Curable composition, film forming method, and method for producing article

Abstract

The present invention provides a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), in which the viscosity of the curable composition at 23 DEG C and 1 atm is 1.3 mPa.s to 60 mPa.s (inclusive); the content of the solvent (d) relative to the whole curable composition is more than 5 vol% and no more than 95 vol%; the boiling point of the solvent (d) at 1atm is less than 250 DEG C; and if [alpha] 1 (DEG) is a contact angle with respect to the substrate of the composition obtained by removing the solvent (d) and the surfactant (c1) from the curable composition, and [alpha] 2 (DEG) is a contact angle with respect to the substrate of the composition obtained by removing the solvent (d) from the curable composition, [alpha] 2 is greater than [alpha] 1.

Description

TECHNICAL FIELD

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

[0002] For semiconductor devices and MEMS, the demand for miniaturization is increasing, and as a micro-patterning technique, an imprint technique (optical imprint technique) is attracting great attention as a microfabrication technique. In the imprint technique, a curable composition is cured in a state in which a mold in which a fine concave-convex pattern is formed on a surface is in contact with the curable composition supplied (applied) to a substrate. Thus, the pattern of the mold is transferred to a cured film of the curable composition, thereby forming a pattern on the substrate. According to the imprint technique, a fine pattern (structure) of several nanometers in size can be formed on the substrate.

[0003] An example of a pattern forming method using the imprint technique is described. First, a curable composition in a liquid form is discretely dropped (disposed) in a pattern forming region on a substrate. The droplet of the curable composition disposed in the pattern forming region spreads on the substrate. This phenomenon is called pre-spreading. Next, a mold is brought into contact (pressed) with the curable composition on the substrate. Thus, the droplet of the curable composition spreads to the entire region of the gap between the substrate and the mold by capillary phenomenon. This phenomenon is called spreading. Further, the curable composition is caused to fill the concave portions forming the pattern of the mold by capillary phenomenon. This phenomenon is called filling. Note that the time until the spreading and the filling are completed is called a filling time. If the filling of the curable composition is completed, the curable composition is irradiated with light to cure the curable composition. Then, the mold is detached from the cured curable composition on the substrate. By carrying out these steps, the pattern of the mold is transferred to the curable composition on the substrate, and a pattern of the curable composition is formed. Here, the pattern of the curable composition formed on the substrate includes a residual film. The residual film is a cured film remaining between the substrate and the concave portions (convex portions of the pattern of the mold) of the cured film of the curable composition.

[0004] A lithography step for manufacturing a semiconductor device requires planarization of a substrate. For example, in an extreme ultraviolet exposure technique (EUV) that is an attention-getting lithography technique in recent years, as miniaturization progresses, the depth of focus of a projection image decreases, and thus unevenness on the surface of the substrate to which the curable composition is supplied must be reduced to several tens of nm or less. In order to improve the filling property and line width accuracy of the curable composition, planarity equivalent to EUV is also required in the imprint technique. As a planarization technique, a technique of obtaining a planar surface by discretely dropping a droplet of a curable composition in an amount corresponding to a concave-convex on a concave-convex substrate, and curing the curable composition in a state in which a mold having a planar surface is in contact with the curable composition is known.

[0005] In a pattern forming method using an imprint technique or a planarization technique, since the mold is contacted in a state in which the droplets of the curable composition dropped on the substrate do not contact each other, a bubble is inevitably trapped between the mold, the substrate, and the curable composition. Therefore, a long time is required until the bubble diffuses to the mold or the substrate and disappears, and this is one of factors of low productivity (production amount). Therefore, a technique in which the droplets of the curable composition are combined with each other before the curable composition on the substrate and the mold are contacted with each other is proposed (see Patent Literature 1).

[0006] Prior Art Documents

[0007] Patent Literature

[0008] Patent Literature 1: Japanese Patent Laid-Open No. 2022-188736 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] However, in the technique disclosed in Patent Literature 1, since the droplets of the curable composition dropped on the substrate spread at a high speed so that the droplets are combined with each other, the curable composition can be squeezed out from the desired region (pattern forming region). The length of the curable composition squeezed out from the desired region is referred to as "squeeze-out amount".

[0011] Further, in the technique disclosed in Patent Literature 1, since the curable composition has fluidity at the time when the mold is contacted with the curable composition on the substrate, it can be squeezed out from the contact surface of the mold and adhere to (climb up) the side wall of the mold. The phenomenon in which the curable composition climbs up and adheres to the side wall (side surface) of the mold is referred to as "bleeding out". The cured product of the curable composition adhered to the side wall of the mold remains on the substrate as an unnecessary substance, or drops from the side wall of the mold to the substrate at an unexpected time, resulting in a large defect on the substrate.

[0012] The present application provides a new technique relating to a curable composition.

[0013] SOLUTION TO PROBLEM

[0014] The curable composition according to an aspect of the present application is a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), wherein the viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa-s or more and 60 mPa-s or less, the content of the solvent (d) with respect to the entire curable composition is more than 5 vol% and 95 vol% or less, the boiling point of the solvent (d) at 1 atm is less than 250°C, and α2 [°] is the contact angle of a composition obtained by removing the solvent (d) from the curable composition with respect to a substrate, and α1 [°] is the contact angle of a composition obtained by removing the solvent (d) and the surfactant (c1) from the curable composition with respect to a substrate, and α2 is larger than α1.

[0015] Effects of the Invention

[0016] According to the present application, a new technology regarding a curable composition is provided.

[0017] Other features and advantages of the present application will be apparent from the following description taken in connection with the accompanying drawings. Note that, in all the drawings shown herein, the same or similar components are designated by the same reference numerals, and the explanation will not be repeated. BRIEF DESCRIPTION OF DRAWINGS

[0018] The accompanying drawings, which are incorporated herein and constitute part of the specification, illustrate embodiments of the application and, together with the description, serve to explain the principles of the application.

[0019] [ FIG. 1A ] is a view for explaining a pattern forming method (film forming method) according to an aspect of the present application.

[0020] [ FIG. 1B ] is a view for explaining a pattern forming method (film forming method) according to an aspect of the present application.

[0021] [ FIG. 1C ] is a view for explaining a pattern forming method (film forming method) according to an aspect of the present application.

[0022] [ FIG. 1D ] is a view for explaining a pattern forming method (film forming method) according to an aspect of the present application.

[0023] [ FIG. 1E ] is a view for explaining a pattern forming method (film forming method) according to an aspect of the present application.

[0024] [ FIG. 1F ] is a view for explaining a pattern forming method (film forming method) according to an aspect of the present application.

[0025] [ FIG. 1Gis a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present application.

[0026] [ FIG. 2 is a diagram illustrating the behavior of a droplet of a curable composition after dropping.

[0027] [ FIG. 3 is a diagram showing the shape of a droplet in the case where the droplet flows due to the Marangoni effect.

[0028] [ FIG. 4 is a diagram illustrating the behavior of a droplet of a curable composition after dropping.

[0029] [ FIG. 5 is a diagram illustrating the behavior of a droplet of a curable composition after dropping.

[0030] [ FIG. 6 is a diagram illustrating the behavior of a droplet of a curable composition after dropping.

[0031] [ FIG. 7A is a diagram illustrating the flow behavior of a droplet of a curable composition during a waiting step.

[0032] [ FIG. 7B is a diagram illustrating the flow behavior of a droplet of a curable composition during a waiting step.

[0033] [ FIG. 7C is a diagram illustrating the flow behavior of a droplet of a curable composition during a waiting step.

[0034] [ FIG. 7D is a diagram illustrating the flow behavior of a droplet of a curable composition during a waiting step.

[0035] [ FIG. 8 is a diagram showing a comparison between a contact step in the prior art and a contact step in the present application;

[0036] [ FIG. 9 is a diagram illustrating the concept of a penetration phenomenon;

[0037] [ FIG. 10 is a diagram showing the state in which a curable composition climbs up the side wall of a mold;

[0038] [ FIG. 11 is a diagram showing the results of measuring the contact angle with a substrate;

[0039] [ FIG. 12 is a diagram showing the results of measuring the surface tension;

[0040] [ FIG. 13is a graph showing the time rate of change of the radius of the droplet;

[0041] [ FIG. 14 ] is a graph showing the results of measuring the extrusion amount of the liquid film;

[0042] [ FIG. 15 ] is a graph showing the state of the droplets isolated on the substrate;

[0043] [ FIG. 16 ] is a graph showing the state of the virtually continuous liquid film formed on the substrate;

[0044] [ FIG. 17 ] is a graph showing a summary of the experimental results on three types of compositions;

[0045] [ FIG. 18 ] is a graph showing the dependence of the maximum radius of the droplet on Δγ;

[0046] [ FIG. 19 ] is a graph showing the results of measuring the contact angle with the mold; and

[0047] [ FIG. 20 ] is a graph showing the results of obtaining the bleeding height by numerical calculation. DETAILED DESCRIPTION

[0048] Embodiments of the present application are described in detail below with reference to the accompanying drawings. Note that the following embodiments do not limit the scope of the application according to the claims attached hereto. Although a plurality of features are described in the embodiments, not all of the features are necessarily required, and a plurality of the features can be combined. The same reference numerals are used throughout the drawings and repeated descriptions are omitted.

[0049] When a new technology on a curable composition was provided, the present inventors found a curable composition in which droplets of a curable composition discretely dropped (arranged) on a substrate are combined with each other, and a solvent contained in the curable composition can be volatilized, and process conditions thereof.

[0050] [Curable composition]

[0051] The curable composition (A) according to the present application can be a curable composition for inkjet. The curable composition (A) according to the present application is a composition containing at least a component (a) which is a polymerizable compound, a component (b) which is a photopolymerization initiator, and a component (d) which is a solvent.

[0052] In this specification, a cured film means a film cured by polymerizing a curable composition on a substrate. Note that the shape of the cured film is not particularly limited, and thus the film can have a pattern shape on a surface. Furthermore, the cured film remaining between a recess of the cured film of the curable composition (a convex portion of a mold pattern) and a substrate is referred to as a residual film.

[0053] <component (a): polymerizable compound>

[0054] Component (a) is a polymerizable compound. In this specification, a polymerizable compound is a compound that reacts with a polymerization factor (for example, a radical) generated from a photopolymerization initiator (component (b)) and forms a film made of a high molecular compound through a chain reaction (polymerization reaction).

[0055] An example of the polymerizable compound described above is a radical polymerizable compound. The polymerizable compound as component (a) can be formed of only one type of polymerizable compound, and can also be formed of a plurality of types (one or more) of polymerizable compounds.

[0056] Examples of the radical polymerizable compound are (meth)acrylic compounds, styrene compounds, ethylene compounds, allyl compounds, fumaric acid compounds, and maleic acid compounds.

[0057] A (meth)acrylic compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or methacryloyl group are as follows, but the compounds are not limited to these examples.

[0058] (Meth)acrylate phenoxyethyl ester, (Meth)acrylate phenoxy-2-methylethyl ester, (Meth)acrylate phenoxyethoxyethyl ester, (Meth)acrylate 3-phenoxy-2-hydroxypropyl ester, (Meth)acrylate 2-phenylphenoxyethyl ester, (Meth)acrylate 4-phenylphenoxyethyl ester, (Meth)acrylate 3-(2-phenylphenyl)-2-hydroxypropyl ester, EO-modified p-cumylphenol (meth)acrylate, (Meth)acrylate 2-bromophenoxyethyl ester, (Meth)acrylate 2,4-dibromophenoxyethyl ester, (Meth)acrylate 2,4,6-tribromophenoxyethyl ester, EO-modified (Meth)acrylate phenoxy ester, PO-modified (Meth)acrylate phenoxy ester, poly Oxyvinylnonylphenyl ether (meth)acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, bornyl methacrylate, tricyclodecyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, cyclohexyl methacrylate, 4-butylcyclohexyl methacrylate, acryloylmorpholine, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Propylene acrylate, Isopropyl acrylate, Butyl acrylate, Amyl acrylate, Isobutyl acrylate, Tert-butyl acrylate, Amyl acrylate, Isoamyl acrylate, Hexyl acrylate, Octyl acrylate, Isooctyl acrylate, 2-Ethylhexyl acrylate, Nonyl acrylate, Decyl acrylate, Isodecyl acrylate, Undecyl acrylate, Dodecyl acrylate, Lauryl acrylate, Stearyl acrylate, Isostearyl acrylate, Propylene acrylate Benzyl acrylate, Tetrahydrofurfuryl acrylate, Butoxyethyl methacrylate, Ethoxydiethylene glycol (meth)acrylate, Polyethylene glycol mono(meth)acrylate, Polypropylene glycol mono(meth)acrylate, Methoxyethylene glycol (meth)acrylate, Ethoxyethyl methacrylate, Methoxypolyethylene glycol (meth)acrylate, Methoxypolypropylene glycol (meth)acrylate, Diacetone (meth)acrylamide, Isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, Tert-octyl (meth)acrylamide, Dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-ethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, cyanobenzyl(meth)acrylate, naphthylmethyl(meth)acrylate.

[0059] Examples of commercially available products of the above monofunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0060] ARONIX ® M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, and M156 (manufactured by TOAGOSEI); MEDOL 10, MIBDOL 10, CHDOL 10, MMDOL 30, MEDOL 30, MIBDOL 30, CHDOL 30, LA, IBXA, 2-MTA, HPA, and Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, and #2150 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY); light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A, and OPP-EA (manufactured by KYOEISHA CHEMICAL); KAYARAD ® TC110S, R-564, and R-128H (manufactured by NIPPON KAYAKU); NK ester AMP-10G, AMP-20G, and A-LEN-10 (manufactured by SHIN-NAKAMURA CHEMICAL); FA-511A, 512A, and 513A (manufactured by Hitachi Chemical); PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, and BR-32 (manufactured by DKS); VP (manufactured by BASF); ACMO, DMAA, and DMAPAA (manufactured by Kohjin); and HRD-01 (manufactured by NIPPON SHOKUBAI).

[0061] Examples of the multifunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups are as follows, but the compounds are not limited to these examples.

[0062] trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO- and 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 di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, EO- and PO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, o-, m- or p-phenylene di(meth)acrylate, and o-, m- or p-xylylene di(meth)acrylate.

[0063] Examples of commercially available products of the above-mentioned polyfunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0064] Yupimer ® UV SA1002 and SA2007 (manufactured by Mitsubishi Chemical); Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, and 3PA (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY); light acrylates 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, and DPE-6A (manufactured by KYOEISHA CHEMICAL); KAYARAD ® PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, and -120, HX-620, D-310, and D-330 (manufactured by NIPPON KAYAKU); ARONIX ®M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, and M400 (manufactured by TOAGOSEI); Ripoxy ® VR-77, VR-60, and VR-90 (manufactured by Showa Highpolymer); OGSOL EA-0200 and OGSOL EA-0300 (manufactured by Osaka Gas Chemicals); and SR295 and SR355 (manufactured by Sartomer).

