Composition for lithography and method for forming a pattern

Abstract

The present invention aims to provide a lithography composition, etc., which is capable of forming a pattern with excellent exposure sensitivity and is in contact with a resist layer or a lower layer. The above objective can be achieved by a lithography composition comprising 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 said compound, wherein the total mass of said atoms in said compound is 15 mass% or more and 75 mass% or less.

Description

Technology Field

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

[0002] Recently, in the manufacturing of semiconductor devices and liquid crystal display devices, the miniaturization of semiconductors (patterns) and pixels is progressing rapidly due to advancements in lithography technology. Generally, the wavelength of the exposure light source is shortened as a method for pixel miniaturization. Specifically, while ultraviolet rays, represented by g-rays and i-rays, were conventionally used, far-ultraviolet exposure such as KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) is currently the focus of mass production, and furthermore, the introduction of Extreme Ultraviolet (EUV) lithography (13.5 nm) is underway. In addition, electron beams (EB) are also utilized for the formation of fine patterns.

[0003] Among these, lithography using extreme ultraviolet rays, in particular, is seeing an increase in adoption due to recent technological advancements.

[0004] Conventional resist materials to date are polymeric resist materials capable of forming an amorphous film. Examples include polymeric resist materials such as polymethyl methacrylate, polyhydroxystyrene having acid-dissociating groups, or polyalkyl methacrylate (see, for example, Non-Patent Literature 1).

[0005] Conventionally, a line pattern of about 10 to 100 nm is formed by irradiating a resist thin film, which is fabricated by applying a solution of these resist materials onto a substrate, with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, etc.

[0006] Furthermore, the reaction mechanism of electron beam or electron ultraviolet lithography differs from that of conventional photolithography (Non-patent Literature 2, Non-patent Literature 3). Moreover, electron beam or extreme ultraviolet lithography aims to form fine patterns ranging from several nanometers to several tens of nanometers. As the dimensions of the resist pattern become smaller, a resist composition that is more sensitive to the exposure light source is required. In particular, in extreme ultraviolet lithography, it is required to achieve additional sensitivity in terms of throughput.

[0007] As a resist material that improves the problem described above, inorganic resist materials having metal elements such as titanium, tin, hafnium, or zirconium have been proposed (see, for example, Patent Document 1). Prior art literature

[0008] Japanese Patent Publication No. 2015-108781

[0009] Shinji Okazaki, et al., "40 Years of Lithography Technology," S&T Publishing, December 9, 2016. H. Yamamoto, et al., Jpn.J.Appl.Phys.46, L142(2007). H. Yamamoto, et al., J.Vac.Sci.Technol.b23, 2728(2005). The problem to be solved

[0010] However, conventionally developed resist compositions with high sensitivity have challenges such as insufficient pattern quality, including large pattern defects or roughness, or insufficient sensitivity and etching resistance. Based on these situations, a lithography technology that achieves both high resolution and high sensitivity is required.

[0011] In addition, in extreme ultraviolet lithography, a short wavelength of 13.5 nm is used, so compared to conventional exposure technology, the transmittance of photons is high and the number of photons at the same exposure intensity is low, so it is necessary to efficiently convert extreme ultraviolet rays into protons required for exposure. Furthermore, it is necessary to supply protons from a layer adjacent to the resist as well.

[0012] Taking the above circumstances into account, the present invention aims to provide a lithography composition and a method for forming a pattern, wherein a film in contact with a resist layer (hereinafter referred to as a "resist layer contact film") or a lower layer film is obtained, which is capable of forming a pattern with excellent exposure sensitivity. means of solving the problem

[0013] As a result of careful consideration to solve the above-mentioned problem, the inventors discovered that the exposure sensitivity of the lithography process can be increased by using a compound having a specific elemental composition or a resin containing said compound as a structural unit in the resist layer contact film or the lower film, and thus completed the present invention.

[0014] That is, the present invention is as follows.

[0015] [1]

[0016] A lithography composition comprising 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 said compound,

[0017] A lithography composition in which the total mass of the atoms in the above compound is 15 mass% or more and 75 mass% or less.

[0018] [2]

[0019] A lithography composition described in [1], wherein at least one of the above elements is selected from the group consisting of iodine and tellurium.

[0020] [3]

[0021] A lithography composition described in [1] or [2], wherein at least one of the above elements is iodine, and the mass of the iodine in the compound is 15 mass% or more and 75 mass% or less.

[0022] [4]

[0023] A lithography composition in which the above compound is represented by formula (A-4a) and described in any one of [1] to [3].

[0024] [Chemical Formula 1]

[0025]

[0026] (among Equation (A-4a),

[0027] X represents an oxygen atom, a sulfur atom, a single bond, or is non-crosslinked, and

[0028] Y is a 2n group or single bond with 1 to 60 carbon atoms, and

[0029] Here, when X is uncrosslinked, Y is the group of the above 2n, and

[0030] R 0 Each is independently an alkyl group having 1 to 40 carbon atoms that may have substituents, an aryl group having 6 to 40 carbon atoms that may have substituents, an alkenyl group having 2 to 40 carbon atoms that may have substituents, an alkynyl group having 2 to 40 carbon atoms that may have substituents, an alkoxy group having 1 to 40 carbon atoms that may have substituents, a halogen atom, a thiol group, or a hydroxyl group, and

[0031] Here, R 0 At least one of them is a hydroxyl group, and

[0032] m are each independently integers from 1 to 9, and

[0033] Q represents an alkyl group having 1 to 30 carbon atoms comprising at least iodine, tellurium, fluorine, or iodine, tellurium, or fluorine, or an aryl group having 6 to 40 carbon atoms comprising at least iodine, tellurium, or fluorine, and

[0034] n is an integer from 1 to 4, and

[0035] p are each independently integers from 0 to 3, and

[0036] Q, R 0 At least one of , Y comprises at least one element selected from iodine, tellurium, and fluorine, and

[0037] q are each independently integers from 0 to (4+2×pm).

[0038] [4-1]

[0039] A lithography composition described in [4], in which X is an oxygen atom or is non-crosslinked.

[0040] [4-2]

[0041] A lithography composition for which Q is iodine, as described in [4] or [4-1].

[0042] [4-3]

[0043] Q, R 0 A lithography composition described in any one of [4] to [4-2], wherein at least one of Y comprises iodine.

[0044] [4-4]

[0045] A lithography composition described in any one of [4] to [4-3], where q is an integer from 1 to (4+2×pm) independently.

[0046] [5]

[0047] A lithography composition described in any one of [4] to [4-4], wherein Y is a 2n hydrocarbon group having an aryl group having 6 to 60 carbon atoms that may have a substituent.

[0048] [5-1]

[0049] A lithography composition described in [5], wherein the above 2n hydrocarbon group is a methylene group.

[0050] [5-2]

[0051] A lithography composition described in [5] or [5-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.

[0052] [5-3]

[0053] A lithography composition described in any one of [5] to [5-2], wherein the above-mentioned substituent is iodine.

[0054] [6]

[0055] A lithography composition in which the above compound is represented by formula (A-4c) as described in any one of [1] to [3].

[0056] [Chemical Formula 2]

[0057]

[0058] (Among Equation (A-4c),

[0059] X represents an oxygen atom, a sulfur atom, a single bond, or is non-crosslinked, and

[0060] Y is a 2n group or single bond with 1 to 60 carbon atoms, and

[0061] Here, when X is uncrosslinked, Y is the group of the above 2n, and

[0062] R 0 Each is independently an alkyl group having 1 to 40 carbon atoms that may have substituents, an aryl group having 6 to 40 carbon atoms that may have substituents, an alkenyl group having 2 to 40 carbon atoms that may have substituents, an alkynyl group having 2 to 40 carbon atoms that may have substituents, an alkoxy group having 1 to 40 carbon atoms that may have substituents, a halogen atom, a thiol group, or a hydroxyl group, and

[0063] Here, R 0 At least one of them is a hydroxyl group, and

[0064] R 0 At least one of the is iodine, or a group containing iodine, and

[0065] m are each independently integers from 1 to 9, and

[0066] n is an integer from 1 to 4, and

[0067] p are independent integers from 0 to 3.

[0068] [6-1]

[0069] A lithography composition described in [6], in which X is an oxygen atom or is non-crosslinked.

[0070] [7]

[0071] A lithography composition described in either [6] or [6-1], wherein Y is a 2n hydrocarbon group having an aryl group having 6 to 60 carbon atoms that may have a substituent.

[0072] [7-1]

[0073] A lithography composition described in [7], wherein the above 2n hydrocarbon group is a methylene group.

[0074] [7-2]

[0075] A lithography composition described in [7] or [7-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.

[0076] [7-3]

[0077] A lithography composition described in any one of [7] to [7-2], wherein the above-mentioned substituent is iodine.

[0078] [8]

[0079] A lithography composition described in any one of [1] to [3], wherein the above compound is represented by the general formula (AM1).

[0080] [Chemical Formula 3]

[0081]

[0082] (during the meal (AM1),

[0083] R 1 Representing silver, hydrogen atoms, methyl, or halogen groups,

[0084] R 2Each independently represents a hydrogen atom, a straight-chain 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, and

[0085] A represents an organic group having 1 to 30 carbon atoms, and

[0086] n 1 represents 0 or 1, and

[0087] n 2 represents an integer from 1 to 20.)

[0088] [8-1]

[0089] R 1 This is a lithography composition described in [8], which is methyl.

[0090] [8-2]

[0091] n 1 A lithography composition described in [8] or [8-1], which is 0.

[0092] [8-3]

[0093] A composition for lithography described in any one of [8] to [8-2], wherein A is a cycloaliphatic hydrocarbon group.

[0094] [8-4]

[0095] A composition for lithography in which A is an adamantyl group, as described in any one of [8] to [8-3].

[0096] [9]

[0097] A lithography composition described in any one of [1] to [3], wherein the above compound is represented by the general formula (A-7).

[0098] [Chemical Formula 4]

[0099]

[0100] (Among Equation (A-7),

[0101] X represents an organic group having 1 to 30 carbon atoms, each independently having 1 to 5 substituents selected from the group consisting of tellurium, I, F, or tellurium, I, and F, and at least one of X is tellurium or I.

[0102] L 1 It represents a single bond, ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, or phosphate group,

[0103] m is an integer greater than or equal to 1, and

[0104] Y represents, respectively, 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 phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and

[0105] n is an integer greater than or equal to 0, and

[0106] Z is, respectively, an alkoxy group, an ester group, an acetal group, or a carbonate ester group, and

[0107] r is an integer greater than or equal to 0, and

[0108] A is an organic group having 1 to 30 carbon atoms, and

[0109] R a , R b , and R c is an organic group having 1 to 60 carbon atoms that may each independently have H, I, F, Cl, Br, or a substituent.

[0110] p is an integer greater than or equal to 1.

[0111] [9-1]

[0112] X is iodine, a lithography composition described in [9].

[0113] [9-2]

[0114] L 1This is a lithography composition described in [9] or [9-1], which is a single bond.

[0115] [9-3]

[0116] A lithography composition described in any one of [9] to [9-2], wherein Y is a hydroxyl group and n is an integer greater than or equal to 1.

[0117] [9-4]

[0118] A lithography composition described in any one of [9] to [9-3], where r is 0.

[0119] [9-5]

[0120] A composition for lithography described in any one of [9] to [9-4], wherein A is an aromatic ring having 6 to 14 carbon atoms.

[0121] [9-6]

[0122] R a , R b , and R c A composition for lithography described in any one of [9] to [9-5], hydrogen.

[0123]

[10]

[0124] A lithography composition described in any one of [1] to [9-6], additionally containing a solvent.

[0125]

[11]

[0126] A lithography composition described in any one of [1] to

[10] , additionally containing an acid-generating agent.

[0127]

[12]

[0128] A lithography composition described in any one of [1] to

[11] , additionally containing an acid diffusion promoter.

[0129]

[13]

[0130] A lithography composition described in any one of [1] to

[12] , additionally containing an acid diffusion inhibitor.

[0131]

[14]

[0132] A lithography composition described in any one of [1] to

[13] , additionally containing a crosslinking agent.

[0133]

[15]

[0134] A lithography composition described in any one of [1] to

[14] that hardens after forming a thin film.

[0135]

[16]

[0136] A lithography composition for forming a resist layer contact film as described in any one of [1] to

[15] .

[0137]

[17]

[0138] A lithography composition for forming a lower layer, as described in any one of [1] to

[15] .

