained.

[0161] When NMR measurement was performed on the obtained compound (MAC-ADI2) under the above measurement conditions, the following peaks were found, and it was confirmed that it had the chemical structure of the following formula (MAC-ADI2). δ (ppm) (d-DMSO): 6.4 - 6.5 (2H, =CH2), 1.5 - 3.9 (16H, Ad-H, -C(CH3)=C) [Chemical formula]

[0162] Synthesis Example 9: Synthesis of P-MAC-ADI Resin MAC-ADI (4.2 g), 1.5 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-ADI). The molecular weight (Mw) of this resin was 9300, and the dispersity (Mw / Mn) was 1.9. Also, 13 As a result of measuring 13C-NMR, the composition ratio (molar ratio) in the following chemical formula (P-MAC-ADI) was a:b:c:d = 20:30:15:35. The following chemical formula (P-MAC-ADI) is described simply to show the ratio of each structural unit, but P-MAC-ADI is not a block copolymer in which each structural unit forms an independent block.

Chemical formula

[0163] Synthesis Example 10: Synthesis of P-MAC-ADI2 Resin MAC-ADI2 (5.6 g), 1.5 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-ADI2). The molecular weight (Mw) of this resin was 8350, and the dispersity (Mw / Mn) was 2.0. Also, 13As a result of measuring the 13C-NMR, the composition ratio (molar ratio) in the following chemical formula (MAC-ADI2) was a:b:c:d = 20:30:15:35. Note that the following chemical formula (P-MAC-ADI2) is described simply to indicate the ratio of each structural unit, but P-MAC-ADI2 is not a block copolymer in which each structural unit forms an independent block.

[0164] [Chemical formula]

[0165] Synthesis Comparative Example AR1: Synthesis of P-PHS-MMA 1.0 g of the compound p-hydroxystyrene and 1.2 g of methyl 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 polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer P-PHS-MMA represented by the following formula (P-PHS-MMA). The weight average molecular weight (Mw) of this polymer was 9100, and the dispersity (Mw / Mn) was 1.60. Also, as a result of measuring the 13C-NMR, the composition ratio (molar ratio) in the following formula (P-PHS-MMA) was a:b = 1:1. Note that the following formula (P-PHS-MMA) is described simply to indicate the ratio of each structural unit, but the sequence order of each structural unit is random, and it is not a block copolymer in which each structural unit forms an independent block.

[0166] [Chemical formula]

[0167] (Synthesis of Polymer MAR1 for Resist) 0.5 g of p-hydroxystyrene (manufactured by Toho Chemical Industry Co., Ltd.), 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 polymer was separated by filtration and dried under reduced pressure to obtain a white powdery polymer MAR1 represented by the following formula (MAR1). The weight average molecular weight (Mw) of this polymer 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 formula (MAR1) was a:b:c:d = 40:30:15:15. The following formula (MAR1) is described simply to show the ratio of each structural unit, but the sequence order of each structural unit is random, and it is not a block copolymer in which each structural unit forms an independent block. For the polystyrene-based monomer (p-hydroxystyrene), the molar ratio was determined based on the integral ratio of the carbon at the root of the benzene ring, and for the methacrylate-based monomers (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate), the molar ratio was determined based on the integral ratio of the carbonyl carbon of the ester bond.

[0168] [Chemical formula]

[0169] (Synthesis of Polymer MAR2 for Resist) 1.0 g of p-hydroxystyrene (manufactured by Toho Chemical Industry Co., Ltd.), 3.8 g of 2-methyl-2-adamantyl methacrylate, 0.7 g of γ-butyrolactone methacrylate, and 1.0 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 polymer was filtered off and dried under reduced pressure to obtain a white powdery polymer MAR2 represented by the following formula (MAR2). The weight average molecular weight (Mw) of this polymer 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 formula (MAR2) was a:b:c:d = 50:10:10:30. The following formula (MAR2) is described simply to show the ratio of each structural unit, but the sequence order of each structural unit is random, and it is not a block copolymer in which each structural unit forms an independent block. For the polystyrene-based monomer (p-hydroxystyrene), the carbon at the root of the benzene ring, and for the methacrylate-based monomers (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate), the molar ratio was determined based on the integral ratio of each carbonyl carbon of the ester bond.