[0065] Note that, in the above compound groups, (meth)acrylate means acrylate or methacrylate having an alcohol residue equivalent to acrylate. (Meth)acryloyl means acryloyl or methacryloyl having an alcohol residue equivalent to acryloyl. EO represents ethylene oxide, and EO-modified compound A represents 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 group. Furthermore, PO represents propylene oxide, and PO-modified compound B represents 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 group.

[0066] Actual examples of the styrene-based compounds are as follows, but the compounds are not limited to these examples.

[0067] Alkylstyrenes such as styrene, 2,4-dimethyl-a-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; styrene halides such as fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodostyrene; and compounds having a styryl group as a polymerizable functional group such as nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, a-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-a-methylstyrene, 3,5-dimethyl-a-methylstyrene, p-isopropyl-a-methylstyrene, a-ethylstyrene, a-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl.

[0068] Actual examples of the vinyl compounds are as follows, but the compounds are not limited to these examples.

[0069] Vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate, and acrylonitrile; conjugated diene monomers such as butadiene, isoprene, and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; compounds having a vinyl group as a polymerizable functional group such as, for example, vinylidene halides such as vinylidene chloride, vinyl esters of organic carboxylic acids and derivatives thereof (for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate), and (meth)acrylonitrile.

[0070] Note that, in this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0071] Examples of the acrylic compounds are as follows, but the compounds are not limited to these examples.

[0072] Alkylstyrenes such as styrene, 2,4-dimethyl-a-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; styrene halides such as fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodostyrene; and compounds having a styryl group as a polymerizable functional group such as nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinyl naphthalene, 2-vinyl naphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, a-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-a-methylstyrene, 3,5-dimethyl-a-methylstyrene, p-isopropyl-a-methylstyrene, a-ethylstyrene, a-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl.

[0073] Examples of the fumaric acid compound are as follows, but the compound is not limited to these examples.

[0074] dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

[0075] Examples of the maleic acid compound are as follows, but the compound is not limited to these examples.

[0076] dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

[0077] Other examples of the radical polymerizable compound are as follows, but the compound is not limited to these examples.

[0078] dialkyl esters of itaconic acid and derivatives thereof (e.g., dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, and dibenzyl itaconate), N-vinylamide derivatives of organic carboxylic acids (e.g., N-methyl-N-vinylacetamide), and maleimides and derivatives thereof (e.g., N-phenylmaleimide and N-cyclohexylmaleimide).

[0079] If component (a) is formed of a plurality of types of compounds having one or more polymerizable functional groups, it is preferable to include both monofunctional polymerizable compounds and polyfunctional polymerizable compounds. The proportion of the polyfunctional polymerizable compounds in component (a) is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 40% by weight or more. This is because if a monofunctional compound and a polyfunctional compound are combined, a cured film having a good balance of properties, such as high mechanical strength, high dry etching resistance, and high heat resistance, can be obtained.

[0080] The film forming method according to the present application requires several milliseconds to several hundred seconds until the droplets of the curable composition (A) discretely arranged on the substrate combine with each other and form a practically continuous liquid film, and thus a waiting step (described later) is necessary. In this waiting step, the solvent (d) volatilizes, but the polymerizable compound (a) must not volatilize. Therefore, the boiling point of the one or more polymerizable compounds contained in the polymerizable compound (a) at normal pressure is preferably 250°C or higher, more preferably 300°C or higher, and further preferably 350°C or higher. Furthermore, in order to obtain high dry etching resistance and high heat resistance, the cured film of the curable composition (A) preferably contains at least a compound having a ring structure, such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that normal pressure is 1 atm (atmospheric pressure).

[0081] The boiling point of the polymerizable compound (a) is substantially related to the molecular weight. Therefore, the molecular weight of the one or more polymerizable compounds contained in the polymerizable compound (a) is preferably 200 or higher, more preferably 240 or higher, and further preferably 250 or higher. However, even when the molecular weight is 200 or lower, if the boiling point is 250°C or higher, the compound is preferably usable as the polymerizable compound (a) of the present application. As described above, the boiling point of the one or more polymerizable compounds contained in the polymerizable compound (a) at normal pressure is preferably 250°C or higher.

[0082] Furthermore, the vapor pressure of the polymerizable compound (a) at 80°C is preferably 0.001 mmHg or lower. If the polymerizable compound (a) contains one or more polymerizable compounds, the vapor pressure of the one or more polymerizable compounds at 80°C is preferably 0.001 mmHg or lower. This is because, although it is advantageous to heat the curable composition when volatilization of the solvent (component (d)) (described later) is accelerated, volatilization of the polymerizable compound (a) must be suppressed during heating.

[0083] Note that the boiling point and the vapor pressure at normal pressure of each of various organic compounds can be calculated by, for example, Hansen Solubility Parameters in Practice (HSPiP) 5th edition 5.3.04.

[0084] <Ohnishi Parameter of Component (a)>

[0085] It is known that the dry etching rate V of an organic compound, the total number of atoms N in the organic compound, the total number of carbon atoms Nc in the composition, and the total number of oxygen atoms No in the composition have the following formula (1) relationship (see NPL 1).

[0086] ...(1)

[0087] wherein N / (Nc-No) is also called "Ozawa parameter" (hereinafter referred to as "OP"). For example, US-2020-0286740 has disclosed a technique of obtaining a photocurable composition having high dry etching resistance by using a polymeric compound having a small OP.

[0088] Formula (1) indicates that an organic compound having many oxygen atoms in the molecule or having few aromatic ring structures or alicyclic structures has a large OP and a high dry etching speed.

[0089] In the curable composition (A) according to the present application, the OP of component (a) is 1.80 or more and 4.00 or less. The OP of component (a) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or less. When the OP of component (a) is 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. In addition, when the OP of component (a) is 1.80 or more, the cured film of the curable composition (A) can be easily removed when a bottom layer is processed by using the cured film of the curable composition (A). When component (a) is composed of a plurality of polymeric compounds a1, a2,..., an, the OP of component (a) is calculated as a molar fraction weighted average value of the N / (Nc-No) values of each molecule of the plurality of polymeric compounds a1, a2,..., an. n At the time of formation, the OP is calculated as a weighted average value (molar fraction weighted average value) based on the molar fraction, as shown in the following Formula (2). If component (a) contains one or more polymeric compounds, the OP of component (a) is calculated as a molar fraction weighted average value of the N / (Nc-No) values of each molecule of the one or more polymeric compounds.

[0090] ...(2)

[0091] wherein OP n is the OP of component a n , and n n is the molar fraction occupied by component a n in the entirety of component (a).

[0092] In order to set the OP of component (a) to 1.80 or more and 2.70 or less, it is preferable that component (a) contains at least a compound (a-1) having two or more ring structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0093] <Compound (a-1): Polymeric compound having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure>

[0094] The polymerizable compound (a) according to the present application can include a polymerizable compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Furthermore, the proportion of the component (a-1) in the component (a) is preferably 65% by weight or more. When the proportion of the component (a-1) is 65% by weight or more, the OP can be suppressed to 2.70 or less.

[0095] Examples of the cyclic structure are an aromatic structure, an aromatic heterocyclic structure, and an alicyclic structure.

[0096] The number of carbons of the aromatic structure is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. Actual examples of the aromatic ring are as follows.

[0097] A benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a fluorene ring, a benzocyclooctene ring, an acenaphthene ring, a biphenylene ring, an indene ring, an indane ring, a triphenylene ring, a pyrene ring, a chrysene ring, a perylene ring, and a tetrahydronaphthalene ring.

[0098] Note that, among the above-described aromatic rings, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring can have a structure in which a plurality of rings are connected. Examples are a biphenyl ring and a bisphenyl ring.

[0099] The number of carbons of the aromatic heterocyclic structure is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 5. Actual examples of the aromatic heterocyclic ring are as follows.

[0100] A thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, an oxadiazole ring, an oxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an isoindole ring, an indole ring, an indazole ring, a purine ring, a quinolizine ring, an isoquinoline ring, a quinoline ring, a phthalazine ring, a naphthylidine ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a carbazole ring, an acridine ring, a phenazine ring, a phenothiazine ring, a phenoxathiyne ring, and a phenoxazine ring.

[0101] The number of carbons of the alicyclic structure is preferably 3 or more, more preferably 4 or more, and further preferably 6 or more. Furthermore, the number of carbons of the alicyclic structure is preferably 22 or less, more preferably 18 or less, further preferably 6 or less, and still further preferably 5 or less. Actual examples are as follows.

[0102] A cyclopropane ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, a dicyclopentadiene ring, a spirodecane ring, a spirononane ring, a tetrahydrodicyclopentadiene ring, an octahydronaphthalene ring, a decahydronaphthalene ring, a hexahydroindane ring, a norbornane ring, a norbornene ring, an isonorbornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring.

[0103] Actual examples of the polymerizable compound (a-1) having a boiling point of 250°C or more are as follows, but the compounds are not limited to these examples.

[0104] Acrylic acid 3-phenoxybenzyl ester (mPhOBzA, OP = 2.54, boiling point = 367.4°C, 80°C vapor pressure = 0.0004 mm Hg, molecular weight = 254.3)

[0105] [Formula 1]

[0106]

[0107] Acrylic acid 1-naphthyl ester (NaA, OP = 2.27, boiling point = 317°C, 80°C vapor pressure = 0.0422 mm Hg, molecular weight = 198)

[0108] [Formula 2]

[0109]

[0110] Acrylic acid 2-phenylphenoxyethyl ester (PhPhOEA, OP = 2.57, boiling point = 364.2°C, 80°C vapor pressure = 0.0006 mm Hg, molecular weight = 268.3)

[0111] [Formula 3]

[0112]

[0113] Acrylic acid 1-naphthylmethyl ester (Na1MA, OP = 2.33, boiling point = 342.1°C, 80°C vapor pressure = 0.042 mm Hg, molecular weight = 212.2)

[0114] [Formula 4]

[0115]

[0116] Acrylic acid 2-naphthylmethyl ester (Na2MA, OP = 2.33, boiling point = 342.1°C, 80°C vapor pressure = 0.042 mm Hg, molecular weight = 212.2)

[0117] [Formula 5]

[0118]

[0119] DPhPA is represented by the following formula (OP = 2.38, boiling point = 354.5°C, 80°C vapor pressure = 0.0022 mm Hg, molecular weight = 266.3)

[0120] [Formula 6]

[0121]

[0122] PhBzA is represented by the following formula (OP = 2.29, boiling point = 350.4°C, 80°C vapor pressure = 0.0022 mm Hg, molecular weight = 238.3)

[0123] [Formula 7]

[0124]

[0125] FLMA is represented by the following formula (OP = 2.20, boiling point = 349.3°C, 80°C vapor pressure = 0.0018 mm Hg, molecular weight = 250.3)

[0126] [Formula 8]

[0127]

[0128] ATMA is represented by the following formula (OP = 2.13, boiling point = 414.9°C, 80°C vapor pressure = 0.0001 mm Hg, molecular weight = 262.3)

[0129] [Formula 9]

[0130]

[0131] DNaMA is represented by the following formula (OP = 2.00, boiling point = 489.4°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 338.4)

[0132] [Formula 10]

[0133]

[0134] BPh44DA is represented by the following formula (OP = 2.63, boiling point = 444°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 322.3)

[0135] [Formula 11]

[0136]

[0137] BPh43DA is represented by the following formula (OP = 2.63, boiling point = 439.5°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 322.3)

[0138] [Formula 12]

[0139]

[0140] DPhEDA is represented by the following formula (OP = 2.63, boiling point = 410°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 322.3)

[0141] [Formula 13]

[0142]

[0143] BPMDA is represented by the following formula (OP = 2.68, boiling point = 465.7°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 364.4)

[0144] [Formula 14]

[0145]

[0146] Na13MDA is represented by the following formula (OP = 2.71, boiling point = 438.8°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 296.3)

[0147] [Formula 15]

[0148]

[0149] the following formula (a-1-1) (OP = 2.40, boiling point = 333.4°C, 80°C vapor pressure = 0.0181 mm Hg, molecular weight = 199.2)

[0150] [Formula 16]

[0151]

[0152] the following formula (a-1-2) (OP = 2.40, boiling point = 333.4°C, 80°C vapor pressure = 0.0181 mm Hg, molecular weight = 199.2)

[0153] [Formula 17]

[0154]

[0155] the following formula (a-1-3) (OP = 1.86, boiling point = 369.5°C, 80°C vapor pressure = 0.0053 mm Hg, molecular weight = 193.3)

[0156] [Formula 18]

[0157]

[0158] the following formula (a-1-4) (OP = 2.85, boiling point = 438.8°C, 80°C vapor pressure < 0.0001 mm Hg, molecular weight = 296.3)

[0159] [Formula 19]

[0160]

[0161] Formula (a-1-5) (OP = 2.71, boiling point = 438.8°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 296.3)

[0162] [Formula 20]

[0163]

[0164] Formula (a-1-6) (OP = 2.87, boiling point = 421.0°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 338.4)

[0165] [Formula 21]

[0166]

[0167] Formula (a-1-7) (OP = 2.87, boiling point = 465.2°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 338.4)

[0168] [Formula 22]

[0169]

[0170] Formula (a-1-8) (OP = 2.68, boiling point = 465.7°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 364.4)

[0171] [Formula 23]

[0172]

[0173] Formula (a-1-9) (OP = 2.50, boiling point = 433.1°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 320.3)

[0174] [Formula 24]

[0175]

[0176] Formula (a-1-10) (OP = 2.64, boiling point = 468.1°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 326.4)

[0177] [Formula 25]

[0178]

[0179] Formula (a-1-11) (OP = 3.25, boiling point = 553.4°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 358.4)

[0180] [Formula 26]

[0181]

[0182] Formula (a-1-12) (OP = 2.63, boiling point = 443.9°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 322.4)

[0183] [Formula 27]

[0184]

[0185] Formula (a-1-13) (OP = 2.89, boiling point = 509.3°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 406.4)

[0186] [Formula 28]

[0187]

[0188] Formula (a-1-14) (OP = 2.63, boiling point = 450.0°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 322.4)

[0189] [Formula 29]

[0190]

[0191] Formula (a-1-15) (OP = 3.00, boiling point = 476.5°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 366.4)

[0192] [Formula 30]

[0193]

[0194] Formula (a-1-16) (OP = 2.68, boiling point = 447.4°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 364.4)

