Composition for lithography and pattern forming method

Abstract

Provided is a photoresist composition that forms a pattern with excellent exposure sensitivity and that can be used to form a film in contact with an antireflection layer or a lower layer film. The photoresist composition comprises a compound having at least one element selected from the group consisting of iodine, tellurium, and fluorine, or a resin having a structural unit derived from the compound, the total mass of the atoms in the compound being 15 mass% or greater and 75 mass% or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition for photolithography, and a pattern forming method. BACKGROUND

[0002] In recent years, in the production of semiconductor elements, liquid crystal display elements, with the progress of photolithography technology, the miniaturization of semiconductors (patterns), pixels is rapidly developing. As a method of miniaturization of pixels, shortening of the wavelength of the exposure light source is generally performed. Specifically, in the past, ultraviolet rays typified by g-rays, i-rays were used, but currently, far ultraviolet exposure such as KrF excimer laser (248 nm), ArF excimer laser (193 nm) has become the center of mass production, and further, the introduction of extreme ultraviolet (EUV) lithography (13.5 nm) is progressing. In addition, electron beams (EB) are also used to form fine patterns.

[0003] Among them, in particular, the lithography based on extreme ultraviolet is increasing in the number of introductions due to the technical progress in recent years.

[0004] So far, the general resist material is a high molecular resist material capable of forming an amorphous film. For example, polymethyl methacrylate, polyhydroxystyrene or polyalkyl methacrylate having an acid dissociation group, and the like can be exemplified as high molecular resist materials (for example, refer to Non-Patent Document 1).

[0005] In the past, by irradiating ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, and the like to a resist film made by applying a solution of such a resist material to a substrate, a line pattern of about 10 to 100 nm has been formed.

[0006] In addition, the reaction mechanism of the lithography based on electron beams or extreme ultraviolet rays is different from that of ordinary lithography (Non-Patent Document 2, Non-Patent Document 3). Further, in the lithography based on electron beams or extreme ultraviolet rays, a fine pattern of several nm to several tens of nm is targeted. If the size of the resist pattern becomes smaller, a resist composition having higher sensitivity to the exposure light source is required. In particular, in the lithography based on extreme ultraviolet rays, higher sensitivity is required in terms of throughput.

[0007] As a resist material that improves the above-mentioned problems, an inorganic resist material having a metal element such as titanium, tin, hafnium, zirconium, and the like has been proposed (for example, refer to Patent Document 1).

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2015-108781

[0011] Non-patent literature

[0012] Non-patent literature 1: Shinji Takanashi, et al., "40 years of lithography technology", S&T Publishing, December 9, 2016

[0013] Non-patent literature 2: H. Yamamoto, et al., Jpn. J. Appl. Phys. 46, L142 (2007)

[0014] Non-patent literature 3: H. Yamamoto, et al., J. Vac. Sci. Technol. b 23, 2728 (2005) SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] However, the resist compositions having a high sensitivity feature developed in the past have problems such as insufficient pattern quality, large roughness, or insufficient improvement in sensitivity, or insufficient etching resistance. In view of these circumstances, there is a demand for a lithography technology that balances high resolution and high sensitivity.

[0017] In addition, in lithography based on extreme ultraviolet, since a short wavelength of 13.5 nm is used, the number of photons is small at the same exposure intensity due to the high transmittance of photons, compared to the existing exposure technology, and thus it is necessary to efficiently convert the extreme ultraviolet into the protons required for exposure. Furthermore, it is necessary to supply protons from a layer adjacent to the resist layer.

[0018] In view of the above circumstances, the object of the present application is to provide a lithography composition for a resist layer contact film, a lower layer film, and a pattern forming method, which can form a pattern with excellent exposure sensitivity and can obtain a resist layer contact film.

[0019] SOLUTION TO THE PROBLEM

[0020] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that by using a compound having a specific element composition, or a resin containing the compound as a structural unit, for a resist layer contact film, a lower layer film, it is possible to improve the exposure sensitivity of the lithography process, and thus have completed the present application.

[0021] That is, the present application is as follows. [1]

[0023] A lithography composition comprising a compound having at least one element selected from the group consisting of iodine, tellurium, and fluorine, or a resin containing a structural unit derived from the aforementioned compound,

[0024] The total mass of the aforementioned atoms in the aforementioned compound is 15 mass% or more and 75 mass% or less. [2]

[0026] The photoresist composition according to [1], wherein the at least one element is at least one element selected from the group consisting of iodine and tellurium. [3]

[0028] The photoresist composition according to [1] or [2], wherein the at least one element is iodine, and the mass of the iodine in the aforementioned compound is 15 mass% or more and 75 mass% or less. [4]

[0030] The photoresist composition according to any one of [1] to [3], wherein the aforementioned compound is represented by formula (A-4a).

[0031]

[0032] (In formula (A-4a),

[0033] X represents an oxygen atom, a sulfur atom, a single bond, or no bridging,

[0034] Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond,

[0035] Here, when X is no bridging, Y is the aforementioned 2n-valent group,

[0036] R 0 each independently is an optionally substituted alkyl group having a carbon number of 1 to 40, an optionally substituted aryl group having a carbon number of 6 to 40, an optionally substituted alkenyl group having a carbon number of 2 to 40, an optionally substituted alkynyl group having a carbon number of 2 to 40, an optionally substituted alkoxy group having a carbon number of 1 to 40, a halogen atom, a thiol group, or a hydroxyl group,

[0037] Here, at least one of R 0 is a hydroxyl group,

[0038] each m is independently an integer of 1 to 9,

[0039] Q represents iodine, tellurium, fluorine, or an alkyl group having a carbon number of 1 to 30 containing at least iodine or tellurium or fluorine, or an aryl group having a carbon number of 6 to 40 containing at least iodine or tellurium or fluorine,

[0040] n is an integer of 1 to 4,

[0041] each p is independently an integer of 0 to 3,

[0042] at least one of Q, R 0 , and Y contains at least one element of iodine, tellurium, and fluorine,

[0043] each q is independently an integer of 0 to (4 + 2 x p - m).

[0044] [4-1]

[0045] The photoresist composition according to [4], wherein X is an oxygen atom or no bridge.

[0046] [4-2]

[0047] The photoresist composition according to [4] or [4-1], wherein Q is iodine.

[0048] [4-3]

[0049] The photoresist composition according to any one of [4] to [4-2], wherein at least one of Q, R 0 , and Y contains iodine.

[0050] [4-4]

[0051] The photoresist composition according to any one of [4] to [4-3], wherein each q is independently an integer of 1 to (4 + 2 x p - m). [5]

[0053] The photoresist composition according to any one of [4] to [4-4], wherein Y is a 2n-valent hydrocarbon group having an aromatic group having a carbon number of 6 to 60 optionally having a substituent.

[0054] [5-1]

[0055] The photoresist composition according to [5], wherein the aforementioned 2n-valent hydrocarbon group is methylene.

[0056] [5-2]

[0057] The photoresist composition according to [5] or [5-1], wherein the aforementioned aromatic group having a carbon number of 6 to 60 is phenyl or biphenyl.

[0058] [5-3]

[0059] The photoresist composition according to any one of [5] to [5-2], wherein the aforementioned substituent is iodine. [6]

[0061] The photoresist composition according to any one of [1] to [3], wherein the aforementioned compound is represented by formula (A-4c).

[0062]

[0063] (In formula (A-4c),

[0064] X represents an oxygen atom, a sulfur atom, a single bond, or no bridge,

[0065] Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond,

[0066] Here, when X is no bridge, Y is the aforementioned 2n-valent group,

[0067] R 0 each independently is an optionally substituted alkyl group having a carbon number of 1 to 40, an optionally substituted aryl group having a carbon number of 6 to 40, an optionally substituted alkenyl group having a carbon number of 2 to 40, an optionally substituted alkynyl group having a carbon number of 2 to 40, an optionally substituted alkoxy group having a carbon number of 1 to 40, a halogen atom, a thiol group, or a hydroxyl group,

[0068] Here, at least one of R 0 is a hydroxyl group,

[0069] R 0 is iodine, or a group containing iodine,

[0070] each independently is an integer of 1 to 9,

[0071] n is an integer of 1 to 4,

[0072] each independently is an integer of 0 to 3.

[0073] [6-1]

[0074] The photoresist composition according to [6], wherein X is an oxygen atom or no bridge. [7]

[0076] The photoresist composition according to any one of [6] or [6-1], wherein Y is a 2n-valent hydrocarbon group of an aryl group having a carbon number of 6 to 60 optionally having a substituent.

[0077] [7-1]

[0078] The photoresist composition according to [7], wherein the aforementioned 2n-valent hydrocarbon group is a methylene group.

[0079] [7-2]

[0080] The photoresist composition according to [7] or [7-1], wherein the aforementioned aryl group having a carbon number of 6 to 60 is a phenyl group or a biphenyl group.

[0081] [7-3]

[0082] The photoresist composition according to any one of [7] to [7-2], wherein the aforementioned substituent is iodine. [8]

[0084] The photoresist composition according to any one of [1] to [3], wherein the aforementioned compound is represented by General Formula (AM1).

[0085]

[0086] (In Formula (AM1),

[0087] R 1 represents a hydrogen atom, a methyl group, or a halogen group,

[0088] R 2 each independently represents a hydrogen atom, a linear organic group having a carbon number of 1 to 20, a branched organic group having a carbon number of 3 to 20, or a cyclic organic group having a carbon number of 3 to 20,

[0089] A represents an organic group having a carbon number of 1 to 30,

[0090] n 1 represents 0 or 1,

[0091] n 2 represents an integer of 1 to 20.

[0092] [8-1]

[0093] The photoresist composition according to [8], wherein R 1 is a methyl group.

[0094] [8-2]

[0095] The photoresist composition according to [8] or [8-1], wherein n 1 is 0.

[0096] [8-3]

[0097] The photoresist composition according to any one of [8] to [8-2], wherein A is an alicyclic hydrocarbon group.

[0098] [8-4]

[0099] The photoresist composition according to any one of [8] to [8-3], wherein A is an adamantyl group. [9]

[0101] The photoresist composition according to any one of [1] to [3], wherein the aforementioned compound is represented by General Formula (A-7).

[0102]

[0103] (In Formula (A-7),

[0104] X each independently represents tellurium, I, F, or a carbon number 1 to 30 organic group having 1 or more and 5 or less substituents selected from the group consisting of tellurium, I, and F, and at least one X is tellurium or I,

[0105] L 1 represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group,

[0106] m is an integer of 1 or more,

[0107] Y each independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group,

[0108] n is an integer of 0 or more,

[0109] Z each independently is an alkoxy group, an ester group, an acetal group, or a carbonate group,

[0110] r is an integer of 0 or more,

[0111] A is a carbon number 1 to 30 organic group,

[0112] R a , R b , and R c each independently is H, I, F, Cl, Br, or a carbon number 1 to 60 organic group optionally having a substituent,

[0113] p is an integer of 1 or more.

[0114] [9-1]

[0115] The photoresist composition according to [9], wherein X is iodine.

[0116] [9-2]

[0117] The photoresist composition according to [9] or [9-1], wherein L 1 is a single bond.

[0118] [9-3]

[0119] The photoresist composition according to any one of [9] to [9-2], wherein Y is a hydroxyl group, and n is an integer of 1 or more.

[0120] [9-4]

[0121] The photoresist composition according to any one of [9] to [9-3], wherein r is 0.

[0122] [9-5]

[0123] The photoresist composition according to any one of [9] to [9-4], wherein A is an aromatic ring having 6 to 14 carbon atoms.

[0124] [9-6]

[0125] The photoresist composition according to any one of [9] to [9-5], wherein R a , R b , and R c are hydrogen.

[10]

[0127] The photoresist composition according to any one of [1] to [9-6], further comprising a solvent.

[11]

[0129] The photoresist composition according to any one of [1] to

[10] , further comprising an acid generator.

[12]

[0131] The photoresist composition according to any one of [1] to

[11] , further comprising an acid diffusion promoter.

[13]

[0133] The photoresist composition according to any one of [1] to

[12] , further comprising an acid diffusion inhibitor.

[14]

[0135] The photoresist composition according to any one of [1] to

[13] , further comprising a crosslinking agent.

[15]

[0137] The photoresist composition according to any one of [1] to

[14] , which is cured after thin film formation.

[16]

[0139] The photoresist composition according to any one of [1] to

[15] , which is used for forming a resist layer contact film.

[17]

[0141] The photoresist composition according to any one of [1] to

[15] , which is used for forming an underlayer film.

[18]

[0143] A resist pattern forming method comprising the following steps:

[0144] an underlayer film forming step of forming an underlayer film on a substrate using the photoresist composition according to

[17] ;

[0145] a photoresist film formation step of forming at least one layer of a photoresist film on the underlayer film formed by the underlayer film formation step; and

[0146] a step of irradiating a prescribed region of the photoresist film formed by the photoresist film formation step with a radiation line and developing.

[19]

[0148] A circuit pattern formation method including the steps of:

[0149] an underlayer film formation step of forming an underlayer film on a substrate;

[0150] a resist layer contact film formation step of forming a resist layer contact film on the underlayer film formed by the underlayer film formation step using the composition for photolithography described in

[16] ;

[0151] a photoresist film formation step of forming at least one layer of a photoresist film on the resist layer contact film formed by the resist layer contact film formation step;

[0152] a resist pattern formation step of irradiating a prescribed region of the photoresist film formed by the photoresist film formation step with a radiation line and developing to form a resist pattern;

[0153] a pattern formation step of etching the aforementioned resist layer contact film, or the aforementioned resist layer contact film and the aforementioned underlayer film using the resist pattern formed by the resist pattern formation step as a mask to form a pattern; and

[0154] a substrate pattern formation step of etching the aforementioned substrate using the pattern formed by the pattern formation step as a mask to form a pattern on the substrate.

[20]

[0156] A compound represented by formula (A-4a).