[0170] [Chemical formula]

[0171] (Examples 1 to 10, Comparative Example 1) The safe solvent solubility, storage stability, thin film formability, sensitivity, and etching resistance of the compounds or resins obtained in Synthesis Examples 1 to 10 and Synthesis Comparative Example AR1 were evaluated as described above. The results are shown in Table 1.

[0172] (Comparative Example 2) Evaluation was carried out in the same manner as in Examples 1 to 10, except that the compound (XBisN-C1) represented by the following formula described in International Publication No. 2013 / 024779 was used instead of the compounds or resins obtained in Synthesis Examples 1 to 10. The results are shown in Table 1.

[0173]

Chemical formula

[0174]

Table 1

[0175] As is clear from Table 1, in Examples 1 to 10 using a compound containing a total of 15 to 75% by mass of iodine atoms or a resin having a structural unit derived from the compound, it was confirmed that the sensitivity was significantly superior as compared with Comparative Example 1 and Comparative Example 2.

[0176] (Preparation of Lower Layer Film Composition) The compositions described in Table 2 below were blended to prepare a lower layer film composition solution containing the compound of the present invention.

Table 2

[0177] The components used in the preparation of the lower layer film composition solution are as follows. <Acid Diffusion Controller> The following were used as acid diffusion promoters. ·WPAG199 (Bis(4-methylphenylsulfonyl)diazomehtane) (manufactured by Fujifilm Wako Pure Chemical Corporation)

Chemical formula

Chemical formula

Chemical formula

[0178] The following were used as acid diffusion inhibitors. (Compound ADCS-1)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0179] <Thermal acid generator · Thermal base generator> · WPBG300 (manufactured by Fujifilm Wako Pure Chemical Corporation)

Chemical formula

[0180] <Crosslinking agent> · TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.)

Chemical formula

[0181] (4) Sensitivity evaluation (EUV sensitivity - n-butyl acetate development) 5 parts by mass of the polymer MAR2 obtained in the above polymer synthesis example for resist, 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 were blended to prepare resist solution 2 for sensitivity evaluation and pattern evaluation. The prepared lower layer film composition was applied onto a silicon wafer and baked at 240°C for 60 seconds to form a lower layer film with a film thickness of 100 nm on the silicon wafer. Furthermore, resist solution 2 was applied onto the lower layer film of the present invention formed on the silicon wafer and baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. Next, using an extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.), shot exposure without a mask was performed while increasing the exposure dose from 1 mJ / cm 2 to 1 mJ / cm 2 in increments of 80 mJ / cm 2 up to. After that, baking (PEB) was performed at 110°C for 90 seconds, and development was carried out with n-butyl acetate for 30 seconds to obtain a wafer on which shot exposure for 80 shots was performed on the wafer. For each shot exposure area obtained, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.) to obtain profile data of the film thickness with respect to the exposure dose, and the exposure dose at which the slope of the film thickness variation amount with respect to the exposure dose was the largest was calculated as the sensitivity value (mJ / cm 2 ) and used as an index for the EUV sensitivity of the resist.