[0195] [Formula 31]

[0196]

[0197] Formula (a-1-17) (OP = 2.36, boiling point = 543.8°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 398.5)

[0198] [Formula 32]

[0199]

[0200] Formula (a-1-18) (OP = 3.27, boiling point = 526.9°C, 80°C vapor pressure < 0.0001 mmHg, molecular weight = 396.4)

[0201] [Formula 33]

[0202]

[0203] Formula (a-1-19) (OP = 2.71, boiling point = 333.7°C, 80°C vapor pressure = 0.0302 mmHg, molecular weight = 244.3)

[0204] [Formula 34]

[0205]

[0206] Formula (a-1-20) (OP = 2.73, boiling point = 333.7°C, 80°C vapor pressure = 0.0134 mmHg, molecular weight = 258.3)

[0207] [Formula 35]

[0208]

[0209] Formula (a-1-21) (OP = 2.71, boiling point = 319.2°C, 80°C vapor pressure = 0.0566 mmHg, molecular weight = 262.3)

[0210] [Formula 36]

[0211]

[0212] Formula (a-1-22) (OP = 2.71, boiling point = 336.9°C, 80°C vapor pressure = 0.0055 mmHg, molecular weight = 244.3)

[0213] [Formula 37]

[0214]

[0215] Formula (a-1-23) (OP = 3.00, boiling point = 370.9°C, 80°C vapor pressure = 0.0021 mmHg, molecular weight = 274.4)

[0216] [Formula 38]

[0217]

[0218] Formula (a-1-24) (OP = 3.00, boiling point = 376.4°C, 80°C vapor pressure = 0.0005 mmHg, molecular weight = 274.4)

[0219] [Formula 39]

[0220]

[0221] (a-1-25) (OP = 3.00, boiling point = 379.4°C, vapor pressure at 80°C = 0.0002 mmHg, molecular weight = 288.4)

[0222] [Formula 40]

[0223]

[0224] (a-1-26) (OP = 2.33, boiling point = 360.8°C, vapor pressure at 80°C = 0.0006 mmHg, molecular weight = 252.3)

[0225] [Formula 41]

[0226]

[0227] (a-1-27) (OP = 2.54, boiling point = 371.5°C, vapor pressure at 80°C = 0.0003 mmHg, molecular weight = 254.3)

[0228] [Formula 42]

[0229]

[0230] (a-1-28) (OP = 2.57, boiling point = 381.2°C, vapor pressure at 80°C = 0.0001 mmHg, molecular weight = 268.3)

[0231] [Formula 43]

[0232]

[0233] (a-1-29) (OP = 2.57, boiling point = 381.8°C, vapor pressure at 80°C = 0.0004 mmHg, molecular weight = 268.3)

[0234] [Formula 44]

[0235]

[0236] (a-1-30) (OP = 2.50, boiling point = 487.4°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 374.4)

[0237] [Formula 45]

[0238]

[0239] Formula (a-1-31) (OP = 2.67, boiling point = 417.2°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 268.3)

[0240] [Formula 46]

[0241]

[0242] Formula (a-1-32) (OP = 2.67, boiling point = 417.2°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 268.3)

[0243] [Formula 47]

[0244]

[0245] Formula (a-1-33) (OP = 2.67, boiling point = 417.2°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 268.3)

[0246] [Formula 48]

[0247]

[0248] Formula (a-1-34) (OP = 2.67, boiling point = 417.2°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 268.3)

[0249] [Formula 49]

[0250]

[0251] Formula (a-1-35) (OP = 2.71, boiling point = 438.8°C, vapor pressure < 0.0001 mmHg at 80°C, molecular weight = 296.3)

[0252] [Formula 50]

[0253]

[0254] <Compound (a-2): Polymerizable compound containing at least Si atom>

[0255] The polymerizable compound (a) according to the present application can contain a polymerizable compound (a-2) containing at least a Si atom. Furthermore, if the polymerizable compound (a) contains the polymerizable compound (a-2), the curable composition (A) from which the solvent (d) is removed preferably contains 10% by weight or more of Si atoms with respect to the entire curable composition (A).

[0256] As examples of the polymerizable compound (a-2) containing at least a Si atom, it can have a linear structure or a branched structure. For example, as a cyclic siloxane compound, the following structures can be used. Examples of the polymerizable functional group in the group Q having a polymerizable functional group are a radical polymerizable functional group. Actual examples of the radical polymerizable functional group are a (meth)acrylic group, a (meth)acrylamide group, a vinylphenyl group, an allyl ether group, a vinyl ether group, and a maleimide group. The group Q having a polymerizable functional group only needs to be a group having the above-described polymerizable functional group.

[0257] [Formula 51]

[0258]

[0259] Other examples of the polymerizable compound (a-2) are a silsesquioxane skeleton as represented by the following Chemical Formula (I) and an organosilicon skeleton as represented by Chemical Formula (II). In Chemical Formula (I), m + n = 8 (8 ≥ m ≥ 1), and R1is a divalent organic group. Further, in Chemical Formula (II), A, B, R2, and R3are independently an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, and a hydroxyl group having a carbon number of 1 to 6, t is an integer of 1 to 3, and at least one of A and B is a polymerizable functional group.

[0260] [Formula 52]

[0261]

[0262] [Formula 53]

[0263]

[0264] Examples of the polymerizable functional group in the group Q, A, and B having a polymerizable functional group are a radical polymerizable functional group. Detailed examples of the radical polymerizable functional group are a (meth)acrylate-based compound, a (meth)acrylamide-based compound, a vinylphenyl-based compound, an aryl ether-based compound, a vinyl ether-based compound, and a maleimide-based compound. The group Q having a polymerizable functional group can be a group having the above-described polymerizable functional group.

[0265] A silicon-containing (meth)acrylate-based compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of a silicon-containing monofunctional (meth)acrylate-based compound having one acryloyl group or methacryloyl group are as follows, but the compounds are not limited to these examples.

[0266] (2-acryloyloxyethyl)trimethylsilane,

[0267] N-(3-acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane,

[0268] Acryloyloxymethyltrimethoxysilane,

[0269] (Acryloyloxymethyl)phenylethyltrimethoxysilane,

[0270] Acryloyloxymethyltrimethylsilane,

[0271] (3-Acryloyloxypropyl)dimethylmethoxysilane,

[0272] (3-Acryloyloxypropyl)methylbis(trimethylsiloxy)silane,

[0273] (3-Acryloyloxypropyl)methyldichlorosilane,

[0274] (3-Acryloyloxypropyl)methyldiethoxysilane,

[0275] (3-Acryloyloxypropyl)methyldimethoxysilane,

[0276] (3-Acryloyloxypropyl)trichlorosilane,

[0277] (3-Acryloyloxypropyl)trimethoxysilane,

[0278] (3-Acryloyloxypropyl)tris(trimethylsiloxy)silane,

[0279] Acryloyltriisopropylsilane,

[0280] Acryloyltrimethylsilane,

[0281] Methacryloyloxymethyltrimethoxysilane,

[0282] O-(Methacryloyloxyethoxy)carbamylpropylmethyldimethoxysilane,

[0283] (Methacryloyloxymethyl)bis(trimethylsiloxy)methylsilane,

[0284] N-(3-Methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane

[0285] (Methacryloyloxymethyl)methyldimethoxysilane,

[0286] (Methacryloyloxymethyl)methyldiethoxysilane,

[0287] Methacryloyloxymethyltriethoxysilane,

[0288] Methacryloyloxypropyltrimethoxysilane,

[0289] Methacryloylpropyltriisopropoxysilane,

[0290] O-(methacryloyloxyethyl)-N-(triethoxysilylpropyl)carbamate,

[0291] Methacryloyloxypropylmethyldimethoxysilane,

[0292] Methacryloyloxypropylmethyldiethoxysilane,

[0293] Methacryloyloxypropyldimethylmethoxysilane,

[0294] Methacryloyloxypropyldimethylethoxysilane,

[0295] (Methacryloyloxymethyl)dimethylethoxysilane,

[0296] Methacryloyloxypropyltriethoxysilane,

[0297] Methacryloxypropylsilatrane,

[0298] Methacryloyloxypentamethyldisiloxane,

[0299] (Methacryloyloxymethyl)phenyldimethylsilane,

[0300] Methacryloyltrimethylsilane,

[0301] Methacryloylmethyltrimethylsilane,

[0302] (3-Methacryloyloxy-2-hydroxypropyloxypropyl)methylbis(trimethylsiloxy)silane,

[0303] Methacryloylpropylpentamethyldisiloxane,

[0304] O-(Methacryloyloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propyl carbamate,

[0305] Methacryloyloxymethyltris(trimethylsiloxy)silane,

[0306] Methacryloyloxyethoxytrimethylsilane,

[0307] (3-Methacryloyloxy-2-hydroxypropyloxypropyl)methylbis(trimethylsiloxy)silane,

[0308] Methacryloylpropyltris(vinyl dimethylsiloxy)silane,

[0309] Methacryloylpropyltris(trimethylsiloxy)silane,

[0310] 3-methacryloyloxypropyltriacetoxysilane,

[0311] methacryloyloxypropylmethyldichlorosilane,

[0312] methacryloyloxypropyltrichlorosilane,

[0313] 3-methacryloyloxypropyldi(trimethylsiloxy)methylsilane,

[0314] 3-methacryloyloxypropyldimethylchlorosilane,

[0315] O-methacryloyloxy(polyethyleneoxy)trimethylsilane,

[0316] poly(methacryloyloxypropylsilsesquioxane),

[0317] methacryloyloxypropylhepta-isobutyl-T8-silsesquioxane, and

[0318] methacryloyloxypropyltris(trimethylsiloxy)silane.

[0319] Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylic compounds are as follows, but the products are not limited to these examples.

[0320] SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0, SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481.43, SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM6486.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM6491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, SIM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, and SIM6486.65 (manufactured by GELEST), and TM-0701T, FM-0711, FM-0721, and FM-0725 (manufactured by JNC).

[0321] The silicon-containing (meth)acrylamide-based compound is a compound having one or more acrylamide groups or methacrylamide groups. Examples of the silicon-containing monofunctional (meth)acrylamide-based compound having one acrylamide group or methacrylamide group are as follows, but the compound is not limited to these examples.

[0322] 3-acrylamidopropyltrimethoxysilane and 3-acrylamidopropyltris(trimethylsiloxy)silane.

[0323] Examples of commercially available products of the above-described silicon-containing monofunctional (meth)acrylamide-based compound are as follows, but the product is not limited to these examples.

[0324] SIA0146.0 and SIA0150.0 (manufactured by GELEST).

[0325] Examples of the multifunctional (meth)acrylate compound having two or more acryloyl groups or methacryloyl groups are as follows, but the compounds are not limited to these examples.

[0326] Linear dimethylpolysiloxane modified at both ends with acryloxypropyl groups,

[0327] Linear dimethylpolysiloxane modified at both ends with methacryloxypropyl groups,

[0328] Cyclic siloxane modified with a plurality of acryloxypropyl groups,

[0329] Cyclic siloxane modified with a plurality of methacryloxypropyl groups,

[0330] Silsesquioxane modified with a plurality of acryloxypropyl groups, and

[0331] Silsesquioxane modified with a plurality of methacryloxypropyl groups.

[0332] Examples of commercially available products of the above-described silicon-containing multifunctional (meth)acrylate compound are as follows, but the products are not limited to these examples.

[0333] SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (manufactured by GELEST),

[0334] FM-7711, FM-7721, FM-7725 (manufactured by JNC),

[0335] X-22-2445 (manufactured by Shin-Etsu Chemical), and

[0336] AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20 (manufactured by TOAGOSEI).

[0337] Further, according to, for example, known document 1, the following can be synthesized and / or obtained.

[0338] Linear modified dimethylpolysiloxane having a methacryloxypropyl group at both ends (MA-Si-12), 8-membered cyclic siloxane modified with four methacryloxypropyl groups (8-ring), and 10-membered cyclic siloxane modified with five methacryloxypropyl groups (10-ring).

[0339] Known Document 1: "Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography" by Ogawa et al.

[0340] The blending ratio of component (a) in the curable composition (A) is preferably 40% by weight or more and 99% by weight or less with respect to the total mass of component (a), component (b) (described later) and component (c) (described later), that is, all components except for the solvent (d). The blending ratio is more preferably 50% by weight or more and 95% by weight or less, and further preferably 60% by weight or more and 90% by weight or less. When the blending ratio of component (a) is 40% by weight or more, the mechanical strength of the cured film of the curable composition increases. In addition, when the blending ratio of component (a) is 99% by weight or less, the blending ratio of components (b) and (c) can be increased, and properties such as a high photopolymerization speed are obtained. At least a part of component (a) including one or more polymerizable compounds can be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a cyclic structure, for example, an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure. For example, the polymer preferably contains at least one of the constituent units represented by the following structures (1) to (6):

[0341] [Formula 54]

[0342]

[0343] In structures (1) to (6), the substituent R is a substituent containing a partial structure including an aromatic ring independently each, and R 1 is a hydrogen atom or a methyl group. In this specification, in the constituent units represented by structures (1) to (6), the part other than R is the main chain of the specific polymer. The formula mass of the substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and further preferably 150 or more. The upper limit of the formula mass of the substituent R is practically 500 or less.

[0344] The polymer having a polymerizable functional group is generally a compound having a weight average molecular weight of 500 or more. The weight average molecular weight is preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight is not particularly determined, but is preferably, for example, 50,000 or less. When the weight average molecular weight is set to be the above lower limit or more, the boiling point can be set to be 250°C or more, and the mechanical properties after curing are further improved. Further, when the weight average molecular weight is set to be the above upper limit or less, the solubility to a solvent is increased, and the fluidity of the liquid droplets arranged discretely is maintained because the viscosity is not too high. This makes it possible to further improve the planarity of the liquid film surface. Note that the weight average molecular weight (Mw) in the present application is a molecular weight measured by gel permeation chromatography (GPC), unless otherwise particularly specified.

[0345] Actual examples of the polymerizable functional group of the polymer are a (meth)acryloyl group, an epoxy group, an oxetanyl group, a methylol group, a methylol ether group, and a vinyl ether group. From the viewpoint of easiness of polymerization, a (meth)acryloyl group is particularly advantageous.

