Curable composition, film forming method, and article manufacturing method

Abstract

In a curable composition containing at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), the viscosity of the curable composition at 23 DEG C is not less than 1.3 mPa.s and not more than 60 mPa.s, the content of the solvent (d) is more than 5 vol% and not more than 95 vol% with respect to the entire curable composition, the boiling point of the solvent (d) is less than 250 DEG C, and the photopolymerization initiator (b) is a photopolymerization initiator. And such that gamma1 (mN / m) is the surface tension of the curable composition at 23 DEG C in a state where the solvent (d) is removed, and gamma2 (mN / m) is the surface tension of the solvent (d) at 23 DEG C, then gamma1 is greater than gamma2.

Description

Technical Field

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

[0002] For semiconductor devices and MEMS, there is an increasing demand for miniaturization. As a micro-patterning technique, imprint technology (optical imprint technology) has received great attention as a microfabrication technique. In imprint 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 onto the cured film of the curable composition, thereby forming a pattern on the substrate. According to imprint technology, a fine pattern (structure) of several nanometers can be formed on the substrate (see Patent Document 1).

[0003] As an example of a pattern-forming method using imprint technology, the jet and flash imprint lithography (JFIL) technique 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 (pressed against) 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 recesses 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 released from the cured curable composition on the substrate. By performing these steps, the pattern of the mold is transferred onto 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 may include a residual film. The residual film is a cured film remaining between the substrate and the recesses (protrusions 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 supplied with the curable composition must be reduced to less than several tens of nm. In the imprint technology, flatness equivalent to that of EUV is also required to improve the filling performance of the curable composition and the line width accuracy (see Non-Patent Document 1). As a planarization technique, a technique is known in which droplets of a curable composition corresponding to the unevenness are discretely dropped onto an 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 to obtain a flat surface (see Patent Documents 2 and 3).

[0005] In the pattern formation method or planarization technique based on the above-mentioned JFIL, since the mold is brought into contact in a state where the droplets dropped onto the substrate do not contact each other, air bubbles are inevitably trapped between the mold, the substrate, and the curable composition. Therefore, 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 (throughput). To improve the throughput of JFIL, a technique of combining droplets of a curable composition before the mold is brought into contact is known, as shown in Patent Document 4.

[0006] Citation List

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent No. 6,584,578

[0009] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2019-140394

[0010] Patent Document 3: US-2020-0286740

[0011] Patent Document 4: Japanese Unexamined Patent Application Publication No. 2010-530641

[0012] Patent Document 5: Japanese Unexamined Patent Application Publication No. 2022-99271

[0013] Non-Patent Documents

[0014] Non-Patent Document 1: Proc. SPIE 11324-11 (2020)

[0015] Non-Patent Document 2: J. Electrochem. Soc., 130, p. 143 (1983) Summary of the Invention

[0016] Technical Problem

[0017] However, in the JFIL technology described in Patent Document 4, since the curable composition contains a solvent, it is necessary to perform a step of volatilizing the solvent before contacting the mold and waiting until the droplets combine with each other. There is a problem of reduced productivity due to the waiting step.

[0018] The present invention has been made in view of the problems of the conventional technology, and an object thereof is to provide a new technology regarding a curable composition.

[0019] Solution to the Problem

[0020] In order to achieve the above object, according to one aspect of the present invention, there is provided a curable composition containing at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), characterized in that: the curable composition has a viscosity at 23°C of not less than 1.3 mPa·s and not more than 60 mPa·s, the content of the solvent (d) relative to the entire curable composition is more than 5% by volume and not more than 95% by volume, the boiling point of the solvent (d) is lower than 250°C, and letting γ1 (mN / m) be the surface tension of the curable composition at 23°C in a state where the solvent (d) is removed, and γ2 (mN / m) be the surface tension of the solvent (d) at 23°C, then γ1 is greater than γ2.

[0021] Advantageous Effects of the Invention

[0022] According to the present invention, for example, a new technology regarding a curable composition can be provided.

[0023] Other features and advantages of the present invention will become clear from the following description in conjunction with the accompanying drawings. Note that throughout the drawings, the same reference numerals denote the same or similar components. Brief Description of the Drawings

[0024] The drawings incorporated in the specification and constituting a part of the specification illustrate embodiments of the present invention and, together with the specification, are used to explain the principles of the present invention.

[0025] Figure 1 is a diagram for explaining a pattern forming method (film forming method) according to an embodiment;

[0026] Figure 2 is a diagram for explaining the behavior of droplets after dropping;

[0027] Figure 3 is a diagram for explaining the shape of droplets in the case where the flow of droplets is caused by the Marangoni effect;

[0028] Figure 4 is a diagram for explaining the flow behavior of droplets of the curable composition during the waiting step; ​​​​

[0029] Figure 5 is a diagram showing a comparison between the contact step in the prior art and the contact step according to an embodiment;

[0030] Figure 6 is a diagram showing the time-rate change of the droplet radius;

[0031] Figure 7 is a diagram showing the dependence of the maximum radius of the droplet on Δγ; and

[0032] Figure 8 is a diagram showing the dependence of the droplet evaporation time on Δγ. DETAILED DESCRIPTION

[0033] 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 present invention. In the embodiments, a plurality of features are described, but the invention is not limited to inventions that require all of these features, and 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.

[0034] When a new technology regarding a curable composition is provided, the present inventors have found a curable composition and its process conditions in which droplets of a curable composition discretely dropped (arranged) on a substrate rapidly combine with each other and the solvent contained in the curable composition rapidly volatilizes.

[0035] [Curable Composition]

[0036] The curable composition (A) according to an embodiment of the present invention may be a curable composition for inkjet. The curable composition (A) according to the present embodiment is a composition containing at least a component (a) as a polymerizable compound, a component (b) as a photopolymerization initiator, and a component (d) as a solvent.

[0037] 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 film may have a pattern shape on its surface.

[0038] [Component (a): Polymerizable Compound]

[0039] 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 composed of a polymer compound through a chain reaction (polymerization reaction).

[0040] ​​​​Examples of the above polymerizable compounds are free-radical polymerizable compounds. The polymerizable compound as component (a) may be formed of only one type of polymerizable compound, or may be formed of multiple types (one or more types) of polymerizable compounds.

[0041] Examples of the free-radical polymerizable compounds are (meth)acrylic compounds, styrenyl compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleic compounds.

[0042] (Meth)acrylic compounds are compounds having one or more acryloyl groups or methacryloyl groups. Examples of the monofunctional (meth)acrylic compounds having one acryloyl group or methacryloyl group are as follows, but the compounds are not limited to these examples.

[0043] (Phenyl)phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenethylphenoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 4-phenoxyethyl (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 (meth)phenoxyacrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, boron (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, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, 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, (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, (meth)acrylonitrile benzyl ester, and (meth)naphthylmethyl acrylate.,

[0044] Examples of commercially available products of the above-mentioned monofunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0045] M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, and M156 (manufactured by TOAGOSEI); MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, and CHDOL30, LA, IBXA, 2-MMA, HPA, and Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, and #2150 (manufactured by Sakamoto Yakuhin Kogyo 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 KYOEI SHACHEMICAL); TC110S, R-564, and R-128H (manufactured by NIPPON KAYAKU); NK Ester AMP-10G, AMP-20G, and A-LEN-10 (manufactured by SHIN-NAKAMURA CHEMICAL); FA-511A, 512A, and 513A (manufactured by Hitachi Chemical); PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, and BR-32 (manufactured by DKS); VP (manufactured by BASF); ACMO, DMAA, and DMAPAA (manufactured by Kohjin); and HRD-01 (manufactured by NIPPON SHOKUBAI).

[0046] Examples of polyfunctional (meth)acrylic compounds having two or more acryloyl or methacryloyl groups are as follows, but the compounds are not limited to these examples.

[0047] Propane 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, o-, m- or p-phenylene di(meth)acrylate, and o-, m- or p-xylene di(meth)acrylate.

[0048] Examples of commercially available products of the above polyfunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0049] 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 KYOEISHACHEMICAL); 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); VR-77, VR-60, and VR-90 (manufactured by Showa High Polymer); OGSOL EA-0200 and OGSOL EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd.); and SR295 and SR355 (manufactured by Sartomer).

[0050] Note that in the above compound groups, (meth)acrylate refers to acrylate or methacrylate having an alcohol residue equivalent to that of acrylate. (Meth)acryloyl refers to acryloyl or methacryloyl having an alcohol residue equivalent to that of acryloyl. EO indicates ethylene oxide, and an EO-modified compound A indicates a compound in which the (meth)acrylic acid residue and the alcohol residue of compound A are bonded via a block structure of an ethylene oxide group. In addition, PO indicates propylene oxide, and a PO-modified compound B indicates a compound in which the (meth)acrylic acid residue and the alcohol residue of compound B are bonded via a block structure of a propylene oxide group.

[0051] Actual examples of styrenic compounds are as follows, but the compounds are not limited to these examples.

[0052] 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-dipropylstyrene, 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, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, 2-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenylbutene, p-isopropenylpentene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl.

[0053] Actual examples of vinyl compounds are as follows, but the compounds are not limited to these examples.

[0054] 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, for example, vinylidene dihalides 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.

[0055] Note that in this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0056] Examples of allyl compounds are as follows, but the compounds are not limited to these examples.

[0057] Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and allyl phthalate.

[0058] Examples of fumaric acid compounds are as follows, but the compounds are not limited to these examples.

[0059] Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

[0060] Examples of maleic acid compounds are as follows, but the compounds are not limited to these examples.

[0061] Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

[0062] Other examples of free-radical polymerizable compounds are as follows, but the compounds are not limited to these examples.

[0063] Dialkyl esters of itaconic acid and their derivatives (e.g., dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, sec-butyl itaconate, diisobutyl itaconate, di-2-ethylhexyl itaconate, and bisbenzyl 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).

[0064] If component (a) is formed of multiple types of compounds having one or more polymerizable functional groups, it preferably includes monofunctional polymerizable compounds and polyfunctional polymerizable compounds. The proportion 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 (e.g., high mechanical strength, high dry etching resistance, and high heat resistance) can be obtained.

[0065] In the film forming method according to an embodiment of the present invention, it takes several milliseconds to several hundred seconds before the droplets of the curable composition (A) discretely arranged on the substrate are combined with each other to form a substantially continuous liquid film, and thus a waiting step (described later) may be required. In this waiting step, the solvent (d) volatilizes, but the polymerizable compound (a) surely does not volatilize. Therefore, the boiling points of all of the one or more types of polymerizable compounds that may be included in the polymerizable compound (a) are preferably 250 °C or higher, more preferably 300 °C or higher, and further preferably 350 °C or higher under 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 may be 1 atm (atmospheric pressure).

