Film forming method, article manufacturing method, and curable composition

Abstract

The invention relates to a film forming method, an article manufacturing method, and a curable composition. Provided is a film forming method for forming a film of a curable composition on a substrate using a mold. The method includes discretely disposing a plurality of droplets of a curable composition on a substrate, after the disposing, bringing the plurality of droplets on the substrate and a mold into contact with each other, thereby forming a liquid film between the substrate and the mold, after bringing the droplets and the mold into contact with each other, curing the liquid film, thereby forming a cured film, and after the curing, forming the cured film between the substrate and the mold. And separating the cured film and the mold from each other, in which the viscosity [mu] [mPa.s] of the non-volatile composition in the curable composition and the average liquid film thickness h [m] formed from the non-volatile composition have values satisfying a predetermined expression.

Description

Technical Field

[0001] The present disclosure relates to a film forming method, an article manufacturing method, and a curable composition. Background Art

[0002] For semiconductor devices and MEMS, there is an increasing demand for miniaturization, and as a micropatterning technique, imprinting technology (optical imprinting technology) has received a great deal of attention as a micromanufacturing technique. In the imprinting technology, a curable composition is cured in a state where a mold having a fine concavo-convex pattern formed on its surface is in contact with the curable composition supplied (applied) onto a substrate. Therefore, the pattern of the mold is transferred to the cured film of the curable composition, and a pattern is formed on the substrate. According to the imprinting technology, a fine pattern (structure) on the order of several nanometers can be formed on the substrate (see Japanese Patent No. 6584578).

[0003] An example of a pattern forming method using the imprinting technology will be described. First, a liquid curable composition is discretely dropped (arranged) in a pattern forming region on a substrate. The droplets of the curable composition arranged in the pattern forming region spread on the substrate. This phenomenon is called pre-spreading. Next, the mold is brought into contact with (pressed onto) the curable composition on the substrate. Therefore, the droplets of the curable composition spread to the entire gap region between the substrate and the mold by capillary action. This phenomenon is called spreading. Further, by capillary action, the curable composition fills the concave portions forming the mold pattern. This phenomenon is called filling. Note that the time until spreading and filling are completed is called the filling time. If the filling of the curable composition is completed, the curable composition is irradiated with light to cure the curable composition. Then, the mold is detached from the cured curable composition on the substrate. By performing these steps, the pattern of the mold is transferred to the curable composition on the substrate, and a pattern of the curable composition is formed. Here, the pattern of the curable composition formed on the substrate includes a residual film. The residual film is a cured film remaining between the substrate and the concave portions (convex portions of the mold pattern) of the cured film of the curable composition.

[0004] The lithography step of manufacturing semiconductor devices requires planarization of the substrate. For example, in extreme ultraviolet lithography (EUV), which has attracted attention in recent years as a lithography technology, as miniaturization progresses, the depth of focus for forming a projected image decreases. Therefore, the unevenness on the surface of the substrate to which the curable composition is supplied must be reduced to less than several tens of nm. In the imprinting technique, flatness equivalent to that of EUV is also required to improve the filling performance of the curable composition and the line width accuracy (see Proc. SPIE 11324-11 (2020)). As a planarization technique, a technique for obtaining a flat surface by the following method is known: droplets of a curable composition corresponding to the unevenness are discretely dropped onto the uneven substrate, and the curable composition is cured in a state where a mold having a flat surface is in contact with the curable composition (see Japanese Patent Application No. 2019-140394 and US Patent Application Publication No. 2020 / 0286740).

[0005] In a pattern formation method or a planarization technique using the imprinting technique, since the droplets of the curable composition dropped onto the substrate are in contact with the mold in a state where they do not contact each other, air bubbles may be entrapped between the mold, the substrate, and the curable composition. It takes a long time for the air bubbles to diffuse into the mold or the substrate and disappear, which is one of the factors reducing productivity (production volume). Therefore, before bringing the curable composition on the substrate into contact with the mold, the droplets of the curable composition are combined with each other (see Japanese Patent Publication No. 2010-530641 and Japanese Patent Publication No. 2022-188736).

[0006] However, in the technique described in Japanese Patent Publication No. 2022-188736, after the droplets of the curable composition have spread to the extent that the droplets are joined to each other, it is necessary to fill the end portion of the contact area between the mold and the substrate with the curable composition by bringing the mold into contact with the curable composition. Filling the end portion of the contact area between the mold and the substrate with the curable composition is referred to as edge filling. The speed of edge filling is referred to as the edge filling speed. In a pattern formation method or a planarization technique using an imprint technique, since the mold is brought into contact with the droplets of the curable composition on the substrate, it takes time until the curable composition fills the end portion of the desired area, which is one of the factors reducing the productivity (production volume). In addition, in some cases, edge filling proceeds excessively, and the curable composition protrudes from the edge and climbs up the side wall of the mold. The cured product of the curable composition attached to the side wall remains on the substrate as an unnecessary cured product, remains on the side wall of the mold, and drops onto the substrate at an unexpected time after the next operation (shot), or causes large defects on the substrate. Hereinafter, the phenomenon in which the curable composition climbs up the side wall of the mold will be referred to as "extrusion". The time until the curable composition spreads to the entire contact area between the substrate and the mold and is extruded from the contact surface of the mold, and the height at which the curable composition climbs up the side wall of the mold reaches 50 nm will be referred to as the "extrusion grace period".

[0007] In the technique described in Japanese Patent Publication No. 2022-188736, it is necessary to achieve both the edge filling speed and extrusion suppression simultaneously. Summary of the Invention

[0008] The present disclosure provides a technique that facilitates achieving both the edge filling speed and extrusion suppression simultaneously.

[0009] In a first aspect of the present invention, there is provided a film forming method for forming a film of a curable composition on a substrate using a mold, including discretely arranging a plurality of droplets of the curable composition on the substrate, after the arrangement, bringing the plurality of droplets on the substrate into contact with the mold to form a liquid film between the substrate and the mold, after bringing the droplets and the mold into contact with each other, curing the liquid film to form a cured film, and after curing, separating the cured film and the mold from each other, wherein the viscosity μ [mPa·s] of the non-volatile composition in the curable composition and the average liquid film thickness h [m] formed by the non-volatile composition have values that satisfy the following expressions Expression 1: 20 [μm / sec] ≤ C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s], Expression 2: 0.5 [sec] ≤ C·h α ·μ / μ0, and C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s].

[0010] In a second aspect thereof, the present invention provides a method for manufacturing an article, including forming a film of a curable composition on a substrate using the film-forming method defined in the first aspect above, processing the substrate on which the film is formed during the formation, and manufacturing an article from the substrate processed during the processing.

[0011] In a third aspect thereof, the present invention provides a curable composition containing a polymerizable compound (a), a photoinitiator (b), and a solvent (d), wherein the curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm, the content of the solvent (d) relative to the entire curable composition is more than 5% by volume and 95% by volume or less, the boiling point of the solvent (d) at 1 atm is less than 250°C, and the viscosity of the curable composition at 23°C and 1 atm in a state where the solvent (d) is removed is 20 mPa·s or more and 135 mPa·s or less.

[0012] Other features of the present invention will become clear from the following description of exemplary embodiments (with reference to the accompanying drawings). BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figures 1A to 1G is a view for explaining a pattern formation method (film-forming method);

[0014] Figures 2A to 2D is a view for explaining the flow behavior of droplets of a curable composition;

[0015] Figure 3 is a view for explaining an extrusion phenomenon;

[0016] Figure 4 is a view showing a state where a curable composition climbs up the side wall of a mold;

[0017] Figure 5 is a view for explaining a contact step;

[0018] Figure 6 is a view showing a change in the edge filling speed when the viscosity coefficient of a liquid film changes;

[0019] Figure 7 is a view showing the relationship between time and the viscosity coefficient;

[0020] Figure 8 is a view showing a change in the edge filling speed when the average liquid film thickness changes;

[0021] Figure 9is a view showing the relationship between the average liquid film thickness and the edge filling speed;

[0022] Figure 10 is a view showing the time-rate change of the extrusion height; and

[0023] Figure 11 is a view showing the relationship between the average liquid film thickness and the extrusion allowance time. DETAILED DESCRIPTION [Curable Composition]

[0024] Hereinafter, embodiments will be described in detail with reference to the drawings. Note that the following embodiments are not intended to limit the scope of the claimed invention. In the embodiments, a plurality of features are described, but the invention is not limited to the invention that requires all of these features, and a plurality of these features can be appropriately combined. In addition, in the drawings, the same or similar configurations are given the same reference numerals, and redundant descriptions thereof will be omitted.

[0025] The curable composition (A) of the present disclosure may be a curable composition for inkjet. The curable composition (A) of the present disclosure is a composition containing at least a component (a) as a polymerizable compound and a component (b) as a photopolymerization initiator. In addition, the curable composition (A) of the present disclosure may contain a component (d) as a solvent. In the present specification, the non-volatile composition (A') is a composition made of the component (a), the component (b), and the component (c), which remains after the component (d) as the solvent of the curable composition (A) volatilizes. Note that "component (d)" may be hereinafter referred to as "solvent (d)".

[0026] In the present specification, a cured film refers to a film cured by polymerizing a curable composition on a substrate. Note that the shape of the cured film is not particularly limited, and thus the cured film may have a pattern shape on the surface. In addition, the cured film remaining between the concave portion (convex portion of the mold pattern) of the cured film remaining in the curable composition and the substrate will be referred to as a residual film.

[0027] <Component (a): Polymerizable Compound> Component (a) is a polymerizable compound. In the present specification, a polymerizable compound is a compound that reacts with a polymerization factor (e.g., a free radical) generated by a polymerization initiator (component (b)) and forms a film made of a polymer compound through a chain reaction (polymerization reaction).

[0028] Examples of the above polymerizable compound are free radical polymerizable compounds. The polymerizable compound as the component (a) may be formed of only one type of polymerizable compound or may be formed of a plurality of types of polymerizable compounds.

[0029] Examples of the radically polymerizable compound are (meth)acrylic compounds, styrenic compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleic compounds.

[0030] (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 are as follows, but the compounds are not limited to these examples.

[0031] (Phenyl)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, (meth)acrylate of EO-modified p-cumylphenol, 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, borneol (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)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, pentyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (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, tert-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, cyanobenzyl (meth)acrylate, naphthylmethyl (meth)acrylate.,

[0032] Examples of commercially available products of the above-mentioned monofunctional (meth)acrylic acid compounds are as follows, but the products are not limited to these examples.

[0033] M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150 and M156 (manufactured by Toagosei Co., Ltd.); MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA and Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100 and #2150 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A and OPP-EA (manufactured by Kyoeisha Chemical Co., Ltd.); TC110S, R-564 and R-128H (manufactured by Nippon Kayaku Co., Ltd.); NK Ester AMP-10G, AMP-20G and A-LEN-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.); FA-511A, 512A and 513A (manufactured by Hitachi Chemical Co., Ltd.); PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M and BR-32 (manufactured by DKS Co., Ltd.); VP (manufactured by BASF); ACMO, DMAA and DMAPAA (manufactured by Kohjin Co., Ltd.); and HRD-01 (manufactured by Nippon Shokubai Co., Ltd.).

[0034] Examples of polyfunctional (meth)acrylic acid compounds having two or more acryloyl or methacryloyl groups are as follows, but the compounds are not limited to these examples.

[0035] Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO- and 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-adamantanedi(meth)acrylate, tris(2-hydroxyethyl) 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)acryloxyphenyl)) propane, PO-modified 2,2-bis(4-((meth)acryloxyphenyl)) propane, EO- and PO-modified 2,2-bis(4-((meth)acryloxyphenyl)) propane, phthalic di(meth)acrylate, isophthalic di(meth)acrylate or terephthalic di(meth)acrylate, and phthalylene di(meth)acrylate, isophthalylene di(meth)acrylate or terephthalylene di(meth)acrylate.

[0036] Examples of commercially available products of the above polyfunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0037] UV SA1002 and SA2007 (manufactured by Mitsubishi Chemical); Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT and 3PA (manufactured by Osaka Organic Chemical Industry); Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A and DPE-6A (manufactured by Kyoeisha Chemical); PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60 and -120, HX-620, D-310 and D-330 (manufactured by Nippon Kayaku); M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, and M400 (manufactured by Toagosei Co., Ltd.); VR-77, VR-60, and VR-90 (manufactured by Showa Highpolymer Co., Ltd.); OGSOL EA-0200 and OGSOL EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd.); and SR295 and SR355 (manufactured by Sartomer).