[0346] When the polymer having a polymerizable functional group is added as at least a part of the component (a), the blending ratio can be freely set as long as the blending ratio falls within the range of the viscosity regulation described later. For example, the blending ratio is preferably 0.1% by mass or more and 60% by mass or less, more preferably 1% by mass or more and 50% by mass or less, and further preferably 10% by mass or more and 40% by mass or less, with respect to the total mass of all components except for the solvent (d). When the blending ratio of the polymer having a polymerizable functional group is set to be 0.1% by mass or more, the heat resistance, dry etching resistance, mechanical strength, and low volatility can be improved. Further, when the blending ratio of the polymer having a polymerizable functional group is set to be 60% by mass or less, the blending ratio can be made to fall within the range of the upper limit regulation of the viscosity (described later).

[0347] <component (b): photopolymerization initiator>

[0348] The component (b) is a photopolymerization initiator. In this specification, the photopolymerization initiator is a compound that senses light having a prescribed wavelength and generates the aforementioned polymerization factor (radical). More specifically, the photopolymerization initiator is a polymerization initiator (radical generator) that generates a radical by light (infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, a charged particle beam such as an electron beam, or a radioactive ray). The component (b) can be formed of only one photopolymerization initiator, and can also be formed of a plurality of photopolymerization initiators.

[0349] Examples of the radical generator are as follows, but the radical generator is not limited to these examples.

[0350] 2,4,5-triarylimidazole dimers which can have substituents, such as 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenyl imidazole dimer; benzophenone derivatives such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1-one; quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)]ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime); and xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1-one.

[0351] Examples of commercially available products of the above radical generating agents are as follows, but the products are not limited to these examples.

[0352] Irgacure 184, 369, 651, 500, 819, 907, 784, and 2959, CGI-1700, -1750, and -1850, CG24-61, Darocur 1116 and 1173, Lucirin ® TPO, LR8893, and LR8970 (manufactured by BASF), and Ubecryl P36 (manufactured by UCB).

[0353] Among the above radical generators, component (b) is preferably an acylphosphine oxide-based polymerization initiator. Note that, among the above radical generators, the acylphosphine oxide-based polymerization initiator is as follows.

[0354] An acylphosphine oxide compound such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0355] The blending ratio of component (b) in the curable composition (A) is preferably 0.1% by mass or more and 50% by mass or less, with respect to the total mass of component (a), component (b), and component (c) (described later), that is, all components except for the solvent (d). Furthermore, the blending ratio of component (b) in the curable composition (A) is more preferably 0.1% by mass or more and 20% by mass or less, and further preferably 1% by mass or more and 20% by mass or less, with respect to the total mass of all components except for the solvent (d). When the blending ratio of component (b) is set to 0.1% by mass or more, the curing speed of the composition increases, and thus the reaction efficiency can be improved. Furthermore, when the blending ratio of component (b) is set to 50% by mass or less, a cured film having a certain degree of mechanical strength can be obtained.

[0356] <component (c): non-polymerizable compound>

[0357] In addition to the above component (a) and (b), the curable composition (A) according to the present application can further include a non-polymerizable compound as component (c) within a range not impairing the effects of the present application. An example of component (c) is a compound that does not include a polymerizable functional group such as a (meth)acryl group, and does not have the ability to sense light having a certain wavelength and generate the aforementioned polymerization factor (radical). Examples of the non-polymerizable compound are a photosensitizer, a hydrogen donor, a surfactant (cl), an antioxidant, a polymer component, and other additives. Component (c) can include multiple types of the above compounds.

[0358] A photosensitizer is a compound that is appropriately added for the purpose of promoting the polymerization reaction and improving the reaction conversion rate. As the photosensitizer, one compound can be used alone, or two or more compounds can be used by mixing them.

[0359] An example of the photosensitizer is a sensitizing dye. The sensitizing dye is a compound that is excited by absorbing light having a specific wavelength and interacts with the photopolymerization initiator as component (b). The "interaction" mentioned herein is energy transfer or electron transfer from the excited state of the sensitizing dye to the photopolymerization initiator as component (b). Actual examples of the sensitizing dye are as follows, but the sensitizing dye is not limited to these examples.

[0360] anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thioxopyrylium salt-based dyes, merocyanine-based dyes, quinoline-based dyes, styrylquinoline-based dyes, ketocoumarin-based dyes, thioxanthene-based dyes, xanthene-based dyes, oxonol-based dyes, cyanine-based dyes, rhodamine-based dyes, and pyrylium salt-based dyes.

[0361] A hydrogen donor is a compound that reacts with the initiating radical generated by the photopolymerization initiator as component (b) or the radical at the polymer growth end, and generates a radical having higher reactivity. When the photopolymerization initiator as component (b) is a photoradical generator, the hydrogen donor is preferably added.

[0362] Actual examples of the hydrogen donor as described above are as follows, but the hydrogen donor is not limited to these examples.

[0363] amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allyl thiourea, s-benzylisothiouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, N,N-dimethylaminoethyl benzoate, N,N-dimethylaminoisopropyl benzoate, pentyl-4-dimethylamino benzoate, triethanolamine, and N-phenylglycine; and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

[0364] One hydrogen donor can be used alone, or two or more hydrogen donors can be used by mixing them. The hydrogen donor can also have the function as a photosensitizer.

[0365] In the present application, for the purpose of suppressing extrusion and bleeding, a surfactant (c1) is added to the curable composition (A). The surfactant (c1) also functions as an internal mold release agent that reduces the interfacial adhesion between the mold and the curable composition, i.e., reduces the mold release force in the mold release step (described later). In this specification, "internal" means that the mold release agent is added to the curable composition in advance before the curable composition placement step. As the surfactant (c1), a surfactant such as a silicon-based surfactant, a fluorine-based surfactant, and a hydrocarbon-based surfactant can be used. However, in the present application, as described later, the amount of the surfactant (c1) added is limited. Note that the surfactant (c1) according to the present application is not polymerizable. One surfactant (c1) can be used alone, or two or more surfactants (c1) can be used by mixing them.

[0366] The fluorine-based surfactant includes the following.

[0367] Polyoxyalkylene (e.g., polyethylene oxide or polypropylene oxide) adducts of alcohols having a perfluoroalkyl group and polyoxyalkylene (e.g., polyethylene oxide or polypropylene oxide) adducts of perfluoropolyethers.

[0368] Note that the fluorine-based surfactant can have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, or a thiol group in a part of the molecular structure (e.g., an end group). An example is pentadecaethylene glycol mono 1H, 1H, 2H, 2H-perfluorooctyl ether.

[0369] Commercially available products can also be used as the fluorine-based surfactant. Examples of commercially available products of the fluorine-based surfactant are as follows.

[0370] MEGAFACE ® F-444, TF-2066, TF-2067, and TF-2068, and DEO-15 (trade name) (manufactured by DIC); Fluorad FC-430 and FC-431 (manufactured by Sumitomo 3M); Surflon ® S-382 (manufactured by AGC); EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, and MF-100 (manufactured by Tochem Products); PF-636, PF-6320, PF-656, and PF-6520 (manufactured by OMNOVA Solutions); UNIDYNE ® DS-401, DS-403, and DS-451 (manufactured by DAIKIN); and FUTAGENT ®250, 251, 222F and 208G (manufactured by NEOS).

[0371] The surfactant (c1) can also be a hydrocarbon-based surfactant. The hydrocarbon-based surfactant includes an alkyl alcohol polyoxyalkylene adduct obtained by adding an oxyalkylene alcohol having a carbon number of 2 to 4 to an alkyl alcohol having a carbon number of 1 to 50, and a polyoxyalkylene alcohol.

[0372] Examples of the alkyl alcohol polyoxyalkylene adduct are as follows.

[0373] Methanol ethylene oxide adduct, decanol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, and stearyl alcohol ethylene oxide / propylene oxide adduct.

[0374] Note that the end group of the alkyl alcohol polyoxyalkylene adduct is not limited to a hydroxyl group that can be manufactured by simply adding a polyoxyalkylene adduct to an alkyl alcohol. The hydroxyl group can also be substituted with a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a mercaptan group, or a silanol group, or a hydrophobic group such as an alkyl group or an alkoxy group.

[0375] Examples of the polyoxyalkylene alcohol are as follows.

[0376] Polyethylene glycol, polypropylene glycol, their monomethyl or dimethyl ether, mono- or di-octyl ether, mono- or di-nonyl ether, and mono- or di-decyl ether, mono- hexanedioate, mono-oleate, mono-stearate, and mono-succinate.

[0377] Commercially available products can also be used as the alkyl alcohol polyoxyalkylene adduct. Examples of the commercially available products of the alkyl alcohol polyoxyalkylene adduct are as follows.

[0378] polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) manufactured by AOKI OIL INDUSTRIAL (FINESURF D-1303, D-1305, D-1307, and D-1310), polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) manufactured by AOKI OIL INDUSTRIAL (BLAUNON EL-1505), polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) manufactured by AOKI OIL INDUSTRIAL (BLAUNON CH-305 and CH-310), polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) manufactured by AOKI OIL INDUSTRIAL (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, and SR-750), randomly polymerized polyoxyethylene polyoxypropylene stearyl ether manufactured by AOKI OIL INDUSTRIAL (BLAUNON SA-50 / 50 1000R and SA-30 / 70 2000R), polyoxyethylene methyl ether (Pluriol E4M) manufactured by BASF, and polyoxyethylene alkyl ether (EMULGEN series) manufactured by KAO. ® A760E) manufactured by BASF, and polyoxyethylene alkyl ether (EMULGEN series) manufactured by KAO.

[0379] Commercially available products can also be used as polyoxyalkylenes. An example is an ethylene oxide / propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0380] Further, the surfactant (c1) can be a silicone-based surfactant. Examples of silicone-based surfactants are the product name SI-10 series manufactured by TAKEMOTO OIL & FAT, MEGAFACE Paintad 31 manufactured by DIC, and KP-341 manufactured by Shin-Etsu Chemical.

[0381] The surfactant (c1) can contain at least both a fluorine atom and a silicon atom. Examples of surfactants containing both a fluorine atom and a silicon atom are as follows.

[0382] the product name X-70-090, X-70-091, X-70-092, X-70-093 manufactured by Shin-Etsu Chemical, and the product name MEGAFACE R-08 and XRB-4 manufactured by DIC.

[0383] The blending ratio of the component (c) other than the surfactant in the curable composition (A) is preferably 0.01% by mass or more and 50% by mass or less with respect to the total mass of the components (a), (b), and (c), that is, the total mass of all the components except for the solvent (d). The blending ratio of the component (c) other than the surfactant in the curable composition (A) is more preferably 0.01% by mass or more and 50% by mass or less, and further preferably 0.01% by mass or more and 20% by mass or less with respect to the total mass of all the components except for the solvent (d). When the blending ratio of the component (c) other than the surfactant is set to 50% by mass or less, a cured film having a certain degree of mechanical strength can be obtained.

[0384] The upper limit of the blending ratio of the surfactant (c1) according to the present application is determined by the surface tension of the composition obtained by removing the solvent (d) from the curable composition (A) and the contact angle with the surface of the substrate and the surface of the mold, as described later. When the blending ratio of the surfactant (c1) is set to 0.01% by mass or more, the effects of the present application can be obtained.

[0385] <component (d): solvent>

[0386] The curable composition according to the present application contains, as the component (d), a solvent having a boiling point of 100°C or higher and less than 250°C at normal pressure. The component (d) is a solvent that dissolves the components (a), (b), and (c). Examples are alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. As the component (d), one component can be used alone, or two or more components can be used by combining them. The component (d) has a boiling point of 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher at normal pressure. The component (d) has a boiling point of less than 250°C, and preferably less than 200°C at normal pressure. If the component (d) has a boiling point of less than 100°C at normal pressure, the evaporation speed is too fast in the waiting step described later. For this reason, the component (d) can evaporate before the droplets of the curable composition (A) combine with each other, and the droplets of the curable composition (A) can not combine with each other. In addition, if the component (d) has a boiling point of 250°C or higher at normal pressure, the evaporation of the solvent (d) can be insufficient in the waiting step described later, and thus the component (d) remains in the cured product of the curable composition (A). Here, if the component (d) contains one or more solvents, each of the one or more solvents has a boiling point of 100°C or higher and less than 250°C (for example, 100°C or higher and less than 200°C) at normal pressure.

[0387] Examples of the alcohol-based solvent are as follows.

[0388] Monohydric alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, t-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-undecanol, trimethyl nonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; and polyhydric alcohol solvents such as ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0389] Examples of ketone solvents are as follows.

[0390] Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetylacetone, diacetone alcohol, phenylacetone, and fenchone.

[0391] Examples of ether solvents are as follows.

[0392] Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, oxirane, 1,2-oxepane, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexyloxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol 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, and 2-methyltetrahydrofuran.

[0393] Examples of ester solvents are as follows.

[0394] diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0395] Examples of the nitrogen-containing solvent are as follows.

[0396] N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone.

[0397] Among the above-mentioned solvents, the ether-based solvent and the ester-based solvent are advantageous. Note that, from the viewpoint of good film formability, the ether-based solvent and the ester-based solvent each having a glycol structure are more advantageous.

[0398] Other advantageous examples of the solvent are as follows.

[0399] propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0400] A particularly advantageous example is propylene glycol monomethyl ether acetate. Note that (ethyl)isocyanurate di(meth)acrylate is also advantageous.

[0401] In the present application, an advantageous solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure. More specifically, an advantageous solvent is one solvent or a solvent mixture selected from the group consisting of propylene glycol monomethyl ether acetate (boiling point = 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate.

[0402] In the present application, a polymerizable compound having a boiling point of 80°C or higher and less than 250°C at normal pressure can also be used as component (d). Examples of a polymerizable compound having a boiling point of 80°C or higher and less than 250°C at normal pressure are as follows.

[0403] Cyclohexyl acrylate (boiling point = 198°C), benzyl acrylate (boiling point = 229°C), isobornyl acrylate (boiling point = 245°C), tetrahydrofurfuryl acrylate (boiling point = 202°C), trimethylcyclohexyl acrylate (boiling point = 232°C), isooctyl acrylate (217°C), n-octyl acrylate (boiling point = 228°C), ethoxyethoxyethyl acrylate (boiling point = 230°C), divinylbenzene (boiling point = 193°C), 1,3-diisopropenylbenzene (boiling point = 218°C), styrene (boiling point = 145°C), and α-methylstyrene (boiling point = 165°C).

[0404] In the present application, when the entirety 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 further preferably 40% by volume or more and 80% by volume or less. For example, the content of the solvent (d) is 40% by volume or more and 85% by volume or less. If the content of the solvent (d) is less than 5% by volume, it is not possible to obtain a thin film after the solvent (d) is volatilized under conditions in which an actually continuous liquid film can be obtained. Furthermore, if the content of the solvent (d) is greater than 95% by volume, it is not possible to obtain a thick film after the solvent (d) is volatilized even when liquid droplets are closely dropped by an inkjet method.

