Membrane formation method and article manufacturing method

Abstract

The film formation method of the present invention includes the following steps: a preparation step of preparing a curable composition on a substrate; a contact step of contacting the curable composition with a film formation area of ​​a mold after the preparation step; a curing step of curing the curable composition after the contact step; and a separation step of separating the curable composition from the mold after the curing step. In the contact step, a gas is present filling the space between the substrate and the mold, the solubility coefficient of the gas for the curable composition is 0.5 kg / m³·atm or more and 10 kg / m³·atm or less, and the average liquid film thickness, calculated by dividing the volume of the curable composition by the area of ​​the film formation area, is 70 nm or more.

Description

[Technical Field]

[0002] This invention relates to a membrane formation method and an article manufacturing method. [Previous Technology]

[0003] In semiconductor devices such as MEMS, the demand for miniaturization is increasing, and photoimaging technology, as a microfabrication technology, has attracted much attention. In photoimaging technology, a mold with a micro-unfolded pattern on its surface is pressed onto a substrate (wafer) coated with a curable component, causing the curable component to harden. This transfers the mold's unfolded pattern onto the hardened film of the curable component, forming a pattern on the substrate. According to photoimaging technology, microstructures at the nanometer scale can be formed on a substrate.

[0004] This section describes an example of a film formation method using photoimprint technology. First, a liquid curable composition is discretely dropped onto a pattern forming area on a substrate. The droplets of curable composition dropped onto the pattern forming area spread on the substrate. This phenomenon can be called pre-spreading. Next, a mold with a pattern is pressed against the curable composition on the substrate. Thereby, the droplets of curable composition spread to the entire gap between the substrate and the mold through capillary action. This phenomenon can be called spreading. The curable composition then fills the recesses forming the mold pattern through capillary action. This filling phenomenon can be called filling. The time until spreading and filling are complete can be called filling time. After the curable composition is filled, it is irradiated with light to harden it. Subsequently, the mold is pulled away from the hardened curable composition. By performing these steps, the mold pattern is transferred to the curable composition on the substrate, forming a pattern of the curable composition.

[0005] Furthermore, in the photolithography process used to manufacture semiconductor devices, substrate planarization is also required. For example, in the extreme ultraviolet (EUV) photolithography technology, which has attracted much attention in recent years, the depth of focus of the projected image becomes shallower due to the miniaturization process, so the unevenness of the substrate surface on which the curable composition is coated must be suppressed to below 4 nm. In another photolithography technology, nanoimprint lithography (NIL), a planarity of the same degree as EUV is required to improve fillability and linewidth accuracy (Non-Patent Document 1). As a planarization technique, it is known to discretely drop droplets of liquid curable composition with a component corresponding to the unevenness onto a substrate, and to harden the curable composition by pressing it against a mold with a flat surface to obtain a flat surface (Patent Documents 1, 2).

[0006] In the above-mentioned pattern forming and planarization technologies, high throughput is required to improve productivity, but the most time-consuming steps are expansion and filling. In photoimprint lithography, it is known to increase the filling speed by using helium and air as ambient gases (Non-Patent Document 2). [Prior Art Documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2019-140394 [Patent Document 2] U.S. Patent Application Publication No. 2020 / 0286740 [Patent Document 3] Japanese Patent Application Publication No. 2009-503139 [Non-Patent Documents]

[0008] [Non-Patent Literature 1] N. Shiraishi / Int. J. Microgravity Sci. No.31 Supplement 2014 (S5-S12) [Non-Patent Literature 2] Proc. SPIE 11324-11 (2020) [Non-Patent Literature 3] Susumu Okazaki, "The Foundation of Computer Simulation", Chemical Writers (2000) [Non-Patent Literature 4] BH Besler, KM Merz Jr., and PA Kollman, J. Comp. Chem. 11, 431 (1990). [Non-Patent Literature 5] UC Singh and PA Kollman, J. Comp. Chem. 5, 129 (1984). [Non-Patent Literature 6] Wang, J., Wolf, RM, Caldwell, JW, Kollman, PA, Case, DA, J. Comp. Chem. 25, 1157 (2004). [Summary of the Invention]

[0009] The inventors of this application have discovered the following problem: the thicker the liquid film of the hardening component, the longer the time required for expansion and filling.

[0010] The present invention provides an advantageous technique that can suppress the decrease in filling speed even when the liquid film thickness of the hardening composition is relatively thick.

[0011] One aspect of the present invention relates to a film forming method, comprising the following steps: a placement step of placing a curable composition on a substrate; a contact step of contacting the curable composition with a film forming region of a mold after the placement step; a curing step of curing the curable composition after the contact step; and a separation step of separating the curable composition from the mold after the curing step. In the contact step, a gas is present filling the space between the substrate and the mold, the solubility coefficient of the gas for the curable composition is 0.5 kg / m³·atm or more and 10 kg / m³·atm or less, and the average liquid film thickness, calculated by dividing the volume of the curable composition by the area of ​​the film forming region, is 70 nm or more.

[0012] Other features and advantages of the present invention will become apparent from the following description with reference to the accompanying drawings. In the drawings, the same or identical components are labeled with the same reference numerals.

Implementation Method

[0014] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. These embodiments do not limit the scope of the invention as claimed. Although multiple features are described in the embodiments, not all of these multiple features are essential to the present invention, and the multiple features can be arbitrarily combined. Furthermore, in the accompanying drawings, identical or similar components are labeled with the same reference numerals, and repeated descriptions are omitted.

[0015] [Curing Composition] The curing composition (A) of this embodiment is a composition having at least one component (a) of a polymerizable compound. The curing composition of this embodiment may further contain a component (b) of a photopolymerization initiator, a nonpolymerizable compound (c), and a component (d) of a solvent.

[0016] Furthermore, the term "curing film" in this specification refers to a film on a substrate where a curing component is polymerized and cured. Also, the shape of the curing film is not particularly limited, and it may have a patterned shape on its surface.

[0017] <Component (a): Polymerizable compound> Component (a) is a polymerizable compound. Here, the polymerizable compound referred to in this specification is a compound that forms a film of polymeric compound by reacting with polymerization factors (free radicals, etc.) generated by a self-photopolymerization initiator (component (b)) in a chain reaction (polymerization reaction).

[0018] Examples of such polymeric compounds include, for instance, free radical polymeric compounds. The polymeric compound of component (a) may consist of only one polymeric compound or may consist of a plurality of polymeric compounds.

[0019] Examples of free radical polymerizable compounds include (meth)acrylic acid compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric acid compounds, and maleic acid compounds. Preferably, the free radical polymerizable compound is a compound having one or more acrylonitrile or methacrylic acid groups, i.e., a (meth)acrylic acid compound. Therefore, the curable composition of this embodiment preferably contains a (meth)acrylic acid compound as component (a), more preferably the main component of component (a) is a (meth)acrylic acid compound, and most preferably a (meth)acrylic acid compound. Furthermore, the statement that the main component of component (a) is a (meth)acrylic acid compound indicates that 90% by mass or more of component (a) is a (meth)acrylic acid compound.

[0020] When the free radical polymerizable compound is composed of a plurality of compounds having one or more acrylonitrile or methacrylonitrile, it preferably includes monofunctional (meth)acrylic acid monomers and polyfunctional (meth)acrylic acid monomers. The reason is that by combining monofunctional (meth)acrylic acid monomers and polyfunctional (meth)acrylic acid monomers, a hardened film with stronger mechanical strength can be obtained.

