Method for forming a film, curable composition, and method for manufacturing an article

Abstract

This invention provides a new technology for forming films of curable compositions. [Solution] The method comprises the steps of: placing a curable composition containing a polymerizable compound and a solvent onto a substrate using a spin coating method; and flattening the curable composition placed on the substrate to form a film, wherein the viscosity μ [mPa·s] of the composition from which the solvent has been removed is equal to the period λ [um] of the uneven surface of the substrate, and the thickness d of the cured curable composition at the convex portion of the uneven surface. f The function f is determined by [nm] TIFF2026056304000071.tif25108 The present invention provides a film formation method characterized by having a value smaller than [a certain value].

Description

[Technical Field]

[0001] The present invention relates to a film-forming method, a curable composition, and a method for manufacturing articles. [Background technology]

[0002] In photolithography processes for manufacturing devices such as semiconductor elements, it is necessary to flatten the surface (underlay) of the substrate. For example, in extreme ultraviolet (EUV) lithography, one of the photolithography technologies that has attracted attention in recent years, the depth of focus at which the projection image is formed becomes shallower as miniaturization progresses. Therefore, the surface irregularities of the substrate to which the resist is supplied must be kept to a few nanometers or less.

[0003] One planarization technique for flattening the surface of a substrate has been proposed, which involves forming an underlayer film on a substrate with uneven surfaces (the substrate to be planarized) (see Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] T.Endo, R. Sakamoto, et. al, “Novel Spin on Planarization Technology by PhotoCuring SOC”, Journal of Photopolymer Science and Technology 30 (2017) 373. [Overview of the project] [Problems that the invention aims to solve]

[0005] In the technology disclosed in Non-Patent Document 1, a spin coating method is used to form the underlying film, but sufficient flatness cannot be obtained with the spin coating method alone. Therefore, the composition forming the underlying film is heated to reduce its viscosity and promote its fluidity, thereby forming a flatter film.

[0006] The present invention has been made in view of such problems of the prior art, and an exemplary object thereof is to provide a new technique related to the formation of a film of a curable composition.

Means for Solving the Problems

[0007] In order to achieve the above object, as one aspect of the present invention, a film forming method includes a step of disposing a curable composition containing a polymerizable compound and a solvent on a substrate using a spin coating method, a step of flattening the curable composition disposed on the substrate to form a film, and the viscosity μ [mPa·s] of the composition from which the solvent has been removed from the curable composition is a function f determined by the period λ [μm] of the uneven shape of the substrate and the thickness d f [nm] of the cured curable composition at the convex portion of the uneven shape,

Equation

[0008] and is smaller than the value of

[0009] A further object or other aspect of the present invention will be clarified by the embodiments described below with reference to the accompanying drawings.

Advantages of the Invention

[0010] According to the present invention, for example, a new technique related to the formation of a film of a curable composition can be provided.

Brief Description of the Drawings

[0011] [Figure 1] It is a diagram for explaining a film forming method as one aspect of the present invention. [Figure 2] It is a diagram showing a state where the composition for forming a lower layer film is flattened. [Figure 3] It is a diagram showing an example of the relationship between the uneven shape of the substrate and the initial liquid film distribution. [Figure 4] It is a diagram showing the time change of the liquid film distribution of the curable composition. [Figure 5] It is a diagram showing the time change of the height difference of the liquid film distribution of the curable composition. [Figure 6] It is a diagram showing the time required for the flattening process when the viscosity of the curable composition is changed. [Figure 7] It is a diagram showing the result of calculating the upper limit value of the viscosity of the curable composition that flattens within 200 seconds by varying the period of the uneven shape of the substrate. [Figure 8] It is a diagram showing the result of calculating the time required for the flattening process by varying the thickness of the thinnest part of the lower layer film. [Embodiments for Carrying out the Invention]

[0012] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although a plurality of features are described in the embodiments, not all of these plurality of features are essential to the invention, and the plurality of features may be arbitrarily combined. Further, in the accompanying drawings, the same or similar configurations are given the same reference numerals, and redundant descriptions are omitted.

[0013] In providing a new technique related to the formation of a film of a curable composition, the present inventors have found a film formation method capable of forming a film of a curable composition having high flatness at about room temperature (for example, 23°C).

[0014] [Curable Composition (A)] The curable composition (A) in the present invention is a composition for a lower layer film. The curable composition (A) is a composition containing a polymerizable compound (a) (component (a) having polymerizability) and a solvent (d) (component (d)). The curable composition (A) may further contain at least one of a polymerization initiator (component (b)) and a non-polymerizable compound (c) (component (c)).

[0015] [Polymerizable Compound (a)] In the present invention, polymerizable compound (a) is a compound that reacts with polymerization factors (such as radicals and cations) generated from polymerization initiator (b) and forms a polymer compound or film through a chain reaction (polymerization reaction).

[0016] Examples of polymerizable compounds (a) include radical polymerizable compounds and cationic polymerizable compounds. Polymerizable compound (a) may consist of only one type of polymerizable compound, or it may consist of multiple types (one or more) of polymerizable compounds.

[0017] The polymerizable compound (a) in the present invention includes at least a compound (a-1) comprising one or more aromatic rings or aromatic heterocycles and two or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles.

[0018] <Compound (a-1): Polymerizable compound> Specific examples of compound (a-1) include, but are not limited to, the following.

[0019] [ka]

[0020] 1,4-Divinylbenzene

[0021] [ka]

[0022] 1,3-Diisopropenylbenzene

[0023] [ka]

[0024] 3,3'-Divinylbiphenyl

[0025] [ka]

[0026] 1,2-bis(3-vinylphenyl)ethane

[0027] [ka]

[0028] Bis-(3-vinylphenyl)methanone

[0029] [ka]

[0030] 3,3'-Oxybis(1-vinylbenzene)

[0031] [ka]

[0032] 3,4',5-trivinylbiphenyl

[0033] [ka]

[0034] 3,3',5-trivinylbiphenyl

[0035] [ka]

[0036] 1,3-Divinyl-5-(3-vinylbenzyl)benzene

[0037] [ka]

[0038] 1,3-Divinyl-5-[(3-vinylbenzyl)oxy]benzene

[0039] [ka]

[0040] 1,3-Divinyl-5-[(3-vinylphenoxy)methyl]benzene

[0041] [ka]

[0042] Bis(3,5-divinylphenyl)methane

[0043] [ka]

[0044] 1,2,4,5-Tetravinylbenzene

[0045] [ka]

[0046] 3,3',4,4'-Tetravinyl-1,1'-biphenyl

[0047] [ka]

[0048] 3,3',5,5'-Tetravinyl-1,1'-Biphenyl

[0049] [ka]

[0050] 5,5'-Oxybis(1,4-divinylbenzene)

[0051] [ka]

[0052] 5,5'-Oxybis(1,3-divinylbenzene)

[0053] [ka]

[0054] Bis(3,5-divinylphenyl)methanone

[0055] [ka]

[0056] 4,4'-Oxybis(1,2-divinylbenzene)

[0057] [ka]

[0058] Bis(3,4-divinylphenyl)methanone

[0059] [ka]

[0060] Bis(2,5-divinylphenyl)methanone

[0061] [ka]

[0062] 1,3,5,7-Tetravinylnaphthalene

[0063] [ka]

[0064] 1,3,6,8-Tetravinylnaphthalene

[0065] [ka]

[0066] 1,4,5,8-Tetravinylnaphthalene

[0067] [ka]

[0068] 1,3,5,8-Tetravinylnaphthalene Polymerizable compound (a) may include a compound (a-2) that does not fall under compound (a-1), which comprises one or more aromatic rings or aromatic heterocycles and two or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles. Examples of compound (a-2) include radical polymerizable compounds such as (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fuma compounds, and myrel compounds.