[0182] (Etching defect evaluation - TMAH) The prepared lower layer film composition was applied onto a silicon wafer and baked at 240°C for 60 seconds to form a lower layer film with a film thickness of 100 nm on the silicon wafer. Furthermore, a resist solution was applied onto the lower layer film of the present invention formed on the silicon wafer and baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm. Next, using the extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" (product name, manufactured by Lithotech Japan Co., Ltd.), shot exposure was performed on the entire wafer at an exposure dose 3% higher than the EUV sensitivity value obtained in the EUV sensitivity evaluation in the above TMAH development. Further, baking (PEB) was carried out at 110°C for 90 seconds, and development was performed for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), to obtain a wafer on which shot exposure for 80 shots was performed on the entire wafer. For the fabricated exposed wafer, etching treatment was carried out using the etching apparatus "Telius SCCM" (product name, manufactured by Tokyo Electron Limited) until the oxide film was etched by 60 nm using CF4 / Ar gas. For the wafer fabricated by etching, defect evaluation was performed using the defect inspection apparatus "Surfscan SP5" (product name, manufactured by KLA Corporation), and the number of cone defects of 19 nm or more was determined as an index of etching defects. (Evaluation Criteria) A: Number of cone defects ≤ less than 20 B: 20 < number of cone defects ≤ 200 C: 200 < number of cone defects ≤ 1000 D: 1000 < number of cone defects The obtained evaluation results are shown in Table 3.

[0183] (Etching Defect Evaluation - n-Butyl Acetate) In the above etching evaluation - TMAH method, resist solution 2 was used as the resist solution, exposure was performed at an exposure dose 3% less than the EUV sensitivity in n-butyl acetate development, and development was carried out for 30 seconds using n-butyl acetate instead of the TMAH aqueous solution as the developer, and etching defect evaluation was performed in the same manner. The obtained evaluation results are shown in Table 3.

Table 3

[0184] As is clear from Table 3, it was confirmed that the sensitivity can be significantly controlled by using the acid diffusion controller in combination.

Claims

1. A composition for lithography comprising a compound having at least one element selected from the group consisting of iodine, tellurium and fluorine, or a resin having a structural unit derived from the compound, The composition for lithography as described above, wherein the total mass of the atoms in the compound is 15 mass % or more and 75 mass % or less.

2. 2. The lithographic composition of claim 1, wherein the at least one element is at least one element selected from the group consisting of iodine and tellurium.

3. 3. The composition for lithography according to claim 1, wherein the at least one element is iodine, and a mass of the iodine in the compound is 15 mass % or more and 75 mass % or less.

4. The composition for lithography according to any one of claims 1 to 3, wherein the compound is represented by formula (A-4a): 【Chemistry 1】 (In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. Y is a 2n-valent group having 1 to 60 carbon atoms or a single bond; wherein when X is uncrosslinked, Y is the 2n-valent group; R 0 each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, Here, R 0 at least one of the groups is a hydroxyl group; Each m is independently an integer from 1 to 9; Q represents iodine, tellurium, fluorine, an alkyl group having 1 to 30 carbon atoms containing at least iodine, tellurium, or fluorine, or an aryl group having 6 to 40 carbon atoms containing at least iodine, tellurium, or fluorine, n is an integer from 1 to 4, Each p is independently an integer from 0 to 3; Q, R 0 At least one of Y contains at least one element selected from the group consisting of iodine, tellurium, and fluorine; Each q is independently an integer from 0 to (4+2×p-m).

5. 5. The composition for lithography according to claim 4, wherein Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent.

6. The composition for lithography according to any one of claims 1 to 3, wherein the compound is represented by formula (A-4c): 【Chemistry 2】 (In formula (A-4c), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. Y is a 2n-valent group having 1 to 60 carbon atoms or a single bond; wherein when X is uncrosslinked, Y is the 2n-valent group; R 0 each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, Here, R 0 at least one of the groups is a hydroxyl group; R 0 at least one of is iodine or a group containing iodine; Each m is independently an integer from 1 to 9; n is an integer from 1 to 4, Each p is independently an integer of 0 to 3.

7. 7. The composition for lithography according to claim 6, wherein Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent.

8. The composition for lithography according to any one of claims 1 to 3, wherein the compound is represented by general formula (AM1): 【Chemistry 3】 (In formula (AM1), R 1 represents a hydrogen atom, a methyl group, or a halogen group; R 2 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 1 represents 0 or 1, n 2 represents an integer from 1 to 20.)