[0157]

[0158] (In formula (A-4a),

[0159] X represents an oxygen atom, a sulfur atom, a single bond or no bridge,

[0160] Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond,

[0161] Here, when X is no bridge, Y is the aforementioned 2n-valent group,

[0162] R 0each independently an optionally substituted alkyl group having a carbon number of 1 to 40, an optionally substituted aryl group having a carbon number of 6 to 40, an optionally substituted alkenyl group having a carbon number of 2 to 40, an optionally substituted alkynyl group having a carbon number of 2 to 40, an optionally substituted alkoxy group having a carbon number of 1 to 40, a halogen atom, a thiol group, or a hydroxyl group,

[0163] at least one of R 0 is a hydroxyl group,

[0164] each m is independently an integer of 1 to 9,

[0165] Q represents iodine, tellurium, fluorine, or an alkyl group having a carbon number of 1 to 30 containing at least iodine or tellurium or fluorine, or an aryl group having a carbon number of 6 to 40 containing at least iodine or tellurium or fluorine,

[0166] n is an integer of 1 to 4,

[0167] each p is independently an integer of 0 to 3,

[0168] at least one of Q, R 0 , and Y contains at least one kind of element among iodine, tellurium, and fluorine,

[0169] each q is independently an integer of 0 to (4 + 2 × p - m).

[0170] [20-1]

[0171] The compound according to

[20] , wherein X is an oxygen atom or no bridge.

[0172] [20-2]

[0173] The compound according to

[20] or [20-1], wherein Q is iodine.

[0174] [20-3]

[0175] The compound according to any one of

[20] to [20-2], wherein at least one of Q, R 0 , and Y contains iodine.

[0176] [20-4]

[0177] The compound according to any one of

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

[21]

[0179] The compound according to any one of

[20] to [20-4], wherein Y is a 2n-valent hydrocarbon group of an aryl group having a carbon number of 6 to 60 optionally having a substituent.

[0180] [21-1]

[0181] The compound according to

[21] , wherein the aforementioned 2n-valent hydrocarbon group is methylene.

[0182] [21-2]

[0183] The compound according to

[21] or [21-1], wherein the aforementioned aromatic group having a carbon number of 6 to 60 is phenyl or biphenyl.

[0184] [21-3]

[0185] The compound according to any one of

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

[22]

[0187] A compound represented by formula (A-4c).

[0188]

[0189] (In formula (A-4c),

[0190] X represents an oxygen atom, a sulfur atom, a single bond, or no bridge,

[0191] Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond,

[0192] Here, when X is no bridge, Y is the aforementioned 2n-valent group,

[0193] R 0 each independently is an alkyl group having a carbon number of 1 to 40 optionally having a substituent, an aryl group having a carbon number of 6 to 40 optionally having a substituent, an alkenyl group having a carbon number of 2 to 40 optionally having a substituent, an alkynyl group having a carbon number of 2 to 40 optionally having a substituent, an alkoxy group having a carbon number of 1 to 40 optionally having a substituent, a halogen atom, a thiol group, or a hydroxyl group,

[0194] Here, at least one of R 0 is a hydroxyl group,

[0195] at least one of R 0 is iodine or a group containing iodine,

[0196] each independently is an integer of 1 to 9,

[0197] n is an integer of 1 to 4,

[0198] each independently is an integer of 0 to 3.

[0199] [22-1]

[0200] The compound according to

[22] , wherein X is an oxygen atom or no bridge.

[23]

[0202] The compound according to

[22] or [22-1], wherein Y is a 2n-valent hydrocarbon group of an aryl group having a carbon number of 6 to 60 optionally having a substituent.

[0203] [23-1]

[0204] The compound according to

[23] , wherein the aforementioned 2n-valent hydrocarbon group is methylene.

[0205] [23-2]

[0206] The compound according to

[23] or [23-1], wherein the aforementioned aryl group having a carbon number of 6 to 60 is phenyl or biphenyl.

[0207] [23-3]

[0208] The compound according to any one of

[23] to [23-2], wherein the aforementioned substituent is iodine.

[0209] Effects of the Invention

[0210] According to the present application, it is possible to provide a composition for lithography and a pattern forming method capable of improving the exposure sensitivity of a lithography process. DETAILED DESCRIPTION

[0211] An embodiment of the present application will be described below. (Hereinafter, sometimes referred to as "the present embodiment".) Note that the present embodiment is an example for explaining the present application, and the present application is not limited to the present embodiment.

[0212] [Compound (A) and Resin (A)]

[0213] The compound of the present embodiment (hereinafter, also referred to as "compound (A)",) and the resin having a structural unit derived from the aforementioned compound (hereinafter, also referred to as "resin (A)",) have at least one element selected from the group consisting of iodine, tellurium, and fluorine (preferably, selected from the group consisting of iodine and tellurium). Iodine and tellurium have high ultraviolet absorption ability, and thus absorb ultraviolet rays to ionize the compound (A), and can effectively generate protons.

[0214] The total content of iodine and tellurium atoms is 15% by mass or more and 75% by mass or less of the entire compound (A), and is preferably 20% by mass or more and 75% by mass or less.

[0215] When the total content of iodine and tellurium is 15% by mass or less, the absorption ability of ultraviolet rays decreases, and thus the efficiency of generation of protons decreases. In addition, when the total content of iodine and tellurium is 75% by mass or more, the stability of the compound decreases, and decomposition becomes easy.

[0216] From the viewpoint of high density, the compound (A) preferably contains an aromatic ring. If the density is increased, the absorption per unit length of the extreme ultraviolet light increases.

[0217] In addition, from the viewpoint of adhesion to a substrate and a resist layer, the compound (A) also preferably contains a hydrophilic group such as a hydroxyl group.

[0218] The "hydrophilic group" refers to a group that improves the affinity of an organic compound with water by bonding to the organic compound. As the hydrophilic group, for example, a hydroxyl group, a nitro group, an amino group, a carboxyl group, a thiol group, a phosphine group, a phosphite group, a phosphoric acid group, an ether group, a sulfide group, a carbamate group, a urea group, an amide group, and an imide group can be exemplified.

[0219] The compound (A) preferably has a curing property and a solvent resistance after curing to form a film and not to be dissolved in a resist liquid at the time of applying a resist. Therefore, for example, the compound (A) also preferably contains a crosslinkable group and a polymerizable group.

[0220] The "crosslinkable group" refers to a group that is crosslinked in the presence of a catalyst or in the absence of a catalyst. As the crosslinkable group, there is no particular limitation, and, for example, an alkoxy group having a carbon number of 1 to 20, 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 carbamate (meth)acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group can be exemplified.

[0221] In addition, the "polymerizable group" refers to a group that is polymerized in the presence of a catalyst or in the absence of a catalyst. As the polymerizable group, there is no particular limitation, and, for example, a group having a (meth)acryloyl group, a group having an unsaturated double bond such as a vinyl group, and a group having an unsaturated triple bond such as a propargyl group can be exemplified.

[0222] The compound (A) also preferably contains a dissociable group.

[0223] The "dissociable group" refers to a group that is dissociated in the presence of a catalyst or in the absence of a catalyst. Among the dissociable groups, an acid dissociable group refers to a characteristic group that is cleaved in the presence of an acid to become a base-soluble group or the like. As specific examples of the acid dissociable group, the groups described in International Publication No. 2016 / 158168 can be exemplified. As preferred examples of the acid dissociable group, a group having a property of being dissociated by an acid selected from the group consisting of a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group can be exemplified.

[0224] As the resin (A), in addition to the resin obtained by polymerizing the compound (A) alone, a resin obtained by polymerizing with a crosslinking agent as appropriate, a resin obtained by copolymerizing with another compound, and the like are not particularly limited.

[0225] The weight average molecular weight of the resin (A) is preferably 300 to 20,000, more preferably 300 to 10,000, and further preferably 300 to 8,000, from the viewpoint of reduction in defects of the formed film and good pattern shape. The aforementioned weight average molecular weight can be a value obtained by measuring the weight average molecular weight in terms of polystyrene using GPC.

[0226] In the production of the resin (A), a publicly known method can be used without limitation as long as it is a method capable of producing a resin having the compound (A) as a structural unit. For example, a method of crosslinking using an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amino compound, an imino compound, an isocyanate, and the like; and a method of copolymerizing using an unsaturated hydrocarbon group-containing compound, and the like can be exemplified. As examples of the "unsaturated hydrocarbon group-containing compound", there are no particular limitations, and for example, a compound having a (meth)acryloyl group, a compound having an unsaturated double bond such as a vinyl group, a compound having an unsaturated triple bond such as a propargyl group can be exemplified.

[0227] The resin (A) can also be obtained at the time of the synthesis reaction of the compound (A). For example, in the synthesis of the compound (A), a method of obtaining the resin (A) from a raw material of the compound (A) is also sometimes employed.

[0228] The compound (A) is preferably a compound (A-1) represented by formula (A-1) containing a prescribed amount of one or more selected from the group consisting of iodine, tellurium, and fluorine.

[0229]

[0230] (In the aforementioned general formula (A-1), each X independently represents an oxygen atom, a sulfur atom, or no bridge, R 1 is a single bond or a 2n-valent group having a carbon number of 1 to 30, R 2 and R 3 each independently is a halogen atom, a linear, branched, or cyclic alkyl group having a carbon number of 1 to 10, an aryl group having a carbon number of 6 to 10, an alkenyl group having a carbon number of 2 to 10, an alkoxy group having a carbon number of 1 to 30, a thiol group, or a hydroxyl group, each m independently is an integer of 0 to 7, wherein at least one m is an integer of 1 to 7, each p independently is 0 or 1, and n is an integer of 1 to 4. Among them, at least one selected from the group consisting of R 1 , R 2 , and R 3 is a group containing one or more selected from the group consisting of an iodine atom, a tellurium atom, and a fluorine atom, R 2at least one of R 3 at least one of R

[0231] Compound (A) is also preferably a compound (A-2) represented by formula (A-2) containing a prescribed amount of one or more selected from the group consisting of iodine, tellurium, and fluorine.

[0232]

[0233] (in formula (A-2), R 1 is a 2n-valent group having a carbon number of 1 to 30, R 2 ~R 5 each independently is a linear, branched, or cyclic alkyl group having a carbon number of 1 to 10, an aryl group having a carbon number of 6 to 10, an alkenyl group having a carbon number of 2 to 10, an alkoxy group having a carbon number of 1 to 30, a halogen atom, a thiol group, or a hydroxyl group, wherein at least one of R 1 ~R 5 is a group containing one or more selected from the group consisting of an iodine atom, a tellurium atom, and a fluorine atom, R 4 at least one of R 5 is one or more selected from a hydroxyl group and a thiol group, m 2 and m 3 each independently is an integer of 0 to 8, m 4 and m 5 each independently is an integer of 0 to 9, wherein m 4 and m 5 are not simultaneously 0, n is an integer of 1 to 4, p 2 ~p 5 each independently is an integer of 0 to 2.

[0234] Compound (A) is also preferably a compound (A-3) represented by formula (A-3) containing a prescribed amount of one or more selected from the group consisting of iodine, tellurium, and fluorine.

[0235]

[0236] (in formula (A-3), R each independently is selected from the group consisting of a hydrogen atom and an alkyl group having a carbon number of 1 to 4, an aryl group having a carbon number of 6 to 12, Z is an n-valent hydrocarbon group having a carbon number of 1 to 100 optionally containing a hetero atom, n is 2 or more, and at least one selected from Z or R is a group containing one or more selected from the group consisting of an iodine atom, a tellurium atom, and a fluorine atom.)

[0237] The compound (A) is also preferably a compound (A-4a) or a compound (A-4b) represented by formula (A-4a) or formula (A-4b) containing a prescribed amount of one or more selected from the group consisting of iodine, tellurium, and fluorine. The resin having a structural unit derived from the compound (A) of the present application can be a polycyclic polyphenol resin having a structural unit derived from the compound (A-4a) and / or the compound (A-4b). The polycyclic polyphenol resin in the present embodiment is a polycyclic polyphenol resin having repeating units derived from at least one monomer selected from the group consisting of the aromatic hydroxyl compounds (A-4a) and (A-4b), the aforementioned repeating units being linked to each other by direct bonding of the aromatic rings to each other. The film-forming composition of the present embodiment is thus constituted, and thus has excellent film-forming properties, and heat resistance, sublimation resistance.

[0238]

[0239] (In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or no bridging, and Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond. Here, when X is no bridging, Y is the aforementioned 2n-valent group. In addition, in formula (A-4b), A represents a benzene ring or a fused ring. Furthermore, in formula (A-4a) and formula (A-4b), R 0 each independently is an optionally substituted alkyl group having a carbon number of 1 to 40, an optionally substituted aryl group having a carbon number of 6 to 40, an optionally substituted alkenyl group having a carbon number of 2 to 40, an optionally substituted alkynyl group having a carbon number of 2 to 40, an optionally substituted alkoxy group having a carbon number of 1 to 40, a halogen atom, a thiol group, or a hydroxyl group, here, at least one of R 0 is a hydroxyl group, and m each independently is an integer of 1 to 9. Q represents iodine, tellurium, fluorine, or an alkyl group having a carbon number of 1 to 30 containing at least iodine or tellurium or fluorine, or an aryl group having a carbon number of 6 to 40 containing at least iodine or tellurium or fluorine. n is an integer of 1 to 4, and p each independently is an integer of 0 to 3. At least any one of Q, R 0 , X, and Y contains at least any one of the elements of iodine, tellurium, and fluorine. In formula (A-4a), q each independently is an integer of 0 to (4 + 2 x p - m). In addition, in formula (A-4b), q each independently is an integer of 0 to (2 + 2 x p - m) (here, p represents the number of fused rings in the fused ring structure in formula (A-4b).).

[0240] From the viewpoints of heat resistance and reactivity, X of formula (A-4a) is preferably an oxygen atom. Furthermore, from the viewpoints of heat resistance and solubility, p of formula (A-4a) is preferably 1. Furthermore, from the viewpoint of reactivity, in formula (A-4a), it is preferable that at least one of R 0 contains an iodine atom, and from the viewpoint of storage stability, it is more preferable that Y does not contain an iodine atom.

[0241] Preferably, formula (A-4a) is formula (A-4c).

[0242]

[0243] (In formula (A-4c), X represents an oxygen atom, a sulfur atom, a single bond, or no bridge, Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond, here, when X is no bridge, Y is the aforementioned 2n-valent group, R 0 each independently is an optionally substituted alkyl group having a carbon number of 1 to 40, an optionally substituted aryl group having a carbon number of 6 to 40, an optionally substituted alkenyl group having a carbon number of 2 to 40, an optionally substituted alkynyl group having a carbon number of 2 to 40, an optionally substituted alkoxy group having a carbon number of 1 to 40, a halogen atom, a thiol group, or a hydroxyl group, here, at least one of R 0 each independently is a hydroxyl group, R 0 each independently is an iodine atom or a group containing iodine, m each independently is an integer of 1 to 9, n is an integer of 1 to 4, and p each independently is an integer of 0 to 3.)

