Film forming method, article manufacturing method, and curable composition

Abstract

To provide a technique advantageous for achieving both edge filling speed and exudation prevention.SOLUTION: A film forming method includes: an arrangement step of discretely arranging a plurality of droplets of a curable composition on a substrate; a contact step of bringing a mold and the plurality of droplets on the substrate into contact with each other to form a liquid film between the mold and the substrate; a curing step of curing the liquid film to form a cured film; and a separation step of separating the cured film and the mold from each other. The viscosity μ [mPa s] of a non-volatile composition of the curable composition, and an average thickness h [m] of the liquid film formed by the non-volatile composition satisfy a relational expression 1: 20 [μm / sec]≤C hα μ0 / μ, C=9.75e-2, α=0.489, μ0=50 [mPa s], and a relational expression 2: 0.5 [sec]≤C hα μ / μ0, C=1.89e-15, α=-2.1, μ0=50 [mPa s].SELECTED DRAWING: Figure 5

Description

Technical Field

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

Background Art

[0002] In semiconductor devices, MEMS, etc., the demand for miniaturization is increasing, and as a microfabrication technique, imprint technology (photoimprint technology) has attracted attention. In imprint technology, a mold with a fine concavo-convex pattern formed on its surface is brought into contact with a curable composition supplied (coated) onto a substrate, and the curable composition is cured in this state. Thereby, the pattern of the mold is transferred to the cured film of the curable composition, and the pattern is formed on the substrate. According to imprint technology, a fine pattern (structure) on the order of several nanometers can be formed on the substrate (see Patent Document 1).

[0003] An example of a pattern forming method using imprint technology will be described. First, a liquid curable composition is discretely dropped (arranged) on a pattern forming region on a substrate. The droplets of the curable composition arranged in the pattern forming region spread on the substrate. Such a phenomenon is called a pre-press spread. Next, a mold is brought into contact with (pressed against) the curable composition on the substrate. Thereby, the droplets of the curable composition spread over the entire gap between the substrate and the mold due to capillary action. Such a phenomenon is called a spread. Further, the curable composition is filled into the recesses constituting the pattern of the mold due to capillary action. Such a phenomenon is called filling. The time until the spread and filling are completed is called the filling time. When the filling of the curable composition is completed, light is irradiated onto the curable composition to cure the curable composition. Then, the mold is separated from the cured curable composition on the substrate. By performing these steps, the pattern of the mold is transferred to the curable composition on the substrate, and the pattern of the curable composition is formed. Here, the pattern of the curable composition formed on the substrate includes a residual film. The residual film is a cured film remaining between the recess (the convex portion of the pattern of the mold) of the cured film of the curable composition and the substrate.

[0004] In the photolithography process for manufacturing semiconductor devices, it is also necessary to planarize the substrate. For example, in extreme ultraviolet lithography (EUV), a photolithography technology that has attracted attention in recent years, as the miniaturization progresses, the depth of focus at which the projected image is formed becomes shallower. Therefore, the surface unevenness of the substrate to which the curable composition is supplied must be suppressed to several tens of nm or less. Also in imprint technology, flatness comparable to that of EUV is required to improve the filling property and line width accuracy of the curable composition (see Non-Patent Document 1). As a planarization technique, there is known a technique for obtaining a flat surface by discretely dropping droplets of a curable composition in an amount corresponding to the unevenness on a substrate having unevenness and curing the curable composition while bringing a mold having a flat surface into contact therewith (see Patent Documents 2 and 3).

[0005] In the pattern formation method and planarization technique using imprint technology, since the mold is brought into contact with the substrate in a state where the droplets of the curable composition dropped on the substrate do not contact each other, air bubbles can be entrapped between the mold, the substrate, and the curable composition. It takes a long time until such air bubbles diffuse and disappear in the mold or the substrate, and this is one of the factors that reduce productivity (throughput). Therefore, it has been proposed to bond the droplets of the curable composition to each other before bringing the curable composition on the substrate into contact with the mold (see Patent Documents 4 and 5).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Non-Patent Documents

[0007]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, in the technique described in Patent Document 5, after the droplets of the curable composition spread to such an extent that the droplets of the curable composition bond to each other, it is necessary to fill the curable composition up to the end of the contact region between the mold and the substrate by bringing the mold into contact with the curable composition. Filling the curable composition up to the end of the contact region between the mold and the substrate is called edge filling. The speed at which edge filling occurs is called the edge filling rate. In a pattern formation method or a planarization technique using an imprint technique, since the mold is brought into contact with the droplets of the curable composition on the substrate, it takes time to fill the curable composition up to the end of the desired region, which is one of the factors that reduce productivity (throughput). In addition, edge filling may proceed excessively and the curable composition may overflow from the edge and creep up the side wall of the mold. The cured product of the curable composition adhering to this side wall may remain on the substrate as an unnecessary cured product, remain on the mold side wall and fall onto the substrate at an unintended timing after the next shot, or cause a large defect on the substrate. Hereinafter, the phenomenon in which the curable composition creeps up the side wall of the mold is called "bleeding". The time until the curable composition spreads over the entire contact region between the substrate and the mold, the curable composition overflows from the contact surface of the mold, and the height of bleeding where the curable composition creeps up the side wall of the mold reaches 50 nm is called the "bleeding allowance time".

[0009] In the technology described in Patent Document 5, it is a problem to achieve both an edge filling speed and suppression of bleeding.

[0010] The present invention provides a technology advantageous for achieving both an edge filling speed and suppression of bleeding.

Means for Solving the Problems

[0011] According to one aspect of the present invention, there is provided a film forming method for forming a film of a curable composition on a substrate using a mold, the method including: an arranging step of discretely arranging a plurality of droplets of the curable composition on the substrate; a contacting step of contacting the plurality of droplets on the substrate with the mold after the arranging step to form a liquid film between the substrate and the mold; a curing step of curing the liquid film to form a cured film after the contacting step; and a separating step of separating the cured film from the mold after the curing step, wherein the viscosity μ [mPa·s] of the non-volatile composition in the curable composition and the average liquid film thickness h [m] formed by the non-volatile composition satisfy Relational Expression 1: 20 [μm / sec] ≦ C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s], and Relational Expression 2: 0.5 [sec] ≦ C·h α ·μ / μ0, C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s] and a film forming method is provided, which is characterized by being a value that satisfies the above.

[0012] A further object or other aspect of the present invention will be clarified by the embodiments described below with reference to the accompanying drawings.

Effects of the Invention

[0013] According to the present invention, it is possible to provide a technology advantageous for achieving both an edge filling speed and suppression of bleeding.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

[0015] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although a plurality of features are described in the embodiments, not all of these plurality of features are essential to the invention, and the plurality of features may be arbitrarily combined. Further, in the accompanying drawings, the same or similar configurations are denoted by the same reference numerals, and redundant descriptions are omitted.

[0016] [Curable Composition] The curable composition (A) in the present disclosure can be a curable composition for inkjet. The curable composition (A) in the present disclosure is a composition containing at least a component (a) which is a polymerizable compound and a component (b) which is a photopolymerization initiator. Further, the curable composition (A) in the present disclosure may contain a component (d) which is a solvent. Also, in the present specification, the non-volatile composition (A') refers to a composition composed of the component (a), the component (b), and the component (c) remaining when the component (d) which is a solvent in the curable composition (A) volatilizes. Hereinafter, "component (d)" is also referred to as "solvent (d)".

[0017] Also, in the present specification, the cured film means a film obtained by polymerizing and curing the curable composition on a substrate. The shape of the cured film is not particularly limited and may have a pattern shape on the surface. Further, the cured film remaining between the concave portion (convex portion of the mold pattern) of the cured film of the curable composition and the substrate is referred to as a residual film.

[0018] <Component (a): Polymerizable compound> Component (a) is a polymerizable compound. In the present specification, the polymerizable compound is a compound that reacts with a polymerization factor (such as a radical) generated from a photopolymerization initiator (component (b)) and forms a film composed of a high molecular compound by a chain reaction (polymerization reaction).

[0019] Examples of such polymerizable compounds include radical polymerizable compounds. The polymerizable compound which is component (a) may be composed of only one type of polymerizable compound or may be composed of a plurality of types (one or more types) of polymerizable compounds.

[0020] Examples of the radical polymerizable compound include (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleic compounds.

[0021] (Meth)acrylic compounds refer to compounds having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or methacryloyl group include, but are not limited to, the following. Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, (meth)acrylate of EO-modified p-cumylphenol, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-Tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy (meth)acrylate, PO-modified phenoxy (meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (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, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (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, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, 1- or 2-naphthyl (meth)acrylate, 1- or 2-naphthylmethyl (meth)acrylate, 3- or 4-phenoxybenzyl (meth)acrylate, cinobenzyl (meth)acrylate, naphthalenemethyl (meth)acrylate,

[0022] Examples of commercially available products of the above-mentioned monofunctional (meth)acrylic compounds include, but are not limited to, the following. Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (manufactured by Toagosei Co., Ltd.), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Biscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light Acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, Epoxy Ester M-600A, POB-A, OPP-EA (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD (registered trademark) TC110S, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.), NK Ester AMP-10G, AMP-20G, A-LEN-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (manufactured by Hitachi Chemical Co., Ltd.), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (manufactured by Kojin Co., Ltd.), HRD-01 (manufactured by Nippon Shokubai Co., Ltd.)

[0023] Examples of the polyfunctional (meth)acrylic compound having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane 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-adamantanediol dimethacrylate, 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)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m- or p-benzenedi(meth)acrylate, o-, m- or p-xylylene di(meth)acrylate

[0024] Examples of commercially available products of the above polyfunctional (meth)acrylic compounds include, but are not limited to, the following. Upimer (registered trademark) UV SA1002, SA2007 (both manufactured by Mitsubishi Chemical), Biscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (all 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, DPE-6A (all manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku), Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei), Lipoxy (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Highpolymer), Ogsoal EA-0200, Ogsoal EA-0300 (both manufactured by Osaka Gas Chemical), SR295, SR355 (both manufactured by Sartomer)

[0025] In the above-described group of compounds, (meth)acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. (Meth)acryloyl group means acryloyl group or methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A means a compound in which the (meth)acrylic acid residue and the alcohol residue of compound A are bonded via a block structure of ethylene oxide groups. Further, PO represents propylene oxide, and PO-modified compound B means a compound in which the (meth)acrylic acid residue and the alcohol residue of compound B are bonded via a block structure of propylene oxide groups.

[0026] Specific examples of styrene-based compounds include, but are not limited to, the following. Alkylstyrenes such as styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; Halogenated styrenes such as fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodostyrene; Nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, divinylbiphenyl, etc., compounds having a styryl group as a polymerizable functional group

[0027] Specific examples of the vinyl-based compound include, but are not limited to, the following. Vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, vinyl acetate and acrylonitrile; conjugated diene monomers such as butadiene, isoprene and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride, vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc., (meth)acrylonitrile, etc., compounds having a vinyl group as a polymerizable functional group

[0028] In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0029] Examples of acrylic compounds include, but are not limited to, the following. Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate

[0030] Examples of fumaric compounds include, but are not limited to, the following. Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate

[0031] Examples of maleic compounds include, but are not limited to, the following. Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate

[0032] Examples of other radically polymerizable compounds include, but are not limited to, the following. Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, dibenzyl itaconate, etc.), N-vinylamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimide and its derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.)

[0033] When component (a) is composed of a plurality of types of compounds having one or more polymerizable functional groups, it is preferable to include both a monofunctional polymerizable compound and a polyfunctional polymerizable compound. Among component (a), the ratio of the polyfunctional polymerizable compound 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 by combining a monofunctional polymerizable compound and a polyfunctional polymerizable compound, a cured film with excellent performance balance such as high mechanical strength, high dry etching resistance, and high heat resistance can be obtained.