[0069] (Meth)acrylic compounds are compounds having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or methacryloyl group include, but are not limited to, the following: Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-Tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy(meth)acrylate, PO-modified phenoxy(meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate Acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pliers Isoamyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, undecyl(meth)acrylate, dodecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, benzyl(meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, cynoabenzyl(meth)acrylate,

[0070] Examples of commercially available monofunctional (meth)acrylic compounds mentioned above include, but are not limited to, the following: Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (manufactured by Toagosei), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) Light acrylates BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy esters M-600A, POB-A, OPP-EA (all manufactured by Kyoeisha Chemical Co., Ltd.) KAYARAD (registered trademark) TC110S, R-564, R-128H (all manufactured by Nippon Kayaku Co., Ltd.) NK Ester AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.) FA-511A, 512A, 513A (all manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Seiyaku), VP (made by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kojin)

[0071] Furthermore, examples of polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,3-Adamantane dimethanol di(meth)acrylate, Tris(2-Hydoxyethyl)isocyanurate tri(meth)acrylate, Tris(Acryloyloxy)isocyanurate, Bis(Hydroxymethyl)tricyclodecane di(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m- or p-Benzene di(meth)acrylate, o-, m- or p-Xylylene di(meth)acrylate

[0072] Examples of commercially available polyfunctional (meth)acrylic compounds mentioned above include, but are not limited to, the following: Yupimer (registered trademark) UV SA1002, SA2007 (both manufactured by Mitsubishi Chemical Corporation), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) Light acrylates 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.) KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku Co., Ltd.) Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (manufactured by Toagosei), Lipoxy® VR-77, VR-60, VR-90 (all manufactured by Showa Polymer Co., Ltd.) Ogusol EA-0200, Ogusol EA-0300 (both manufactured by Osaka Gas Chemical Co., Ltd.)

[0073] In the above-mentioned group of compounds, (meth)acrylate means acrylate or methacrylate having an equivalent alcohol residue. (meth)acryloyl group means acryloyl group or methacryloyl group having an equivalent alcohol residue. EO represents ethylene oxide, and EO-modified compound A represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are linked via a block structure of ethylene oxide group. Furthermore, PO represents propylene oxide, and PO-modified compound B represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are linked via a block structure of propylene oxide group.

[0074] Specific examples of styrene compounds include, but are not limited to, the following. Alkylstyrenes such as styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene and iodose Halide styrenes such as ethylene; compounds having a styryl group as a polymerizable functional group, such as nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl.

[0075] Specific examples of vinyl compounds include, but are not limited to, the following. Compounds having a vinyl group as a polymerizable functional group, such as vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate, and acrylonitrile; conjugated diene monomers such as butadiene, isoprene, and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidenes such as vinylidene chloride; vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc., (meth)acrylonitrile, etc.)

[0076] In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0077] Examples of acrylic compounds include, but are not limited to, the following: Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate

[0078] Examples of fumaric compounds include, but are not limited to, the following: Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate

[0079] Examples of maleyl compounds include, but are not limited to, the following: Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate

[0080] Other radical polymerizable compounds include, but are not limited to, the following: Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconic acid, diethyl itaconic acid, diisopropyl itaconic acid, di-sec-butyl itaconic acid, diisobutyl itaconic acid, di-n-butyl itaconic acid, di-2-ethylhexyl itaconic acid, dibenzyl itaconic acid, etc.), N-vinylamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimides and their derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.)

[0081] When polymerizable compound (a) is composed of multiple types of compounds, the ratio of compound (a-1) to polymerizable compound (a) is preferably 20% by weight or more, more preferably 50% by weight or more, and even more preferably 90% by weight or more. This is because the higher the proportion of compound (a-1) in polymerizable compound (a), the higher the heat resistance.

[0082] <Oonishi parameters for polymerizable compound (a)> V is the dry etching rate of the organic compound, N is the total number of atoms in the organic compound, and N is the total number of carbon atoms in the composition. C , and the total number of oxygen atoms in the composition N O It is known that the following relationship (1) holds true (see reference A). V∝N / (Nc-No) Equation (1) Document A: Proc. SPIE 11324-11 (2020)

[0083] Here, N / (Nc-No) is also called the "Onishi parameter" (hereinafter referred to as "OP"). For example, Japanese Patent Publication No. 2009-503139 discloses a technique for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP.

[0084] According to equation (1), organic compounds with a higher oxygen content or fewer aromatic or alicyclic structures in the molecule have a larger OP value and a faster dry etching rate.

[0085] In the curable composition (A) of the present invention, it is preferable that the OP of the polymerizable compound (a) is 1.80 or more and 2.70 or less, more preferably 2.00 or more and 2.60 or less, and still more preferably 2.30 or more and 2.60 or less. By setting the OP of the polymerizable compound (a) to 2.70 or less, the cured film of the curable composition (A) has high dry etching resistance. Further, by setting the OP of the polymerizable compound (a) to 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing its underlying layer using the cured film of the curable composition (A). When the polymerizable compound (a) is composed of a plurality of types of polymerizable compounds (components) a1, a2, ···, a n as shown in the following formula (2), OP is calculated as a weighted average value (mole fraction weighted average value) based on the mole fraction. Thus, when the polymerizable compound (a) contains one or more types of polymerizable compounds, the OP of the polymerizable compound (a) is the N / (N C -N O ) value of each molecule of one or more types of polymerizable compounds, calculated as a mole fraction weighted average value.

[0086]

Equation

[0087] Here, OP n is the OP of component a n and n n is the mole fraction of component a n in the whole polymerizable compound (a).

[0088] In the film (underlayer film) formation method of the present invention, in the planarization step, a curable composition (A) disposed as an underlayer film forming composition is planarized on the substrate to be planarized, that is, a substrate (underlayment) having an uneven shape (uneven pattern). In the planarization step, the solvent (d) is volatilized, while the polymerizable compound (a) must not volatilize. Therefore, the boiling point of one or more polymerizable compounds contained in the polymerizable compound (a) at atmospheric pressure is preferably 250°C or higher, more preferably 300°C or higher, and even more preferably 350°C or higher. Furthermore, in order to obtain high dry etching resistance and high heat resistance in the cured film of the curable composition (A), it is preferable to include at least a compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Atmospheric pressure is defined as 1 atmosphere (atmospheric pressure).

[0089] The boiling point of polymerizable compound (a) generally correlates with its molecular weight. Therefore, the molecular weight of each of the one or more polymerizable compounds contained in polymerizable compound (a) is preferably 200 or higher, more preferably 240 or higher, and even more preferably 300 or higher. Thus, the lower limit of the polymerizable functional group in polymerizable compound (a) is a molecular weight of 200 or higher. However, even if the molecular weight is 200 or less, if the boiling point is 250°C or higher, it can be preferably used as a polymerizable compound in the present invention.

[0090] Furthermore, the vapor pressure of polymerizable compound (a) at 80°C is preferably 0.001 mmHg or less. This is to suppress the volatilization of polymerizable compound (a) during heating, such as in the heating process to accelerate the volatilization of solvent (d), which will be described later, or in the curing process of the curable composition from which solvent (d) has been removed.

[0091] The boiling points and vapor pressures of various organic compounds under normal pressure can be calculated using methods such as Hansen Solubility Parameters in Practice (HSPiP) 5th Edition, section 5.3.04.