[0038] Note that in the above compounds, (meth)acrylate refers to acrylate or methacrylate having an alcohol residue equivalent to acrylate. (Meth)acryloyl refers to acryloyl or methacryloyl having an alcohol residue equivalent to acryloyl. EO represents ethylene oxide, and the EO-modified compound A represents a compound in which the (meth)acrylic acid residue and the alcohol residue of compound A are bonded by a block structure of an ethylene oxide group. In addition, PO represents propylene oxide, and the PO-modified compound B represents a compound in which the (meth)acrylic acid residue and the alcohol residue of compound B are bonded by a block structure of a propylene oxide group.

[0039] Practical examples of styrenic compounds are as follows, but the compounds are not limited to these examples.

[0040] 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; halogenated styrenes such as fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodostyrene; and compounds having a styryl group as a polymerizable functional group such as nitrostyrene, acetostyrene, 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.

[0041] Examples of vinyl compounds are as follows, but the compounds are not limited to these examples.

[0042] 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; compounds having a vinyl group as a polymerizable functional group such as vinylidene halides such as vinylidene chloride, vinyl esters of organic carboxylic acids and their derivatives (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate), and (meth)acrylonitrile.

[0043] Note that in this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0044] Examples of allyl compounds are as follows, but the compounds are not limited to these examples.

[0045] Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

[0046] Examples of fumaric acid compounds are as follows, but the compounds are not limited to these examples.

[0047] Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

[0048] Examples of maleic acid compounds are as follows, but the compounds are not limited to these examples.

[0049] Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

[0050] Other examples of free-radical polymerizable compounds are as follows, but the compounds are not limited to these examples.

[0051] Dialkyl esters of itaconic acid and their derivatives (e.g., dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, and dibenzyl itaconate), N-vinylamide derivatives of organic carboxylic acids (e.g., N-methyl-N-vinylacetamide), and maleimide and its derivatives (e.g., N-phenylmaleimide and N-cyclohexylmaleimide).

[0052] If component (a) is formed of multiple types of compounds having one or more polymerizable functional groups, it preferably includes both monofunctional polymerizable compounds and polyfunctional polymerizable compounds. The ratio of the polyfunctional polymerizable compound in component (a) is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 40% by weight or more. This is because, when a monofunctional compound and a polyfunctional compound are combined, a cured film having well-balanced properties such as high mechanical strength, high dry etching resistance, and high heat resistance can be obtained.

[0053] The film-forming method of the present disclosure requires several milliseconds to several hundred seconds until the droplets of the curable composition (A) discretely arranged on the substrate merge with each other to form a substantially continuous liquid film, and thus a waiting step (described later) is required. In this waiting step, the solvent (d) volatilizes, but the polymerizable compound (a) should not volatilize. Therefore, the boiling point of one or more types of polymerizable compounds included in the polymerizable compound (a) is preferably 250 °C or higher, more preferably 300 °C or higher, and further preferably 350 °C or higher at normal pressure. In addition, in order to obtain high dry etching resistance and high heat resistance, the cured film of the curable composition (A) preferably contains at least a compound having a cyclic structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that the normal pressure is 1 atm (atmospheric pressure).

[0054] The boiling point of the polymerizable compound (a) is almost associated with the molecular weight. Therefore, the molecular weight of one or more types of polymerizable compounds included in the polymerizable compound (a) is preferably 200 or higher, more preferably 240 or higher, and further preferably 250 or higher. However, even when the molecular weight is 200 or less, if the boiling point is 250 °C or higher, the compound is preferably usable as the polymerizable compound (a) of the present disclosure. As described above, the boiling point of one or more types of polymerizable compounds included in the polymerizable compound (a) is preferably 250 °C or higher at normal pressure.

[0055] In addition, the vapor pressure of the polymerizable compound (a) at 80 °C and 1 atm is preferably 0.001 mmHg or less. If the polymerizable compound (a) includes one or more types of polymerizable compounds, the vapor pressure of the one or more types of polymerizable compounds at 80 °C and 1 atm is preferably 0.001 mmHg or less. This is because, although it is advantageous to heat the curable composition during the accelerated volatilization of the solvent (component (d)) (described later), it is necessary to suppress the volatilization of the polymerizable compound (a) during heating.

[0056] Note that the boiling points and vapor pressures of various organic compounds at atmospheric pressure can be calculated, for example, by Hansen Solubility Parameters in Practice (HSPiP) 5th Edition 5.3.04. <Ohnishi Parameter of Component (a)>

[0057] The dry etching rate V of a known organic compound, the number N of all atoms in the organic compound (in the molecule), the number N C of all carbon atoms in the composition (in the molecule), and the number N O of all oxygen atoms in the composition (in the molecule) have the relationship of the following equation (1) (see Non-Patent Document 1). V ∝ N / (N C - N o )...(1) where N / (N C - N o ) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, US-2020-0286740 discloses a technique for obtaining a photocurable composition having high dry etching resistance by using a polymerizable compound having a small OP.

[0058] Equation (1) indicates that an organic compound having many oxygen atoms in the molecule or having few aromatic ring structures or alicyclic ring structures has a large OP and a high dry etching rate.

[0059] In the curable composition (A) according to the present disclosure, the OP of component (a) is 1.80 or more and 4.00 or less. The OP of component (a) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or less. When the OP of component (a) is 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. In addition, when the OP of component (a) is 1.80 or more, the cured film of the curable composition (A) can be easily removed when processing the underlying layer using the cured film. When component (a) is formed of multiple types of polymerizable compounds a1, a2,..., a n is formed, the OP is calculated as a weighted average (mole fraction weighted average) based on the mole fraction shown in the following equation (2). If component (a) contains one or more types of polymerizable compounds, the OP of component (a) can be calculated as the mole fraction weighted average of the N / (Nc - No) values of the respective molecules of one or more types of polymerizable compounds. where OP n is component a nOP, and n n is component a n The mole fraction in the entire component (a).

[0060] In order to set the OP of component (a) to 1.80 or more and 2.70 or less, it is preferable to contain at least a compound (a-1) having two or more ring structures as component (a), wherein at least one of the ring structures is an aromatic structure or an aromatic heterocyclic structure. <Compound (a-1): A polymerizable compound having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure>

[0061] The polymerizable compound (a) according to the present disclosure may contain a polymerizable compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. In addition, the ratio of component (a-1) in component (a) is preferably 65% by weight or more. When the ratio of component (a-1) is 65% by weight or more, the OP can be suppressed to 2.70 or less.

[0062] Examples of the ring structure are an aromatic structure, an aromatic heterocyclic structure, and an alicyclic structure.

[0063] The number of carbon atoms of the aromatic structure is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10. Actual examples of the aromatic ring are as follows.

[0064] Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, benzophenanthrene ring, pyrene ring, Ring, perylene ring, and tetrahydronaphthalene ring.

[0065] Note that among the above aromatic rings, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The aromatic ring may have a structure in which multiple rings are connected. For example, a biphenyl ring and a diphenyl ring.

[0066] The number of carbon atoms of the aromatic heterocyclic structure is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 5. Actual examples of the aromatic heterocycle are as follows.

[0067] Thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinoxaline ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxathiin ring, and phenoxazine ring.

[0068] The number of carbon atoms in the alicyclic structure is preferably 3 or more, more preferably 4 or more, and further preferably 6 or more. In addition, the number of carbon atoms in the alicyclic structure is preferably 22 or less, more preferably 18 or less, further preferably 6 or less, and still further preferably 5 or less. Practical examples are as follows.

[0069] Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, spirodecane ring, spirnonane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindane ring, camphane ring, norcamphane ring, norcamphene ring, isocamphene ring, tricyclodecane ring, tetracyclododecane ring, and adamantane ring.

[0070] Practical examples of the polymerizable compound (a-1) having a boiling point of 250 °C or higher are as follows, but the compound is not limited to these examples.

[0071] 3-Phenoxybenzyl acrylate (mPhOBzA, OP = 2.54, boiling point = 367.4 °C, vapor pressure at 80 °C = 0.0004 mmHg, molecular weight = 254.3)

[0072] 1-Naphthyl acrylate (NaA, OP = 2.27, boiling point = 317 °C, vapor pressure at 80 °C = 0.0422 mmHg, molecular weight = 198)

[0073] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP = 2.57, boiling point = 364.2 °C, vapor pressure at 80 °C = 0.0006 mmHg, molecular weight = 268.3)

[0074] 1-Naphthylmethyl acrylate (Na1MA, OP = 2.33, boiling point = 342.1 °C, vapor pressure at 80 °C = 0.042 mmHg, molecular weight = 212.2)

[0075] 2-Naphthylmethyl acrylate (Na2MA, OP = 2.33, boiling point = 342.1 °C, vapor pressure at 80 °C = 0.042 mmHg, molecular weight = 212.2)

[0076] DPhPA represented by the following formula (OP = 2.38, boiling point = 354.5 °C, vapor pressure at 80 °C = 0.0022 mmHg, molecular weight = 266.3)

[0077] PhBzA represented by the following formula (OP = 2.29, boiling point = 350.4 °C, vapor pressure at 80 °C = 0.0022 mmHg, molecular weight = 238.3)

[0078] FLMA represented by the following formula (OP = 2.20, boiling point = 349.3 °C, vapor pressure at 80 °C = 0.0018 mmHg, molecular weight = 250.3)

[0079] ATMA represented by the following formula (OP = 2.13, boiling point = 414.9 °C, vapor pressure at 80 °C = 0.0001 mmHg, molecular weight = 262.3)

[0080] DNaMA represented by the following formula (OP = 2.00, boiling point = 489.4 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 338.4)

[0081] BPh44DA represented by the following formula (OP = 2.63, boiling point = 444 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.3)

[0082] BPh43DA represented by the following formula (OP = 2.63, boiling point = 439.5 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.3)

[0083] DPhEDA represented by the following formula (OP = 2.63, boiling point = 410 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.3)

[0084] BPMDA represented by the following formula (OP = 2.68, boiling point = 465.7 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 364.4)

[0085] Na13MDA represented by the following formula (OP = 2.71, boiling point = 438.8 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 296.3)

[0086] The following formula (a-1-1) (OP = 2.40, boiling point = 333.4 °C, vapor pressure at 80 °C = 0.0181 mmHg, molecular weight = 199.2)

[0087] The following formula (a-1-2) (OP = 2.40, boiling point = 333.4 °C, vapor pressure at 80 °C = 0.0181 mmHg, molecular weight = 199.2)

[0088] The following formula (a-1-3) (OP = 1.86, boiling point = 369.5 °C, vapor pressure at 80 °C = 0.0053 mmHg, molecular weight = 193.3)

[0089] The following formula (a-1-4) (OP = 2.85, boiling point = 438.8 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 296.3)

[0090] The following formula (a-1-5) (OP = 2.71, boiling point = 438.8 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 296.3)

[0091] The following formula (a-1-6) (OP = 2.87, boiling point = 421.0 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 338.4)

[0092] The following formula (a-1-7) (OP = 2.87, boiling point = 465.2 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 338.4)

[0093] The following formula (a-1-8) (OP = 2.68, boiling point = 465.7 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 364.4)

[0094] The following formula (a-1-9) (OP = 2.50, boiling point = 433.1 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 320.3)

[0095] The following formula (a-1-10) (OP = 2.64, boiling point = 468.1 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 326.4)

[0096] The following formula (a-1-11) (OP = 3.25, boiling point = 553.4 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 358.4)

[0097] The following formula (a-1-12) (OP = 2.63, boiling point = 443.9 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.4)

[0098] The following formula (a-1-13) (OP = 2.89, boiling point = 509.3 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 406.4)

[0099] The following formula (a-1-14) (OP = 2.63, boiling point = 450.0 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.4)

[0100] The following formula (a-1-15) (OP = 3.00, boiling point = 476.5 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 366.4)

[0101] The following formula (a-1-16) (OP = 2.68, boiling point = 447.4 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 364.4)

[0102] The following formula (a-1-17) (OP = 2.36, boiling point = 543.8 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 398.5)

[0103] The following formula (a-1-18) (OP = 3.27, boiling point = 526.9 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 396.4)