[0244] (polycyclic polyphenol resin)

[0245] The polycyclic polyphenol resin in the present embodiment is not limited to the following, and typically has the following (1) to (5).

[0246] (1) The polycyclic polyphenol resin in the present embodiment has excellent solubility with respect to organic solvents (particularly, a safe solvent). Therefore, for example, when the polycyclic polyphenol resin in the present 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, screen printing, and the like.

[0247] (2) The polycyclic polyphenol resin in the present embodiment has a high carbon concentration and a low oxygen concentration. In addition, since it has a phenolic hydroxyl group in the molecule, it is useful for the formation of a cured product based on a reaction with a curing agent, but when alone, the phenolic hydroxyl group undergoes a crosslinking reaction at the time of high-temperature baking and thus a cured product can also be formed. Due to these, the polycyclic polyphenol resin in the present embodiment can exhibit high heat resistance, and if used as a film forming material for lithography, deterioration of the film at the time of high-temperature baking is suppressed, and a film for lithography excellent in etching resistance to oxygen plasma etching and the like can be formed.

[0248] (3) The polycyclic polyphenol resin in the present embodiment, as described above, can exhibit high heat resistance and etching resistance, and has excellent adhesion to a resist layer, a resist intermediate layer film material. Therefore, if used as a film forming material for lithography, a film for lithography excellent in resist pattern formability can be formed. Note that, the "resist pattern formability" here refers to a property in which the resist pattern shape does not have a large defect, and both resolution and sensitivity are excellent.

[0249] (4) The polycyclic polyphenol resin in the present embodiment has a high aromatic ring density, and thus has a high refractive index. Further, the polycyclic polyphenol resin in the present embodiment can suppress coloring even when heat-treated over a wide range from low temperature to high temperature, and thus has excellent transparency. Therefore, the polycyclic polyphenol resin in the present embodiment is also useful as a material for various optical members.

[0250] (5) The polycyclic polyphenol resin in the present embodiment has Q as a functional group, and thus can improve the absorption rate of an EUV exposure light source. In the case where the polycyclic polyphenol resin in the present embodiment is used as an underlayer film for photolithography, the polycyclic polyphenol resin in the present embodiment can improve the production rate by improving the sensitivity and suppressing pattern defects such as pattern collapse.

[0251] The polycyclic polyphenol resin in the present embodiment can be preferably used as a film-forming material for photolithography according to the above-described characteristics, and thus it is considered that the film-forming composition of the present embodiment can be endowed with the above-described desired characteristics. The film-forming composition of the present embodiment is not particularly limited as long as it contains the above-described polycyclic polyphenol resin. That is, any arbitrary component can be included at any blending ratio, and the film-forming composition can be appropriately adjusted depending on the specific use thereof.

[0252] The above-described formula (A-4a) and formula (A-4b) will be described in detail below.

[0253] In formula (A-4a), X represents an oxygen atom, a sulfur atom, a single bond, or is unbridged. From the viewpoint of heat resistance, X is preferably an oxygen atom.

[0254] In formula (A-4a), Y is a 2n-valent group having a carbon number of 1 to 60 or a single bond. Here, when X is unbridged, Y is the above-described 2n-valent group.

[0255] The 2n-valent group having a carbon number of 1 to 60 is, for example, a 2n-valent hydrocarbon group, which optionally has various functional groups described later as a substituent. In addition, with respect to the 2n-valent hydrocarbon group, when n = 1, it represents an alkylene group having a carbon number of 1 to 60, when n = 2, it represents an alkatetra group having a carbon number of 1 to 60, when n = 3, it represents an alkanexa group having a carbon number of 2 to 60, and when n = 4, it represents an alkanocta group having a carbon number of 3 to 60. As the 2n-valent hydrocarbon group, for example, a group in which a 2n+1-valent hydrocarbon group is bonded to a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group, or the like can be mentioned. Here, with respect to the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included.

[0256] As the 2n+1-valent hydrocarbon group, not limited to the following, for example, a 3-valent methine group, an ethynyl group, or the like can be mentioned.

[0257] In addition, the above-described 2n-valent hydrocarbon group optionally has a double bond, a hetero atom, and / or an aryl group having a carbon number of 6 to 59. Note that Y optionally includes a group derived from a compound having a fluorene skeleton such as fluorene, benzofluorene, or the like, and in the present specification, the term "aryl group" is used as a group not including a group derived from a compound having a fluorene skeleton such as fluorene, benzofluorene, or the like.

[0258] In the present embodiment, the 2n-valent group optionally contains a halogen group, a nitro group, an amino group, a hydroxyl group, an alkoxy group, a mercapto group, or an aromatic group having 6 to 40 carbons. Furthermore, the 2n-valent group optionally contains an ether bond, a ketone bond, an ester bond, or a double bond.

[0259] For the 2n-valent group in the present embodiment, from the viewpoint of heat resistance, a branched hydrocarbon group or an alicyclic hydrocarbon group is preferable to a linear hydrocarbon group, and an alicyclic hydrocarbon group is more preferable. In addition, in the present embodiment, an aromatic group having 6 to 60 carbons is particularly preferable for the 2n-valent group.

[0260] For the linear hydrocarbon group and the branched hydrocarbon group as the substituents that can be contained in the 2n-valent group, there is no particular limitation, and for example, unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-dodecyl, pentyl, and the like can be given.

[0261] For the alicyclic hydrocarbon group and the aromatic group having 6 to 60 carbons as the substituents that can be contained in the 2n-valent group, there is no particular limitation, and for example, unsubstituted phenyl, naphthyl, biphenyl, anthryl, pyrenyl, cyclohexyl, cyclododecyl, dicyclopentyl, tricyclodecyl, adamantyl, phenylene, naphthalene diyl, biphenyl diyl, anthracene diyl, pyrene diyl, cyclohexane diyl, cyclododecane diyl, dicyclopentane diyl, tricyclodecane diyl, adamantane diyl, benzene triyl, naphthalene triyl, biphenyl triyl, anthracene triyl, pyrene triyl, cyclohexane triyl, cyclododecane triyl, dicyclopentane triyl, tricyclodecane triyl, adamantane triyl, benzene tetrayl, naphthalene tetrayl, biphenyl tetrayl, anthracene tetrayl, pyrene tetrayl, cyclohexane tetrayl, cyclododecane tetrayl, dicyclopentane tetrayl, tricyclodecane tetrayl, adamantane tetrayl, and the like can be given.

[0262] R 0 Each independently is an optionally substituted alkyl group having 1 to 40 carbons, an optionally substituted aryl group having 6 to 40 carbons, an optionally substituted alkenyl group having 2 to 40 carbons, an optionally substituted alkynyl group having 2 to 40 carbons, an optionally substituted alkoxy group having 1 to 40 carbons, a halogen atom, a mercapto group, or a hydroxyl group. Here, the aforementioned alkyl group can be linear, branched, or cyclic, any of which is acceptable.

[0263] Here, at least one of R 0 is a hydroxyl group.

[0264] As the alkyl group having 1 to 40 carbons, there is no particular limitation, and for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-dodecyl, pentyl, and the like can be given.

[0265] As the aryl group having a carbon number of 6 to 40, the following are not limited, and for example, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a pyrenyl group, a perylenyl group, or the like can be mentioned.

[0266] As the alkenyl group having a carbon number of 2 to 40, the following are not limited, and for example, an ethynyl group, a propenyl group, a butynyl group, a pentynyl group, or the like can be mentioned.

[0267] As the alkynyl group having a carbon number of 2 to 40, the following are not limited, and for example, an acetylene group, an ethynyl group, or the like can be mentioned.

[0268] As the alkoxy group having a carbon number of 1 to 40, the following are not limited, and for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, or the like can be mentioned.

[0269] Each of m is independently an integer of 1 to 9. From the viewpoint of solubility, 1 to 6, and more preferably 1 to 4, and further preferably 1 from the viewpoint of raw material availability.

[0270] n is an integer of 1 to 4. From the viewpoint of solubility, 1 to 2, and further preferably 1 from the viewpoint of raw material availability.

[0271] Each of p is independently an integer of 0 to 3. From the viewpoint of heat resistance, 1 to 2, and further preferably 1 from the viewpoint of raw material availability.

[0272] In the present embodiment, the aromatic hydroxyl compound can be used alone by the compound represented by any one of the above formulae (A-4a) and (A-4b), and two or more kinds thereof can also be used at the same time. In the present embodiment, from the viewpoint of balancing solvent solubility and heat resistance, it is preferable to use the compound represented by the above formula (A-4a) as the aromatic hydroxyl compound. In addition, from the viewpoint of balancing solvent solubility and heat resistance, it is also preferable to use the compound represented by the above formula (A-4b) as the aromatic hydroxyl compound.

[0273] The compound (A) of the present embodiment can be an oligomer (A-5) having an aralkyl structure represented by the following formula (A-5) containing a prescribed amount of one or more selected from iodine, tellurium, and fluorine.

[0274]

[0275] (In formula (A-5),

[0276] Ar 0 Each of independently can be the same group or a different group, and represents a divalent group including a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrenylene group, a fluorenylene group, a biphenylene group, or a terphenylene group;

[0277] R 0Each independently can be the same group or a different group, represents an optionally substituted alkyl group having a carbon number of 1 to 30, or an optionally substituted aryl group, iodine, tellurium, fluorine, or an alkyl group, aryl group having a carbon number of 1 to 30 containing at least iodine or tellurium or fluorine;

[0278] n represents an integer of 1 to 50;

[0279] r 0 Each independently represents an integer of 0 to 3;

[0280] Each of p independently represents an integer of 0 or more. Among them, all of r 0 are not 0 at the same time. In addition, all of p are not 0 at the same time. In addition, at least one of R 0 contains any of iodine, tellurium, fluorine.

[0281] In the oligomer (A-5), Ar 0 represents a divalent group containing a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrenylene group, a fluorenylene group, a biphenylene group, or a terphenylene group, preferably a divalent group containing a phenylene group, a naphthylene group, an anthrylene group, or a pyrenylene group. Ar 0 Each independently can be the same group or a different group.

[0282] As Ar 0 , specifically, 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 2,4'-biphenylene, 2,2'-biphenylene, 2,3'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene, 2,6-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,8-naphthylene, 1,3-naphthylene, 1,4-naphthylene, anthrylene, phenanthrylene, or pyrenylene, fluorenylene, terphenylene, and the like can be listed. In addition, as the aforementioned Ar 0 , a divalent group containing a diphenylmethyl structure, a bisphenol structure, or a bis(hydroxyphenyl)diisopropylphenyl structure, and the like, a divalent group in which a plurality of phenylene groups and the like are connected by an alkylene group and the like.

[0283] R 0 is a substituent of Ar 0 , each independently can be the same group or a different group, represents an optionally substituted alkyl group having a carbon number of 1 to 30, or an optionally substituted aryl group. As specific examples of R 0 , specific examples of R a and R b described later can be listed.

[0284] In the oligomer (A-5), n represents an integer of 1 to 50. As n, from the viewpoint of the planarization performance of the film, 3 to 40, further preferably 3 to 30, particularly preferably 3 to 20 is preferable.

[0285] In the oligomer (A-5), r 0 each independently represents an integer of 0 to 3. Among them, all of r 0 are not 0 at the same time. As r 0 from the viewpoint of improvement in curability and solubility, 1 to 3 are preferable.

[0286] In the oligomer (A-5), p each independently represents an integer of 0 or more. Among them, all of p are not 0 at the same time. P is appropriately changed depending on the kind of Ar 0 .

[0287] The compound (A) is also preferably a compound (A-6) represented by the formula (A-6) containing a prescribed amount of one or more selected from the group consisting of iodine, tellurium and fluorine.

[0288]

[0289] In the formula (A-6),

[0290] R 1 represents a hydrogen atom or a methyl group or a halogen group,

[0291] R 2 each independently represents a hydrogen atom, a linear organic group having a carbon number of 1 to 20, a branched organic group having a carbon number of 3 to 20, or a cyclic organic group having a carbon number of 3 to 20,

[0292] A represents an organic group having a carbon number of 1 to 30,

[0293] Q each independently is a group representing iodine, tellurium, fluorine, or an alkyl group, an aryl group having a carbon number of 1 to 30 containing at least iodine or tellurium or fluorine, preferably Q is iodine,

[0294] n 1 represents 0 or 1,

[0295] n 2 represents an integer of 1 to 20.

[0296] R 1 A hydrogen atom or a methyl group or a halogen group can be used. As the halogen group, known atoms can be used, and F, Cl, Br, I and the like can be appropriately used. From the viewpoint of exposure sensitivity when the compound of the present application is used as a structural unit of a resist-oriented resin, and stability of the material, R 1 is preferably a methyl group or a halogen group, and in particular from the viewpoint of exposure sensitivity, it is more preferably a halogen group, and further preferably I.

[0297] R 2Two or more combinations selected from the group consisting of a linear organic group having a carbon number of 1 to 20, a branched organic group having a carbon number of 3 to 20, and a cyclic organic group having a carbon number of 3 to 20 can be combined.

[0298] From the viewpoint of suppressing the increase in the Tg of the resin and improving the effect of introducing iodine elements, R 2 is preferably a hydrogen atom. In addition, from the viewpoint of controlling the solubility in a developer, in order to improve acid decomposability, it is also preferable to be an organic group having a carbon number of 1 or more. In addition, from the viewpoint of suppressing acid decomposability, and particularly, ensuring solubility in an alkali developer, suppressing residues, it is also preferable to be a hydrogen atom.

[0299] R 2 optionally has a substituent. As R 2 , for example, an alkyl group having a carbon number of 1 to 20, 1 to 10, or 1 to 6, optionally having a substituent; an alkenyl group having a carbon number of 2 to 20, 2 to 10, or 2 to 6, optionally having a substituent; an alkynyl group having a carbon number of 2 to 20, 2 to 10, or 2 to 6, optionally having a substituent; a cycloalkyl group having a carbon number of 3 to 20, 3 to 10, or 3 to 6, optionally having a substituent; a cycloalkenyl group having a carbon number of 3 to 20, 3 to 10, or 3 to 6, optionally having a substituent; a cycloalkynyl group having a carbon number of 3 to 20, 3 to 10, or 3 to 6, optionally having a substituent; an aryl group having a carbon number of 5 to 20, 5 to 10, or 5 to 6, optionally having a substituent; a combination thereof; and the like can be exemplified.