[0092] Specific examples of polymerizable compounds (a) having a boiling point of 250°C or higher include, but are not limited to, the following. Dicyclopentanyl acrylate (boiling point 262°C, molecular weight 206), Dicyclopentenyl acrylate (boiling point 270°C, molecular weight 204), 1,3-Cyclohexanedimethanol diacrylate (boiling point 310°C, molecular weight 252), 1,4-Cyclohexanedimethanol diacrylate (boiling point 339°C, molecular weight 252), 4-Hexylresorcinol diacrylate (boiling point 379°C, molecular weight 302), 6-Phenylhexane-1,2-diol diacrylate (boiling point 381°C, molecular weight 302), 7-Phenylheptane-1,2-diol diacrylate (boiling point 393°C, molecular weight 316), 1,3-Bis((2-hydroxyethoxy)methyl)cyclohexanediacrylate (boiling point 403°C, molecular weight 340), 8-Phenyloctane-1,2-diol diacrylate (boiling point 404°C, molecular weight 330), 1,3-Bis((2-hydroxyethoxy)methyl)benzenediaacrylate (boiling point 408°C, molecular weight 334), 1,4-Bis((2-hydroxyethoxy)methyl)cyclohexanediacrylate (boiling point 445°C, molecular weight 340), 3-Phenoxybenzylacrylate (mPhOBzA, OP2.54, boiling point 367.4℃, vapor pressure at 80℃ 0.0004mmHg, molecular weight 254.3),

[0093] [ka]

[0094] 1-Naphthyl acrylate (NaA, OP2.27, boiling point 317°C, vapor pressure 0.0422 mmHg at 80°C, molecular weight 198),

[0095] [ka]

[0096] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2℃, vapor pressure at 80℃ 0.0006 mmHg, molecular weight 268.3),

[0097] [ka]

[0098] 1-Naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1℃, vapor pressure 0.042 mmHg at 80℃, molecular weight 212.2),

[0099] [ka]

[0100] 2-Naphthylmethyl acrylate (Na2MA, OP2.33, boiling point 342.1℃, vapor pressure 0.042 mmHg at 80℃, molecular weight 212.2),

[0101] [ka]

[0102] 4-Cyanobenzyl acrylate (CNBzA, OP2.44, boiling point 316°C, molecular weight 187),

[0103] [ka]

[0104] DVBzA (OP2.50, boiling point 304.6℃, vapor pressure at 80℃ 0.0848mmHg, molecular weight 214.3) is shown in the following formula.

[0105] [ka]

[0106] DPhPA (OP2.38, boiling point 354.5°C, vapor pressure 0.0022 mmHg at 80°C, molecular weight 266.3), as shown in the following formula,

[0107] [ka]

[0108] The following formula shows PhBzA (OP2.29, boiling point 350.4℃, vapor pressure at 80℃ 0.0022mmHg, molecular weight 238.3),

[0109] [ka]

[0110] FLMA (OP2.20, boiling point 349.3°C, vapor pressure 0.0018 mmHg at 80°C, molecular weight 250.3) as shown in the following formula,

[0111] [ka]

[0112] ATMA (OP2.13, boiling point 414.9°C, vapor pressure 0.0001 mmHg at 80°C, molecular weight 262.3), as shown in the following formula,

[0113] [ka]

[0114] The following formula represents DNaMA (OP2.00, boiling point 489.4°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 338.4),

[0115] [ka]

[0116] Tricyclodecanedimethanol diacrylate (DCPDA, OP3.29, boiling point 342°C, vapor pressure 0.0024 mmHg at 80°C, molecular weight 304),

[0117] [ka]

[0118] m-Xylylenediacrylate (mXDA, OP3.20, boiling point 336°C, vapor pressure 0.0043 mmHg at 80°C, molecular weight 246),

[0119] [ka]

[0120] 1-Phenylethane-1,2-diyldiaacrylate (PhEDA, OP3.20, vapor pressure 0.0057 mmHg at 80°C, boiling point 354°C, molecular weight 246),

[0121] [ka]

[0122] 2-Phenyl-1,3-propanediol diacrylate (PhPDA, OP3.18, boiling point 340°C, vapor pressure 0.0017 mmHg at 80°C, molecular weight 260),

[0123] [ka]

[0124] The following formula shows VmXDA (OP3.00, boiling point 372.4°C, vapor pressure at 80°C 0.0005 mmHg, molecular weight 272.3),

[0125] [ka]

[0126] BPh44DA (OP2.63, boiling point 444°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3), as shown in the following formula,

[0127] [ka]

[0128] BPh43DA (OP2.63, boiling point 439.5℃, vapor pressure <0.0001mmHg at 80℃, molecular weight 322.3), as shown in the following formula,

[0129] [ka]

[0130] The following formula shows DPhEDA (OP2.63, boiling point 410°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 322.3),

[0131] [ka]

[0132] The following formula shows BPMDA (OP2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4),

[0133] [ka]

[0134] Na13MDA (OP2.71, boiling point 438.8°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 296.3), as shown in the following formula,

[0135] [ka]

[0136] At least a portion of the polymerizable compound (a), which may contain multiple types of additives, may be polymers having polymerizable functional groups. Such polymers preferably contain at least a ring structure, such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, it is preferable to contain at least one of the constituent units represented by any of the following structures (1) to (6).

[0137] [ka]

[0138] In structures (1) to (6), each substituent R is a substituent that independently contains a substructure containing an aromatic ring, and R 1 This is a hydrogen atom or a methyl group. In this specification, the portion of the structural unit represented by structures (1) to (6), excluding R, is used as the main chain of a specific polymer. The formula weight of substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and even more preferably 150 or more. In practice, the upper limit of the formula weight of substituent R is 500 or less.

[0139] Polymers having polymerizable functional groups are typically compounds with a weight-average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. There is no specific upper limit for the weight-average molecular weight, but for example, 50,000 or less is preferred. By setting the weight-average molecular weight above the lower limit mentioned above, the boiling point can be set to 250°C or higher, and the mechanical properties after curing can be further improved. Furthermore, by setting the weight-average molecular weight below the upper limit mentioned above, solubility in solvents is high, the viscosity is not too high, the fluidity immediately after the curable composition (A) is placed using the spin-coating method is maintained, and the flatness (reflowability) due to fluidity can be further improved. In this invention, unless otherwise specified, the weight-average molecular weight (Mw) refers to that measured by gel permeation chromatography (GPC).

[0140] Specific examples of polymerizable functional groups in polymers include (meth)acryloyl groups, epoxy groups, oxetane groups, methylol groups, methylol ether groups, and vinyl ether groups. From the viewpoint of ease of polymerization, (meth)acryloyl groups are particularly preferred.

[0141] When a polymer having polymerizable functional groups is added as at least a portion of the polymerizable compound (a), its blending ratio can be freely set as long as it falls within the viscosity specifications described later. For example, it is preferable that the blending ratio be 0.1% to 60% by weight, more preferably 0.1% to 50% by weight, and even more preferably 0% to 40% by weight, based on the total mass of all components excluding the solvent (d). By blending the polymer having polymerizable functional groups at a ratio of 0.1% by weight or more, heat resistance, dry etching resistance, mechanical strength, and low volatility can be improved. Furthermore, by blending the polymer having polymerizable functional groups at a ratio of 60% by weight or less, the viscosity can be kept within the upper limit specifications described later.

[0142] The polymerizable compound (a) selected as the curable composition (A) may be one or more types, and it is preferable that they have a viscosity of less than 10,000 mPa·s at 20 to 170°C, and more preferably less than 1,000 mPa·s. By using such low-viscosity polymerizable compound (a), fluidity can be obtained.

[0143] Furthermore, in the present invention, polymerizable compound (a) is represented by any one of the following chemical formulas.