[0139]

[18]

[0140] A process for forming a lower layer on a substrate using a lithography composition described in

[17] , and a process for forming a lower layer on a substrate, and

[0141] A photoresist film formation process for forming at least one layer of photoresist film on a lower film formed by this lower film formation process, and

[0142] A process of irradiating a predetermined area of ​​a photoresist film formed by this photoresist film formation process with radiation and performing development,

[0143] A method for forming a resist pattern including

[0144]

[19]

[0145] A lower layer formation process for forming a lower layer on a substrate, and,

[0146] A resist layer contact film forming process, wherein a resist layer contact film is formed on a lower layer formed by this lower layer forming process using a lithography composition described in

[16] , and

[0147] A photoresist film formation process for forming at least one layer of photoresist film on a resist layer contact film formed by this resist layer contact film formation process, and

[0148] A resist pattern formation process that irradiates a predetermined area of ​​a photoresist film formed by this photoresist film formation process with radiation and develops it to form a resist pattern, and

[0149] A pattern formation process for forming a pattern by etching the resist layer contact film, or the resist layer contact film and the lower layer film, using a resist pattern formed by this resist pattern formation process as a mask, and

[0150] A substrate pattern formation process that forms a pattern on a substrate by etching the substrate using a pattern formed by this pattern formation process as a mask,

[0151] A circuit pattern forming method including

[0152]

[20]

[0153] A compound represented by formula (A-4a).

[0154] [Chemical Formula 5]

[0155]

[0156] (among Equation (A-4a),

[0157] X represents an oxygen atom, a sulfur atom, a single bond, or is non-crosslinked, and

[0158] Y is a 2n group or single bond with 1 to 60 carbon atoms, and

[0159] Here, when X is uncrosslinked, Y is the group of the above 2n, and

[0160] R 0 Each is independently an alkyl group having 1 to 40 carbon atoms that may have substituents, an aryl group having 6 to 40 carbon atoms that may have substituents, an alkenyl group having 2 to 40 carbon atoms that may have substituents, an alkynyl group having 2 to 40 carbon atoms that may have substituents, an alkoxy group having 1 to 40 carbon atoms that may have substituents, a halogen atom, a thiol group, or a hydroxyl group, and

[0161] Here, R 0At least one of them is a hydroxyl group, and

[0162] m are each independently integers from 1 to 9, and

[0163] Q represents an alkyl group having 1 to 30 carbon atoms comprising at least iodine, tellurium, fluorine, or iodine, tellurium, or fluorine, or an aryl group having 6 to 40 carbon atoms comprising at least iodine, tellurium, or fluorine, and

[0164] n is an integer from 1 to 4, and

[0165] p are each independently integers from 0 to 3, and

[0166] Q, R 0 At least one of , Y comprises at least one element selected from iodine, tellurium, and fluorine, and

[0167] q are each independently integers from 0 to (4+2×pm).

[0168] [20-1]

[0169] A compound described in

[20] in which X is an oxygen atom or is non-crosslinked.

[0170] [20-2]

[0171] Q is iodine, a compound described in

[20] or [20-1].

[0172] [20-3]

[0173] Q, R 0 A compound described in any one of

[20] to [20-2], wherein at least one of Y contains iodine.

[0174] [20-4]

[0175] A compound described in any one of

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

[0176]

[21]

[0177] A compound described in any one of

[20] to [20-4], wherein Y is a 2n hydrocarbon group having an aryl group having 6 to 60 carbon atoms that may have a substituent.

[0178] [21-1]

[0179] The above 2n hydrocarbon group is a methylene group, a compound described in

[21] .

[0180] [21-2]

[0181] A compound described in

[21] or [21-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.

[0182] [21-3]

[0183] A compound described in any one of

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

[0184]

[22]

[0185] A compound represented by the formula (A-4c).

[0186] [Chemical Formula 6]

[0187]

[0188] (Among Equation (A-4c),

[0189] X represents an oxygen atom, a sulfur atom, a single bond, or is non-crosslinked, and

[0190] Y is a 2n group or single bond with 1 to 60 carbon atoms, and

[0191] Here, when X is uncrosslinked, Y is the group of the above 2n, and

[0192] R 0 Each is independently an alkyl group having 1 to 40 carbon atoms that may have substituents, an aryl group having 6 to 40 carbon atoms that may have substituents, an alkenyl group having 2 to 40 carbon atoms that may have substituents, an alkynyl group having 2 to 40 carbon atoms that may have substituents, an alkoxy group having 1 to 40 carbon atoms that may have substituents, a halogen atom, a thiol group, or a hydroxyl group, and

[0193] Here, R 0 At least one of them is a hydroxyl group, and

[0194] R 0At least one of the is iodine, or a group containing iodine, and

[0195] m are each independently integers from 1 to 9, and

[0196] n is an integer from 1 to 4, and

[0197] p are independent integers from 0 to 3.

[0198] [22-1]

[0199] A compound described in

[22] in which X is an oxygen atom or is non-crosslinked.

[0200]

[23]

[0201] A compound described in

[22] or [22-1], wherein Y is a 2n hydrocarbon group having an aryl group having 6 to 60 carbon atoms that may have a substituent.

[0202] [23-1]

[0203] The above 2n hydrocarbon group is a methylene group, a compound described in

[23] .

[0204] [23-2]

[0205] The above aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group,

[23] or [23-1] described in the compound.

[0206] [23-3]

[0207] A compound described in any one of

[23] to [23-2], wherein the above substituent is iodine. Effects of the invention

[0208] According to the present invention, a lithography composition capable of increasing the exposure sensitivity of a lithography process and a pattern formation method can be provided. Specific details for implementing the invention

[0209] Hereinafter, embodiments of the present invention will be described (hereinafter referred to as “the present embodiment”). Meanwhile, the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.

[0210] [Compound (A) and Resin (A)]

[0211] The compound according to the present embodiment (hereinafter also referred to as "compound (A)"), and the resin having a constituent 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 ability to absorb extreme ultraviolet rays, they can absorb extreme ultraviolet rays to ionize compound (A) and efficiently generate protons.

[0212] The total content of iodine and tellurium atoms is 15 mass% or more and 75 mass% or less of the total compound (A), preferably 20 mass% or more and 75 mass% or less.

[0213] If the total content of iodine and tellurium is 15 mass% or less, the absorption capacity for extreme ultraviolet rays is reduced, and thus the efficiency of proton generation is reduced. In addition, if the total content of iodine and tellurium is 75 mass% or more, the stability of the compound is reduced and it becomes prone to decomposition.

[0214] It is desirable for compound (A) to contain an aromatic ring for high sensitivity. As the density is improved, the absorption rate per path length of extreme ultraviolet rays is improved.

[0215] In addition, it is also desirable that the compound (A) contains hydrophilic groups, such as hydroxyl groups, in terms of adhesion to the substrate or resist layer.

[0216] "Hydrophilic group" refers to a group that improves the affinity between the organic compound and water by bonding to the organic compound. Examples of hydrophilic groups include hydroxyl groups, nitro groups, amino groups, carboxyl groups, thiol groups, phosphine groups, phosphon groups, phosphate groups, ether groups, thioether groups, urethane groups, urea groups, amide groups, and imide groups.

[0217] It is desirable that the compound (A) has curability and solvent resistance after curing so that it forms a film and does not dissolve in the resist liquid when the resist is applied. For this reason, it is also desirable that, for example, the compound (A) contains crosslinkable groups or polymerizable groups.

[0218] "Crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but examples 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.

[0219] In addition, "polymerizable group" refers to a group that polymerizes in the presence or absence of a catalyst. Polymerizable groups are not particularly limited, but examples include groups having (meth)acrylic groups, groups having unsaturated double bonds such as vinyl groups, and groups having unsaturated triple bonds such as propagyl groups.

[0220] It is also desirable that the compound (A) contains a dissociable group.

[0221] "Dissociable group" refers to a group that dissociates in the presence of a catalyst or without a catalyst. Among dissociable groups, an acid dissociable group refers to a characteristic group that cleaves in the presence of an acid and changes into an alkali-soluble group, etc. Specific examples of acid dissociable groups include those described in International Publication No. 2016 / 158168. Preferred examples of acid dissociable groups include groups selected from the group consisting of 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, silyl groups, acyl groups, 1-substituted alkoxymethyl groups, cyclic ether groups, alkoxycarbonyl groups, and alkoxycarbonylalkyl groups, which have the property of dissociating by acid.

[0222] As for the resin (A), in addition to the resin obtained by polymerizing compound (A) alone, a resin polymerized using a crosslinking agent or a resin copolymerized with other compounds may also be used, and is not particularly limited.

[0223] The weight-average molecular weight of the resin (A) is preferably 300 to 20,000, more preferably 300 to 10,000, and even more preferably 300 to 8,000 in terms of reducing defects in the formed film and having a good pattern shape. The weight-average molecular weight can be the value obtained by measuring the weight-average molecular weight equivalent to polystyrene using GPC.

[0224] For the manufacture of the resin (A), any known method capable of producing a resin having compound (A) as a constituent unit may be used without limitation. Examples include crosslinking with aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, etc., and copolymerizing with compounds containing unsaturated hydrocarbon groups, etc. Examples of "compounds containing unsaturated hydrocarbon groups" are not particularly limited, but examples include compounds having (meth)acrylic groups, compounds having unsaturated double bonds such as vinyl groups, and compounds having unsaturated triple bonds such as propargyl groups.

[0225] 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.

[0226] It is preferable that the compound (A) be a compound (A-1) represented by the formula (A-1), comprising one or more selected from the group consisting of iodine, tellurium, and fluorine in a predetermined amount.

[0227] [Chemical Formula 7]

[0228]

[0229] (In the above general formula (A-1), X represents, respectively, an oxygen atom, a sulfur atom, or a non-crosslinked atom, and R 1 It is a single bond or a 2n group with 1 to 30 carbon atoms, and R 2 and R 3 Each is independently a halogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a thiol group, or a hydroxyl group; each m is independently an integer from 0 to 7, provided that at least one m is an integer from 1 to 7; each p is independently 0 or 1; and n is an integer from 1 to 4. provided that R 1 , R 2 and R 3 At least one selected from the group consisting of is a group comprising one or more selected from the group consisting of iodine atoms, tellurium atoms, and fluorine atoms, and R 2 At least one of and / or R 3 At least one of the groups is one or more selected from hydroxyl groups and thiol groups.)

[0230] It is also preferable that the compound (A) be a compound (A-2) represented by formula (A-2) comprising one or more selected from the group consisting of iodine, tellurium, and fluorine in a predetermined amount.

[0231] [Chemical Formula 8]

[0232]

[0233] (In Equation (A-2), R 1 It is a 2n group with 1 to 30 carbon atoms, and R 2 ~R 5 Each is independently a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a thiol group, or a hydroxyl group, provided that R 1 ~R 5At least one selected from is a group comprising one or more selected from the group consisting of iodine atoms, tellurium atoms, and fluorine atoms, and R 4 At least one of and / or R 5 At least one of is one or more selected from hydroxyl groups and thiol groups, and m 2 and m 3 are each independently integers from 0 to 8, and m 4 and m 5 are each independently integers from 0 to 9, provided that m 4 and m 5 It never becomes 0 at the same time, n is an integer from 1 to 4, and p 2 ~p 5 are each independently integers from 0 to 2.)

[0234] It is also preferable that the compound (A) be a compound (A-3) represented by formula (A-3) comprising one or more selected from the group consisting of iodine, tellurium, and fluorine in a predetermined amount.

[0235] [Chemical Formula 9]

[0236]

[0237] (In formula (A-3), R is each 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 that may contain a heteroatom; n is 2 or more; and at least one selected from Z or R is a group comprising 1 or more selected from the group consisting of an iodine atom, a tellurium atom, and a fluorine atom.)

[0238] It is also preferable that compound (A) be a compound (A-4a) or compound (A-4b) represented by formula (A-4a) or formula (A-4b), comprising one or more selected from the group consisting of iodine, tellurium, and fluorine in a predetermined amount. A resin having a constituent unit derived from compound (A) of the present invention may be a polycyclic polyphenol resin having a constituent unit derived from compound (A-4a) and / or compound (A-4b). The polycyclic polyphenol resin in the present 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), wherein the repeating units are connected to each other by direct bonding between aromatic rings. The film-forming composition of the present embodiment has excellent film-forming properties, heat resistance, and sublimation resistance due to being configured in this manner.

[0239] [Chemical Formula 10]

[0240]

[0241] (In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or a non-crosslinked group, and Y represents a 2n group having 1 to 60 carbon atoms or a single bond, wherein when X is non-crosslinked, Y is the 2n group. Also, in formula (A-4b), A represents a benzene ring or a condensed ring. Furthermore, in formulas (A-4a) and (A-4b), R 0 Each is independently an alkyl group having 1 to 40 carbon atoms that may have substituents, an aryl group having 6 to 40 carbon atoms that may have substituents, an alkenyl group having 2 to 40 carbon atoms that may have substituents, an alkynyl group having 2 to 40 carbon atoms that may have substituents, an alkoxy group having 1 to 40 carbon atoms that may have substituents, a halogen atom, a thiol group, or a hydroxyl group, where R 0At least one of is a hydroxyl group, and m is 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, 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, and p is independently an integer from 0 to 3. Q, R 0 At least one of , X, and Y contains at least one element selected from iodine, tellurium, and fluorine. In Equation (A-4a), q is independently an integer from 0 to (4+2×pm). Also, in Equation (A-4b), q is independently an integer from 0 to (2+2×pm) (where p represents the number of condensation rings in the condensation ring structure in Equation (A-4b)).