[0104] The following formula (a-1-19) (OP = 2.71, boiling point = 333.7 °C, vapor pressure at 80 °C = 0.0302 mmHg, molecular weight = 244.3)

[0105] The following formula (a-1-20) (OP = 2.73, boiling point = 333.7 °C, vapor pressure at 80 °C = 0.0134 mmHg, molecular weight = 258.3)

[0106] The following formula (a-1-21) (OP = 2.71, boiling point = 319.2 °C, vapor pressure at 80 °C = 0.0566 mmHg, molecular weight = 262.3)

[0107] The following formula (a-1-22) (OP = 2.71, boiling point = 336.9 °C, vapor pressure at 80 °C = 0.0055 mmHg, molecular weight = 244.3)

[0108] The following formula (a-1-23) (OP = 3.00, boiling point = 370.9 °C, vapor pressure at 80 °C = 0.0021 mmHg, molecular weight = 274.4)

[0109] The following formula (a-1-24) (OP = 3.00, boiling point = 376.4 °C, vapor pressure at 80 °C = 0.0005 mmHg, molecular weight = 274.4)

[0110] The following formula (a-1-25) (OP = 3.00, boiling point = 379.4 °C, vapor pressure at 80 °C = 0.0002 mmHg, molecular weight = 288.4)

[0111] The following formula (a-1-26) (OP = 2.33, boiling point = 360.8 °C, vapor pressure at 80 °C = 0.0006 mmHg, molecular weight = 252.3)

[0112] The following formula (a-1-27) (OP = 2.54, boiling point = 371.5 °C, vapor pressure at 80 °C = 0.0003 mmHg, molecular weight = 254.3)

[0113] The following formula (a-1-28) (OP = 2.57, boiling point = 381.2 °C, vapor pressure at 80 °C = 0.0001 mmHg, molecular weight = 268.3)

[0114] The following formula (a-1-29) (OP = 2.57, boiling point = 381.8 °C, vapor pressure at 80 °C = 0.0004 mmHg, molecular weight = 268.3)

[0115] The following formula (a-1-30) (OP = 2.50, boiling point = 487.4 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 374.4)

[0116] The following formula (a-1-31) (OP = 2.67, boiling point = 417.2 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 268.3)

[0117] The following formula (a-1-32) (OP = 2.67, boiling point = 417.2 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 268.3)

[0118] The following formula (a-1-33) (OP = 2.67, boiling point = 417.2 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 268.3)

[0119] The following formula (a-1-34) (OP = 2.67, boiling point = 417.2 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 268.3)

[0120] The following formula (a-1-35) (OP = 2.71, boiling point = 438.8 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 296.3) <Compound (a-2): A polymerizable compound containing at least Si atoms>

[0121] The polymeric compound (a) according to the present disclosure may contain at least a polymeric compound (a-2) containing a Si atom. Further, if the polymeric compound (a) contains the polymeric compound (a-2), the curable composition (A) from which the solvent (d) has been removed preferably contains 10% by weight or more of Si atoms, relative to the entire curable composition (A).

[0122] As an example of the polymeric compound (a-2) containing at least a Si atom, it may have a linear structure or a branched structure. For example, as the cyclic siloxane compound, the following structure may be used. Examples of the polymerizable functional group in the group Q having a polymerizable functional group are free-radical polymerizable functional groups. Practical examples of the free-radical polymerizable functional group are (meth)acrylic groups, (meth)acrylamide groups, vinylbenzene groups, allyl ether groups, vinyl ether groups, and maleimide groups. The group Q having a polymerizable functional group only needs to be a group having the above polymerizable functional group.

[0123]

[0124] Other examples of the polymeric compound (a-2) are a silsesquioxane skeleton represented by the following chemical formula (I) and a silicone skeleton represented by chemical formula (II). In chemical formula (I), m + n = 8 (8 ≥ m ≥ 1), and R1 is a divalent organic group. Further, in chemical formula (II), A, B, R2, and R3 are independently an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, and a hydroxyl group having 1 to 6 carbon atoms, t is an integer of 1 to 3, and at least one of A and B is a polymerizable functional group.

[0125]

[0126] Examples of the polymerizable functional group in the group Q, A, and B having a polymerizable functional group are free-radical polymerizable functional groups. Detailed examples of the free-radical polymerizable functional group are (meth)acrylate-based compounds, (meth)acrylamide-based compounds, vinylbenzene-based compounds, aryl ether-based compounds, vinyl ether-based compounds, and maleimide-based compounds. The group Q having a polymerizable functional group may be a group having the above polymerizable functional group.

[0127] The silicon-containing (meth)acrylate-based compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of the silicon-containing monofunctional (meth)acrylate-based compound having one acryloyl group or methacryloyl group are as follows, but the compound is not limited to these examples.

[0128] (2-Acryloylethoxy)trimethylsilane, N-(3-Acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, Acryloxymethyltrimethoxysilane, (Acryloxymethyl)phenethyltrimethoxysilane, Acryloxymethyltrimethylsilane, (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-Acryloxypropyl)methyldichlorosilane, (3-Acryloxypropyl)methyldiethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trichlorosilane, (3-Acryloxypropyl)trimethoxysilane, (3-Acryloxypropyl)tris(trimethylsiloxy)silane, acryloxytriisopropylsilane, Acryloxytrimethylsilane, Methacryloxymethyltrimethoxysilane, O-(Methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (Methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-Methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (Methacryloxymethyl)methyldimethoxysilane, (Methacryloxymethyl)methyldiethoxysilane, Methacryloxymethylmethyldiethoxysilane, Methacryloxypropyltrimethoxysilane, Methacryloylpropyltriisopropoxysilane, O-(Methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, methacryloxypropylmethyldimethoxysilane, Methacryloxypropylmethyldiethoxysilane, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropylmethyldiethoxysilane, (Methacryloxymethyl)methyldiethoxysilane, Methacryloxypropyltriethoxysilane, Methacryloxypropylazatricyclosilane, Methacryloxypentamethyldisiloxane, (Methacryloxymethyl)phenylmethylsilane, Trimethylsilyl methacrylate, Methyltrimethylsilyl methacrylate, (3-Methacryloyloxy-2-hydroxypropoxypropyl)methylbis(trimethylsilyloxy)silane, Methacryloyloxypropylpentamethyldisiloxane, O-(Methacryloyloxyethyl)-3-[bis(trimethylsilyloxy)methylsilyl]propyl carbamate, Methyltrimethoxysilyl methacrylate, Methacryloyloxyethoxymethylsilane, (3-Methacryloyloxy-2-hydroxypropoxypropyl)methylbis(trimethylsilyloxy)silane, Methacryloyloxypropyltris(vinyldimethylsilyloxy)silane, Methacryloyloxypropyltris(trimethylsilyloxy)silane, 3-Methacryloyloxypropyltriacetoxysilane, Methacryloyloxypropylmethyldichlorosilane, Methacryloyloxypropyltrichlorosilane, 3-Methacryloyloxypropylbis(trimethylsilyloxy)methylsilane, 3-Methacryloyloxypropyldimethylchlorosilane, O-Methacryloyloxy(polyethyleneoxy)trimethylsilane, Poly(methacryloyloxypropylsilsesquioxane), Methacryloyloxypropylheptaisobutyl-T8-silsesquioxane, and Methacryloyloxypropyltris(trimethylsilyloxy)silane

[0129] Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0130] SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0, SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481.43, SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM6486.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM6491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, SIM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01 and SIM6486.65 (manufactured by GELEST), and TM-0701T, FM-0711, FM-0721 and FM-0725 (manufactured by JNC).

[0131] The silicon-containing (meth)acrylamide-based compound is a compound having one or more acrylamide groups or methacrylamide groups. Examples of the silicon-containing monofunctional (meth)acrylamide-based compound having one acrylamide group or methacrylamide group are as follows, but the compound is not limited to these examples.

[0132] 3-Acrylamidopropyltrimethoxysilane, and 3-acrylamidopropyltris(trimethylsilyloxy)silane

[0133] Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylamide compounds are as follows, but the products are not limited to these examples.

[0134] SIA0146.0 and SIA0150.0 (manufactured by GELEST)

[0135] Examples of polyfunctional (meth)acrylate compounds having two or more acryloyl or methacryloyl groups are as follows, but the compounds are not limited to these examples.

[0136] Linear polydimethylsiloxane modified with acryloxypropyl groups at both ends, Linear polydimethylsiloxane modified with methacryloxypropyl groups at both ends, Cyclic siloxane modified with multiple acryloxypropyl groups, Cyclic siloxane modified with multiple methacryloxypropyl groups, Sesquisiloxane modified with multiple acryloxypropyl groups, and Sesquisiloxane modified with multiple methacryloxypropyl groups

[0137] Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylate compounds are as follows, but the products are not limited to these examples.

[0138] SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (manufactured by GELEST), FM-7711, FM-7721, FM-7725 (manufactured by JNC), X-22-2445 (manufactured by Shin-Etsu Chemical), and AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SK SI-20 (manufactured by Toagosei)

[0139] In addition, according to, for example, Ogawa et al.'s "Ultraviolet curable branched siloxanes as low-k dielectrics for imprint lithography", the following substances can be synthesized and / or obtained.

[0140] Linear modified polydimethylsiloxane having methacryloxypropyl groups at both ends (MA-Si-12), 8-membered ring siloxane modified with four methacryloxypropyl groups (8-ring), and 10-membered ring siloxane modified with five methacryloxypropyl groups (10-ring).

[0141] With respect to the total of component (a), component (b) (described later), and component (c) (described later), that is, the total mass of all components except solvent (d), the mixing ratio of component (a) in the curable composition (A) is preferably 40% by weight or more and 99% by weight or less. The mixing ratio is more preferably 50% by weight or more and 95% by weight or less, and still more preferably 60% by weight or more and 90% by weight or less. When the mixing ratio of component (a) is 40% by weight or more, the mechanical strength of the cured film of the curable composition increases. In addition, when the mixing ratio of component (a) is 99% by weight or less, the mixing ratios of components (b) and (c) can be increased, thereby obtaining properties such as a high photopolymerization rate. At least a part of component (a) including one or more types of polymerizable compounds may be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a cyclic structure, such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, the polymer preferably contains at least one of the structural units represented by the following formulas (1) to (6):

[0142] In structures (1) to (6), the substituent R is a substituent containing a partial structure having an aromatic ring independently of each other, and R 1 is a hydrogen atom or a methyl group. In the present specification, in the structural units represented by structures (1) to (6), the part other than R is the main chain of a specific polymer. The molecular weight of the substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and still more preferably 150 or more. The upper limit of the molecular weight of the substituent R is actually 500 or less.

[0143] A polymer having a polymerizable functional group is usually a compound having a weight average molecular weight of 500 or more. The weight average molecular weight is preferably 1000 or more, and more preferably 2000 or more. The upper limit of the weight average molecular weight is not particularly determined, but is preferably 50000 or less, for example. When the weight average molecular weight is set above the above-mentioned lower limit, the boiling point can be set at 250°C or more, and the mechanical properties after curing can be further improved. In addition, when the weight average molecular weight is set below the above-mentioned upper limit, the solubility in the solvent increases, and the fluidity of the discretely arranged droplets is maintained because the viscosity is not too high. This makes it possible to further improve the flatness of the liquid film surface. Note that the weight average molecular weight (Mw) in the present disclosure is the molecular weight measured by gel permeation chromatography (GPC) unless otherwise specifically stated.

[0144] Actual examples of the polymerizable functional group of the polymer are (meth)acryloyl group, epoxy group, oxetanyl group, hydroxymethyl group, hydroxymethyl ether group, and vinyl ether group. From the viewpoint of ease of polymerization, the (meth)acryloyl group is particularly advantageous.

[0145] When a polymer having a polymerizable functional group is added as at least a part of the component (a), the mixing ratio can be freely set as long as the mixing ratio falls within the viscosity adjustment range described later. For example, the mixing ratio relative to the total mass of all components except the solvent (d) is preferably 0.1% by weight or more and 60% by weight or less, more preferably 1% by weight or more and 50% by weight or less, and still more preferably 10% by weight or more and 40% by weight or less. When the mixing ratio of the polymer having a polymerizable functional group is set to 0.1% by weight or more, heat resistance, dry etching resistance, mechanical strength, and low volatility can be improved. In addition, when the mixing ratio of the polymer having a polymerizable functional group is set to 60% by weight or less, the mixing ratio can be made to fall within the upper limit adjustment range of the viscosity (described later).