[0034] In the film-forming method of the present disclosure, since it takes several milliseconds to several hundred seconds for the droplets of the curable composition (A) discretely arranged on the substrate to combine with each other to form a substantially continuous liquid film, a standby step described later is required. In the standby step, while the solvent (d) is volatilized, the polymerizable compound (a) must not be volatilized. Therefore, the boiling point of each of the one or more polymerizable compounds contained in the polymerizable compound (a) under normal pressure is preferably 250°C or higher, more preferably 300°C or higher, and still more preferably 350°C or higher. Further, in the cured film of the curable composition (A), in order to obtain high dry etching resistance and high heat resistance, it is preferable to contain at least a compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that normal pressure is defined as 1 atm (atmospheric pressure).

[0035] The boiling point of the polymerizable compound (a) generally correlates with the molecular weight. Therefore, the molecular weight of each of the one or more polymerizable compounds contained in the polymerizable compound (a) is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. However, even if the molecular weight is 200 or less, if the boiling point is 250°C or more, it can be preferably used as the polymerizable compound (a) in the present disclosure. Thus, the boiling point of each of the one or more polymerizable compounds contained in the polymerizable compound (a) under normal pressure is preferably 250°C or more.

[0036] Also, the vapor pressure of the polymerizable compound (component (a)) at 80°C and 1 atm is preferably 0.001 mmHg or less. When the polymerizable compound (a) contains one or more polymerizable compounds, the vapor pressure of each of the one or more polymerizable compounds at 80°C and 1 atm is preferably 0.001 mmHg or less. This is because it is preferable to heat the curable composition in order to accelerate the volatilization of the solvent (component (d)) described later, and this is to suppress the volatilization of the polymerizable compound (a) during such heating.

[0037] Incidentally, the boiling point and vapor pressure of various organic compounds under normal pressure can be calculated by, for example, Hansen Solubility Parameters in Practice (HSPiP) 5th Edition.5.3.04.

[0038] <Ohnishi parameter of component (a)> The dry etching rate V of an organic compound, the total number of atoms N in the organic compound (in the molecule), the total number of carbon atoms N in the composition (in the molecule) c , and the total number of oxygen atoms N in the composition (in the molecule) o are known to have the relationship of the following formula (1).

[0039] V ∝ N / (N c - N o ) Formula (1) Here, N / (N c - N o) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, in U.S. Patent Application Publication No. 2020 / 0286740 (Patent Document 3), a technique for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP is disclosed.

[0040] According to formula (1), it is suggested that the more oxygen atoms in the molecule, or the fewer aromatic ring structures and alicyclic ring structures, the larger the OP and the faster the dry etching rate of the organic compound.

[0041] Among the curable compositions (A) in the present disclosure, the OP of component (a) is 1.80 or more and 4.00 or less. The OP of component (a) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or more. By setting the OP of component (a) to 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. In addition, by setting the OP of component (a) to 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing its underlying layer using the cured film of the curable composition (A). When component (a) is composed of a plurality of types of polymerizable compounds a1, a2, ···, a n When it is composed of, as shown in the following formula (2), the OP is calculated as a weighted average value based on the mole fraction (mole fraction weighted average value). Thus, when component (a) contains one or more types of polymerizable compounds, the OP of component (a) can be calculated as the mole fraction weighted average value of the N / (N c -N o ) values of each molecule of one or more types of polymerizable compounds.

[0042]

Number

[0043] Here, OP n is the OP of component a n and n n is the mole fraction of component a n in the total amount of component (a).

[0044] In order to make the OP of component (a) 1.80 or more and 2.70 or less, it is preferable to contain, as at least component (a), a compound (a-1) having two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0045] <Compound (a-1): A polymerizable compound having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure> The polymerizable compound (a) in the present disclosure may contain a polymerizable compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Further, among component (a), the ratio of component (a-1) is preferably 65% by weight or more. By setting the ratio of component (a-1) to 65% by weight or more, it becomes possible to suppress the OP to 2.70 or less.

[0046] Examples of the cyclic structure include an aromatic structure, an aromatic heterocyclic structure, and an alicyclic structure.

[0047] For the aromatic structure, the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10. Specific examples of the aromatic ring include the following. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring Among the above-mentioned aromatic rings, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a structure in which a plurality are linked, and examples include a biphenyl ring and a bisphenyl ring.

[0048] For the aromatic heterocyclic structure, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 5. Specific examples of the aromatic heterocyclic ring include the following. 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, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring

[0049] As the alicyclic structure, the number of carbon atoms is preferably 3 or more, more preferably 4 or more, and still more preferably 6 or more. Further, as the alicyclic structure, the number of carbon atoms is preferably 22 or less, more preferably 18 or less, still more preferably 6 or less, and even more preferably 5 or less. Specific examples thereof include the following. 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, bornane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring

[0050] Specific examples of the polymerizable compound (a-1) having a boiling point of 250 ° C or higher include, for example, the following, but are not limited thereto. 3-Phenoxybenzyl acrylate (mPhOBzA, OP2.54, boiling point 367.4 ° C, vapor pressure 0.0004 mmHg at 80 ° C, molecular weight 254.3),

[0051]

Chemical formula

[0052] 1-Naphthyl acrylate (NaA, OP 2.27, boiling point 317 °C, vapor pressure at 80 °C 0.0422 mmHg, molecular weight 198),

[0053]

Chem.

[0054] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP 2.57, boiling point 364.2 °C, vapor pressure at 80 °C 0.0006 mmHg, molecular weight 268.3),

[0055]

Chem.

[0056] 1-Naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1 °C, vapor pressure at 80 °C 0.042 mmHg, molecular weight 212.2),

[0057]

Chem.

[0058] 2-Naphthylmethyl acrylate (Na2MA, OP 2.33, boiling point 342.1 °C, vapor pressure at 80 °C 0.042 mmHg, molecular weight 212.2)

[0059]

Chem.

[0060] DPhPA shown in the following formula (OP 2.38, boiling point 354.5 °C, vapor pressure at 80 °C 0.0022 mmHg, molecular weight 266.3),

[0061]

Chem.

[0062] PhBzA (OP 2.29, boiling point 350.4 °C, vapor pressure at 80 °C 0.0022 mmHg, molecular weight 238.3) shown by the following formula,

[0063]

Chem.

[0064] FLMA (OP 2.20, boiling point 349.3 °C, vapor pressure at 80 °C 0.0018 mmHg, molecular weight 250.3) shown by the following formula,

[0065]

Chem.

[0066] ATMA (OP 2.13, boiling point 414.9 °C, vapor pressure at 80 °C 0.0001 mmHg, molecular weight 262.3) shown by the following formula,

[0067]

Chem.

[0068] DNaMA (OP 2.00, boiling point 489.4 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 338.4) shown by the following formula,

[0069]

Chem.

[0070] BPh44DA (OP 2.63, boiling point 444 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 322.3) shown by the following formula,

[0071]

Chem.

[0072] BPh43DA shown in the following formula (OP2.63, boiling point 439.5 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 322.3),

[0073]

Chem.

[0074] DPhEDA shown in the following formula (OP2.63, boiling point 410 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 322.3),

[0075]

Chem.

[0076] BPMDA shown in the following formula (OP2.68, boiling point 465.7 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 364.4),

[0077]

Chem.

[0078] Na13MDA shown in the following formula (OP2.71, boiling point 438.8 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 296.3),

[0079]

Chem.

[0080] The following formula (a-1-1) (OP2.40, boiling point 333.4 °C, vapor pressure at 80 °C 0.0181 mmHg, molecular weight 199.2),

[0081]

Chem.

[0082] The following formula (a-1-2) (OP2.40, boiling point 333.4 °C, vapor pressure at 80 °C 0.0181 mmHg, molecular weight 199.2),

[0083]

Chem.

[0084] The following formula (a-1-3) (OP1.86, boiling point 369.5 °C, vapor pressure at 80 °C 0.0053 mmHg, molecular weight 193.3),

[0085]

Chem.

[0086] The following formula (a-1-4) (OP2.85, boiling point 438.8 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 296.3),

[0087]

Chem.

[0088] The following formula (a-1-5) (OP2.71, boiling point 438.8 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 296.3),

[0089]

Chem.

[0090] The following formula (a-1-6) (OP2.87, boiling point 421.0 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 338.4),

[0091]

Chem.

[0092] The following formula (a-1-7) (OP2.87, boiling point 465.2 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 338.4),

[0093] [Chemistry]

[0094] 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),

[0095] [Chemistry]

[0096] 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),

[0097] [Chemistry]

[0098] The following formula (a-1-10) (OP 2.64, boiling point 468.1 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 326.4),

[0099] [Chemistry]

[0100] 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),

[0101] [Chemistry]

[0102] 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),

[0103] [Chemistry]

[0104] The following formula (a-1-13) (OP2.89, boiling point 509.3 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 406.4),

[0105]

Chem.

[0106] The following formula (a-1-14) (OP2.63, boiling point 450.0 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 322.4),

[0107]

Chem.

[0108] The following formula (a-1-15) (OP3.00, boiling point 476.5 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 366.4)

[0109]

Chem.

[0110] The following formula (a-1-16) (OP2.68, boiling point 447.4 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 364.4)

[0111]

Chem.

[0112] The following formula (a-1-17) (OP2.36, boiling point 543.8 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 398.5),

[0113]

Chem.

[0114] The following formula (a-1-18) (OP3.27, boiling point 526.9 °C, vapor pressure at 80 °C <0.0001 mmHg, molecular weight 396.4),

[0115]

Chemical

[0116] The following formula (a-1-19) (OP2.71, boiling point 333.7 °C, vapor pressure at 80 °C 0.0302 mmHg, molecular weight 244.3),

[0117]

Chemical

[0118] The following formula (a-1-20) (OP2.73, boiling point 333.7 °C, vapor pressure at 80 °C 0.0134 mmHg, molecular weight 258.3),

[0119]

Chemical

[0120] The following formula (a-1-21) (OP2.71, boiling point 319.2 °C, vapor pressure at 80 °C 0.0566 mmHg, molecular weight 262.3),

[0121]

Chemical

[0122] The following formula (a-1-22) (OP2.71, boiling point 336.9 °C, vapor pressure at 80 °C 0.0055 mmHg, molecular weight 244.3),

[0123]

Chemical

[0124] The following formula (a-1-23) (OP3.00, boiling point 370.9 °C, vapor pressure at 80 °C 0.0021 mmHg, molecular weight 274.4),

[0125] [Chemical formula]

[0126] The following formula (a-1-24) (OP3.00, boiling point 376.4 °C, vapor pressure at 80 °C 0.0005 mmHg, molecular weight 274.4),

[0127] [Chemical formula]

[0128] The following formula (a-1-25) (OP3.00, boiling point 379.4 °C, vapor pressure at 80 °C 0.0002 mmHg, molecular weight 288.4),

[0129] [Chemical formula]

[0130] The following formula (a-1-26) (OP2.33, boiling point 360.8 °C, vapor pressure at 80 °C 0.0006 mmHg, molecular weight 252.3),

[0131] [Chemical formula]

[0132] The following formula (a-1-27) (OP2.54, boiling point 371.5 °C, vapor pressure at 80 °C 0.0003 mmHg, molecular weight 254.3),

[0133] [Chemical formula]

[0134] The following formula (a-1-28) (OP2.57, boiling point 381.2 °C, vapor pressure at 80 °C 0.0001 mmHg, molecular weight 268.3),

[0135]

Chem.

[0136] 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),

[0137]

Chem.

[0138] 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),

[0139]

Chem.

[0140] 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),

[0141]

Chem.

[0142] 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),

[0143]

Chem.

[0144] 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),

[0145] [ka]

[0146] The following formula (a-1-34) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0147] [ka]

[0148] The following formula (a-1-35) (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0149] [ka]

[0150] <Compound (a-2): Polymerizable compound containing at least Si atom> The polymerizable compound (a) in the present disclosure may contain a polymerizable compound (a-2) containing at least a Si atom. Furthermore, when the polymerizable compound (a) contains the polymerizable compound (a-2), the curable composition (A) in a state in which the solvent (d) has been removed preferably contains 10% by weight or more of Si atoms based on the entire curable composition (A).