[0405] <When blending the curable composition>

[0406] When the curable composition (A) according to the present application is prepared, at least components (a), (b), and (d) are mixed and dissolved under a predetermined temperature condition. The predetermined temperature condition is 0°C or more and 100°C or less. Note that this is also applicable to the case where the curable composition (A) includes component (c).

[0407] <Viscosity of the curable composition>

[0408] The curable composition (A) according to the present application is liquid. This is because liquid droplets of the curable composition (A) are discretely dropped on a substrate by an inkjet method. The viscosity of the curable composition (A) according to the present application at 23°C and 1 atm is 1.3 mPa s or more and 60 mPa s or less, preferably 2 mPa s or more and 30 mPa s or less, and more preferably 5 mPa s or more and 15 mPa s or less. If the viscosity of the curable composition (A) is less than 2 mPa s, the discharge property of liquid droplets by an inkjet method is unstable. Furthermore, if the viscosity of the curable composition (A) is greater than 60 mPa s, it is not possible to form liquid droplets having a volume of about 1.0 pL to 3.0 pL, which is advantageous in the present application.

[0409] The viscosity of the mixture of components of the curable composition (A) other than the solvent (d) at 23°C and 1 atm in a state where the solvent (d) has been volatilized from the curable composition (A) is 30 mPa-s or more and 10,000 mPa-s or less. The viscosity of the mixture of components of the curable composition (A) other than the solvent (d) at 23°C and 1 atm is preferably 90 mPa-s or more and 2,000 mPa-s or less, for example, 120 mPa-s or more and 1,000 mPa-s or less. Further, the viscosity of the mixture of components of the curable composition (A) other than the solvent (d) at 23°C and 1 atm is further preferably 150 mPa-s or more and 500 mPa-s or less. When the viscosity of the components of the curable composition (A) other than the solvent (d) is set to 1,000 mPa-s or less, the spreading and filling are rapidly completed at the time of bringing the curable composition (A) into contact with a mold. Therefore, the use of the curable composition (A) according to the present application makes it possible to perform the imprinting process at a high production rate, and to suppress pattern defects caused by insufficient filling. Further, when the viscosity of the components of the curable composition (A) other than the solvent (d) is set to 1 mPa-s or more, it is possible to prevent unnecessary flow of droplets of the curable composition (A) after volatilization of the solvent (d). Further, at the time of bringing the curable composition (A) into contact with a mold, the curable composition (A) is not easily flowed out from the end portion of the mold.

[0410] <Surface tension of the curable composition>

[0411] The surface tension γ1 at 23°C and 1 atm in a state where the solvent (d) has been volatilized from the curable composition (A) according to the present application is preferably 5 mN / m or more and 70 mN / m or less. Further, the surface tension at 23°C and 1 atm of a composition containing components other than the solvent (component (d)) is more preferably 7 mN / m or more and 50 mN / m or less, and further preferably 10 mN / m or more and 40 mN / m or less. Note that when the surface tension is high, for example, 5 mN / m or more, the capillary action strongly acts, and therefore the filling (spreading and filling) is completed in a short period of time when the curable composition (A) and the mold are brought into contact with each other. Further, when the surface tension is 70 mN / m or less, the cured film obtained by curing the curable composition has surface smoothness.

[0412] In the present application, if the surface tension of the curable composition in the state where the solvent (d) is removed is γ1 (mN / m), and the surface tension of the solvent (d) at 23°C is γ2 (mN / m), the curable composition is configured so that γ1 is larger than γ2. In other words, when Δγ = γ1 - γ2, the curable composition is configured so that Δγ is larger than zero. More specifically, the solvent (d) is selected so that Δγ is larger than zero. If Δγ is larger than zero, in the waiting step described later, the spreading of each droplet of the curable composition is accelerated by the Marangoni effect, and the droplets quickly join each other to form a continuous liquid film. Furthermore, since the volatilization of the solvent is accelerated by the rapid spreading of the droplets, the waiting step described later is completed in a short time, or the conditions of the baking step are relaxed or omitted. Δγ is preferably 0.1 or more, particularly preferably 1.0 or more, and further preferably 2.0 or more. Note that γ1 and γ2 are each the surface tension under normal pressure.

[0413] <contact angle of the curable composition>

[0414] With respect to the composition of the components other than the solvent (component (d)), the contact angle of the curable composition (A) according to the present application with respect to both the surface of the substrate and the surface of the mold is preferably 0° or more and 90° or less. If the contact angle is larger than 90°, the capillary action acts in the negative direction (in which the direction in which the contact interface between the mold and the curable composition shrinks) within the pattern of the mold or in the gap between the substrate and the mold, and the curable composition (A) can not be filled in the mold. When the contact angle is small, the capillary action strongly acts, and the filling speed increases.

[0415] With respect to the contact angle of the curable composition (A) according to the present application, the contact angle of the composition of the components other than the solvent (component (d)) and the surfactant (c1) with respect to the surface of the substrate is defined as α1 [°], and the contact angle of the composition of the components other than the solvent (component (d)) with respect to the surface of the substrate is defined as α2 [°]. In this case, the type and the amount of the surfactant (c1) are selected so that α2 is larger than α1. More specifically, when the surfactant (c1) is selected so that α2 is larger than α1, the spreading of the droplets exhibits a pinning effect, the spreading of the droplets on the substrate can stop at a desired size, and the amount of the extrusion of the curable composition can be suppressed.

[0416] Further, regarding the contact angle of the curable composition (A) according to the present application, when the contact angle of the composition of the components other than the solvent (component (d)) with respect to the surface of a mold is defined as β [°], the type and amount of the surfactant (c1) are selected so that β is 25° or more. More specifically, when the surfactant (c1) is selected so that β is 25° or more, the spreading of a liquid droplet exhibits a pinning effect, and bleeding can be inhibited. β is preferably 30° or more, and more preferably 40° or more.

[0417] <Contaminants mixed in the curable composition>

[0418] The curable composition (A) according to the present application preferably contains as few contaminants as possible. Note that the contaminants mean components other than the above-described components (a), (b), (c), and (d). Therefore, the curable composition (A) according to the present application is advantageously a composition obtained through a refining step. Such a refining step is preferably filtration using a filter.

[0419] As such filtration using a filter, it is advantageous to mix the above-described components (a), (b), and (c), and to filter the mixture by using, for example, a filter having a pore diameter of 0.001 μm or more and 5.0 μm or less. When filtration is performed using a filter, it is further advantageous to perform filtration in multiple stages, or to repeatedly perform filtration a plurality of times (recycle filtration). The liquid filtered once through a filter can be further filtered, or filtered by using a filter having a different pore diameter. Examples of the filter used for filtration are filters made of, for example, polyethylene resin, polypropylene resin, fluororesin, and nylon resin, but the filter is not particularly limited. Contaminants, such as particles mixed in the curable composition, can be removed by the refining step as described above. Therefore, it is possible to prevent pattern defects caused by formation of an undesirable unevenness on a cured film obtained after curing of the curable composition.

[0420] Note that when the curable composition according to the present application is used to manufacture a semiconductor integrated circuit, it is advantageous to avoid as much as possible the mixing of contaminants containing metal atoms (metal contaminants) in the curable composition, so as not to hinder the operation of the product. The concentration of metal contaminants contained in the curable composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0421] <Glass transition temperature of the curable composition>

[0422] If the glass transition temperature is much higher than the temperature at the time of demolding, the solidified product at the time of demolding exhibits a strong glass state, i.e., high mechanical strength, and thus, it is difficult for pattern collapse or breakage due to impact at the time of demolding to occur. Therefore, when the demolding step is performed at room temperature, the glass transition temperature of the solidified product (after the solidification of the polymerizable compound (a)) is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0423] As a method for measuring the glass transition temperature of the solidified product (photocured product), a method using differential scanning calorimetry (DSC) or a dynamic viscoelasticity measuring apparatus can be applied. For example, a case where DSC is used to measure the glass transition temperature is considered. In this case, a line segment obtained by extending the baseline of the DSC curve on the low temperature side (the portion of the DSC curve in the temperature region in which no transition and reaction occur in the test piece) to the high temperature side, and a tangent line drawn at the point where the slope of the curve of the step change portion of the glass transition is the largest are obtained. From the intersection between the line segment and the tangent line, an extrapolated glass transition start temperature (Tig) is obtained, and this can be obtained as the glass transition temperature. An example of the main apparatus is STA-6000 (manufactured by Perkin Eimer). On the other hand, when the dynamic viscoelasticity measuring apparatus is used to measure the glass transition temperature, the temperature at the maximum of the loss angle sine (tan δ) of the solidified product is defined as the glass transition temperature. An example of the main apparatus for measuring dynamic viscoelasticity is MCR301 (manufactured by Anton Paar).

[0424] [Substrate]

[0425] In this specification, a member on which the droplets of the curable composition (A) are discretely dropped is described as a substrate.

[0426] The substrate is a processed substrate, and a silicon wafer is generally used. The substrate can have a processed layer on the surface. On the substrate, other layers can also be formed below the processed layer. When a quartz substrate is used as the substrate, a replica of a mold for imprinting (replica mold) can be manufactured. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate can be freely selected from those known semiconductor device substrates such as aluminum, titanium tungsten alloy, aluminum silicon alloy, aluminum copper silicon alloy, silicon oxide, and silicon nitride. Note that the surface of the substrate or the processed layer is preferably treated by surface treatment such as silane coupling treatment, silazane treatment, or deposition of an organic thin film, so as to improve the adhesion to the curable composition (A). As a deposited organic thin film as a practical example of the surface treatment, the adhesion layer described in Japanese Patent Laid-Open No. 2009-503139 can be used.

[0427] [Pattern forming method]

[0428] ReferenceFIGS. 1A-1G The pattern forming method according to the present application is described. The cured film formed by the present application is preferably a film having a pattern with a size of 1 nm or more and 10 mm or less, and more preferably a film having a pattern with a size of 10 nm or more and 100 pm or less. Generally, a film forming method for forming a film having a pattern (a concave-convex structure) with a nanometer size (1 nm or more and 100 nm or less) by using light is called a photopress method. The film forming method of the present application forms a film of the curable composition in a space between a mold and a substrate by using the photopress method. However, the curable composition can also be cured by other energy (for example, heat or electromagnetic waves). The film forming method according to the present application can be performed as a method for forming a film having a pattern, that is, as a pattern forming method, and also can be performed as a method for forming a film not having a pattern (for example, a planarization film), that is, as a planarization film forming method.

[0429] Examples in which the film forming method according to the present application is applied to a pattern forming method are described below. The pattern forming method includes, for example, a forming step, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step. The forming step is a step of forming a bottom layer. The disposing step is a step of discretely disposing droplets of the curable composition (A) on the bottom layer. The waiting step is a step of performing waiting until the droplets of the curable composition (A) are combined with each other and the solvent (d) is volatilized. The contacting step is a step of bringing the curable composition (A) and a mold into contact with each other. The curing step is a step of curing the curable composition (A). The demolding step is a step of demolding the cured film of the curable composition (A). The disposing step is performed after the forming step, the waiting step is performed after the disposing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0430] <Disposing Step>

[0431] In the disposing step, as FIG. 1A As schematically shown, the droplets 102 of the curable composition (A) are discretely disposed on the substrate 101. In the disposing step, the droplets 102 of the curable composition (A) with a volume of 1.0 pL or more are disposed at 80 droplets / mm 2 The above density is disposed. As the substrate 101, a substrate on which a bottom layer is stacked can also be used as the substrate 101. In addition, the adhesiveness of the surface of the substrate 101 with respect to the curable composition (A) can be improved by surface treatment such as silane coupling treatment, silazane treatment, or deposition of an organic thin film.

[0432] The inkjet method is particularly advantageous as a method of disposing droplets 102 of the curable composition (A) on the substrate. It is advantageous to densely dispose droplets 102 of the curable composition (A) on the area of the substrate 101 facing the area where the recesses of the pattern forming the mold 106 are densely present, and sparsely dispose droplets 102 of the curable composition (A) on the area of the substrate 101 facing the area where the recesses of the pattern forming the mold 106 are sparsely present. Thus, regardless of the sparseness and density of the pattern of the mold 106, the film (residual film) 109 (described later) of the curable composition (A) formed on the substrate 101 is controlled to have a uniform thickness.

[0433] An index called average residual liquid film thickness is defined to specify the volume of the disposed curable composition (A). The average residual liquid film thickness is a value obtained by dividing the volume of the curable composition (A) (except for the solvent (d)) disposed in the disposing step by the area of the film-forming region of the mold. The volume of the curable composition (A) (except for the solvent (d)) is the sum of the volumes of the individual droplets of the curable composition (A) after the volatilization of the solvent (d). According to this definition, even when the surface of the substrate is uneven, the average residual liquid film thickness can be specified regardless of the state of the unevenness. Here, the average residual liquid film thickness can be understood as a value obtained by dividing the volume of the curable composition (A) remaining after the waiting step described later by the area of the film-forming region of the mold, and is preferably 20 nm or less.

[0434] <Waiting Step>

[0435] In the present application, a waiting step is provided after the disposing step and before the contacting step. Here, a value obtained by dividing the total volume of the droplets of the curable composition (A) dropped in one pattern formation by the total area of the region where the pattern is formed (pattern-forming region) in one pattern formation is defined as the average initial liquid film thickness. In the waiting step, as FIG. 1B As illustrated schematically, the droplets 102 of the curable composition (A) spread on the substrate 101. Thus, the entire pattern-forming region of the substrate 101 is covered with the curable composition (A).

[0436] As described above, in the present application, if the surface tension of the curable composition in the state where the solvent (d) is removed is γ1 [mN / m], and the surface tension of the solvent (d) is γ2 [mN / m], the curable composition (A) is formed so that γ1 is greater than γ2. More specifically, since the solvent (d) is selected so that γ1 is greater than γ2, the droplets 102 of the curable composition (A) dropped on the substrate 101 spread significantly (i.e., the spreading speed of the droplets 102 increases). The factors thereof are described below.

[0437] Since the droplet of the curable composition (A) dropped on the substrate contains a volatile component, the concentration of the volatile component changes due to volatilization after dropping. The surface tension γ1 of the non-volatile component is larger than the surface tension γ2 of the volatile component. For this reason, if the concentration of the volatile component decreases as volatilization proceeds, the surface tension becomes large. Generally, the dropped droplet gradually spreads, and the spreading of the droplet stops at a static contact angle. When the contact angle of the end portion of the droplet with the substrate is greatly different from the static contact angle, the spreading speed is fast. Furthermore, since the thickness of the cured film is very thin compared with the radius of the droplet, the concentration diffusion in the radial direction is very slow compared with the concentration diffusion in the thickness direction.