[0242] In Formula (A-4a), X is preferably an oxygen atom in terms of heat resistance and reactivity. Furthermore, in Formula (A-4a), p is preferably 1 in terms of heat resistance and solubility. In addition, in Formula (A-4a), R in terms of reactivity 0 It is desirable to include at least one iodine atom, and from the perspective of storage stability, it is more desirable not to include an iodine atom in Y.

[0243] It is preferable that Equation (A-4a) be Equation (A-4c).

[0244] [Chemical Formula 11]

[0245]

[0246] (In Equation (A-4c), X represents an oxygen atom, a sulfur atom, a single bond, or is non-crosslinked, and Y represents a 2n group having 1 to 60 carbon atoms or a single bond, where, when X is non-crosslinked, Y is the above 2n group, and R 0Each is independently an alkyl group having 1 to 40 carbon atoms that may have substituents, an aryl group having 6 to 40 carbon atoms that may have substituents, an alkenyl group having 2 to 40 carbon atoms that may have substituents, an alkynyl group having 2 to 40 carbon atoms that may have substituents, an alkoxy group having 1 to 40 carbon atoms that may have substituents, a halogen atom, a thiol group, or a hydroxyl group, where R 0 At least one of is a hydroxyl group, and R 0 At least one of them is an iodine atom or an iodine-containing group, m is independently an integer from 1 to 9, n is an integer from 1 to 4, and p is independently an integer from 0 to 3.

[0247] (Polycyclic polyphenol resin)

[0248] The polycyclic polyphenol resin in the present embodiment is not limited to the following, but typically has the characteristics of (1) to (5) below.

[0249] (1) The polycyclic polyphenol resin in this embodiment has excellent solubility in organic solvents (especially safe solvents). For this reason, for example, if 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.

[0250] (2) In the polycyclic polyphenol resin of the present 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 forming a cured product through reaction with a curing agent, and even alone, a cured product can be formed by the phenolic hydroxyl groups undergoing a cross-linking reaction during high-temperature baking. Due to these factors, the polycyclic polyphenol resin of the present embodiment can exhibit high heat resistance, and when used as a film-forming material for lithography, the deterioration of the film during high-temperature baking is suppressed, and a lithography film with excellent etching resistance against oxygen plasma etching, etc. can be formed.

[0251] (3) The polycyclic polyphenol resin in this embodiment can exhibit high heat resistance and etching resistance as described above, and also has excellent adhesion to the resist layer or the resist intermediate layer material. Therefore, when used as a film-forming material for lithography, it is possible to form a lithography film with excellent resist pattern forming properties. Meanwhile, the "resist pattern forming properties" mentioned here refer to properties in which no major defects are seen in the shape of the resist pattern, and both resolution and sensitivity are excellent.

[0252] (4) The polycyclic polyphenol resin in this embodiment has a high refractive index because it has a high aromatic ring density, and it is also useful as a material for forming various optical components because it has excellent transparency and is resistant to discoloration even with heat treatment ranging from low to high temperatures.

[0253] (5) In this embodiment, the polycyclic polyphenol resin has Q as a functional group, which can improve the absorption rate of the EUV exposure light source, and when used as a lower layer for lithography, it can lead to improved productivity by improving sensitivity and suppressing pattern defects such as pattern collapse.

[0254] The polycyclic polyphenol resin in this embodiment can be preferably applied as a film-forming material for lithography due to these characteristics, and thus it is believed that the film-forming composition of this embodiment is endowed with the necessary characteristics described above. As long as the film-forming composition of this embodiment contains the polycyclic polyphenol resin described above, other components are not particularly limited. That is, any arbitrary component may be included in any mixing ratio, and can be appropriately adjusted according to the specific use of the film-forming composition.

[0255] The aforementioned equations (A-4a) and (A-4b) will be explained in detail below.

[0256] In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or a non-crosslinked bond. As for X, an oxygen atom is preferred from the perspective of heat resistance.

[0257] In formula (A-4a), Y is a 2n group or a single bond having 1 to 60 carbon atoms, where X is non-crosslinked, Y is the 2n group.

[0258] A 2n-valent group having 1 to 60 carbon atoms is, for example, a 2n-valent hydrocarbon group, and the said hydrocarbon group may have various functional groups described below as substituents. In addition, the 2n-valent hydrocarbon group indicates that when n=1, it is an alkylene group having 1 to 60 carbon atoms; when n=2, it is an alkanetetary group having 1 to 60 carbon atoms; when n=3, it is an alkanetary group having 2 to 60 carbon atoms; and when n=4, it is an alkanetary group having 3 to 60 carbon atoms. Examples of this 2n-valent hydrocarbon group include a 2n+1-valent hydrocarbon group combined with a straight-chain hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, regarding alicyclic hydrocarbon groups, cyclic hydrocarbon groups are also included.

[0259] Hydrocarbon groups of 2n+1 valence are not limited to the following, but include, for example, trivalent methine groups, ethine groups, etc.

[0260] In addition, the above 2n hydrocarbon group may have a double bond, a heteroatom, and / or an aryl group having 6 to 59 carbon atoms. Meanwhile, 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 mean that it does not include a group derived from a compound having a fluorene skeleton, such as fluorene or benzofluorene.

[0261] In the present embodiment, the 2n group may include 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. Furthermore, the 2n group may include an ether bond, a ketone bond, an ester bond, or a double bond.

[0262] In the present embodiment, from the perspective of heat resistance, it is preferable for the 2n group to include a branched hydrocarbon group or an alicyclic hydrocarbon group rather than a straight-chain hydrocarbon group, and it is more preferable for it to include an alicyclic hydrocarbon group. In addition, in the present embodiment, it is particularly preferable for the 2n group to have an aryl group having 6 to 60 carbon atoms.

[0263] Substituents that may be included in the 2n group are not particularly limited to straight-chain hydrocarbon groups and branched hydrocarbon groups, such as unsubstituted methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, i-butyl groups, t-butyl groups, n-pentyl groups, n-hexyl groups, n-dodecyl groups, valerian groups, etc.

[0264] As substituents that may be included in the 2n group, alicyclic hydrocarbon groups and aromatic groups 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, anthracendiyl group, pyrendiyl group, cyclohexanediyl group, cyclododecanediyl group, dicyclopentanediyl group, tricyclodecanediyl group, adamantanediyl group, benzenetriyl group, naphthalenetriyl group, biphenyltriyl group, anthracentriyl group, pyrentriyl group, cyclohexanetriyl group, cyclododecanetriyl group, dicyclopentanetriyl group, Examples include tricyclodecane triyl group, adamantan triyl group, benzene tetrayl group, naphthalene tetrayl group, biphenyl tetrayl group, anthracene tetrayl group, pyrene tetrayl group, cyclohexane tetrayl group, cyclododecane tetrayl group, dicyclopentane tetrayl group, tricyclodecane tetrayl group, adamantan tetrayl group, etc.

[0265] R 0 Each is independently an alkyl group having 1 to 40 carbon atoms that may have a substituent, an aryl group having 6 to 40 carbon atoms that may have a substituent, an alkenyl group having 2 to 40 carbon atoms that may have a substituent, an alkynyl group having 2 to 40 carbon atoms that may have a substituent, an alkoxy group having 1 to 40 carbon atoms that may have a substituent, a halogen atom, a thiol group, or a hydroxyl group. Here, the alkyl group may be straight-chain, branched, or cyclic.

[0266] Here, R 0 At least one of them is a hydroxyl group.

[0267] Alkyl groups having 1 to 40 carbon atoms are not limited to the following, but examples include methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, i-butyl groups, t-butyl groups, n-pentyl groups, n-hexyl groups, n-dodecyl groups, valerian groups, etc.

[0268] Examples of aryl groups having 6 to 40 carbon atoms include, but are not limited to, phenyl groups, naphthalene groups, biphenyl groups, anthracyl groups, pyrenyl groups, perylene groups, etc.

[0269] Alkenyl groups having 2 to 40 carbon atoms are not limited to the following, but examples include ethinyl groups, propenyl groups, butynyl groups, fentinyl groups, etc.

[0270] Alkynyl groups having 2 to 40 carbon atoms are not limited to the following, but examples include acetylene groups, ethynyl groups, etc.

[0271] Examples of alkoxy groups having 1 to 40 carbon atoms include, but are not limited to, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentoxy groups, etc.

[0272] m is an integer from 1 to 9, each independently. From the perspective of solubility, 1 to 6 is preferred, 1 to 4 is more preferred, and from the perspective of raw material availability, 1 is even more preferred.

[0273] n is an integer from 1 to 4. From the perspective of solubility, 1 to 2 is preferable, and from the perspective of raw material availability, 1 is more preferable.

[0274] p is an integer from 0 to 3, each independently. From the perspective of heat resistance, 1 to 2 is preferable, and from the perspective of raw material availability, 1 is more preferable.

[0275] In the present embodiment, the aromatic hydroxy compound represented by either formula (A-4a) or (A-4b) may be used alone or two or more may be used together. In the present embodiment, from the perspective of achieving compatibility between solvent solubility and heat resistance, it is preferable to use the one represented by formula (A-4a) as the aromatic hydroxy compound. Additionally, from the perspective of achieving compatibility between solvent solubility and heat resistance, it is also preferable to use the one represented by formula (A-4b) as the aromatic hydroxy compound.

[0276] The compound (A) of the present embodiment may be an oligomer (A-5) having an aralkyl structure represented by the following formula (A-5), comprising one or more selected from iodine, tellurium, and fluorine in a predetermined amount.

[0277] [Chemical Formula 12]

[0278]

[0279] (during the meal,

[0280] Ar 0 Each represents a divalent group comprising a phenylene group, a naphthylene group, anthrylene group, phenanthrylene group, pyrylene group, fluorylene group, biphenylene group, or terphenylene group, which may be the same group or different groups, respectively;

[0281] R 0 Each independently represents an alkyl group having 1 to 30 carbon atoms that may be the same group or different groups and may have a substituent, or an aryl group that may have a substituent, iodine, tellurium, fluorine, or an alkyl group having 1 to 30 carbon atoms or an aryl group comprising at least iodine, tellurium, or fluorine;

[0282] n represents an integer from 1 to 50;

[0283] r 0 Each independently represents an integer from 0 to 3;

[0284] p represents an integer greater than or equal to 0, each independently. However, for all r 0 There is no case where this becomes 0 simultaneously. Also, there is no case where all p become 0 simultaneously. Also, R 0 At least one of them includes any one of iodine, tellurium, and fluorine.)

[0285] In the oligomer (A-5), Ar 0Ar represents a divalent group comprising a phenylene group, a naphthylene group, anthrylene group, phenanthrylene group, pyrylene group, fluorylene group, biphenylene group, or terphenylene group, and a divalent group comprising a phenylene group, a naphthylene group, anthrylene group, or pyrylene group is preferred. 0 Each can be independently the same period or a different period.

[0286] Ar 0 Specifically, examples include 1,4-phenylene groups, 1,3-phenylene groups, 4,4'-biphenylene groups, 2,4'-biphenylene groups, 2,2'-biphenylene groups, 2,3'-biphenylene groups, 3,3'-biphenylene groups, 3,4'-biphenylene groups, 2,6-naphthylene groups, 1,5-naphthylene groups, 1,6-naphthylene groups, 1,8-naphthylene groups, 1,3-naphthylene groups, 1,4-naphthylene groups, anthrylene groups, phenanthrylene groups, or pyrylene groups, fluorylene groups, terphenylene groups, etc. In addition, the above Ar 0 The divalent groups include a plurality of phenylene groups connected to alkylene groups, such as a divalent group comprising a diphenylmethyl structure, a bisphenol structure, or a bis(hydroxyphenyl)diisopropylphenyl structure.

[0287] R 0 Ar 0 It is a substituent of which represents, independently, an alkyl group having 1 to 30 carbon atoms that may be the same or different group and may have a substituent, or an aryl group that may have a substituent. R 0 Specific examples of this include R described below. a and R b Specific examples of this can be given.

[0288] In the oligomer (A-5), n represents an integer from 1 to 50. As for n, 3 to 40 is preferred from the perspective of the film planarization performance, 3 to 30 is more preferred, and 3 to 20 is particularly preferred.

[0289] In the oligomer (A-5), r 0Each represents an integer from 0 to 3, independently. However, for all r 0 There is no simultaneous occurrence of this becoming 0. r 0 In terms of improving curability and solubility, 1 to 3 is preferred.