[0021] Examples of monofunctional (meth)acrylic acid compounds having one acrylonitrile or methacrylonitrile include, for example, phenoxyethyl (meth)acrylic acid, phenoxy-2-methylethyl (meth)acrylic acid, phenoxyethoxyethyl (meth)acrylic acid, 3-phenoxy-2-hydroxypropyl (meth)acrylic acid, 2-phenylphenoxyethyl (meth)acrylic acid, 4-phenylphenoxyethyl (meth)acrylic acid, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylic acid, EO-modified p-cumylphenol (meth)acrylic acid, 2-bromophenoxyethyl (meth)acrylic acid, 2,4-dibromophenoxyethyl (meth)acrylic acid, 2,4,6-tribromophenoxyethyl (meth)acrylic acid, EO-modified ( Phthalate acrylate, PO-modified phenoxy acrylate, polyoxyethylene nonylphenyl ether methacrylate, isoborneol acrylate, 1-adamantane acrylate, 2-methyl-2-adamantane acrylate, 2-ethyl-2-adamantane acrylate, borneol acrylate, tricyclodecyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, cyclohexyl acrylate, 4-butylcyclohexyl acrylate, acrylmorpholine, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, methyl acrylate, propyl acrylate Ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, isobutyl acrylate, tributyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecanyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, isostearyl acrylate, benzyl acrylate, (methyl) Tetrahydrofurfuryl acrylate, (meth)acrylate butoxyethyl acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, (meth)acrylate ethoxyethyl acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, tert-octyl (meth)acrylamide, (meth)acrylate dimethylaminoethyl acrylate, (meth)acrylate diethylaminoethyl acrylate, (meth)acrylate 7-amino-3,7-dimethyloctyl acrylate, N,N-diethyl (meth)acrylamide, N,N-Dimethylaminopropyl(meth)acrylamide, etc., but not limited to these.

[0022] Examples of commercially available monofunctional (meth)acrylic acid compounds include ARONIX (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (all manufactured by Toa Synthetic), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, BISCOTE #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (all manufactured by Osaka Organic Chemical Industry), and 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 (all manufactured by Kyoei Chemicals), KAYARAD (registered trademark) TC110S, R-564, R-128H (all manufactured by Nippon Kayaku), NK ESTER AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin-Nakamura Chemical Industry), FA-511A, 512A, 513A (all manufactured by Hitachi Chemicals), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Pharmaceutical), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kojin), etc., but not limited to these.

[0023] Furthermore, examples of polyfunctional (meth)acrylic acid compounds having two or more acrylonitrile or methacrylonitrile include, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO, PO-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 6-Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,3-adamantanediethanol diacrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO and PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, etc., but not limited to these.

[0024] Examples of commercially available polyfunctional (meth)acrylic acid compounds include YUPIMER (registered trademark) UV SA1002, SA2007 (manufactured by Mitsubishi Chemical), BISCOTE #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (manufactured by Osaka Organic Chemical Industry), LIGHT ACRYLATE 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (manufactured by Kyoei Chemicals), and KAYARAD (registered trademark). PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku), ARONIX (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toa Synthetic), RIPOXY (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Polymer), etc., but not limited to these.

[0025] Furthermore, in the above-mentioned group of compounds, the term "(meth)acrylate" refers to acrylate or methacrylate having an equivalent number of alcohol residues. The term "(meth)acryl" refers to acrylonitrile or methacrylonitrile having an equivalent number of alcohol residues. EO represents ethylene oxide, and the term "EO-modified compound A" refers to a compound in which the (meth)acrylate residues and alcohol residues of compound A are bonded through a block structure of ethylene oxide. Furthermore, PO represents propylene oxide, and the term "PO-modified compound B" refers to a compound in which the (meth)acrylate residues and alcohol residues of compound B are bonded through a block structure of propylene oxide.

[0026] Specific examples of styrene compounds include, but are not limited to, the following.

[0027] Styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene, etc., alkylstyrene; fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, Halogenated styrene such as dibromostyrene and iodostyrene; compounds having a styrene group as a polymerizable functional group, such as nitrostyrene, acetyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl. Specific examples of vinyl compounds are given below, but are not limited to these.

[0028] Vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate and acrylonitrile; conjugated diene monomers such as butadiene, isoprene and chloroprene; ethylene halogenates such as vinyl chloride and vinyl bromide; vinyl halogenates such as vinylidene chloride; vinyl esters and their derivatives of organic carboxylic acids (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc., (meth)acrylonitrile, etc., compounds having vinyl groups as polymerizable functional groups. Furthermore, in this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0029] Examples of allyl compounds include, but are not limited to, the following.

[0030] Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate. Examples of fumaric acid compounds include, but are not limited to, the following.

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

[0032] Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-dibutyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate. Other examples of free radical polymerizable compounds include, but are not limited to, the following.

[0033] Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconic acid, diethyl itaconic acid, diisopropyl itaconic acid, di-dibutyl itaconic acid, diisobutyl itaconic acid, di-n-butyl itaconic acid, di-2-ethylhexyl itaconic acid, dibenzyl itaconic acid, etc.), N-vinylacetamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimide and its derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.). When component (a) is composed of a plurality of compounds having one or more polymerizable functional groups, it is preferable to include monofunctional compounds and polyfunctional compounds. This is because by combining monofunctional compounds and polyfunctional compounds, a well-balanced and excellent hardened film with high mechanical strength, high dry etching resistance, and high heat resistance can be obtained.

[0034] Since the polymerizable compound (a) is preferably low in volatility, it may contain a plurality of compounds. The boiling point of the polymerizable compound (a) at normal pressure is preferably all above 250°C, more preferably all above 300°C, and even more preferably all above 350°C. The boiling point of the polymerizable compound (a) is approximately related to its molecular weight. Therefore, the polymerizable compound (a) is preferably all above 200, more preferably all above 240, and even more preferably all above 250. However, even if the molecular weight is below 200, if the boiling point is above 250°C, it can still be preferably used as the polymerizable compound (a) of the present invention.

[0035] Furthermore, the vapor pressure of the polymeric compound (a) at 80°C is preferably 0.001 mmHg or higher. The reason for this is that heating is preferred to accelerate the volatilization of the solvent (d) described later, but heating inhibits the volatilization of the polymeric compound (a).

[0036] Furthermore, the boiling point and vapor pressure of various organic compounds under normal pressure can be calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th edition, 5.3.04, etc.

[0037] Examples of polymeric compounds (a) having a boiling point of 250°C or higher include the following, but are not limited to these.

[0038] Dicyclopentyl acrylate (boiling point 262℃, molecular weight 206), Dicyclopentenyl acrylate (boiling point 270℃, molecular weight 204), 1,3-cyclohexanediethanol diacrylate (boiling point 310℃, molecular weight 252), 1,4-cyclohexanediethanol diacrylate (boiling point 339℃, molecular weight 252), 4-hexylresorcinol diacrylate (boiling point 379℃, molecular weight 302), 6-phenylhexane-1,2-diol diacrylate (boiling point 381℃, molecular weight 302), 7-phenylheptane-1,2-diol diacrylate (boiling point 393℃, molecular weight 316), 1,3-bis((2-hydroxyethoxy)methyl)cyclohexanediacrylate (boiling point 403℃, molecular weight 340), 8-phenyloctane-1,2-diol diacrylate (boiling point 404℃, molecular weight 330) 1,3-Bis((2-hydroxyethoxy)methyl)phenyl diacrylate (boiling point 408℃, molecular weight 334), 1,4-Bis((2-hydroxyethoxy)methyl)cyclohexane diacrylate (boiling point 445℃, molecular weight 340), 3-phenoxybenzyl acrylate (mPhOBzA, OP2.54, boiling point 367.4℃, vapor pressure at 80℃ 0.0004mmHg, molecular weight 254.3),

[0039]

[0040] 1-Naphthalene acrylate (NaA, OP 2.27, boiling point 317℃, vapor pressure at 80℃ 0.0422 mmHg, molecular weight 198),

[0041]

[0042] 2-Phenylenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2℃, vapor pressure at 80℃ 0.0006mmHg, molecular weight 268.3)

[0043]

[0044] 1-Naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1℃, vapor pressure at 80℃ 0.042mmHg, molecular weight 212.2)

[0045]

[0046] 2-Naphthylmethyl acrylate (Na2MA, OP2.33, boiling point 342.1℃, vapor pressure at 80℃ 0.042mmHg, molecular weight 212.2)

[0047]

[0048] 4-Cyanobenzyl acrylate (CNBzA, OP2.44, boiling point 316℃, molecular weight 187),

[0049]

[0050] DVBzA (OP2.50, boiling point 304.6℃, vapor pressure at 80℃ 0.0848 mmHg, molecular weight 214.3) as shown in the following formula.

[0051]

[0052] DPhPA (OP 2.38, boiling point 354.5℃, vapor pressure at 80℃ 0.0022 mmHg, molecular weight 266.3) as shown in the following formula.

[0053]

[0054] PhBzA (OP 2.29, boiling point 350.4℃, vapor pressure at 80℃ 0.0022 mmHg, molecular weight 238.3) as shown in the following formula.