[0151] An example of the polymerizable compound (a-2) containing at least a Si atom may be linear or branched. For example, the cyclic siloxane compound may have the structure shown below. The polymerizable functional group in the group Q having a polymerizable functional group may be, for example, a radically polymerizable functional group. Specific examples of the radically polymerizable functional group include a (meth)acrylic group, a (meth)acrylamide group, a vinylbenzene group, an allyl ether group, a vinyl ether group, and a maleimide group. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0152] [Chemistry]

[0153] As another example of the polymerizable compound (a-2), for example, a silsesquioxane skeleton represented by the following chemical formula (I) and a silicone skeleton represented by the following chemical formula (II) can be mentioned. Here, in Chemical Formula (I), m + n = 8 (8 ≥ m ≥ 1), and R1 is a divalent organic group. In Chemical Formula (II), A, B, R2, and R3 are independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an alkoxy group, a phenyl group, or a hydroxyl group, t is an integer of 1 to 3, and at least one of A and B is a polymerizable functional group.

[0154] [Chemistry]

[0155] [Chemistry]

[0156] As the polymerizable functional groups in the group Q, A, and B having a polymerizable functional group, for example, radical polymerizable functional groups can be mentioned. Specific examples of the radical polymerizable functional group include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0157] The silicone-containing (meth)acrylate compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of the monofunctional (meth)acrylate compound having one silicone-containing acryloyl group or methacryloyl group include, but are not limited to, the following. (2-Acryloylethoxy)trimethylsilane, N-(3-Acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, Acryloxymethyltrimethoxysilane, (Acryloxymethyl)phenethyltrimethoxysilane, Acryloxymethyltrimethylsilane, (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-Acryloxypropyl)methyldichlorosilane, (3-Acryloxypropyl)methyldiethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trichlorosilane, (3-Acryloxypropyl)trimethoxysilane, (3-Acryloxypropyl)tris(trimethylsiloxy)silane, Acryloxytriisopropylsilane, Acryloxytrimethylsilane, Methacryloxymethyltrimethoxysilane, 0-(Methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (Methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-Methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (Methacryloxymethyl)methyldimethoxysilane, (Methacryloxymethyl)methyldiethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxypropyltrimethoxysilane, Methacryloylpropyltriisopropoxysilane, 0-(Methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropylmethyldiethoxysilane, Methacryloxypropyldimethylmethoxysilane, Methacryloxypropyldimethylethoxysilane, (Methacryloxymethyl)dimethylethoxysilane, Methacryloxypropyltriethoxysilane, Methacryloxypropylsilatrane, Methacryloxypentamethyldisiloxane, (Methacryloxymethyl)phenyl dimethylsilane, Methacryloxytrimethylsilane, Methacryloxymethyltrimethylsilane, (3-Methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, Methacryloxypropylpentamethyldisiloxane, 0-(Methacryloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propylcarbamate, Methacryloxymethyltris(trimethylsiloxy)silane, Methacryloxyethoxytrimethylsilane, (3-Methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, Methacryloxypropyltris(vinyldimethylsiloxy)silane, Methacryloxypropyltris(trimethylsiloxy)silane, 3-Methacryloxypropyltriacetoxysilane, Methacryloxypropylmethyldichlorosilane, Methacryloxypropyltrichlorosilane, 3-Methacryloxypropylbis(trimethylsiloxy)methylsilane, 3-Methacryloxypropyldimethylchlorosilane, 0-Methacryloxy(polyethyleneoxy)trimethylsilane, Poly(methacryloxypropylsilsesquioxane), Methacryloxypropylheptaisobutyl-T8-silsesquioxane, Methacryloxypropyltris(trimethylsiloxy)silane

[0158] Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following. 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, SIM6486.65 (all of the above are manufactured by Gelest), TM-0701T, FM-0711, FM-0721, FM-0725 (all of the above are manufactured by JNC)

[0159] Silicon-containing (meth)acrylamide compounds are compounds having one or more acrylamide groups or methacrylamide groups. Examples of monofunctional (meth)acrylamide compounds having one silicon-containing acrylamide group or methacrylamide group include, but are not limited to, the following. 3-Acrylamidopropyltrimethoxysilane, 3-acrylamidopropyltris(trimethylsiloxy)silane

[0160] Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylamide compounds include, but are not limited to, the following. SIA0146.0, SIA0150.0 (both manufactured by Gelest)

[0161] Examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following. Linear polydimethylsiloxane modified with acryloxypropyl groups at both ends Linear polydimethylsiloxane modified with methacryloxypropyl groups at both ends Cyclic siloxane modified with a plurality of acryloxypropyl groups Cyclic siloxane modified with a plurality of methacryloxypropyl groups Silsesquioxane modified with a plurality of acryloxypropyl groups Silsesquioxane modified with a plurality of methacryloxypropyl groups

[0162] Examples of commercially available products of the above-mentioned silicon-containing polyfunctional (meth)acrylate compounds include, but are not limited to, the following. SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (all manufactured by Gelest) FM-7711, FM-7721, FM-7725 (manufactured by JNC above), X-22-2445 (Shin-Etsu Chemical), AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20 (manufactured by Toagosei above)

[0163] Also, for example, from "Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography" by Ogawa et al., the following can be synthesized and / or obtained. Linear modified polydimethylsiloxane (MA-Si-12) modified with methacryloxypropyl groups at both ends, 8-membered ring siloxane (8-ring) modified with four methacryloxypropyl groups, 10-membered ring siloxane (10-ring) modified with five methacryloxypropyl groups

[0164] The blending ratio of component (a) in the curable composition (A) is preferably 40% by weight or more and 99% by weight or less, based on the total mass of all components excluding the solvent (d), that is, the synthesis of component (a), component (b) described later, and component (c) described later. More preferably, it is 50% by weight or more and 95% by weight or less, and even more preferably, it is 60% by weight or more and 90% by weight or less. By setting the blending ratio of component (a) to 40% by weight or more, the mechanical strength of the cured film of the curable composition is increased. Also, by setting the blending ratio of component (a) to 99% by weight or less, the blending ratios of component (b) and component (c) can be increased, and characteristics such as a fast photopolymerization rate can be obtained. At least a part of component (a) containing one or more polymerizable compounds may be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, it preferably contains at least one kind of structural unit represented by any of the following structures (1) to (6).

[0165] [Chemistry]

[0166] In Structures (1) to (6), the substituent R is, independently of one another, a substituent containing a partial structure containing an aromatic ring, and R 1 is a hydrogen atom or a methyl group. In the present specification, in the structural units represented by Structures (1) to (6), the part other than R is the main chain of a specific polymer. The formula weight of the substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and still more preferably 150 or more. The upper limit of the formula weight of the substituent R is preferably 500 or less for practical purposes.

[0167] The polymer having a polymerizable functional group is usually a compound having a weight average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight is not particularly defined, but for example, it is preferably 50,000 or less. By setting the weight average molecular weight to be equal to or higher than the above-mentioned lower limit value, the boiling point can be set to 250°C or higher, and the mechanical properties after curing can be further improved. Further, by setting the weight average molecular weight to be equal to or lower than the above-mentioned upper limit value, the solubility in a solvent is high, the viscosity is not too high, the fluidity of the droplets arranged discretely is maintained, and the flatness of the liquid film plane can be further improved. In addition, the weight average molecular weight (Mw) in the present disclosure refers to that measured by gel permeation chromatography (GPC) unless otherwise specified.

[0168] Specific examples of the polymerizable functional group possessed by the polymer include a (meth)acryloyl group, an epoxy group, an oxetane group, a methylol group, a methylol ether group, a vinyl ether group, and the like. From the viewpoint of ease of polymerization, a (meth)acryloyl group is particularly preferable.

[0169] When adding a polymer having a polymerizable functional group as at least a part of component (a), its blending ratio can be freely set as long as it falls within the range that satisfies the viscosity regulation described later. For example, it is preferably 0.1% by weight or more and 60% by weight or less, more preferably 1% by weight or more and 50% by weight or less, and still more preferably 10% by weight or more and 40% by weight or less, based on the total mass of all components excluding the solvent (d). By setting the blending ratio of the polymer having a polymerizable functional group to 0.1% by weight or more, heat resistance, dry etching resistance, mechanical strength, and low volatility can be improved. Also, by setting the blending ratio of the polymer having a polymerizable functional group to 60% by weight or less, the upper limit regulation of the viscosity described later can be satisfied.

[0170] <Component (b): Photoinitiator> Component (b) is a photoinitiator. In this specification, a photoinitiator is a compound that senses light of a predetermined wavelength and generates the above-described polymerization factor (radical). Specifically, a photoinitiator is a polymerization initiator (radical generator) that generates radicals by light (such as infrared rays, visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams such as electron beams, and radiation). Component (b) may be composed of only one type of photoinitiator or may be composed of a plurality of types of photoinitiators.

[0171] Examples of radical generators include, but are not limited to, the following. 2,4,5-Triaryl imidazole dimers which may have substituents such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzophenone 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, 4,4'-diaminobenzophenone; α-Amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; Quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-t-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, 2,3-dimethylanthraquinone; Benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; Benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin, propyl benzoin; Benzyl derivatives such as benzyldimethyl ketal; Acridine derivatives such as 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; Acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone; Thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone;Acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acet yloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one;

[0172] Examples of commercially available products of the above radical generators include, but are not limited to, the following. Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO, LR8893, LR8970 (all manufactured by BASF), Ubecryl P36 (manufactured by UCB)

[0173] Among the above radical generators, component (b) is preferably an acylphosphine oxide-based polymerization initiator. Among the above radical generators, the acylphosphine oxide-based polymerization initiators are as follows. Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide

[0174] The blending ratio of component (b) in the curable composition (A) is preferably 0.1% by weight or more and 50% by weight or less based on the total of component (a), component (b), and component (c) described below, that is, the total mass of all components excluding the solvent (d). Further, the blending 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 based on the total mass of all components excluding the solvent (d). By setting the blending ratio of component (b) to 0.1% by weight or more, the curing rate of the composition can be increased and the reaction efficiency can be improved. Further, by setting the blending ratio of component (b) to 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0175] <Component (c): Non-polymerizable compound> In addition to the above-described components (a) and (b), the curable composition (A) in the present disclosure can further contain a non-polymerizable compound as component (c) within a range not impairing the effects of the present disclosure according to various purposes. Examples of such component (c) include compounds that do not have a polymerizable functional group such as a (meth)acryloyl group and do not have the ability to generate the above-described polymerization factor (radical) by sensing light of a predetermined wavelength. Examples of the non-polymerizable compound include a sensitizer, a hydrogen donor, a surfactant (c1), an antioxidant, a polymer component, and other additives. Component (c) may contain a plurality of the above-described compounds.

[0176] The sensitizer is a compound that is appropriately added for the purpose of promoting the polymerization reaction and improving the reaction conversion rate. The sensitizer may be used alone or in combination of two or more.

[0177] Examples of the sensitizer include, for example, sensitizing dyes. The sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and interacts with the photopolymerization initiator as component (b). Here, the interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator as component (b). Specific examples of the sensitizing dye include, but are not limited to, the following. Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes

[0178] The hydrogen donor is a compound that reacts with the initiating radicals generated from the photopolymerization initiator as component (b) or the radicals at the polymerization growing terminals to generate more reactive radicals. When the photopolymerization initiator as component (b) is a photo radical generator, it is preferable to add a hydrogen donor.

[0179] Specific examples of such hydrogen donors include, but are not limited to, the following. n-Butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl 4-dimethylaminobenzoate, triethanolamine, amine compounds such as N-phenylglycine, mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate esters

[0180] The hydrogen donor may be used alone or in combination of two or more. Further, the hydrogen donor may have a function as a sensitizer.