[0290] In the oligomer (A-5), p represents an integer greater than or equal to 0, each independently. However, not all p are simultaneously 0. p is Ar 0 It changes appropriately depending on the type.

[0291] It is also preferable that the compound (A) be a compound (A-6) represented by formula (A-6) comprising one or more selected from iodine, tellurium, and fluorine in a predetermined amount.

[0292] [Chemical Formula 13]

[0293]

[0294] Among Equation (A-6),

[0295] R 1 Representing silver, a hydrogen atom, or a methyl group or a halogen group,

[0296] R 2 Each independently represents a hydrogen atom, a straight-chain 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, and

[0297] A represents an organic group having 1 to 30 carbon atoms, and

[0298] Q each independently represents iodine, tellurium, fluorine, or an alkyl group or aryl group having 1 to 30 carbon atoms comprising at least iodine, tellurium, or fluorine, and preferably, Q is iodine, and

[0299] n 1 represents 0 or 1, and

[0300] n 2 represents an integer from 1 to 20.

[0301] R 1Silver, hydrogen atoms, methyl groups, or halogen groups may be used. Known atoms may be used as halogen groups, and F, Cl, Br, I, etc. may be used appropriately. R 1 When the compound of the present invention is used as a constituent unit of a resin for a resist, it is preferable that it be a methyl group or a halogen group in terms of exposure sensitivity and material stability, and more preferably a halogen group in terms of exposure sensitivity, and even more preferably I.

[0302] R 2 It may be a combination of two or more selected from the group consisting of a straight-chain 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.

[0303] R 2 It is preferable that the element be a hydrogen atom for the purpose of enhancing the effect of introducing iodine by suppressing the rise in the Tg of the resin. In addition, it is preferable that the element be an organic group having one or more carbon atoms for the purpose of controlling solubility in the developer and enhancing acid decomposition. Furthermore, it is preferable that the element be a hydrogen atom for the purpose of suppressing acid decomposition, ensuring solubility in alkaline developer, and suppressing residue.

[0304] R 2 may have substituents. R 2Roe, for example, 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; Examples include aryl groups having 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have substituents; combinations thereof.

[0305] R 2 Specific examples include, for instance, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, icosyl groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclononyl groups, cyclodecyl groups, cycloicosyl groups, adamantyl groups, ethylene groups, propylene groups, butylene groups, phenyl groups, naphthyl groups, anthracene groups, phenanthrene groups, tetracene groups, chrysene groups, triphenylene groups, pyrene groups, benzopyrene groups, azulene groups, fluorene groups, etc. These may include ether bonds, ketone bonds, ester bonds.

[0306] Here, the exemplified groups include isomers. For example, the propyl group includes n-propyl and isopropyl groups, and the butyl group includes n-butyl, sec-butyl, isobutyl, and tert-butyl groups.

[0307] R 2The substituents are not particularly limited, but examples include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aryl groups, alkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkylloyloxy groups, aryloyloxy groups, alkylsilyl groups, various crosslinking groups, and acid-dissociating groups.

[0308] "Crossifying group" refers to a group that crosslinks by acid, alkali, light, or heat, and crosslinks in the presence or absence of a catalyst. The above-mentioned crosslinking group is not particularly limited, but examples include a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy (meth)acryloyl group, a group having a urethane (meth)acryloyl group, a group having a hydroxyl group, a group having a glycidyl group, a group having a vinylphenylmethyl group, a group having a styrene group, a group having an alkynyl group, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and groups including these groups.

[0309] "An acid dissociable group" refers to a group that cleaves in the presence of acid to generate an alkali-soluble group (e.g., phenolic hydroxyl group, carboxyl group, sulfonic acid group, hexafluoroisopropanol group, etc.). The acid dissociable group is not particularly limited, but can be appropriately selected and used from those proposed in, for example, hydroxystyrene resins and (meth)acrylic acid resins used in chemical amplification type resist compositions for KrF or ArF. Specific examples of acid dissociable groups include, for example, those described in International Publication No. 2016 / 158168.

[0310] A may have a substituent. Compounds forming the backbone of A include, for example, alkanes having 1–30, 1–20, 1–10, or 1–6 carbon atoms that may have a substituent; alkenes having 2–30, 2–20, 2–10, or 2–6 carbon atoms that may have a substituent; alkynes having 2–30, 2–20, 2–10, or 2–6 carbon atoms that may have a substituent; cycloalkanes having 3–30, 3–20, 3–10, or 3–6 carbon atoms that may have a substituent; and cycloalkenes having 3–30, 3–20, 3–10, or 3–6 carbon atoms that may have a substituent. Examples include cycloalkynes having 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms, or 3 to 6 carbon atoms, which may have substituents; arenes having 5 to 30 carbon atoms, 5 to 20 carbon atoms, 5 to 10 carbon atoms, or 5 to 6 carbon atoms, which may have substituents; combinations thereof.

[0311] Specific examples of compounds forming the backbone of A include, for example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, icosan, triacontan, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloicosan, cyclotriacontan, adamantane, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, icosene, triacontene, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, pentacene, benzopyrene, coronene, azulene, fluorene, combinations thereof, etc. These may include ether bonds, ketone bonds, or ester bonds.

[0312] The substituents of the compound forming the backbone of A are not particularly limited, but examples include halogen atoms (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aryl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkylloyloxy groups, aryloyloxy groups, alkylsilyl groups, or various crosslinking groups and acid dissociating groups.

[0313] "Bridge-forming group" and "acid-dissociating group" are not specifically limited, for example, the above R 2 You can use what is described in the explanation.

[0314] n 1 It represents 0 or 1, and it is preferable that it be 1.

[0315] n 2 is an integer from 1 to 20, preferably an integer from 2 to 20, more preferably an integer from 2 to 10, and even more preferably an integer from 2 to 5.

[0316] The compound (A) according to the present embodiment may be a compound (A-7) represented by the following formula (A-7), comprising one or more selected from iodine, tellurium, and fluorine in a predetermined amount. The compound (A-7) preferably includes a functional group that improves solubility in an alkaline developer solution through the action of an acid or a base. It is preferable that any one of the following Z, Y, and X includes a functional group that improves solubility in an alkaline developer solution through the action of an acid or a base.

[0317] [Chemical Formula 14]

[0318]

[0319] Among Equation (A-7),

[0320] X is an organic group having 1 to 30 carbon atoms, each independently having 1 to 5 substituents selected from the group consisting of tellurium, I, F, Cl, Br, or tellurium, I, F, Cl, and Br. At least one of X is tellurium or I.

[0321] L 1 It 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 It is, preferably, a single bond.

[0322] m is an integer greater than or equal to 1, preferably an integer greater than or equal to 1 and less than or equal to 5, more preferably an integer greater than or equal to 2 and less than or equal to 4, and even more preferably 2 or 3.

[0323] Y is, each independently, 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 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 ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have substituents.

[0324] Y is preferably a group represented independently by the following formula (Y-1).

[0325] [Chemical Formula 15]

[0326]

[0327] Among equation (Y-1),

[0328] L 2 is a group that cleaves under the action of an acid. Groups that cleave under the action of an acid include, for example, ester groups[* 1 -O-(C=O)-* 2 or *1 -(C=O)-O-* 2 ], acetal group[* 1 -O-(C(R 21 )2)-O-* 2 (R 21 Each is independently H, or a hydrocarbon group having 1 to 10 carbon atoms.)], carboxylkoxy group[* 1 -OR 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms.)], and carbonate ester group[* 1 -O-(C=O)-O-* 2 At least one type of divalent linker selected from the group consisting of ] can be cited. Meanwhile, among the formulas, * 1 Silver, the bonding site with A, * 2 is, R 2 It is the binding site with. Among these, L 2 An acetal group, a carbonate ester group, or a carboxylkoxy group is preferred.

[0329] R 2 is a straight-chain, branched, or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a straight-chain, branched, or cyclic aliphatic group containing a heteroatom having 1 to 30 carbon atoms, an aromatic group containing a heteroatom having 1 to 30 carbon atoms, and the above R 2 The aliphatic groups, aromatic groups, aliphatic groups containing heteroatoms, and aromatic groups containing heteroatoms may additionally have substituents. Meanwhile, substituents here include straight-chain, branched, or cyclic aliphatic groups having 1 to 20 carbon atoms, and aromatic groups having 6 to 20 carbon atoms. R 2 Among these, an aliphatic group is desirable. R 2In the above, the aliphatic group is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and even more preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, but examples 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 preferred.

[0330] L 2 go * 1 -(C=O)-O-* 2 Alternatively, if it is a carboxyl group, it is desirable because when cleaved by the action of an acid, a carboxylic acid group is formed, and the difference in solubility and dissolution rate between the heat-reducing and non-heat-reducing parts during the development process is amplified, thereby improving resolution and, in particular, suppressing residue at the bottom of the pattern in fine line patterns.

[0331] Y is preferably a group represented independently by any one of the following formulas (Y-1-1) to (Y-1-7).

[0332] [Chemical Formula 16]

[0333]

[0334] n is an integer greater than or equal to 0, preferably an integer greater than or equal to 1, more preferably an integer greater than or equal to 1 and less than or equal to 5, even more preferably an integer greater than or equal to 1 and less than or equal to 3, and even more preferably 1 or 2.

[0335] R a , R b , and R cEach is an organic group having 1 to 60 carbon atoms that may independently have H, I, F, Cl, Br, or a substituent. The substituents of the organic group having 1 to 60 carbon atoms are not particularly limited, but examples include I, F, Cl, Br, or other substituents. Other substituents are not particularly limited, but examples 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 phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. Among these, the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, and phosphate group may additionally have substituents. Meanwhile, substituents here may include straight-chain, branched, or cyclic aliphatic groups having 1 to 20 carbon atoms, and aromatic groups having 6 to 20 carbon atoms.

[0336] R a , R b , and R c In the case of, the number of carbon atoms of an organic group that may have a substituent is preferably 1 to 30.

[0337] Organic groups having 1 to 60 carbon atoms that may have substituents are not particularly limited, but may include straight or branched aliphatic hydrocarbon groups having 1 to 60 carbon atoms, alicyclic hydrocarbon groups having 4 to 60 carbon atoms, and aromatic groups having 6 to 60 carbon atoms that may contain heteroatoms.

[0338] Straight or branched aliphatic hydrocarbon groups having 1 to 60 carbon atoms are not particularly limited, but examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-dodecyl, valer, and 2-ethylhexyl groups.

[0339] The alicyclic hydrocarbon groups are not particularly limited, but examples include cyclohexyl groups, cyclododecyl groups, dicyclopentyl groups, tricyclodecyl groups, adamantyl groups, etc. Furthermore, aromatic groups that may contain heteroatoms such as benzodiazole groups, benzotriazole groups, benzothiadiazole groups, etc., may also be appropriately selected. In addition, combinations of these organic groups may be selected.

[0340] Aromatic groups that may contain heteroatoms having 6 to 60 carbon atoms are not particularly limited, but examples include phenyl groups, naphthalene groups, biphenyl groups, anthracyl groups, pyrenyl groups, benzodiazole groups, benzotriazole groups, and benzothiadiazole groups.

[0341] Among the organic groups having 1 to 60 carbon atoms that may have these substituents, a methyl group is preferred.

[0342] A is an organic group having 1 to 30 carbon atoms. A can be a monocyclic organic group or a compound 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.

[0343] A is preferably represented by any one of the following formulas (A-1) to (A-4), and more preferably represented by the following formula (A-1).

[0344] [Chemical Formula 17]

[0345]

[0346] p represents the number of vinyl groups, p is an integer greater than or equal to 1, preferably an integer greater than or equal to 3, more preferably an integer greater than or equal to 1, and even more preferably 1.

[0347] Z is, independently, an alkoxy group, an ester group, an acetal group, or a carbonate ester group. r is an integer greater than or equal to 0, preferably an integer greater than or equal to 2, more preferably an integer greater than or equal to 0, and even more preferably 0.

[0348] A resin having a constituent unit derived from compound (A) of the present embodiment may have a constituent unit represented by the following formula (A-8). By a resist composition containing this resin component, high sensitivity in the lithography process and high resolution can be achieved by expanding the solubility contrast of the resin during development.

[0349] [Chemical Formula 18]

[0350]

[0351] In Equation (A-8), R 1 , R 2 , A, n 1 , n 2 is as defined in the above equation (A-6), and the symbol * indicates the location of connection with an adjacent repeating unit.

[0352] 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 said (meth)acrylate (co)polymer can be used as a film-forming material for lithography.