[0300] As R 2 , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an eicosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, an adamantyl group, an ethenyl group, a propenyl group, a butenyl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a tetracenyl group, a triphenylenyl group, a pyrenyl group, a benzopyrenyl group, an azulenyl group, a fluorenyl group, and the like can be exemplified. These can also include an ether bond, a ketone bond, an ester bond.

[0301] Here, the exemplified groups include isomers. For example, a propyl group includes n-propyl and isopropyl, and a butyl group includes n-butyl, sec-butyl, isobutyl, and t-butyl.

[0302] As a substituent of R 2 , there is no particular limitation, and for example, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an aryloxycarbonyl group, an alkylsilyl group, various crosslinkable groups, acid dissociable groups can be exemplified.

[0303] "Crosslinkable group" means a group that is crosslinked by acid, base, light, or heat, and means a group that is crosslinked in the presence of a catalyst or in the absence of a catalyst. As the aforementioned crosslinkable group, there is no particular limitation, and for example, 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 styryl group, a group having an alkynyl group, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and a group containing these groups can be exemplified.

[0304] "Acid dissociable group" means a group that is cleaved in the presence of an acid to generate a base-soluble group (e.g., phenolic hydroxyl group, carboxyl group, sulfonic acid group, hexafluoroisopropanol group), and the like. As the acid dissociable group, there is no particular limitation, and for example, a hydroxystyrene resin, a (meth)acrylic resin, and the like used in a KrF, ArF, and the like can be suitably selected and used. As a specific example of the acid dissociable group, for example, the acid dissociable group described in International Publication No. 2016 / 158168 can be exemplified.

[0305] A optionally has a substituent. As a compound that is a skeleton of A, for example, an alkane having a carbon number of 1 to 30, a carbon number of 1 to 20, a carbon number of 1 to 10, or a carbon number of 1 to 6, optionally having a substituent; an alkene having a carbon number of 2 to 30, a carbon number of 2 to 20, a carbon number of 2 to 10, or a carbon number of 2 to 6, optionally having a substituent; an alkyne having a carbon number of 2 to 30, a carbon number of 2 to 20, a carbon number of 2 to 10, or a carbon number of 2 to 6, optionally having a substituent; a cycloalkane having a carbon number of 3 to 30, a carbon number of 3 to 20, a carbon number of 3 to 10, or a carbon number of 3 to 6, optionally having a substituent; a cycloalkene having a carbon number of 3 to 30, a carbon number of 3 to 20, a carbon number of 3 to 10, or a carbon number of 3 to 6, optionally having a substituent; a cycloalkyne having a carbon number of 3 to 30, a carbon number of 3 to 20, a carbon number of 3 to 10, or a carbon number of 3 to 6, optionally having a substituent; an arene having a carbon number of 5 to 30, a carbon number of 5 to 20, a carbon number of 5 to 10, or a carbon number of 5 to 6, optionally having a substituent; a combination thereof; and the like can be exemplified.

[0306] As a specific example of the compound that becomes the skeleton of A, for example, there can be mentioned methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, eicosane, triacontane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclotriacontane, adamantane, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, eicosylene, triacontylene, benzene, phenol, naphthalene, anthracene, phenanthrene, tetracene, fused dinaphthyl, triphenylene, pyrene, pentacene, benzopyrene, coronene, ovalene, fluorene, combinations thereof, and the like, optionally having a substituent. These can also contain an ether bond, a ketone bond, an ester bond.

[0307] As a substituent of the compound that becomes the skeleton of A, there is no particular limitation, and for example, there can be mentioned a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a straight-chain aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an aroyloxycarbonyl group, an alkylsilyl group, various cross-linkable groups, acid dissociable groups.

[0308] As the "cross-linkable group", the "acid dissociable group", there is no particular limitation, and for example, the groups described in the aforementioned R 2 may be used.

[0309] n 1 represents 0 or 1, and preferably 1.

[0310] n 2 is an integer of 1 to 20, preferably an integer of 2 to 20, more preferably an integer of 2 to 10, and further preferably an integer of 2 to 5.

[0311] The compound (A) of the present embodiment can be a compound (A-7) represented by the following formula (A-7) containing a prescribed amount of one or more selected from iodine, tellurium, and fluorine. The compound (A-7) preferably contains a functional group that improves solubility in an alkali developer by the action of an acid or a base. Any of the following Z, Y, X preferably contains a functional group that improves solubility in an alkali developer by the action of an acid or a base.

[0312]

[0313] In formula (A-7),

[0314] X is each independently tellurium, I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms having one or more substituents selected from the group consisting of tellurium, I, F, Cl, and Br. At least one of X is tellurium or I.

[0315] L 1is 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 phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group. Among these, L 1 is preferably a single bond.

[0316] m is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and further preferably 2 or 3.

[0317] Y is each independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, the ester group, the carbonate group, the amino group, the ether group, the thioether group, the phosphine group, the phosphite group, the carbamate group, the urea group, the amide group, the imide group, and the phosphate group of the aforementioned Y optionally has a substituent.

[0318] Y is each independently preferably a group represented by the following formula (Y-1).

[0319] -L 2 -R 2 (Y-1)

[0320] In formula (Y-1),

[0321] L 2 is a group cleaved by the action of an acid. As the group cleaved by the action of an acid, at least one of 2-valent linking groups selected from the group consisting of an ester group [* 1 -O-(C=O)-* 2 or 1 -(C=O)-O-* 2 ], an acetal group [* 1 -O-(C(R 21 )2)-O-* 2 (R 21 are each independently H or a hydrocarbon group having a carbon number of 1 to 10.], a carboxyalkoxy group [* 1 -O-R 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having a carbon number of 1 to 10.], and a carbonate group [* 1 -O-(C=O)-O-* 2 ] can be exemplified. Note that, in the formula, * 1 is a bonding site to A, and 2 is a bonding site to R 2 . Among these, L 2 is preferably an acetal group, a carbonate group, or a carboxyalkoxy group.

[0322] R 2 a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched or cyclic heteroatom-containing aliphatic group having 1 to 30 carbon atoms, a heteroatom-containing aromatic group having 1 to 30 carbon atoms, the aforementioned R 2 The aliphatic group, the aromatic group, the heteroatom-containing aliphatic group, and the heteroatom-containing aromatic group of R 2 The aliphatic group of R 2 The aliphatic group of R 2 is preferably a branched or cyclic aliphatic group. The number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, and a methylcyclohexyl group. Among these, a tert-butyl group or a cyclohexyl group is preferred.

[0323] If L 2 is 1 -(C=O)-O-* 2 or a carboxyalkoxy group, the solubility difference and the dissolution rate difference between the unexposed portions and the exposed portions in the development treatment are enlarged when the carboxylic acid group is formed by cleavage by the action of an acid, and thus the resolution is improved. In particular, residue at the bottom of a pattern in a fine line pattern can be suppressed, and thus this is preferred.

[0324] Y is preferably each independently a group represented by any one of the following formulae (Y-1-1) to (Y-1-7).

[0325]

[0326] n is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 1 or more and 5 or less, further preferably an integer of 1 or more and 3 or less, and still further preferably 1 or 2.

[0327] R a , R b , and R ceach independently H, I, F, Cl, Br, or an optionally substituted organic group having a carbon number of 1 to 60. As the substituent of the organic group having a carbon number of 1 to 60, there is no particular limitation, and for example, I, F, Cl, Br, or other substituents can be listed. As the other substituents, there is no particular limitation, and for example, a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a sulfide group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, a phosphate group can be listed. Among them, the alkoxy group, the ester group, the carbonate group, the amino group, the ether group, the sulfide group, the phosphine group, the phosphite group, the carbamate group, the urea group, the amide group, the imide group, and the phosphate group optionally further have a substituent. Note that, as the substituent here, a linear, branched, or cyclic aliphatic group having a carbon number of 1 to 20, an aromatic group having a carbon number of 6 to 20 can be listed.

[0328] R a , R b , and R c The carbon number of the organic group optionally having a substituent in R

[0329] As the organic group having a carbon number of 1 to 60 optionally having a substituent, there is no particular limitation, and a linear or branched aliphatic hydrocarbon group having a carbon number of 1 to 60, an alicyclic hydrocarbon group having a carbon number of 4 to 60, an aromatic group having a carbon number of 6 to 60 optionally containing a hetero atom can be listed.

[0330] As the linear or branched aliphatic hydrocarbon group having a carbon number of 1 to 60, there is no particular limitation, and for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a pentyl group, a 2-ethylhexyl group can be listed.

[0331] As the alicyclic hydrocarbon group, there is no particular limitation, and for example, a cyclohexyl group, a cyclododecyl group, a bicyclopentyl group, a tricyclodecyl group, an adamantyl group, and the like can be listed. Further, an aromatic group optionally containing a hetero atom such as a benzoxadiazolyl group, a benzotriazolyl group, a benzothiadiazolyl group can also be selected. In addition, a combination of these organic groups can be selected.

[0332] As the aromatic group having a carbon number of 6 to 60 optionally containing a hetero atom, there is no particular limitation, and for example, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a pyrenyl group, a benzoxadiazolyl group, a benzotriazolyl group, a benzothiadiazolyl group can be listed.

[0333] Among these organic groups having a carbon number of 1 to 60 optionally having a substituent, a methyl group is preferred.

[0334] A is an organic group having a carbon number of 1 to 30. A can be a monocyclic organic group or a polycyclic organic group. A is preferably an aromatic ring. The carbon number of A is preferably 6 to 14, and more preferably 6 to 10.

[0335] A is preferably a group represented by any one of the following formulae (A-1) to (A-4), more preferably a group represented by the following formula (A-1).

[0336]

[0337] p represents the number of vinyl groups, and p is an integer of 1 or more, preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, further preferably 1.

[0338] Z each independently represents an alkoxy group, an ester group, an acetal group, or a carbonate group. r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, further preferably 0.

[0339] The resin having a structural unit derived from the compound (A) of the present embodiment can have a structural unit represented by the following formula (A-8). By including the resist composition of this resin component, it is possible to achieve high sensitivity in a photolithography process, and high resolution due to the expansion of the solubility contrast of the resin at the time of development.

[0340]

[0341] In formula (A-8), R 1 , R 2 , A, n 1 , n 2 The symbol * represents a bonding site with an adjacent repeating unit, as defined in the aforementioned formula (A-6).

[0342] The (meth)acrylate (co)polymer represented by the aforementioned formula (A-8) can be obtained by polymerizing one or more (meth)acrylate compounds represented by the aforementioned formula (A-6), or by polymerizing one or more (meth)acrylate compounds represented by the aforementioned formula (A-6) together with other monomers. This (meth)acrylate (co)polymer can be used as a material for forming a film for photolithography.

[0343] Note that, when the compound (A) and the resin derived from the compound (A) of the present embodiment are used as an underlayer film of a resist in an exposure process, in a process in which the underlayer film is used as an underlayer film of a resist layer and is formed on a processed layer to be processed, and the processed layer to be processed is processed in a dry etching or the like process after pattern formation, from the viewpoint of etching mask performance that makes the pattern quality of the processed layer to be processed after processing good, it is preferable that the carbon content be high, the hydrogen content be low, and the ring structure introduction rate be high in order to be able to suppress the etching rate, and, as the compound structure, it is preferable to use a resin having a fused ring structure in which a monocyclic ring and two or more polycyclic rings are fused. At this time, the ring structure preferably has an aromatic structure or a heteroaromatic structure.

[0344] In addition, in a case where the compound (A) and the resin derived from the compound (A) of the present embodiment are used as an underlayer film of a resist, and further, one or more other spin-on carbon (SOC) layers or inorganic hard mask layers are used as an etching mask layer, from the viewpoint of the processability of the etching mask layer that becomes the object of the pattern shape of the resist layer by etching transfer, and the viewpoint of not deteriorating the pattern shape by etching from the shape of the resist immediately after development, it is also preferable that, in order to improve the quality of the pattern shape of the processed layer to be processed after processing, an underlayer film of a resist containing the compound (A) or the resin derived from the compound (A) of the present embodiment, which has a faster etching rate than the resist and exhibits easy etching properties, be used, at least one or more etching mask layers be layered on a substrate having a processed layer to be processed, and further, a layer formed of the compound (A) or the resin containing the compound (A) of the present embodiment be layered on the upper side of the etching mask layer. From these viewpoints, a resin having a small number of aromatic ring structures, or a structure that does not have a novolak structure, is preferable, and a polyacrylic resin, a polyvinyl resin, a resin having an aliphatic structure such as a polyalkylene ether resin in the main chain, or a resin having a high ratio of carbon skeleton constituting an aliphatic structure is preferable.

[0345] The following shows specific examples of the compound (A), but the compound (A) is not limited thereto.

[0346]

[0347]

[0348]

[0349] [Composition containing compound (A) or / and resin (A)]

[0350] The composition of the present embodiment contains the compound (A) or / and the resin (A).

[0351] (Solvent)

[0352] The solvent in the present embodiment can be appropriately used as long as it dissolves at least the above-mentioned compound (A) or / and the resin (A). Specific examples of the solvent are not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, 3-methoxy-2-methylpropionic acid methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionic acid butyl ester, 3-methoxy-3-methylbutyric acid butyl ester, acetoacetic acid methyl ester, pyruvic acid methyl ester, pyruvic acid ethyl ester, and other esters; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone; and the like. The solvent used in the present embodiment is preferably a safe solvent, and more preferably at least one selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactate, and further preferably at least one selected from the group consisting of PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0353] The amount of the solid component and the amount of the solvent in the present embodiment are not particularly limited, and the amount of the solid component is preferably 1 to 80 mass% and the amount of the solvent is preferably 20 to 99 mass%, more preferably 1 to 50 mass% and 50 to 99 mass%, further preferably 2 to 40 mass% and 60 to 98 mass%, and particularly preferably 2 to 10 mass% and 90 to 98 mass%, with respect to the total mass of the solid component and the solvent.