[0144] [ka]

[0145] R1 and R2 are vinyl groups or propenyl groups. R3 and R4 are hydrogen atoms or vinyl groups.

[0146] [ka]

[0147] R5 and R6 are vinyl groups or propenyl groups. R7 and R8 are hydrogen atoms or vinyl groups. R9 is a single bond or a linear chain with 1-2 carbon atoms or an oxygen atom or a carbonyl group.

[0148] [ka]

[0149] R10 and R11 are vinyl groups or propenyl groups. R12 and R13 are hydrogen atoms or vinyl groups.

[0150] <Polymerization initiator (b)> In this specification, polymerization initiator (b) is a compound that generates polymerization factors (such as radicals and cations) upon heat or light. Specifically, polymerization initiator (b) includes radical generators that generate radicals upon heat or light, and acid generators that generate protons (H+) upon heat or light. Radical generators are mainly used when the polymerizable compound (a) contains a radical polymerizable compound. On the other hand, acid generators are mainly used when the polymerizable compound (a) contains a cationic polymerizable compound. In the present invention, a thermal polymerization initiator (bt) and / or a photopolymerization initiator (bp) can be used as polymerization initiator (b).

[0151] <Thermal polymerization initiator (bt)> Examples of thermal radical generators include organic peroxides and azo compounds.

[0152] Examples of organic peroxides include, but are not limited to, the following: Peroxy esters such as t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-butyl peroxyisopropyl carbonates; peroxyketals such as 1,1-bis(t-hexyl peroxy)3,3,5-trimethylcyclohexane; and diacyl peroxides such as lauroyl peroxides.

[0153] Examples of azo compounds include, but are not limited to, the following. Azonitriles such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexane-1-carbonnitrile)

[0154] Examples of thermal acid generators include well-known iodonium salts, sulfonium salts, phosphonium salts, and ferrocenes.

[0155] Specific examples of thermal acid generators include, but are not limited to, the following. Diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroborate

[0156] <Photopolymerization initiator (bp)> In this specification, a photopolymerization initiator (bp) is a compound that senses light of a predetermined wavelength and generates the aforementioned polymerization factors (such as radicals and cations). Specifically, a photopolymerization initiator (bp) is a polymerization initiator that generates radicals and cations in response to light (infrared rays, visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams such as electron beams, and radiation). A photopolymerization initiator (bp) may consist of only one type of photopolymerization initiator or may consist of multiple types of photopolymerization initiators.

[0157] Examples of radical generators include, but are not limited to, the following: 2,4,5-triarylimidazole dimers which may have substituents such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone Benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, and 1,2-benz Quinones such as anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl Benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;Acyl phosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one;

[0158] Examples of commercially available radical generators mentioned above include, but are not limited to, the following: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO, LR8893, LR8970 (all manufactured by BASF), Yubekrill P36 (manufactured by UCB)

[0159] Of the radical generators mentioned above, polymerization initiator (b) is preferably an acylphosphine oxide-based polymerization initiator. The acylphosphine oxide-based polymerization initiators among the radical generators mentioned above are as follows: Acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0160] Specific examples of photoacid generators include, but are not limited to, the following. Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t- Onium salt compounds such as ethylphenyl-diphenylsulfonium benzenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium-bis(trifluoromethanesulfonyl)imide anion, 4,7-di-n-butoxynaphthyltetrahydrothiophenium-bis(nonafluorobutylsulfonyl)imide anion, and 4,7-di-n-butoxynaphthyltetrahydrothiophenium-tris(nonafluorobutylsulfonyl)methide; Halogen-containing compounds such as 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, and naphthyl-bis(trichloromethyl)-s-triazine; Sulfone compounds such as 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis(phenylsulfonyl)methane; Sulfonic acid compounds such as benzointosylate, pyrogallol trifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, and o-nitrobenzyl-p-toluenesulfonate; Sulfonimide compounds such as N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)-4-butylnaphthylimide, N-(trifluoromethylsulfonyloxy)-4-propylthionaphthylimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)phthalimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.1.1]heptan-5,6-oxy-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)naphthylimide, and N-(10-camphor-sulfonyloxy)naphthylimide; Diazomethane compounds such as bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl-1,1-dimethylethylsulfonyldiazomethane, and bis(1,1-dimethylethylsulfonyl)diazomethane;

[0161] The blending ratio of polymerization initiator (b) in the curable composition (A) is preferably 0.1% by weight or more and 50% by weight or less, relative to the total mass of the polymerizable compound (a), polymerization initiator (b), and non-polymerizable compound (c) described later, i.e., the total mass of all components excluding the solvent (d). Furthermore, the blending ratio of polymerization initiator (b) in the curable composition (A) is more preferably 0.1% by weight or more and 20% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less, relative to the total mass of all components excluding the solvent (d). By blending the polymerization initiator (b) at 0.1% by weight or more, the curing rate of the composition can be increased and the reaction efficiency can be improved. Furthermore, by blending the polymerization initiator (b) at 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0162] <Non-polymerizable compound (c)> In addition to the polymerizable compound (a) and polymerization initiator (b), the curable composition (A) in the present invention may further contain a non-polymerizable compound (c) depending on the purpose. Examples of non-polymerizable compounds (c) include compounds that do not have polymerizable functional groups such as (meth)acryloyl groups and that do not have the ability to generate the polymerization factors (radicals) described above on their own. Examples of non-polymerizable compounds include sensitizers, surfactants, polymerization inhibitors, antioxidants, polymer components, and other additives. The non-polymerizable compound (c) may contain multiple types of the compounds described above.

[0163] Sensitizers are compounds added as needed to accelerate polymerization reactions or improve the conversion rate. Sensitizers may be used individually or in combination of two or more types.

[0164] Examples of sensitizers include sensitizing dyes. Sensitizing dyes are compounds that are excited by absorbing light of a specific wavelength and interact with photopolymerization initiators (bp). Here, interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator (bp).

[0165] Specific examples of sensitizing dyes include, but are not limited to, the following. Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphaquinone derivatives, acridine dyes, thiopyrillium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes

[0166] <Solvent (d)> The curable composition (A) contains a solvent (d) having a boiling point of 80°C or higher and less than 250°C under normal pressure. The solvent (d) can be a solvent in which the polymerizable compound (a), polymerization initiator (b), and non-polymerizable compound (c) dissolve, such as an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, or a nitrogen-containing solvent. The solvent (d) can be used alone or in combination of two or more types. The boiling point of the solvent (d) under normal pressure should be 80°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of the solvent (d) under normal pressure should be less than 250°C, preferably less than 200°C. If the boiling point of the solvent (d) under normal pressure is less than 80°C, the evaporation rate will be too fast in the planarization step described later, making it impossible to obtain a uniform film. Furthermore, if the boiling point of solvent (d) at atmospheric pressure is 250°C or higher, volatilization may be insufficient during the bake process following the arrangement process described later, and solvent (d) may remain in the film.

[0167] Examples of alcohol-based solvents include the following: Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, s Monoalcohol solvents such as ec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0168] Examples of ketone solvents include the following: Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, phenthone

[0169] Examples of ether-based solvents include the following: Ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol Diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran

[0170] Examples of ester solvents include the following: Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Ethers, diethylene glycol acetate mono-n-butyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether, propylene glycol acetate monobutyl ether, dipropylene glycol acetate monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate

[0171] Examples of nitrogen-containing solvents include the following: N-methyl methyl phosphate Formamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone

[0172] As solvent (d), ether-based solvents and ester-based solvents are preferred among the solvents mentioned above. Furthermore, from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a glycol structure are more preferred as solvent (d). In addition, the following are even more preferred as solvent (d). Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether

[0173] Furthermore, particularly preferred solvents (d) include propylene glycol monomethyl ether acetate and isocyanurate di(meth)acrylate.