[0353] Meanwhile, when using the compound (A) of the present embodiment and the resin derived from compound (A) as a resist underlayer in an exposure process, and when using a process in which the resist layer is processed by forming a lower layer layer by laminating it on a workpiece layer to be processed in a processing process such as dry etching after pattern formation, it is desirable to have a high carbon content, a low hydrogen content, and a high ring structure introduction rate in order to suppress the etching rate from the perspective of etching mask performance to improve pattern quality, such as rectangularity or roughness, after processing the workpiece layer, and it is desirable to use a resin having a single ring or a ring structure formed by the condensation of two or more ring structures as the compound structure. At this time, it is desirable for the ring structure to have an aromatic structure or a heteroaromatic structure.

[0354] In addition, when using the compound (A) of the present embodiment and a resin derived from the compound (A) as a resist lower layer, and additionally using one or more other spin-on-carbon (SOC) layers or inorganic hard mask layers as an etching mask layer, it is also desirable to use a resist lower layer made of the compound (A) of the present embodiment or a resin derived from the compound (A), which exhibits an etching rate faster and easier etching properties than the resist, in order to improve the quality of the pattern shape of the workpiece layer after processing, from the perspective of the processability of the etching mask layer to be transferred by etching and the shape of the resist immediately after development, and to use a resist lower layer made of the compound (A) of the present embodiment or a resin derived from the compound (A) which exhibits an etching rate faster and easier etching properties than the resist, and to additionally laminate at least one etching mask layer on a substrate having a workpiece layer, and to additionally laminate a layer made of the compound (A) of the present embodiment or a resin containing the compound (A) on the upper side above the etching mask layer. From these perspectives, it is preferable to have a resin with few aromatic ring structures or a structure that does not have a novolak structure, and it is preferable to have a resin having an aliphatic structure in its main chain, such as polyacrylic resin, polyethylene resin, or polyalkylene ether resin, or a resin having a high content of carbon skeletons constituting the aliphatic structure.

[0355] Specific examples of compound (A) are given below, but compound (A) is not limited to these.

[0356] [Chemical Formula 19]

[0357]

[0358] [Chemical Formula 20]

[0359]

[0360] [Chemical Formula 21]

[0361]

[0362] [Composition comprising compound (A) or / and resin (A)]

[0363] The composition of the present embodiment includes a compound (A) or / and a resin (A).

[0364] (menstruum)

[0365] In the present embodiment, the solvent may be any known solvent suitable as long as the compound (A) or / and the resin (A) described above are at least dissolved. Specific examples of the solvent are not particularly limited, but 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; and 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; lactic acid esters such as methyl lactic acid, ethyl lactic acid, n-propyl lactic acid, n-butyl lactic acid, and n-amyl lactic acid; 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 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, 3-methyl-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionate butyl, 3-methoxy-3-methylbutyrate butyl, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc.; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); Examples include amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone, but are not particularly limited.The solvent used in the present embodiment is preferably a safety solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactic acid, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactic acid.

[0366] In the present embodiment, the amount of solid component and the amount of solvent are not particularly limited, but with respect to the total mass of the amount of solid component and the solvent, it is preferable that the solid component is 1 to 80 mass% and the solvent is 20 to 99 mass%, more preferably the solid component is 1 to 50 mass% and the solvent is 50 to 99 mass%, even more preferably the solid component is 2 to 40 mass% and the solvent is 60 to 98 mass%, and particularly preferably the solid component is 2 to 10 mass% and the solvent is 90 to 98 mass%.

[0367] (Acid-generating agent)

[0368] In the composition of the present embodiment, it is preferable to include one or more acid-generating agents that generate acid directly or indirectly by irradiation with any one of radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam, or by heating. The acid-generating agents are not particularly limited, and either nonionic or ionic agents may be used. Examples of nonionic acid-generating agents include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oximesulfonate, N-sulfonylmide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid-generating agents are onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, and sulfonylmedide anions. For example, acid-generating compounds described in International Publication WO2013 / 024778, Japanese Patent Publication No. 2009-134088, Japanese Patent Publication No. S63-26653, Japanese Patent Publication No. S55-164824, Japanese Patent Publication No. S62-69263, Japanese Patent Publication No. S63-146038, Japanese Patent Publication No. S63-163452, Japanese Patent Publication No. S62-153853, Japanese Patent Publication No. S63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. may be used. Acid-generating agents may be used alone or in combination of two or more.

[0369] The amount of acid-generating agent used is preferably 0.001 to 49 mass% of the total mass of the solid component, more preferably 1 to 40 mass%, even more preferably 3 to 30 mass%, and particularly preferably 10 to 25 mass%. By using the acid-generating agent within the above range, the curability tends to be improved. In this embodiment, when acid is generated in the system, the method of generating the acid is not particularly limited.

[0370] (Acid diffusion control agent)

[0371] In addition, as other compounds that can be used in combination, a compound capable of promoting or inhibiting the diffusion of the generated acid may be included as an acid diffusion control agent.

[0372] Acid Diffusion Promoter

[0373] A preferred acid diffusion promoter may include a compound having a low pKa value of 2.0 or less for the purpose of maintaining the generated acid while enabling the release of acid when necessary, and also having a molecular weight of 1000 or less, a clogP value of 30 or less, or a Tg of 250°C or less, which can promote thermal diffusivity within the resin matrix and also have heat resistance at least at 250°C. As for the specific structure of the acid diffusion promoter, either nonionic or ionic types may be used. Examples of nonionic acid diffusion promoters include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oximesulfonate, N-sulfonylimide, sulfonyloxyketone), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative ionic acid diffusion promoters are onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, and sulfonylmethane anions.

[0374] As for the cation in the ionic compound, any cation that satisfies the above molecular weight, clogP, Tg, and heat resistance while forming a salt with an anion can be used without special limitation. Specific examples of cations that may preferably be used are organic ammonium cations, organic iodonium cations, and organic sulfonium cations.

[0375] Acid Diffusion Inhibitor

[0376] Acid diffusion inhibitors can be used to suppress the diffusion of acids generated from acid generators, etc., by exposure into the resist film or sublayer during each process of exposure, PEB, and development, and to suppress the reaction of the resist resin or sublayer resin caused by the influence of acids present in trace amounts or diffusion in unexposed areas. Furthermore, as other effects, this leads to improved time stability of the resist resin composition or sublayer resin composition, improved resolution in lithography, and enhanced process robustness by suppressing the time dependence of pattern quality from exposure to development, thereby providing a resist resin composition or sublayer resin composition with excellent process stability. As for the acid diffusion inhibitor, even if it is a low-molecular-weight compound, it may be applied in a form loaded as part of a polymer, or both of these forms may be used in combination.

[0377] In addition, as an acid diffusion inhibitor, a salt that forms an acid with weaker acid dissociation compared to the acid generated from the acid-generating agent used may be used. Acidity, as an indicator of acid dissociation, is expressed by the acid dissociation constant (pKa). When a salt that generates an acid with weaker acidity than the acid generated from the acid-generating agent is used as an acid diffusion inhibitor, the acid dissociation constant of the acid generated from the acid diffusion inhibitor is -3 <pKa이며, 바람직하게는 -1<pKa<7이며, 보다 바람직하게는 0<pKa<5이다.

[0378] Examples of acid diffusion inhibitors include nitrogen-containing compounds and photobase generators that generate a weak acid upon exposure to light.

[0379] Examples of nitrogen-containing compounds include amine compounds such as tripentylamine and trioctylamine, amide-containing compounds such as formamide and N,N-dimethylacetamide, urea compounds such as urea and 1,1-dimethylurea, nitrogen-containing heterocyclic compounds such as pyridine, N-(undecylcarbonyloxyethyl)morpholine and Nt-pentyloxycarbonyl-4-hydroxypiperidine.

[0380] Examples of photobase generators include compounds containing onium cations and weak acid anions that decompose upon exposure to light. In photodisintegrable bases, the acid diffusion control ability is reduced because a weak acid is generated from the protons produced by the decomposition of onium cations and the weak acid anions in the exposure area.

[0381] Examples of salts that generate an acid with a lower acidity than the acid generated from an acid-generating agent include the salt represented by formula (D) described in Japanese Patent Publication No. 2015-147926, Japanese Patent Publication No. 2012-229206, Japanese Patent Publication No. 2012-6908, Japanese Patent Publication No. 2012-72109, Japanese Patent Publication No. 2011-39502 and Japanese Patent Publication No. 2011-191745.

[0382] Other desirable examples of acid diffusion inhibitors include, but are not limited to, the following.

[0383] [Chemical Formula 22]

[0384]

[0385] [Chemical Formula 23]

[0386]

[0387] When the underlying film resin composition contains an acid diffusion control agent, the lower limit of the acid diffusion control agent content is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, and even more preferably 1 part by mass, per 100 parts by mass of the polymer component (or resin component). The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and even more preferably 5 parts by mass.

[0388] When the underlying film resin composition contains an acid diffusion control agent, the lower limit of the acid diffusion control agent content is preferably 1 mol% with respect to 100 mol% of the acid-generating agent, more preferably 5 mol%, and even more preferably 10 mol%. The upper limit of the content is preferably 250 mol%, more preferably 150 mol%, and even more preferably 100 mol%.

[0389] By setting the content of the acid diffusion control agent to the above range, the defect suppression and LWR performance of the lower film resin composition can be further improved. The acid diffusion control agent may contain one or two or more types.

[0390] (Crosslinking agent)

[0391] In the present embodiment, one or more crosslinking agents may be included in the composition. A crosslinking agent refers to a compound capable of crosslinking at least one of the compound (A) or the resin (A). Preferably, the crosslinking agent is 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-generating agent. Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the compound (A) or the resin (A).

[0392] The above-mentioned crosslinking groups include, for example, (i) hydroxyalkyl groups such as hydroxy (alkyl group having 1 to 6 carbon atoms), alkoxy (alkyl group having 1 to 6 carbon atoms), or acetoxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups such as formyl groups or carboxy (alkyl group having 1 to 6 carbon atoms), or groups derived therefrom; (iii) nitrogen-containing groups such as dimethylaminomethyl groups, diethylaminomethyl groups, dimethylolaminomethyl groups, diethylolaminomethyl groups, or morpholinomethyl groups; and (iv) glycidyl-containing groups such as glycidyl ether groups, glycidyl ester groups, or glycidyl amino groups. (v) groups derived from aromatic groups such as benzyloxymethyl groups, benzoyloxymethyl groups, etc., allyloxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), aralkyloxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms); (vi) polymerizable multiple bond-containing groups such as vinyl groups, isopropenyl groups, etc. As for the crosslinking groups of the crosslinking agent in the present embodiment, hydroxyalkyl groups and alkoxyalkyl groups are preferred, and alkoxymethyl groups are particularly preferred.

[0393] The crosslinking agent having the above-mentioned crosslinking group is not particularly limited, but for example, an acid crosslinking agent described in International Publication WO2013 / 024778 may be used. The crosslinking agent may be used alone or in combination of two or more types.

[0394] In the present embodiment, the amount of crosslinking agent used is preferably 0.5 to 50 mass% of the total mass of the solid component, more preferably 0.5 to 40 mass%, even more preferably 1 to 30 mass%, and particularly preferably 2 to 20 mass%. If the mixing ratio of the crosslinking agent is 0.5 mass% or more, it tends to improve solvent resistance and suppress dissolution in the resist solvent applied after curing, whereas if it is 50 mass% or less, it tends to suppress a decrease in heat resistance after curing.

[0395] (Other ingredients)

[0396] In the composition of the present embodiment, as other components, one or more types of various additives such as solubility promoters, solubility control agents, sensitizers, surfactants, and organic carboxylic acids or phosphoric oxo acids or derivatives thereof may be added as necessary.

[0397] (Solution accelerator)

[0398] A solubility accelerator is a component that increases the solubility of a solid component in a developer solution when its solubility is too low, thereby excessively increasing the dissolution rate of the compound during development. It is preferable that the solubility accelerator be of low molecular weight, and examples include low molecular weight phenolic compounds. Examples of low molecular weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. These solubility accelerators may be used alone or in a mixture of two or more types.

[0399] The amount of the solubility accelerator is appropriately adjusted according to the type of solid component used, and is preferably 0 to 49 mass% of the total mass of the solid component, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0400] (Solubility control agent)

[0401] A dissolution control agent is a component that controls the solubility of solid components in the developer when their solubility is too high, thereby appropriately reducing the dissolution rate during development. It is desirable that such a dissolution control agent does not undergo chemical changes during processes such as film calcination, radiation irradiation, or the coating of the upper layer.

[0402] Solubility control agents are not particularly limited, but examples include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. These solubility control agents may be used alone or in combination of two or more.

[0403] The amount of the solvent control agent is appropriately adjusted according to the type of compound used, and is preferably 0 to 49 mass% of the total mass of the solid component, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0404] (Increase / Decrease System)

[0405] Sensitizers are components that absorb the energy of irradiated radiation, transfer that energy to acid-generating agents, and thereby increase the amount of acid produced and improve hardening properties. Examples of such sensitizers include benzophenones, nonacetyls, pyrenes, phenothiazines, fluorenes, etc., but are not particularly limited. These sensitizers may be used alone or in combination of two or more types.