[0181] For the purpose of reducing the interfacial bonding force between the mold and the curable composition, that is, reducing the release force in the demolding process described later, an internal release agent can be added to the curable composition. In this specification, "internal addition type" means that it is added to the curable composition in advance before the placement process of the curable composition. As the internal release agent, surfactants such as silicone surfactants, fluorine surfactants, and hydrocarbon surfactants can be used. It should be noted that the internal release agent in the present disclosure is assumed not to have polymerizability. The internal release agent may be used alone or in combination of two or more.

[0182] The following are included as fluorine surfactants. Polyalkylene oxide (such as polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having a perfluoroalkyl group, polyalkylene oxide (such as polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers

[0183] Note that the fluorine surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in a part of the molecular structure (for example, the terminal group). For example, pentadecaethylene glycol mono 1H,1H,2H,2H-perfluorooctyl ether and the like can be mentioned.

[0184] Commercially available products may be used as the fluorine surfactant. Examples of commercially available products of the fluorine surfactant include the following. Megafac (registered trademark) F-444, TF-2066, TF-2067, TF-2068, abbreviated as DEO-15 (all of the above are manufactured by DIC), Fluorad FC-430, FC-431 (all of the above are manufactured by Sumitomo 3M), Surflon (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all of the above are manufactured by Tokem Products), PF-636, PF-6320, PF-656, PF-6520 (all of the above are manufactured by OMNOVA Solutions), Unidine (registered trademark) DS-401, DS-403, DS-451 (all of the above are manufactured by Daikin Industries), Futagent (registered trademark) 250, 251, 222F, 208G (all of the above are manufactured by Neos)

[0185] Further, the surfactant (c1) may be a hydrocarbon surfactant. Examples of the hydrocarbon surfactant include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms.

[0186] Examples of the alkyl alcohol polyalkylene oxide adducts include the following. Methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / propylene oxide adduct

[0187] Note that the terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to the hydroxyl group that can be simply produced by adding polyalkylene oxide to an alkyl alcohol. Such a hydroxyl group may be substituted with other substituents, for example, polar functional groups such as carboxyl group, amino group, pyridyl group, thiol group, silanol group, and hydrophobic functional groups such as alkyl group and alkoxy group.

[0188] Examples of the polyalkylene oxide include the following. Polyethylene glycol, polypropylene glycol, their mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monoadipic esters, monooleic esters, monostearic esters, monosuccinic esters

[0189] Commercially available products may be used as the alkyl alcohol polyalkylene oxide adducts. Examples of the commercially available products of the alkyl alcohol polyalkylene oxide adducts include the following. Polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750) manufactured by Aoki Yushi Kogyo Co., Ltd., random polymerization type polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R) manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene methyl ether (Pluriol® A760E) manufactured by BASF, polyoxyethylene alkyl ether (Emulgen series) manufactured by Kao Moreover, commercially available products may be used as the polyalkylene oxide, and examples thereof include ethylene oxide·propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0190] Examples of the silicon-based surfactant include the following. For example, trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), Megafac Painted 31 (manufactured by Dainippon Ink and Chemicals, Inc.), and KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0191] Moreover, a surfactant containing at least both a fluorine atom and a silicon atom may be used. Examples of the surfactant containing both a fluorine atom and a silicon atom include the following. Trade names X-70-090, X-70-091, X-70-092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), trade names Megafac R-08, XRB-4 (all manufactured by Dainippon Ink and Chemicals, Inc.)

[0192] The blending ratio of the component (c) excluding the surfactant in the curable composition (A) is preferably 0.01% by weight or more and 50% by weight or less with respect to the total of the component (a), the component (b), and the component (c), that is, the total mass of all components excluding the solvent (d). Further, the blending ratio of the component (c) excluding the surfactant in the curable composition (A) is more preferably 0.01% by weight or more and 50% by weight or less, and still more preferably 0.01% by weight or more and 20% by weight or less with respect to the total mass of all components excluding the solvent (d). By setting the blending ratio of the component (c) excluding the surfactant to 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0193] <Component (d): Solvent> The curable composition (A) in the present disclosure may contain, as component (d), a solvent having a boiling point of 100°C or higher and lower than 250°C under normal pressure. Examples of component (d) include solvents in which components (a), (b), and (c) are soluble, such as alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing solvents. Component (d) can be used alone or in combination of two or more. The boiling point of component (d) under normal pressure is 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of component (d) under normal pressure is lower than 250°C, preferably lower than 200°C. If the boiling point of component (d) under normal pressure is less than 100°C, the volatilization rate in the standby process described below is too fast, so component (d) may volatilize before the droplets of the curable composition (A) combine, and the droplets of the curable composition (A) may not combine. Also, if the boiling point of component (d) under normal pressure is 250°C or higher, the volatilization of solvent (d) becomes insufficient in the standby process described below, and component (d) may remain in the cured product of the curable composition (A). Here, when component (d) contains one or more solvents, the boiling point of each of the one or more solvents under normal pressure may be 100°C or higher and lower than 250°C (for example, 100°C or higher and lower than 200°C).

[0194] Examples of the alcohol solvent include the following. Monoalcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptan-4-ol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc.; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 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, glycerin

[0195] Examples of ketone solvents include the following. Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl iso-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone

[0196] Examples of ether solvents include the following. Ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran

[0197] Examples of ester solvents include, for example, the following. Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-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, diglycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate

[0198] Examples of the nitrogen-containing solvents include, for example, the following. N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone

[0199] Among the above-mentioned solvents, ether solvents and ester solvents are preferred. From the viewpoint of excellent film-forming properties, more preferred are ether solvents and ester solvents having a glycol structure.

[0200] Furthermore, the following are more preferred. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate More preferably, propylene glycol monomethyl ether acetate is mentioned. In addition, ethyl) isocyanurate di (meth) acrylate and the like are also mentioned.

[0201] In the present disclosure, a preferable solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure. Specifically, it is propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl lactate, or a mixed solvent thereof.

[0202] In the present disclosure, as component (d), a polymerizable compound having a boiling point of 80 ° C or higher and less than 250 ° C under normal pressure can also be used. Examples of the polymerizable compound having a boiling point of 80 ° C or higher and less than 250 ° C under normal pressure include the following. Cyclohexyl acrylate (198 ° C), benzyl acrylate (229 ° C), isobornyl acrylate (245 ° C), tetrahydrofurfuryl acrylate (202 ° C), trimethylcyclohexyl acrylate (232 ° C), isooctyl acrylate (217 ° C), n-octyl acrylate (228 ° C), ethoxyethoxyethyl acrylate (boiling point 230 ° C), divinylbenzene (193 ° C), 1,3-diisopropenylbenzene (218 ° C), styrene (145 ° C), α-methylstyrene (165 ° C)

[0203] In the present disclosure, when the total amount of the curable composition (A) is 100% by volume, the content of the solvent (d) is greater than 5% by volume and 95% by volume or less, preferably 15% by volume or more and 85% by volume or less, and more preferably 40% by volume or more and 80% by volume or less. For example, the content of the solvent (d) can be 40% by volume or more and 85% by volume or less. When the content of the solvent (d) is less than 5% by volume, it is difficult to obtain a thin film after the volatilization of the solvent (d) under the condition of obtaining a substantially continuous liquid film. Further, when the content of the solvent (d) is more than 95% by volume, it is difficult to obtain a thick film after the volatilization of the solvent (d) even if the droplets are dropped most densely by the inkjet method.

[0204] <Temperature at the time of blending the curable composition> When preparing the curable composition (A) in the present disclosure, at least the component (a), the component (b), and the component (d) may be mixed and dissolved under a predetermined temperature condition. The predetermined temperature condition can specifically be in the range of 0°C or more and 100°C or less. The same applies when the curable composition (A) contains the component (c).

[0205] <Viscosity of the curable composition> The curable composition (A) in the present disclosure is in a liquid state. This is because, in the placement step described later, the droplets of the curable composition (A) are discretely dropped onto the substrate by the inkjet method. The viscosity of the curable composition (A) in the present disclosure is 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm, preferably 2 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less. When the viscosity of the curable composition (A) is less than 2 mPa·s, the dischargeability of the droplets by the inkjet method may become unstable. Further, when the viscosity of the curable composition (A) is greater than 60 mPa·s, it is difficult to form droplets having a volume of about 1.0 to 3.0 pL, which is preferable in the present disclosure.

[0206] Regarding the viscosity μ of the non-volatile composition (A') in the present disclosure, it is preferably 20 mPa·s or more and 135 mPa·s or less at 23°C and 1 atm. Further, for the non-volatile composition (A'), the viscosity at 23°C and 1 atm is more preferably 40 mPa·s or more and 100 mPa·s or less, and even more preferably 60 mPa·s or more and 80 mPa·s or less. Note that the lower the viscosity, for example, if it is less than 20 mPa·s, the fluidity of the non-volatile composition (A') is high, and when the non-volatile composition (A') is brought into contact with the mold, the non-volatile composition (A') easily flows out from the end of the mold and the bleeding allowance time is short. Also, when the viscosity is greater than 135 mPa·s, the fluidity of the non-volatile composition (A') is low, so when the non-volatile composition (A') is brought into contact with the mold, the edge filling speed is slow. Therefore, by using the curable composition (A) of the present disclosure in which the viscosity of the non-volatile composition (A') is adjusted to 20 mPa·s or more and 135 mPa·s or less, imprint processing can be carried out with high throughput, and defects on the substrate due to bleeding can be suppressed.

[0207] <Surface tension of the curable composition> Regarding the surface tension γ1 of the non-volatile composition (A') in the present disclosure, it is preferably 5 mN / m or more and 70 mN / m or less at 23°C and 1 atm. Further, for the composition of the components excluding the solvent (component (d)), the surface tension at 23°C and 1 atm is more preferably 7 mN / m or more and 50 mN / m or less, and even more preferably 10 mN / m or more and 40 mN / m or less. Note that the higher the surface tension, for example, if it is 5 mN / m or more, the capillary force acts strongly, so when the non-volatile composition (A') is brought into contact with the mold, filling (spread and fill) is completed in a short time. Also, by making the surface tension 70 mN / m or less, the cured film obtained by curing the curable composition becomes a cured film having surface smoothness.

[0208] <Contact angle of the curable composition> The contact angle of the curable composition (A) in the present disclosure is preferably 0° or more and 90° or less with respect to the surface of the substrate. When the contact angle is greater than 90°, the droplets on the substrate do not contact each other, and a continuous liquid film cannot be formed. The contact angle of the non-volatile composition (A') in the present disclosure is preferably 0° or more and 90° or less with respect to both the surface of the substrate and the surface of the mold. When the contact angle is greater than 90°, capillary force acts in the negative direction (the direction of contracting the contact interface between the mold and the curable composition) inside the pattern of the mold or in the gap between the substrate and the mold, and there is a possibility that the non-volatile composition (A') may not fill the mold. The smaller the contact angle, the stronger the capillary force acts, and the faster the filling speed becomes.

[0209] <Impurities mixed in the curable composition> The curable composition (A) in the present disclosure preferably contains no impurities as much as possible. Here, impurities mean those other than the above-described components (a), (b), (c), and (d). Therefore, the curable composition (A) in the present disclosure is preferably obtained through a purification process. Such a purification process is preferably filtration using a filter.

[0210] As filtration using a filter, after mixing the above-described components (a), (b), and (c), it is preferably filtered with a filter having a pore size of 0.001 μm or more and 5.0 μm or less, for example. When performing filtration using a filter, it is more preferable to perform it in multiple stages or repeat it a large number of times (circulation filtration). Also, the liquid filtered through the filter may be filtered again, or it may be filtered using a plurality of filters having different pore sizes. Examples of the filter used for filtration include filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc., but it is not particularly limited. By passing through such a purification process, impurities such as particles mixed in the curable composition can be removed. Thereby, it is possible to prevent the cured film obtained after curing the curable composition from being accidentally uneven due to the impurities mixed in the curable composition, resulting in pattern defects.