[0174] Preferred solvents are those having at least one of the following structures: ester structure, ketone structure, hydroxyl group, and ether structure. Specifically, these are solvents selected individually or in mixtures thereof from propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate.

[0175] Furthermore, as solvent (d), a polymerizable compound having a boiling point of 80°C or higher and less than 250°C under normal pressure can also be used. Examples of polymerizable compounds having a boiling point of 80°C or higher and less than 250°C under normal pressure include the following: Cyclohexyl acrylate (198°C), benzyl acrylate (229°C), isobornyl acrylate (245°C), tetrahydrofurfuryl acrylate (202°C), trimethylcyclohexyl acrylate (232°C), isooctyl acrylate (217°C), n-octyl acrylate (228°C), ethoxyethoxyethyl acrylate (boiling point 230°C), divinylbenzene (193°C), 1,3-diisopropenylbenzene (218°C), styrene (145°C), α-methylstyrene (165°C)

[0176] When the total curable composition (A) is considered to be 100% by volume, the content of solvent (d) should be 70% by volume or more, preferably 80% by volume or more, and particularly preferably 90% by volume or more. If the content of solvent (d) is less than 80% by volume, it becomes difficult to obtain a thin film in the arrangement process using the spin coating method.

[0177] <Temperature when compounding the curable composition> When preparing the curable composition (A) in the present invention, at least a polymerizable compound (a), a polymerization initiator (b), and a solvent (d) are mixed and dissolved under predetermined temperature conditions. Specifically, the predetermined temperature conditions are in the range of 0°C to 100°C. The same applies when the curable composition (A) contains a non-polymerizable compound (c).

[0178] <Viscosity of curable composition> The curable composition (A) is positioned using a spin-coating method during the positioning process. Therefore, the viscosity of the curable composition (A) is preferably between 1 mPa·s and 100 mPa·s at 23°C and 1 atm, more preferably between 1 mPa·s and 20 mPa·s, and particularly preferably between 1 mPa·s and 5 mPa·s. If the viscosity of the curable composition (A) is greater than 100 mPa·s, it becomes difficult to obtain a thin film.

[0179] The curable composition (A) from which solvent (d) has completely evaporated, i.e., the composition from which solvent (d) has been removed from curable composition (A), has a viscosity at 23°C of, for example, 10 mPa·s to 10,000 mPa·s. Hereinafter, the composition from which solvent (d) has been removed from curable composition (A) will also be referred to as curable composition (A'). The viscosity of curable composition (A') at 23°C may be 20 mPa·s to 1,000 Pa·s, preferably 50 mPa·s to 500 mPa·s, and more preferably 50 mPa·s to 150 mPa·s. Fluidity can be obtained by making the viscosity of curable composition (A') at 23°C 1,000 Pa·s or less.

[0180] <Impurities Mixed in the Curable Composition> The curable composition (A) preferably contains no impurities as much as possible. Here, the impurities mean substances other than the polymerizable compound (a), the polymerization initiator (b), the non-polymerizable compound (c), and the solvent (d). Therefore, the curable composition (A) is preferably obtained through a purification process. Such a purification process preferably includes filtration using a filter.

[0181] As the filtration using a filter, after mixing the polymerizable compound (a), the polymerization initiator (b), and the non-polymerizable compound (c), it is preferable to filter with a filter having a pore size of 0.001 μm or more and 5.0 μm or less, for example. When performing filtration using a filter, it is more preferable to perform it in multiple stages or repeat it many times (circulation filtration). Also, the liquid filtered with a filter may be filtered again, or may be filtered using a plurality of filters having different pore sizes. Examples of the filter used for filtration include filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc., but it is not particularly limited. By undergoing such a purification process, impurities such as particles mixed in the curable composition (A) can be removed. Thereby, it is possible to prevent irregularities from accidentally occurring in the cured film (lower layer film) obtained after curing the curable composition (A) due to the impurities mixed in the curable composition (A), resulting in pattern defects.

[0182] When the curable composition (A) is used for manufacturing a semiconductor integrated circuit, in order not to inhibit the operation of the product, it is preferably avoided as much as possible that impurities containing metal atoms (metal impurities) are mixed into the curable composition (A). The concentration of metal impurities contained in the curable composition (A) is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0183] [Film Formation Method] Referring to FIGS. 1(a) to 1(d), a film forming method as one aspect of the present invention will be described. The film forming method in the present invention is applied to, for example, a planarization technique for planarizing the surface of a substrate, and forms a lower layer film as a film of a curable composition (A) on a substrate having irregularities (concavo-convex shape) on its surface. The film forming method in the present invention includes an arrangement step, a planarization step, and a curing step. The planarization step is carried out after the arrangement step, and the curing step is carried out after the arrangement step.

[0184] <Arrangement step> Referring to FIGS. 1(a) and 1(b), the arrangement step will be described. The arrangement step is a step of arranging a lower layer film forming composition 102 on a substrate 101 (base) having a concavo-convex shape as shown in FIG. 1(a) as shown in FIG. 1(b). Specifically, using the spin coating method, as the lower layer film forming composition 102, a curable composition (A) containing a polymerizable compound (a) and a solvent (d) is arranged (spin-coated) on the substrate. As shown in FIG. 1(b), when the concavo-convex shape of the substrate 101 is large, the lower layer film forming composition 102 is affected by the concavo-convex shape, so that a step 104 occurs in the lower layer film forming composition 102 immediately after the spin coating is completed, and it tends to be non-uniform. The lower layer film forming composition 102 is typically composed of a curable composition (A) in which the solvent (d) has completely volatilized, that is, a curable composition (A') from which the solvent (d) has been removed. Hereinafter, the lower layer film forming composition 102 from which the solvent (d) has been removed will be referred to as a lower layer film composition.

[0185] <Planarization step> The planarization process will be described with reference to Figures 1(b) and 1(c). The planarization process is a process of forming a base layer by planarizing the base layer film-forming composition 102 placed on the substrate. Specifically, the step 104 shown in Figure 1(b) is planarized using the fluidity of the base layer film-forming composition 102 until it reaches a desired (acceptable) step 105, as shown in Figure 1(c). In this embodiment, the planarization process is carried out by waiting for the base layer film-forming composition 102 immediately after spin coating is completed until the step 104 reaches the desired step 105. The desired step 105 is basically less than 15 nm, preferably 4 nm, and more preferably less than 0.1 nm. Since the planarization process utilizes the fluidity of the base layer film-forming composition 102, the substrate 101 on which the base layer film-forming composition 102 is placed should be left in a room temperature environment of about 23°C. If it is desired to achieve faster planarization of the lower film-forming composition 102, a heating step may be provided to accelerate the planarization of the lower film-forming composition 102 by heating it to reduce its viscosity. In the heating step, the temperature at which the lower film-forming composition 102 is heated is appropriately adjusted depending on the composition of the composition, but is usually 23°C to 120°C, and preferably 50°C to 100°C.