9. The composition for lithography according to any one of claims 1 to 3, wherein the compound is represented by general formula (A-7): 【Chemistry 4】 (In formula (A-7), X's each independently represent tellurium, I, F, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of tellurium, I, and F, and at least one of X's is tellurium or I; L 1 represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, m is an integer of 1 or more, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; n is an integer of 0 or more, Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; r is an integer equal to or greater than 0; A is an organic group having 1 to 30 carbon atoms; R a , R b , and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent. p is an integer of 1 or more.

10. The composition for lithography according to any one of claims 1 to 9, further comprising a solvent.

11. The composition for lithography according to any one of claims 1 to 10, further comprising an acid generator.

12. The composition for lithography according to any one of claims 1 to 11, further comprising an acid diffusion promoter.

13. The composition for lithography according to any one of claims 1 to 12, further comprising an acid diffusion inhibitor.

14. The composition for lithography according to any one of claims 1 to 13, further comprising a crosslinking agent.

15. The composition for lithography according to any one of claims 1 to 14, which is cured after being formed into a thin film.

16. The composition for lithography according to any one of claims 1 to 15, for forming a resist layer contact film.

17. The composition for lithography according to any one of claims 1 to 15, for forming an underlayer film.

18. An underlayer film forming step of forming an underlayer film on a substrate using the composition for lithography according to claim 17; a photoresist film forming step of forming at least one layer of a photoresist film on the underlayer film formed in the underlayer film forming step; a step of irradiating a predetermined region of the photoresist film formed in the photoresist film forming step with radiation and developing the same; A method for forming a resist pattern comprising the steps of:

19. an underlayer film forming step of forming an underlayer film on a substrate; a resist layer contact film forming step of forming a resist layer contact film on the underlayer film formed in the underlayer film forming step by using the composition for lithography according to claim 16; a photoresist film forming step of forming at least one layer of photoresist film on the resist layer contact film formed in the resist layer contact film forming step; a resist pattern forming step of irradiating a predetermined region of the photoresist film formed in the photoresist film forming step with radiation and developing the photoresist film to form a resist pattern; a pattern forming step of etching the resist layer contact film, or the resist layer contact film and the underlayer film, using the resist pattern formed in the resist pattern forming step as a mask to form a pattern; a substrate pattern forming step of etching the substrate using the pattern formed in the pattern forming step as a mask to form a pattern on the substrate; A method for forming a circuit pattern comprising the steps of:

20. A compound represented by formula (A-4a): 【Chemistry 5】 (In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. Y is a 2n-valent group having 1 to 60 carbon atoms or a single bond; wherein when X is uncrosslinked, Y is the 2n-valent group; R 0 each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, Here, R 0 at least one of the groups is a hydroxyl group; Each m is independently an integer from 1 to 9; Q represents iodine, tellurium, fluorine, an alkyl group having 1 to 30 carbon atoms containing at least iodine, tellurium, or fluorine, or an aryl group having 6 to 40 carbon atoms containing at least iodine, tellurium, or fluorine, n is an integer from 1 to 4, Each p is independently an integer from 0 to 3; Q, R 0 At least one of Y contains at least one element selected from the group consisting of iodine, tellurium, and fluorine; Each q is independently an integer from 0 to (4+2×p-m).

21. The compound according to claim 20, wherein Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent.

22. A compound represented by formula (A-4c): 【Chemistry 6】 (In formula (A-4c), X represents an oxygen atom, a sulfur atom, a single bond, or no crosslinking. Y is a 2n-valent group having 1 to 60 carbon atoms or a single bond; wherein when X is uncrosslinked, Y is the 2n-valent group; R 0 each independently represents an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group or a hydroxyl group, Here, R 0 at least one of the groups is a hydroxyl group; R 0 at least one of is iodine or a group containing iodine; Each m is independently an integer from 1 to 9; n is an integer from 1 to 4, Each p is independently an integer of 0 to 3.

23. The compound according to claim 22, wherein Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent.

Images