[0066] The boiling point of the polymerizable compound (a) is roughly related to the molecular weight. Therefore, the molecular weights of all of the one or more types of polymerizable compounds that may be included in the polymerizable compound (a) are preferably 200 or higher, more preferably 240 or higher, and further preferably 250 or higher. However, even if the molecular weight is less than 200, if the boiling point is 250 °C or higher, the compound is preferably used as the polymerizable compound (a) according to an embodiment of the present invention. That is, the boiling point of the one or more types of polymerizable compounds included in the polymerizable compound (a) is preferably 250 °C or higher under normal pressure.

[0067] In addition, the vapor pressure of the polymerizable compound (a) at 80 °C 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 is preferably 0.001 mmHg or less. This is because, although it is advantageous to heat the curable composition to accelerate the volatilization of the solvent (d) (described later), it is necessary to suppress the volatilization of the polymerizable compound (a) during the heating process.

[0068] Note that the boiling points and vapor pressures of various organic compounds under atmospheric pressure can be calculated, for example, by the Hansen Solubility Parameter in "Practice (HSPiP) 5th Edition. 5.3.04".

[0069] <Ohnishi Parameter (OP) of Component (a)>

[0070] The dry etching rate V of a known organic compound, the number N of all atoms in the organic compound, the number N C of all carbon atoms in the composition, and the number N O of all oxygen atoms in the composition have the following relationship of formula (1) (Non-Patent Document 2).

[0071] V ∝ N / (N C - N O )...(1)

[0072] wherein, N / (N C - N O ) is also referred to as the "Ohnishi Parameter" (hereinafter referred to as "OP"). For example, Patent Document 3 describes a technique for obtaining a photocurable composition having high dry etching resistance by using a polymerizable compound having a small OP.

[0073] Formula (1) indicates that an organic compound having many oxygen atoms in the molecule or having a small number of aromatic ring structures or alicyclic ring structures has a large OP and a high dry etching rate.

[0074] In the curable composition (A) according to an embodiment of the present invention, 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. When the OP of component (a) is 1.80 or more, after treating the underlying layer with the cured film of the curable composition (A), the cured film of the curable composition (A) can be easily removed. When component (a) is formed of multiple types of polymerizable compounds a1, a2,..., a n , the OP can be calculated as a weighted average (mole fraction weighted average) based on the mole fraction shown in the following formula (2). That is, 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 / (N C - N O ) values of the respective molecules of one or more types of polymerizable compounds.

[0075]

[0076] Among them, OP n is the OP of component a n and n n is the mole fraction of component a n in the entire component (a).

[0077] In order to set the OP of component (a) to be above 1.80 and below 2.70, it is preferred to contain at least a compound (a-1) having two or more cyclic structures (where at least one cyclic structure is an aromatic structure or an aromatic heterocyclic structure) as component (a).

[0078] <Compound (a-1): A polymerizable compound having an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure>

[0079] The polymerizable compound (a) according to an embodiment of the present invention 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 below 2.70.

[0080] Examples of the cyclic structure are an aromatic structure, an aromatic heterocyclic structure and an alicyclic structure.

[0081] The number of carbon atoms of the aromatic structure is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. Actual examples of the aromatic ring are as follows.

[0082] Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenylalanine ring, fluorene ring, benzocyclooctene ring, acenaphthene ring, biphenyl ring, indene ring, indanone ring, phenylacetylene ring, pyrene ring, chrysene ring, perylene ring and tetrahydronaphthalene ring.

[0083] 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. Examples are a biphenyl ring and a bisphenyl ring.

[0084] The number of carbon atoms of the aromatic heterocyclic structure is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 5. Actual examples of the aromatic heterocycle are as follows.

[0085] 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, phenothiotiazine ring and phenoxazine ring.

[0086] 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. Actual examples are as follows.

[0087] Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, spirodecane ring, spirononane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindane ring, borane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring and adamantane ring.

[0088] Actual examples of the polymerizable compound (a-1) having a boiling point of 250 °C or higher are as follows, but the compounds are not limited to these examples.

[0089] 3-Phenoxybenzyl acrylate (mPhOBzA, OP = 2.54, boiling point = 367.4 °C, vapor pressure at 80 °C = 0.0004 mmHg, molecular weight = 254.3)

[0090]

[0091] 1-Naphthyl acrylate (NaA, OP = 2.27, boiling point = 317 °C, vapor pressure at 80 °C = 0.0422 mmHg, molecular weight = 198)

[0092]

[0093] 2-Phenoxyethyl acrylate (PhPhOEA, OP = 2.57, boiling point = 364.2 °C, vapor pressure at 80 °C = 0.0006 mmHg, molecular weight = 268.3)

[0094]

[0095] 1-Naphthylmethyl acrylate (Na1MA, OP = 2.33, boiling point = 342.1 °C, vapor pressure at 80 °C = 0.042 mmHg, molecular weight = 212.2)

[0096]

[0097] 2-Naphthyl acrylate (Na2MA, OP = 2.33, boiling point = 342.1 °C, vapor pressure at 80 °C = 0.042 mmHg, molecular weight = 212.2)

[0098]

[0099] DPhPA indicated by the following formula (OP = 2.38, boiling point = 354.5 °C, vapor pressure at 80 °C = 0.0022 mmHg, molecular weight = 266.3)

[0100]

[0101] PhBzA indicated by the following formula (OP = 2.29, boiling point = 350.4 °C, vapor pressure at 80 °C = 0.0022 mmHg, molecular weight = 238.3)

[0102]

[0103] FLMA indicated by the following formula (OP = 2.20, boiling point = 349.3 °C, vapor pressure at 80 °C = 0.0018 mmHg, molecular weight = 250.3)

[0104]

[0105] ATMA indicated by the following formula (OP = 2.13, boiling point = 414.9 °C, vapor pressure at 80 °C = 0.0001 mmHg, molecular weight = 262.3)

[0106]

[0107] DNaMA indicated by the following formula (OP = 2.00, boiling point = 489.4 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 338.4)

[0108]

[0109] BPh44DA indicated by the following formula (OP = 2.63, boiling point = 444 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.3)

[0110]

[0111] BPh43DA indicated by the following formula (OP = 2.63, boiling point = 439.5 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.3)

[0112]

[0113] DPhEDA indicated by the following formula (OP = 2.63, boiling point = 410 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 322.3)

[0114]

[0115] BPMDA indicated by the following formula (OP = 2.68, boiling point = 465.7 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 364.4)

[0116]

[0117] Na13MDA indicated by the following formula (OP = 2.71, boiling point = 438.8 °C, vapor pressure at 80 °C < 0.0001 mmHg, molecular weight = 296.3)

[0118]

[0119] 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)

[0120]

[0121] 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)

[0122]

[0123] The following formula (a - 1 - 3) (OP = 1.86, boiling point = 369.5 °C, at 80 °C, vapor pressure = 0.0053 mmHg, molecular weight = 193.3)

[0124]

[0125] 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)

[0126]

[0127] 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)

[0128]

[0129] 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)

[0130]

[0131] The following formula (a-1-7) (OP = 2.87, boiling point = 465.2 °C, at 80 °C, vapor pressure < 0.0001 mmHg, molecular weight = 338.4)

[0132]

[0133] 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)

[0134]

[0135] 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)

[0136]

[0137] The following formula (a-1-10) (OP = 2.64, boiling point = 468.1 °C, at 80 °C, vapor pressure < 0.0001 mmHg, molecular weight = 326.4)

[0138]

[0139] 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)

[0140]

[0141] 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)

[0142]

[0143] 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)

[0144]

[0145] 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)

[0146]

[0147] 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)

[0148]

[0149] 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)

[0150]

[0151] 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)

[0152]

[0153] 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)

[0154]

[0155] 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)

[0156]

[0157] 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)

[0158]

[0159] 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)

[0160]

[0161] 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)

[0162]

[0163] 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)

[0164]

[0165] 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)

[0166]

[0167] 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)

[0168]

[0169] 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)

[0170]

[0171] 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)

[0172]

[0173] 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)

[0174]

[0175] 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)

[0176]

[0177] 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)

[0178]

[0179] 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)

[0180]

[0181] 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)

[0182]

[0183] 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)

[0184]

[0185] 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)

[0186]

[0187] 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)

[0188]

[0189] <Compound (a-2): A polymerizable compound containing at least Si atoms>

[0190] The polymerizable compound (a) according to an embodiment of the present invention may contain a polymerizable compound (a-2) containing at least Si atoms. In addition, if the polymerizable compound (a) contains the polymerizable compound (a-2), the curable composition (A) excluding the solvent (d) preferably contains 10% by weight or more of Si atoms based on the entire curable composition (A).

[0191] As an example of the polymerizable compound (a-2) containing at least Si atoms, it may have a linear structure or a branched structure. For example, the following structures can be used as cyclic siloxane compounds. 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 groups.

[0192]

[0193] Other examples of the polymerizable compound (a-2) are the silsesquioxane skeleton represented by the following chemical formula (I) and the silicone skeleton represented by the chemical formula (II). In the chemical formula (I), m + n = 8 (8 ≥ m ≥ 1), and R1 is a divalent organic group. In addition, in the 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 from 1 to 3, and at least one of A and B is a polymerizable functional group.

[0194]

[0195] Examples of the polymerizable functional groups 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, vinylphenyl-based compounds, aryl ether-based compounds, alkenyl ether-based compounds, and maleimide-based compounds. The group Q having a polymerizable functional group can be a group having the above polymerizable functional groups.