[0354] (Acid generator)

[0355] In the composition of the present embodiment, it is preferable to contain one or more kinds of acid-generating agents that directly or indirectly generate an acid by irradiation with any of the radiation lines selected from the group consisting of visible light, ultraviolet light, excimer laser light, electron beams, extreme ultraviolet light (EUV), X-rays, and ion beams, or by heating. The acid-generating agent is not particularly limited, and any of the nonionic or ionic systems can be used. As the nonionic acid-generating agent, sulfonic acid esters (such as 2-nitrobenzyl ester, aromatic sulfonic acid ester, oxime sulfonic acid ester, N-sulfonyloxy imide, sulfonyloxy ketone, diazonium naphthoquinone 4-sulfonic acid ester), sulfones (such as disulfone, ketone sulfone, sulfonyl diazomethane), and the like can be exemplified. As the ionic acid-generating agent, onium salts (such as diazonium onium salt, phosphonium salt, sulfonium salt, iodonium salt) containing onium cations are representative. As the anion of the onium salt, sulfonic acid anions, sulfonylimide anions, sulfonylmethylate anions, and the like can be exemplified. For example, acid-generating compounds described in International Publication No. WO2013 / 024778, Japanese Patent Application Publication No. 2009-134088, Japanese Patent Application Publication No. Sho 63-26653, Japanese Patent Application Publication No. Sho 55-164824, Japanese Patent Application Publication No. Sho 62-69263, Japanese Patent Application Publication No. Sho 63-146038, Japanese Patent Application Publication No. Sho 63-163452, Japanese Patent Application Publication No. Sho 62-153853, Japanese Patent Application Publication No. Sho 63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, and the like can be used. The acid-generating agent can be used alone or two or more kinds can be used in combination.

[0356] The amount of the acid-generating agent is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, further preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, based on the total mass of the solid content. By using the acid-generating agent within the foregoing range, there is a tendency to improve the curability. In the present embodiment, the method of generating the acid is not limited as long as the acid is generated in the system.

[0357] (Acid diffusion control agent)

[0358] In addition, as the other compound that can be used in combination, a compound capable of promoting or inhibiting the diffusion of the generated acid can be contained as an acid diffusion control agent.

[0359] <Acid diffusion promoter>

[0360] As a preferred acid diffusion promoter, from the viewpoint of maintaining the generation of acid and enabling the release of acid when necessary, by making the pKa value be 2.0 or less, and the molecular weight be 1000 or less or the clogP value be 30 or less or the Tg be 250°C or less, it is possible to promote the thermal diffusion in the resin matrix, and it is also possible to include a compound having at least heat resistance of 250°C. As the structure of the specific acid diffusion promoter, any of the nonionic or ionic systems can be used. As the nonionic acid diffusion promoter, sulfonic acid esters (such as 2-nitrobenzyl ester, aromatic sulfonic acid ester, oxime sulfonic acid ester, N-sulfonyloxy imide, sulfonyloxy ketone), sulfones (such as disulfone, ketone sulfone, sulfonyl diazomethane), and the like can be listed. As the ionic acid diffusion promoter, the onium salt (such as diazonium onium salt, phosphonium salt, sulfonium salt, iodonium salt) including onium cation is representative. As the anion of the onium salt, sulfonic acid anion, sulfonylimide anion, sulfonylmethylate anion, and the like can be listed.

[0361] As the cation in the ionic compound, any of the cations that satisfy any of the above-mentioned molecular weight, clogP, Tg, and heat resistance in the state of forming a salt with the anion can be used without limitation. As examples of the specific cation, the organic ammonium cation, the organic iodonium cation, the organic sulfonium cation can be preferably used.

[0362] <Acid diffusion inhibitor>

[0363] The acid diffusion inhibitor is used for the purpose of inhibiting the diffusion of the acid generated by the acid generator or the like in the resist film, the underlayer film in each process of exposure, PEB, development, and inhibiting the reaction of the resist resin or the underlayer film resin due to the influence of the acid present in the unexposed portion due to the trace generation or diffusion. In addition, it is possible to provide a resist resin composition or an underlayer film resin composition that is excellent in process stability in association with the improvement in the temporal stability of the resist resin composition or the underlayer film resin composition, the improvement in the resolution in photolithography, the inhibition of the time dependence from after exposure to development in the improvement in the pattern quality, and the like. As the acid diffusion inhibitor, the low molecular compound can be applied as a part of the polymer, and the two forms can be used in combination.

[0364] In addition, as the acid diffusion inhibitor, it is possible to form a salt of an acid that is weaker in acid dissociation property than the acid generated by the acid generator used. The acidity as an index of the acid dissociation property is represented by the acid dissociation constant (pKa). When a salt that generates an acid that is weaker in acidity than the acid generated by the acid generator is used as the acid diffusion inhibitor, the acid dissociation constant of the acid generated by the acid diffusion inhibitor is -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5.

[0365] As the acid diffusion inhibitor, for example, a nitrogen atom-containing compound, a photoalkaligen, which is photosensitive and generates a weak acid by exposure, and the like can be exemplified.

[0366] As the nitrogen atom-containing compound, for example, an amine compound such as triamylamine, trioctylamine, and the like, an amide group-containing compound such as formamide, N,N-dimethylacetamide, and the like, a urea compound such as urea, 1,1-dimethylurea, and the like, a nitrogen-containing heterocyclic compound such as pyridine, N-(undecylcarbonyloxyethyl)morpholine, N-tert-pentyl oxycarbonyl-4-hydroxypiperidine, and the like, and the like can be exemplified.

[0367] As the photoalkaligen, for example, a compound containing an onium cation which is decomposed by exposure and a weak acid anion, and the like can be exemplified. As for the photodegradable base, in the exposed portion, a proton generated by the decomposition of the onium cation and the weak acid anion generate a weak acid, and thus the acid diffusion control property is reduced.

[0368] As an example of a salt which can generate an acid having a degree of acidity weaker than that of the acid generated by the acid generator, a salt represented by the formula (D) described in Japanese Patent Application Laid-Open No. 2015-147926, a salt described in Japanese Patent Application Laid-Open No. 2012-229206, Japanese Patent Application Laid-Open No. 2012-6908, Japanese Patent Application Laid-Open No. 2012-72109, Japanese Patent Application Laid-Open No. 2011-39502, and Japanese Patent Application Laid-Open No. 2011-191745 can be exemplified.

[0369] The following can be exemplified as examples of other preferable acid diffusion inhibitors, but are not limited thereto.

[0370]

[0371]

[0372] As a lower limit of the content of the acid diffusion control agent when the underlayer film resin composition contains the acid diffusion control agent, 0.1 parts by mass, more preferably 0.5 parts by mass, and further preferably 1 part by mass, relative to 100 parts by mass of the polymer component (or the resin component) is preferable. As an upper limit of the content, 20 parts by mass, more preferably 10 parts by mass, and further preferably 5 parts by mass is preferable.

[0373] As a lower limit of the content of the acid diffusion control agent when the underlayer film resin composition contains the acid diffusion control agent, 1 mole%, more preferably 5 mole%, and further preferably 10 mole%, relative to 100 mole% of the acid generator is preferable. As an upper limit of the content, 250 mole%, more preferably 150 mole%, and further preferably 100 mole% is preferable.

[0374] By setting the content of the acid diffusion control agent to the above range, it is possible to further improve the defect inhibition property and the LWR performance of the underlayer film resin composition. The acid diffusion control agent can contain one or two or more kinds.

[0375] (crosslinking agent)

[0376] In the present embodiment, one or more crosslinking agents can be contained in the composition. The crosslinking agent refers to a compound that can crosslink at least any of the compound (A) or the resin (A). As the aforementioned crosslinking agent, an acid crosslinking agent that can cause intramolecular or intermolecular crosslinking of the compound (A) or the resin (A) in the presence of an acid generated by an acid generator is preferred. As such an acid crosslinking agent, for example, a compound having one or more groups capable of crosslinking the compound (A) or the resin (A) (hereinafter referred to as "crosslinkable group") can be exemplified.

[0377] As the aforementioned crosslinkable group, for example, (i) a hydroxyl group (alkyl group having 1 to 6 carbons), an alkoxy group having 1 to 6 carbons (alkyl group having 1 to 6 carbons), an acetoxy group (alkyl group having 1 to 6 carbons), or the like hydroxylalkyl group or a group derived therefrom; (ii) a formyl group, a carboxyl group (alkyl group having 1 to 6 carbons), or the like carbonyl group or a group derived therefrom; (iii) a dimethylaminomethyl group, a diethylaminomethyl group, a dihydroxymethylaminomethyl group, a dihydroxyethylaminomethyl group, a morpholinomethyl group, or the like nitrogen-containing group-containing group; (iv) a glycidyl ether group, a glycidyl ester group, a glycidylamino group, or the like glycidyl group-containing group; (v) a benzyloxymethyl group, a benzoyloxymethyl group, or the like group derived from an allyloxy group having 1 to 6 carbons (alkyl group having 1 to 6 carbons), an aralkyloxy group having 1 to 6 carbons (alkyl group having 1 to 6 carbons), or the like aromatic group; and (vi) a vinyl group, an isopropenyl group, or the like polymerizable multiple bond-containing group can be exemplified. As the crosslinkable group of the acid crosslinking agent in the present embodiment, a hydroxylalkyl group, an alkoxyalkyl group, or the like, and particularly an alkoxymethyl group is preferred.

[0378] As the crosslinking agent having the aforementioned crosslinkable group, there is no particular limitation, and for example, the acid crosslinking agent described in International Publication No. WO2013 / 024778 can be used. The crosslinking agent can be used alone or two or more kinds thereof can be used.

[0379] The amount of the crosslinking agent used in the present embodiment is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, further preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass, based on the total mass of the solid content. If the compounding ratio of the aforementioned crosslinking agent is 0.5% by mass or more, there is a tendency to improve solvent resistance and inhibit dissolution into a solvent for the resist after curing. On the other hand, if it is 50% by mass or less, there is a tendency to be able to inhibit a decrease in heat resistance after curing.

[0380] (other components)

[0381] In the composition of the present embodiment, as the other component, one or two or more kinds of various additives such as a dissolution promoter, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid or an oxygen-containing acid of phosphorus or a derivative thereof can be added as needed.

[0382] (dissolution promoter)

[0383] The dissolution promoter is a component that has an effect of increasing the solubility of the solid component when the solubility of the solid component with respect to the developer is too low, and an effect of moderately increasing the dissolution speed of the aforementioned compound during development. As the aforementioned dissolution promoter, a low-molecular-weight one is preferred, and a low-molecular-weight phenolic compound can be cited, for example. As the low-molecular-weight phenolic compound, a bisphenol, a tris(hydroxyphenyl)methane, or the like can be cited, for example. These dissolution promoters can be used alone or in a mixture of two or more kinds.

[0384] The compounding amount of the dissolution promoter can be appropriately adjusted depending on the kind of the aforementioned solid component used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid component.

[0385] (dissolution controller)

[0386] The dissolution controller is a component that has an effect of controlling the solubility of the solid component when the solubility of the solid component with respect to the developer is too high, and an effect of moderately reducing the dissolution speed during development. As such a dissolution controller, one that does not undergo a chemical change in the process of baking of the film, irradiation of a radiation line, coating of an upper layer, or the like is preferred.

[0387] As the dissolution controller, there is no particular limitation, and an aromatic hydrocarbon such as phenanthrene, anthracene, acenaphthene, or the like; a ketone such as acetophenone, benzophenone, phenylnaphthyl ketone, or the like; a sulfone such as methylphenyl sulfone, diphenyl sulfone, dinaphthyl sulfone, or the like, or the like can be cited, for example. These dissolution controllers can be used alone or in two or more kinds.

[0388] The compounding amount of the dissolution controller can be appropriately adjusted depending on the kind of the aforementioned compound used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid component.

[0389] (sensitizer)

[0390] The sensitizer is a component that has an effect of absorbing the energy of the irradiated radiation line and transferring the energy to the acid generator, thereby increasing the amount of generated acid, and improving the curability. As such a sensitizer, a benzophenone, a biacetyl, a pyrene, a phenothiazine, a fluorene, or the like can be cited, and there is no particular limitation. These sensitizers can be used alone or in two or more kinds.

[0391] The compounding amount of the sensitizing agent can be appropriately adjusted depending on the kind of the aforementioned compound used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0392] (Surfactant)

[0393] The surfactant is a component having an effect of improving the coatability, streak, coatability of the upper layer film, and the like of the composition of the present embodiment. The surfactant can be any of anionic surfactants, cationic surfactants, nonionic surfactants, or amphoteric surfactants. As a preferred surfactant, nonionic surfactants can be listed. Nonionic surfactants have good affinity with the solvent used in the production of the composition of the present embodiment, and can further improve the effects of the composition of the present embodiment. As examples of the nonionic surfactants, polyoxyethylene higher alkyl ether, polyoxyethylene higher alkyl phenyl ether, higher fatty acid diesters of polyethylene glycol, and the like can be listed, without particular limitation. As commercial products of these surfactants, Eftop (manufactured by Jemco), MEGAFACE (manufactured by Dainippon Ink and Chemicals, Incorporated), FLUORAD (manufactured by Sumitomo 3M Limited), AsahiGuard, Surflon (both manufactured by Asahi Glass Company, Limited), PEPPOL (manufactured by Nippon Shokubai Co., Ltd.), KP (manufactured by Shin-ETV Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the like can be listed.

[0394] The compounding amount of the surfactant can be appropriately adjusted depending on the kind of the aforementioned solid component used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0395] (Other additives)

[0396] Further, one or two or more kinds of additives other than the aforementioned components can be compounded in the composition of the present embodiment as needed. As such additives, for example, dyes, pigments, and adhesion aids, and the like can be listed. For example, if a dye or a pigment is compounded, the latent image of the exposed portion is visualized, the influence of the vignetting at the time of exposure can be alleviated, and thus is preferred. In addition, if an adhesion aid is compounded, the adhesion to the substrate, the layer in contact can be improved, and thus is preferred. Further, as other additives, antihalation agents, storage stabilizers, defoaming agents, shape improvers, and the like can be listed, and specifically, 4-hydroxy-4'-methylchalcone and the like can be listed.