[0211] When the curable composition in the present disclosure is used for manufacturing a semiconductor integrated circuit, in order not to inhibit the operation of the product, it is preferably to avoid as much as possible the mixing of impurities containing metal atoms (metal impurities) into the curable composition. The concentration of metal impurities contained in the curable composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0212] <Glass transition temperature of the curable composition> When the glass transition temperature (Tg) is sufficiently higher than the temperature at the time of mold release, the cured product at the time of mold release shows a strong glass state, that is, a high mechanical strength, so that it is less likely to cause the pattern to fall or break due to the impact of mold release. Therefore, when the mold release process is carried out at room temperature, the glass transition temperature of the cured product (cured film) of the non-volatile composition (A’) is preferably 70 °C or higher, more preferably 100 °C or higher, and particularly preferably 150 °C or higher.

[0213] As a method for measuring the glass transition temperature of the cured product (photo-cured product), it is possible to apply a method of measuring using a differential scanning calorimeter (DSC) or a dynamic viscoelasticity apparatus, etc. For example, the measurement of the glass transition temperature using DSC can be carried out as follows. (1) Obtain the intersection point between the straight line obtained by extending the baseline on the low-temperature side of the DSC curve of the cured product (the part of the DSC curve in the temperature region where no transition and reaction occur in the test piece) to the high-temperature side and the tangent line drawn at the point where the gradient of the curve of the stepwise change part of the glass transition becomes maximum. (2) From the obtained intersection point, obtain the extrapolated onset glass transition temperature (Tig) as the glass transition temperature.

[0214] Main devices include STA-6000 (manufactured by Perkin Eimer), etc. On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity apparatus, the temperature at which the loss sine (tanδ) of the cured product becomes maximum is defined as the glass transition temperature. Main devices for measuring dynamic viscoelasticity include MCR301 (manufactured by Anton Paar), etc.

[0215] [Substrate] In this specification, the member onto which the droplets of the curable composition (A) are discretely dropped is described as a substrate.

[0216] The substrate is a substrate to be processed, and usually, a silicon wafer is used. The substrate may have a layer to be processed on its surface. The substrate may further have other layers formed under the layer to be processed. Also, if a quartz substrate is used as the substrate, a replica (replica mold) of the imprint mold can be produced. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate can be arbitrarily selected from those known as substrates for semiconductor devices such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride. Incidentally, the surface of the substrate or the layer to be processed is preferably subjected to surface treatment such as silane coupling treatment, silazane treatment, or formation of an organic thin film to improve the adhesion to the curable composition (A). As a specific example of the organic thin film formed as the surface treatment, for example, the adhesion layer described in Japanese Patent Application Laid-Open No. 2009-503139 (Patent Document 7) can be used.

[0217] [Pattern Formation Method] With reference to FIGS. 1(a) to 1(g), the pattern formation method in the present disclosure will be described. The cured film formed by the present disclosure preferably has a pattern with a size of 1 nm or more and 10 mm or less, and more preferably has 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 nano-sized (1 nm or more and 100 nm or less) pattern (concavo-convex structure) using light is called a nanoimprint method. The film formation method in the present disclosure forms a film of the curable composition in the space between the mold and the substrate using the photoimprint method. However, the curable composition may be cured by other energy (for example, heat, electromagnetic wave). Also, the film formation method in the present disclosure may be implemented as a method for forming a film having a pattern, that is, a pattern formation method, or may be implemented as a method for forming a film having no pattern (for example, a planarization film), that is, a planarization film formation method.

[0218] Hereinafter, an example in which the film formation method in the present disclosure is applied to a patterning method will be described. The patterning method includes, for example, a forming step, an arranging step, a waiting step, a contacting step, a curing step, and a mold releasing step (separating step). The forming step is a step of forming an underlayer. The arranging step is a step of discretely arranging droplets of the curable composition (A) on the underlayer. The waiting step is a step of waiting until the droplets of the curable composition (A) are combined and the solvent (d) is volatilized. The contacting 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 mold releasing step is a step of separating the mold from the cured film of the curable composition (A). The arranging step is performed after the forming step, the waiting step is performed after the arranging step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the mold releasing step is performed after the curing step.

[0219] <Arranging step> In the arranging step, as schematically shown in Fig. 1(a), droplets 102 of the curable composition (A) are discretely arranged on the substrate 101. In the arranging step, droplets 102 of the curable composition (A) having a volume of 1.0 pL or more are arranged at a density of 80 droplets / mm 2 or more. As the substrate 101, a substrate on which an underlayer is laminated may be used. Further, the surface of the substrate 101 may have improved adhesion to the curable composition (A) by surface treatment such as silane coupling treatment, silazane treatment, or formation of an organic thin film.

[0220] As the arranging method for arranging droplets 102 of the curable composition (A) on the substrate, the inkjet method is particularly preferable. The droplets 102 of the curable composition (A) are preferably arranged densely on the region of the substrate 101 facing the region where the recesses constituting the pattern of the mold 106 are densely present, and sparsely on the region of the substrate 101 facing the region where the recesses constituting the pattern of the mold 106 are sparsely present. Thereby, the film (remaining film) 109 of the curable composition (A) formed on the substrate 101 is controlled to have a uniform thickness regardless of the density of the pattern of the mold 106.

[0221] In order to define the volume of the non-volatile composition (A’) to be disposed, an index of average liquid film thickness is defined. The average liquid film thickness is a value obtained by dividing the volume of the non-volatile composition (A’) disposed in the disposing step by the area of the film forming region of the mold. The volume of the non-volatile composition (A’) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (d) has volatilized. According to this definition, even when there are irregularities on the substrate surface, the average liquid film thickness can be defined regardless of the irregularity state. Here, the average liquid film thickness may be understood as a value obtained by dividing the volume of the non-volatile composition (A’) remaining after the standby step described later by the area of the film forming region of the mold, and it is preferably 5 nm or more and 170 nm or less.

[0222] <Standby step> In the present disclosure, after the disposing step and before the contacting step, a standby step is provided to wait for the coalescence of the plurality of droplets on the substrate to proceed and for the volatilization of the solvent contained in the liquid film to proceed. Here, a value obtained by dividing the total volume of the droplets of the curable composition (A) dropped in one pattern formation by the entire area of the region (pattern formation region) where the pattern is formed in one pattern formation is defined as the average initial liquid film thickness. In the standby step, as schematically shown in Fig. 1(b), the droplets 102 of the curable composition (A) spread on the substrate 101. Thereby, the pattern formation region of the substrate 101 is covered with the curable composition (A) over the entire area.

[0223] With reference to Figs. 2(a) to 2(d), the flow behavior of the droplets of the curable composition (A) disposed on the substrate during the standby step will be described. The droplets 102 of the curable composition (A) are discretely disposed on the substrate 101 as shown in Fig. 2(a), and as shown in Fig. 2(b), each droplet 102 gradually spreads on the substrate. Then, as shown in Fig. 2(c), the droplets of the curable composition (A) on the substrate start to coalesce to form a liquid film, and as shown in Fig. 2(d), a continuous liquid film is formed (the surface of the substrate 101 is covered with the curable composition (A) and there is no exposed surface). The state of the curable composition (A) as shown in Fig. 2(d) is referred to as a "substantially continuous liquid film".

[0224] Furthermore, in the standby step, as schematically shown in FIG. 1(d), the solvent 105 (solvent (d)) contained in the liquid film 104 is volatilized. The remaining amount of the solvent (d) in the liquid film 103 after the standby step (for example, at the start of the contact step) is preferably 10% by volume or less when the total weight of the components other than the solvent (d) (i.e., the whole liquid film) is 100% by volume. If the remaining amount of the solvent (d) is more than 10% by volume, the mechanical properties of the cured film may be lowered.

[0225] In the standby step, for the purpose of accelerating the volatilization of the solvent (d), a baking step of heating the substrate 101 and the curable composition (A) may be carried out, or the ambient gas around the substrate 101 may be ventilated. The heating is performed, for example, 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. The heating time can be 10 seconds or more and 600 seconds or less. The baking step can be carried out using a known heater such as a hot plate or an oven.

[0226] The standby time in the standby step is, for example, from 0.1 second to 600 seconds, and preferably can be from 10 seconds to 300 seconds. If the standby step is shorter than 0.1 second, the bonding between the droplets of the curable composition (A) becomes insufficient, and a substantially continuous liquid film is not formed. If the standby step exceeds 600 seconds, the productivity decreases. Therefore, in order to suppress the decrease in productivity, the substrates for which the placement step has been completed are sequentially transferred to the standby step, the standby step is carried out in parallel for a plurality of substrates, and the substrates for which the standby step has been completed are sequentially transferred to the contact step. In the prior art, theoretically, it takes several thousand seconds to several tens of thousands of seconds until a substantially continuous liquid film is formed. However, in practice, the spread of the droplets of the curable composition stagnates due to the influence of volatilization, and a continuous liquid film cannot be formed.

[0227] In the standby process, when the solvent (d) volatilizes, a substantially continuous liquid film 104 of the non-volatile composition (A') composed of the component (a), the component (b), and the component (c) remains. The average liquid film thickness of the substantially continuous liquid film 104 from which the solvent (d) has volatilized (been removed) becomes thinner than the liquid film 103 by the amount by which the solvent (d) has volatilized. The pattern formation region of the substrate 101 is maintained in a state of being covered with a substantially continuous liquid film 104 of the curable composition (A) from which the solvent (d) has been removed over the entire area.

[0228] <Contact process> In the contact process, as schematically shown in FIG. 1(e), the curable composition (A) from which the solvent (d) has been removed, that is, a substantially continuous liquid film 104 of the non-volatile composition (A'), is brought into contact with the mold 106. The contact process includes a process of changing from a state where the non-volatile composition (A') and the mold 106 are not in contact to a state where they are in contact, and a process of maintaining the state where they are in contact. As a result, the liquid of the non-volatile composition (A') is filled (filed) into the concave portions of the fine pattern that the mold 106 has on its surface, and such liquid becomes a liquid film filled (filed) into the fine pattern of the mold 106.

[0229] The contact process can be carried out under any conditions of an atmospheric atmosphere, a reduced-pressure atmosphere, or an inert gas atmosphere. However, in order to prevent the influence of oxygen and moisture on the curing reaction, it is preferably carried out under a reduced-pressure atmosphere or an inert gas atmosphere. Specific examples of the inert gas used when carrying out the contact process under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various Freon gases, etc., or a mixed gas thereof. A gas containing 10% or more of carbon dioxide or helium in a molar ratio is preferable, and a gas containing 10% or more of carbon dioxide in a molar ratio is particularly preferable. Since helium gas easily diffuses into the mold, the substrate, the curable composition, etc., the atmospheric gas confined in the pattern of the mold etc. quickly disappears. Since carbon dioxide easily dissolves in the curable composition and the underlying layer on the substrate, the atmospheric gas confined in the pattern of the mold etc. quickly disappears. Also, the solubility coefficient of carbon dioxide with respect to the curable composition is 0.5 kg / m 3 ·atm or more and 10 kg / m 3·It is preferably below 1 atm. Details thereof are disclosed in Japanese Patent Application Laid-Open No. 2022-99271. When the contact step is performed in an atmosphere of a specific gas including an air atmosphere, the preferable pressure is from 0.0001 atm to 10 atm.

[0230] In the present disclosure, in the standby step, since the curable composition (A) becomes a substantially continuous liquid film 104 of the nonvolatile composition (A') from which the solvent (d) has been removed, the volume of the gas entrained between the mold 106 and the substrate 101 is reduced. Therefore, the spread of the nonvolatile composition (A') in the contact step is completed promptly.