[0146] <Component (b): Photoinitiator> Component (b) is a photoinitiator. In this specification, a photoinitiator is a compound that senses light having a predetermined wavelength and generates the polymerization factor (radical) described above. More specifically, a photoinitiator is a polymerization initiator (radical generator) that generates radicals by light (infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams such as electron beams, or radiation). Component (b) can be formed of only one type of photoinitiator or can be formed of multiple types of photoinitiators.

[0147] Examples of radical generators are as follows, but radical generators are not limited to these examples.

[0148] 2,4,5-triaryl imidazole dimers which may have substituents, such as 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenyl imidazole dimer; benzophenone derivatives, such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 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, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; quinones, such as 2-ethylanthraquinone, phenanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 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, methyl benzoin, ethyl benzoin and propyl benzoin; benzyl derivatives, such as benzyl 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; acylphosphine oxide derivatives, such as 2,4,6-trimethylbenzoyl diphenylphosphine 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)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- and 1-(O-acetyl oxime); and 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.

[0149] Examples of commercially available products of the above radical generators are as follows, but the products are not limited to these examples.

[0150] Irgacure 184, 369, 651, 500, 819, 907, 784 and 2959, CGI-1700, -1750 and -1850, CG24-61, Darocur 1116 and 1173, TPO, LR8893 and LR8970 (manufactured by BASF), and Ubecryl P36 (manufactured by UCB).

[0151] Among the above radical generators, component (b) is preferably an acylphosphine oxide-based polymerization initiator. Note that among the above radical generators, the acylphosphine oxide-based polymerization initiators are as follows.

[0152] Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0153] Relative to the sum of component (a), component (b), and component (c) (described later), that is, the total mass of all components except the solvent (d), the mixing ratio of component (b) in the curable composition (A) is preferably 0.1% by weight or more and 50% by weight or less. Furthermore, relative to the total mass of all components except the solvent (d), the mixing ratio of component (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. When the mixing ratio of component (b) is set to 0.1% by weight or more, the curing rate of the composition increases, and thus the reaction efficiency can be improved. In addition, when the mixing ratio of component (b) is set to 50% by weight or less, a cured film having a certain mechanical strength can be obtained.

[0154] <Component (c): Non-polymerizable compound> In addition to the above components (a) and (b), the curable composition (A) of the present disclosure may further contain a non-polymerizable compound as component (c) within a range that does not impair the effects of the present disclosure. Examples of component (c) are compounds that do not contain polymerizable functional groups such as (meth)acryloyl and do not have the ability to sense light having a predetermined wavelength and generate the polymerization factor (radical) described above. Examples of non-polymerizable compounds are sensitizers, hydrogen donors, surfactants (c1), antioxidants, polymer components, and other additives. Component (c) may contain multiple types of the above compounds.

[0155] Sensitizers are compounds appropriately added to promote the polymerization reaction and improve the reaction conversion rate. As sensitizers, one type of compound may be used alone, or two or more types of compounds may be used in combination.

[0156] Examples of the sensitizer are sensitizing dyes. The sensitizing dye is a compound that is excited by absorbing light having a specific wavelength and interacts with the photopolymerization initiator as component (b). The "interaction" mentioned here is energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator as component (b). Practical examples of the sensitizing dye are as follows, but the sensitizing dye is not limited to these examples.

[0157] Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thianthrenium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyranium salt dyes.

[0158] The hydrogen donor is a compound that reacts with the initiating radical generated by the photopolymerization initiator as component (b) or the radical at the polymerization growing end to generate a radical with higher reactivity. When the photopolymerization initiator as component (b) is a photo radical generator, it is preferable to add a hydrogen donor.

[0159] Practical examples of the above hydrogen donor are as follows, but the hydrogen donor is not limited to these examples.

[0160] Amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiourea-p-toluenesulfonate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, N,N-dimethylaminoethyl benzoate, N,N-dimethylaminoisoamyl benzoate, pentyl-4-dimethylaminobenzoate, triethanolamine, and N-phenylglycine; and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

[0161] One type of hydrogen donor can be used alone, or two or more types of hydrogen donors can be used in combination. The hydrogen donor can also have the function of a sensitizer.

[0162] To reduce the interfacial bonding force between the mold and the curable composition, that is, to reduce the demolding force in the demolding step (described later), an internal mold release agent can be added to the curable composition. In this specification, "internal" means that the mold release agent is pre-added to the curable composition before the curable composition placement step. As the internal mold release agent, surfactants such as silicone surfactants, fluorosurfactants, and hydrocarbon surfactants can be used. Note that the internal mold release agent according to the present disclosure is non-polymerizable. One type of internal mold release agent can be used alone, or two or more types of internal mold release agents can be used in combination.

[0163] Fluorine-based surfactants include the following.

[0164] Polyalkylene oxide (e.g., polyethylene oxide or polypropylene oxide) adducts of alcohols having perfluoroalkyl groups, and polyalkylene oxide (e.g., polyethylene oxide or polypropylene oxide) adducts of perfluoropolyethers.

[0165] Note that the fluorine-based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, or a thiol group in a part of the molecular structure (e.g., the terminal group). An example is pentadecaethylene glycol monoperfluoro-1H,1H,2H,2H-octyl ether.

[0166] Commercially available products can also be used as the fluorine-based surfactant. Examples of commercially available products of fluorine-based surfactants are as follows.

[0167] F-444, TF-2066, TF-2067, and TF-2068, and DEO-15 (abbreviation) (manufactured by DIC); Fluorad FC-430 and FC-431 (manufactured by Sumitomo 3M); S-382 (manufactured by AGC); EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, and MF-100 (manufactured by Tochem Products); PF-636, PF-6320, PF-656, and PF-6520 (manufactured by OMNOVA Solutions); DS-401, DS-403, and DS-451 (manufactured by Daikin); 250, 251, 222F, and 208G (manufactured by NEOS).

[0168] The surfactant (c1) can also be a hydrocarbon surfactant. Hydrocarbon surfactants include: alkyl alcohol-polyalkylene oxide adducts obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms, and polyalkylene oxides.

[0169] Examples of the alkyl alcohol-polyalkylene oxide adducts are as follows.

[0170] Methanol-ethylene oxide adduct, decanol-ethylene oxide adduct, lauryl alcohol-ethylene oxide adduct, cetyl alcohol-ethylene oxide adduct, stearyl alcohol-ethylene oxide adduct, and stearyl alcohol-ethylene oxide / propylene oxide adduct.

[0171] Note that the terminal group of the alkyl alcohol-polyalkylene oxide adduct is not limited to a hydroxyl group, and this hydroxyl group can be produced by simply adding the polyalkylene oxide to the alkyl alcohol. This hydroxyl group can also be substituted with a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or with a hydrophobic group such as an alkyl group or an alkoxy group.

[0172] Examples of the polyalkylene oxides are as follows.

[0173] Polyethylene glycol, polypropylene glycol, their monomethyl ethers or dimethyl ethers, monooctyl ethers or dioctyl ethers, monononyl ethers or dinonyl ethers, and monotridecyl ethers or ditridecyl ethers, monoadipates, monooleates, monostearates, and monosuccinates.

[0174] Commercially available products can also be used as the alkyl alcohol-polyalkylene oxide adducts. Examples of the commercially available products of the alkyl alcohol-polyalkylene oxide adducts are as follows.

[0175] Polyoxyethylene methyl ether (methanol-ethylene oxide adduct) (BLAUNON MP-400, MP-550, and MP-1000) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene decyl ether (decanol-ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, and D-1310) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol-ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol-ethylene oxide adduct) (BLAUNON CH-305 and CH-310) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol-ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, and SR-750) manufactured by Aoki Yushi Kogyo Co., Ltd., random-polymerized polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R and SA-30 / 70 2000R) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene methyl ether A760E) manufactured by BASF, and polyoxyethylene alkyl ether (EMULGEN series) manufactured by Kao Corporation.

[0176] Commercially available products can also be used as the polyalkylene oxide. An example is an ethylene oxide / propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0177] Examples of the silicone surfactant are as follows. For example, products named SI-10 series (manufactured by Takemoto Yushi), MEGAFACE Paintad 31 (manufactured by DIC), and KP-341 (manufactured by Shin-Etsu Chemical) can be used.

[0178] The surfactant can contain at least both fluorine atoms and silicon atoms. Examples of the surfactant containing both fluorine atoms and silicon atoms are as follows.

[0179] Product names X-70-090, X-70-091, X-70-092, X-70-093 (manufactured by Shin-Etsu Chemical), and product names MEGAFACE R-08 and XRB-4 (manufactured by DIC)

[0180] With respect to the total of components (a), (b), and (c), that is, the total mass of all components except the solvent (d), the mixing ratio of component (c) other than the surfactant in the curable composition (A) is preferably 0.01% by weight or more and 50% by weight or less. With respect to the total mass of all components except the solvent (d), the mixing ratio of component (c) other than the surfactant in the curable composition (A) is more preferably 0.01% by weight or more and 50% by weight or less, and further preferably 0.01% by weight or more and 20% by weight or less. When the mixing ratio of component (c) other than the surfactant is set to 50% by weight or less, a cured film having a certain mechanical strength can be obtained.

[0181] <Component (d): Solvent> The curable composition (A) of the present disclosure may contain a solvent having a boiling point of 100 °C or higher and lower than 250 °C at normal pressure as component (d). Component (d) is a solvent that dissolves components (a), (b), and (c). Examples are alcoholic solvents, ketone solvents, ether solvents, and nitrogen-containing solvents. As component (d), one type of component may be used alone, or two or more types of components may be used in combination. The boiling point of component (d) at normal pressure is 100 °C or higher, preferably 140 °C or higher, and particularly preferably 150 °C or higher. The boiling point of component (d) at normal pressure is lower than 250 °C, preferably lower than 200 °C. If the boiling point of component (d) at normal pressure is lower than 100 °C, the volatilization rate in the waiting step described later is too high. Therefore, component (d) may volatilize before the droplets of the curable composition (A) combine with each other, so that the droplets of the curable composition (A) may not be able to combine with each other. In addition, if the boiling point of component (d) at normal pressure is 250 °C or higher, the volatilization of solvent (d) may be insufficient in the waiting step described later, so that component (d) remains in the cured product of the curable composition (A). Here, if component (d) includes one or more solvents, each of the one or more solvents preferably has a boiling point of 100 °C or higher and lower than 250 °C (for example, 100 °C or higher and lower than 200 °C).

[0182] Examples of alcoholic solvents are as follows.

[0183] Monoalcoholic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 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-nonanol, 2,6-dimethylheptan-4-ol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzhydrol, diacetone alcohol, and cresol; and polyalcoholic solvents such as ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0184] Examples of ketone solvents are as follows.

[0185] Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl-n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenthion.

[0186] Examples of ether solvents are as follows.

[0187] Diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexyloxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monon-butyl ether, diethylene glycol dibutyl ether, diethylene glycol monon-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol dibutyl 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, and 2-methyltetrahydrofuran.

[0188] Examples of ester solvents are as follows.

[0189] Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl 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, diethylene glycol monon-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isopentyl propionate, diethyl oxalate, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0190] Examples of nitrogen-containing solvents are as follows.

[0191] N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone.

[0192] Among the above solvents, ether solvents and ester solvents are advantageous. Note that, from the viewpoint of good film-forming properties, ether solvents and ester solvents each having a glycol structure are more advantageous.

[0193] Other advantageous examples of the solvent are as follows.

[0194] Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0195] A particularly advantageous example is propylene glycol monomethyl ether acetate. Note that (ethyl) isocyanurate di(meth)acrylate is also advantageous.

[0196] In the present disclosure, an advantageous solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure. More specifically, the advantageous solvent is a solvent or a solvent mixture selected from propylene glycol monomethyl ether acetate (boiling point = 146 °C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate.

[0197] In the present disclosure, a polymerizable compound having a boiling point of 80 °C or higher and lower than 250 °C under normal pressure can also be used as component (d). Examples of the polymerizable compound having a boiling point of 80 °C or higher and lower than 250 °C under normal pressure are as follows.