[0055]

[0056] FLMA (OP 2.20, boiling point 349.3℃, vapor pressure at 80℃ 0.0018 mmHg, molecular weight 250.3) as shown in the following formula.

[0057]

[0058] ATMA (OP 2.13, boiling point 414.9℃, vapor pressure at 80℃ 0.0001 mmHg, molecular weight 262.3) as shown in the following formula.

[0059]

[0060] DNaMA (OP 2.00, boiling point 489.4℃, vapor pressure at 80℃ < 0.0001 mmHg, molecular weight 338.4) as shown in the following formula.

[0061]

[0062] Tricyclodecanediethanol diacrylate (DCPDA, OP 3.29, boiling point 342℃, vapor pressure at 80℃ 0.0024mmHg, molecular weight 304)

[0063]

[0064] m-xylene diacrylate (mXDA, OP 3.20, boiling point 336℃, vapor pressure at 80℃ 0.0043mmHg, molecular weight 246)

[0065]

[0066] 1-Phenylacetyl ether-1,2-diester (PhEDA, OP 3.20, vapor pressure at 80℃ 0.0057 mmHg, boiling point 354℃, molecular weight 246)

[0067]

[0068] 2-Phenylon-1,3-propanediol diacrylate (PhPDA, OP 3.18, boiling point 340℃, vapor pressure at 80℃ 0.0017mmHg, molecular weight 260)

[0069]

[0070] VmXDA (OP 3.00, boiling point 372.4℃, vapor pressure at 80℃ 0.0005mmHg, molecular weight 272.3) as shown in the following formula.

[0071]

[0072] BPh44DA (OP 2.63, boiling point 444℃, vapor pressure at 80℃ < 0.0001 mmHg, molecular weight 322.3) as shown in the following formula.

[0073]

[0074] BPh43DA (OP 2.63, boiling point 439.5℃, vapor pressure at 80℃ < 0.0001 mmHg, molecular weight 322.3) as shown in the following formula.

[0075]

[0076] DPhEDA as shown in the following formula (OP 2.63, boiling point 410℃, vapor pressure at 80℃ < 0.0001 mmHg, molecular weight 322.3).

[0077]

[0078] BPMDA as shown in the following formula (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ < 0.0001 mmHg, molecular weight 364.4).

[0079]

[0080] Na13MDA as shown in the following formula (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ < 0.0001 mmHg, molecular weight 296.3).

[0081]

[0082] The proportion of component (a) in the curing composition (A), relative to the total mass of component (a), component (b) and component (c) described later, i.e., the total mass of all components excluding solvent (d), is preferably 40% by weight or more and 99% by weight or less. More preferably, it is 50% by weight or more and 95% by weight or less, and even more preferably, it is 60% by weight or more and 90% by weight or less. By setting the proportion of component (a) to 40% by weight or more, the mechanical strength of the cured film of the curing composition is increased. Furthermore, by setting the proportion of component (a) to 99% by weight or less, the proportions of components (b) and (c) can be increased, resulting in characteristics such as a rapid photopolymerization rate.

[0083] <Component (b): Photopolymerization Initiator> Component (b) is a photopolymerization initiator. The photopolymerization initiator in this specification is a compound that senses light of a specific wavelength and generates the aforementioned polymerization factors (free radicals). Specifically, the photopolymerization initiator is a polymerization initiator (free radical generator) that generates free radicals by means of light (infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams such as electron beams, radiation, etc.). Component (b) may consist of one photopolymerization initiator or multiple photopolymerization initiators.

[0084] Examples of free radical generating agents include, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazolium dimer, and other 2,4,5-triarylimidazolium dimers that may have substituents; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Mischel ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone Benzyl derivatives such as 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one; 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, 2,3- Quinones such as 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-phenylacridinium and 1,7-bis(9,9'-acridyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanone derivatives such as thioxanone, diethylthioxanone, 2-isopropylthioxanone, and 2-chlorothioxanone; 2,4,6-trimethylbenzoyldimethyl ketal. Phosphorus oxide derivatives such as phenylphosphine 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)]-ethyl ketone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetylgoxime); xanthone, genistein, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1-one, but not limited to these.

[0085] Examples of commercially available free radical generating agents include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO, LR8893, LR8970 (all manufactured by BASF), YUBECRYL P36 (manufactured by UCB), etc., but are not limited to these.

[0086] In these examples, component (b) is preferably a phosphine oxide polymerization initiator. Furthermore, in the above example, the phosphine oxide polymerization initiator is a phosphine oxide compound such as 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, or bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide.

[0087] The proportion of component (b) in the curing composition (A), relative to the total mass of components (a), (b), and (c) described later, i.e., the total mass of all components excluding solvent component (d), is preferably 0.1% by mass to 50% by mass, more preferably 0.1% by mass to 20% by mass, and even more preferably 1% by mass to 20% by mass. By setting the proportion of component (b) to 0.1% by mass or more, the curing speed of the composition can be accelerated, resulting in good reaction efficiency; by setting it to 50% by mass or less, the resulting cured film can become a cured film with a certain degree of mechanical strength.

[0088] <Component (c): Non-polymerizable compound> The curing composition (A) of this embodiment, in addition to the aforementioned components (a) and (b), may further contain a non-polymerizable compound as component (c) for various purposes, without impairing the effects of this embodiment. Examples of such components (c) are compounds that do not have polymerizable functional groups such as (meth)acrylic acid groups and do not have the ability to generate the aforementioned polymerization factors (free radicals) by sensing light of a specific wavelength. Examples include, for instance, sensitizers, hydrogen donors, internally added mold release agents, antioxidants, polymer components, and other additives. Component (c) may also contain a plurality of the aforementioned compounds.

[0089] A sensitizer is a compound that is appropriately added to promote polymerization reactions or increase reaction conversion rates. A sensitizer may be used alone or in combination with two or more other sensitizers.

[0090] Examples of sensitizers include, for example, sensitizing pigments. Sensitizing pigments are compounds that are excited by absorbing light of a specific wavelength and interact with the photopolymerization initiator of component (b).

[0091] Furthermore, the interaction described here refers to the energy transfer or electron transfer of the self-excited sensitizing pigment toward the photopolymerization initiator of component (b). Specific examples of sensitizing pigments include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xantonone derivatives, coumarin derivatives, phenazine derivatives, camphorquinone derivatives, acridine pigments, thiopyridinium salt pigments, anthocyanin pigments, quinoline pigments, styrene-quinoline pigments, ketocumarin pigments, thioxanthracene pigments, oxanthracene pigments, oxonol pigments, cyanin pigments, rhodamine pigments, pyridinium salt pigments, etc., but are not limited to these.

[0092] The hydrogen-donating system reacts with the initiating free radicals or free radicals at the polymerization growth ends generated by the photopolymerization initiator of component (b) to produce compounds with higher reactivity of free radicals. It is preferable to add the photopolymerization initiator of component (b) when it is a photofree radical generator.

[0093] Specific examples of such hydrogen donors include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allyl thiourea, S-benzylisosylurea-p-toluenesulfonate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethanolamine, N-phenylglycine, and other amine compounds, as well as thiol compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate, but are not limited to these. A single hydrogen donor may be used, or two or more may be mixed. Furthermore, the hydrogen donor may also function as a sensitizer.

[0094] To reduce the interfacial bonding force between the mold and the hardened component, i.e., to reduce the demolding force in the demolding step described later, an internally added mold release agent can be added to the hardened component. In this specification, "internally added" means added to the hardened component before the preparation step. As an internally added mold release agent, surfactants such as polysiloxane surfactants, fluorinated surfactants, and hydrocarbon surfactants can be used. However, as described later in this embodiment, the amount of fluorinated surfactant added is limited. Furthermore, the internally added mold release agent in this embodiment does not have polymerizability. An internally added mold release agent can be used alone or in combination with two or more other agents.

[0095] Fluorinated surfactants include adducts of polyoxyethylene (polyethylene oxide, polypropylene oxide, etc.) alcohols having perfluoroalkyl groups, and adducts of polyoxyethylene (polyethylene oxide, polypropylene oxide, etc.) polyethers having perfluoroalkyl groups. Furthermore, fluorinated surfactants may also have hydroxyl, alkoxy, alkyl, amino, or thiol groups in a portion of their molecular structure (e.g., a terminal group). Examples include pentadecyl glycol mono-1H,1H,2H,2H-perfluorooctyl ether.