[0196] 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. (2-Acryloyloxyethyl)trimethylsilane,

[0197] N-(3-Acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, acryloyloxymethyltrimethoxysilane,

[0198] (Acryloyloxymethyl)phenethyltrimethoxysilane,

[0199] Acryloyloxymethyltrimethylsilane,

[0200] (3-Acryloyloxypropyl)dimethylmethoxysilane,

[0201] (3-acryloyloxypropyl)methyldi(trimethylsilyloxy)silane,

[0202] (3-acryloyloxypropyl)methyldichlorosilane,

[0203] (3-acryloyloxypropyl)methyldiethoxysilane,

[0204] (3-acryloyloxypropyl)methyldimethoxysilane,

[0205] (3-acryloyloxypropyl)trichlorosilane,

[0206] (3-acryloyloxypropyl)trimethoxysilane,

[0207] (3-acryloyloxypropyl)tris(trimethylsilyloxy)silane, acryloyloxytriisopropylsilane,

[0208] acryloyloxytriethylsilane,

[0209] methacryloyloxymethyltrimethoxysilane,

[0210] O-(methacryloyloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloyloxymethyl)bis(trimethylsilyloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxy,

[0211] methacryloyloxymethyltriethoxysilane,

[0212] methacryloyloxypropyltrimethoxysilane,

[0213] methacryloylpropyltriisopropoxysilane,

[0214] O-(methacryloyloxyethyl)-N-(triethoxysilylpropyl)carbamate, methacryloyloxypropylmethyldimethoxysilane,

[0215] methacryloyloxypropylmethyldiethoxysilane,

[0216] methacryloyloxypropyldimethylmethoxysilane,

[0217] methacryloyloxypropyldimethylethoxysilane,

[0218] (methacryloyloxymethyl)dimethylethoxysilane,

[0219] methacryloyloxypropyltriethoxysilane,

[0220] methacryloyloxypropylsilane,

[0221] Methacryloyloxypentamethyldisiloxane,

[0222] (Methacryloyloxymethyl)phenyl dimethylsilane,

[0223] Methacryloyloxytrimethylsilane,

[0224] Methacryloyloxymethyltrimethylsilane,

[0225] (3-Methacryloyloxy-2-hydroxypropoxypropyl)methylbis(trimethylsilyloxy)silane,

[0226] Methacryloyloxypropylpentamethyldisiloxane,

[0227] O-(Methacryloyloxyethyl)-3-[(bis(trimethylsilyloxy)methylsilyl]propyl carbamate,

[0228] Methacryloyloxymethyltris(trimethylsilyloxy)silane,

[0229] Methacryloyloxyethoxytrimethylsilane,

[0230] (3-Methacryloyloxy-2-hydroxypropoxypropyl)methylbis(trimethylsilyloxy)silane,

[0231] Methacryloyloxypropyltris(vinyldimethylsilyloxy)silane, Methacryloyloxypropyltris(trimethylsilyloxy)silane,

[0232] 3-Methacryloyloxypropyltriacetoxysilane,

[0233] Methacryloyloxypropylmethyldichlorosilane,

[0234] Methacryloyloxypropyltrichlorosilane,

[0235] 3-Methacryloyloxypropylbis(trimethylsilyloxy)methylsilane,

[0236] 3-Methacryloyloxypropyldimethylchlorosilane,

[0237] O-Methacryloyloxy(polyethyleneoxy)trimethylsilane,

[0238] Poly(methacryloyloxypropylsilsesquioxane),

[0239] Methacryloyloxypropylheptaisobutyl-T8-silsesquioxane, and

[0240] Methacryloyloxypropyltris(trimethylsilyloxy)silane

[0241] Examples of commercially available products of the above-described silicon-containing monofunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0242] 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)

[0243] The silicon-containing (meth)acrylamide group compound is a compound having one or more acrylamide groups or methacrylamide groups. Examples of the silicon-containing monofunctional (meth)acrylamide group compound having one acrylamide group or methacrylamide group are as follows, but the compound is not limited to these examples.

[0244] 3-acrylamidopropyltrimethoxysilane, and 3-acrylamidopropyltris(trimethylsilyloxy)silane

[0245] 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.

[0246] SIA0146.0 and SIA0150.0 (manufactured by GELEST)

[0247] Examples of polyfunctional (meth)acrylate-based compounds having two or more acryloyl or methacryloyl groups are as follows, but the compounds are not limited to these examples.

[0248] Linear polydimethylsiloxane modified with acryloxypropyl groups at both ends,

[0249] Linear polydimethylsiloxane modified with methacryloxypropyl groups at both ends,

[0250] Cyclic siloxane modified with multiple acryloxypropyl groups,

[0251] Cyclic siloxane modified with multiple methacryloxypropyl groups,

[0252] Silsesquioxane modified with multiple acryloxypropyl groups, and

[0253] Polymethacryloxypropyl-modified silsesquioxane

[0254] 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.

[0255] SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (manufactured by GELEST),

[0256] FM-7711, FM-7721, FM-7725 (manufactured by JNC),

[0257] X-22-2445 (manufactured by Shin-Etsu Chemical Co., Ltd.), and

[0258] AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SK SI-20 (manufactured by TOAGOSEI)

[0259] In addition, according to known literature (e.g., "Ultraviolet curable branched siloxanes as low-k dielectrics for imprint lithography" by Ogawa et al. (https: / / doi.org / 10.1116 / 1.4770051)), the following substances can be synthesized and / or obtained.

[0260] Linear modified polydimethylsiloxane (MA-Si-12) having methacryloxypropyl groups at both ends, 8-membered ring siloxane modified with four methacryloyloxypropyl groups (8-ring), and 10-membered ring polysiloxane modified with five methacryloylpropyl groups (10-ring).

[0261] 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 further 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 ratio of components (b) and (c) can be increased, and characteristics such as a high photopolymerization rate can be obtained.

[0262] At least a part of component (a) which can include one or more types of polymerizable compounds can be a polymer having a polymerizable functional group. The 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 constituent units represented by the following chemical formulas (1) to (6):

[0263]

[0264] In Formulas (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 constituent units represented by Chemical Formulas (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 further preferably 150 or more. The upper limit of the molecular weight of the substituent R is actually 500 or less.

[0265] Polymers having polymerizable functional groups are generally compounds with 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 defined, but is preferably 50000 or less, for example. When the weight-average molecular weight is set at the above lower limit or higher, the boiling point can be set at 250 °C or higher, and the mechanical properties after curing can also be improved. In addition, when the weight-average molecular weight is set below the above 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 unless otherwise specifically stated, the weight-average molecular weight (Mw) in this example is the molecular weight measured by gel permeation chromatography (GPC).

[0266] Examples of the polymerizable functional groups of the polymer are (meth)acryloyl, epoxy, oxetanyl, hydroxymethyl, hydroxymethyl ether group, and vinyl ether group. From the perspective of polymerization ease, (meth)acryloyl is particularly advantageous.

[0267] When adding a polymer having a polymerizable functional group as at least a part of 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 of the polymer to the total mass of all components except solvent (d) is preferably 0.1 wt% or more and 60 wt% or less, more preferably 1 wt% or more and 50 wt% or less, and further preferably 10 wt% or more and 40 wt% or less. When the mixing ratio of the polymer having a polymerizable functional group is set at 0.1 wt% or more, the dry etching resistance, heat resistance, mechanical strength, and low volatility can be improved. In addition, when the mixing ratio is set at 60 wt% or less, the mixing ratio can be brought within the range of the upper limit adjustment of the viscosity (described later).

[0268] <Component (b): Photoinitiator>

[0269] 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, and can also be formed of multiple types of photoinitiators.

[0270] Examples of the radical generator are as follows, but the radical generator is not limited to these examples.

[0271] 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-di(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-morpholinopropan-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-methylstyryl ketone, 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); flavone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

[0272] Examples of commercially available products of the above radical generators are as follows, but the products are not limited to these examples.

[0273] 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).

[0274] 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.

[0275] 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.

[0276] Relative to the sum of component (a), component (b), and component (c) (described later), that is, the total mass of all components except 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. Further, relative to the total mass of all components except 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.

[0277] <Component (c): Non-polymerizable compound>

[0278] In addition to the above components (a) and (b), the curable composition (A) according to an embodiment of the present invention may further contain a non-polymerizable compound as component (c) for various purposes within a range that does not impair the effects of the present invention. 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, internal mold release agents, antioxidants, polymer components, and other additives. Component (c) may contain multiple types of the above compounds.

[0279] Sensitizers are compounds appropriately added to promote polymerization reactions and increase the reaction conversion rate. As sensitizers, one type of compound can be used alone, or two or more types of compounds can be used by mixing.

[0280] Examples of sensitizers are sensitizing dyes. Sensitizing dyes are compounds that are excited by absorbing light with a specific wavelength and interact with the photoinitiator as component (b). The "interaction" mentioned here is energy transfer or electron transfer from the excited-state sensitizing dye to the photoinitiator as component (b). Examples of sensitizing dyes are as follows, but sensitizing dyes are not limited to these examples.

[0281] Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthenone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thio-pyranium salt-based dyes, cyanine-based dyes, quinolinyl dyes, styrylquinolinyl dyes, ketocoumarin-based dyes, thioxanthene-based dyes, xanthene-based dyes, cyanine-based dyes, rhodamine-based dyes, and pyranium salt-based dyes.

[0282] Hydrogen donors are compounds that react with the initiating radicals generated by the photoinitiator as component (b) or the radicals at the polymerization growth termini and generate radicals with higher reactivity. When the photoinitiator as component (b) is a photo radical generator, it is preferable to add a hydrogen donor.

[0283] Actual examples of the above hydrogen donors are as follows, but hydrogen donors are not limited to these examples.

[0284] Amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiourea p-toluenesulfonate, triethylamine, diethylaminoethyl methacrylate, 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.

[0285] One hydrogen donor can be used alone, or two or more hydrogen donors can be used by mixing. Hydrogen donors can also have the function of a sensitizer.

[0286] 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. Surfactants such as silicone-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants can be used as internal mold release agents. However, as will be described later, the addition amount of the fluorine-based surfactant according to an embodiment of the present invention is limited. Note that the internal mold release agent according to an embodiment of the present invention 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 by mixing.

[0287] The fluorine-based surfactant includes the following.

[0288] Polyoxyalkylene (e.g., polyoxyethylene or polyoxypropylene) adducts of alcohols having perfluoroalkyl groups and polyoxyalkylene (e.g., polyoxyethylene or polyoxypropylene) adducts of perfluoropolyethers.

[0289] Note that the fluorine-based surfactant can have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, or a mercapto group in a part of the molecular structure (e.g., the terminal group). An example is pentadecanediol mono-1H,1H,2H,2H-perfluorooctyl ether.

[0290] Commercially available products can also be used as the fluorine-based surfactant. Examples of commercially available products of the fluorine-based surfactant are as follows.

[0291] 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); and 250, 251, 222F, and 208G (manufactured by NEOS).

[0292] The internal mold release agent may also be a hydrocarbon surfactant. The hydrocarbon surfactants include: an alkyl alcohol-polyalkylene oxide adduct obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms; and a polyalkylene oxide.

[0293] Examples of the alkyl alcohol-polyalkylene oxide adduct are as follows.

[0294] 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.