[0438] Reference FIG. 2 The behavior of the droplet 102 of the curable composition (A) dropped on the substrate 101 (behavior after dropping) is described. FIG. 2 The state in which the droplet 102 dropped on the substrate spreads is shown. As described above, the volatilization of the solvent component proceeds even during the spreading of the droplet 102. The volatilization speed depends largely on the surface area of the droplet 102. Comparing the central portion 303 of the droplet 102 and the end portion 304 of the droplet 102, since the surface area of the end portion 304 of the droplet 102 is slightly larger than that of the central portion 303 of the droplet 102, the volatilization proceeds rapidly. On the other hand, the volume of the droplet 102 is smaller at the end portion 304 of the droplet 102 than at the central portion 303 of the droplet 102. Therefore, compared with the central portion 303 of the droplet 102, at the end portion 304 of the droplet 102, the volatilization proceeds rapidly and the volume is small. For this reason, the concentration of the volatile component is lower, and the surface tension is higher. Therefore, since the surface tension at the end portion 304 of the droplet 102 is higher than that at the central portion 303 of the droplet 102, a force from the central portion 303 to the end portion 304 of the droplet 102 is generated by the Marangoni effect, and the flow (spreading) of the droplet 102 is induced.

[0439] FIG. 3 is a view showing the shape of the droplet 102 in a case where the flow of the droplet 102 is induced by the Marangoni effect. If the flow of the droplet 102 toward the end portion of the droplet 102 is induced, as shown in FIG. 4 , the droplet 102 takes a shape in which the end portion is raised. Therefore, the contact angle between the end portion of the droplet 102 and the substrate 101 is larger than in a case where the flow of the droplet 102 is not induced, and the spreading speed of the droplet 102 also increases.

[0440] Further, as described above, with respect to the contact angle of the curable composition (A), the type and amount of the surfactant (cl) are selected so that a2 [°] is larger than a1 [°]. Here, a1 is the contact angle of the composition of the components other than the solvent (component (d)) and the surfactant (cl) with respect to the surface of the substrate 101, and a2 is the contact angle of the composition of the components other than the solvent (component (d)) with respect to the surface of the substrate 101. More specifically, since the surfactant (cl) is selected so that a2 is larger than a1, the spreading of the droplet 102 exhibits a pinning effect, the spreading of the droplet 102 on the substrate can stop at a desired size, and the extrusion amount can be suppressed. The factor thereof is described below.

[0441] FIG. 4 is a diagram showing the state in which the droplet 102 of the curable composition (A) is dropped on the substrate 101. The droplet 102 dropped on the substrate 101 spreads while volatilizing. If the surfactant (cl) is not contained in the curable composition (A), the droplet 102 spreads to the contact angle a1, as shown in FIG. 5 . In particular, if the contact angle a1 is close to zero, the droplet 102 continuously spreads to a large range. On the other hand, if the surfactant (cl) is contained in the curable composition (A), the droplet 102 dropped on the substrate 101 spreads so that the contact angle becomes a2 (a2 > a1), as shown in FIG. 6 . Comparing FIG. 5 and FIG. 6 , since the contact angle increases from a1 to a2 because of the surfactant (cl), the pinning of the droplet 102 occurs in the region determined by the contact angle a2, and the spreading can stop, the extrusion amount can be suppressed.

[0442] According to the examples described later, for example, the solvent (d) is selected to be a high-volatility solvent, the volume ratio of the non-volatile component is 20%, and the droplet pitch is 88 μm, that is, the average initial liquid film thickness is 13 nm or more. In this case, as FIG. 1C schematically shown, it is shown by numerical calculation that the droplets of the curable composition (A') are combined with each other on the substrate, and an actually continuous liquid film 103 is formed. Further, this means that the droplets of the curable composition (A) having a volume of 1.0 pL or more are arranged at a density of 130 droplets / mm 2 or more.

[0443] Referring to FIGS. 7A-7D , the flow behavior of the droplets of the curable composition (A) arranged on the substrate during the waiting step is described. The droplets 102 of the curable composition (A) are arranged discretely on the substrate 101 as shown in FIG. 7A , and each droplet 102 spreads on the substrate 101 as shown in FIG. 7Bspread gradually on the substrate. Then, the droplets of the curable composition (A) on the substrate start to join each other to form a liquid film, as FIG. 7C shown, and a continuous liquid film (the surface of the substrate 101 is covered with the curable composition (A) and there is no longer an exposed surface) is formed, as FIG. 7D shown. The state of the curable composition (A) as FIG. 7D shown is called an "almost continuous liquid film".

[0444] In addition, as FIG. 1D schematically shown, the solvent 105 (solvent (d)) contained in the liquid film 104 volatilizes in the waiting step. Assuming that the total weight of the components other than the solvent (d) is 100% by volume, the residual amount of the solvent (d) in the liquid film 103 after the waiting step (for example, at the start of the contacting step) is preferably 10% by volume or less. If the residual amount of the solvent (d) is greater than 10% by volume, the mechanical properties of the cured film can be deteriorated.

[0445] In the waiting 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) or making the ambient gas around the substrate 101 flow can be performed. The heating is performed at, for example, 30°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 110°C or lower. The heating time can be 10 seconds or longer and 600 seconds or shorter. The baking step can be performed by using a known heater such as a hot plate or an oven.

[0446] The waiting step is, for example, 0.1 seconds to 600 seconds, and preferably 10 seconds to 300 seconds. If the waiting step is shorter than 0.1 seconds, the joining of the droplets of the curable composition (A) becomes insufficient, and thus an almost continuous liquid film is not formed. If the waiting step exceeds 600 seconds, the productivity is reduced. Therefore, in order to suppress the reduction in productivity, the substrates that are processed completely in the arranging step can also be sequentially moved to the waiting step, a plurality of substrates are subjected to the waiting step in parallel, and the substrates that are processed completely in the waiting step are sequentially moved to the contacting step. Note that, in the related art, theoretically, several seconds to several tens of seconds are required before an almost continuous liquid film is formed. However, in practice, a continuous liquid film cannot be formed because the spreading of the droplets of the curable composition is stalled due to the influence of volatilization.

[0447] When the solvent (d) is volatilized in the waiting step, the practically continuous liquid film 104 formed from the components (a), (b), and (c) remains. The average residual liquid film thickness of the practically continuous liquid film 104 from which the solvent (d) is volatilized (removed) becomes smaller than the liquid film 103 due to the amount of volatilization of the solvent (d). The entire pattern formation region of the substrate 101 is maintained in a state in which the entire region is covered with the practically continuous liquid film 104 of the curable composition (A) from which the solvent (d) is removed.

[0448] <contacting step>

[0449] In the contacting step, as FIG. 1E The mold 106 is brought into contact with the practically continuous liquid film 104 of the curable composition (A) from which the solvent (d) is removed, as schematically shown. The contacting step includes a step of changing the state in which the curable composition (A) and the mold 106 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. Thus, the liquid of the curable composition (A) is filled in the recesses of the fine pattern on the surface of the mold 106, and the liquid forms a liquid film filled in the fine pattern of the mold 106.

[0450] In the present application, the curable composition (A) forms the practically continuous liquid film 104 from which the solvent (d) is removed in the waiting step, and thus the volume of gas involved between the mold 106 and the substrate 101 becomes small. Thus, the spreading of the curable composition (A) in the contacting step is rapidly completed. FIG. 8 A comparison (difference) between the contacting step in the prior art disclosed in Japanese Patent No. 6584578 and the like and the contacting step in the present application is shown.

[0451] When the spreading and filling of the curable composition (A) are rapidly completed in the contacting step, the time for maintaining the state in which the mold 106 is in contact with the curable composition (A) (time required for the contacting step) can be shortened. The time required for the pattern formation (film formation) is shortened due to the shortening of the time required for the contacting step, and thus the productivity is improved. The contacting 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 contacting step is shorter than 0.1 seconds, the spreading and filling become insufficient, and thus many defects called incomplete filling defects tend to occur.

[0452] As described above, a phenomenon called bleeding can occur in the contacting step. This is a phenomenon in which the curable composition is squeezed out from the contact surface of the mold and adheres to (climbs up) the side wall (side surface) of the mold in the contacting step. Reference is made to FIG. 9 The concept of bleeding is described. As FIG. 16As shown, the curable composition 1602 extruded from the mold 106 is a factor of so-called exudation (defect), which occurs when it climbs up the sidewall of the mold 106 and forms unwanted cured material of the curable composition 1602 outside the contact surface of the mold 106 as a defect. Here, the height of the curable composition 1602 climbing up the sidewall of the mold 106 is defined as the exudation height 1604.

[0453] In this invention, as described above, regarding the contact angle of the curable composition (A), if the composition of components other than the solvent (component (d)) has a contact angle β [°] relative to the mold surface, then the type and amount of surfactant (c1) are selected such that β is 25° or more. Reference FIG. 10 Describe the factors. As described above, the curable composition 1602 extruded from mold 106 climbs up the sidewall of mold 106. If the contact angle β is less than 25°, for example, it forms a mixture of... FIG. 10 Interface 1705 is shown as a solid line in the diagram. The contact angle β between mold 106 and interface 1705 is β < 25°. On the other hand, if the curable composition 1602 contains a surfactant and the contact angle β is 25° or greater, for example, a mixture of... FIG. 10 Interface 1706 is shown as a dashed line. The contact angle β between the mold 106 and interface 1705 is β ≥ 25°. Comparing interface 1705 and interface 1706, it is found that the volume of the curable composition 1602 extruded from the mold 106 is larger at interface 1706, but the exudation height is lower at interface 1706. Therefore, as the contact angle β increases, the dependence of the exudation height on the volume of the curable composition 1602 extruded from the mold 106 decreases, and the exudation height can be suppressed. β is preferably 30° or more, and more preferably 40° or more.

[0454] When the curing step includes a light irradiation step, a mold made of a light-transmitting material is used as mold 106, taking this into consideration. Advantageous practical examples of material types for forming mold 106 are glass, quartz, PMMA, light-transmitting resins such as polycarbonate resin, transparent metal deposition films, soft films such as polydimethylsiloxane, photocurable films, and metal films. When using a light-transmitting resin as the material for forming mold 106, a resin that does not dissolve in the components contained in the curable composition is selected. Quartz is suitable as a material for forming mold 106 because of its low coefficient of thermal expansion and minimal pattern distortion.

[0455] The pattern formed on the surface of the mold 106 has a height of, for example, 4 nm or more and 200 nm or less. As the pattern height of the mold 106 decreases, the force with which the cured film of the curable composition releases the mold 106, that is, the releasing force in the releasing step, can be reduced, and this makes it possible to reduce the number of releasing defects remaining in the mold 106 because the pattern of the curable composition is torn off. Further, in some cases, the pattern of the curable composition is elastically deformed due to an impact at the time of releasing, and adjacent pattern elements come into contact with and adhere to or break with each other. Note that, in order to avoid these inconveniences, it is advantageous to make the height of the pattern element about two times or less of the width of the pattern element (to make the aspect ratio 2 or less). On the other hand, if the height of the pattern element is too small, the processing precision of the substrate 101 decreases.

[0456] The mold 106 can also be subjected to surface treatment before the contact step is performed, in order to improve the releasability of the mold 106 with respect to the curable composition (A). An example of this surface treatment is the formation of a releasing agent layer by coating the surface of the mold 106 with a releasing agent. Examples of the releasing agent applied to the surface of the mold 106 are silicon-based releasing agents, fluorine-based releasing agents, hydrocarbon-based releasing agents, polyethylene-based releasing agents, polypropylene-based releasing agents, paraffin-based releasing agents, montane-based releasing agents, and carnauba wax-based releasing agents. Commercially available coating-type releasing agents such as Optool DSX manufactured by Daikin can also be appropriately used. Note that one kind of releasing agent can be used alone, or two or more kinds of releasing agents can be used together. Among the above-mentioned releasing agents, fluorine-based and hydrocarbon-based releasing agents are particularly advantageous. ® DSX. Note that one kind of releasing agent can be used alone, or two or more kinds of releasing agents can be used together. Among the above-mentioned releasing agents, fluorine-based and hydrocarbon-based releasing agents are particularly advantageous.

[0457] In the contact step, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is not particularly limited, and is, for example, 0 MPa or more and 100 MPa or less. Note that, when the mold 106 is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and further preferably 0 MPa or more and 20 MPa or less.

[0458] The contact step can be performed in any of a normal air atmosphere, a reduced pressure atmosphere, or an inert gas atmosphere. However, a reduced pressure atmosphere or an inert gas atmosphere is advantageous because it prevents the influence of oxygen or water on the curing reaction. When the contact step is performed in an inert gas atmosphere, practical examples of inert gases used are nitrogen, carbon dioxide, helium, argon, various Freon gases, and mixtures thereof. Gases containing 10% or more of carbon dioxide or helium in a molar ratio are preferred, and gases containing 10% or more of carbon dioxide in a molar ratio are particularly preferred. Because helium gas readily diffuses into the mold, substrate, and cured composition, the ambient gas confined within the pattern of the mold disappears rapidly. Because carbon dioxide readily dissolves in the cured composition or underlayer on the substrate, the ambient gas confined within the pattern of the mold also disappears rapidly. Furthermore, the solubility coefficient of carbon dioxide in the cured composition is preferably 0.5 kg / m³. 3 • above atm and 10kg / m 3 • Atm or less. These details are disclosed in Japanese Patent Application Publication No. 2022-99271. When the contact step is performed in a specific gas atmosphere containing a normal air atmosphere, the advantageous pressure is 0.0001 atm or more and 10 atm or less.

[0459] <Curing Steps>

[0460] In the curing step, such as FIG. 1F As illustrated, the curable composition (A) is cured by irradiation with irradiation light 107, which serves as the curing energy, thereby forming a cured film. In the curing step, for example, the curable composition (A) is irradiated with irradiation light 107 through a mold 106. More specifically, the curable composition (A) filled in the fine patterns of the mold 106 is irradiated with irradiation light 107 through the mold 106. Therefore, the curable composition (A) filled in the fine patterns of the mold 106 is cured, and a patterned cured film 108 is formed.

[0461] The irradiation light 107 is selected according to the sensing wavelength of the curable composition (A). More specifically, the irradiation light 107 is suitably selected from ultraviolet light, X-rays, and electron beams, each having a wavelength of 150 nm or more and 400 nm or less. Note that the irradiation light 107 is particularly preferably ultraviolet light. This is because many commercially available compounds, as curing aids, are sensitive to ultraviolet light. Examples of light sources emitting ultraviolet light are high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep ultraviolet lamps, carbon arc lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. Note that ultra-high-pressure mercury lamps are particularly advantageous as light sources emitting ultraviolet light. One or more light sources can be used. The light can be emitted to the entire area of ​​the curable composition (A) filled in the fine pattern of the mold, or only to a portion of it (by restricting the area). The light can also be emitted intermittently to the entire area of ​​the substrate multiple times, or continuously to the entire area of ​​the substrate. Furthermore, a first region of the substrate can be illuminated with light during the first irradiation process, and a second region different from the first region of the substrate can be illuminated with light during the second irradiation process.