[0096] Commercially available products can be used as fluorinated surfactants. Examples of commercially available products include: MEGAFAC (registered trademark) F-444, TF-2066, TF-2067, TF-2068, abbreviated as DEO-15 (all manufactured by DIC), FLUORAD FC-430, FC-431 (all manufactured by Sumitomo 3M), SURFLON (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by TOHKEN PRODUCTS), PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA Solutions), UNIDYNE (registered trademark) DS-401, DS-403, DS-451 (all manufactured by Daikin Industries), and FTERGENT (registered trademark). 250, 251, 222F, 208G (the above are NEOS models), etc.

[0097] Furthermore, the internally added release agent can also be a hydrocarbon-based surfactant. Hydrocarbon-based surfactants include, for example, alkyl alcohol polyepoxide adducts or polyepoxides formed by adding 2-4 carbon alkylene oxides to alkanols having 1-50 carbon atoms.

[0098] Examples of alkyl alcohol polyepoxide adducts include methanol ethylene oxide adducts, decanol ethylene oxide adducts, lauryl ethylene oxide adducts, cetyl ethylene oxide adducts, stearyl ethylene oxide adducts, and stearyl ethylene oxide / propylene oxide adducts. Furthermore, the terminal group of the alkyl alcohol polyepoxide adduct is not limited to the hydroxyl group, which can be produced by simply adding alkyl alcohols to polyepoxides. This hydroxyl group can also be replaced by other substituents, such as polar functional groups like carboxyl, amino, pyridyl, thiol, and silanol groups, or hydrophobic functional groups like alkyl and alkoxy groups.

[0099] Examples of polyepoxides include polyethylene glycol, polypropylene glycol, mono- or dimethyl ether, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monoadipate, monooleate, monostearate, monosuccinate, etc.

[0100] Alkyl alcohol polyoxyethylene adducts can also be used as commercially available products. Examples of commercially available products include polyoxyethylene methyl ether (methanol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Oils & Fats Industry; polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Oils & Fats Industry; polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oils & Fats Industry; polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Oils & Fats Industry; and polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON) manufactured by Aoki Oils & Fats Industry. Examples of polyoxyethylene stearyl ethers include SR-705, SR-707, SR-715, SR-720, SR-730, and SR-750; random polymerized polyoxyethylene and polyoxypropylene stearyl ethers (BLAUNON SA-50 / 50, 1000R, SA-30 / 70, and 2000R) manufactured by Aoki Oils & Fats Co., Ltd.; polyoxyethylene methyl ethers (Pluriol (registered trademark) A760E) manufactured by BASF; and polyoxyethylene alkyl ethers (EMULGEN series) manufactured by Kao Corporation. Commercially available polyoxyethylene ethers can also be used, such as ethylene oxide-propylene oxide copolymers (Pluronic PE6400) manufactured by BASF.

[0101] Fluorinated surfactants are effective as internal release agents because they exhibit excellent mold release force reduction effects. The proportion of component (c) excluding the fluorinated surfactant in the curing composition, relative to the total mass of components (a), (b), and (c), i.e., the total mass of all components excluding the solvent, is preferably 0% to 50% by mass. More preferably, it is 0.1% to 50% by mass, and even more preferably, it is 0.1% to 20% by mass. By setting the proportion of component (c) excluding the fluorinated surfactant to 50% by mass or less, the resulting cured film can be a cured film with a certain degree of mechanical strength.

[0102] <Component (d): Solvent> The curable composition of this embodiment may contain a solvent as component (d). There are no particular limitations on whether component (d) is a solvent capable of dissolving components (a), (b), and (c). A preferred solvent is one with a boiling point of 80°C to 200°C at normal pressure. Examples include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. Component (d) may be used alone or in combination of two or more.

[0103] Examples of alcohol-based solvents include the following: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, dibutanol, tributanol, n-pentanol, isopentanol, 2-methylbutanol, dipentanol, tripentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, dihexanol, 2-ethylbutanol, diheptanol, 3-heptanol, n-octanol, 2-ethylhexanol, dioctanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, di-undecanol, trimethylnonanol, di-tetradecanol, di- Monool solvents such as heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbitol, diacetone alcohol, and cresol; polyol 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. Examples of ketone solvents include the following.

[0104] Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonitrile acetone, diacetone alcohol, acetophenone, and fenchone. Examples of ether solvents include the following.

[0105] Diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxane, 4-methyldioxane, 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 monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, ethoxytriethylene glycol, tetraethylene glycol dibutyl ether, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran. Examples of ester solvents include the following.

[0106] Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-pentyl acetate, dipentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethyl acetate Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetyl glycol, diacetyl glycol, methoxytriethylene glycol, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate. Examples of nitrogen-containing solvents include the following.

[0107] N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionic acid, N-methylpyrrolidone. Among the above solvents, ether-based solvents and ester-based solvents are preferred. Furthermore, from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a diol structure are preferred examples.

[0108] Moreover, as a better alternative, the following are examples.

[0109] Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether.

[0110] <Temperature during preparation of the curing composition> When preparing the curing composition (A) of this embodiment, components (a) and (b) are mixed and dissolved at least under specific temperature conditions. Specifically, this is carried out in a temperature range of 0°C to 100°C. The same applies when components (c) and (d) are present.

[0111] <Viscosity of the curing composition> The curing composition (A) in this embodiment is preferably a liquid. The reason is that in the mold contact step described later, the expansion and filling of the curing composition (A) can be completed quickly, that is, the filling time is shortened.

[0112] <Phase of the curing composition> The curing composition (A) of the present invention is a liquid. The reason is that in the preparation steps described later, droplets of the curing composition (A) are prepared on the substrate by inkjet printing or spin coating.

[0113] When using inkjet printing in the configuration steps of the present invention, the curing composition (A) can be a solvent-free curing composition (AJ1) or a solvent-containing curing composition (AJ2).

[0114] The viscosity of the hardening component (AJ1) is 2 mPa·s or more and 60 mPa·s or less, preferably 5 mPa·s or more and 30 mPa·s or less, and even more preferably 5 mPa·s or more and 15 mPa·s or less.

[0115] The viscosity of the curing composition (AJ2), in the state containing solvent (d), is 2 mPa·s or more and 60 mPa·s or less, preferably 5 mPa·s or more and 30 mPa·s or less, and even more preferably 5 mPa·s or more and 15 mPa·s or less. In the state after the solvent (d) has evaporated from the curing composition (AJ2), that is, the viscosity of the curing composition (AJ2) after removing the solvent (d) at 25°C is 1 mPa·s or more and 10,000 mPa·s or less, preferably 30 mPa·s or more and 1,000 mPa·s or less, even more preferably 30 mPa·s or more and 500 mPa·s or less, and even more preferably 120 mPa·s or more and 500 mPa·s or less.

[0116] When the viscosity of the curable composition (AJ1) or the curable composition containing solvent (d) (AJ2) is less than 2 mPa·s, the ejection properties of the droplets using the inkjet method become unstable. Furthermore, when the viscosity is greater than 60 mPa·s, it is impossible to form droplets with a volume of approximately 1.0 to 3.0 pL, which is preferred in this invention.

[0117] By setting the viscosity of the components of the curing composition (AJ2) excluding the solvent (d) to 1000 mPa·s or less, expansion and filling are completed quickly when the curing composition (AJ2) comes into contact with the mold. Therefore, by using the curing composition (AJ2) of the present invention, imprinting can be performed at high throughput and pattern defects caused by poor filling can be suppressed. Furthermore, by setting the viscosity of the components of the curing composition (AJ2) excluding the solvent (d) to 1 mPa·s or more, unnecessary flow of droplets of the curing composition (A) after the solvent (d) evaporates can be prevented. In addition, when the curing composition (AJ2) comes into contact with the mold, the curing composition (AJ2) is less likely to flow out from the end of the mold.

[0118] The viscosity of the curable composition (AS) used in the spin coating method in the preparation steps of the present invention, in the state containing solvent (d), is 1 mPa·s or more and 100 mPa·s or less. The viscosity of the mixture of components other than solvent (d) of the curable composition (AS) after the solvent (d) has evaporated is 1 mPa·s or more and 10,000 mPa·s or less, preferably 30 mPa·s or more and 1,000 mPa·s or less, more preferably 30 mPa·s or more and 500 mPa·s or less, and even more preferably 120 mPa·s or more and 500 mPa·s or less.