[0295] Note that the terminal group of the alkyl alcohol-polyalkylene oxide adduct is not limited to the hydroxyl group that can be prepared by simply adding a polyalkylene oxide to an alkyl alcohol. The hydroxyl group can also be substituted with a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a mercapto group, or a silanol group, or a hydrophobic group such as an alkyl group or an alkoxy group.

[0296] Examples of the polyalkylene oxide are as follows.

[0297] Polyethylene glycol, polypropylene glycol, their monoethers or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, and mono- or didecyl ethers, monoadipates, monooleates, monostearates, and monosuccinates.

[0298] Commercially available products can also be used as the alkyl alcohol polyalkylene oxide adduct. Examples of commercially available products of the alkyl alcohol-polyalkylene oxide adduct are as follows.

[0299] Polyoxyethylene methyl ethers (methanol - ethylene oxide adducts) (BLAUNON MP - 400, MP - 550, and MP - 1000) manufactured by AOKIOIL INDUSTRIAL, polyoxyethylene decyl ethers (decanol - ethylene oxide adducts) (FINESURF D - 1303, D - 1305, D - 1307, and D - 1310) manufactured by AOKIOIL INDUSTRILD, polyoxyethylene dodecyl ethers (lauryl alcohol ethylene oxide adducts) (BLAUNON EL - 1505) manufactured by AOKIOIL INDUSTRIAL, polyoxyethylene cetyl ethers (a cetyl alcohol ethylene oxide adduct) (BLAUNON CH - 305 and CH - 310) manufactured by AOKIOIL INDUSTRIAL, polyoxyethylene stearyl ethers (stearyl alcohol - ethylene oxide adducts) (BLAUNON SR - 705, SR - 707, SR - 715, SR - 720, SR - 730, and SR - 750) manufactured by AOKIOIL INDUSTRIAL, random copolymer polyoxyethylene polyoxypropylene stearyl ethers (BLAUNON SA - 50 / 50 1000R and SA - 30 / 70 2000R) manufactured by AOKIOIL INDUSTRIAL, polyoxyethylene methyl ethers ( A760E) manufactured by BASF, and polyoxyethylene alkyl ethers (EMULGEN series) manufactured by KAO.

[0300] Commercially available products can also be used as polyalkylene oxides. An example is an ethylene oxide / propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0301] Fluorine - based surfactants exhibit excellent effects of reducing the demolding force and are thus effective as internal demolding agents. With respect to the total mass 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 fluorine - based surfactant in the curable composition (A) is preferably 0 wt% or more and 50 wt% or less. With respect to the total mass of all components except the solvent (d), the mixing ratio of component (c) other than the fluorine - based surfactant in the curable composition (A) is more preferably 0.1 wt% or more and 50 wt% or less, and further preferably 0.1 wt% or more and 20 wt% or less. When the mixing ratio of component (c) other than the fluorine - based surfactant is set to 50 wt% or less, a cured film with certain mechanical strength can be obtained.

[0302] <Component (d): Solvent>

[0303] The curable composition according to an embodiment of the present invention contains a solvent having a boiling point of 100 °C or higher and less than 250 °C at normal pressure as component (d). Component (d) is a solvent that dissolves components (a), (b), and (c). Examples are alcohol-based solvents, ketone-based solvents, ether-based solvents, and nitrogen-containing solvents. One type of component can be used alone, or two or more types of components can be used in combination as component (d). The boiling point of component (d) at normal pressure is 100 °C or higher, preferably 140 °C or higher, 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 evaporation rate in the waiting step described later is too high. Therefore, before the droplets of the curable composition (A) bind to each other, component (d) may evaporate, and the droplets of the curable composition (A) may not bind to each other. In addition, if the boiling point of component (d) at normal pressure is 250 °C or higher, in the waiting step described later, the evaporation of component (d) may be insufficient, so component (d) remains in the cured product of the curable composition (A). Here, if component (d) includes one or more types of solvents, the boiling point of each of the one or more types of solvents at normal pressure is preferably 100 °C or higher and lower than 250 °C (for example, 100 °C or higher and lower than 200 °C).

[0304] Examples of alcohol-based solvents are as follows.

[0305] Monoalcohol-based 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, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzylic alcohol, diacetone alcohol, and cresol; and polyol-based 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.

[0306] Examples of ketone-based solvents are as follows.

[0307] 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.

[0308] Examples of ether solvents are as follows.

[0309] Diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolene, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexylethanol, 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-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.

[0310] Examples of ester solvents are as follows.

[0311] 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-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl 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, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0312] Examples of nitrogen-containing solvents are as follows.

[0313] N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone.

[0314] Among the above solvents, ether solvents and ester solvents are advantageous. Note that, from the perspective of good film-forming performance, ether solvents and ester solvents each having an ethylene glycol structure are more advantageous.

[0315] Other advantageous examples of the solvent are as follows.

[0316] Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0317] A particularly advantageous example is propylene glycol monomethyl ether acetate. Note that isocyanurate di(meth)acrylate(ethyl) is also advantageous.

[0318] In this embodiment, the 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 and a solvent mixture selected from propylene glycol monomethyl ether acetate (boiling point = 146 °C), propylene glycol monomethyl ether, cyclohexanone, 2-semihapten, γ-butyrolactone, and ethyl lactate.

[0319] In this embodiment, if the surface tension of the curable composition in a state where the solvent (d) is removed is γ 1 (mN / m), the surface tension of the solvent (d) at 23 °C is γ2 (mN / m), and Δγ = γ1 - γ2, then the curable composition is configured such that Δγ is greater than zero. More specifically, the solvent (d) is selected such that Δγ is greater than zero. If Δγ is greater than 0 in the waiting step described later, the diffusion of the droplets of the curable composition is accelerated by the Marangoni effect, and the droplets quickly combine with each other to form a continuous liquid film. In addition, since the rapid diffusion of the droplets accelerates the volatilization of the solvent, the waiting step described later is completed in a short time, or the conditions of the baking step are relaxed or omitted. Δγ is preferably 0.1 or more, particularly preferably 1.0 or more, and further preferably 2.0 or more. Note that γ1 and γ2 are each the surface tension under normal pressure.

[0320] In addition, in this embodiment, a polymerizable compound having a boiling point of 80 °C or higher and less than 250 °C under normal pressure can also be used as the component (d). Examples of the polymerizable compound having a boiling point of 80 °C or higher and less than 250 °C under normal pressure are as follows.

[0321] 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).

[0322] In this embodiment, when the total amount of the curable composition (A) is 100% by volume, the content of the solvent (d) is 5% by volume or more and 95% by volume or less, preferably 15% by volume or more and 85% by volume or less, and more preferably 50% by volume or more and 80% by volume or less. In the examples, the content of the solvent (d) can be 50% 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 impossible to obtain a thin film after the solvent (d) has evaporated under the conditions where a practically continuous liquid film can be obtained. Further, if the content of the solvent (d) is more than 95% by volume, it is impossible to obtain a thick film after the solvent (d) has evaporated even when droplets are closely dropped by an inkjet method.

[0323] <Temperature at the time of mixing the curable composition>

[0324] When preparing the curable composition (A) according to the embodiment, components (a), (b), and (d) are at least mixed and dissolved under predetermined temperature conditions. More specifically, the predetermined temperature conditions fall within the range of 0°C or more and 100°C or less. Note that the same applies to the case where the curable composition (A) contains component (c).

[0325] <Viscosity of the curable component>

[0326] The curable composition (A) according to this embodiment 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) according to the embodiment is 1.3 mPa·s or more and 60 mPa·s or less at 23°C, 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 discharge characteristics of the droplets by the inkjet method are unstable. Further, if the viscosity of the curable composition (A) is more than 60 mPa·s, it is impossible to form droplets having a volume of about 1.0 to 3.0 pL, which is advantageous in this embodiment.

[0327] The viscosity of the curable composition (A) in a state where the solvent (d) has volatilized, that is, the viscosity of the mixture of the components other than the solvent (d) in the curable composition (A) at 23°C is 30 mPa·s or more and 10,000 mPa·s or less. The viscosity of the mixture of the components other than the solvent (d) in the curable composition (A) at 23°C is preferably 90 mPa·s or more and 2,000 mPa·s or less, for example, 120 mPa·s or more and 1,000 mPa·s or less. Further, the viscosity is more preferably 150 mPa·s or more and 500 mPa·s or less. When the viscosity of the components other than the solvent (d) of the curable composition (A) is set to 1,000 mPa·s or less, when the curable composition (A) is brought into contact with a mold, diffusion and filling are quickly completed. Therefore, using the curable composition (A) according to an embodiment of the present invention enables the imprint process to be performed at high yield and suppresses pattern defects caused by insufficient filling. Further, when the viscosity of the components other than the solvent (d) of the curable composition (A) is set to 1 mPa or more, unnecessary flow of droplets of the curable composition (A) after the solvent (d) has volatilized can be prevented. Further, when the curable composition (A) is brought into contact with a mold, the curable composition does not easily flow out from the end of the mold.

[0328] <Surface tension of the curable composition>

[0329] Regarding the surface tension γ1 in a state where the solvent (d) has volatilized from the curable composition (a) according to an embodiment of the present invention, the surface tension at 23°C is preferably 5 mN / m or more and 70 mN / m or less. Further, the surface tension at 23°C of the composition of the components other than the solvent (component (d)) is more preferably 7 mN / m or more and 50 mN / m or less, and further 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, capillary action is strong, and thus when the curable composition (A) and the mold are brought into contact with each other, filling (diffusion and filling) is completed in a short time. Further, when the surface tension is 70 mN / m or less, the cured film obtained by curing the curable composition has surface smoothness.

[0330] <Contact angle of the curable composition>

[0331] Regarding the contact angle of the curable composition (A) according to an embodiment of the present invention, for the composition of components other than the solvent (component (d)), the contact angle is preferably 0° or more and 90° or less, particularly preferably 0° or more and 10° or less, with respect to the substrate surface and the mold surface. If the contact angle is greater than 90°, capillary action in the negative direction (the direction in which the contact interface between the mold and the curable composition shrinks) acts within the mold pattern or in the gap between the substrate and the mold, and this may make filling impossible. When the contact angle is small, capillary action is strong, and the filling rate increases.

[0332] <Impurities mixed in the curable composition>

[0333] The curable composition (A) according to an embodiment of the present invention 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) according to an embodiment of the present invention is advantageously a composition obtained through a refining step. Such a refining step preferably uses a filter for filtration.