[0186] The time required for the planarization process largely depends on the viscosity of the base layer forming composition 102, the period (spatial period) of the uneven shape of the substrate 101, and the thickness of the thin film portion of the base layer forming composition 102 (base layer 103). Figure 2 is a diagram corresponding to Figure 1(c), showing the state in which the planarization process has been carried out and the base layer forming composition 102 has been planarized. Referring to Figure 2, the planarized base layer forming composition 102 is formed on the substrate 101. The period 201(λ[µm]) of the uneven shape of the substrate 101 is the length of the unevenness (pattern) when the shape of the surface (substrate) of the substrate 101 has a spatially repeating structure. Also, the thickness 202(d f[nm]) is the thickness of the underlayer film-forming composition 102 at the convex (most convex) portion of the uneven shape of the substrate 101 after planarization is complete. In other words, the thickness 202 of the thinnest part of the underlayer film-forming composition 102 corresponds to the thickness of the curable composition (A) after curing (underlayer film 103) at the convex portion of the uneven shape of the substrate 101. In addition to these, the viscosity of the underlayer film composition (viscosity of the composition obtained by removing the solvent (d) from the curable composition (A)) μ [mPa·s] roughly determines the time required for the planarization process.

[0187] The time required for the planarization process is, in practice, limited from the viewpoint of throughput, and is usually between 0.1 seconds and less than 200 seconds, preferably between 0.1 seconds and less than 60 seconds. The period 201 of the uneven surface shape of the substrate 101 is determined by the substrate to be planarized. The period 201 of the uneven surface shape of the substrate 101 is usually 33 mm or less, preferably 100 μm or less, and more preferably 10 μm or less. The period 201 of the uneven surface shape of the substrate 101 is the maximum period of the pattern in the shot region on the substrate on which the underlayer film is formed. Furthermore, the thickness 202 of the thinnest part of the underlayer film forming composition 102 is determined according to the purpose. The thickness 202 of the thinnest part of the underlayer film forming composition 102 is usually between 1 nm and less than 1 mm, preferably between 10 nm and less than 200 nm, and more preferably between 10 nm and less than 50 nm. Thus, when the period 201 of the uneven shape of the substrate 101 and the thickness 202 of the thinnest part of the underlayer film forming composition 102 are determined, in order to achieve the desired step height 105 in the planarization process, the range of viscosity μ [mPa·s] of the underlayer film composition is limited, as shown in the following equation (3). Note that the function f(λ, d) in equation (3) is... f ) will be discussed later. μ <f(λ、d f )...Equation (3)

[0188] <Curing process> The curing process will be explained with reference to Figures 1(c) and 1(d). The curing process is a process of forming a cured film 103 as shown in Figure 1(d) by curing the underlayer film forming composition 102 (underlayer film composition) shown in Figure 1(c). The cured film 103 is a material that does not flow and does not change shape within a realistic time range, like a solid or glass.

[0189] As a method for curing the underlying film composition, for example, a method of irradiating the underlying film composition with light can be applied, and the light irradiated onto the underlying film composition is selected according to the sensitivity wavelength of the underlying film composition. Specifically, the light irradiated onto the underlying film composition is appropriately selected from ultraviolet light, X-rays, or electron beams with a wavelength of 150 nm to 400 nm. It is particularly preferable that the light irradiated onto the underlying film composition be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that are sensitive to ultraviolet light.

[0190] As a method for curing the underlying film composition, a heating method can also be applied. The heating temperature for the underlying film composition is, for example, 300°C to 400°C, preferably 80°C to 250°C, and particularly preferably 90°C to 220°C. The heating time for the underlying film composition is, for example, 10 seconds to 600 seconds. Heating of the underlying film composition can be carried out using known heating devices such as hot plates or ovens. When a heating step is adopted in the planarization step, in the curing step, the underlying film composition must be heated at a higher temperature than in the heating step of the planarization step, and an underlying film composition that cures at a high temperature (curable composition) must be used.

[0191] Furthermore, as a method for curing the underlying film composition, a method of irradiating the underlying film composition with light and a method of heating the underlying film composition may be used in combination.

[0192] [Method of manufacturing articles] A method for manufacturing an article includes a forming step of forming a film of a curable composition on a substrate using the film forming method described above; a processing step of processing the substrate on which the film of the curable composition formed in the forming step has been formed; and a manufacturing step of manufacturing an article from the substrate processed in the processing step.

[0193] Furthermore, the film (cured film) formed by the film formation method of the present invention can be used as is as a component of at least a part of various articles. The film (cured film) formed by the film formation method of the present invention is temporarily used as a mask for etching, ion implantation, etc., on a substrate (or the layer to be processed if the substrate has a layer to be processed). After etching, ion implantation, etc., is performed in the substrate processing process, the mask is removed. This makes it possible to manufacture various articles.

[0194] When removing hardened material from recesses in a hardened film by etching, the specific method is not particularly limited, and known methods, such as dry etching, can be used. Known dry etching apparatus can be used for dry etching. The source gas for dry etching is appropriately selected according to the elemental composition of the hardened material to be etched. Specifically, halogen-based gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2 can be used as source gases. In addition, gases containing oxygen atoms such as O2, CO, and CO2, inert gases such as He, N2, and Ar, and gases such as H2 and NH3 can also be used as source gases. These gases can also be mixed and used as a source gas. In this case, in order to process the substrate with good yield, the hardened film is required to have high dry etching resistance.

[0195] Articles include electrical circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Electrical circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, as well as semiconductor elements such as LSI, CCD, image sensors, and FPGA. Optical elements include microlenses, light guides, waveguides, anti-reflective coatings, diffraction gratings, polarizing elements, color filters, light-emitting elements, displays, and solar cells. MEMS include DMDs, microfluidics, and electromechanical conversion elements. Recording elements include optical discs such as CDs and DVDs, magnetic discs, magneto-optical discs, and magnetic heads. Sensors include magnetic sensors, optical sensors, and gyro sensors. Molds include molds for imprinting.

[0196] Known photolithography processes such as imprint lithography and extreme ultraviolet (EUV) exposure can be performed on the planarized film formed by the film formation method of the present invention. Alternatively, a spin-on-glass (SOG) film and / or a silicon oxide layer can be laminated, and a curable composition can be applied thereon for photolithography. This makes it possible to manufacture devices such as semiconductor devices. Furthermore, it is possible to form electronic devices including such devices, such as displays, cameras, and medical devices. Examples of devices include LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and NAND flash memory.

[0197] [Examples] To supplement the embodiments described above, more specific examples will be explained.

[0198] <Example 1> In this embodiment, the curable composition (A) (underlayer film composition) is planarized during the planarization process, and the upper limit of the viscosity μ [mPa·s] of the curable composition (A) is the period λ [um] of the uneven shape of the substrate and the thickness d of the thinnest part of the underlayer film. f This demonstrates that it is a function of [nm].

[0199] On the substrate to be subjected to the planarization process, in the placement process, a liquid film of the curable composition (A) is formed by the centrifugal force of the spin coating method. Since the liquid film of the curable composition (A) is mainly formed by centrifugal force, in this numerical calculation, it is assumed that it is formed with a uniform thickness regardless of the uneven shape of the substrate, and the initial liquid film distribution is obtained.

[0200] In the planarization process, the initial liquid film distribution is planarized by utilizing the fluidity of the curable composition (A). In this example, as shown in the following formula (4), the Navier - Stokes equation approximated by a thin film with a free surface (lubrication theory) was solved to calculate the flow process of the curable composition (A).

[0201]

Equation

[0202] In Equation 4, h is the height of the liquid film of the curable composition (A), μ is the viscosity (viscosity coefficient) of the curable composition (A), and σ is the surface tension (surface tension coefficient). In this example, the surface tension of the curable composition (A) was set to 35 mN / m.

[0203] FIG. 3 is a diagram showing an example of the relationship between the uneven shape of the substrate and the initial liquid film distribution. In FIG. 3, the horizontal axis indicates the spatial coordinate [m], and the vertical axis indicates the height of the liquid film of the curable composition (A). Referring to FIG. 3, the uneven shape 301 of the substrate is composed of concave portions and convex portions. In this example, this was calculated under periodic boundary conditions. Also, the height of the uneven shape of the substrate was set to 100 nm.