[0462] <Demolding Steps>

[0463] In the demolding process, such as FIG. 1G As schematically shown, the mold 106 is detached from the cured film 108. When the mold 106 is detached from the patterned cured film 108, a cured film 108 with a pattern formed by inverting the fine pattern of the mold 106 is obtained in an independent state. In this state, the cured film remains in the recesses of the patterned cured film 108. This film is called the residual film.

[0464] The method for removing the patterned cured film 108 from the mold 106 can be any method, as long as the method does not physically damage a portion of the patterned cured film 108 during demolding, and there are no particular limitations on various conditions, etc. For example, the substrate 101 can be fixed and the mold 106 can be moved away from the substrate 101. Alternatively, the mold 106 can be fixed and the substrate 101 can be moved away from the mold 106. Furthermore, the patterned cured film 108 can be removed from the mold 106 by moving both the mold 106 and the substrate 101 in completely opposite directions.

[0465] <Repeat>

[0466] A series of steps (manufacturing process) having the above steps in this order from the configuration step to the demolding step, such that a cured film having a desired raised and recessed pattern shape (a pattern shape conforming to the raised and recessed shape of the mold 106) at a desired location can be obtained.

[0467] In the pattern forming method according to the present invention, the repeating unit (shot) from the configuration step to the demolding step can be repeated multiple times on the same substrate, so that a cured film 108 having multiple desired patterns at desired positions on the substrate can be obtained.

[0468] [Method for forming planarization films]

[0469] The following describes an example of applying the film formation method according to the present invention to a planarization film formation method. The planarization film formation method includes, for example, a preparation step, a waiting step, a contact step, a curing step, and a demolding step. The preparation step is the step of preparing droplets of a curable composition (A) on a substrate. The waiting step is the step of waiting until the droplets of the curable composition (A) combine with each other and the solvent (d) evaporates. The contact step is the step of bringing the curable composition (A) and the mold into contact with each other. The curing step is the step of curing the curable composition (A). The demolding step is the step of separating the cured film from the cured composition (A). In the planarization film formation method, a substrate with unevenness having a height difference of about 10 nm to 1,000 nm is used as the substrate, a mold having a flat surface is used as the mold, and a cured film having a surface consistent with the flat surface of the mold is formed through the contact step, the curing step, and the demolding step. In the preparation step, droplets of the curable composition (A) are densely arranged in the recesses of the substrate and sparsely arranged on the protrusions of the substrate. The waiting step is performed after the configuration step, the contact step is performed after the waiting step, the curing step is performed after the contact step, and the demolding step is performed after the curing step.

[0470] [How to make the item]

[0471] The method for manufacturing an article includes a forming step of forming a film of a curable composition on a substrate using the film forming method described above, a processing step of processing the substrate on which the film of the curable composition has been formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. The film forming method is a pattern forming method or a planarization film forming method as described above.

[0472] The cured film 108 having a pattern formed by the pattern forming method according to the invention can be directly used as at least a partial constituent component of various articles. Furthermore, the cured film 108 having a pattern formed by the pattern forming method according to the invention can be temporarily used as a mask for etching or ion implantation of the substrate 101 (which is the processed layer when the substrate 101 has a processed layer). This mask is removed after etching or ion implantation is performed during the processing step of the substrate 101. Therefore, various articles can be manufactured.

[0473] When removing the cured material from the recesses of a pattern by etching, there are no particular limitations on the actual method, and conventionally known methods, such as dry etching, can be used. Conventionally known dry etching equipment can be used in this dry etching process. The source gas for dry etching is appropriately selected based on the elemental composition of the cured material being etched. More specifically, halogen gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2 can be used as source gases. Gases containing oxygen atoms, such as O2, CO, and CO2, inactive gases such as He, N2, and Ar, and gases such as H2 and NH3 can also be used as source gases. Note that these gases can also be mixed and used as source gases. In this case, the photocurable film needs to have a high-efficiency dry etching system to process the substrate at high yield.

[0474] Examples of items include, for example, circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Examples of circuit elements are volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, as well as semiconductor elements such as LSI, CCD, image sensors, and FPGAs. Examples of optical elements are microlenses, light guides, waveguides, anti-reflective coatings, diffraction gratings, polarizers, color filters, light-emitting elements, displays, and solar cells. Examples of MEMS are DMDs, microchannels, and electromechanical transducers. Examples of recording elements are optical discs such as CDs and DVDs, magnetic disks, magneto-optical discs, and magnetic heads. Examples of sensors are magnetic sensors, photosensitive sensors, and gyroscope sensors. Examples of molds are embossing molds.

[0475] Furthermore, known photolithography steps, such as imprint lithography or extreme ultraviolet (EUV) lithography, can be performed on the planarization film formed by the planarization film formation method according to the present invention. Alternatively, spin-coated glass (SOG) films and / or silicon oxide layers can be stacked, and photolithography can be performed by applying a curable composition thereon. Therefore, devices such as semiconductor devices can be manufactured. Equipment including such devices can also be formed, for example, electronic devices such as displays, cameras, or medical devices. Examples of devices are LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and NAND flash memory.

[0476] [Example]

[0477] To supplement the above implementation scheme, more detailed embodiments are described.

[0478] <Example 1>

[0479] Example 1 illustrates how adding a surfactant to make α2 greater than α1 controls droplet spreading on the substrate through a pinning effect and suppresses extrusion. Example 1 also illustrates how making γ1 greater than γ2 controls extrusion while simultaneously forming a liquid film through droplet spreading.

[0480] In Example 1, experiments were conducted using three types of compositions to assess droplet spreading, as shown in Table 1 below. In Table 1, FS2000M1 (manufactured by CHANGZHOU FOREIGN) is a surfactant. Composition 1 is a composition that does not contain a surfactant, Composition 2 is a composition that contains 0.4% by weight of surfactant added at a mass ratio, and Composition 3 is a composition that contains 3% by weight of surfactant added at a mass ratio.

[0481] [Table 1]

[0482]

[0483] First, this embodiment demonstrates how adding a surfactant can make α2 greater than α1. To measure the contact angle, the amount of liquid compatibility was set to 1 μL, and an automated static contact angle meter, Dropmaster 300 (manufactured by Kyowa InterfaceScience), was used. FIG. 11 This is a graph showing the results of measuring the contact angle between each of compositions 1, 2, and 3 and the substrate. FIG. 11 In the diagram, the horizontal axis represents time, and the vertical axis represents the contact angle, such that... FIG. 11 The rate of change of contact angle over time is shown for each composition. (Reference) FIG. 11 It was found that at each time point, the contact angle of composition 2 was greater than that of composition 1, the contact angle of composition 3 was greater than that of composition 2, and α2 was greater than α1. FIG. 11 In this study, for the contact angle of droplets of each composition 10 seconds after they fall, the contact angle of composition 2 is approximately 0.5° greater than that of composition 1.

[0484] The following shows the change in surface tension related to the addition of surfactant. Surface tension was measured using an automated surface tension meter DY-300 (manufactured by Kyowa Interface Science) and a plate method using platinum plates was performed. FIG. 12 This is a graph showing the results of the surface tension measurement. FIG. 12In the graph, the horizontal axis represents the amount of surfactant added, and the horizontal axis represents the surface tension value. Line 901 shows the dependence of the surface tension of the curable composition on the amount of surfactant added in the solvent-free (d) state, and line 902 shows the surface tension value of the solvent. As mentioned above, if γ1 is greater than γ2, the droplets spread rapidly to form a liquid film. This is the region where the surface tension of line 901 is greater than that of line 902, and it is... FIG. 12 Region 903. Therefore, in composition 2, γ1 is greater than γ2, and in composition 3, γ1 is less than γ2.

[0485] FIG. 13 The rate of change of droplet radius over time is shown when a droplet of approximately 2 pL falls. To photograph (measure) the droplet falling and spreading, a commercially available industrial material printer, DMP-2850 (manufactured by Fuji Film), was used. FIG. 13 In the graph, the horizontal axis represents time, and the vertical axis represents the radius of the droplet. (Reference) FIG. 13 It was found that in composition 1, the droplets spread over time, but in composition 2, the spreading of the droplets stopped at an appropriate radius due to the pinning effect. It was also found that in composition 3, the droplets contracted due to both the pinning and Marangoni effects. Therefore, droplet spreading can be controlled by adding a surfactant and obtaining the pinning effect.

[0486] Next, FIG. 14 The results of measuring the extrusion volume of the liquid film are shown when using an industrial material printer DMP-2850 (manufactured by Fuji Film) with droplets of approximately 2 pL arranged in an array of 6 rows at a spacing of 70 μm. Note that the extrusion volume of the liquid film is defined as the amount obtained by subtracting 70 × 6 μm from the length of the liquid film. FIG. 14 In the diagram, the horizontal axis represents time, and the vertical axis represents the extrusion volume. Note that for composition 3, due to excessive shrinkage, a practically continuous liquid film cannot be formed, and because the purpose of the waiting step cannot be met, the composition is deemed inappropriate. Typically, in composition 3, as... FIG. 15 As shown, droplet 1302 is isolated on substrate 1301. On the other hand, for compositions 1 and 2, a virtually continuous liquid film can be formed, and typically, as... FIG. 16 As shown, droplets combine with each other to form a liquid film 1202 on the substrate 1201.

[0487] For compositions 1 and 2, other than composition 3, which are determined to be inappropriate, refer to FIG. 14 It was found that in composition 1, the extrusion amount was large and increased over time, while in composition 2, the extrusion amount was small and its dependence on time was small.

[0488] FIG. 17 A summary of the experimental results for compositions 1, 2, and 3 is presented. FIG. 17 The value shown is the extrusion rate after 600 seconds. (Reference) FIG. 17 It was found that when α2 is greater than α1, as in the transition from composition 1 to composition 2, the extrusion amount can be suppressed from 120 μm to 48 μm. Furthermore, it was found that when γ1 is greater than γ2, as in the transition from composition 3 to composition 2, both liquid film formation and extrusion amount suppression can be achieved simultaneously.

[0489] As stated above, it is shown that when α2 is greater than α1, the extrusion rate can be suppressed. Furthermore, it is shown that when γ1 is greater than γ2, both liquid film formation and extrusion rate suppression can be achieved simultaneously. Note that, as FIG. 11 As shown, for the contact angle of the droplet 10 seconds after it falls, it is preferable to keep α2-α1>0.5°.

[0490] Next, we will explain the preferred Δγ defined by the following equation (3).

[0491] ...(3)

[0492] FIG. 18 This is a graph showing the dependence of the maximum droplet radius on Δγ in the case of a droplet of approximately 1 pL. FIG. 18 Numerical results obtained by solving the Navier-Stokes equations (lubrication theory) approximating a thin film with a free surface are shown. FIG. 18 In the equation (4), the horizontal axis represents Δγ [mN / m] and the vertical axis represents Δr [μm]. Here, Δr is defined by the following equation (4).

[0493] ...(4)

[0494] Where r is the maximum radius of the droplet, and r0 is the maximum radius of the droplet when Δγ=0.

[0495] refer to FIG. 18 It was found that if Δγ > 0.1 mN / m, then Δr > 1 μm and the droplet spreads more significantly compared to the case where Δγ = 0; and if Δγ > 1 mN / m, then Δr > 10 μm and the droplet spread is more pronounced compared to the case where Δγ = 0. Therefore, it was found that to achieve the effect of maximizing the droplet radius, it is preferable to keep Δγ > 0.1 mN / m, and more preferably to keep Δγ > 1 mN / m.

[0496] <Example 2>

[0497] Example 2 demonstrates that when β is greater than 25° by adding a surfactant, the spread of droplets on the mold surface can be controlled by the pinning effect, and the penetration height towards the mold sidewalls can be suppressed. Also in Example 2, experiments were conducted using the three types of compositions shown in Table 1.

[0498] First, this example demonstrates that β (contact angle) increases with the addition of a surfactant. The contact angle measurement was performed similarly to that in Example 1. FIG. 19 This is a graph showing the results of measuring the contact angle between each of compositions 1, 2, and 3 and the mold. FIG. 19 In the diagram, the horizontal axis represents time, and the vertical axis represents the contact angle, such that... FIG. 19 The rate of change of the contact angle between each composition and the mold surface over time is shown. (Reference) FIG. 19 It was found that at each time point after 1 second, the contact angle of composition 2 was greater than that of composition 1, the contact angle of composition 3 was greater than that of composition 2, and β increased. FIG. 19 In this context, the contact angle 10 seconds after the droplets of each composition fall is approximately 14° in composition 1 and approximately 31° in composition 2.

[0499] Next, FIG. 20 The results of numerical calculations to obtain the exudation height at different contact angles are shown. FIG. 20 The results are shown by approximating the substrate and mold as rigid bodies and solving the Navier-Stokes equations, which approximate thin films. FIG. 20 In the figure, the horizontal axis represents the contact angle, and the vertical axis represents the exudation height.

[0500] refer to FIG. 20 It was found that composition 1, with a contact angle of approximately 14°, had a percolation height of approximately 95 nm, while composition 2, with a contact angle of approximately 31°, had a percolation height of approximately 70 nm. Therefore, it was found that percolation height could be suppressed by selecting composition 2 instead of composition 1. Note that for composition 3, percolation height could be suppressed even more due to its higher contact angle; however, based on Example 1, composition 2, where γ1 is greater than γ2, is required to achieve both liquid film formation and percolation height suppression.

[0501] According to the abbreviations shown in Table 2 below, curable composition (A) was mixed by mixing components (a), (b), (c), and (d) to obtain a total proportion of 100% by weight, and curable composition (A) was mixed without using component (d), as shown in Table 3 below. The results obtained by measuring the viscosity of these curable compositions (A) at 23°C and calculating / measuring the Si atom content of the curable composition when component (d) is removed and the Tg after curing by the above method are shown in Table 4 below. Note that for component (d) in Table 3, PGMEA is an abbreviation for propylene glycol monomethyl ether, and Gly is an abbreviation for glycerol.