[0334] As such filtration using a filter, it is advantageous to mix the above components (a), (b), and (c), and filter the mixture using a filter having, for example, a pore size of 0.001 μm or more and 5.0 μm or less. When filtering using a filter, it is more advantageous to perform filtration in multiple stages, or to repeat filtration multiple times (circulation filtration). The liquid can also be refiltered after filtration through a filter, or filtered 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 through the above refining step. Therefore, it is possible to prevent pattern defects caused by impurities mixed in the curable composition from forming unexpected non-uniformities on the cured film obtained after curing the curable composition.

[0335] <Glass transition temperature of the curable composition after curing>

[0336] If the glass transition temperature 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 breakage due to demolding shock occurs. Therefore, when performing the demolding step at room temperature, the glass transition temperature of the cured product is preferably 70 °C or more, more preferably 100 °C or more, and particularly preferably 150 °C or more.

[0337] As a method for measuring the glass transition temperature of a cured product (photo-cured product), measurements using differential scanning calorimetry (DSC) or a dynamic viscoelasticity measuring device can be applied. For example, when measuring using DSC, a straight line obtained by extending the baseline of the DSC curve of the photo-cured product on the low-temperature side (the part of the DSC curve in the temperature region where neither transition nor reaction occurs in the sample) to the high-temperature side and a tangent line drawn at the point where the gradient of the curve in the step change part of the glass transition is the maximum are obtained. Based on the intersection point between the straight line and the tangent line, the extrapolated glass transition start temperature (Tig) is obtained, and this temperature can be obtained as the glass transition temperature. An example of the main device is STA-6000 (manufactured by PerkinElmer). On the other hand, when measuring using a dynamic viscoelasticity measuring device, the temperature at which the loss tangent (tanδ) of the photo-cured product is the maximum is defined as the glass transition temperature. An example of the main device capable of measuring dynamic viscoelasticity is MCR301 (manufactured by Anton Paar).

[0338] When manufacturing a semiconductor integrated circuit using the curable composition according to an embodiment of the present invention, 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.

[0339] [Substrate]

[0340] In this specification, a member on which droplets of the curable composition (A) are discretely dropped is interpreted as a substrate.

[0341] This substrate is a substrate to be processed, and a silicon wafer is usually used. The substrate may have a layer to be treated on its surface. Another layer may also be formed under the layer to be treated on the substrate. When using a quartz substrate as the substrate, a replica (replication mold) of a mold for imprinting can be manufactured. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate can be freely selected from known 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 treated by surface treatment such as silane coupling treatment on Sunday, silicon nitride treatment, or organic thin film deposition, so as to improve the adhesion to the curable composition (A). The adhesive layer described in Patent Document 4 can be used as an example of the organic thin film to be deposited as the surface treatment.

[0342] [Film formation method]

[0343] Reference will be made to Figure 1 [1] to Figure 1[7] Explain the film formation method according to this embodiment. The film formation method according to this embodiment uses a photolithography method to form a film of a curable composition in the space between a mold and a substrate. However, the curable composition can also be cured by another kind of energy (such as heat or electromagnetic waves). The film formation method according to this embodiment can be carried out as a method for forming a patterned film, that is, as a patterning method, and can also be carried out as a method for forming a non-patterned film (such as a planarizing film), that is, as a planarizing film formation method.

[0344] The cured film formed by the patterning method according to this embodiment is preferably a film having a pattern with a size of 1 nm or more and 10 mm or less, and 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 for forming a film having a pattern (uneven structure) with a nano size (1 nm or more and 100 nm or less) by using light is called a photolithography method.

[0345] Examples of applying the patterning method as the film formation method according to this embodiment will be explained below. The patterning method includes, for example, a forming step, an arranging step, a waiting step, a contacting step, a curing step, and a demolding step. The forming step is a step of forming an underlying layer. The arranging step is a step of discretely arranging 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) volatilizes. 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 arranging step is carried out after the forming step, the waiting step is carried out after the arranging step, the contacting step is carried out after the waiting step, the curing step is carried out after the contacting step, and the demolding step is carried out after the curing step.

[0346] <Arranging step>

[0347] In the arranging step, as Figure 1 [1] schematically shown, droplets of the curable composition (A) are discretely arranged on the substrate. In the arranging step, droplets of the curable composition (A) having a volume of 1.0 pL or more can be arranged at a density of 80 droplets / mm 2 or more. The substrate on which the underlying layer is stacked can be used as the substrate. In addition, the adhesion of the substrate surface to the curable composition (A) can be improved by surface treatment such as silane coupling treatment, silicon nitride treatment, or deposition of an organic film.

[0348] The inkjet method is particularly advantageous as a method for arranging droplets of the curable composition (A) on a substrate. Advantageously, the droplets of the curable composition (A) are densely arranged on the region of the substrate facing the region where the recesses forming the mold pattern are densely present, and are sparsely arranged on the region of the substrate facing the region where the protrusions forming the mold pattern are sparsely present. Accordingly, the film (residual film) of the curable composition (A) formed on the substrate (described later) is controlled to have a uniform thickness regardless of the sparsity and density of the mold pattern.

[0349] An index called the average residual liquid film thickness is defined to specify the volume of the curable composition (A) to be arranged. The average residual liquid film thickness is a value obtained by dividing the total volume of the curable composition (A) (excluding the solvent (d)) to be arranged in the arrangement step by the area of the film-forming region of the mold. The volume of the curable composition (A) (excluding the solvent (d)) is the sum of the volumes of the respective droplets of the curable composition (A) after the solvent (d) has evaporated. According to this definition, the average residual liquid film thickness can be specified even if the substrate surface is uneven, regardless of the uneven state. Here, the average residual liquid film thickness can be understood as a value obtained by dividing another track of the curable composition (A) remaining after the waiting step (described later) by the area of the film-forming region of the mold, and is preferably 20 nm or less.

[0350] <Waiting step>

[0351] In an embodiment of the present invention, a waiting step is provided in the period after the arrangement step and before the contact step. Here, the value obtained by dividing the total volume of the droplets of the curable composition (A) dropped in one pattern formation by the total area of the region where the pattern is formed (pattern-forming region) in one pattern formation process is defined as the average initial liquid film thickness. In the waiting step, as schematically shown in Figure 1 [2], the droplets of the curable composition (A) spread on the substrate. Accordingly, the entire pattern-forming region of the substrate is covered with the curable composition (A). In this embodiment, if the surface tension of the curable composition in the state where the solvent (d) has been removed is γ1 (mN / m) and the surface tension of the solvent (d) is γ2 (mN / m), the curable composition is formed such that γ1 is greater than γ2. More specifically, the solvent (d) is selected such that γ1 is greater than γ2. When the solvent (d) is selected in this way, the dropped droplets spread extensively (i.e., the spreading speed of the dropped droplets increases). The factors thereof will be described below.

[0352] In this embodiment, since the dropped droplet contains volatile components, the concentration of the volatile components changes due to volatilization after dropping. The surface tension γ1 of the non-volatile components is greater than the surface tension γ2 of the volatile components. Therefore, if the concentration of the volatile components decreases with volatilization, the surface tension increases.

[0353] In addition, generally, after the dropped droplet gradually spreads, the spread of the droplet stops at the static contact angle. When the contact angle between the end of the droplet and the substrate is significantly different from the static contact angle, the spreading speed is high.

[0354] In addition, in this embodiment, the thickness of the cured film is very thin compared to the radius of the droplet, and the concentration diffusion in the radial direction is very slow compared to the concentration diffusion in the thickness direction.

[0355] The behavior of the droplet after dropping will be described below with reference to Figure 2 Describe the behavior of the droplet after dropping. Figure 2 FIG. shows the state of the droplet dropped on the substrate spreading, and the reference numeral 301 represents the substrate; 302 represents the droplet dropped on the substrate. As described above, the volatilization of the solvent component proceeds even during the spreading of the droplet. The volatilization speed depends to a large extent on the surface area of the droplet. Therefore, when comparing the central part of the droplet (the region 303 indicated by the dashed rectangle) and the end of the droplet (the region 304 indicated by the dashed rectangle), at the end of the droplet, the surface area is slightly larger and the volatilization speed is higher. On the other hand, the volume of the droplet is smaller at the end of the droplet (region 304) than at the central part of the droplet (region 303). Therefore, at the end of the droplet (region 304), since the volatilization speed is high and the volume is small compared to the central part of the droplet (region 303), the concentration of the volatile components decreases and the surface tension increases. Since the surface tension is higher at the end of the droplet (region 304) than at the central part of the droplet (region 303), a force is generated from the central part of the droplet to the end of the droplet by the Marangoni effect, causing the droplet to flow.

[0356] In the case where the droplet flows due to the Marangoni effect, the shape of the droplet is as Figure 3 shown. In Figure 3 FIG., the reference numeral 301 represents the substrate; and 302 represents the droplet dropped on the substrate. As Figure 3 shown, as a result of causing the droplet to flow toward the end of the droplet, the droplet 302 has a shape with the end rising. By the rising of the end, the contact angle between the substrate and the end of the droplet becomes larger compared to the case where the droplet does not flow, and therefore, the spreading speed of the droplet increases.

[0357] According to the examples described later, for example, the following case is selected: the solvent (d) is a highly volatile solvent, the volume ratio of the non-volatile component is 20%, and the droplet spacing is 88 μm, that is, the average initial liquid film thickness is 13 nm or more. In this case, as Figure 1 [3] schematically shows, numerical calculations show that the droplets of the curable composition (A) combine with each other on the substrate to form a virtually continuous liquid film. In addition, this means that droplets of the curable composition (A) with a volume of 1.0 pL or more are arranged at a density of 130 droplets / mm 2 or more.

[0358] Next, reference will be made to Figure 4 [1] to Figure 4 [4] to explain the flow behavior of the droplets of the curable composition (A) arranged on the substrate during the waiting step. As Figure 4 [1] shows, the droplets of the curable composition (A) are discretely arranged on the substrate, and as Figure 4 [2] shows, each droplet gradually spreads on the substrate. Then, as Figure 4 [3] shows, the droplets of the curable composition (A) on the substrate start to combine with each other to form a liquid film, and as Figure 4 [4] shows, a continuous liquid film is formed (the surface of the substrate is covered with the curable composition and there is no exposed surface). The state of the curable composition (A) as Figure 4 [4] shows is sometimes hereinafter referred to as a "virtually continuous liquid film".

[0359] In addition, as Figure 1 [4] schematically shows, the solvent (d) contained in the liquid film volatilizes during the waiting step. Assuming that the total weight of the components other than the solvent (d) is 100 volume%, the residual amount of the solvent (d) in the liquid film after the waiting step (for example, at the start of the contact step) is preferably 10 volume% or less. If the residual amount of the solvent (d) is greater than 10 volume%, the mechanical properties of the cured film may deteriorate.