[0231] When the spread and filling of the nonvolatile composition (A') in the contact step are completed promptly, the time for maintaining the state in which the mold 106 is in contact with the nonvolatile composition (A') (the time required for the contact step) can be shortened. And shortening the time required for the contact step leads to shortening the time required for pattern formation (film formation), resulting in improved productivity. The contact step is preferably from 0.1 second to 3 seconds, and particularly preferably from 0.1 second to 1 second. If the contact step is shorter than 0.1 second, the spread and filling become insufficient, and defects called unfilled defects tend to occur frequently.

[0232] Let the viscosity of the nonvolatile composition (A') be μ [mPa·s]. Also, let the average liquid film thickness when droplets of the nonvolatile composition (A') combine to form a substantially continuous liquid film 104 be h [m]. At this time, in the present embodiment, h is calculated so that the viscosity μ [mPa·s] and the average liquid film thickness h [m] formed by the nonvolatile composition satisfy the following relational expressions 1 and 2. Relational expression 1: 20 [μm / sec] ≦ C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s], and, Relational expression 2: 0.5 [sec] ≦ C·h α ·μ / μ0, C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s]

[0233] Let the edge filling speed at which the non-volatile composition (A') spreads over the entire gap between the substrate 101 and the mold 106 be v [m / sec], and let the leaching allowance time, which is the time until leaching occurs, be t [sec]. At this time, when the viscosity μ [mPa·s] and the average liquid film thickness h [m] satisfy the above relational expressions 1 and 2, v is 20 [μm / sec] or more and t is 0.5 [sec] or more.

[0234] In the present disclosure, in the contact step, the time for maintaining the state in which the mold 106 is in contact with the non-volatile composition (A') (the time required for the contact step) can be shortened. And shortening the time required for the contact step leads to shortening the time required for pattern formation (film formation), thus bringing about an improvement in productivity (throughput). The contact step is preferably 0.1 seconds or more and 3 seconds or less, and particularly preferably 0.1 seconds or more and 1 second or less. If the contact step is shorter than 0.1 seconds, edge filling becomes insufficient and defects called edge unfilling occur frequently.

[0235] As described above, in the contact step, a phenomenon called leaching may occur. This is a phenomenon in which, in the contact step, the non-volatile composition (A') oozes out from the contact surface of the mold 106 and adheres to (creeps up) the side wall (side surface) of the mold. With reference to FIG. 3, the concept of leaching will be described. As shown in FIG. 4, the non-volatile composition (A') that has oozed out from the mold 106 creeps up the side wall of the mold 106, and an unnecessary cured product of the non-volatile composition (A') is formed outside the contact surface of the mold 106, which becomes a defect. This is the so-called cause of leaching (defect). Here, the higher the viscosity of the non-volatile composition (A'), the more it is possible to prevent unnecessary flow. When the non-volatile composition (A') and the mold 106 are brought into contact, it is difficult for the non-volatile composition (A') to flow out from the end of the mold 106, and the leaching allowance time becomes longer. On the other hand, when the fluidity of the non-volatile composition (A') is low, the edge filling speed becomes slow when the non-volatile composition (A') and the mold 106 are brought into contact. Note that the height at which the non-volatile composition (A') creeps up the side wall of the mold 106 is defined as the leaching height.

[0236] Therefore, by using the non-volatile composition (A’) in the present disclosure, imprint processing can be carried out with high productivity (throughput), and defects on the substrate due to leaching can be suppressed.

[0237] When the curing process of the mold 106 includes a light irradiation process, a mold made of a light-transmissive material is used in consideration of this. Specifically, as the material of the mold 106, glass, quartz, PMMA, a light-transparent resin such as a polycarbonate resin, a transparent metal vapor deposition film, a flexible film such as polydimethylsiloxane, a photocurable film, a metal film, etc. are preferable. However, when a light-transparent resin is used as the material of the mold 106, a resin that is not soluble in the components contained in the curable composition is selected. Quartz is suitable as the material of the mold 106 because it has a small coefficient of thermal expansion and small pattern distortion.

[0238] The pattern formed on the surface of the mold 106 has a height, for example, of 4 nm or more and 200 nm or less. The lower the height of the pattern of the mold 106, the smaller the force required to separate the mold 106 from the cured film of the curable composition in the mold release process, that is, the smaller the mold release force, and the number of mold release defects remaining on the mold 106 due to the pattern of the curable composition being torn off can be reduced. Also, when the mold is separated, the pattern of the curable composition may be elastically deformed by the impact, and adjacent pattern elements may come into contact with each other, resulting in adhesion or breakage. However, it is advantageous to have the height of the pattern element be about 2 times or less (aspect ratio 2 or less) with respect to the width of the pattern element in order to avoid these problems. On the other hand, if the height of the pattern element is too low, the processing accuracy of the substrate 101 will decrease.

[0239] For mold 106, in order to improve the releasability of mold 106 with respect to the curable composition (A), a surface treatment may be performed before the contacting step. Examples of the surface treatment include forming a release agent layer by applying a release agent to the surface of mold 106. Examples of the release agent to be applied to the surface of mold 106 include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, carnauba-based release agents, and the like. For example, commercially available coating-type release agents such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also be preferably used. The release agent may be used alone or in combination of two or more. Among the above-described release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0240] In the contacting step, the pressure applied to the curable composition (A) when contacting mold 106 with the non-volatile composition (A') is not particularly limited and can be, for example, 0 MPa or more and 100 MPa or less. Preferably, the pressure applied to the curable composition (A) when contacting mold 106 with the non-volatile composition (A') is 0 MPa or more and 50 MPa or less. More preferably, the pressure applied to the curable composition (A) is 0 MPa or more and 30 MPa or less, and still more preferably, 0 MPa or more and 20 MPa or less.

[0241] The contact process can be carried out under any conditions, such as in an atmospheric atmosphere, a reduced-pressure atmosphere, or an inert gas atmosphere. However, since it is possible to prevent the influence of oxygen and moisture on the curing reaction, it is preferable to use a reduced-pressure atmosphere or an inert gas atmosphere. Specific examples of the inert gas used when carrying out the contact process under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, etc., or a mixed gas thereof. A gas containing 10% or more of carbon dioxide or helium in a molar ratio is preferable, and a gas containing 10% or more of carbon dioxide in a molar ratio is particularly preferable. Since helium gas easily diffuses into the mold, substrate, curable composition, etc., the atmospheric gas trapped in the mold pattern, etc. quickly disappears. Since carbon dioxide easily dissolves in the curable composition and the underlying layer on the substrate, the atmospheric gas trapped in the mold pattern, etc. quickly disappears (see Patent Document 6). When carrying out the contact process in an atmosphere of a specific gas including an atmospheric atmosphere, the preferable pressure is 0.0001 atm or more and 10 atm or less.

[0242] <Curing process> In the curing process, as schematically shown in FIG. 1(f), the non-volatile composition (A') is cured to form a cured film by irradiating the non-volatile composition (A') with irradiation light 107 as curing energy. In the curing process, for example, the non-volatile composition (A') is irradiated with the irradiation light 107 through the mold 106. More specifically, the non-volatile composition (A') filled in the fine pattern of the mold 106 is irradiated with the irradiation light 107 through the mold 106. As a result, the non-volatile composition (A') filled in the fine pattern of the mold 106 is cured to form a cured film 108 having a pattern.

[0243] The irradiation light 107 is selected according to the sensitivity wavelength of the non-volatile composition (A'). Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, electron beams, etc. having a wavelength of 150 nm or more and 400 nm or less. It should be noted that the irradiation light 107 is particularly preferably ultraviolet light. This is because many commercially available compounds as curing aids (photoinitiators) have sensitivity to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, Deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, F2 lasers, etc. However, as a light source that emits ultraviolet light, an ultra-high-pressure mercury lamp is particularly preferred. The number of light sources may be one or a plurality. Also, the curable composition (A) filled in the fine pattern of the mold may be irradiated with light over the entire area, or may be irradiated with light only in a part of the area (limiting the area). Further, the light irradiation may be performed intermittently a plurality of times over the entire area of the substrate, or may be performed continuously over the entire area of the substrate. Furthermore, the substrate may be irradiated with light in the first region in the first irradiation process, and the substrate may be irradiated with light in the second region different from the first region in the second irradiation process.

[0244] <Demolding step> In the demolding step, as schematically shown in FIG. 1(g), the mold 106 is separated from the cured film 108. By separating the cured film 108 having a pattern from the mold 106, a cured film 108 having a pattern in which the fine pattern of the mold 106 is inverted is obtained in a self-standing state. Here, a cured film also remains in the concave portion of the cured film 108 having a pattern. Such a film is called a residual film.

[0245] As a method of separating the mold 106 from the cured film 108 having the pattern, it is only necessary that a part of the cured film 108 having the pattern is not physically damaged during separation, and various conditions and the like are not particularly limited. For example, the substrate 101 may be fixed and the mold 106 may be moved away from the substrate 101. Alternatively, the mold 106 may be fixed and the substrate 101 may be moved away from the mold 106. The mold 106 may be separated from the cured film 108 having the pattern by moving both the mold 106 and the substrate 101 in opposite directions.

[0246] <Repeat> By a series of steps (manufacturing process) having the above-described placement step and release step in this order, a cured film having a desired concavo-convex pattern shape (a pattern shape following the concavo-convex shape of the mold 106) at a desired position can be obtained.

[0247] In the pattern forming method according to the present disclosure, the repeating unit (shot) from the placement step to the release step can be repeated a plurality of times on the same substrate, and a cured film 108 having a plurality of desired patterns at a desired position on the substrate can be obtained.

[0248] [Planarization film forming method] Hereinafter, an example in which the film formation method in the present disclosure is applied to a planarization film formation method will be described. The planarization film formation method includes, for example, an arrangement step, a standby step, a contact step, a curing step, and a release step. The arrangement step is a step of arranging droplets of the curable composition (A) on a substrate. The standby step is a step of waiting until the droplets of the curable composition (A) are combined and the solvent (d) is volatilized. The contact step is a step of bringing the non-volatile composition (A') into contact with a mold. The curing step is a step of curing the non-volatile composition (A'). The release step is a step of separating the mold from the cured film of the non-volatile composition (A'). In the planarization film formation method, as the substrate, a substrate having irregularities with a height difference of about 10 to 1,000 nm is used, and as the mold, a mold having a flat surface is used. Through the contact step, the curing step, and the release step, a cured film having a surface following the flat surface of the mold is formed. The flat surface refers to a flat (patternless) surface having no pattern formed on the substrate, or a flat surface that is the same as or larger than the pattern formation region of the substrate. In the arrangement step, droplets of the curable composition (A) are densely arranged in the concave portions of the substrate, and the curable composition (A) is sparsely arranged in the convex portions of the substrate. The standby step is carried out after the arrangement step, the contact step is carried out after the standby step, the curing step is carried out after the contact step, and the release step is carried out after the curing step.

[0249] [Article manufacturing method] The article manufacturing method may include a forming step of forming a film of a curable composition on a substrate using the film formation method described above, a processing step of processing the substrate on which the film of the curable composition is formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. The film formation method is, as described above, a pattern formation method or a planarization film formation method.

[0250] In addition, the cured film 108 having the pattern formed by the pattern formation method in the present disclosure is used as it is as at least a partial constituent member of various articles. The cured film 108 having the pattern formed by the pattern formation method in the present disclosure is temporarily used as a mask for etching, ion implantation, etc. with respect to the substrate 101 (the processed layer when the substrate 101 has a processed layer). In the processing step of the substrate 101, after etching, ion implantation, etc. are performed, the mask is removed. Thereby, various articles can be manufactured.

[0251] When removing the cured product in the concave portion of the pattern of the cured product by etching, the specific method is not particularly limited, and a known method, for example, dry etching can be used. For dry etching, a known dry etching apparatus can be used. The source gas for dry etching is appropriately selected according to the elemental composition of the cured product to be etched. Specifically, as the source gas, halogen-based gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, Cl2 can be used. In addition, as the source gas, gases containing oxygen atoms such as O2, CO, CO2, inert gases such as He, N2, Ar, and gases such as H2, NH3 can also be used. Note that these gases can be mixed and used as the source gas. In this case, in order to process the underlying substrate with good yield, the photocurable film is required to have a high dry etching regime.