[0198] Cyclohexyl acrylate (boiling point = 198 °C), benzyl acrylate (boiling point = 229 °C), isobornyl acrylate (boiling point = 245 °C), tetrahydrofurfuryl acrylate (boiling point = 202 °C), trimethylcyclohexyl acrylate (boiling point = 232 °C), isooctyl acrylate (217 °C), n-octyl acrylate (boiling point = 228 °C), ethoxyethoxyethyl acrylate (boiling point = 230 °C), divinylbenzene (boiling point = 193 °C), 1,3-diisopropenylbenzene (boiling point = 218 °C), styrene (boiling point = 145 °C), and α-methylstyrene (boiling point = 165 °C).

[0199] In the present disclosure, when the total amount of the curable composition (A) is 100% by volume, the content of the solvent (d) can be greater than 5% by volume and 95% by volume or less, preferably 15% by volume or more and 85% by volume or less, and more preferably 40% by volume or more and 80% by volume or less. For example, the content of the solvent (d) can be 40% by volume or more and 85% by volume or less. If the content of the solvent (d) is less than 5% by volume, it is difficult to obtain a thin film after the solvent (d) has volatilized under conditions where a substantially continuous liquid film can be obtained. On the other hand, if the content of the solvent (d) is greater than 95% by volume, it is difficult to obtain a thick film even if droplets are closely dropped by an inkjet method after the solvent (d) has volatilized.

[0200] <Temperature at the time of mixing the curable composition> When preparing the curable composition (A) of the present disclosure, at least the components (a), (b), and (d) are mixed and dissolved under predetermined temperature conditions. More specifically, the predetermined temperature conditions may be 0°C or higher and 100°C or lower. Note that this also applies to the case where the curable composition (A) contains the component (c).

[0201] <Viscosity of curable component> The curable composition (A) of the present disclosure is a liquid. This is because the droplets of the curable composition (A) are discretely dropped on the substrate by an inkjet method. The viscosity of the curable composition (A) of the present disclosure is 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm, preferably 2 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less. If the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection characteristics of the droplets by the inkjet method may be unstable. In addition, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is difficult to form droplets having a volume of about 1.0 to 3.0 pL, which is advantageous in the present disclosure.

[0202] At 23°C and 1 atm, the viscosity μ of the non-volatile composition (A') of the present disclosure is preferably 20 mPa·s or more and 135 mPa·s or less. In addition, regarding the non-volatile composition (A'), the viscosity at 23°C and 1 atm is more preferably 40 mPa·s or more and 100 mPa·s or less, and further preferably 60 mPa·s or more and 80 mPa·s or less. Note that if the viscosity is low, for example, less than 20 mPa·s, the fluidity of the non-volatile composition (A') is high, and when the non-volatile composition (A') and the mold come into contact with each other, the non-volatile composition (A') easily flows out from the end of the mold, resulting in a short extrusion allowance time. If the viscosity is greater than 135 mPa·s, the fluidity of the non-volatile composition (A') is low, and when the non-volatile composition (A') and the mold come into contact with each other, the edge filling speed is low. Therefore, when using the curable composition (A) of the present disclosure obtained by adjusting the viscosity of the non-volatile composition (A') to 20 mPa·s or more and 135 mPa·s or less, the imprinting process can be carried out with high productivity, and defects on the substrate caused by extrusion can be suppressed.

[0203] <Surface tension of curable composition> At 23°C and 1 atm, the surface tension γ1 of the non-volatile composition (A') of the present disclosure is preferably 5 mN / m or more and 70 mN / m or less. Further, at 23°C and 1 atm, the surface tension of the composition containing components other than the solvent (component (d)) is more preferably 7 mN / m or more and 50 mN / m or less, and even more preferably 10 mN / m or more and 40 mN / m or less. Note that when the surface tension is high, for example, 5 mN / m or more, the capillary action is strong. Therefore, when the non-volatile composition (A') and the mold come into contact with each other, filling (spreading and filling) is completed in a short period of time. Further, when the surface tension is 70 mN / m or less, the cured film obtained by curing the curable composition has surface smoothness.

[0204] <Contact angle of the curable composition> The contact angle of the curable composition (A) of the present disclosure with respect to the substrate surface is preferably 0° or more and 90° or less. If the contact angle is greater than 90°, the droplets on the substrate do not come into contact with each other, and a continuous liquid film cannot be formed.

[0205] The contact angle of the non-volatile composition (A') of the present disclosure with respect to the substrate surface and the mold surface is preferably 0° or more and 90° or less. If the contact angle is greater than 90°, the capillary force acts in the negative direction (the direction in which the contact interface between the mold and the curable composition shrinks) within the mold pattern or in the gap between the substrate and the mold, and the non-volatile composition (A') does not fill into the mold. When the contact angle is small, the capillary action is strong, and the filling speed increases.

[0206] <Impurities mixed into the curable composition> The curable composition (A) of the present disclosure preferably contains as few impurities as possible. Note that impurities refer to components other than the above components (a), (b), (c), and (d). Therefore, the curable composition (A) of the present disclosure is advantageously a composition obtained through a purification step. Such a purification step is preferably filtration using a filter.

[0207] As such filtration using a filter, it is advantageous to mix the above components (a), (b) and (c) and filter the mixture by using a filter having a pore size of 0.001 μm or more and 5.0 μm or less, for example. When filtering using a filter, it is further advantageous to perform filtration in multiple stages or to repeat filtration a plurality of times (circulation filtration). It is also possible to filter the liquid again after filtering through a filter or to filter using filters having different pore sizes. Examples of the filter for filtration are filters made of, for example, polyethylene resin, polypropylene resin, fluororesin and nylon resin, but the filter is not particularly limited. Impurities (such as particles) mixed in the curable composition can be removed by the above purification step. Therefore, it is possible to prevent pattern defects caused by the impurities mixed in the curable composition from forming accidental unevenness on the cured film obtained after curing the curable composition.

[0208] Note that when manufacturing a semiconductor integrated circuit using the curable composition of the present disclosure, it is advantageous to avoid mixing impurities containing metal atoms (metal impurities) in the curable composition as much as possible so as not to hinder the operation of the product. The concentration of metal impurities contained in the curable composition is preferably 10 ppm or less, more preferably 100 ppb or less.

[0209] <Glass transition temperature of the curable composition> If the glass transition temperature (Tg) is much higher than the temperature at the time of demolding, the cured product at the time of demolding exhibits a rigid glass state, that is, high mechanical strength. Therefore, almost no pattern collapse or damage caused by the impact of demolding occurs. Therefore, when performing the demolding step at room temperature, the glass transition temperature of the cured product (cured film) of the non-volatile composition (A') is preferably 70 °C or higher, more preferably 100 °C or higher, and particularly preferably 150 °C or higher.

[0210] As a method for measuring the glass transition temperature of the cured product (photo-cured product), a method of measuring using differential scanning calorimetry (DSC) or a dynamic viscoelasticity measuring device can be applied. For example, the glass transition temperature can be measured using DSC as follows.

[0211] (1) Obtain the intersection between the following two lines: a line obtained by extending the baseline on the low-temperature side of the DSC curve of the cured product (the part of the DSC curve in the temperature region where neither transition nor reaction occurs in the specimen) to the high-temperature side, and a tangent drawn at the point where the gradient of the curve in the stepwise change part of the glass transition is maximum.

[0212] (2) From the obtained intersection, obtain the extrapolated glass transition start temperature (Tig) as the glass transition temperature.

[0213] Examples of the main equipment include STA-6000 (manufactured by Perkin-Eimer). On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity measuring device, the temperature at which the loss sine (tanδ) of the cured product is maximum is defined as the glass transition temperature. Examples of the main equipment for measuring dynamic viscoelasticity include MCR301 (manufactured by Anton Paar).

[0214] [Substrate] In this specification, the member on which the droplets of the curable composition (A) are discretely dropped is described as a substrate.

[0215] This substrate is a substrate to be processed, and a silicon wafer is usually used. The substrate may have a layer to be processed on its surface. On the substrate, another layer may also be formed under the layer to be processed. When a quartz substrate is used as the substrate, a replica (replicated mold) of the imprint mold can be manufactured. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate can be freely selected from those known in semiconductor device substrates, such as aluminum, titanium tungsten alloy, aluminum silicon alloy, aluminum copper silicon alloy, silicon oxide, and silicon nitride. Note that it is preferable to treat the surface of the substrate or the layer to be processed by surface treatments such as silane coupling treatment, silicon nitride treatment, or organic thin film deposition, so as to improve the adhesion to the curable composition (A). Practical examples of the organic thin film to be deposited as the surface treatment can use the adhesion layer described in Japanese Patent Laid-Open No. 2009-503139.

[0216] [Pattern formation method] The pattern formation method according to the present disclosure will be described with reference to Figures 1A to 1G The cured film formed by the present disclosure is preferably a film having a pattern with a size of 1 nm or more and 10 mm or less, more preferably a film having a pattern with a size of 10 nm or more and 100 μm or less. Generally, a film formation method of forming a film having a pattern (concavo-convex structure) with a nano size (1 nm or more and 100 nm or less) using light is called a nanoimprint method. The film formation method of the present disclosure forms a film of the curable composition in the space between the mold and the substrate by using a photoimprint method. However, the curable composition can also be cured by other energies (for example, heat or electromagnetic waves). The film formation method of the present disclosure can be carried out as a method of forming a film having a pattern, that is, as a pattern formation method, or the film formation method can also be carried out as a method of forming a film without a pattern (for example, a planarizing film), that is, as a planarizing film formation method.

[0217] Examples of applying the film-forming method of the present disclosure to a pattern-forming method will be described below. The pattern-forming method includes, for example, a forming step, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step (separation step). The forming step is a step of forming an underlying layer. The disposing step is a step of discretely disposing droplets of the curable composition (A) on the underlying layer. The waiting step is a step of waiting until the droplets of the curable composition (A) are combined with each other and the solvent (d) evaporates. The contacting step is a step of bringing the curable composition (A) into contact with the mold. The curing step is a step of curing the curable composition (A). The demolding step is a step of detaching the mold from the cured film of the curable composition (A). The disposing step is performed after the forming step, the waiting step is performed after the disposing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0218] <Disposing step> In the disposing step, as Figure 1A schematically shown, droplets 102 of the curable composition (A) are discretely disposed on a substrate 101. In the disposing step, droplets 102 of the curable composition (A) having a volume of 1.0 pL or more are disposed at a density of 80 droplets / mm 2 or more. As the substrate 101, a substrate on which an underlying layer is stacked can also be used as the substrate 101. Further, the adhesion of the surface of the substrate 101 to the curable composition (A) can be improved by surface treatment such as silane coupling treatment, silicon nitride treatment, or deposition of an organic thin film.

[0219] The inkjet method is particularly advantageous as a method of disposing droplets 102 of the curable composition (A) on the substrate. It is advantageous to dispose the droplets 102 of the curable composition (A) densely on the region of the substrate 101 where recesses where the pattern of the forming mold 106 is dense are present, and sparsely on the region of the substrate 101 where recesses where the pattern of the forming mold 106 is sparse are present. Accordingly, the film (residual film) 109 of the curable composition (A) formed on the substrate 101 (described later) is controlled to have a uniform thickness regardless of the sparseness and density of the pattern of the mold 106.

[0220] An index called the average liquid film thickness is defined to specify the volume of the non-volatile composition (A') to be disposed. The average liquid film thickness is a value obtained by dividing the volume of the non-volatile composition (A') to be disposed in the disposing step by the area of the film-forming region of the mold. The volume of the non-volatile composition (A') is the sum of the volumes of the respective droplets of the curable composition (A) after the solvent (d) has volatilized. According to this definition, even when the substrate surface is uneven, the average liquid film thickness can be specified regardless of the uneven state. Here, the average liquid film thickness can be understood as a value obtained by dividing the volume of the non-volatile composition (A') remaining after the waiting step described later by the area of the film-forming region of the mold, and is preferably 5 nm or more and 170 nm or less.

[0221] <Waiting step> In the present disclosure, a waiting step is provided after the disposing step and before the contacting step, in which processing is waited until the coalescence of the plurality of droplets on the substrate proceeds and the volatilization of the solvent contained in the liquid film proceeds. Here, a value obtained by dividing the total volume of the droplets of the curable composition (A) dropped in a single pattern formation by the total area of the region (pattern-forming region) where the pattern is formed in a single pattern formation is defined as the average initial liquid film thickness. In the waiting step, as Figure 1B schematically shown, the droplets 102 of the curable composition (A) spread on the substrate 101. Accordingly, the entire pattern-forming region of the substrate 101 is covered with the curable composition (A), as Figure 1C schematically shown.