[0204] As described above, the liquid film distribution 302 (initial liquid film distribution) of the curable composition (A) at the initial time is assumed to be of uniform thickness and is illustrated in Figure 3. In reality, the liquid film distribution 302 immediately after spin coating is considered to have a smooth distribution rather than a discontinuous shape in the uneven shape 301 of the substrate, as shown in Figure 3. However, by estimating the relaxation time based on the discontinuous shape of the liquid film distribution 302, it is possible to evaluate the upper limit of the relaxation time.

[0205] The periodicity λ of the substrate's uneven surface is 8 μm, and the thickness d of the thinnest part of the underlying film is d f Figure 4 shows the time evolution of the liquid film distribution of the curable composition (A) when the thickness is 25 nm. In Figure 4, the horizontal axis represents spatial coordinates [m], and the vertical axis represents the height of the liquid film of the curable composition (A). Figure 4 illustrates the liquid film distribution 302 0.0 seconds (immediately after spin coating is completed), 0.1 seconds, 1 second, 10 seconds, and 100 seconds after spin coating is completed. Referring to Figure 4, it can be seen that the liquid film of the curable composition (A) gradually flattens as time passes, and 100 seconds after spin coating is completed, the liquid film of the curable composition (A) is almost completely flattened.

[0206] Figure 5 shows the change in the height difference of the liquid film distribution 302 of the curable composition (A) shown in Figure 4 over time 501. In Figure 5, the horizontal axis represents elapsed time [seconds], and the vertical axis represents the height difference of the liquid film distribution 302 of the curable composition (A). Referring to Figure 5, it can be seen that the change in the height difference of the liquid film distribution 302 of the curable composition (A) over time 501 reaches its maximum value after about 0.1 seconds, then decays, and becomes almost flat after 100 seconds.

[0207] Changing the viscosity μ [mPa·s] of the curable composition (A) changes the time required for the planarization process. Figure 6 shows that the period λ of the substrate's surface irregularities is 1 μm, and the thickness d of the thinnest part of the underlying film is 1 μm. fThis figure shows the time required for the planarization process when the viscosity μ [mPa·s] of the curable composition (A) is changed, with a thickness of 15 nm and a desired step height of 0.1 nm, which serves as the criterion for completion of the planarization process. In Figure 6, the horizontal axis represents the viscosity [mPa·s] of the curable composition (A), and the vertical axis represents time [seconds]. Figure 6 illustrates the viscosity dependence 601 of the time required for the planarization process. Referring to Figure 6, if the time available for the planarization process is 200 seconds, then if the viscosity μ of the curable composition (A) is smaller than the viscosity corresponding to the intersection 602 with 200 seconds, the planarization process will be completed within 200 seconds. Therefore, the viscosity corresponding to the intersection 602 is the upper limit of the viscosity of the curable composition (A) that can be planarized within 200 seconds.

[0208] Figure 7 shows the results of calculating the upper limit [mPa·s] of the viscosity μ of a curable composition (A) that flattens within 200 seconds, by varying the period λ [um] of the substrate's surface irregularities. In Figure 7, the horizontal axis represents the period [um] of the substrate's surface irregularities, and the vertical axis represents the upper limit [mPa·s] of the viscosity μ of the curable composition (A). Figure 7 illustrates the dependence 701 of the upper limit of the viscosity of the curable composition (A) on the period (λ) of the substrate's surface irregularities, specifically, the function 702 fitted to the λ dependence 701. Referring to Figure 7, the function 702 is a power function of -4 with respect to the period λ [um] of the substrate's surface irregularities. As shown in Figure 7, as the period λ [um] of the substrate's surface irregularities increases, the upper limit [mPa·s] of the viscosity μ of the curable composition (A) decreases.

[0209] Also, the thickness d of the thinnest part of the lower layer f Figure 8 shows the results of calculating the time [seconds] required for the planarization process by varying the [nm]. In Figure 8, the horizontal axis represents the thickness [um] of the thinnest part of the underlying film, and the vertical axis represents the time [seconds] required for the planarization process. In Figure 8, the period λ of the surface irregularities of the substrate is 1 um, the viscosity μ of the curable composition (A) is 1000 mPa·s, and the time required for the planarization process is calculated based on the thickness (d) of the thinnest part of the underlying film. f ) Dependence 801, specifically, d fThe function 802 fitted to dependency 801 is illustrated. Referring to Figure 8, function 802 is the thickness d of the thinnest part of the underlying film. f It is a power function of 2.7 with respect to [nm]. As shown in Figure 8, the thickness d of the thinnest part of the underlying film. f As [nm] increases, the time required for the planarization process decreases, that is, the upper limit [mPa·s] of the viscosity μ of the curable composition (A) increases.

[0210] In summary, increasing the viscosity μ [mPa·s] of the curable composition (A) increases the time required for the planarization process. Therefore, determining the time required for the planarization process determines the upper limit [mPa·s] of the viscosity μ of the curable composition (A).

[0211] Furthermore, as mentioned above, the time required for the planarization process depends on the period λ [um] of the uneven surface of the substrate and the thickness d of the thinnest part of the underlying film. f It also depends on [nm]. Therefore, the upper limit of the viscosity μ [mPa·s] of the curable composition (A) depends on the period λ [um] of the surface irregularities of the substrate and the thickness d of the thinnest part of the underlying film. f It becomes a function of [nm].

[0212] Furthermore, as described above, the viscosity μ [mPa·s] of the curable composition (A) is a power function of -4 with respect to the period λ [um] of the surface irregularities of the substrate, and the thickness d of the thinnest part of the lower layer film. f The viscosity is a power function of 2.7 with respect to [nm]. Specifically, the viscosity μ [mPa·s] of the curable composition (A) is given by the period λ [um] of the surface irregularities of the substrate and the thickness d of the thinnest part of the film, as shown in the following equation (5). f It is smaller than the value of the function f determined by [nm].

[0213]

number

[0214] The disclosures herein include the following film-forming methods, curable compositions, and methods for producing articles.

[0215] (Item 1) A step of placing a curable composition containing a polymerizable compound and a solvent onto a substrate using a pin coat method, A step of planarizing the curable composition placed on the substrate to form a film, It has, The viscosity μ [mPa·s] of the composition obtained by removing the solvent from the curable composition is given by the period λ [um] of the uneven surface of the substrate and the thickness d of the curable composition after curing at the protrusions of the uneven surface. f The function f is determined by [nm]

number

[0216] (Item 2) The film formation method according to item 1, characterized in that the period λ includes the maximum period of the pattern in the shot region on the substrate on which the film is formed.

[0217] (Item 3) The film formation method according to item 1 or 2, characterized in that the period λ is 10 μm or less.

[0218] (Item 4) The aforementioned thicknessd f A film formation method according to any one of items 1 to 3, characterized in that the film is 10 nm or more and less than 50 nm in length.

[0219] (Item 5) The polymerizable compound includes a compound comprising one or more aromatic rings or aromatic heterocycles and two or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles. The curable composition further comprises a polymerization initiator, The content of the solvent relative to the total curable composition is 80% by volume or more. A film formation method according to any one of items 1 to 4, characterized by the following:

[0220] (Item 6) The polymerizable compound is,

[0221] [ka] R1 and R2 are vinyl groups or propenyl groups. R3 and R4 are hydrogen atoms or vinyl groups. [ka] R5 and R6 are vinyl groups or propenyl groups. R7 and R8 are hydrogen atoms or vinyl groups. R9 is a single bond or a linear chain with 1-2 carbon atoms or an oxygen atom or a carbonyl group. [ka] R10 and R11 are vinyl groups or propenyl groups. R12 and R13 are hydrogen atoms or vinyl groups. Represented by any one of the following: The film formation method described in item 5, characterized by the features described herein.