[0397] The total amount of the arbitrary components in the composition of the present embodiment can be 0 to 99 mass% of the total mass of the solid components, preferably 0 to 49 mass%, more preferably 0 to 10 mass%, further preferably 0 to 5 mass%, further preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0398] The composition of the present embodiment is generally prepared by dissolving each component in a solvent to form a uniform solution at the time of use, and then, if necessary, filtering, for example, with a filter having a pore diameter of about 0.2 μm, whereby it can be prepared.

[0399] The composition of the present embodiment can be used for photolithography. The aforementioned composition is preferably cured after forming a thin film to form an underlayer film or a film in contact with a resist layer (resist layer contact film).

[0400] (Properties of the composition, etc.)

[0401] 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. The composition of the present embodiment, after being cured, generates protons by irradiation of ultraviolet rays, and supplies the protons to an adjacent layer, whereby the sensitivity of the adjacent layer can be improved. The composition of the present embodiment is preferably used after being cured. After being cured, it preferably has solvent resistance so as not to be dissolved in a composition of the adjacent layer.

[0402] [Method for manufacturing an amorphous film]

[0403] An amorphous film can be formed on a substrate using the composition of the present embodiment.

[0404] [Method for forming a resist pattern using the composition]

[0405] The method for forming a resist pattern using the composition of the present embodiment includes an underlayer film forming step of forming an underlayer film on a substrate using the aforementioned composition, a photoresist film forming step of forming at least one photoresist film on the underlayer film formed by the underlayer film forming step, and a step of irradiating a prescribed region of the photoresist film formed by the photoresist film forming step with a radiation line and developing it.

[0406] [Method for forming a circuit pattern using the composition]

[0407] The circuit pattern forming method using the composition of the present embodiment includes the following steps: a lower layer film forming step of forming a lower layer film on a substrate; a resist layer contact film forming step of forming a resist layer contact film on the lower layer film formed by the lower layer film forming step using the aforementioned composition; a photoresist film forming step of forming at least one layer of a photoresist film on the resist layer contact film formed by the resist layer contact film forming step; a resist pattern forming step of forming a resist pattern by irradiating a prescribed region of the photoresist film formed by the photoresist film forming step with a radiation line and performing development; a pattern forming step of forming a pattern by etching the aforementioned resist layer contact film, or the aforementioned resist layer contact film and the aforementioned lower layer film using the resist pattern formed by the resist pattern forming step as a mask; and a substrate pattern forming step of forming a pattern on the substrate by etching the aforementioned substrate using the pattern formed by the pattern forming step as a mask.

[0408] Example

[0409] The present embodiment is described in detail below through synthesis examples and examples, but the present embodiment is not limited by any of these examples.

[0410] [Measurement method]

[0411] (1) Structure of compound

[0412] The structure of the compound was confirmed by 1H-NMR measurement under the following conditions using Advance III 500 manufactured by Bruker.

[0413] Frequency: 500 MHz

[0414] Solvent: d6-DMSO

[0415] Internal standard: TMS

[0416] Measurement temperature: 23°C

[0417] [Measurement method]

[0418] (Preparation of lower layer film composition)

[0419] 10 parts by mass of the compound or polymer obtained in the following synthesis example, 0.2 parts by mass of a thermal acid generator TAG-2689 (quaternary ammonium salt of trifluoromethane sulfonic acid, manufactured by King Industries Inc.), 1 part by mass of TMOM-BP (manufactured by Hokoku Corporation), 76.8 parts by mass of PGMEA, and 12 parts by mass of PGME were compounded to prepare a lower layer film composition solution containing the compound of the present invention.

[0420] Note that, 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 additionally added instead of TMOM-BP.

[0421] (1) Safety solvent solubility test of compound

[0422] The solubility of the compound in PGMEA was evaluated using the amount of dissolution in each solvent and according to the following criteria. Note that the amount of dissolution was measured by accurately weighing the compound into a test tube, adding the solvent to be tested to become a prescribed concentration, performing ultrasonic washing with an ultrasonic washer for 30 minutes, and then measuring by visually observing the state of the liquid.

[0423] A: 5.0 mass% ≤ amount of dissolution

[0424] B: 2.0 mass% ≤ amount of dissolution < 5.0 mass%

[0425] C: amount of dissolution < 2.0 mass%

[0426] (2) Storage stability and film formability of composition

[0427] For the storage stability of the composition containing the compound and the resin, the underlayer film composition described above was prepared, and then, after being left to stand at 23°C for 3 days, the presence or absence of precipitation was observed by visual observation, whereby the evaluation was performed. In addition, after the composition was spin-coated on a clean silicon wafer, baking was performed on a hot plate at 250°C to form an amorphous film having a thickness of 100 nm. For the prepared composition, a case where the solution was uniform and the film was formed well was evaluated as O, a case where the solution was uniform but the film had defects was evaluated as Δ, and a case where there was precipitation was evaluated as X.

[0428] (3) Sensitivity evaluation

[0429] (EUV sensitivity - TMAH aqueous solution development)

[0430] The polymer MAR1 obtained in the following resist polymer synthesis example, triphenylsulfonium nonafluoromethanesulfonate 1 part by mass, tributylamine 0.2 parts by mass, PGMEA 80 parts by mass, and PGME 12 parts by mass were compounded to prepare a resist solution for sensitivity evaluation and pattern evaluation.

[0431] The underlayer film composition described above was applied to a silicon wafer, and baking treatment was performed at 240°C for 60 seconds to form an underlayer film having a film thickness of 100 nm on the silicon wafer.

[0432] Further, an resist solution was applied to the underlayer film of the present application formed on the silicon wafer, and a photoresist layer having a film thickness of 100 nm was formed by baking at 110°C for 60 seconds.

[0433] Next, using an ultraviolet light (EUV) exposure device "EUVES-7000" (product name, Litho Tech Japan Corporation), from 1 mJ / cm 2 The exposure amount was increased to 80 mJ / cm 2 The exposure amount was increased to 80 mJ / cm 2 A shot exposure without a mask was performed, and then baking (PEB) was performed at 110°C for 90 seconds, and development was performed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, to obtain a wafer on which a shot exposure of 80 exposure amount was performed. For each shot exposure region obtained, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, SCREEN Semiconductor Solutions Co., Ltd.), the distribution data of the film thickness with respect to the exposure amount was obtained, and the exposure amount at which the slope of the film thickness variation with respect to the exposure amount became the largest was calculated as the sensitivity value (mJ / cm 2 ), as an index of the EUV sensitivity of the resist.

[0434] (4) Etch Resistance

[0435] Etching device: RIE-10NR, Samco International Inc.

[0436] Power: 50 W

[0437] Pressure: 20 Pa

[0438] Time: 2 minutes

[0439] Etching gas

[0440] Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50: 5: 5 (sccm)

[0441] For the film formed on a silicon wafer using the underlayer film solution containing the material of the present application produced in each of the examples and comparative examples, an etching test was performed under the above conditions, and the etching rate at that time was measured. Furthermore, the etching resistance was evaluated based on the following evaluation criteria, using the etching rate of the underlayer film produced using a novolak (PSM4357, Gungor Chemical Co., Ltd.) as a reference.

[0442] Evaluation Criteria

[0443] A: The difference in etching rate compared to the underlayer film of the novolak was less than 10% or more in terms of the ratio to the novolak

[0444] B: The difference in etching rate compared to the underlayer film of the novolak was within ±10% in terms of the ratio to the novolak

[0445] C: Difference in etching rate compared to the lower layer of novolak is greater than 10% in terms of ratio to novolak

[0446] Synthesis Example 1: Synthesis of BisB-1

[0447] In a container having a stirrer, a condenser, and a burette, with an inner volume of 200 mL, 2,6-dimethylphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 25.0 g (204.7 mmol), 4-iodobenzaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 25.0 g (107.7 mmol), and 1-methoxy-2-propanol 20 mL were put, and sulfuric acid 5.3 g (53.9 mmol) was added to prepare a reaction solution. The reaction solution was stirred at 90°C for 6 hours to perform a reaction. After the reaction was completed, pure water 1 L was added to the reaction solution, sodium bicarbonate was added while being ice-cooled, adjusted to pH 7 to 8, and extracted with ethyl acetate to obtain a solution. The obtained solution was subjected to separation and purification based on column chromatography, whereby the target compound (BisB-1) represented by the following formula was obtained in 24.9 g. With respect to the obtained compound (BisB-1), NMR measurement was performed under the aforementioned measurement conditions, and as a result, the following peaks were found, and it was confirmed that the chemical structure of the following formula (BisB-1) was possessed.

[0448] δ (ppm) 8.1 (2H, -O-H), 6.5 to 7.7 (8H, Ph-H), 5.2 (1H, C-H), 2.1 (12H, CH3)

[0449]

[0450] Synthesis Example 2: Synthesis of BisB-2

[0451] In a container having a stirrer, a condenser, and a burette, with an inner volume of 500 mL, 4,4'-dihydroxybiphenyl (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 42.8 g (230 mmol), and 3,5-diiodosalicylaldehyde (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 21.5 g (57.5 mmol), and γ-butyrolactone 428 mL were put, and sulfuric acid 5.8 g (58 mmol) was added to prepare a reaction solution. The reaction solution was stirred at 90°C for 56 hours to perform a reaction. After the reaction was completed, pure water 1 L was added to the reaction solution, neutralized with sodium hydroxide, and extracted with ethyl acetate to obtain a solution. The obtained solution was subjected to separation and purification based on column chromatography, whereby the target compound (BisB-2) represented by the following formula was obtained in 10 g. With respect to the obtained compound (BisB-2), NMR measurement was performed under the aforementioned measurement conditions, and as a result, the following peaks were found, and it was confirmed that the chemical structure of the following formula (BisB-2) was possessed.

[0452] δ (ppm) 9.4 (4H, -O-H), 8.9 (1H, -O-H), 6.2-7.8 (16H, Ph-H), 6.3 (1H, C-H)

[0453]

[0454] Synthesis Example 3: Synthesis of XbisN-1

[0455] In a container having a stirrer, a condenser tube, and a burette, with an inner volume of 300 ml, 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich Corporation) 7.0 g (40 mmol) and 3-iodobenzaldehyde (reagent manufactured by Tokyo Kasei Industry Co., Ltd.) 4.6 g (20 mmol) were put into 100 ml of γ-butyrolactone, 0.5 g of p-toluenesulfonic acid was added, and the reaction was performed 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 extraction was performed with ethyl acetate, and concentration was performed to obtain a solution.

[0456] After the obtained solution was separated based on column chromatography, washing was performed with chloroform to obtain the target compound (XbisN-1) represented by the following formula (XbisN-1) 4.2 g. For the obtained compound (XbisN-1), the molecular weight was measured using the aforementioned method, and the result was 516.

[0457] For the obtained compound (XbisN-1), NMR measurement was performed under the aforementioned measurement conditions, and as a result, the following peaks were found, and it was confirmed that the chemical structure of the following formula (XbisN-1) was possessed.

[0458] δ (ppm) 9.7 (2H, O-H), 7.0-8.5 (14H, Ph-H), 6.5 (1H, C-H)

[0459]

[0460] Synthesis Example 4: Synthesis of BMI-1

[0461] Reaction of salicyl alcohol with iodine chloride was performed by dissolving neopentyl glycol bis(4-aminophenyl) ether (product name: DANPG, manufactured by Wakayama Seika Kaisha, Ltd.) 5.73 g (20 mmol) using butanol as a solvent, and adding dropwise a 20 mass% iodine chloride aqueous solution (81.2 g, 100 mmol) over 60 minutes at 50°C, and stirring for 2 hours at 50°C. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added, and stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that had been separated by the cooling was filtered, washed, and dried to obtain a brown solid 9.5 g. The sample of the brown solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and as a result, a compound represented by the following formula (X) was confirmed.

[0462]

[0463] Next, the compound (X) obtained in the above was moved to a container having a content volume of 200 ml, provided with a stirrer, a condenser, and a burette, and maleic anhydride (manufactured by Showa Denko K.K.) 2.54 g (26.0 mmol), dimethylformamide 50 ml, and m-xylene 50 ml were put in, and p-toluenesulfonic acid 0.5 g (2.9 mmol) was added to prepare a reaction liquid. The reaction liquid was reacted by stirring at 130°C for 4.0 hours, and water generated was recovered to a Dean-Stark trap by azeotropic dehydration. Next, the reaction liquid was cooled to 40°C, and was added dropwise to a beaker in which distilled water 500 ml was put to precipitate the product. The obtained slurry solution was filtered, and the residue was washed with methanol, and separation and purification based on column chromatography were performed to obtain the target compound (BMI-1) represented by the following formula 1.5 g.

[0464]

[0465] The compound (BMI-1) obtained was subjected to NMR measurement under the aforementioned measurement conditions, and as a result, the following peaks were found, and the chemical structure represented by the following formula (BMI-1) was confirmed.

[0466] 1H-NMR: (d-DMSO, internal standard TMS)

[0467] 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)

[0468] Synthesis Example 5: Synthesis of XBisN-2

[0469] In a 500 mL container equipped with a stirrer, a condenser, and a burette, 32.0 g (20 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich Corporation), 29.9 g (80 mmol) of 3,5-diiodosalicylaldehyde (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 200 mL of 1,4-dioxane were put, 10 mL of 95% sulfuric acid was added, and the reaction was performed by stirring at 100°C for 6 hours. Subsequently, the reaction solution was neutralized with 24% sodium hydroxide aqueous solution, 100 g of pure water was added to precipitate the reaction product, and after cooling to room temperature, the product was separated by filtration. The obtained solid was dried, and then separated and purified by column chromatography to obtain the target compound represented by the following formula (XBisN-2) 2.6 g.

[0470] Note that the following peaks were found by 500 MHz1H-NMR, and the chemical structure represented by the following formula was confirmed.

[0471] 1H-NMR: (d-DMSO, internal standard TMS)

[0472] δ (ppm) 9.6-9.7 (3H, O-H), 6.7-8.5 (12H, Ph-H), 6.2 (1H, C-H)

[0473]

[0474] Synthesis Example 5-1: Synthesis of RXBisN-2

[0475] In a 100 mL container equipped with a stirrer, a condenser, and a burette, 2.6 g (7.0 mmol) of XBisN-2 and 1.0 g (2 mmol) of copper monobutyrate phthalate were put, 20 mL of 1-butanol was added as a solvent, and the reaction was performed by stirring the reaction solution at 100°C for 6 hours. After cooling, the precipitate was filtered, and the obtained crude was dissolved in 20 mL of ethyl acetate. Subsequently, 1 mL of hydrochloric acid was added, and after stirring at room temperature, the solution was neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, 40 mL of methanol was added to precipitate the reaction product, and after cooling to room temperature, the product was separated by filtration. The obtained solid was dried to obtain the target resin (RXBisN-2) 1.0 g having the structure represented by the following formula.