[0360] During the waiting step, in order to accelerate the volatilization of the solvent (d), a baking step of heating the substrate and the curable composition (A) or ventilation of the atmosphere around the substrate can be carried out. For example, heating is carried out at 30°C or higher and 200°C or lower, preferably at 80°C or higher and 150°C or lower, and particularly preferably at 90°C or higher and 110°C or lower. The heating time can be 10 seconds or more and 600 seconds or less. The baking step can be carried out by using a known heater (such as an electric furnace or an oven).

[0361] The time for the waiting step is, for example, from 0.1 second to 600 seconds, preferably from 10 seconds to 300 seconds. If the waiting step is shorter than 0.1 second, the binding of the droplets of the curable composition (A) becomes insufficient, and thus an actually continuous liquid film is not 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 may be sequentially moved to the waiting step, the waiting step may be performed in parallel with a plurality of substrates, and the substrates that have been completely processed in the waiting step may be sequentially moved to the contact step. Note that in the conventional technology, theoretically, it takes several thousand seconds to several tens of thousands of seconds before an actually continuous liquid film is formed. However, in practice, since the diffusion of the droplets of the curable composition stagnates due to the influence of volatilization, a continuous liquid film cannot be formed.

[0362] When the solvent (d) volatilizes in the waiting step, an actually continuous liquid film containing the components (a), (b), and (c) remains. The average remaining liquid film thickness of the actually continuous liquid film from which the solvent (d) has volatilized (been removed) is smaller than the liquid film by the amount of volatilization of the solvent (d). The following state is maintained throughout the region: the actually continuous liquid film of the curable composition (A) from which the solvent (d) has been removed covers the entire pattern formation region of the substrate.

[0363] <Contact step>

[0364] In the contact step, as Figure 1 [5] schematically shows, the mold is brought into contact with the actually continuous liquid film of the curable composition (A) from which the solvent (d) has been removed. The contact step includes a step of changing the state where the curable composition (A) and the mold are not in contact with each other to a state where they are in contact with each other, and a step of maintaining the state where they are in contact with each other. As a result, the liquid of the curable composition (A) fills the recesses of the fine pattern on the mold surface, and the liquid forms a liquid film filling the fine pattern of the mold.

[0365] According to an embodiment of the present invention, in the waiting step, the curable composition (A) forms an actually continuous liquid film from which the solvent (d) has been removed, and thus the volume of the gas trapped between the mold and the substrate becomes smaller. Therefore, the diffusion of the curable composition (A) is quickly completed in the contact step. Figure 5 Shows a comparison (difference) between the contact step in the conventional technology (related art) disclosed in Patent Document 1 etc. and the contact step according to this embodiment. Figure 5 Shows the contact step in the conventional technology (related art) and the contact step according to this embodiment.

[0366] When the diffusion and filling of the curable composition (A) are rapidly completed in the contact step, the time for maintaining the state of contact between the mold and the curable composition (A) (the time required for the contact step) can be shortened. Since shortening the time required for the contact step results in a shortening of the time required for pattern formation (film formation), the productivity 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, the diffusion and filling become insufficient, and thus many defects called incomplete filling defects tend to occur.

[0367] 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. Advantageous practical examples of the material type for forming the mold are glass, quartz, PMMA, a light-transmitting resin such as a polycarbonate resin, a transparent metal deposition film, a soft film such as polydimethylsiloxane, a photocurable film, and a metal film. When a light-transmitting resin is used as the material for forming the mold, a resin that is not soluble in the components contained in the curable composition is selected. Quartz is suitable as the material for forming the mold because it has a small coefficient of thermal expansion and small pattern deformation.

[0368] The height of the pattern formed on the mold surface is, for example, 4 nm or more and 200 nm or less. As the pattern height of the mold decreases, the force for detaching the mold 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 due to tearing of the curable composition pattern. In addition, in some cases, when the mold is detached, the pattern of the curable composition elastically deforms due to impact, and adjacent pattern elements come into contact with each other and adhere or break. 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 will be reduced.

[0369] Before performing the contact step, the mold can also be surface-treated to improve the peelability of the mold with respect to the curable composition (A). Examples of such surface treatment are forming a release agent layer by coating a release agent on the mold surface. Examples of the release agent applied to the mold surface are a silicone-based release agent, a fluorine-based release agent, a hydrocarbon-based release agent, a polyvinyl-based release agent, a polypropylene-based release agent, a paraffin-based release agent, a lignite-based release agent, and a carnauba-based release agent. Commercially available coating-type release agents such as DSX manufactured by Daikin can also be appropriately used. Note that one type of release agent can be used alone, or two or more types of release agents can be used simultaneously. 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 simultaneously. Among the above release agents, fluorine-based and hydrocarbon-based release agents are particularly advantageous.

[0370] In the contact step, the pressure applied to the curable composition (A) when bringing the mold into contact with the curable composition (A) is not particularly limited, for example, it is 0 MPa or more and 100 MPa or less. Note that when bringing the mold into contact with the curable composition (A), the pressure applied to the curable composition (A) is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and further preferably 0 MPa or more and 20 MPa or less.

[0371] The contact step can be carried out under any one 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 contact step in an inert gas atmosphere are nitrogen, carbon dioxide, helium, argon, various Freon gases, and their gas mixtures. A gas containing carbon dioxide or helium in a molar ratio of 10% or more is preferred, and a gas containing carbon dioxide in a molar ratio of 10% or more is particularly preferred. Since helium easily diffuses into the mold, substrate, curable composition, etc., the atmospheric gas confined in the mold pattern quickly disappears. Since carbon dioxide easily dissolves in the curable composition or the underlying layer on the substrate, the atmospheric gas confined 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 Application Laid-Open No. 2022-99271 (Patent Document 5). When carrying out the contact step in a specific gas atmosphere including a normal air atmosphere, a favorable pressure is 0.0001 atm or more and 10 atm or less.

[0372] <Curing step>

[0373] In the curing step, as Figure 1 [6] schematically shows, the curable composition (A) is cured by irradiating with irradiation light as curing energy, thereby forming a cured film. In the curing step, for example, the curable composition (A) is irradiated with irradiation light through the mold. More specifically, the curable composition (A) filled in the fine pattern of the mold is irradiated with irradiation light through the mold. Therefore, the curable composition (A) filled in the fine pattern of the mold is cured, and a cured film having the pattern is formed.

[0374] The irradiation light is selected according to the sensitivity wavelength of the curable composition (A). More specifically, the irradiation light 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 is particularly preferably ultraviolet light. This is because many commercially available compounds as curing aids are sensitive to ultraviolet rays. 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, 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 multiple light sources can be used. The light can be emitted to the entire area of the curable composition (A) filled in the fine pattern of the mold, or (by restricting the area) only to a partial area thereof. The light can also be intermittently emitted to the entire area of the substrate multiple times, or continuously emitted to the entire area of the substrate. In addition, in the second irradiation treatment, the first area of the substrate can be irradiated with light, and the second area different from the first area of the substrate can be irradiated with light in the second irradiation treatment.

[0375] <Demolding step>

[0376] In the demolding step, as Figure 1 [7] schematically shown, the mold is detached from the cured film. When the mold is detached from the cured film having a pattern, a cured film having a pattern formed by inverting the fine pattern of the mold is obtained in an independent state. In this state, the cured film remains in the concave portion of the cured film having a pattern. This film is called a residual film.

[0377] The method of detaching the mold from the cured film having a pattern can be any method as long as the method does not physically damage a part of the cured film having a pattern during the detachment process, and various conditions and the like are not particularly limited. For example, the substrate can be fixed and the mold can be removed from the substrate. The mold can also be fixed and the substrate can be removed from the mold. In addition, by moving the mold and the substrate in completely opposite directions, the mold can be detached from the cured film having a pattern.

[0378] <Repeat>

[0379] A series of steps (manufacturing process) having the above steps from the arrangement step to the demolding step in order enables a cured film having a desired concavo-convex pattern shape (a pattern shape conforming to the uneven shape of the mold) to be obtained at a desired position.

[0380] In the above pattern formation method, the repeating unit (projection) from the arrangement step to the demolding step can be repeatedly performed multiple times on the same substrate, so that a cured film having a plurality of desired patterns at desired positions on the substrate can be obtained.

[0381] [Planarization film formation method]

[0382] An example in which the film formation method according to an embodiment of the present invention is applied to a planarization film formation method will be explained below. The planarization film formation method includes, for example, an arrangement step, a waiting step, a contact step, a curing step, and a demolding step. The arrangement step is a step of arranging 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 (d1) evaporates. The contact step is a step of bringing the curable composition (A) into contact with a 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). In the planarization film formation method, a substrate having an unevenness with a height difference of about 10 nm 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 conforming to the flat surface of the mold is formed through the contact step, the curing step, and the demolding step. In the arrangement step, the droplets of the curable composition (A) are densely arranged in the concave portions of the substrate and sparsely arranged on the convex portions of the substrate. The waiting step is performed after the arrangement 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.

[0383] [Article manufacturing method]

[0384] The article manufacturing method according to the present embodiment includes: a forming step of forming a film of a curable composition on a substrate using the above-described film formation method, a processing step of processing the substrate having the film of the curable composition 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 formation method may be a pattern formation method or a planarization film formation method.

[0385] A cured film having a pattern formed by the pattern formation method according to an embodiment of the present invention is directly used as at least a partial constituent member of various articles. Alternatively, a cured film having a pattern formed by the pattern formation method according to an embodiment of the present invention is temporarily used as a mask for etching or ion implantation of a substrate (a layer to be processed when the substrate has a layer to be processed). After etching or ion implantation is performed in the substrate processing step, the mask is removed. Thus, various articles can be manufactured.

[0386] When removing the cured product in the pattern recess of the cured product by etching, the actual method is not particularly limited, and conventional known methods such as dry etching can be used. Conventional known dry etching equipment can be used in this dry etching. The source gas for dry etching is appropriately selected according to the elemental composition of the cured product to be etched. As the source gas, halogen gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2, oxygen atom-containing gases such as O2, CO, and CO2, inert gases such as He, N2, and Ar, and gases such as H2 and NH3 can be used. Note that these gases can also be used as gas mixtures. In this case, the photocurable film needs to have high dry etching resistance in order to process the base substrate with high yield.

[0387] For example, the article is a circuit element, an optical element, an 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 sensors, 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.