[0222] (Item 7) The film-forming method according to item 5 or 6, characterized in that the curable composition has a viscosity of 1 mPa·s or more and 100 mPa·s or less at 23°C.

[0223] (Item 8) The film-forming method according to any one of items 5 to 7, characterized in that the composition obtained by removing the solvent from the curable composition has a viscosity of less than 1000 mPa·s at 23°C.

[0224] (Item 9) The film-forming method according to any one of items 5 to 8, characterized in that the vapor pressure at 80°C of the composition obtained by removing the solvent from the curable composition is 0.001 mmHg or less.

[0225] (Item 10) The film-forming method according to any one of items 5 to 9, characterized in that the lower limit of the polymerizable functional group of the polymerizable compound is a molecular weight of 200 or more.

[0226] (Item 11) A curable composition, One or more polymerizable compounds comprising one or more aromatic rings or aromatic heterocycles and two or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles, Polymerization initiator and It contains a solvent, The content of the solvent relative to the total curable composition is 80% by volume or more. A curable composition characterized by the following features.

[0227] (Item 12) The polymerizable compound is, [ka] R1 and R2 are vinyl groups or propenyl groups. R3 and R4 are hydrogen atoms or vinyl groups. [ka] R5 and R6 are vinyl groups or propenyl groups. R7 and R8 are hydrogen atoms or vinyl groups. R9 is a single bond or a linear chain with 1-2 carbon atoms or an oxygen atom or a carbonyl group. [ka] R10 and R11 are vinyl groups or propenyl groups. R12 and R13 are hydrogen atoms or vinyl groups. Represented by any one of the following: A curable composition according to item 11, characterized by the features described herein.

[0228] (Item 13) The curable composition according to item 11 or 12, characterized in that the curable composition has a viscosity of 1 mPa·s or more and 100 mPa·s or less at 23°C.

[0229] (Item 14) The curable composition according to any one of items 11 to 13, characterized in that the composition obtained by removing the solvent from the curable composition has a viscosity of less than 1000 mPa·s at 23°C.

[0230] (Item 15) The curable composition according to any one of items 11 to 14, characterized in that the vapor pressure at 80°C of the composition obtained by removing the solvent from the curable composition is 0.001 mmHg or less.

[0231] (Item 16) The curable composition according to any one of items 11 to 15, characterized in that the lower limit of the polymerizable functional group of the polymerizable compound is a molecular weight of 200 or more.

[0232] (Item 17) A step of placing a curable composition described in any one of items 11 to 16 onto a substrate using a spin coating method, A step of planarizing the curable composition placed on the substrate to form a film, A film formation method characterized by having the following:

[0233] (Item 18) A forming step of forming a film of a curable composition on a substrate using a film forming method described in any one of items 1 to 10 and 17, A processing step for processing the substrate on which the film has been formed in the forming step, A manufacturing process for producing an article from the substrate processed in the above-mentioned processing step, A method for manufacturing an article, characterized by having the following:

[0234] The invention is not limited to the embodiments described above, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, claims are attached to disclose the scope of the invention. [Explanation of Symbols]

[0235] 101: Substrate 102: Composition for forming lower layer film 103: Lower layer film

Claims

1. A step of placing a curable composition containing a polymerizable compound and a solvent onto a substrate using a spin-coating method, A step of planarizing the curable composition placed on the substrate to form a film, It has, The viscosity μ [mPa·s] of the composition obtained by removing the solvent from the curable composition is given by the period λ [um] of the uneven shape of the substrate and the thickness d of the cured curable composition at the protrusions of the uneven shape. ｆ The function f is determined by [nm] [Math 6] A film formation method characterized by being smaller than the value of .

2. The film formation method according to claim 1, characterized in that the period λ includes the maximum period of the pattern in the shot region on the substrate on which the film is formed.

3. The film formation method according to claim 1, characterized in that the period λ is 10 μm or less.

4. The aforementioned thickness d ｆ The film formation method according to claim 1, characterized in that the wavelength is 10 nm or more and less than 50 nm.

5. The polymerizable compound includes a compound comprising one or more aromatic rings or aromatic heterocycles and two or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles. The curable composition further comprises a polymerization initiator, The content of the solvent relative to the total curable composition is 80% by volume or more. The film formation method according to feature 1.

6. The polymerizable compound is, 【Transformation 58】 R1 and R2 are vinyl groups or propenyl groups. R3 and R4 are hydrogen atoms or vinyl groups. 【Chemistry 59】 R5 and R6 are vinyl groups or propenyl groups. R7 and R8 are hydrogen atoms or vinyl groups. R9 is a single bond or a linear chain with 1 to 2 carbon atoms or an oxygen atom or a carbonyl group. 【Transformation 60】 R10 and R11 are vinyl groups or propenyl groups. R12 and R13 are hydrogen atoms or vinyl groups. Represented by any one of the following: The film formation method according to feature 5.

7. The film-forming method according to claim 5, characterized in that the curable composition has a viscosity of 1 mPa·s or more and 100 mPa·s or less at 23°C.

8. The film-forming method according to claim 5, characterized in that the composition obtained by removing the solvent from the curable composition has a viscosity of less than 1000 mPa·s at 23°C.

9. The film-forming method according to claim 5, characterized in that the vapor pressure at 80°C of the composition obtained by removing the solvent from the curable composition is 0.001 mmHg or less.

10. The film-forming method according to claim 5, characterized in that the lower limit of the polymerizable functional groups of the polymerizable compound is a molecular weight of 200 or more.

11. A curable composition, One or more polymerizable compounds comprising one or more aromatic rings or aromatic heterocycles and two or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles, Polymerization initiator and It contains a solvent, The content of the solvent relative to the total curable composition is 80% by volume or more. A curable composition characterized by the following features.

12. The polymerizable compound is, 【Chemistry 61】 R1 and R2 are vinyl groups or propenyl groups. R3 and R4 are hydrogen atoms or vinyl groups. 【Transformation 62】 R5 and R6 are vinyl groups or propenyl groups. R7 and R8 are hydrogen atoms or vinyl groups. R9 is a single bond or a linear chain with 1 to 2 carbon atoms or an oxygen atom or a carbonyl group. 【Transformation 63】 R10 and R11 are vinyl groups or propenyl groups. R12 and R13 are hydrogen atoms or vinyl groups. Represented by any one of the following: The curable composition according to feature 11.

13. The curable composition according to claim 11, characterized in that the curable composition has a viscosity of 1 mPa·s or more and 100 mPa·s or less at 23°C.

14. The curable composition according to claim 11, characterized in that the composition obtained by removing the solvent from the curable composition has a viscosity of less than 1000 mPa·s at 23°C.

15. The curable composition according to claim 11, characterized in that the vapor pressure at 80°C of the composition obtained by removing the solvent from the curable composition is 0.001 mmHg or less.

16. The curable composition according to claim 11, characterized in that the lower limit of the polymerizable functional group of the polymerizable compound is a molecular weight of 200 or more.

17. A step of placing the curable composition described in claim 11 onto a substrate using a spin coating method, A step of planarizing the curable composition placed on the substrate to form a film, A film formation method characterized by having the following:

18. A forming step of forming a film of a curable composition on a substrate using the film forming method described in claim 1 or 17, A processing step for processing the substrate on which the film has been formed in the forming step, A manufacturing process for producing an article from the substrate processed in the above-mentioned processing step, A method for manufacturing an article, characterized by having the following:

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