[0252] The article is an electric circuit element, an optical element, MEMS, a recording element, a sensor, or a mold, etc. Examples of the electric circuit element include a volatile or non-volatile semiconductor memory such as DRAM, SRAM, flash memory, MRAM, and semiconductor elements such as LSI, CCD, image sensor, FPGA, etc. Examples of the optical element include a microlens, a light guide, a waveguide, an antireflection film, a diffraction grating, a polarization element, a color filter, a light-emitting element, a display, a solar cell, etc. Examples of MEMS include DMD, a microchannel, an electromechanical conversion element, etc. Examples of the recording element include an optical disk such as CD, DVD, a magnetic disk, a magneto-optical disk, a magnetic head, etc. Examples of the sensor include a magnetic sensor, an optical sensor, a gyro sensor, etc. Examples of the mold include a mold for imprinting, etc.

[0253] In addition, known photolithography processes such as imprint lithography technology and extreme ultraviolet lithography (EUV) can be performed on the planarization film formed by the planarization film forming method in the present disclosure. Also, a spin-on glass (SOG) film and / or a silicon oxide layer can be laminated, and a curable composition can be applied thereon to perform a photolithography process. Thereby, a device such as a semiconductor device can be manufactured. Also, an apparatus including such a device, for example, an electronic apparatus such as a display, a camera, a medical device, etc. can be formed. Examples of the device include, for example, LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, NAND flash, etc.

[0254] [Examples] To supplement the above-described embodiments, more specific examples will be described. <Example 1> In this embodiment, it is shown that the edge filling rate v and the bleeding delay time t are expressed by the following formulas E1 and E2 using the viscosity μ [mPa·s] of the non-volatile composition and the average liquid film thickness h [m]. Also, it is shown using numerical calculations that it is desirable to satisfy the above relational expressions 1 and 2 in order for v to be 20 [μm / sec] or more and t to be 0.5 [sec] or more. Formula E1: v(μ,h)=C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s] Formula E2: t(μ,h)=C·h α ·μ / μ0, C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s]

[0255] In this embodiment, assuming the contact process, the edge filling rate and the bleeding delay time were obtained by solving the Navier-Stokes equation approximated by a thin film sandwiched between walls and the equation of elastic deformation of the mold simultaneously. The state of the calculation region is shown in FIG. 5. In FIG. 5, the initial position 110 of the end of the liquid film 102 between the substrate 101 and the mold 106 is set inside (on the negative x-axis side) the end 109 of the pattern formation region. The negative x-axis end was set as a symmetric boundary, and it was assumed that the direction perpendicular to the plane of FIG. 5 was symmetric, and the calculation was approximated as a two-dimensional problem.

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

[0257] Figure 6 shows the change in the edge filling rate when the average liquid film thickness is 40 nm and the viscosity coefficient of the liquid film is changed. In Figure 6, the horizontal axis is time and the vertical axis is the distance between the liquid film end and the edge. Note that the downward direction is the positive direction for the vertical axis. Each of B01, B02, and B03 corresponds to the result when the liquid film has viscosities of 50, 150, and 300 mPa·s, respectively. According to this, it can be seen that the lower the viscosity, the faster the edge filling rate.

[0258] Figure 7 shows the calculation results for the same calculation results as in Figure 6, with the horizontal axis being time / viscosity coefficient. As shown in C01, it can be seen that each curve shown in Figure 6 overlaps the same curve. This means that it shows that the edge filling rate is inversely proportional to the viscosity coefficient. In this way, it has been shown that the flow rate of the liquid film is inversely proportional to the viscosity coefficient.

[0259] Figure 8 shows the change in the edge filling rate when the viscosity coefficient of the liquid film is 50 mPa·s and the average liquid film thickness is changed. In Figure 8, the horizontal axis is time and the vertical axis is the distance between the end of the liquid film and the edge. Note that the downward direction is the positive direction for the vertical axis. Each of D01, D02, D03, D04, and D05 corresponds to the result when the average liquid film thickness is 1000, 200, 100, 80, and 40 nm, respectively. According to this, it can be seen that the thicker the average liquid film thickness, the faster the edge filling rate.

[0260] Figure 9 shows a graph with the average liquid film thickness on the horizontal axis and the edge filling rate on the vertical axis. The plots are the calculation results and the curve corresponds to Equation E1. In this way, Equation E1 can be used to represent the dependence of the edge filling rate on the average liquid film thickness. Also, as discussed above, since the edge filling rate is inversely proportional to the viscosity coefficient, it can be seen that the viscosity coefficient dependence can also be represented by Equation E1.

[0261] Next, FIG. 10 shows the time change of the bleeding height when the viscosity coefficient of the liquid film is 50 mPa·s and the average liquid film thickness is changed. In FIG. 10, the horizontal axis represents the elapsed time, indicating the elapsed time with the time when the liquid film is filled up to the edge set to 0. The vertical axis represents the bleeding height. Each of F01, F02, F03, F04, and F05 corresponds to the results when the average liquid film thickness is 1000, 200, 100, 80, and 40 nm, respectively. According to this, it can be seen that the thicker the average liquid film thickness, the earlier the bleeding occurs. When the bleeding height reaches approximately 50 nm, it causes defects. Therefore, in FIG. 10, the value on the horizontal axis when the vertical axis reaches 50 nm, that is, the elapsed time from the time when the liquid film is filled up to the edge until the bleeding height reaches 50 nm, is defined as the bleeding delay time.

[0262] FIG. 11 shows the change of the bleeding delay time when the average liquid film thickness is changed. In FIG. 11, the horizontal axis represents the average liquid film thickness and the vertical axis represents the bleeding delay time. The plots are the calculation results and the curve corresponds to Equation B. Thus, it can be seen that Equation B can represent approximately the dependence of the bleeding delay time on the average liquid film thickness. Also, as discussed above, since the flow rate of the liquid film is inversely proportional to the viscosity coefficient, it can be understood that the bleeding delay time is proportional to the viscosity coefficient. Therefore, it can be seen that the viscosity coefficient dependence can also be represented by Equation B.

[0263] As described above, it has been shown that the edge filling rate is represented by Equation E1 with μ and h as variables, and the bleeding delay time is represented by Equation E2 with μ and h as variables. Therefore, in order for the edge filling rate to be 20 μm / sec or more and the bleeding delay time to be 0.5 sec or more, it has been found that it is desirable to satisfy the inequalities shown in Relational Expression 1 and Relational Expression 2.

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

Table 1

Table 2

[0265] <Evaluation of edge filling rate> The evaluation of the edge filling rate was carried out using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). Under the conditions that the thickness of the liquid film after the solvent (d) volatilized was 40 nm, 80 nm, and 120 nm, the curable compositions (A) of Examples 2 to 6 and Comparative Examples 1 to 3 were discretely dropped (placed) on a silicon substrate, and a standby process and a contact process were carried out. All of these placement process, standby process, and contact process were carried out in a carbon dioxide atmosphere, and a quartz blank mold was used in the contact process. Here, let the distance between the end position of the pattern formation region of the substrate and the initial position of the liquid film end of the curable composition (A) on the substrate immediately before the contact process be D, and the time required for the non-volatile component (A') to be filled to the end of the pattern formation region of the substrate in the contact process be T. At this time, the edge filling rate is defined as D / T. The edge filling rate defined in this way was evaluated according to the following criteria. ·A: Edge filling was carried out at a speed of 20 μm / sec or more. ·B: Edge filling was carried out at a speed of less than 20 μm / sec.

[0266] <Evaluation of leaching delay time> The evaluation of the leaching delay time was carried out using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). Under the conditions where the thickness of the liquid film after the solvent (d) volatilized was 40 nm, 80 nm, and 120 nm, the curable compositions (A) of Examples 2 to 6 and Comparative Examples 1 to 3 were discretely dropped (placed) on a silicon substrate, and a standby step and a contact step were carried out. All of these placement steps, standby steps, and contact steps were carried out in a carbon dioxide atmosphere, and a quartz blank mold was used in the contact step.

[0267] When the non-volatile component (A') continues to be in contact with the mold even after the non-volatile component (A') fills up to the end of the pattern formation region of the substrate in the contact step, the non-volatile component (A') oozes out from the end of the mold and climbs up the side wall of the mold. The height of the component that climbed up the side wall of this mold is measured as the leaching height. The time until the leaching height reaches 50 nm was measured and evaluated according to the following criteria. ·A: The leaching delay time was 0.5 seconds or more. ·B: The leaching delay time was less than 0.5 seconds. Table 3 shows the evaluation results of the edge filling rate and the leaching delay time.

Table 3

[0268] Consider satisfying the following conditions. (1) The imprint process at an average liquid film thickness of 40 nm can be carried out with high throughput, (2) The edge filling rate that can suppress defects on the substrate due to leaching is 20 μm / sec or more, and (3) The leaching delay time is 0.5 seconds or more. As suggested by the above-mentioned relational expressions 1 and 2, it can be seen that in order to satisfy the above conditions, it is preferable that the viscosity of the non-volatile component (A') is 20 mPa·s or more and 60 mPa·s or less.

[0269] Also, consider satisfying the following conditions. (1) The imprint process at an average liquid film thickness of 80 nm can be carried out with high throughput, (2) The edge filling rate for suppressing defects on the substrate due to leaching is 20 μm / sec or more, and (3) The leaching delay time is 0.5 sec or more. In order to satisfy the above conditions, it can be understood that the viscosity of the non-volatile component (A’) is preferably 20 mPa·s or more and 100 mPa·s or less.

[0270] Also, consider satisfying the following conditions. (1) The imprint process at an average liquid film thickness of 120 nm can be carried out with high throughput, (2) The edge filling rate for suppressing defects on the substrate due to leaching is 0 m / sec or more, and (3) The leaching delay time is 0.5 sec or more. In order to satisfy the above conditions, it can be understood that the viscosity of the non-volatile component (A’) excluding the solvent is preferably 60 mPa·s or more and 135 mPa·s or less.