[0119] By setting the viscosity of the components of the curable composition (AS) excluding the solvent (d) to 10,000 mPa·s or less, filling is completed quickly when the curable composition (AS) comes into contact with the mold. Therefore, by using the curable composition (AS) of the present invention, imprinting can be performed at high throughput and pattern defects caused by poor filling can be suppressed. Furthermore, by setting the viscosity of the components of the curable composition (AS) excluding the solvent (d) to 1 mPa·s or more, unnecessary flow of droplets of the curable composition (AS) after the solvent (d) evaporates can be prevented. Consequently, when the curable composition (AS) comes into contact with the mold, the curable composition (AS) is less likely to flow out from the mold end.

[0120] <Surface Tension of the Curable Composition> The surface tension of the curable composition (A) in this embodiment, for the composition excluding the solvent (component (d)), is preferably 5 mN / m or more and 70 mN / m or less at 23°C. More preferably, it is 7 mN / m or more and 50 mN / m or less, and even more preferably, it is 10 mN / m or more and 40 mN / m or less. Here, the higher the surface tension, for example, 5 mN / m or more, the stronger the capillary force, so when the curable composition (A) comes into contact with the mold, the filling (expansion and filling) can be completed in a short time. Furthermore, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition becomes a cured film with a smooth surface.

[0121] <Contact Angle of the Curable Composition> The contact angle of the curable composition (A) in this embodiment refers to the composition containing components other than the solvent (component (d)). It is preferably 0˚ to 90˚ and particularly preferably 0˚ to 10˚ for both the substrate surface and the mold surface. When the contact angle is greater than 90˚, capillary forces act in the negative direction (the direction that causes the contact interface between the mold and the curable composition to contract) within the mold pattern and the gap between the substrate and the mold, and there is a possibility that filling may not be possible. The smaller the contact angle, the stronger the capillary force, and therefore the faster the filling speed.

[0122] <Impurities mixed into the curing composition> The curing composition (A) of this embodiment is preferably free of impurities as much as possible. The impurities described herein refer to those other than the aforementioned components (a), (b), (c), and (d). Therefore, the curing composition of this embodiment is preferably obtained through a purification step. As such a purification step, filtration using a filter is preferred.

[0123] When performing filtration using a filter, specifically, the aforementioned components (a), (b), and (c) are mixed and then preferably filtered using a filter with a pore size of 0.001 μm to 5.0 μm. Filtration using a filter is preferably performed in multiple stages or repeated several times. Furthermore, the filtered liquid can be filtered again. Filtration can also be performed using filters with different pore sizes. Filters used for filtration can be made of polyethylene resin, polypropylene resin, fluoropolymer resin, nylon resin, etc., but are not particularly limited. Through these purification steps, impurities such as particles mixed into the curing composition can be removed. This prevents the hardened film obtained after the curing composition has hardened from unexpectedly developing unevenness and pattern defects due to impurities such as particles.

[0124] Furthermore, when the curable composition of this embodiment is used in the manufacture of semiconductor integrated circuits, in order not to hinder the operation of the product, it is preferable to avoid the introduction of impurities containing metal atoms (metal impurities) into the curable composition. In such cases, the concentration of metal impurities contained in the curable composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0125] [Substrate (Base Material)] The substrate that is the object to which the curable composition (A) is disposed is the substrate to be processed, and silicon wafers are typically used. The substrate may have a processed layer on its outermost layer. Examples of processed layers are insulating layers containing at least silicon atoms, such as SiO2 layers. Other layers may be formed on the substrate below the processed layer. Furthermore, if a quartz substrate is used as the substrate, a replica of a quartz embossing mold (mold replica) can be made. However, the substrate is not limited to silicon wafers or quartz substrates. The substrate may be selected arbitrarily from those known as substrates for semiconductor devices, such as aluminum, titanium-tungsten alloys, aluminum-silicon alloys, aluminum-copper-silicon alloys, silicon oxide, and silicon nitride. In addition, the surface of the substrate or the processed layer may be improved to enhance adhesion to the curable composition (A) by surface treatments such as silane coupling treatment, silazane treatment, or organic thin film formation. As a specific example of the aforementioned organic thin film formed by surface treatment, the adhesion layer described in Patent Document 3 can be used, for example.

[0126] [Membrane Formation Method] Next, the membrane formation method of this embodiment will be described using the cross-sectional schematic diagram in FIG1. ​​Furthermore, the numbers 1 to 4 in FIG1 will be represented hereinafter as [1], [2], [3], and [4]. The membrane formation method of this embodiment can also be implemented as a method for forming a patterned membrane (pattern formation method), or as a method for forming a non-patterned membrane (e.g., a planarization membrane) (planarization membrane formation method).

[0127] The film formed in this embodiment as a pattern forming method is preferably a film with a pattern size of 1 nm to 10 mm on its surface, and more preferably a film with a pattern size of 10 nm to 100 μm. Furthermore, the pattern forming technique that generally utilizes light to manufacture films with nanoscale patterns (uneven structures) is called photoimprint lithography. Although the film forming method of this embodiment utilizes photoimprint lithography, the curable component (A) can also be cured by other energies (e.g., heat, electromagnetic waves).

[0128] In this embodiment, the planarization film formed as a planarization film formation method preferably has a surface elevation difference of 8 nm or less.

[0129] The film forming method includes, for example, a placement step of placing a curable composition on a substrate; a contact step of bringing the curable composition into contact with a film forming region of a mold; a curing step of curing the curable composition; and a separation step of separating the curable composition from the mold. The contact step is performed after the placement step, the curing step is performed after the contact step, and the separation step is performed after the curing step. The film forming region is the region that is slowest to come into contact with the curable composition at the beginning of the curing step. When this embodiment is implemented as a pattern forming method, the film forming region has a pattern. When this embodiment is implemented as a planarization film forming method, the film forming region has a flat surface.

[0130] <Configuration Steps [1]> The configuration steps are schematically shown in Figure 1[1], in which the curable component (A) 102 is configured on the substrate 101.

[0131] When this embodiment is implemented as a pattern forming method, inkjet printing or spin coating is preferred as the placement method. When using the inkjet printing placement step, droplets of the curable component (A) 102 are discretely placed. FIG1 illustrates an inkjet printing method as a representative example. In the schematic example shown in FIG1, the entire underside of the mold 107 is the film-forming area. The droplets of the curable component (A) 102 are preferably placed more densely on the area of ​​the substrate 101 opposite to the area where the recesses constituting the pattern of the mold 107 are more densely distributed, and less densely distributed on the area of ​​the substrate 101 opposite to the area where the recesses are less densely distributed. In this way, the residual film 110, described later, can be controlled to a uniform thickness regardless of the pattern of the mold 107.

[0132] In this embodiment, when implementing a method for forming a planarization film on a substrate 101 with an uneven surface, inkjet printing is preferred as the placement method. Preferably, droplets of the curable composition (A) 102 are more densely distributed in the recesses of the substrate 101 and more sparsely distributed in the protrusions. This allows the formation of a planarization film with a smaller elevation difference than the surface of the substrate 101.

[0133] When using inkjet printing in the preparation step, in order to specify the volume of the curable component (A) to be prepared, an index for the average liquid film thickness is defined as shown in Figure 2. The average liquid film thickness is obtained by dividing the volume of the curable component (A) (excluding solvent (d)) prepared in the preparation step by the area of ​​the film-forming region of the mold. The volume of the curable component (A) (excluding solvent (d)) is the sum of the volumes of each droplet of the curable component (A) (excluding solvent (d)). According to this definition, even if there are unevenness on the substrate surface, the average liquid film thickness can be defined regardless of the unevenness.

[0134] In this embodiment, when a curable composition containing solvent (d) such as curable composition (AJ2) or (AS) is used, a baking step of heating the substrate 101 and the curable composition (A) can be performed after the preparation step and before the contact step to accelerate the evaporation of the solvent (d), or the ambient gas around the substrate 101 can be ventilated. Heating is performed, for example, at 30°C to 200°C, preferably at 80°C to 150°C, and particularly preferably at 90°C to 110°C. The heating time can be 10 seconds to 3000 seconds. The baking step can be performed using known heaters such as heating plates or ovens.