[0502] [Table 2]

[0503]

[0504] [Table 3]

[0505]

[0506] [Table 4]

[0507]

[0508] <Evaluation of inkjet ejection>

[0509] To evaluate inkjet ejection, a commercially available industrial material printer, DMP-2850 (manufactured by Fuji Film), was used. The curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3 were each filled into a cartridge. The droplet ejection status was observed using an internal ejection observation camera, and inkjet ejection was evaluated based on the following evaluation criteria.

[0510] (Evaluation Criteria)

[0511] AAA: At exhaust velocities (flight speeds) of 6 m / sec or higher, no deviation in landing position was observed.

[0512] AA: Slight deviations in landing position were observed at discharge velocities above 6 m / sec, but had no practical impact.

[0513] A: Slight deviations in landing position were observed at discharge velocities above 4 m / sec, but had no practical impact.

[0514] B: Cannot be expelled.

[0515] <Evaluation of Extrusion Volume>

[0516] To evaluate the extrusion rate, a commercially available industrial material printer, the DMP-2850 (manufactured by Fuji Film), was used. The curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2, as shown in Table 3, were each filled into a cartridge. Approximately 2 pL of liquid was dropped and arranged in an array of 6 rows with a spacing of 70 μm. In all examples and comparative examples, it was confirmed that a virtually continuous liquid film was formed after 600 seconds, and the extrusion rate was measured. Note that the extrusion rate of the liquid film was defined as the amount obtained by subtracting 70 × 6 μm from the length of the liquid film, and the extrusion rate was evaluated based on the following evaluation criteria.

[0517] (Evaluation Criteria)

[0518] AAA: Extrusion depth is below 50μm.

[0519] AA: Extrusion depth is below 70μm.

[0520] A: The extrusion depth is less than 100μm.

[0521] B: Extrusion depth greater than 100μm.

[0522] <Evaluation of Exudate>

[0523] To evaluate the exudation amount, a commercially available industrial material printer, the DMP-2850 (manufactured by Fuji Film), was used. The curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2, as shown in Table 3, were each filled into a cartridge at a rate of 1 μL. Using the pattern editor software DMP-2850, a pattern array was generated where the X width was set to 25.5 mm, the Y height to 32.5 mm, and the droplet spacing to 50 μm. Droplets were dropped onto a silicon substrate, and a configuration, waiting, and contacting step was performed using a quartz preform. The configuration, waiting, and contacting steps were performed under a carbon dioxide atmosphere, and images of the outer periphery of the planar mold after each step were taken at 500 μm intervals, resulting in a total of 232 images. All images were observed, and the exudation amount was evaluated based on the following evaluation criteria.

[0524] (Evaluation Criteria)

[0525] AAA: Confirmed that the proportion of the oozing images is less than 1% of the total.

[0526] AA: The proportion of images showing exudation is confirmed to be less than 3% of the total.

[0527] A: The proportion of images showing oozing is confirmed to be less than 5% of the total.

[0528] B: Confirm that the proportion of the oozing image is greater than 5% of the total.

[0529] <Evaluation of droplet binding>

[0530] With a liquid film thickness of 80 nm before solvent (d) evaporation, the curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3 were discretely dropped (configured) onto a silicon substrate. The time until a virtually continuous liquid film was formed was measured, and droplet adhesion was evaluated based on the following evaluation criteria.

[0531] (Evaluation Criteria)

[0532] AAA: Formation of a virtually continuous liquid film in less than 100 seconds.

[0533] AA: A virtually continuous liquid film is formed within a time frame of more than 100 seconds but less than 200 seconds.

[0534] A: A practically continuous liquid film is formed within a time frame of more than 200 seconds but less than 300 seconds.

[0535] B: Even after 300 seconds, no actually continuous liquid film was formed.

[0536] <Evaluation of Pattern Collapse>

[0537] For each of the curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3, a configuration step, a waiting step, a contact step, a curing step, and a demolding step were performed using a quartz mold that forms a line-spaced (L / S) pattern with a depth of 50 nm and a width of 20 nm over the entire area. The patterns obtained through these steps were observed, and pattern collapse was evaluated based on the following evaluation criteria.

[0538] (Evaluation Criteria)

[0539] AAA: Pattern collapse was observed in areas smaller than 0.5% of the pattern-forming area.

[0540] AA: Pattern collapse was observed in areas less than 1% of the pattern-forming area.

[0541] A: Pattern collapse was observed in areas smaller than 10% of the pattern-forming area.

[0542] B: Pattern collapse was observed in more than 10% of the pattern-forming area.

[0543] <Evaluation of resistance to dry etching>

[0544] The cured films obtained from the curable compositions of Examples 3 to 22 and Comparative Examples 1 and 2 shown in Table 3 were exposed to oxygen plasma in a dry etching apparatus. Furthermore, the cured films obtained from the curable compositions of Examples 23 to 28 shown in Table 3 were exposed to CF4 plasma in a dry etching apparatus. The weight change of the remaining cured film after exposure was measured, and dry etching resistance was evaluated based on the following evaluation criteria.

[0545] (Evaluation Criteria)

[0546] AAA: The weight of the residual cured film is more than 46% of the weight before etching.

[0547] AA: The weight of the residual cured film is more than 42% of the weight before etching.

[0548] A: The weight of the residual cured film is more than 38% of the weight before etching.

[0549] B: The weight of the residual cured film is less than 38% of the weight before etching.

[0550] The evaluation results are shown in Table 5.

[0551] [Table 5]

[0552]

[0553] It was found that inkjet ejection is satisfactory if the viscosity of the curable composition at 23°C is 2 mPa·s or more and 60 mPa·s or less, and preferably 5 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less.

[0554] Regarding the extrusion amount, it was found that α1[°] is the contact angle between the composition and the substrate obtained by removing the solvent (d) and surfactant (c1), and α2[°] is the contact angle between the composition and the substrate obtained by removing the solvent (d). If α2 is greater than α1, the extrusion amount is satisfactory. It was also found that α2-α1>0.5 is preferred, and α2-α1≥3.0 is further preferred.

[0555] It was found that if the contact angle β[°] between the composition obtained by removing the solvent (d) and the quartz is β≥25°, the amount of exudation is satisfactory, β≥30° is preferred, and β≥40° is further preferred.

[0556] It was found that when γ1 [mN / m] is the surface tension of the composition obtained by removing solvent (d) at 23°C, and γ2 [mN / m] is the surface tension of solvent (d) at 23°C, droplet binding is satisfactory if γ1 is greater than γ2. It was also found that γ1-γ2 ≥ 1.0 is preferred, and γ1-γ2 ≥ 2.0 is further preferred.

[0557] Regarding pattern collapse, it was found that the glass transition temperature of the curable composition after curing is preferably 70°C or higher, more preferably 100°C or higher, and even more preferably 130°C or higher.

[0558] Regarding resistance to dry etching, as found in Examples 3 to 22 and Comparative Examples 1 and 2, the OP of the polymeric compound (a) is preferably 1.80 or more and 4.00 or less, more preferably 2.00 or more and 3.50 or less, and even more preferably 2.40 or more and 3.00 or less. Furthermore, regarding resistance to dry etching, as found in Examples 3 to 28, the Si content of the polymeric compound (a) is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 20% by weight or more.

[0559] This invention is not limited to the above-described embodiments, and various changes and modifications can be made within the spirit and scope of this invention. Therefore, the claims are appended to inform the scope of this invention.

[0560] This application claims priority to Japanese Patent Application No. 2023-119299, filed on July 21, 2023, the entire contents of which are incorporated herein by reference.

Claims

1. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (cl), wherein the viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa-s or more and 60 mPa-s or less, the content of the solvent (d) with respect to the entire curable composition is more than 5% by volume and 95% by volume or less, the boiling point of the solvent (d) at 1 atm is less than 250°C, and α1 is the contact angle of a composition obtained by removing the solvent (d) and the surfactant (cl) from the curable composition with a substrate, and α2 is the contact angle of a composition obtained by removing the solvent (d) from the curable composition with the substrate, wherein α2 is more than α1.

2. The curable composition according to claim 1, wherein α2 - α1 > 0.5°.

3. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (cl), wherein the viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa-s or more and 60 mPa-s or less, the content of the solvent (d) with respect to the entire curable composition is more than 5% by volume and 95% by volume or less, the boiling point of the solvent (d) at 1 atm is less than 250°C, and the contact angle β of a composition obtained by removing the solvent (d) from the curable composition with a mold is 25° or more.

4. The curable composition according to claim 1 or 3, wherein γ1 is the surface tension of a composition obtained by removing the solvent (d) from the curable composition at 23°C and 1 atm, and γ2 is the surface tension of the solvent (d) at 23°C and 1 atm, wherein γ1 is more than γ2.

5. The curable composition according to claim 4, wherein γ1 - γ2 > 0.1 mN / m.

6. The curable composition according to claim 4, wherein γ1 - γ2 > 1 mN / m.

7. The curable composition according to claim 1 or 3, wherein the surfactant (cl) contains a fluorine atom.

8. The curable composition according to claim 1 or 3, wherein the surfactant (cl) contains a silicon atom.

9. The curable composition according to claim 1 or 3, wherein the viscosity of a composition obtained by removing the solvent (d) from the curable composition at 23°C and 1 atm is 30 mPa-s or more and 10,000 mPa-s or less.

10. The curable composition according to claim 1 or 3, wherein the solvent (d) contains one or more solvents, and each of the one or more solvents has a boiling point of 100°C or more and less than 250°C at 1 atm. ​ ​ ​ ​ ​ ​ ​ ​ 11. The curable composition according to claim 1 or 3, wherein the solvent (d) comprises a polymerizable compound having a boiling point of 100°C or higher and less than 250°C at 1 atm.

12. The curable composition according to claim 1 or 3, wherein the solvent (d) comprises one or more solvents, and each of the one or more solvents has a boiling point of 100°C or higher and less than 200°C at 1 atm.

13. The curable composition according to claim 1 or 3, wherein the content of the solvent (d) relative to the entire curable composition is 40% by volume or more and 85% by volume or less.

14. The curable composition according to claim 1 or 3, wherein the proportion of the multifunctional polymerizable compound in the polymerizable compound (a) is 20% by weight or more.

15. The curable composition according to claim 1 or 3, wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and each of the one or more polymerizable compounds has a boiling point of 250°C or higher at 1 atm.

16. The curable composition according to claim 1 or 2, wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and each of the one or more polymerizable compounds has a molecular weight of 200 or more.

17. The curable composition according to claim 1 or 2, wherein the polymerizable compound (a) comprises a polymer having a polymerizable functional group.

18. The curable composition according to claim 1 or 3, wherein the polymerizable compound (a) has a glass transition temperature of 70°C or higher after curing.

19. The curable composition according to claim 1 or 3, wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and each of the one or more polymerizable compounds has a vapor pressure of 0.001 mmHg or less at 80°C and 1 atm.

20. The curable composition according to claim 1 or 3, wherein the polymerizable compound (a) comprises a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

21. The curable composition according to claim 1 or 3, wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and 22. The curable composition according to claim 1 or 3, wherein the polymerizable compound (a) comprises a compound (a-2) containing a silicon atom. The polymeric compound (a) has an Okada parameter OP of 1.80 or more and 4.00 or less, and a molar fraction-weighted average value of N / (N C -N O ) values of each molecule of the one or more polymeric compounds, where N is the total number of atoms in the molecule, N C is the number of carbon atoms in the molecule, and N O is the number of oxygen atoms in the molecule. The polymeric compound (a) has an Okada parameter OP of 1.80 or more and 4.00 or less, and a molar fraction-weighted average value of N / (N C -N O ) values of each molecule of the one or more polymeric compounds, where N is the total number of atoms in the molecule, N C is the number of carbon atoms in the molecule, and N O is the number of oxygen atoms in the molecule.

23. The curable composition according to claim 22, wherein the compound (a-2) comprises a polymerizable compound having a silsesquioxane skeleton or a cyclic siloxane compound.

24. The curable composition according to claim 1 or 3, wherein a composition obtained by removing the solvent (d) from the curable composition contains 10% by weight or more of Si atoms.

25. The curable composition according to claim 1 or 3, wherein the curable composition is an inkjet composition. ​ 26. The curable composition according to claim 1 or 3, wherein a solubility coefficient of carbon dioxide to the curable composition is 0.5 kg / m 3 ·atm or more and 10 kg / m 3 ·atm or less.

27. A film forming method which is a film forming method of forming a film of a curable composition in a space between a mold and a substrate, comprising: a disposing step of discretely disposing a plurality of droplets of the curable composition defined in claim 1 or 3 on the substrate; a waiting step of waiting until the plurality of droplets join with adjacent droplets to form a liquid film; and a contacting step of bringing the mold and the liquid film into contact with each other after the waiting step.

28. The film forming method according to claim 27, wherein in the waiting step, waiting is performed until a solvent contained in the liquid film volatilizes and the content of the solvent is 10% by volume or less with respect to the entirety of the liquid film.

29. The film forming method according to claim 27, wherein in the waiting step, the substrate is heated under conditions of 30°C or higher and 200°C or lower and 10 seconds or longer and 600 seconds or shorter.

30. The film forming method according to claim 27, wherein in the arranging step, the droplets of the curable composition having a volume of 1.0 pL or more are arranged at 80 droplets / mm2 or more. 2 The above densities are arranged on the substrate.

31. The film forming method according to claim 27, wherein an average residual liquid film thickness is 20 nm or less, the average residual liquid film thickness being a value obtained by dividing the volume of the curable composition remaining after the waiting step by the area of a film forming region.

32. The film forming method according to claim 27, wherein 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, and the film forming method further includes, after the contacting step, a curing step of curing the liquid film to form a cured film having a pattern corresponding to the pattern of the mold.

33. The film forming method according to claim 27, wherein 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, and the film forming method further includes, after the contacting step, a curing step of curing the liquid film to form a cured film having a surface coinciding with the flat surface of the mold.

34. The film forming method according to claim 27, wherein in the disposing step, the plurality of droplets are discretely disposed on the substrate using an inkjet method.

35. The film forming method according to claim 27, wherein in the contacting step, a gas filling a space between the mold and the substrate contains carbon dioxide at a molar ratio of 10% or more.

36. A method of manufacturing an article, comprising: a forming step of forming a film of a curable composition on a substrate using the film forming method defined in claim 27; a processing step of processing the substrate on which the film is formed in the forming step; and a manufacturing step of manufacturing an article from the substrate processed in the processing step.

37. The method of manufacturing an article according to claim 36, wherein in the forming step, the film is formed on the substrate using the film forming method defined in claim 27.

38. The method of manufacturing an article according to claim 36, wherein in the processing step, the substrate on which the film is formed in the forming step is processed.

39. The method of manufacturing an article according to claim 36, wherein in the manufacturing step, an article is manufactured from the substrate processed in the processing step.

Images