[0388] Furthermore, a known lithography step such as imprint lithography technology or extreme ultraviolet exposure technology (EUV) can be performed on the planarization layer formed by the planarization film forming method according to an embodiment of the present invention. A spin-on glass (SOG) film and / or a silicon oxide layer can also be stacked, and a lithography step can be performed by applying a curable composition thereon. Therefore, devices such as semiconductor devices can be manufactured. An apparatus including the device can also be formed, such as an electronic apparatus such as a display, a camera, or a medical device. Examples of the device are LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, and NAND flash memory.

[0389] [Examples]

[0390] To supplement the above embodiments, more detailed examples will be described.

[0391] [Example 1]

[0392] In Example 1, numerical calculations showed that when γ1 is greater than γ2, the dropped liquid droplet spreads significantly (i.e., the spreading rate of the liquid droplet increases) and the solvent evaporates rapidly. Note that, as described above, γ1 is the surface tension of the curable composition at 23 °C in a state where the solvent (d) has been removed, and γ2 is the surface tension of the solvent (d) at 23 °C.

[0393] Under the initial condition that the contact angle is 90°, a 1 pL liquid droplet was placed on a flat substrate. By solving the Navier-Stokes equation through the thin film approximation (lubrication theory) for the free surface, how the liquid droplet spreads while evaporating was obtained. The liquid droplet is a binary fluid containing non-volatile components and volatile components, and the volume ratio of the non-volatile components under the initial condition is 20%. For the non-volatile components, the molecular weight is 300 g / mol, the viscosity is 150 cP, and the surface tension (γ1) is 35 mN / m. For the volatile components, the molecular weight is 125 g / mol, the viscosity is 1.1 cP, and the surface tension (γ2) was set to 30 mN / m, 34 mN / m, 34.9 mN / m, and 35 mN / m for calculation. The viscosity and surface tension of the curable composition change as evaporation proceeds. For the volume ratio function of the non-volatile components, the viscosity is interpolated by an exponential function, and the surface tension is interpolated by a linear function. In addition, when evaporation is complete, the calculation ends.

[0394] For the spreading of the liquid droplet, it was assumed that a preliminary film exists as a precursor film, and the volume ratio of the non-volatile components in the precursor film is equal to the volume ratio at the end of the liquid droplet.

[0395] Volatility was regarded as a source term for the time rate of change of the height of the liquid droplet, which is proportional to the mole fraction of the volatile components and was modeled as a uniform distribution in the spatial direction. As the proportionality coefficient, 10 -8 m / sec was used. The diffusion coefficient of the concentration diffusion of the non-volatile components was obtained through the Wilke-Chang equation, and the dependence of the non-volatile components on the concentration was interpolated by an exponential function.

[0396] Figure 6 Shows the time rate of change of the liquid droplet radius. The abscissa indicates the elapsed time [seconds], and the ordinate indicates the radius of the liquid droplet [m]. The change of Δγ defined by the following equation (3) between the curves. In 501, Δγ = 0, in 502, Δγ = 0.1, in 503, Δγ = 1, and in 504, Δγ = 5. From this result, it was found that: compared with Δγ = 0, when Δγ > 0, the maximum radius of the liquid droplet is larger and the time required to complete evaporation is shorter. It was also found that the larger Δγ is, the larger the maximum radius of the liquid droplet is and the shorter the time required to complete evaporation is.

[0397] Δγ := γ1 - γ2...(3)

[0398] Figure 7 Shows the dependence of the maximum radius of the droplet on Δγ. The abscissa indicates Δγ [mN / m], while the ordinate indicates Δr [μm]. Here, Δr is defined by the following equation (4). In equation (4), r is the maximum radius of the droplet, and r0 is the maximum radius of the droplet when Δγ = 0. As Figure 7 shown, Δr increases monotonically with the change of Δγ. It is found that: if Δγ > 0.1 mN / m, then Δr > 1 μm, that is, the droplet diffuses more than when Δγ = 0. In addition, it is found that: if Δγ > 1 mN / m, then Δr > 10 μm, that is, the diffusion of the droplet is more obvious than when Δγ = 0.

[0399] Δr := r - r0...(4)

[0400] Figure 8 Shows the dependence of the evaporation time on Δγ. The abscissa indicates Δγ [mN / m], while the ordinate indicates Rt. Here, Rt is defined by the following equation (5). In equation (5), t is the evaporation time of the droplet, and t0 is the evaporation time of the droplet when Δγ = 0. It can be clearly seen from Figure 8 it that Rt decreases monotonically with the change of Δγ. It is found that: if Δγ > 0.1 mN / m, then Rt < 0.85, that is, the time required to complete evaporation is shorter compared to when Δγ = 0. It is found that if Δγ > 1 mN / m, then Rt < 0.6, that is, the time required to complete evaporation is significantly shorter compared to when Δγ = 0.

[0401] Rt := t / t0...(5)

[0402] It can be clearly seen from the above results that compared with when Δγ = 0, when Δγ > 0, the maximum radius of the droplet is larger and the time required to complete evaporation is shorter. In addition, in order to obtain the influence on the maximum radius of the droplet and the time required to complete evaporation, preferably, Δγ > 0.1 mN / m is ideal, and more preferably, Δγ > 1 mN / m is ideal.

[0403] [Example 2]

[0404] In Example 2, numerical calculations show that when γ1 is greater than γ2, a thinner cured film can be formed.

[0405] Generally speaking, if the arranged droplet spacing is small, the droplets will combine with each other to form a continuous liquid film. If the droplet spacing is large, the droplets cannot combine with each other and cannot form a continuous liquid film. Hereinafter, the maximum value of the droplet spacing that can form a continuous liquid film until evaporation is completed will be referred to as the critical droplet spacing. As described in Example 1 above, compared with Δγ = 0, when Δγ > 0, the maximum radius of the droplet at the end of evaporation is larger. This indicates that when Δγ > 0, the critical droplet spacing is larger than when Δγ = 0.

[0406] Under the initial condition where the droplets are arranged in a square array, numerical calculations are performed according to the same process as in Example 1 above to check the critical droplet spacing. The results are shown in Tables 1 and 2 below. In each table, for each droplet spacing, it is indicated whether a continuous liquid film can be formed until evaporation is completed under each of the cases of Δγ = 0 and Δγ = 5. In each table, "OK" indicates that a continuous liquid film can be formed, and "NG" indicates that a continuous liquid film cannot be formed. Note that Table 1 shows the results for a highly volatile solvent with a evaporation rate coefficient of about 5×10 -8 m / s, while Table 2 shows the results for a low volatile solvent with an evaporation rate coefficient of about 7×10 -10 m / s.

[0407] [Table 1]

[0408]

[0409] [Table 2 ]

[0410]

[0411] According to Table 1, in the case of the highly volatile solvent, it is found that the critical droplet spacing when Δγ = 0 is from 56 μm to 63 μm, and the critical droplet spacing when Δγ = 5 is from 88 μm to 94 μm. Therefore, it is found that when Δγ > 0, the critical droplet spacing is larger than when Δγ = 0. A droplet spacing of 56 μm indicates a film thickness of 63 nm, while a droplet spacing of 88 μm indicates a film thickness of 26 nm. It is found that when Δγ > 0, a thinner cured film can be formed compared with when Δγ = 0.

[0412] According to Table 2, in the case of the low volatile solvent, it is found that the critical droplet spacing when Δγ = 0 is from 88 μm to 94 μm, and the critical droplet spacing when Δγ = 5 is from 119 μm to 125 μm. Therefore, it is found that when Δγ > 0, the critical droplet spacing is larger than when Δγ = 0. A droplet spacing of 0.88 μm indicates a film thickness of 26 nm, and a droplet spacing of 119 μm indicates a film thickness of 14 nm. It is found that when Δγ > 0, a thinner cured film can be formed compared with when Δγ = 0.

[0413] <Evaluation of Inkjet Emission Performance and Filling Performance>

[0414] According to Table 3 below, the curable composition (A) was mixed so that the sum of the monofunctional polymerizable compound (a), the polyfunctional polymerizable compound (a), the photopolymerization initiator (b), and the solvent (d) became 100% by weight. The abbreviations in Table 4 and the various physical property values of the individual materials are shown in Tables 4 and 5. The viscosity of the curable composition (A) at 23°C and the curable composition (A) mixed without using the solvent (d) were measured. In addition, the OP of the polymerizable compound (a) {the sum of the monofunctional compound and the polyfunctional compound} in the state where the solvent (d) was removed (when the solvent was removed) was calculated by the above method. In addition, the glass transition temperature of the curable composition after curing was measured. The results are shown in Table 6. In addition, the details of the photopolymerization initiator used in Table 3 are shown below.

[0415] <<Photopolymerization Initiator (b)>>

[0416] “Omnirad 819: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide” (manufactured by IGM Resin)

[0417] <<Surfactant>>

[0418] S1: MEGAFACE F-444 (manufactured by DIC)

[0419] S2: NOL L-44 (manufactured by ADEKA)

[0420] [Table 3]

[0421]

[0422] [Table 4]

[0423]

[0424] [Table 5]

[0425]

[0426] [Table 6]

[0427]

[0428] <Inkjet Emission Evaluation>

[0429] For inkjet emission evaluation, a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm) was used. Examples 3 to 22 and Comparative Examples 1 to 6 obtained in Table 3 were filled into 1-pL ink cartridges. The emission state was observed with an internal emission observation camera and evaluated according to the following determination criteria.

[0430] (Evaluation Criteria)

[0431] AAA: At a flight speed of 11 m / sec or more, no deformation was observed at all.

[0432] AA: At a flight speed of 11 m / sec or more, very slight deformation with no practical effect was observed.

[0433] A: At a flight speed of 10 m / sec or more, very slight deformation with no practical effect was observed.

[0434] B: Emission was not performed.

[0435] <Filling Performance Evaluation>

[0436] Under the condition that the liquid film thickness before the evaporation of solvent (d) was 80 nm, each curable composition (A) of Examples 3 to 22 and Comparative Examples 1 to 6 was discretely dropped (arranged) on a silicon substrate. The time until a practically continuous liquid film was formed was measured, and the filling performance was evaluated based on the following determination criteria.

[0437] (Evaluation Criteria)

[0438] AAA: An almost continuous liquid film was formed in less than 100 seconds.

[0439] AA: An almost continuous liquid film was formed in 100 seconds or more and less than 200 seconds.

[0440] A: An almost continuous liquid film was formed in 200 seconds or more and less than 300 seconds.

[0441] B: An almost continuous liquid film was not formed even after 300 seconds.