[0222] Reference will be made to Figures 2A to 2D to describe the flow behavior of the droplets of the curable composition (A) disposed on the substrate during the waiting step. The droplets 102 of the curable composition (A) are discretely disposed on the substrate 101, as Figure 2A shown, and each droplet 102 gradually spreads on the substrate, as Figure 2B shown. Then, the droplets of the curable composition (A) on the substrate start to coalesce with each other to form a liquid film, as Figure 2C shown; and a continuous liquid film (the surface of the substrate 101 is covered with the curable composition (A) and there is no longer an exposed surface) is formed, as Figure 2D shown. The state of the curable composition (A) as Figure 2D shown is referred to as a "substantially continuous liquid film".

[0223] Furthermore, as Figure 1DAs shown schematically, the solvent 105 (solvent (d)) contained in the liquid film 104 evaporates during the waiting step. Assuming that the total weight of the components other than the solvent (d) (i.e., the entire liquid film) is 100% by volume, the residual amount of the solvent (d) in the liquid film 103 after the waiting step (e.g., at the start of the contact step) is preferably 10% by volume or less. If the residual amount of the solvent (d) is greater than 10% by volume, the mechanical properties of the cured film will deteriorate.

[0224] During the waiting step, a baking step of heating the substrate 101 and the curable composition (A) can be performed, or the atmosphere gas around the substrate 101 can be ventilated to accelerate the evaporation of the solvent (d). Heating is performed at a temperature of, for example, 30°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 110°C or lower. The heating time can be 10 seconds or longer and 600 seconds or shorter. The baking step can be performed by using a known heater (e.g., a hot plate or an oven).

[0225] The waiting time of the waiting step is, for example, 0.1 to 600 seconds (sec), preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 second, the bonding of the droplets of the curable composition (A) becomes insufficient, and thus a substantially continuous liquid film cannot be formed. If the waiting step exceeds 600 seconds, the productivity decreases. Therefore, in order to suppress the decrease in productivity, the substrates that have been completely processed in the arrangement step can also be sequentially moved to the waiting step, the waiting step can be performed in parallel on a plurality of substrates, and the substrates that have been completely processed in the waiting step can be sequentially moved to the contact step. Note that in the prior art, theoretically, several thousand seconds to several tens of thousands of seconds are required before forming a substantially continuous liquid film. However, in practice, due to the influence of evaporation, the expansion of the droplets of the curable composition stagnates, and thus a continuous liquid film cannot be formed.

[0226] When the solvent (d) evaporates during the waiting step, a substantially continuous liquid film 104 containing the non-volatile composition (A') of the components (a), (b), and (c) is left. Due to the evaporation amount of the solvent (d), the average liquid film thickness of the substantially continuous liquid film 104 from which the solvent (d) evaporates (is removed) becomes smaller than the liquid film 103. The following state is maintained throughout the region: the entire pattern formation region of the substrate 101 is covered with the substantially continuous liquid film 104 of the curable composition (A) from which the solvent (d) has been removed.

[0227] <Contact step> In the contact step, as Figure 1EAs shown schematically, the mold 106 is brought into contact with a substantially continuous liquid film 104 of the curable composition (A) from which the solvent (d) has been removed (i.e., the non-volatile composition (A')). The contacting step includes a step of changing the state in which the non-volatile composition (A') and the mold 106 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. Thus, the liquid of the non-volatile composition (A') is filled into the recesses of the fine pattern on the surface of the mold 106, and the liquid forms a liquid film filled in the fine pattern of the mold 106.

[0228] The contacting step can be carried out under any conditions such as a normal air atmosphere, a reduced-pressure atmosphere, and an inert gas atmosphere, and is preferably carried out under a reduced-pressure atmosphere or an inert gas atmosphere because oxygen or water can be prevented from affecting the curing reaction. Practical examples of the inert gas used when carrying out the contacting step under an inert gas atmosphere are nitrogen, carbon dioxide, helium, argon, various Freon gases, and gas mixtures thereof. A gas containing 10% or more in molar ratio of carbon dioxide or helium is preferred, and a gas containing 10% or more in molar ratio of carbon dioxide is particularly preferred. Since helium easily diffuses into the mold, the substrate, the curable composition, etc., the atmosphere gas enclosed in the mold pattern quickly disappears. Since carbon dioxide easily dissolves into the curable composition or the underlying layer on the substrate, the atmosphere gas enclosed in the mold pattern quickly disappears. The solubility coefficient of carbon dioxide in the curable composition is preferably 0.5 kg / m 3 ·atm or more and 10 kg / m 3 ·atm or less. Details are disclosed in Japanese Patent Publication No. 2022-99271. When carrying out the contacting step under a specific gas atmosphere (including a normal air atmosphere), the pressure is preferably 0.0001 atm or more and 10 atm or less.

[0229] In the present disclosure, in the waiting step, the curable composition (A) forms a substantially continuous liquid film 104 of the non-volatile composition (A') from which the solvent (d) has been removed. Therefore, the volume of the gas involved between the mold 106 and the substrate 101 becomes smaller. Thus, the spreading of the non-volatile composition (A') is quickly completed in the contacting step.

[0230] When the spreading and filling of the non-volatile composition (A') are quickly completed in the contacting step, the time required to maintain the state in which the mold 106 is in contact with the non-volatile composition (A') (the time required for the contacting step) can be shortened. Since shortening the time required for the contacting step results in shortening the time required for pattern formation (film formation), the productivity is improved. The contacting step is preferably 0.1 second or more and 3 seconds or less, and particularly preferably 0.1 second or more and 1 second or less. If the contacting step is shorter than 0.1 second, the spreading and filling become insufficient, and thus many defects called incomplete filling defects tend to occur.

[0231] Let μ [mPa·s] be the viscosity of the non-volatile composition (A'). Let h [m] be the average liquid film thickness when droplets of the non-volatile composition (A') combine with each other to form a substantially continuous liquid film 104. At this time, in the present embodiment, h is calculated such that the viscosity μ [mPa·s] and the average liquid film thickness h [m] formed by the non-volatile composition satisfy the following Expressions 1 and 2. Expression 1: 20 [μm / sec] ≤ C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s], and Expression 2: 0.5 [sec] ≤ C·h α ·μ / μ 0， C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s].

[0232] Let v [m / sec] be the edge filling speed, that is, the speed at which the non-volatile composition (A') spreads over the entire area of the gap between the substrate 101 and the mold 106, and t [seconds] be the extrusion grace time, that is, the time until extrusion occurs. At this time, if the viscosity μ [mPa·s] and the average liquid film thickness h [m] satisfy the above Expressions 1 and 2, then v is 20 [μm / sec] or more, and t is 0.5 [seconds] or more.

[0233] In the present disclosure, in the contact step, the time for maintaining the state of contact between the mold 106 and the non-volatile composition (A') (the time required for the contact step) can be shortened. Since shortening the time required for the contact step results in shortening the time required for pattern formation (film formation), the productivity (production volume) is improved. The contact step is preferably 0.1 second or more and 3 seconds or less, and particularly preferably 0.1 second or more and 1 second or less. If the contact step is shorter than 0.1 second, edge filling is insufficient, resulting in many defects called incomplete filling defects.

[0234] As described above, a phenomenon called extrusion may occur in the contact step. This is a phenomenon in which the non-volatile composition (A') protrudes from the contact surface of the mold 106 and adheres to (climbs up) the side wall (side surface) of the mold during the contact step. The concept of extrusion will be described with reference to Figure 3 as Figure 4As shown, the protrusion of the non-volatile composition (A') from the mold 106 is a factor in so-called extrusion (defects), which occurs when it climbs up the side wall of the mold 106 and forms an unnecessary cured product of the non-volatile composition (A') (as a defect) outside the contact surface of the mold 106. Here, the higher the viscosity of the non-volatile composition (A'), the more it can prevent unnecessary flow. When the non-volatile composition (A') and the mold 106 are brought into contact with each other, the non-volatile composition (A') hardly flows out from the end of the mold 106, and the extrusion allowance time becomes longer. On the other hand, when the non-volatile composition (A') and the mold 106 are brought into contact with each other, the fluidity of the non-volatile composition (A') is low, and the edge filling speed is low. Note that the height at which the non-volatile composition (A') climbs up the side wall of the mold 106 is defined as the extrusion height.

[0235] Therefore, when using the non-volatile composition (A') of the present disclosure, the imprinting process can be performed with high productivity (production volume), and defects on the substrate caused by extrusion can be suppressed.

[0236] When the curing step includes a light irradiation step, in view of this, a mold made of a light-transmitting material is used as the mold 106. Advantageous practical examples of the material type for forming the mold 106 are glass, quartz, PMMA, light-transmitting resins (such as polycarbonate resins), transparent metal deposition films, soft films (such as polydimethylsiloxane), photocurable films, and metal films. When using a light-transmitting resin as the material for forming the mold 106, a resin that is insoluble in the components contained in the curable composition is selected. Quartz is suitable as the material for forming the mold 106 because of its small thermal expansion coefficient and small pattern distortion.

[0237] The height of the pattern formed on the surface of the mold 106 is, for example, 4 nm or more and 200 nm or less. As the pattern height of the mold 106 decreases, the force for detaching the mold 106 from the cured film of the curable composition, that is, the demolding force in the demolding step, can be reduced, which makes it possible to reduce the number of demolding defects remaining in the mold 106 due to the pattern of the curable composition being torn off. In addition, in some cases, the pattern of the curable composition is elastically deformed due to the impact during demolding, and adjacent pattern elements come into contact with each other and adhere to or damage each other. Note that in order to avoid these inconveniences, it is advantageous that the height of the pattern element is about twice or less the width of the pattern element (the aspect ratio is 2 or less). On the other hand, if the height of the pattern element is too small, the processing accuracy of the substrate 101 decreases.

[0238] To improve the peelability of the mold 106 with respect to the curable composition (A), the mold 106 may be surface-treated before the contacting step. Examples of such surface treatment are forming a release agent layer by coating the surface of the mold 106 with a release agent. Examples of the release agent applied to the surface of the mold 106 are silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montane-based release agents, and palm wax-based release agents. Commercially available coating-type release agents, such as DSX manufactured by Daikin, can also be used appropriately. Note that one type of release agent can be used alone, or two or more types of release agents can be used in combination. Among the above release agents, fluorine-based and hydrocarbon-based release agents are particularly advantageous. DSX. Note that one type of release agent can be used alone, or two or more types of release agents can be used in combination. Among the above release agents, fluorine-based and hydrocarbon-based release agents are particularly advantageous.

[0239] In the contacting step, when the mold 106 is brought into contact with the non-volatile composition (A'), the pressure applied to the curable composition (A') is not particularly limited and can be, for example, 0 MPa or more and 100 MPa or less. When the mold 106 is brought into contact with the non-volatile composition (A'), the pressure applied to the curable composition (A) is preferably 0 MPa or more and 50 MPa or less. The pressure applied to the curable composition (A) is more preferably 0 MPa or more and 30 MPa or less, and further preferably 0 MPa or more and 20 MPa or less.

[0240] The contacting step can be carried out in any of a normal air atmosphere, a reduced-pressure atmosphere, and an inert gas atmosphere. However, a reduced-pressure atmosphere or an inert gas atmosphere is advantageous because it can prevent the influence of oxygen or water on the curing reaction. Practical examples of the inert gas used when carrying out the contacting step in an inert gas atmosphere are nitrogen, carbon dioxide, helium, argon, various Freon gases, and gas mixtures thereof. A gas containing 10% or more in molar ratio of carbon dioxide or helium is preferred, and a gas containing 10% or more in molar ratio of carbon dioxide is particularly preferred. Since helium easily diffuses into the mold, substrate, curable composition, etc., the atmosphere gas enclosed in the mold pattern quickly disappears. Since carbon dioxide easily dissolves into the curable composition or the underlying layer on the substrate, the atmosphere gas enclosed in the mold pattern quickly disappears (see Japanese Patent Publication No. 2022-99271). When the contacting step is carried out in a specific gas atmosphere including a normal air atmosphere, a favorable pressure is 0.0001 atm or more and 10 atm or less.