[0406] The amount of sensitizer is appropriately adjusted according to the type of compound used, and is preferably 0 to 49 mass% of the total mass of the solid component, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0407] (Surfactant)

[0408] A surfactant is a component that has the function of improving the coating properties, sintering properties, and coating properties of the upper film of the composition of the present embodiment. The surfactant may be any of anionic surfactants, cationic surfactants, nonionic surfactants, or amphoteric surfactants. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in the preparation of the composition of the present embodiment and can further enhance the effect of the composition of the present embodiment. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and polyethylene glycol higher fatty acid diesters, but are not particularly limited. Commercial products of these surfactants include, by the following product names: F-Top (manufactured by Gemco), Megapak (manufactured by Dai Nippon Ink & Chemical Co.), Fluorad (manufactured by Sumitomo 3M), Asahi Guard, Suflon (both manufactured by Asahi Glass Co.), Pepol (manufactured by Toho Chemical Co.), KP (manufactured by Shin-Etsu Chemical Co.), and Polyflow (manufactured by Kyoei Chemical Co.).

[0409] The amount of surfactant is appropriately adjusted according to the type of solid component used, and is preferably 0 to 49 mass% of the total mass of the solid component, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0410] (Other additives)

[0411] In addition, the composition of the present embodiment may include one or more additives other than the components described above, as needed. Examples of such additives include dyes, pigments, and adhesion promoters. For example, incorporating a dye or pigment is desirable because it can visualize the latent image of the exposed portion and mitigate the effects of halation during exposure. In addition, incorporating an adhesion promoter is desirable because it can improve adhesion to the substrate and the adjacent layer. Furthermore, other additives include anti-halation agents, preservative stabilizers, defoaming agents, shape modifiers, etc., specifically 4-hydroxy-4'-methylchalcone.

[0412] In the composition of the present embodiment, the total amount of optional components can be 0 to 99 mass% of the total mass of the solid components, 0 to 49 mass% is preferred, 0 to 10 mass% is more preferred, 0 to 5 mass% is even more preferred, 0 to 1 mass% is even more preferred, and 0 mass% is particularly preferred.

[0413] The composition of the present embodiment is typically prepared by dissolving each component in a solvent to form a homogeneous solution at the time of use, and then, if necessary, filtering it with, for example, a filter with a hole diameter of about 0.2 μm.

[0414] The composition of the present embodiment is used for lithography purposes. It is preferable that the composition be cured after thin film formation to form a film in contact with an underlayer or a resist layer (resist layer contact film).

[0415] (Physical properties of the composition, etc.)

[0416] The composition of the present embodiment can form an amorphous film by spin coating. In addition, the composition of the present embodiment can be applied to a general semiconductor manufacturing process. After curing, the composition of the present embodiment can improve the sensitivity of an adjacent layer by generating protons through irradiation with extreme ultraviolet rays and supplying protons to the adjacent layer. It is preferable to use the composition of the present embodiment after curing. After curing, it is preferable that the composition be solvent-resistant so as not to dissolve into the composition of the adjacent layer.

[0417] [Method for manufacturing an amorphous film]

[0418] It is possible to form an amorphous film on a substrate using the composition of the present embodiment.

[0419] [Method for forming a resist pattern using a composition]

[0420] A method for forming a resist pattern using the composition of the present embodiment comprises: a lower layer forming process of forming a lower layer on a substrate using the composition; a photoresist film forming process of forming at least one layer of photoresist film on the lower layer formed by the lower layer forming process; and a process of irradiating a predetermined area of ​​the photoresist film formed by the photoresist film forming process with radiation and performing development.

[0421] [Method for forming a circuit pattern using a composition]

[0422] A circuit pattern forming method using the composition of the present embodiment comprises: a lower layer forming process for forming a lower layer on a substrate; a resist layer contact film forming process for forming a resist layer contact film on the lower layer formed by the lower layer forming process using the composition; a photoresist film forming process for forming at least one photoresist film on the resist layer contact film formed by the resist layer contact film forming process; a resist pattern forming process for forming a resist pattern by irradiating a predetermined area of ​​the photoresist film formed by the photoresist film forming process with radiation and developing; a pattern forming process for forming a pattern by etching the resist layer contact film, or the resist layer contact film and the lower layer, using the resist pattern formed by the resist pattern forming process as a mask; and a substrate pattern forming process for forming a pattern on the substrate by etching the substrate using the pattern formed by the pattern forming process as a mask.

[0423] Examples

[0424] The present embodiment is described in more detail below through synthetic examples and examples, but the present embodiment is not limited in any way by these examples.

[0425] [Measurement Method]

[0426] (1) Structure of the compound

[0427] The structure of the compound was confirmed by performing 1H-NMR measurements using a Bruker Advance III 500 under the following conditions.

[0428] Frequency: 500MHz

[0429] Solvent: d6-DMSO

[0430] Internal Standard: TMS

[0431] Measured temperature: 23℃

[0432] [Evaluation Method]

[0433] (Adjustment of lower film composition)

[0434] A solution of a lower film composition containing the compound of the present invention was prepared by combining 10 parts by mass of the compound or polymer obtained in the following synthesis example, 0.2 parts by mass of the thermal acid generating agent TAG-2689 (manufactured by King Industries, a quaternary ammonium salt of trifluoromethanesulfonic acid), 1 part by mass of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 76.8 parts by mass of PGMEA, and 12 parts by mass of PGME.

[0435] Meanwhile, for 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.

[0436] (1) Safety solvent solubility test of the compound

[0437] The solubility of the compound in PGMEA was evaluated using the solubility amount for each solvent according to the following criteria. Meanwhile, the solubility amount was measured by weighing the compound into a test tube at 23°C, adding the target solvent to a predetermined concentration, applying ultrasound with an ultrasonic cleaner for 30 minutes, and then visually observing the state of the liquid.

[0438] A: 5.0 mass% ≤ amount dissolved

[0439] B: 2.0 mass% ≤ Soluble amount < 5.0 mass%

[0440] C: Solubility < 2.0 mass%

[0441] (2) Storage stability and thin film formation of the composition

[0442] The storage stability of the composition containing the compound or resin was evaluated by preparing the above-described lower film composition, allowing it to stand at 23°C for 3 days, and visually observing for the presence or absence of precipitation. In addition, the composition was spin-coated onto a clean silicon wafer and baked on a hot plate at 250°C to form an amorphous film with a thickness of 100 nm. For the prepared composition, ○ was evaluated if it was a homogeneous solution and the thin film formation was good, △ if it was a homogeneous solution but the thin film had defects, and × if there was precipitation.

[0443] (3) Sensitivity evaluation

[0444] (EUV Sensitivity-TMAH Aqueous Solution Development)

[0445] A resist solution for sensitivity evaluation and pattern evaluation was prepared by combining 5 parts by mass of polymer MAR1 obtained in the polymer synthesis example for resist below, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.2 parts by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME.

[0446] The above-described lower layer composition was applied onto a silicon wafer, and a baking treatment was performed at 240°C for 60 seconds to form a lower layer with a thickness of 100 nm on the silicon wafer.

[0447] Furthermore, a resist solution was applied to the lower layer of the present invention formed on a silicon wafer, and baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0448] Next, using the extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Risotec Japan Co., Ltd.), 1 mJ / cm² 2 From 1 mJ / cm² 2 80 mJ / cm² 2 After performing maskless shot exposure with the exposure amount increased to [value], the wafer was baked (PEB) at 110°C for 90 seconds, developed with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds, and a wafer with 80 shots of shot exposure was obtained. For each obtained shot exposure area, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and profile data of the film thickness against the exposure amount was acquired. The exposure amount at which the slope of the film thickness variation amount against the exposure amount is greatest was [defined] as the sensitivity value (mJ / cm²). 2 It was calculated as ) and used as an indicator of the EUV sensitivity of the resist.

[0449] (4) Etching resistance

[0450] Etching device: Samco International RIE-10NR

[0451] Output: 50W

[0452] Pressure: 20Pa

[0453] Time: 2 min

[0454] Etching gas

[0455] Ar gas flow rate:CF4 gas flow rate:O2 gas flow rate = 50:5:5 (sccm)

[0456] For a film formed on a silicon wafer using a sublayer film solution made of the material of the present invention prepared in each example and comparative example, an etching test was performed under the conditions described above, and the etching rate at that time was measured. Then, based on the etching rate of a sublayer film prepared using novolak ("PSM4357" manufactured by Gun-A Chemical Co., Ltd.), etching resistance was evaluated according to the following evaluation criteria.

[0457] Evaluation criteria

[0458] A: The difference in etching rate compared to the novolac underlayer is more than 10% smaller relative to the novolac ratio.

[0459] B: Difference in etching rate compared to the novolac underlayer is within ±10% of the novolac-to-novolac ratio.

[0460] C: The difference in etching rate compared to the novolac underlayer is greater than 10% in terms of the ratio to novolac.

[0461] Synthesis Example 1: Synthesis of BisB-1

[0462] In a container with a capacity of 200 mL equipped with a stirrer, a cooling tube, and a burette, 25.0 g (204.7 mmol) of 2,6-dimethylphenol (reagent manufactured by Tokyo Kasei Co.), 25.0 g (107.7 mmol) of 4-iodobenzaldehyde (reagent manufactured by Tokyo Kasei), and 20 mL of 1-methoxy-2-propanol were added, and 5.3 g (53.9 mmol) of sulfuric acid was added to prepare a reaction solution. The reaction solution was stirred at 90°C for 6 hours to carry out the reaction. After the reaction was completed, 1 L of pure water was added to the reaction solution, and baking soda was added while cooling on ice to adjust the pH to 7-8. The solution was then extracted and concentrated with ethyl acetate 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. As a result of performing NMR measurements on the obtained compound (BisB-1) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (BisB-1).

[0463] δ(ppm)8.1(2H, -OH), 6.5~7.7(8H, Ph-H), 5.2(1H, CH), 2.1(12H, CH3)

[0464] [Chemical Formula 24]

[0465]

[0466] Synthesis Example 2: Synthesis of BisB-2

[0467] In a 500 mL container equipped with a stirrer, a cooling tube, and a burette, 42.8 g (230 mmol) of 4,4'-biphenol (reagent from Tokyo Kasei Co.), 21.5 g (57.5 mmol) of 3,5-diiodosalicylaldehyde (reagent from Tokyo Kasei), and 428 mL of γ-butyrolactone were added, and 5.8 g (58 mmol) of sulfuric acid was added to prepare a reaction solution. The reaction solution was stirred at 90°C for 56 hours to carry out the reaction. After the reaction was completed, 1 L of pure water was added to the reaction solution, neutralized with sodium hydroxide, and extracted and concentrated with ethyl acetate to obtain a solution. The obtained solution was separated and purified by column chromatography to obtain 10 g of the target compound (BisB-2) represented by the following formula. As a result of performing NMR measurements on the obtained compound (BisB-2) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (BisB-2).

[0468] δ(ppm)9.4(4H, -OH), 8.9(1H, -OH), 6.2~7.8(16H, Ph-H), 6.3(1H, CH)

[0469] [Chemical Formula 25]

[0470]

[0471] Synthesis Example 3: Synthesis of XbisN-1

[0472] 7.0 g (40 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich) and 4.6 g (20 mmol) of 3-iodobenzaldehyde (reagent manufactured by Tokyo Kasei Kogyo) were added to 100 ml of γ-butyrolactone in a 300 ml container equipped with a stirrer, a cooling tube, and a burette, and 0.5 g of p-toluenesulfonic acid was added. The reaction was carried out by stirring at 90°C for 23 hours 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.

[0473] After separating the obtained solution by column chromatography, chloroform washing was performed, and 4.2 g of the target compound (XbisN-1) represented by the following formula (XbisN-1) was obtained. The molecular weight of the obtained compound (XbisN-1) was measured by the above method and was 516.

[0474] As a result of performing NMR measurements on the obtained compound (XbisN-1) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (XbisN-1).

[0475] δ(ppm)9.7(2H,OH), 7.0~8.5(14H,Ph-H), 6.5(1H,CH)

[0476] [Chemical Formula 26]

[0477]

[0478] Synthesis Example 4: Synthesis of BMI-1

[0479] A 200 mL glass flask was used as a reaction vessel, and 5.73 g (20 mmol) of neopentyl glycol bis(4-aminophenyl) ether (product name: DANPG, manufactured by Wakayama Seika Kogyo Co., Ltd.) was dissolved in butanol as a solvent. Then, a 20 mass% aqueous solution of iodine chloride (81.2 g, 100 mmol) was added dropwise over 60 minutes at 50°C, followed by stirring at 50°C for 2 hours to react salicyl alcohol with iodine chloride. After the reaction, an aqueous solution of sodium thiosulfate was added to the reaction solution and stirred for 1 hour, after which the liquid temperature was cooled to 10°C. The precipitate formed by cooling was filtered, washed, and dried to obtain 9.5 g of brown solid. As a result of analyzing a brown solid sample by liquid chromatography-mass spectrometry (LC-MS), a compound (X) represented by the following formula (X) was identified.