[0442] <Pattern Collapse Evaluation>

[0443] Using a quartz mold with a line and space (L / S) pattern having a depth of 50 nm and a width of 20 nm formed over the entire area, each curable composition (A) of Examples 3 to 22 and Comparative Examples 1 to 6 was subjected to an arrangement step, a waiting step, a contact step, a curing step, and a demolding step. The patterns obtained through these steps were observed and evaluated based on the following determination criteria.

[0444] (Evaluation Criteria)

[0445] AAA: Pattern collapse is observed in an area less than 0.5% of the pattern formation area.

[0446] AA: Pattern collapse is observed in an area less than 1% of the pattern formation area.

[0447] A: Pattern collapse is observed in an area less than 10% of the pattern formation area.

[0448] B: Pattern collapse is observed in an area more than 10% of the pattern formation area.

[0449] <Dry Etching Resistance Evaluation>

[0450] The cured films obtained in Examples 3 to 18 and Comparative Examples 1 to 6 were exposed to oxygen plasma in a dry etching apparatus. In addition, the cured films obtained in Examples 19 to 22 were exposed to CF4 plasma in a dry etching apparatus. The weight change of the remaining film in each example was measured and evaluated based on the following determination criteria.

[0451] (Evaluation Criteria)

[0452] AAA: The weight of the remaining cured film is 46% or more of the weight before etching.

[0453] AA: The weight of the remaining cured film is 42% or more of the weight before etching.

[0454] A: The weight of the remaining cured film is 38% or more of the weight before etching.

[0455] B: The weight of the remaining cured film is less than 38% of the weight before etching.

[0456] Table 7 shows the above evaluation results. It was found that if the viscosity of the curable composition at 23 °C is 1.3 mPa·s or more and 60 mPa·s or less, the inkjet discharge performance is excellent. It was found that if the viscosity of the curable composition at 23 °C is preferably 3 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 15 mPa·s or less, the inkjet discharge is more excellent. It was found that if the surface tension γ1 (mN / m) of the curable composition in the state where the solvent is removed is greater than the surface tension γ2 of the solvent, the inkjet filling performance is excellent. It is preferred that Δγ = γ1 - γ2 > 0.1 (mN / m), more preferably Δγ = γ1 - γ2 > 1. (mN / m), and even more preferably Δγ = γ1 - γ2 > 2.0 (mN / m).

[0457] If the glass transition temperature of the cured curable composition after curing is 130°C or higher, pattern collapse is observed in an area less than 0.5% of the pattern formation area. If the glass transition temperature is 100°C or higher and less than 130°C, pattern collapse is observed in an area less than 1% of the pattern formation area. If the glass transition temperature is 70°C or higher and less than 100°C, pattern collapse is observed in an area less than 10% of the pattern formation area. If the glass transition temperature is lower than 70°C, pattern collapse is observed in an area more than 10% of the pattern formation area. In all cases, the degree of pattern collapse is very slight.

[0458] In addition, in Examples 3 to 18 and Comparative Examples 1 to 6, if the OP of the polymerizable compound (a) is 2.50 or more and 3.00 or less, the weight of the remaining cured film is 46% of that before etching. If the OP of the polymerizable compound (a) is 3.00 or more and less than 3.50, 42% or more of the curable composition remains as a cured film. If the OP in the polymerizable compound (a) is 3.50 or more and less than 4.00, 38% or more of the curable composition remains as a cured film. If the curable composition (A) in Examples 19 to 22 contains 10% by weight or more of Si atoms in a state where the solvent (d) is removed, 38% or more of the curable composition remains as a cured film.

[0459] [Table 7]

[0460]

[0461]

[0462] The present invention is not limited to the above embodiments, and various changes and modifications can be made within the spirit and scope of the present invention. Therefore, the appended claims are presented to enable the public to understand the scope of the present invention.

[0463] This application claims the priority of Japanese Patent Application No. 2022-190577 filed on November 29, 2022, and No. 2023-163584 filed on September 26, 2023, which are incorporated herein by reference.

Claims

1. A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), characterized in that: The curable composition has a viscosity at 23 °C of not less than 1.3 mPa·s and not more than 60 mPa·s, The content of the solvent (d) relative to the entire curable composition is greater than 5% by volume and not more than 95% by volume, The boiling point of the solvent (d) is lower than 250 °C, and Let γ1 (mN / m) be the surface tension of the curable composition at 23 °C in the state where the solvent (d) is removed, and γ2 (mN / m) be the surface tension of the solvent (d) at 23 °C, then γ1 is greater than γ2.

2. The curable composition according to claim 1, characterized in that, Δγ = γ1 - γ2 > 0.1 (mN / m).

3. The curable composition according to claim 1, wherein Δγ = γ1 - γ2 > 1 (mN / m).

4. The curable composition according to claim 1, characterized in that, In the state where the solvent (d) is removed, the viscosity of the curable composition at 23 °C is not less than 30 mPa·s and not more than 10000 mPa·s.

5. The curable composition according to claim 1, characterized in that, The solvent (d) contains not less than one type of solvent, and the boiling point of each type of solvent in the not less than one type of solvent under normal pressure is not lower than 100 °C and lower than 250 °C.

6. The curable composition according to claim 1, wherein The solvent (d) contains a polymerizable compound having a boiling point under normal pressure of not lower than 100 °C and lower than 250 °C.

7. The curable composition according to claim 1, characterized in that, The solvent (d) contains not less than one type of solvent, and the boiling point of each type of solvent in the not less than one type of solvent under normal pressure is not lower than 100 °C and lower than 200 °C.

8. The curable composition according to claim 1, characterized in that, The content of the solvent (d) relative to the entire curable composition is not less than 50% by volume and not more than 85% by volume.

9. The curable composition according to claim 1, wherein, The proportion of the polyfunctional polymerizable compound in the polymerizable compound (a) is not less than 20% by weight.

10. The curable composition according to claim 1, characterized in that, The polymerizable compound (a) contains not less than one type of polymerizable compound, and the boiling point of each type of polymerizable compound in the not less than one type of polymerizable compound under normal pressure is not lower than 250 °C.

11. The curable composition according to claim 1, characterized in that, The polymerizable compound (a) contains not less than one type of polymerizable compound, and the molecular weight of each type of polymerizable compound in the not less than one type of polymerizable compound is not less than 200.

12. The curable composition according to claim 1, wherein At least a polymer having a polymerizable functional group is included as the polymerizable compound (a).

13. The curable composition according to claim 1, wherein The glass transition temperature of the cured product obtained by curing the polymerizable compound (a) in the state where the solvent (d) is removed is not lower than 70 °C.

14. The curable composition according to claim 1, wherein The polymerizable compound (a) contains not less than one type of polymerizable compound, and the vapor pressure of each type of polymerizable compound in the not less than one type of polymerizable compound at 80 °C is not more than 0.001 mmHg.

15. The curable composition according to claim 1, wherein At least a compound (a-1) having at least one of an aromatic structure, an aromatic heterocyclic structure, and an alicyclic structure is included as the polymerizable compound (a).

16. The curable composition according to claim 1, wherein The polymerizable compound (a) contains not less than one type of polymerizable compound, and The Ohnishi parameter OP of the polymerizable compound (a) is not less than 1.80 and not greater than 4.00, and is the mole fraction weighted average of the N / (N C -N O ) values of the respective molecules of the at least one type of polymerizable compound, where N is the number of all atoms in the molecule, N C is the number of carbon atoms in the molecule, and N O is the number of oxygen atoms in the molecule.

17. The curable composition according to claim 1, characterized in that, At least a compound (a-2) containing at least a Si atom is included as the polymerizable compound (a).

18. The curable composition according to claim 17, characterized in that, At least a polymerizable compound having at least one of a silsesquioxane skeleton and a cyclic siloxane compound is included as the compound (a-2) containing at least a Si atom.

19. The curable composition according to claim 1, wherein The curable composition in a state where the solvent (d) has been removed contains not less than 10% by weight of Si atoms.

20. The curable composition according to claim 1, characterized in that, The curable composition is a curable composition for inkjet.

21. The curable composition according to claim 1, wherein The solubility coefficient of carbon dioxide in the curable composition is not less than 0.5 kg / m 3 ·atm and not greater than 10 kg / m 3 ·atm.

22. A method for forming a film of a curable composition in a space between a mold and a substrate, characterized in that, The film forming method includes: a disposing step of discretely disposing a plurality of droplets of the curable composition defined in any one of claims 1 to 21 on a substrate; a waiting step of waiting until the plurality of droplets discretely disposed on the substrate combine with their respective adjacent droplets to form a continuous liquid film on the substrate; and a contacting step of bringing the mold and the liquid film on the substrate into contact with each other after the waiting step.

23. The film forming method according to claim 22, wherein, In the waiting step, waiting is performed until the solvent contained in the liquid film volatilizes, and the content of the solvent is not more than 10% by volume with respect to the entire liquid film.

24. The film forming method according to claim 22, wherein, In the waiting step, the substrate is heated at not less than 30°C and not higher than 200°C for not less than 10 seconds and not more than 600 seconds.

25. The film forming method according to claim 22, characterized in that, In the dispensing step, droplets of the curable composition each having a volume of not less than 1.0 pL are dispensed onto a substrate at a density of not less than 80 droplets / mm 2 .

26. The film forming method according to claim 22, characterized in that, The average residual liquid film thickness, which is a value obtained by dividing the volume of the curable composition remaining after the waiting step by the area of the film forming region, is not more than 20 nm.

27. The film forming method according to claim 22, wherein the mold includes a pattern, in the contacting step, the pattern of the mold and the liquid film on the substrate are brought into contact with each other, and the film forming method further includes a curing step of curing the liquid film after the contacting step, thereby forming a cured film having a pattern corresponding to the pattern of the mold.

28. The film forming method according to claim 22, wherein the mold includes a flat surface, in the contacting step, the flat surface of the mold and the liquid film on the substrate are brought into contact with each other, and the film forming method further includes a curing step of curing the liquid film after the contacting step, thereby forming a cured film having a surface consistent with the flat surface of the mold.

29. The film forming method according to claim 22, wherein, In the disposing step, the plurality of droplets are discretely disposed on the substrate by using an inkjet method.

30. The film forming method according to claim 22, wherein, In the contacting step, the gas filling the space between the substrate and the mold contains not less than 10% by mole of carbon dioxide.

31. A method for manufacturing an article, characterized in that, The article manufacturing method includes: a forming step of forming a film of a curable composition on a substrate by using the film forming method defined in claim 22; a processing step of processing the substrate on which the film has been formed in the forming step; and a manufacturing step of manufacturing an article from the substrate processed in the processing step.

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