[0241] <Curing step> In the curing step, as Figure 1FAs schematically shown, the nonvolatile composition (A') is cured by irradiation with irradiation light 107 as curing energy, thereby forming a cured film. In the curing step, for example, the transmissive mold 106 irradiates the nonvolatile composition (A') with the irradiation light 107. More specifically, the transmissive mold 106 irradiates the nonvolatile composition (A') filled in the fine pattern of the mold 106 with the irradiation light 107. Accordingly, the nonvolatile composition (A') filled in the fine pattern of the mold 106 is cured, and a cured film 108 having the pattern is formed.

[0242] The irradiation light 107 is selected according to the sensitivity wavelength of the nonvolatile composition (A'). More specifically, the irradiation light 107 is suitably selected from ultraviolet light, X-rays, and electron beams, each having a wavelength of 150 nm or more and 400 nm or less. Note that the irradiation light 107 is particularly preferably ultraviolet light. This is because many commercially available compounds as curing aids are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light are high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep ultraviolet lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. Note that an ultra-high-pressure mercury lamp is particularly advantageous as a light source that emits ultraviolet light. One light source or a plurality of light sources can be used. The light can be emitted to the entire region of the curable composition (A) filled in the fine pattern of the mold, or only to a partial region thereof (by restricting the region). The light can also be intermittently emitted to the entire region of the substrate a plurality of times, or continuously emitted to the entire region of the substrate. In addition, in the first irradiation process, the first region of the substrate can be irradiated with light, and in the second irradiation process, the second region different from the first region of the substrate can be irradiated with light.

[0243] <Demolding step> In the demolding step, as Figure 1G schematically shown, the mold 106 is detached from the cured film 108. When the mold 106 is detached from the cured film 108 having the pattern, a cured film 108 having a pattern formed by inverting the fine pattern of the mold 106 is obtained in an independent state. In this state, a residual film remains in the concave portion of the cured film 108 having the pattern. This film is called a residual film.

[0244] The method of detaching the mold 106 from the cured film 108 having the pattern can be any method as long as the method does not physically damage the patterned portion of the cured film 108 during the demolding process, and various conditions and the like are not particularly limited. For example, the substrate 101 can be fixed and the mold 106 can be removed from the substrate 101. The mold 106 can also be fixed and the substrate 101 can be removed from the mold 106. In addition, by moving both the mold 106 and the substrate 101 in completely opposite directions, the mold 106 can be detached from the cured film 108 having the pattern.

[0245] <Duplicate> A series of steps (manufacturing process) having the above steps, in the order from the placement step to the demolding step, such that a cured film having a desired concavo-convex pattern shape (a pattern shape conforming to the concavo-convex shape of the mold 106) can be obtained at a desired position.

[0246] In the pattern forming method of the present disclosure, the repeating unit (shot) from the placement step to the demolding step can be repeatedly executed multiple times on the same substrate, and thus a cured film 108 having a plurality of desired patterns at desired positions on the substrate can be obtained.

[0247] [Planarization film forming method] An example of applying the film forming method of the present disclosure to a planarization film forming method will be described below. The planarization film forming method includes, for example, a placement step, a waiting step, a contact step, a curing step, and a demolding step. The placement step is a step of placing droplets of the curable composition (A) on a substrate. The waiting step is a step of waiting until the droplets of the curable composition (A) are combined with each other and the solvent (d) evaporates. The contact step is a step of bringing the non-volatile composition (A') into contact with the mold. The curing step is a step of curing the non-volatile composition (A'). The demolding step is a step of detaching the mold from the cured film of the non-volatile composition (A'). In the planarization film forming method, a substrate having a concavo-convex degree of about 10 to 1000 nm is used as the substrate, a mold having a flat surface is used as the mold, and a cured film having a surface consistent with the flat surface of the mold is formed through the contact step, the curing step, and the demolding step. The flat surface means a flat (patternless) surface on the substrate where no pattern is to be formed, or a flat surface equal to or larger than the pattern forming region of the substrate. In the placement step, droplets of the curable composition (A) are densely placed in the concave portions of the substrate and sparsely placed on the convex portions of the substrate. The waiting step is performed after the placement step, the contact step is performed after the waiting step, the curing step is performed after the contact step, and the demolding step is performed after the curing step.

[0248] [Article manufacturing method] The article manufacturing method may include: a forming step of forming a film of a curable composition on a substrate using the above film forming method, a processing step of processing the substrate on which the film of the curable composition is formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. As described above, the film forming method is a pattern forming method or a planarization film forming method.

[0249] The patterned cured film 108 formed by the pattern forming method of the present disclosure can be directly used as at least a partial constituent member of various articles. Further, the patterned cured film 108 formed by the pattern forming method of the present disclosure can be temporarily used as a mask for etching or ion implantation with respect to the substrate 101 (when the substrate 101 has a layer to be processed, this layer to be processed). After the etching or ion implantation in the processing step of the substrate 101, the mask is removed. Thus, various articles can be manufactured.

[0250] When removing the cured product in the concave portion of the pattern of the cured product by etching, the implementation method is not particularly limited, and conventionally known methods such as dry etching can be used. In such dry etching, conventionally known dry etching equipment can be used. The source gas for dry etching is appropriately selected according to the elemental composition of the cured product to be etched. More specifically, halogen-containing gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2 can be used as the source gas. As the source gas, 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. Note that these gases can also be mixed and used as the source gas. In this case, the photocured film needs to have high dry etching resistance in order to process the base substrate with high yield.

[0251] The article is, for example, a circuit element, an optical element, a MEMS, a recording element, a sensor, or a mold. Examples of circuit elements are volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensor, and FPGA. Examples of optical elements are microlenses, light guides, waveguides, antireflection films, diffraction gratings, polarizers, color filters, light emitting elements, displays, and solar cells. Examples of MEMS are DMD, microchannels, and electromechanical transducers. Examples of recording elements are optical discs such as CD and DVD, magnetic disks, magneto-optical discs, and magnetic heads. Examples of sensors are magnetic sensors, optical sensors, and gyro sensors. Examples of molds are molds for imprinting.

[0252] Further, known photolithography steps such as imprint lithography technology or extreme ultraviolet exposure technology (EUV) can be performed on the planarized film formed by the planarizing film forming method of the present disclosure. A spin-on glass (SOG) film and / or a silicon oxide layer can also be stacked, and a photolithography step can be performed by applying a curable composition thereon. Thus, devices such as semiconductor devices can be manufactured. An apparatus including the device, such as an electronic apparatus such as a display, a camera, or a medical device, can also be formed. Examples of the device are LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, and NAND flash memory.

[0253] [Embodiment] More detailed embodiments will be described to supplement the above-described embodiments.

[0254] <Embodiment 1> In this embodiment, using the viscosity μ [mPa·s] and the average liquid film thickness h [m] of the non-volatile composition, the edge filling speed v and the extrusion margin time t are represented by the following equations E1 and E2. Further, it is shown that, using numerical calculation, in order to satisfy the condition that v is 20 [μm / sec] or more and t is 0.5 [sec] or more, it is preferable to satisfy the above Expressions 1 and 2. Equation E1: v(μ,h) = C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s] Equation E2: t(μ,h) = C·h α ·μ / μ0, C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s]

[0255] In this embodiment, assuming a contact step, by simultaneously solving the Navier-Stokes equations approximating the thin film sandwiched between the wall surfaces and the elastic deformation equation of the mold, the edge filling speed and the extrusion margin time are obtained. Figure 5 The calculation region is shown. In Figure 5 , the initial position 110 of the end of the liquid film 102 between the substrate 101 and the mold 106 is set inside the end 109 of the pattern formation region (on the negative x-axis side). The end in the negative x-axis direction is set as a symmetric boundary, assuming that the direction perpendicular to Figure 5 the paper surface is symmetric, and the calculation is performed by approximating it as a two-dimensional problem.

[0256] The mold 106 is a linear elastic body with a Young's modulus of 72 GPa and a Poisson's ratio of 0.17. The surface tension coefficient of the liquid film is 30 mN / m. The initial condition of the average liquid film thickness is uniform, and the distance between the initial position 110 of the end of the liquid film 102 and the end 109 of the pattern formation region is 100 μm. In the region along the negative x-axis from the initial position 110 of the end of the liquid film 102, the gap between the mold 106 and the substrate 101 is filled with the liquid film 102, and there is no gap between the liquid film 102 and the mold 106. Further, at the initial position 110 of the end of the liquid film 102, the liquid film 102 contacts the mold 106 and the substrate 101 at a contact angle of 0°. The liquid film 102 starts from a stationary state. The numerical calculation method shown in this embodiment is merely an example, and other calculation methods can also be used.

[0257] Figure 6 shows the change in the edge filling speed when the average liquid film thickness is 40 nm and the viscosity coefficient of the liquid film changes. In Figure 6 , the abscissa represents time and the ordinate represents the distance between the end of the liquid film and the edge. Note that the positive direction of the ordinate is the downward direction. B01, B02, and B03 correspond to the results in the cases where the viscosities of the liquid film are 50, 150, and 300 mPa·s, respectively. It can be seen from this that the lower the viscosity, the higher the edge filling speed.

[0258] Figure 7 The same calculation results as those in Figure 6 are shown by plotting time / viscosity coefficient along the abscissa. As shown in C01, Figure 6 the curve shown overlaps with the same curve. This indicates that the edge filling speed is inversely proportional to the viscosity coefficient. It is found that the flow rate of the liquid film is inversely proportional to the viscosity coefficient.

[0259] Figure 8 shows the change in the edge filling speed when the viscosity coefficient of the liquid film is 50 mPa·s and the average liquid film thickness changes. In Figure 8 , the abscissa represents time and the ordinate represents the distance between the end of the liquid film and the edge. Note that the positive direction of the ordinate is the downward direction. D01, D02, D03, D04, and D05 correspond to the results in the cases where the average liquid film thicknesses are 1000, 200, 100, 80, and 40 nm, respectively. It can be seen from this that the thicker the average liquid film thickness, the higher the edge filling speed.

[0260] Figure 9 A coordinate diagram is shown, where the abscissa represents the average liquid film thickness and the ordinate represents the edge filling speed. This diagram is the calculation result, and the curve corresponds to Equation E1. In this way, the correlation between the average liquid film thickness and the edge filling speed can be expressed by Equation E1. It is also found that since the edge filling speed is inversely proportional to the viscosity coefficient, as described above, the correlation with the viscosity coefficient can also be expressed by Equation E1.

[0261] Figure 10 shows the time-rate change of the extrusion height when the viscosity coefficient of the liquid film is 50 mPa·s and the average liquid film thickness changes. In Figure 10 , the abscissa represents the elapsed time, that is, the time elapsed when the time for the liquid film to fill up to the edge is set to 0. The ordinate represents the extrusion height. F01, F02, F03, F04, and F05 correspond to the results in the cases where the average liquid film thicknesses are 1000, 200, 100, 80, and 40 nm, respectively. It can be seen from this that the thicker the liquid film thickness, the faster the extrusion proceeds. When the extrusion height reaches about 50 nm, defects appear. Therefore, in Figure 10In [the figure], when the ordinate reaches 50 nm, the value on the abscissa, that is, the time elapsed from when the liquid film is filled to the edge until the extrusion height reaches 50 nm, is defined as the extrusion grace time.

[0262] Figure 11 Shows the change in the extrusion grace time when the average liquid film thickness changes. In Figure 11 the figure, the abscissa represents the average liquid film thickness and the ordinate represents the extrusion grace time. This figure is the calculation result, and the curve corresponds to Equation E2. In this way, Equation E2 can substantially represent the average liquid film thickness correlation of the extrusion grace time. It was also found that since the flow rate of the liquid film is inversely proportional to the viscosity coefficient, as described above, the extrusion grace time is proportional to the viscosity coefficient. Therefore, it was found that the viscosity coefficient correlation can also be represented by Equation E2.

[0263] As described above, the edge filling speed is represented by Equation E1 including μ and h as variables, and the extrusion grace time is represented by Equation E2 including μ and h as variables. Therefore, it was found that in order to satisfy the conditions that the edge filling speed is 20 μm / sec or more and the extrusion grace time is 0.5 seconds or more, it is preferable to satisfy the inequalities represented by Expressions 1 and 2.