[0135] <Contact Step [2]> In the contact step, as schematically shown in FIG1[3], the curable composition (A) 102 is brought into contact with the film-forming area of ​​the mold 107. The contact step includes a step of changing from a state in which the curable composition (A) 102 and the film-forming area of ​​the mold 107 are not in contact to a state in which the two are in contact, and a step of maintaining the state in which the two are in contact. Thereby, when this embodiment is implemented as a pattern forming method, the curable composition (A) fills 106 into the recess of the micro-pattern of the film-forming area on the surface of the mold 107, and the liquid fills the micro-pattern of the mold 107.

[0136] As mold 107, when the next hardening step includes a light irradiation step, a mold made of a light-transmitting material is used with this in mind. Specifically, the materials constituting mold 107 are preferably glass-based materials such as soda lime glass, borosilicate glass, alkali barium silicate glass, aluminate silicate glass, synthetic quartz, fused silica, PMMA, polycarbonate resin, fluoropolymers, polydimethylsiloxane, transparent resins, transparent metal vapor-deposited films, or materials composed of two or more of these materials. However, when using a light-transmitting resin as the material constituting mold 107, a resin that is insoluble in the components contained in the hardening composition (A) must be selected. Quartz is particularly preferred as the material constituting mold 107 because it has a small coefficient of thermal expansion and small pattern deformation.

[0137] When this embodiment is implemented as a pattern forming method, the fine pattern on the surface of the film forming area of ​​the mold 107 has a height of, for example, 4 nm to 200 nm. The lower the height of the pattern, the smaller the force that pulls the hardened film of the hardened composition away from the mold 106 during the separation step, i.e., the demolding force, and the fewer demolding defects that remain on the mold 107 side due to the pattern of the hardened composition (A) being torn off during the separation step. Due to the impact when pulling away from the mold 106, the pattern of the hardened composition (A) elastically deforms, which may cause adjacent pattern elements to come into contact with each other, resulting in fusion or breakage. However, it is advantageous to avoid such defects when the height of the pattern element is about twice or less (aspect ratio of 2 or less) relative to the width of the pattern element. On the other hand, when the height of the pattern element is too low, the processing accuracy of the substrate 101 is lower, and the processing depth becomes shallower.

[0138] When this embodiment is implemented as a planarization film formation method, the unevenness of the surface of the film formation area of ​​the mold 107 is preferably less than 4 nm. After the contact step of contacting the film formation area of ​​the mold 107 with the curable component, a curing step [4] and a separation step [5] are performed to form a curable film having a surface that simulates the flat surface of the mold 107.

[0139] To improve the peelability of the self-curing composition (A) 102 on the surface of mold 107 in the film-forming area of ​​mold 107, surface treatment may be performed before the contact step. An example of a surface treatment method is to apply a release agent to the surface of the film-forming area of ​​mold 107 to form a release agent layer. Examples of release agents applied to the surface of mold 107 include polysiloxane-based release agents, fluorinated release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, lignite-based release agents, and carnauba wax-based release agents. Commercially available coating-type release agents such as OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd., may also be appropriately used. Furthermore, a single release agent may be used, or two or more may be used in combination. Among these, fluorinated and hydrocarbon-based release agents are particularly preferred.

[0140] During the contact step, when the film-forming area of ​​the mold 107 comes into contact with the curable composition (A) 102, the pressure applied to the curable composition (A) 102 is not particularly limited. This pressure can be, for example, 0 MPa or more and 100 MPa or less. More preferably, this pressure is 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0141] In the contact step, for example, the contact is carried out under conditions where a gas (hereinafter referred to as interstitial gas) exists in the space between the substrate 101 and the mold 107, and the solubility coefficient of the interstitial gas for the curable component (A) 102 is 0.5 kg / m³·atm or more and 10 kg / m³·atm or less. Here, if the solubility coefficient is greater than 10 kg / m³·atm, the dry etching resistance and / or mechanical strength of the curable film 109 may decrease.

[0142] Furthermore, when the solubility coefficient of the gas in the interstitial space for the hardening composition (A) 102 is set as S [kg / m³·atm], the diffusion coefficient of the gas in the interstitial space of the hardening composition (A) 102 is set as D [m² / s], and the average liquid film thickness is set as T [nm], it is preferable that S‧D‧T is 1.75 × 10⁻⁹ or more and S is 10 or less. Here, S is preferably 0.5 or more. D is preferably 5 × 10⁻¹² or more and 1 × 10⁻⁸ or less. The method for calculating S and D will be described later.

[0143] Specific examples of gases used in the gap include, for example, carbon dioxide, methane, various fluorocarbon gases, or mixtures of two or more of these gases. Mixtures of carbon dioxide, methane, various chlorocarbon gases, or two or more of these gases can also be used with gases with low solubility coefficients, such as nitrogen, oxygen, helium, and argon. When using a mixed gas, the diffusion coefficient and solubility coefficient of the mixed gas can be calculated as a weighted average based on the molar ratio of each gas. The contact step is performed, for example, at a pressure between 0.0001 atm and 10 atm. The diffusion coefficients and solubility coefficients of the aforementioned gases for the hardening component (A) will be described later.

[0144] <Curing Step [3]> The curing step is as shown in Figure 1[3], in which the curable component (A) 102 is irradiated with light 108, which is the energy for curing, to form a curable film. In the curing step, for example, the layer of the curable component (A) 102 is irradiated with light through the mold 107. More specifically, the curable component (A) filled in the micro-pattern of the mold 107 is irradiated with light through the mold 107. Thereby, the curable component (A) 102 filled in the micro-pattern of the mold 107 is cured to form a curable film 109.

[0145] Here, the irradiating light 108 can be selected according to the sensitivity wavelength of the curing component (A) 102. Specifically, the light 108 can be appropriately selected from ultraviolet light, X-rays, or electron beams with wavelengths between 150 nm and 400 nm. Among these, ultraviolet light is particularly preferred. This is because most commercially available curing aids (photopolymerization initiators) are compounds sensitive to ultraviolet light. Examples of light sources emitting ultraviolet light include, for example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, F2 excimer lasers, etc., but ultra-high-pressure mercury lamps are particularly preferred. The number of light sources used can be one or more. Furthermore, the light irradiation can be performed on the entire area of ​​the curing component (A) filled in the micro-pattern of the mold, or it can be limited to only a portion of the area. Furthermore, light irradiation can be performed intermittently or continuously over the entire substrate. In addition, light can be irradiated onto the first region during the first irradiation process, and onto a second region that is different from the first region during the second irradiation process.

[0146] <Separation Step [4]> The separation step is schematically shown in Figure 1[4], in which the hardened film 109 is pulled away from the mold 107. For example, by pulling the hardened film 109 away from the mold 107, the hardened film 109 with the fine pattern of the mold 107 is reversed and obtained in a self-supporting state. Here, the hardened film 109 also remains in the recess of the hardened film 109 with the pattern. This film is called residual film 110.

[0147] As a method for separating the hardened film 109 from the mold 107, any method is acceptable as long as no part of the hardened film 109 is physically damaged during separation, and there are no particular restrictions on various conditions. For example, the substrate 101 can be fixed and the mold 107 can be moved away from the substrate 101. Alternatively, the mold 107 can be fixed and the substrate 101 can be moved away from the mold 107. Or, the two can be peeled off by pulling them in opposite directions.

[0148] In the pattern forming method of one embodiment of this invention, the repeating units (processes (shots)) formed by steps [1] to [4] can be repeated multiple times on the same substrate. Furthermore, step [1] can be performed multiple times continuously in different areas, and the processes formed by steps [2] to [4] can be performed continuously on areas where only step [1] has been performed. When spin coating is used as the application method, step [1] can be performed on the entire substrate, and the processes formed by steps [2] to [4] can be repeated multiple times on the same substrate. The aforementioned processes can be repeated multiple times, and multiple desired hardened films 109 can be obtained at the desired locations on the substrate.

[0149] The planarization film formation method of one embodiment of this invention can repeat the repetitive units (processes) formed by steps [1] to [4] multiple times on the same substrate. Furthermore, step [1] can be performed multiple times continuously in different areas, and the process formed by steps [2] to [4] can be performed continuously on areas where only step [1] has been performed. When spin coating is used as the application method, step [1] can be performed on the entire substrate, and the process formed by steps [2] to [4] can be repeated multiple times on the same substrate. The aforementioned process can be repeated multiple times, and a planar hardened film 109 with a flat surface having a simulated mold 107 can be obtained at the desired location on the substrate.