[0476] The obtained resin was measured for the polystyrene-conversion molecular weight by the aforementioned method, and as a result, Mn: 4300, Mw: 5500, and Mw / Mn: 1.28 were obtained.

[0477] The obtained resin was measured for NMR under the aforementioned measurement conditions, and as a result, the following peaks were found, and the chemical structure represented by the following formula was confirmed.

[0478] δ (ppm) 9.5-9.7 (3H, O-H), 6.7-8.5 (12H, Ph-H), 6.0-6.3 (1H, C-H)

[0479]

[0480] Synthesis Example 6: Synthesis of NAFP-AL

[0481] Into a 300 mL four-necked flask under nitrogen, 1,4-bis(chloromethyl)benzene (28.8 g, 0.148 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-naphthol (30.0 g, 0.1368 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (5.7 g, 0.029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and then propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) 150.4 g was further added, and stirring was performed, and the temperature was increased to dissolve until reflux was confirmed, and polymerization was started. After 16 hours, the temperature was naturally cooled to 60°C, and then the obtained precipitate was reprecipitated in methanol 1600 g.

[0482] The obtained precipitate was filtered, and dried at 60°C for 16 hours using a reduced pressure drier, and thus 38.6 g of the target oligomer having a structural unit represented by the following formula (NAFP-AL) was obtained. The weight average molecular weight of the obtained oligomer was 2020, and the dispersity was 1.86, which were measured based on polystyrene converted by GPC.

[0483]

[0484] Synthesis Example 6-1: Synthesis of I-NAFP-AL

[0485] Using a 200 mL glass flask as a reaction vessel, 8 g (20 mmol) of NAFP-AL obtained in the above was dissolved using butanol as a solvent, and then 20 mass% iodine chloride aqueous solution (81.2 g, 100 mmol) was added dropwise at 50°C for 60 minutes, and saligenin was reacted with iodine chloride by stirring at 50°C for 2 hours. To the reaction solution after the reaction, 1 hour stirring was performed after adding an aqueous sodium thiosulfate solution, and then the liquid temperature was cooled to 10°C. The precipitate precipitated by the cooling was filtered, washed, and dried, and thus 11.5 g of a brown solid was obtained.

[0486]

[0487] Synthesis Example 7: Synthesis of 2I-PHS

[0488] Reaction of salicyl alcohol with iodine was performed by dissolving salicyl alcohol 4.96 g (40 mmol) using butanol as a solvent, and then adding a 20 mass% iodine chloride aqueous solution (81.2 g, 100 mmol) dropwise over 60 minutes at 50°C, and stirring for 2 hours at 50°C, using a 200 mL glass flask as a reaction vessel. To the reaction solution after the reaction, an aqueous sodium thiosulfate solution was added, and stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that had separated by the cooling was filtered, washed, and dried, to obtain 12.1 g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the result confirmed 4-hydroxy-3,5-diiodobenzyl alcohol.

[0489] After stirring after adding MnO2(3.4 g, 40 mmol) in dichloromethane solvent, a 50 mass% solution of the total amount of 4-hydroxy-3,5-diiodobenzyl alcohol synthesized was dissolved in dichloromethane and added dropwise while stirring for 1 hour, and then stirring was performed for 4 hours at room temperature. The reaction liquid was filtered, and the solvent was distilled off, to thereby obtain 4-hydroxy-3,5-diiodobenzaldehyde.

[0490] A solution of dimethyl malonate (5.3 g, 40 mmol) and the total amount of 4-hydroxy-3,5-diiodobenzaldehyde synthesized in the above was dissolved in DMF solvent, and then a solution of ethylenediamine (0.3 g) dissolved in DMF was added dropwise while stirring for 1 hour, and then the liquid temperature was controlled to be 150°C in an oil bath while stirring for 6 hours to perform the reaction. Then, ethyl acetate and water were added, and then an aqueous 2 mol / L HCl solution was added to control the pH to be 4 or less, and then the organic phase was separated by liquid separation. The obtained organic phase was further washed with an aqueous 2 mol / L sodium carbonate solution, water, and brine by liquid separation, and then purified by a filter, and then the solvent was distilled off from the organic phase, to thereby obtain the compound 2I-PHS (4-hydroxy-3,5-diiodostyrene) represented by the following formula (2I-PHS) 8.1 g.

[0491]

[0492] Synthesis Example 7-1: Synthesis of P-2I-PHS-MMA

[0493] Compound 2I-PHS, 3.0 g, and methyl methacrylate 1.2 g were dissolved in 45 mL of tetrahydrofuran, and azobisisobutyronitrile 0.20 g 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 powder of the polymer represented by the following formula (P-2I-PHS-MMA). The weight average molecular weight (Mw) of the polymer was 8000, and the dispersity (Mw / Mn) was 1.50. In addition, the composition ratio (molar ratio) in the following formula (P-2I-PHS-MMA) was a:b = 1:1 by C-NMR. Note that the following formula (P-2I-PHS-MMA) is simply written to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and is not a block copolymer in which each structural unit forms an independent block. 13 C-NMR, the composition ratio (molar ratio) in the following formula (P-2I-PHS-MMA) was a:b = 1:1. Note that the following formula (P-2I-PHS-MMA) is simply written to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and is not a block copolymer in which each structural unit forms an independent block.

[0494]

[0495] Synthesis Example 8: Synthesis of XBisN-3

[0496] In a container having a stirrer, a condenser, and a burette, and having a content volume of 3 L, 100 g (0.214 mol) of the compound represented by the following formula (XBisN-C1) and 71.2 g (0.429 mol) of potassium iodide described in International Publication No. 2013 / 024779 were put, 1 L of methanol was added as a solvent, and further, 146 g (1.5 mol) of sulfuric acid was added dropwise under ice cooling, and the reaction was performed by stirring at 10°C for 4 hours. After the reaction, extraction was performed with butyl acetate, and after washing with water and neutralization, the target compound (RBisN-3) represented by the following formula (XBisN-3) was obtained by filtration and drying in an amount of 87.8 g.

[0497] For the obtained compound, NMR measurement was performed under the aforementioned measurement conditions, and as a result, the following peaks were found, and the chemical structure represented by the following formula was confirmed.

[0498] δ (ppm) 10.6 (2H, O-H), 7.2-8.6 (17H, Ph-H), 6.7 (1H, C-H)

[0499]

[0500] Synthesis Example 9-1: Synthesis of MAC-ADI

[0501] To 1,3-adamantanediol (manufactured by Mitsubishi Gas Chemicals) 16.8 g (0.1 mol) dissolved in toluene 200 mL, 57% hydrogen iodide aqueous solution 89.8 g (0.4 mol) was added, and the reaction was carried out by stirring at 80°C for 8 hours. After the reaction, water was added, and washing was carried out with sodium bicarbonate. The organic layer was concentrated and purified by column chromatography, whereby 3-iodo-l-hydroxyadamantane represented by the following formula was obtained in 12 g.

[0502]

[0503] To 3-iodo-l-hydroxyadamantane 2.78 g (10 mmol) obtained in the above-mentioned example dissolved in chloroform, pyridine 0.96 g (12 mmol) was added under ice cooling, and methacryloyl chloride 1.25 g (12 mmol) was added dropwise. Subsequently, the reaction was carried out by stirring at ice cooling for 1 hour and at room temperature for 3 hours. After the reaction, water was added to the reaction solution, and washing was carried out with saturated sodium bicarbonate aqueous solution. Drying was carried out by adding sodium sulfate to the organic phase, and concentration was carried out. Purification was carried out by column chromatography, whereby the target product (MAC-ADI) represented by the following formula was obtained in 2.7 g.

[0504] NMR measurement was carried out on the obtained compound (MAC-ADI) under the aforementioned measurement conditions, and as a result, the following peaks were found, and the chemical structure of the formula (MAC-ADI) was confirmed.

[0505] δ (ppm) (d-DMSO): 6.4-6.5 (2H, =CH2), 1.3-3.2 (17H, Ad-H, -C(CH3)=C)

[0506]

[0507] Synthesis Example 10-1: Synthesis of MAC-ADI 2

[0508] To 1,3,5-adamantanetriol (manufactured by Mitsubishi Gas Chemicals) 2.3 g (12.5 mmol) dissolved in toluene 100 mL, 57% hydrogen iodide aqueous solution 28.1 g (125 mmol) was added, and the reaction was carried out by stirring at 80°C for 13 hours. After the reaction, water was added, and washing was carried out with sodium bicarbonate. The organic layer was concentrated and purified by column chromatography, whereby 3,5-diiodo-l-hydroxyadamantane represented by the following formula was obtained in 0.9 g.

[0509]

[0510] Instead of 3-iodo-l-hydroxyadamantane 2.78 g, 3,5-diiodo-l- hydroxyadamantane 4.04 g (10 mmol) obtained in the above was used, and otherwise the same as in Synthesis Example 9-1 was conducted to obtain the target compound (MAC-ADI2) represented by the following formula (MAC-ADI2) 3.5 g.

[0511] For the obtained compound (MAC-ADI2), NMR measurement was conducted under the aforementioned measurement conditions, and as a result, the following peaks were found, and the chemical structure represented by the following formula (MAC-ADI2) was confirmed.

[0512] δ (ppm) (d-DMSO): 6.4-6.5 (2H, =CH2), 1.5-3.9 (16H, Ad-H, -C(CH3)=C)

[0513]

[0514] Synthesis Example 9: Synthesis of P-MAC-ADI resin

[0515] MAC-ADI (4.2 g), and 2-methyl-2-adamantyl methacrylate 1.5 g, γ-butyrolactone methacrylate 2.0 g, and hydroxyadamantyl methacrylate 1.5 g were dissolved in 45 mL of tetrahydrofuran, and azobisisobutyronitrile 0.20 g 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 resin represented by the following formula (P-MAC-ADI) as a white powder. The molecular weight (Mw) of the resin was 9300, and the dispersity (Mw / Mn) was 1.9. In addition, the composition ratio (molar ratio) in the following formula (P-MAC-ADI) was a:b:c:d = 20:30:15:35 as a result of C-NMR measurement. Note that the following formula (P-MAC-ADI) is simply written to indicate the ratio of each structural unit, but P-MAC-ADI is not a block copolymer in which each structural unit forms an independent block. 13 C-NMR, and as a result, the composition ratio (molar ratio) in the following formula (P-MAC-ADI) was a:b:c:d = 20:30:15:35. Note that the following formula (P-MAC-ADI) is simply written to indicate the ratio of each structural unit, but P-MAC-ADI is not a block copolymer in which each structural unit forms an independent block.

[0516]

[0517] Synthesis Example 10: Synthesis of P-MAC-ADI2 resin

[0518] The compound 2-methyl-2-adamantyl methacrylate (1.5 g), methyl acrylate (1.5 g), and γ-butyrolactone methacrylate (2.0 g) were dissolved in 45 mL of tetrahydrofuran, and azobisisobutyronitrile (0.20 g) 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 powder of a resin represented by the following formula (P-MAC-ADI2). The molecular weight (Mw) of the resin was 8350, and the dispersity (Mw / Mn) was 2.0. Further, the composition ratio (molar ratio) in the following formula (MAC-ADI2) was a:b:c:d = 20:30:15:35 by C-NMR. Note that the following formula (P-MAC-ADI2) is simply written to indicate the ratio of each structural unit, but P-MAC-ADI2 is not a block copolymer in which each structural unit forms an independent block. 13 C-NMR, and the result was a composition ratio (molar ratio) of a:b:c:d = 20:30:15:35 in the following formula (MAC-ADI2). Note that the following formula (P-MAC-ADI2) is simply written to indicate the ratio of each structural unit, but P-MAC-ADI2 is not a block copolymer in which each structural unit forms an independent block.

[0519]

[0520] Synthesis of Comparative Example AR1: Synthesis of P-PHS-MMA

[0521] The compound 2-methyl-2-adamantyl methacrylate (1.5 g), methyl acrylate (1.5 g), and γ-butyrolactone methacrylate (2.0 g) were dissolved in 45 mL of tetrahydrofuran, and azobisisobutyronitrile (0.20 g) 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 powder of a resin represented by the following formula (P-MAC-ADI2). The molecular weight (Mw) of the resin was 8350, and the dispersity (Mw / Mn) was 2.0. Further, the composition ratio (molar ratio) in the following formula (MAC-ADI2) was a:b:c:d = 20:30:15:35 by C-NMR. Note that the following formula (P-MAC-ADI2) is simply written to indicate the ratio of each structural unit, but P-MAC-ADI2 is not a block copolymer in which each structural unit forms an independent block. 13 C-NMR, and the result was a composition ratio (molar ratio) of a:b:c:d = 20:30:15:35 in the following formula (MAC-ADI2). Note that the following formula (P-MAC-ADI2) is simply written to indicate the ratio of each structural unit, but P-MAC-ADI2 is not a block copolymer in which each structural unit forms an independent block.

[0522]

[0523] (Synthesis of a resist polymer MAR1)

[0524] Dissolved in 45 mL of tetrahydrofuran were 0.5 g of p-hydroxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.0 g of 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate, 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 powder of the polymer represented by the following formula (MAR1). The weight average molecular weight (Mw) of the polymer was 12000, and the dispersity (Mw / Mn) was 1.90. Further, the composition ratio (molar ratio) in the following formula (MAR1) was a: b: c: d = 40: 30: 15: 15 by C-NMR. Note that the following formula (MAR1) is simply written to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and is not a block copolymer in which each structural unit forms an independent block. The molar ratio was calculated based on the cumulative ratio of each of the carbon of the benzene ring group of the polystyrene-based monomer (p-hydroxystyrene), the carbonyl carbon of the ester bond of the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate). 13 C-NMR, the result of the composition ratio (molar ratio) in the following formula (MAR1) was a: b: c: d = 40: 30: 15: 15. Note that the following formula (MAR1) is simply written to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and is not a block copolymer in which each structural unit forms an independent block. The molar ratio was calculated based on the cumulative ratio of each of the carbon of the benzene ring group of the polystyrene-based monomer (p-hydroxystyrene), the carbonyl carbon of the ester bond of the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate).