[0480] [Chemical Formula 27]

[0481]

[0482] Next, the compound (X) obtained above was transferred to a container with a volume of 200 ml equipped with a stirrer, a cooling tube, and a burette. 2.54 g (26.0 mmol) of maleic anhydride (manufactured by Kanto Chemical Co., Ltd.), 50 ml of dimethylformamide, and 50 ml of m-xylene were added, and 0.5 g (2.9 mmol) of p-toluenesulfonic acid was added to prepare a reaction solution. The reaction solution was stirred at 130°C for 4.0 hours to carry out the reaction, and the water produced by azeotropic dehydration was recovered using a Dean Stark trap. Subsequently, the reaction solution was cooled to 40°C and then dropped into a beaker containing 500 ml of distilled water to precipitate the product. The obtained slurry solution was filtered, the residue was washed with methanol, and separation and purification were performed by column chromatography to obtain 1.5 g of the target compound (BMI-1) represented by the following formula.

[0483] [Chemical Formula 28]

[0484]

[0485] As a result of performing NMR measurements on the obtained compound (BMI-1) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (BMI-1).

[0486] 1H-NMR: (d-DMSO, internal standard TMS)

[0487] δ(ppm)7.0~7.5(4H,Ph-H), 3.2(4H,-CH=CH), 2.4(4H,-CH2-), 1.6~1.7(6H,CH3-C-CH3)

[0488] Synthesis Example 5: Synthesis of XBisN-2

[0489] 32.0 g (20 mmol) of 2,6-naphthalenediol (reagent from Sigma-Aldrich), 29.9 g (80 mmol) of 3,5-diiodosalicylaldehyde (reagent from Tokyo Kasei), and 200 mL of 1,4-dioxane were added to a 500 mL container equipped with a stirrer, a condenser, and a burette; 10 mL of 95% sulfuric acid was added, and the reaction was carried out by stirring at 100°C for 6 hours. Next, the reaction mixture was neutralized with a 24% aqueous sodium hydroxide solution, and 100 g of pure water was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. The obtained solid was dried and then purified by column chromatography, thereby obtaining 2.6 g of the target compound (XBisN-2) represented by the following formula.

[0490] Meanwhile, the following peaks were detected by 500 MHz 1H NMR, and it was confirmed that it has the chemical structure of the following formula.

[0491] 1H-NMR:(d-DMSO, internal standard TMS)

[0492] δ(ppm)9.6~9.7(3H,OH), 6.7~8.5(12H,Ph-H), 6.2(1H,CH)

[0493] [Chemical Formula 29]

[0494]

[0495] Synthesis Example 5-1: Synthesis of RXBisN-2

[0496] 2.6 g (7.0 mmol) of XBisN-2 and 1.0 g (2 mmol) of monobutyl copper phthalate were added to a 100 mL container equipped with a stirrer, a cooling tube, and a burette. 20 mL of 1-butanol was added as a solvent, and the reaction mixture was stirred at 100°C for 6 hours to carry out the reaction. After cooling, the precipitate was filtered, and the resulting crude material was dissolved in 20 mL of ethyl acetate. Next, 1 mL of hydrochloric acid was added, and after stirring at room temperature, neutralization treatment with sodium bicarbonate was performed. The ethyl acetate solution was concentrated, and 40 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. By drying the obtained solid, 1.0 g of the target resin (RXBisN-2) having a structure represented by the following formula was obtained.

[0497] For the obtained resin, the molecular weight equivalent to polystyrene was measured by the above method, and the results were Mn: 4300, Mw: 5500, and Mw / Mn: 1.28.

[0498] As a result of performing NMR measurements on the obtained resin under the above measurement conditions, the following peaks were detected, and it was confirmed that it has a chemical structure of the following formula.

[0499] δ(ppm)9.5~9.7(3H,OH), 6.7~8.5(12H,Ph-H), 6.0~6.3(1H,CH)

[0500] [Chemical Formula 30]

[0501]

[0502] Synthesis Example 6: Synthesis of NAFP-AL

[0503] Under nitrogen, 1,4-bis(chloromethyl)benzene (28.8g, 0.148mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1-naphthol (30.0g, 0.1368mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.), and p-toluenesulfonic acid monohydrate (5.7g, 0.029mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to a 300mL four-necked flask, and 150.4g of propylene glycol monomethyl ether acetate (hereinafter referred to by the abbreviation PGMEA) was added and stirred. The temperature was raised and dissolved until reflux was confirmed, and polymerization was initiated. After 16 hours, the mixture was cooled to 60℃ and then reprecipitated in 1600g of methanol.

[0504] 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 of the obtained oligomer, measured by polystyrene conversion via GPC, was 2020, and the degree of dispersion was 1.86.

[0505] [Chemical Formula 31]

[0506]

[0507] Synthesis Example 6-1: Synthesis of I-NAFP-AL

[0508] A 200 mL glass flask was used as a reaction vessel, and 8 g (20 mmol) of NAFP-AL obtained above was dissolved in butanol as a solvent. Then, a 20 mass% aqueous solution of iodine chloride (81.2 g, 100 mmol) was added dropwise over 60 minutes at 50°C, followed by stirring at 50°C for 2 hours to react salicyl alcohol with iodine chloride. After the reaction, an aqueous solution of sodium thiosulfate was added to the reaction solution and stirred for 1 hour, after which the liquid temperature was cooled to 10°C. The precipitate formed by cooling was filtered, washed, and dried to obtain 11.5 g of brown solid.

[0509] [Chemical Formula 32]

[0510]

[0511] Synthesis Example 7: Synthesis of 2I-PHS

[0512] A 200 mL glass flask was used as a reaction vessel, and 4.96 g (40 mmol) of salicyl alcohol was dissolved in butanol as a solvent. Then, a 20 mass% aqueous solution of iodine chloride (81.2 g, 100 mmol) was added dropwise over 60 minutes at 50°C, followed by stirring at 50°C for 2 hours to react the salicyl alcohol with iodine chloride. After the reaction, an aqueous solution of sodium thiosulfate was added to the reaction solution and stirred for 1 hour, after which the liquid temperature was cooled to 10°C. The precipitate formed by cooling was filtered, washed, and dried to obtain 12.1 g of white specimens. As a result of analyzing the white specimen samples by liquid chromatography-mass spectrometry (LC-MS), 4-hydroxy-3,5-diiodobenzyl alcohol was identified.

[0513] After adding MnO2 (3.4 g, 40 mmol) in a methylene chloride solvent and stirring, a 50 mass% solution in which the entire amount of the synthesized 4-hydroxy-3,5-diiodobenzyl alcohol was dissolved in methylene chloride was added dropwise while stirring for 1 hour, and then stirring was performed at room temperature for 4 hours, after which the reaction mixture was filtered and the solvent was removed to obtain 4-hydroxy-3,5-diiodobenzaldehyde.

[0514] After preparing a solution in which dimethyl malonicate (5.3 g, 40 mmol) and the entire amount of 4-hydroxy-3,5-diiodobenzaldehyde synthesized above were dissolved in DMF solvent, a solution in which ethylenediamine (0.3 g) was dissolved 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 in an oil bath. After that, ethyl acetate and water were added, and then a 2 mol / L aqueous HCl solution was added to control the pH to 4 or lower, and then the organic phase was separated by liquid separation. 8.1 g of the compound 2I-PHS(4-hydroxy-3,5-diiodostyrene) represented by the following formula (2I-PHS) was obtained by further washing the obtained organic phase by separating it in the order of a 2 mol / L aqueous sodium carbonate solution, water, and saline solution, purifying it by filtering, and removing the solvent from the organic phase.

[0515] [Chemical Formula 33]

[0516]

[0517] Synthesis Example 7-1: Synthesis of P-2I-PHS-MMA

[0518] 3.0 g of compound 2I-PHS and 1.2 g of methyl methacrylic acid were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered and dried under reduced pressure to obtain a white powdery polymer P-2I-PHS-MMA represented by the following formula (P-2I-PHS-MMA). The weight-average molecular weight (Mw) of this polymer was 8000, and the degree of dispersion (Mw / Mn) was 1.50. In addition, 13C-NMR analysis revealed that the compositional ratio (molar ratio) in the following formula (P-2I-PHS-MMA) was a:b=1:1. Meanwhile, the following formula (P-2I-PHS-MMA) is briefly described to indicate the ratio of each constituent unit; the arrangement order of each constituent unit is random, and it is not a block copolymer in which each constituent unit forms an independent block.

[0519] [Chemical Formula 34]

[0520]

[0521] Synthesis Example 8: Synthesis of XBisN-3

[0522] In a 3L container equipped with a stirrer, a cooling tube, and a burette, 100g (0.214mol) of a compound (XBisN-C1) represented by the following formula described in International Publication 2013 / 024779 and 71.2g (0.429mol) of potassium iodide were added, 1L of methanol was added as a solvent, and additionally, 146g (1.5mol) of sulfuric acid was added dropwise under ice cooling, and the reaction was carried out by stirring at 10℃ for 4 hours. After the reaction was completed, the mixture was extracted with butyl acetate, washed with water, neutralized, and then filtered and dried to obtain 87.8g of the target compound (RBisN-3) represented by the following formula (XBisN-3).

[0523] As a result of performing NMR measurements on the obtained compound under the above measurement conditions, the following peaks were detected, and it was confirmed that the compound has a chemical structure of the following formula.

[0524] δ(ppm)10.6(2H,OH), 7.2~8.6(17H,Ph-H), 6.7(1H,CH)

[0525] [Chemical Formula 35]

[0526]

[0527] [Chemical Formula 36]

[0528]

[0529] Synthesis Example 9-1: Synthesis of MAC-ADI

[0530] 16.8 g (0.1 mol) of 1,3-adamantanediol (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. After the reaction, water was added, washed with sodium bicarbonate, and the organic layer was concentrated and then separated and purified by column chromatography, thereby obtaining 12 g of 3-iodo-1-hydroxyadamantan represented by the following formula.

[0531] [Chemical Formula 37]

[0532]

[0533] 2.78 g (10 mmol) of 3-iod-1-hydroxyadamantan obtained above was dissolved in chloroform, and 0.96 g (12 mmol) of pyridine was added under ice cooling, followed by the dropwise addition of 1.25 g (12 mmol) of chloride methacrylate. The reaction was then carried out by stirring for 1 hour under ice cooling and 3 hours at room temperature. After the reaction was complete, water was added to the reaction solution, washed with an aqueous solution of saturated sodium bicarbonate, sodium sulfate was added to the organic phase to dry it, and after concentration, purified by column chromatography to obtain 2.7 g of the target product (MAC-ADI) shown below.

[0534] As a result of performing NMR measurements on the obtained compound (MAC-ADI) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (MAC-ADI).

[0535] δ(ppm)(d-DMSO): 6.4~6.5(2H, =CH2), 1.3~3.2(17H, Ad-H, -C(CH3)=C)

[0536] [Chemical Formula 38]

[0537]

[0538] Synthesis Example 10-1: Synthesis of MAC-ADI2

[0539] 2.3 g (12.5 mmol) of 1,3,5-adamantantriol (Mitsubishi Gas Chemical) was dissolved in 100 mL of toluene, 28.1 g (125 mmol) of 57% aqueous hydrogen iodide solution was added, and the mixture was stirred at 80°C for 13 hours. After the reaction, water was added, washed with sodium bicarbonate, and the organic layer was concentrated and then separated and purified by column chromatography to obtain 0.9 g of 3,5-diiodo-1-hydroxyadamantan represented by the following formula.

[0540] [Chemical Formula 39]

[0541]

[0542] 3.5 g of the target compound (MAC-ADI2) represented by the following formula (MAC-ADI2) was obtained by performing the same procedure as Synthesis Example 9-1, except that 4.04 g (10 mmol) of the 3,5-diiod-1-hydroxyadamantan obtained above was used instead of 2.78 g of 3-iod-1-hydroxyadamantan.

[0543] As a result of performing NMR measurements on the obtained compound (MAC-ADI2) under the above measurement conditions, the following peak was detected, and it was confirmed that it has the chemical structure of the following formula (MAC-ADI2).