[0150] *Manufacturing Method of Circuit Board, Electronic Components, and Optical Machines* Using a hardened film 109 having a pattern formed according to one embodiment of this method as a mask, a substrate 101 (which is the processed layer if the substrate 101 has a processed layer) can be processed using a processing method such as etching. Furthermore, after forming the processed layer on the hardened film 109 having the pattern, pattern transfer can be performed using a processing method such as etching. Thus, a fine structure such as a circuit structure can be formed on the substrate 101 using the hardened film 109 having the pattern. Based on the fine structure formed on the substrate 101, articles can be manufactured. Devices containing such articles, such as displays, cameras, medical devices, etc., can also be formed. The term "article" refers to circuit elements, MEMS, recording elements, sensors, or molds, etc. Examples of circuit elements include volatile or non-volatile semiconductor memories such as SRAM, DRAM, MRAM, SDRAM, RDRAM, D-RDRAM, and flash memory, as well as semiconductor components such as LSI, system LSI, CCD, image sensors, and FPGAs. Examples of MEMS include DMD, microfluidic circuits, and electromechanical conversion components. Examples of sensors include magnetic sensors, light sensors, and gyroscope sensors. Examples of recording elements include optical discs such as CDs and DVDs, magnetic disks, magneto-optical disks, and magnetic heads. Examples of molds include embossing molds.

[0151] Furthermore, it is also possible to obtain an optical component that utilizes the patterned hardened film 109 as an optical component (including the case where it is used as part of an optical component). In this case, an optical component having at least a substrate 101 and a patterned hardened film 109 on the substrate 101 can be manufactured. Examples of optical components include, for example, microlenses, light guides, waveguides, antireflective films, diffraction gratings, polarizing elements, color filters, light-emitting elements, displays, solar cells, etc.

[0152] Furthermore, by performing known photolithography steps such as nanoimprint lithography (NIL) or extreme ultraviolet (EUV) exposure on the planarization film formed according to one embodiment of this invention, devices such as semiconductor devices can be manufactured. Furthermore, devices including such devices, such as displays, cameras, and medical devices, can also be formed. Examples of such devices include LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, NAND flash memory, etc. [Examples]

[0153] To supplement the above embodiments, more specific embodiments are described below.

[0154] <Calculation of Bubble Disappearance Time During Pattern Formation> After the mold comes into contact with droplets of liquid curable composition (A) arranged in a square on the substrate, adjacent droplets collide with each other to form bubbles. Based on the following theory, the time it takes for the generated bubbles to dissolve completely in the curable composition (A) and the mold is calculated. This time is the bubble disappearance time. Furthermore, in this embodiment, it is assumed that the gas does not dissolve in the substrate.

[0155] The bubble disappearance time is the sum of the dynamic spread time and the static spread time. The dynamic spread time is the time from when the mold comes into contact with the curing composition until adjacent droplets come into contact with each other and the gas (gas in the gap) is sealed in the three-phase interface of the mold, substrate, and droplets, until a bubble is formed. The static spread time is the time until the aforementioned bubble dissolves in the curing composition (A) and completely disappears.

[0156] The dynamic spread time is calculated by combining the lubrication equation for the cylindrical hardened component (A) droplets with the motion equation for the mold. The lubrication equation is used because the droplet spacing is approximately 100 μm, the droplet height is on the order of several nm to several μm, and since it is high lateral, the pressure change in the height direction is negligible. Furthermore, since the Reynolds number is considered sufficiently small, it is treated as an incompressible fluid. The above combined equations have an analytical solution, and the dynamic spread time TDS becomes...

[0157] .

[0158] Here, V is the volume of one droplet, R is half the distance between droplets, R0 is the cylindrical radius of the droplet of the hardening composition (A), μ is the viscosity of the hardening composition (A), σ is the surface tension, θu is the contact angle between the hardening composition (A) and the mold, and θd is the contact angle between the hardening composition and the substrate.

[0159] Next, the calculation method for the time TSS required for static expansion is shown. As shown in Figure 3, at the instant the droplets of the hardening component (A) collide with each other, the bubble shown as a blank is approximated by a cylinder with the same volume and radius rg, and the calculation area is approximated by a cylinder with the same volume and radius rc. Under the initial conditions thus established, by simultaneously solving the equation of state for an ideal gas, the equation for gas mass, the equation for gas diffusion towards the mold, the equation for gas diffusion towards the hardening component (A), the equation representing the mass conservation of the hardening component (A), the lubrication equation for the hardening component region, and the equation for the motion of the mold, the time evolution equations for the bubble volume, pressure pg, and mold height h are obtained. The equation for the ideal gas is as follows.

[0160]

[0161] Here, pg represents gas pressure, ρg represents gas density, R represents gas constant, and T represents temperature. The equation for gas mass is as follows.

[0162]

[0163] Here, M g refers to the mass of the gas.

[0164] The diffusion equation for gas diffusion to the mold is as follows.

[0165]

[0166] Here, Cg is the gas concentration in the mold, and Dg is the diffusion coefficient of the gas toward the mold. The boundary condition is that dissolution according to Henry's law occurs only at the surface where the mold contacts the bubble, and no mass exchange occurs from the surface where it contacts the hardening component (A).

[0167] The diffusion equations related to the diffusion of gas toward the hardening component (A) are the same as those related to the diffusion of gas toward the mold. However, the boundary conditions only result in dissolution according to Henry's Law at the surface where the hardening component (A) contacts the bubble, and no mass exchange occurs from the surface in contact with the mold or the cylindrical side surface of the calculation region. The equation representing the conservation of mass of the hardening component (A) is as follows.

[0168]

[0169] Here, ρI is the density of the hardening component (A), Vd is the droplet volume of the hardening component (A), and Mr is the total mass of the hardening component (A2). The lubrication equation for the region of the hardening component (A) is as follows.

[0170]

[0171] Here, μ refers to the viscosity of the hardening component (A) as described above. The equation of motion for the mold is as follows.

[0172]

[0173] The average liquid film thickness is set as T, and the thickness h of the hardening component (A) is the termination condition in the static expansion calculation.

[0174] <Calculation of the diffusion coefficient of gas in the hardening composition> In this embodiment, the gas diffusion coefficient in the hardening composition (A) is calculated using molecular dynamics calculations for a molecular aggregate containing 10 gas molecules out of 500 molecules constituting the hardening composition (A). In this embodiment, molecular dynamics calculations are performed using GROMACS-2016.4 (Copyright (c)2001-2017, The GROMACS development team at Uppsala University, Stockholm University and the Royal Institute of Technology, Sweden.). The method for molecular dynamics calculations is described in Non-Patent Literature 3.

[0175] The sampling of equilibrium states in molecular dynamics calculations is obtained by arranging the target molecules within a unit lattice with imposed periodic boundary conditions, calculating the interatomic forces contained in each molecule at each time, and calculating the trajectory of the entire atom over time.

[0176] To perform molecular dynamics calculations, it is necessary to pre-set the parameters of interatomic interactions used to define the force field parameters; however, the method for setting these parameters will be described later. Molecular dynamics calculations consist of four stages: compression, relaxation, equilibration, and formal calculation. The compression process is performed to form a suitable molecular aggregate; the equilibration process is performed to bring the calculation system to thermodynamic equilibrium; and the formal calculation samples the equilibrium state. The calculation conditions used for the compression process are: simulation time 40 ps, ​​temperature 700 K, compression ratio setpoint 0.000045, and pressure setpoint 10000 atm, using an isothermal and isobaric simulation with the Berendsen method. The calculation conditions used for the equilibration process are: simulation time 5 ns, temperature 300 K, compression ratio setpoint 0.000045, and pressure setpoint 1 atm, using an isothermal and isobaric simulation with the Berendsen method. The calculation conditions used in the formal calculation were: simulation time 20 ns, temperature 300 K, compression ratio setpoint 0.000045, and air pressure setpoint 1 atm, using the Berendsen method for isothermal and isobaric simulation.

[0177] The diffusion coefficient is calculated from the mean square displacement of gas molecules by means of the molecular motion process obtained by the aforementioned formal calculation, as follows.