[0525]

[0526] (Synthesis of the resist polymer MAR2)

[0527] Dissolved in 45 mL of tetrahydrofuran were 0.5 g of p-hydroxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.0 g of 2-methyl-2-adamantyl methacrylate, 2.0 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate, 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 powder of the polymer represented by the following formula (MAR1). The weight average molecular weight (Mw) of the polymer was 12000, and the dispersity (Mw / Mn) was 1.90. Further, the composition ratio (molar ratio) in the following formula (MAR1) was a: b: c: d = 40: 30: 15: 15 by C-NMR. Note that the following formula (MAR1) is simply written to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and is not a block copolymer in which each structural unit forms an independent block. The molar ratio was calculated based on the cumulative ratio of each of the carbon of the benzene ring group of the polystyrene-based monomer (p-hydroxystyrene), the carbonyl carbon of the ester bond of the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate). 13The composition ratio (molar ratio) of a : b : c : d = 50 : 10 : 10 : 30 in the following formula (MAR2) was found from the results of C-NMR. Note that the following formula (MAR2) is simply written to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and is not a block copolymer in which each structural unit forms an independent block. The molar ratio was found based on the cumulative ratio of each of the carbon of the benzene ring group of the polystyrene-based monomer (p-hydroxystyrene), the carbonyl carbon of the ester bond of the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate).

[0528]

[0529] (Examples 1 to 10, Comparative Example 1)

[0530] The safety solvent solubility, storage stability, film formability, sensitivity, and etching resistance of the compounds or resins obtained in Synthesis Examples 1 to 10 and Synthesis Comparative Example AR1 were evaluated as described above. The results are shown in Table 1.

[0531] (Comparative Example 2)

[0532] Instead of the compounds or resins obtained in Synthesis Examples 1 to 10, the compound (XBisN-C1) represented by the following formula described in International Publication No. 2013 / 024779 was used, and evaluation was performed in the same manner as in Examples 1 to 10 except for this. The results are shown in Table 1.

[0533]

[0534] [Table 1]

[0535]

[0536] As is clear from Table 1, it was confirmed that Examples 1 to 10 in which a compound containing a total of 15 to 75 mass% of iodine atoms, or a resin having a structural unit derived from the aforementioned compound was used were significantly superior in sensitivity compared to Comparative Example 1 and Comparative Example 2.

[0537] (Preparation of the lower layer film composition)

[0538] The lower layer film composition solution containing the compound of the present application was prepared by compounding the composition described in Table 2 below.

[0539] [Table 2]

[0540]

[0541] Solvent composition A: PGMEA 76 parts by mass / PGME 11.8 parts by mass

[0542] The ingredients used in the preparation of the lower layer film composition solution are described below.

[0543] < Acid diffusion controller >

[0544] The following was used as an acid diffusion accelerator.

[0545] • WPAG199 (Bis(4-methylphenylsulfanyl)azomethane,

[0546] Bis(4-methylphenylsulfanyl)azomethane) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0547]

[0548] • WPAG367 (Diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0549]

[0550] • WPAG336 (Diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0551]

[0552] The following was used as an acid diffusion inhibitor.

[0553] (Compound ADCS-1)

[0554]

[0555] • C-1

[0556]

[0557] • C-2

[0558]

[0559] • WPBG-018 (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0560]

[0561] • WPBG-345 (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0562]

[0563] <Thermal acid generator / thermal base generator>

[0564] • WPBG300 (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0565]

[0566] • TAG-2689 (manufactured by King, quaternary ammonium salt of trifluoromethane sulfonic acid)

[0567]

[0568] • TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.)

[0569]

[0570] (4) Sensitivity evaluation

[0571] (EUV sensitivity - n-butyl acetate development)

[0572] A resist solution 2 for sensitivity evaluation and pattern evaluation was prepared by compounding 5 parts by mass of the polymer obtained in the above-described resist polymer synthesis example, 1 part by mass of triphenyl sulfonium nonafluoromethane sulfonate, 0.2 parts by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME.

[0573] The prepared lower layer film composition was applied to a silicon wafer, and a baking treatment was performed at 240°C for 60 seconds to form a lower layer film having a film thickness of 100 nm on the silicon wafer.

[0574] Further, resist solution 2 was applied to the lower layer film of the present application formed on the silicon wafer, and a photoresist layer having a film thickness of 100 nm was formed by baking at 110°C for 60 seconds.

[0575] Next, using an ultraviolet ray (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation), exposure was performed from 1 mJ / cm​2 At 1 mJ / cm each time 2 Increase exposure to 80 mJ / cm 2 Maskless exposure was performed, followed by baking at 110°C (PEB) for 90 seconds and developing with n-butyl acetate for 30 seconds, resulting in a wafer with 80% exposure. For each exposed area, the film thickness was measured using a VM3200 optical thickness gauge (manufactured by SCREEN Semiconductor Solutions Co., Ltd.). The distribution data of film thickness relative to the exposure amount was obtained, and the slope of the film thickness variation relative to the exposure amount was calculated as the exposure amount with the largest value, which was used as the sensitivity value (mJ / cm²). 2 (), which serves as an indicator of the EUV sensitivity of the resist.

[0576] (Etching Defect Evaluation - TMAH)

[0577] The prepared lower layer film composition was coated onto a silicon wafer and baked at 240°C for 60 seconds to form a lower layer film with a thickness of 100 nm on the silicon wafer.

[0578] Furthermore, a photoresist solution is coated onto the lower layer film 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.

[0579] Next, using an EUV ES-7000 ultraviolet (EUV) exposure device (manufactured by Litho Tech Japan Corporation), the entire wafer was photographed and exposed with an exposure value 3% greater than the EUV sensitivity value obtained in the EUV sensitivity evaluation during the TMAH development process described above. Then, it was baked for 90 seconds at 110°C (PEB) and developed for 60 seconds with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, resulting in a wafer with an exposure value of 80% on the entire wafer surface.

[0580] For the fabricated exposed wafers, the etching process is carried out using the "Telius SCCM" etching device (manufactured by Tokyo Electron Limited) with CF4 / Ar gas until the oxide film is etched to 60nm. For the wafers fabricated by etching, the defect evaluation is carried out using the "Surfscan SP5" defect detection device (manufactured by KLA Corporation), and the number of cone defects above 19nm is used as an indicator of etching defects.

[0581] (Evaluation Criteria)

[0582] A: Number of cone defects ≤ 20

[0583] B: 20 < number of cone defects < 200

[0584] C: 200 < number of cone defects < 1000

[0585] D: 1000 < number of cone defects

[0586] The evaluation results obtained are shown in Table 3.

[0587] (Etching defect evaluation - n-butyl acetate)

[0588] In the above-described etching evaluation - TMAH method, resist solution 2 was used as the resist solution, exposure was performed at an exposure amount that was 3% lower than the EUV sensitivity in n-butyl acetate development, n-butyl acetate was used instead of TMAH aqueous solution as the developing solution, the developing time was set to 30 seconds, and etching defect evaluation was performed using the same method except for these.

[0589] The evaluation results obtained are shown in Table 3.

[0590] [Table 3]

[0591]

[0592] As is clear from Table 3, by using the acid diffusion control agent in combination, it is possible to significantly control the sensitivity.

Claims

1. An underlayer film formed from a lithography composition comprising a compound having at least one element selected from the group consisting of iodine, tellurium and fluorine, or a resin comprising a structural unit derived from the compound, wherein the compound is represented by the general formula (AMl), ###0001### (AMl) in the formula (AMl), A represents an organic group having a carbon number of 1 to 30, wherein the underlayer film is used for a resist pattern forming method comprising the following steps: an underlayer film forming step of forming the underlayer film on a substrate using the lithography composition; a photoresist film forming step of forming at least one photoresist film on the underlayer film formed by the underlayer film forming step; and a step of irradiating a prescribed region of the photoresist film formed by the photoresist film forming step with a radiation line and developing.

2. A resist layer contact film formed from a lithography composition comprising a compound having at least one element selected from the group consisting of iodine, tellurium and fluorine, or a resin comprising a structural unit derived from the compound, wherein the compound is represented by the general formula (AMl), ###0002### (AMl) in the formula (AMl), A represents an organic group having a carbon number of 1 to 30, wherein the resist layer contact film is used for a circuit pattern forming method comprising the following steps: an underlayer film forming step of forming an underlayer film on a substrate; a resist layer contact film forming step of forming the resist layer contact film on the underlayer film formed by the underlayer film forming step using the lithography composition; a photoresist film forming step of forming at least one photoresist film on the resist layer contact film formed by the resist layer contact film forming step; a resist pattern forming step of irradiating a prescribed region of the photoresist film formed by the photoresist film forming step with a radiation line and developing to form a resist pattern; a pattern forming step of etching the resist layer contact film, or the resist layer contact film and the underlayer film, using the resist pattern formed by the resist pattern forming step as a mask to form a pattern; and a substrate pattern forming step of etching the substrate using the pattern formed by the pattern forming step as a mask to form a pattern on the substrate. The 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. R 1 represents a hydrogen atom, a methyl group, or a halogen group, R 2 each independently represents a hydrogen atom, a linear organic group having a carbon number of 1 to 20, a branched organic group having a carbon number of 3 to 20, or a cyclic organic group having a carbon number of 3 to 20, The lithography composition further contains: a solvent; and at least one component selected from the group consisting of an acid generator, an acid diffusion accelerator, an acid diffusion inhibitor and a crosslinking agent. n 1 represents 0 or 1, n 2 represents an integer of 1 to 20, The 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. The lithography composition further contains: a solvent; and at least one component selected from the group consisting of an acid generator, an acid diffusion accelerator, an acid diffusion inhibitor and a crosslinking agent.

7. An underlayer film formed from a lithography composition comprising a compound having at least one element selected from the group consisting of iodine, tellurium and fluorine, or a resin comprising a structural unit derived from the compound, wherein the compound is represented by the general formula (A-7): ###0003### (A-7) in the formula (A-7), A represents an organic group having a carbon number of 1 to 30. ​ ​ ​ ​ ​ ​ R 1 represents a hydrogen atom, a methyl group, or a halogen group, R 2 each independently represents a hydrogen atom, a linear organic group having a carbon number of 1 to 20, a branched organic group having a carbon number of 3 to 20, or a cyclic organic group having a carbon number of 3 to 20, ​ n 1 represents 0 or 1, n 2 represents an integer of 1 to 20, ​ ​ ​ ​ ​ ​ ​ ​ ​ 3. The resist contact film according to claim 2, wherein ​ 4. The resist contact film according to claim 2, wherein ​ ​ ​ 5. The underfilm of claim 1, wherein, ​ 6. The underfilm of claim 1, wherein, ​ ​ ​ ​ ​ ​ X each independently represents tellurium, I, F, or a carbon number 1 to 30 organic group having 1 or more and 5 or less substituents selected from the group consisting of tellurium, I, and F, and at least one X is tellurium or I, L 1 represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, m is an integer of 1 or more, Y each independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a sulfide group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, n is an integer of 0 or more, Z each independently is an alkoxy group, an ester group, an acetal group, or a carbonate group, r is an integer of 0 or more, A is a carbon number 1 to 30 organic group, R a , R b , and R c are each independently H, I, F, Cl, Br, or an organic group having a carbon number of 1 to 60 optionally having a substituent, p is an integer of 1 or more, wherein, the underlayer film is used for a resist pattern forming method including the following steps: an underlayer film forming step of forming the underlayer film on a substrate using the composition for photolithography; a photoresist film forming step of forming at least one layer of a photoresist film on the underlayer film formed by the underlayer film forming step; and a step of irradiating a prescribed region of the photoresist film formed by the photoresist film forming step with a radiation line and developing.

8. The underfilm of claim 7, wherein, the 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.

9. The underfilm of claim 7, wherein, the composition for photolithography further contains: a solvent; and at least one component selected from the group consisting of an acid generator, an acid diffusion promoter, an acid diffusion inhibitor, and a crosslinking agent.

10. A resist layer contact film formed from a composition for photolithography, the composition for photolithography containing a compound having at least one element selected from the group consisting of iodine, tellurium, and fluorine, or a resin containing a structural unit derived from the compound, wherein the compound is represented by General Formula (A-7): in Formula (A-7), X each independently represents tellurium, I, F, or a carbon number 1 to 30 organic group having 1 or more and 5 or less substituents selected from the group consisting of tellurium, I, and F, and at least one X is tellurium or I, L 1 represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphate group, m is an integer of 1 or more, Y each independently represents a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a sulfide group, a phosphine group, a phosphite group, a carbamate group, a urea group, an amide group, an imide group, or a phosphoric acid group, n is an integer of 0 or more, Z each independently is an alkoxy group, an ester group, an acetal group, or a carbonate group, r is an integer of 0 or more, A is a carbon number 1 to 30 organic group, R a , R b , and R c are each independently H, I, F, Cl, Br, or an organic radical of carbon number 1 to 60 optionally having a substituent, p is an integer of 1 or more, wherein, the resist layer contact film is used for a circuit pattern forming method including the following steps: an underlayer film forming step of forming an underlayer film on a substrate; a resist layer contact film forming step of forming the resist layer contact film on the underlayer film formed by the underlayer film forming step using the composition for photolithography; a photoresist film forming step of forming at least one layer of a photoresist film on the resist layer contact film formed by the resist layer contact film forming step; a resist pattern forming step of irradiating a prescribed region of the photoresist film formed by the photoresist film forming step with a radiation line and developing to form a resist pattern; a resist pattern formation step of forming a resist pattern by the resist pattern formation step as a mask, etching the resist layer contact film or the resist layer contact film and the underlayer film to form a pattern; and a substrate pattern formation step of etching the substrate to form a pattern on the substrate by the pattern formation step as a mask.

11. The resist contact film according to claim 10, wherein The 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.

12. The resist contact film according to claim 10, wherein, The photoresist composition further contains: a solvent; and at least one component selected from the group consisting of an acid generator, an acid diffusion promoter, an acid diffusion inhibitor, and a crosslinking agent.

Images