[0271] The disclosure of this specification includes the following technical ideas. (Item 1) A film forming method for forming a film of a curable composition on a substrate using a mold, An arranging step of discretely arranging a plurality of droplets of the curable composition on the substrate, After the arranging step, a contacting step of bringing the plurality of droplets on the substrate into contact with the mold to form a liquid film between the substrate and the mold, After the contacting step, a curing step of curing the liquid film to form a cured film, After the curing step, a separating step of separating the cured film from the mold, and The viscosity μ [mPa·s] of the non-volatile composition in the curable composition and the average liquid film thickness h [m] formed by the non-volatile composition are Relationship 1: 20 [μm / sec] ≦ C·h α ·μ0 / μ, C = 9.75e-2, α = 0.489, μ0 = 50 [mPa·s], Relational expression 2: 0.5 [sec] ≤ C·h α ·μ / μ0, C = 1.89e-15, α = -2.1, μ0 = 50 [mPa·s] A film forming method characterized by being a value that satisfies the above conditions. (Item 2) The curable composition contains a polymerizable compound (a) and a photopolymerization initiator (b), and has a viscosity of 20 mPa·s or more and 135 mPa·s or less at 23°C, The film forming method according to Item 1, characterized by the above conditions. (Item 3) The average liquid film thickness of the curable composition is 5 nm or more and 170 nm or less. The film forming method according to Item 2, characterized by the above conditions. (Item 4) The ratio of the polyfunctional polymerizable compound in the polymerizable compound (a) is 20% by weight or more. The film forming method according to Item 2 or 3, characterized by the above conditions. (Item 5) The polymerizable compound (a) contains one or more polymerizable compounds, and the boiling point of each of the one or more polymerizable compounds at 1 atm is 250°C or more. The film forming method according to Item 2 or 3, characterized by the above conditions. (Item 6) The polymerizable compound (a) contains one or more polymerizable compounds, and the molecular weight of each of the one or more polymerizable compounds is 200 or more. The film forming method according to Item 2 or 3, characterized by the above conditions. (Item 7) The polymerizable compound (a) contains a polymer having a polymerizable functional group. The film forming method according to any one of Items 2 to 6, characterized by the above conditions. (Item 8) The polymerizable compound (a) contains one or more polymerizable compounds, and the vapor pressure of each of the one or more polymerizable compounds at 80°C and 1 atm is 0.001 mmHg or less. The film forming method according to Item 2 or 3, characterized by the above conditions. (Item 9) The film-forming method according to any one of Items 2 to 8, wherein the polymerizable compound (a) includes a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. (Item 10) The polymerizable compound (a) includes one or more types of polymerizable compounds. The Ohnishi parameter (OP) of the polymerizable compound (a) is 1.80 or more and 4.00 or less. When the total number of atoms in the molecule is N, the total number of carbon atoms in the molecule is N c and the total number of oxygen atoms in the molecule is N o then the Ohnishi parameter (OP) is the mole fraction weighted average value of N / (N C -N O ) values for each molecule of the one or more types of polymerizable compounds. The film-forming method according to Item 2 or 3, characterized by the above. (Item 11) The film-forming method according to any one of Items 2 to 10, wherein the polymerizable compound (a) includes a compound (a-2) containing an Si atom. (Item 12) The film-forming method according to Item 11, wherein the compound (a-2) includes a polymerizable compound having a silsesquioxane skeleton or a cyclic siloxane compound. (Item 13) The curable composition further includes a solvent (d). The curable composition in a state where the solvent (d) is removed contains 10% by weight or more of Si atoms. The film-forming method according to Item 11 or 12, characterized by the above. (Item 14) The curable composition further includes a solvent (d). has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C. The curable composition in a state where the solvent (d) is removed has a viscosity of 20 mPa·s or more and 135 mPa·s or less at 23°C. After the placement step and before the contact step, there is further a waiting step of waiting for the coalescence of the plurality of droplets on the substrate to proceed and for the evaporation of the solvent contained in the liquid film to proceed. The film forming method according to any one of items 1 to 13, characterized in that. (Item 15) The average liquid film thickness of the curable composition in a state where the solvent (d) has been removed is 5 nm or more and 170 nm or less. The film forming method according to item 14, characterized in that. (Item 16) In the waiting step, waiting is performed until the content of the solvent (d) becomes 10% by volume or less with respect to the entire liquid film. The film forming method according to item 14 or 15, characterized in that. (Item 17) The waiting step includes a step of heating the substrate under conditions of 30 °C or more and 200 °C or less, and 10 seconds or more and 600 seconds or less. The film forming method according to any one of items 14 to 16, characterized in that. (Item 18) In the placement step, droplets of the curable composition having a volume of 1.0 pL or more are placed on the substrate at a density of 80 droplets / mm 2 or more. The film forming method according to any one of items 14 to 17, characterized in that. (Item 19) The solvent (d) includes one or more solvents, and the boiling point of each of the one or more solvents at 1 atm is 100 °C or more and less than 250 °C. The film forming method according to any one of items 14 to 18, characterized in that. (Item 20) The solvent (d) includes a polymerizable compound having a boiling point of 80 °C or more and less than 250 °C at 1 atm. The film forming method according to any one of items 14 to 19, characterized in that. (Item 21) The content of the solvent (d) with respect to the entire curable composition is 40% by volume or more and 85% by volume or less. The film forming method according to any one of items 14 to 20, characterized in that. (Item 22) The glass transition temperature of the cured film is 70 °C or higher, and the film forming method according to any one of Items 1 to 21 is characterized by this. (Item 23) The curable composition is a curable composition for inkjet, and the film forming method according to any one of Items 1 to 22 is characterized by this. (Item 24) The mold includes a pattern, In the contacting step, the pattern of the mold and the liquid film are brought into contact with each other, The film forming method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a pattern corresponding to the pattern of the mold. The film forming method according to any one of Items 1 to 23 is characterized by this. (Item 25) The mold includes a flat surface, In the contacting step, the flat surface of the mold and the liquid film are brought into contact with each other, The film forming method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a surface following the flat surface of the mold. The film forming method according to any one of Items 1 to 23 is characterized by this. (Item 26) In the arranging step, the plurality of droplets are discretely arranged on the substrate by using an inkjet method, and the film forming method according to any one of Items 1 to 25 is characterized by this. (Item 27) The solubility coefficient of carbon dioxide with respect to the curable composition is 0.5 kg / m 3 ·atm or more and 10 kg / m 3 ·atm or less, and the film forming method according to any one of Items 1 to 26 is characterized by this. (Item 28) In the contacting step, the gas filling the space between the substrate and the mold contains 10% or more of carbon dioxide in molar ratio, and the film forming method according to any one of Items 1 to 27 is characterized by this. (Item 29) Using the film forming method according to any one of Items 1 to 28, a forming step of forming a film of a curable composition on a substrate, A processing step of processing the substrate on which the film is formed in the forming step, A manufacturing step of manufacturing an article from the substrate processed in the processing step, An article manufacturing method, characterized by comprising: (Item 30) A curable composition containing a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), The curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm, The content of the solvent (d) with respect to the whole curable composition is more than 5% by volume and 95% by volume or less, The boiling point of the solvent (d) is less than 250°C at 1 atm, The viscosity of the curable composition in a state where the solvent (d) is removed is 20 mPa·s or more and 135 mPa·s or less at 23°C and 1 atm, A curable composition, characterized by the above. (Item 31) The solubility coefficient of carbon dioxide with respect to the curable composition is 0.5 kg / m 3 ·atm or more and 10 kg / m 3 ·atm or less, and the curable composition according to Item 30, characterized by the above.

[0272] The invention is not limited to the above embodiments, and various changes and modifications are possible without departing from the spirit and scope of the invention. Therefore, claims are attached to disclose the scope of the invention.

Explanation of Signs

[0273] 101: Substrate, 102: Droplet, 103: Liquid film, 105: Solvent, 106: Mold, 107: Irradiation light, 108: Cured film

Claims

1. A film forming method for forming a film of a curable composition on a substrate using a mold, comprising: a disposing step of discretely disposing a plurality of droplets of the curable composition on the substrate; a contacting step of contacting the plurality of droplets on the substrate with the mold after the disposing step to form a liquid film between the substrate and the mold; a curing step of curing the liquid film to form a cured film after the contacting step; a separating step of separating the cured film from the mold after the curing step, wherein the viscosity μ [mPa·s] of the non-volatile composition in the curable composition and the average liquid film thickness h [m] formed by the non-volatile composition satisfy Relational Expression 1: 20 [μm / sec] ≤ C・h α ・μ ０ / μ, C = 9.75e-2, α = 0.489, μ ０ = 50 [mPa·s], and, Relational Expression 2: 0.5 [sec] ≦ C · h α · μ / μ ０ , C = 1.89e-15, α = -2.1, μ ０ = 50 [mPa·s] a value satisfying the above, and a film forming method characterized by this.

2. The curable composition contains a polymerizable compound (a) and a photopolymerization initiator (b), and has a viscosity of 20 mPa·s or more and 135 mPa·s or less at 23°C. The film forming method according to claim 1, characterized by this.

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

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

5. The polymerizable compound (a) contains one or more polymerizable compounds, and the boiling point of each of the one or more polymerizable compounds at 1 atm is 250°C or higher, and the film forming method according to claim 2, characterized by this.

6. The polymerizable compound (a) contains one or more polymerizable compounds, and the molecular weight of each of the one or more polymerizable compounds is 200 or more, and the film forming method according to claim 2, characterized by this.

7. The polymerizable compound (a) contains a polymer having a polymerizable functional group, and the film forming method according to claim 2, characterized by this.

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

9. The polymerizable compound (a) contains a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure, and the film forming method according to claim 2, characterized by this.

10. The polymerizable compound (a) contains one or more polymerizable compounds, The Oonishi parameter (OP) of the polymerizable compound (a) is 1.80 or more and 4.00 or less, Let the total number of atoms in the molecule be N, the total number of carbon atoms in the molecule be N ｃ and the total number of oxygen atoms in the molecule be N ｏ When this is the case, the Oonishi parameter (OP) is the mole fraction weighted average value of the N / (N Ｃ −N Ｏ ) value for each molecule of the one or more polymerizable compounds. The film forming method according to claim 2, characterized in that.

11. The polymerizable compound (a) includes a compound (a-2) containing an Si atom, and the film forming method according to claim 2, characterized in that.

12. The compound (a-2) includes a polymerizable compound having a silsesquioxane skeleton or a cyclic siloxane compound, and the film forming method according to claim 11, characterized in that.

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

14. The curable composition further includes a solvent (d), has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C, The curable composition in a state where the solvent (d) is removed has a viscosity of 20 mPa·s or more and 135 mPa·s or less at 23°C, After the placement step and before the contact step, there is a further waiting step of waiting for the coalescence of the plurality of droplets on the substrate to proceed and for the evaporation of the solvent contained in the liquid film to proceed, The film forming method according to claim 1, characterized in that.

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

16. In the waiting step, waiting is performed until the content of the solvent (d) becomes 10% by volume or less with respect to the entire liquid film, and the film forming method according to claim 14, characterized in that.

17. The waiting step includes a step of heating the substrate under conditions of 30°C or more and 200°C or less, and 10 seconds or more and 600 seconds or less, and the film forming method according to claim 14, characterized in that.

18. In the placement step, droplets of the curable composition having a volume of 1.0 pL or more are placed on the substrate at a density of 80 droplets / mm ２ or higher. The method for forming a film according to claim 14, characterized by the above.

19. The solvent (d) includes one or more solvents, and the boiling point of each of the one or more solvents at 1 atm is 100°C or more and less than 250°C, and the film forming method according to claim 14, characterized in that.

20. The solvent (d) includes a polymerizable compound having a boiling point of 80°C or more and less than 250°C at 1 atm, and the film forming method according to claim 14, characterized in that.

21. The content of the solvent (d) with respect to the whole of the curable composition is 40% by volume or more and 85% by volume or less, and the film forming method according to claim 14 is characterized by this.

22. The glass transition temperature of the cured film is 70°C or higher, and the film forming method according to claim 1 is characterized by this.

23. The curable composition is a curable composition for inkjet, and the film forming method according to claim 1 is characterized by this.

24. The mold includes a pattern, In the contact step, the pattern of the mold and the liquid film are brought into contact, The film forming method further includes a curing step of curing the liquid film after the contact step to form a cured film having a pattern corresponding to the pattern of the mold. The film forming method according to claim 1 is characterized by this.

25. The mold includes a flat surface, In the contact step, the flat surface of the mold and the liquid film are brought into contact, The film forming method further includes a curing step of curing the liquid film after the contact step to form a cured film having a surface following the flat surface of the mold. The film forming method according to claim 1 is characterized by this.

26. In the arranging step, the plurality of droplets are discretely arranged on the substrate by using an inkjet method, and the film forming method according to claim 1 is characterized by this.

27. The solubility coefficient of carbon dioxide with respect to the curable composition is 0.5 kg / m ３ ·atm or more and 10 kg / m ３ ·atm or less, and the method for forming a film according to claim 1, characterized in that.

28. In the contact step, the gas filling the space between the substrate and the mold contains 10% or more of carbon dioxide in molar ratio, and the film forming method according to claim 1 is characterized by this.

29. A forming step of forming a film of a curable composition on a substrate using the film forming method according to any one of claims 1 to 28, A processing step of processing the substrate on which the film is formed in the forming step, A manufacturing step of manufacturing an article from the substrate processed in the processing step, An article manufacturing method characterized by having these.

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

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

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