[0544] δ(ppm)(d-DMSO): 6.4~6.5(2H, =CH2), 1.5~3.9(16H, Ad-H, -C(CH3)=C)

[0545] [Chemical Formula 40]

[0546]

[0547] Synthesis Example 9: Synthesis of P-MAC-ADI Resin

[0548] MAC-ADI (4.2 g), 1.5 g of 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated resin was filtered 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 degree of dispersion (Mw / Mn) was 1.9. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (P-MAC-ADI) was a:b:c:d = 20:30:15:35. Meanwhile, the following chemical formula (P-MAC-ADI) is described briefly to indicate the ratio of each constituent unit; P-MAC-ADI is not a block copolymer in which each constituent unit forms an independent block.

[0549] [Chemical Formula 41]

[0550]

[0551] Synthesis Example 10: Synthesis of P-MAC-ADI2 Resin

[0552] MAC-ADI2 (5.6 g), 2-methyl-2-adamantyl methacrylate 1.5 g, γ-butyrolactone methacrylic acid ester 2.0 g, and hydroxyadamantyl methacrylic acid ester 1.5 g were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated resin was filtered 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 degree of dispersion (Mw / Mn) was 2.0. In addition, 13As a result of measuring C-NMR, the compositional ratio (molar ratio) of the following chemical formula (MAC-ADI2) was a:b:c:d = 20:30:15:35. Meanwhile, the following chemical formula (P-MAC-ADI2) is described briefly to indicate the ratio of each constituent unit, but P-MAC-ADI2 is not a block copolymer in which each constituent unit forms an independent block.

[0553] [Chemical Formula 42]

[0554]

[0555] Comparative Synthesis Example AR1: Synthesis of P-PHS-MMA

[0556] 1.0 g of the compound p-hydroxystyrene and 1.2 g of methyl methacrylic acid were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered 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 degree of dispersion (Mw / Mn) was 1.60. In addition, 13C-NMR analysis revealed that the compositional ratio (molar ratio) in the following formula (P-PHS-MMA) was a:b = 1:1. Meanwhile, the following formula (P-PHS-MMA) is briefly described to indicate the ratio of each constituent unit; the arrangement order of each constituent unit is random, and it is not a block copolymer in which each constituent unit forms an independent block.

[0557] [Chemical Formula 43]

[0558]

[0559] (Synthesis of Resist Polymer MAR1)

[0560] 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 methacrylic acid ester, and 1.5 g of hydroxyadamantyl methacrylic acid ester were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered 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 degree of dispersion (Mw / Mn) was 1.90. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) in the following formula (MAR1) was a:b:c:d = 40:30:15:15. Meanwhile, the following formula (MAR1) is briefly described to indicate the ratio of each constituent unit, but the arrangement order of each constituent unit is random, and it is not a block copolymer in which each constituent unit forms an independent block. For the polystyrene-based monomer (p-hydroxystyrene), the molar ratio was determined based on the integration ratio of the carbon originating from the benzene ring, and for the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylic acid ester, and hydroxyadamantyl methacrylic acid ester), the molar ratio was determined based on the integration ratio of the carbonyl carbon of the ester bond.

[0561] [Chemical Formula 44]

[0562]

[0563] (Synthesis of MAR2 polymer for resist)

[0564] 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 methacrylic acid ester, and 1.0 g of hydroxyadamantyl methacrylic acid ester were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered 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 degree of dispersion (Mw / Mn) was 1.90. In addition, 13 As a result of measuring C-NMR, the compositional ratio (molar ratio) in the following formula (MAR2) was a:b:c:d = 50:10:10:30. Meanwhile, the following formula (MAR2) is briefly described to represent the ratio of each constituent unit, but the arrangement order of each constituent unit is random, and it is not a block copolymer in which each constituent unit forms an independent block. For the polystyrene-based monomer (p-hydroxystyrene), the molar ratio was determined based on the integration ratio of the carbon originating from the benzene ring, and for the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylic acid ester, and hydroxyadamantyl methacrylic acid ester), the molar ratio was determined based on the integration ratio of the carbonyl carbon of the ester bond.

[0565] [Chemical Formula 45]

[0566]

[0567] (Examples 1–10, Comparative Example 1)

[0568] The safe solvent solubility, storage stability, thin film formation ability, 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.

[0569] (Comparative Example 2)

[0570] Evaluation was performed in the same manner as in Examples 1 to 10, except that a compound (XBisN-C1) represented by the following formula described in International Publication 2013 / 024779 was used instead of the compounds or resins obtained in Synthesis Examples 1 to 10. The results are shown in Table 1.

[0571] [Chemical Formula 46]

[0572]

[0573] [Table 1]

[0574]

[0575] As is evident from Table 1, Examples 1 to 10 using a compound containing 15 to 75 mass% of iodine atoms in total, or a resin having a constituent unit derived from said compound, were confirmed to have significantly superior sensitivity compared to Comparative Example 1 and Comparative Example 2.

[0576] (Preparation of lower layer composition)

[0577] A lower film composition solution containing the compound of the present invention was prepared by combining the compositions listed in Table 2 below.

[0578] [Table 2]

[0579]

[0580] The components used in the preparation of the lower layer composition solution are as follows.

[0581] Acid Diffusion Control Agent

[0582] The following were used as acid diffusion promoters.

[0583] ·WPAG199(Bis(4-methylphenylsulfonyl)diazomehtane)(Fujifilm Wako Pure Pharmaceuticals)

[0584] [Chemical Formula 47]

[0585]

[0586] WPAG367 (Diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate) (Fujifilm Wako Pure Pharmaceutical)

[0587] [Chemical Formula 48]

[0588]

[0589] WPAG336 (Diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate) (Fujifilm Wako Pure Pharmaceutical)

[0590] [Chemical Formula 49]

[0591]

[0592] The following were used as acid diffusion inhibitors.

[0593] (Compound ADCS-1)

[0594] [Chemical Formula 50]

[0595]

[0596] [Chemical Formula 51]

[0597]

[0598] [Chemical Formula 52]

[0599]

[0600] [Chemical Formula 53]

[0601]

[0602] [Chemical Formula 54]

[0603]

[0604] <Thermal Acid Generators · Thermal Base Generators>

[0605] ·WPBG300 (Fujifilm Wako Pure Pharmaceutical)

[0606] [Chemical Formula 55]

[0607]

[0608] ·TAG-2689 (King, quaternary ammonium salt of trifluoromethanesulfonic acid)

[0609] <Cross-linking agent>

[0610] ·TMOM-BP (Honshu Chemical)

[0611] [Chemical Formula 56]

[0612]

[0613] (4) Sensitivity evaluation

[0614] (EUV sensitivity - n-butyl acetate phenomenon)

[0615] A resist solution 2 for sensitivity evaluation and pattern evaluation was prepared by combining 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 parts by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME.

[0616] The prepared lower layer composition was applied onto a silicon wafer, and a baking treatment was performed at 240°C for 60 seconds to form a lower layer with a thickness of 100 nm on the silicon wafer.

[0617] Furthermore, a resist solution 2 was applied to the lower layer of the present invention formed on a silicon wafer, and baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0618] Next, using the extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Risotec Japan Co., Ltd.), 1 mJ / cm² 2 From 1 mJ / cm² 2 80 mJ / cm² 2After performing maskless shot exposure with the exposure amount increased to [value], the wafer was baked (PEB) at 110°C for 90 seconds and developed with n-butyl acetate for 30 seconds to obtain a wafer with 80 shot exposures. For each obtained shot exposure area, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and profile data of the film thickness against the exposure amount was acquired. The exposure amount at which the slope of the film thickness variation amount against the exposure amount is greatest was [defined] as the sensitivity value (mJ / cm²). 2 It was calculated as ) and used as an indicator of the EUV sensitivity of the resist.

[0619] (Etching Defect Evaluation-TMAH)

[0620] The prepared lower layer composition was applied onto a silicon wafer, and a baking treatment was performed at 240°C for 60 seconds to form a lower layer with a thickness of 100 nm on the silicon wafer.

[0621] Furthermore, a resist solution was applied to the lower layer of the present invention formed on a silicon wafer, and baked at 110°C for 60 seconds to form a photoresist layer with a film thickness of 100 nm.

[0622] Next, using the extreme ultraviolet (EUV) exposure device “EUVES-7000” (product name, manufactured by Risotec Japan Co., Ltd.), shot exposure was performed on the entire wafer with an exposure amount 3% greater than the EUV sensitivity value obtained from the EUV sensitivity evaluation in the above TMAH development, and additionally, baking (PEB) was performed 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 with 80 shots of shot exposure on the entire wafer.

[0623] For the prepared photolithography-completed wafer, etching treatment was performed using the etching device “Telius SCCM” (product name, manufactured by Tokyo Electron Co., Ltd.) with CF4 / Ar gas until the oxide film was etched to 60 nm. For the wafer prepared by etching, defect evaluation was performed using the defect inspection device “Surfscan SP5” (product name, manufactured by KLA), and the number of cone defects of 19 nm or larger was determined as an indicator of etching defects.

[0624] (Evaluation Criteria)

[0625] A: Number of cone defects ≤ less than 20

[0626] B: 20 ​​< Number of cone defects ≤ 200

[0627] C: 200 < Number of cone defects ≤ 1000

[0628] D: 1000 < Number of cone defects

[0629] The obtained evaluation results are shown in Table 3.

[0630] (Etching defect evaluation - n-butyl acetate)

[0631] In the above-described etching evaluation-TMAH method, etching defect evaluation was performed by the same method except that resist solution 2 was used as the resist solution, exposure was performed with an exposure amount 3% less than the EUV sensitivity in n-butyl acetate development, and n-butyl acetate was used instead of the TMAH aqueous solution as the developer, and the development time was set to 30 seconds.

[0632] The obtained evaluation results are shown in Table 3.

[0633] [Table 3]

[0634]

[0635] As is evident from Table 3, it was confirmed that sensitivity could be significantly controlled by using an acid diffusion control agent in combination.

Claims

Claim 1 A lower film formed using a lithography composition comprising a compound having at least one element selected from the group consisting of iodine and tellurium, or a resin having a constituent unit derived from said compound, wherein said lower film is used in a resist pattern forming method, said resist pattern forming method comprises a photoresist film forming process of forming at least one layer of photoresist film on the lower film, and a process of irradiating a predetermined area of ​​the photoresist film formed by said photoresist film forming process with radiation and performing development, said compound is a compound represented by the following general formula (AM1). (Equation (AM1), R 1 Representing silver, hydrogen atoms, methyl, or halogen groups, R 2 Each represents, independently, a hydrogen atom, a straight-chain 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, and A represents an organic group having 1 to 30 carbon atoms, and n 1 represents 0 or 1, and n 2 (represents an integer from 1 to 20.) A lower film in which the total mass of the element in the above compound is 15 mass% or more and 75 mass% or less. Claim 2 A lower film according to claim 1, wherein in the lithography composition, at least one element is iodine, and the mass of the iodine in the compound is 15 mass% or more and 75 mass% or less. Claim 3 A lower film according to claim 1 or 2, wherein the lithography composition further comprises: a solvent; and at least one selected from the group consisting of an acid generating agent, an acid diffusion promoting agent, an acid diffusion inhibiting agent, and a crosslinking agent. Claim 4 In claim 1 or 2, the lower layer of the lithography composition that is cured after thin film formation. Claim 5 A resist layer contact film formed using a lithography composition comprising a compound having at least one element selected from the group consisting of iodine and tellurium, or a resin having a constituent unit derived from said compound, wherein said resist layer contact film is used in a circuit pattern forming method, said circuit pattern forming method comprises: a photoresist film forming process of forming at least one photoresist film on a resist layer contact film; a resist pattern forming process of irradiating a predetermined region of the photoresist film formed by said photoresist film forming process with radiation and developing to form a resist pattern; a pattern forming process of etching the resist layer contact film to form a pattern using the resist pattern formed by said resist pattern forming process as a mask; and a substrate pattern forming process of etching a substrate to form a pattern on a substrate using the pattern formed by said pattern forming process as a mask, said substrate pattern forming process, said compound is a compound represented by the following general formula (AM1). (Equation (AM1), R 1 Representing silver, hydrogen atoms, methyl, or halogen groups, R 2 Each represents, independently, a hydrogen atom, a straight-chain 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, and A represents an organic group having 1 to 30 carbon atoms, and n 1 represents 0 or 1, and n 2 (represents an integer from 1 to 20.) A resist layer contact film in which the total mass of the element in the above compound is 15 mass% or more and 75 mass% or less. Claim 6 A resist layer contact film according to claim 5, wherein in the lithography composition, at least one element is iodine, and the mass of the iodine in the compound is 15 mass% or more and 75 mass% or less. Claim 7 A resist layer contact film according to claim 5 or 6, wherein the lithography composition further comprises: a solvent; and at least one selected from the group consisting of an acid generating agent, an acid diffusion promoting agent, an acid diffusion inhibiting agent, and a crosslinking agent. Claim 8 In claim 5 or 6, the resist layer contact film that is cured after thin film formation in the lithography composition. Claim 9 delete Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete

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