[0264] Table 2 shows the measurement results of the viscosity of the curable composition (A). The measurement was carried out as follows. First, according to the abbreviations shown in Table 1, components (a), (b), (c), and (d) were mixed so as to obtain a total ratio of 100% by weight, thereby obtaining the curable composition (A). Next, the viscosities of the curable composition (A) and the non-volatile composition (A') mixed without using component (d) were measured at 23°C. After that, the Tg of the curable composition after removing component (d) was measured by the above method. Note that for component (d) in Table 2, PGMEA is the abbreviation for propylene glycol monomethyl ether and Gly is the abbreviation for glycerol.

[0265] [Table 1] Name Chemical Structure Manufacturer Mono-functional organic monomer (a) 2-Phenoxyethyl acrylate Kyoeisha Chemical Co., Ltd. Mono-functional organic monomer (b) Tetrahydrofurfuryl acrylate Osaka Organic Chemical Industry Co., Ltd. Mono-functional organic monomer (c) Isobornyl acrylate Osaka Organic Chemical Industry Co., Ltd. Mono-functional organic monomer (d) 2-(o-Phenylphenoxy)ethyl acrylate Nippon Shokubai Co., Ltd. Mono-functional organic monomer (e) 1-Naphthylmethyl acrylate Kyoeisha Chemical Co., Ltd. Mono-functional Si monomer (f) 3-Methacryloxypropyltris(trimethylsiloxysilane) JNC Poly-functional organic monomer (A) Dimethyloltricyclodecane diacrylate Kyoeisha Chemical Co., Ltd. Poly-functional organic monomer (B) Pentaerythritol tetraacrylate Sartomer Poly-functional organic monomer (C) Bis-trimethylolpropane tetraacrylate Sartomer Poly-functional Si monomer (D) Acryloyl-modified sesquioxane derivative Toagosei Co., Ltd.

[0266] Table 2

[0267] <Evaluation of Edge Filling Speed> To evaluate the edge filling speed, a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm) was used. Under the conditions where the liquid film thickness obtained after the evaporation of the solvent (d) was 40 nm, 80 nm, and 120 nm, each curable composition (A) of Examples 2 to 6 and Comparative Examples 1 to 3 was discretely dropped (arranged) on a silicon substrate, and a waiting step and a contact step were performed. All the arranging steps, waiting steps, and contact steps were carried out under a carbon dioxide atmosphere, and a blank mold made of quartz was used in the contact step. Here, let D be the distance between the end position of the pattern formation region of the substrate and the initial position of the end of the liquid film of the curable composition (A) on the substrate immediately before the contact step, and T be the time required for the non-volatile composition (A') to fill to the end of the pattern formation region of the substrate during the contact step. At this time, the edge filling speed was defined as D / T. The edge filling speed defined in this way was evaluated based on the following criteria.

[0268] A: The edge filling proceeds at a speed of 20 μm / sec or more.

[0269] B: The edge filling proceeds at a speed of less than 20 μm / sec. <Evaluation of the extrusion grace time>

[0270] To evaluate the extrusion grace time, a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm) was used. Under the conditions where the liquid film thickness obtained after the evaporation of the solvent (d) was 40 nm, 80 nm, and 120 nm, each curable composition (A) of Examples 2 to 6 and Comparative Examples 1 to 3 was discretely dropped (arranged) on a silicon substrate, and a waiting step and a contact step were performed. All the arranging steps, waiting steps, and contact steps were carried out under a carbon dioxide atmosphere, and a blank mold made of quartz was used in the contact step.

[0271] In the contact step, if the non-volatile composition (A') and the mold further remained in contact with each other immediately after the non-volatile composition (A') filled to the end of the pattern formation region of the substrate, the non-volatile composition (A') was extruded from the end of the mold and climbed up the side wall of the mold. The height at which the component climbed up the side wall of the mold was measured as the extrusion height. The time when the extrusion height reached 50 nm was measured and evaluated based on the following criteria.

[0272] A: The extrusion grace time is 0.5 seconds or more.

[0273] B: The extrusion grace time is less than 0.5 seconds.

[0274] Table 3 shows the evaluation results of the edge filling speed and the extrusion grace time.

[0275] Table 3

[0276] It is considered that the following conditions are satisfied. (1) Imprinting with an average liquid film thickness of 40 nm can be performed at a high production volume, (2) The edge filling speed of defects on the substrate caused by extrusion can be suppressed to 20 μm / sec or more, and (3) The extrusion grace time is 0.5 seconds or more.

[0277] It has been found that in order to satisfy the above conditions, the viscosity of the non-volatile composition (A') is preferably 20 mPa·s or more and 60 mPa·s or less, as shown in the above Expressions 1 and 2.

[0278] In addition, it is considered that the following conditions are satisfied.

[0279] (1) Imprinting with an average liquid film thickness of 80 nm can be performed at a high production volume, (2) The edge filling speed of defects on the substrate caused by extrusion can be suppressed to 20 μm / sec or more, and (3) The extrusion grace time is 0.5 seconds or more.

[0280] It has been found that in order to satisfy the above conditions, the viscosity of the non-volatile composition (A') is preferably 20 mPa·s or more and 100 mPa·s or less.

[0281] In addition, it is considered that the following conditions are satisfied.

[0282] (1) Imprinting with an average liquid film thickness of 120 nm can be performed at a high production volume, (2) The edge filling speed of defects on the substrate caused by extrusion can be suppressed to 20 μm / sec or more, and (3) The extrusion grace time is 0.5 seconds or more.

[0283] It has been found that in order to satisfy the above conditions, the viscosity of the non-volatile composition (A') is preferably 60 mPa·s or more and 135 mPa·s or less.

[0284] Although the present invention has been described with reference to exemplary embodiments, it should be understood that the present invention is not limited to the disclosed exemplary embodiments. The scope of the following claims should be given the broadest interpretation to cover all such modifications and equivalent structures and functions.

Claims

1. A method for forming a film of a curable composition on a substrate using a mold, comprising: Discretely arranging a plurality of droplets of the curable composition on the substrate; After the arrangement, bringing the plurality of droplets on the substrate and the mold into contact with each other, thereby forming a liquid film between the substrate and the mold; After bringing the droplets and the mold into contact with each other, curing the liquid film to form a cured film; And After curing, separating the cured film and the mold from each other, Wherein the viscosity μ [mPa·s] of the non-volatile composition in the curable composition and the average liquid film thickness h [m] formed by the non-volatile composition have values satisfying the following expressions Expression 1: 20 [μm / sec] ≤ C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s], Expression 2: 0.5 [sec] ≤ C·h α ·μ / μ0, and C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s].

2. The method according to claim 1, wherein the curable composition Contains a polymerizable compound (a) and a photoinitiator (b), and Has a viscosity of 20 mPa·s or more and 135 mPa·s or less at 23°C.

3. The method according to claim 2, wherein the average liquid film thickness of the curable composition is 5 nm or more and 170 nm or less.

4. The method according to claim 2, wherein the ratio of the polyfunctional polymerizable compound in the polymerizable compound (a) is 20% by weight or more.

5. The method according to claim 2, wherein the polymerizable compound (a) contains one or more types of polymerizable compounds, and each of the one or more types of polymerizable compounds has a boiling point of 250°C or more at 1 atm.

6. The method according to claim 2, wherein the polymerizable compound (a) contains one or more types of polymerizable compounds, and the molecular weight of each of the one or more types of polymerizable compounds is 200 or more.

7. The method according to claim 2, wherein the polymerizable compound (a) contains a polymer having a polymerizable functional group.

8. The method according to claim 2, wherein the polymerizable compound (a) contains one or more types of polymerizable compounds, and the vapor pressure of the one or more types of polymerizable compounds at 80°C and 1 atm is 0.001 mmHg or less.

9. The method according to claim 2, wherein the polymerizable compound (a) contains a compound (a-1) having one of an aromatic structure, an aromatic heterocyclic structure, and an alicyclic structure.

10. The method according to claim 2, wherein The polymerizable compound (a) contains one or more types of polymerizable compounds, The Oishi parameter (OP) of the polymerizable compound (a) is 1.80 or more and 4.00 or less, and Let N be the number of all atoms in the molecule, N C be the number of all carbon atoms in the molecule, and N O be the number of all oxygen atoms in the molecule. Then, the Ohmori parameter (OP) is the mole fraction weighted average of the N / (N C - N O ) value for each molecule of each of the above-described polymerizable compounds of more than one type.

11. The method according to claim 2, wherein the polymerizable compound (a) contains a compound (a-2) including a Si atom.

12. The method according to claim 11, wherein the compound (a-2) includes a polymerizable compound containing one of a silsesquioxane skeleton and a cyclic siloxane compound.

13. The method according to claim 11, wherein The curable composition further contains a solvent (d), and The curable composition in a state where the solvent (d) is removed contains 10% by weight or more of Si atoms.

14. According to the method of claim 1, wherein the curable composition further contains a solvent (d), and has a viscosity at 23°C of 1.3 mPa·s or more and 60 mPa·s or less, the curable composition in a state where the solvent (d) is removed has a viscosity at 23°C of 20 mPa·s or more and 135 mPa·s or less, and the method further includes waiting after the arrangement and before bringing the droplets and the mold into contact with each other until the coalescence of the plurality of droplets on the substrate proceeds and the volatilization of the solvent contained in the liquid film proceeds.

15. According to the method of claim 14, wherein the average liquid film thickness of the curable composition in a state where the solvent (d) is removed is 5 nm or more and 170 nm or less.

16. According to the method of claim 14, wherein in the waiting, the processing is waited until the content of the solvent (d) becomes 10% by volume or less with respect to the entire liquid film.

17. According to the method of claim 14, wherein the waiting includes heating the substrate under conditions of 30°C or more and 200°C or less and 10 seconds or more and 600 seconds or less.

18. The method according to claim 14, wherein in the arrangement, droplets of the curable composition having a volume of 1.0 pL or more are arranged on the substrate at a density of 80 droplets / mm or more. 2 ​ 19. According to the method of claim 14, wherein the solvent (d) includes one or more types of solvents, and each of the one or more types of solvents has a boiling point at 1 atm of 100°C or more and less than 250°C.

20. According to the method of claim 14, wherein the solvent (d) contains a polymerizable compound having a boiling point at 1 atm of 80°C or more and less than 250°C.

21. According to the method of claim 14, wherein the content of the solvent (d) with respect to the entire curable composition is 40% by volume or more and 85% by volume or less.

22. According to the method of claim 1, wherein the glass transition temperature of the cured film is 70°C or more.

23. According to the method of claim 1, wherein the curable composition is a curable composition for inkjet.

24. According to the method of claim 1, wherein the mold includes a pattern, when bringing the droplets and the mold into contact with each other, the pattern of the mold and the liquid film are brought into contact with each other, and the film forming method further includes curing the liquid film after bringing the droplets and the mold into contact with each other, thereby forming a cured film having a pattern corresponding to the mold pattern.

25. According to the method of claim 1, wherein the mold includes a flat surface, when bringing the droplets and the mold into contact with each other, the flat surface of the mold and the liquid film are brought into contact with each other, and the film forming method further includes curing the liquid film after bringing the droplets and the mold into contact with each other, thereby forming a cured film having a surface consistent with the flat surface of the mold.

26. According to the method of claim 1, wherein in the arrangement, the plurality of droplets are discretely arranged on the substrate using an inkjet method.

27. The method according to claim 1, wherein the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m 3 ·atm or more and 10 kg / m 3 ·atm or less.

28. The method according to claim 1, wherein when the droplet and the mold are brought into contact with each other, the gas filling the space between the substrate and the mold contains 10% or more of carbon dioxide in terms of molar ratio.

29. A method for manufacturing an article, comprising: forming a film of a curable composition on a substrate using the film-forming method according to any one of claims 1 to 28; processing the substrate on which the film is formed in the formation; and manufacturing an article from the substrate processed in the processing.

30. A curable composition containing a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), wherein the viscosity of the curable composition at 23 °C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less, the content of the solvent (d) relative to the entire curable composition is more than 5% by volume and 95% by volume or less, the boiling point of the solvent (d) at 1 atm is less than 250 °C, and at 23 °C and 1 atm, the viscosity of the curable composition in a state where the solvent (d) is removed is 20 mPa·s or more and 135 mPa·s or less.

31. The curable composition according to claim 30, wherein the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m 3 ·atm or more and 10 kg / m 3 ·atm or less.

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