[0178] The force field parameters consist of two types: electrostatic force field parameters and non-electrostatic force field parameters. For the electrostatic force field parameters, the electrostatic potential calculated using the Kohn-Sham method (with the exchange-correlation functional B3LYP and the basis function 6-31g*) based on the MERZ-Singh-Killmans distribution method is obtained by applying charges to points, using the proportion of charge to each atom.Available as a specific, high-quality designer with a range of Gaussian-based designs Gaussian09 (Gaussian09, RevisionC.01, MJFrisch, GWTrucks, HBSchlegel, GEScuseria, MARobb, JRCheeseman, G. Scalmani, V. Barone, B. Mennucci, GAPetersson, H. Nakatsuji, M. Caricato, X. Li, HPHratchian, AFIzmaylov, J. Bloino, G. Zheng, JLSonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. Montgomery, Jr., J. Peralta, F. Ogliaro, M. Bearpark, J. Heyd, E. Brothers, K. Kudin, V. Taroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, JCBurant, SSIyengar, J. Thomas, M. Cossi, N. Rega, JMMillam, M. Klene, JEKnox, JBCross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, REStratmann, O. Yazyev, AJAustin, R. Cammi, C. Pomelli, JWOchterski, RL Martin, K.Morokuma, VGZakrzewski, GAVoth, P.Salvador, JJDannenberg, S.Dapprich, ADDaniels, O.Farkas, JBForesman, JVOrtiz, J.Cioslowski, and DJFox, Gaussian, Inc., Wallingford CT, 2010.)The Merz-Singh-Killmans process is described in Non-Patent Literature 4 and 5. As a non-electrostatic force field parameter, the general amber force field (GAFF, gaff, Non-Patent Literature 6) used for organic molecules is employed.

[0179] <Method for determining the pattern formation method by means of filling time experiment> A curing composition (AJ1-1) was prepared by mixing 9.0 parts by weight of isoborneol acrylate (Kyoeisha Chemical, trade name: IB-XA), 38 parts by weight of benzyl acrylate (Osaka Organic Chemical Industry, trade name: V#160), 47 parts by weight of neopentyl glycol diacrylate (Kyoeisha Chemical, trade name: NP-A) and 3 parts by weight of Lucirin TPO (BASF).

[0180] A 3.25pl droplet of the curing composition (AJ1-1) is uniformly dropped into a square arrangement with one side of 140 μm within a 26×33 mm area on a silicon substrate and brought into contact with a quartz blank mold (hereinafter also referred to as the mold).

[0181] Using an optical microscope with a magnification of 5x, the expansion behavior of droplets in the curing composition (AJ1-1) that crosses the mold was observed, that is, the shrinkage and disappearance behavior of bubbles sealed in the three-phase interface of the mold, substrate and curing composition (AJ1-1), and the time until the bubbles disappeared was measured. The time from the contact between the curing composition and the mold until the bubbles disappeared was measured as the bubble disappearance time.

[0182] In a helium environment (gase in the gap = helium), the bubble disappears in 2.7 seconds. In an air environment (gase in the gap = air), the bubble does not disappear even after 24 seconds. In a carbon dioxide environment (gase in the gap = carbon dioxide), the bubble disappears 2.67 times faster than in the helium environment.

[0183] <Liquid Properties of the Curing Composition Used in the Pattern Forming Method> In order to perform theoretical calculations of bubble disappearance time, the viscosity, surface tension, contact angle with the substrate, and contact angle with the mold of the curing composition (A) were measured, and the results are shown in Table 1.

[0184] [Table 1] Viscosity of hardening components [mPa·s] 5.6 Surface tension of hardening components [mN / m] 31 Contact angle of the hardening component to the substrate [˚] 0 Contact angle of the hardened component with the mold [˚] 0

[0185] <Theoretical Calculation Example of Bubble Disappearance Time> The diffusion coefficients and solubility coefficients of the necessary hardening component (A) and the gases (helium, carbon dioxide, oxygen) in the mold in the theoretical calculation of bubble disappearance time are summarized in Table 2.

[0186] [Table 2] helium carbon dioxide oxygen Solubility coefficient in silicon substrate [kg / m 3 ‧atm] 0 0 0 Diffusion coefficient in silicon substrate [m 2 / s] 0 0 0 Solubility coefficient in mold [kg / m 3 ‧atm] 0.0027 0 0 Diffusion coefficient in mold [m 2 / s] 1.2×10 -12 0 0 Solubility coefficient in hardened components [kg / m 3 ‧atm] 0.004 1.8 0.126 Diffusion coefficient in hardening components [m 2 / s] 5.0×10 -9 5×10 -11 2.5×10 -10

[0187] The basis for the material property values ​​recorded in Table 2 is explained as follows.

[0188] The solubility coefficient and diffusion coefficient of helium and carbon dioxide in silicon substrates are both zero. This is based on the known fact that gases can hardly pass through silicon crystals.

[0189] The diffusion coefficient and solubility coefficient of helium in the mold are known values.

[0190] The diffusion coefficient and solubility coefficient of carbon dioxide and oxygen in the mold are both zero. This is based on the known fact that carbon dioxide and oxygen, compared with helium, hardly pass through the mold.

[0191] Regarding the diffusion coefficients of helium, carbon dioxide and oxygen to the curing composition (A), the calculated values ​​are obtained by means of the mean square displacement of gas molecules when isobornyl acrylate, one of the components of the curing composition (A), is used as a solvent, based on the aforementioned molecular dynamics calculations.

[0192] The solubility coefficient of helium for the hardening component (A) is the same as that of Comparative Example 1 in Table 3 below, calculated using the bubble disappearance time when the average liquid film thickness is 28 nm, which is consistent with the aforementioned measured value (2.7 seconds).

[0193] The solubility coefficient of carbon dioxide for the hardening component (A) is the same as that of Comparative Example 2 in Table 3 below, calculated using the bubble disappearance time when the average liquid film thickness is 28 nm, which is consistent with the aforementioned measured value (7.2 seconds).

[0194] The solubility coefficient of oxygen for the curable component (A) is a known value.

[0195] [Comparative Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, Example 1, Example 2, Example 3] In the pattern forming method, when the ambient gas (gas within the gap) is set to helium and carbon dioxide, and the average liquid film thickness is set to 28nm, 50nm, 60nm, 70nm, 100nm, and 200nm, the various coefficients recorded in Tables 1 and 2 are input to calculate the time until the 0.7pl bubble disappears at the three-phase interface of the mold, substrate, and curable composition (A) when the droplets of the 3.25pl curable composition (A) come into contact with each other. Initially, the droplet diameter is set to 100μm. The mold thickness is set to 1mm. The calculated results and measured values ​​of the bubble disappearance time are shown in Table 3.

[0196] [Table 3] Ambient gases Average liquid film thickness [nm] Theoretical bubble disappearance time [s] Measured bubble disappearance time [s] Comparative Example 1 helium 28 2.7 2.7 Comparative Example 2 carbon dioxide 28 7.3 7.2 Comparative Example 3 helium 50 4.4 No data Comparative Example 4 carbon dioxide 50 7.0 No data Comparative Example 5 helium 60 5.9 No data Comparative Example 6 carbon dioxide 60 6.9 No data Comparative Example 7 helium 70 10.2 No data Example 1 carbon dioxide 70 6.8 No data Comparative Example 8 helium 100 >14 No data Example 2 carbon dioxide 100 6.6 No data Comparative Example 9 helium 200 >15 No data Example 3 carbon dioxide 200 6.3 No data

[0197] The results of Comparative Examples 1, 2, 3, 4, 5, and 6 show that when using the curing composition (A), theoretical calculations confirm that when the average liquid film thickness is 60 nm or less, the bubble disappearance time in the carbon dioxide environment (interstitial gas = carbon dioxide) is longer than that in the helium environment. On the other hand, the results of Comparative Examples 7, 8, 9, Examples 1, 2, and 3 show that when using the curing composition (A), theoretical calculations confirm that when the average liquid film thickness is 70 nm or more, the bubble extinction time in the carbon dioxide environment (interstitial gas = carbon dioxide) is shorter than that in the helium environment.

[0198] Furthermore, the results of Comparative Examples 1, 3, 5, 7, 8, and 9 show that when using the hardening composition (A2-1), theoretical calculations confirm that in a helium environment, the thicker the average liquid film thickness, the longer the bubble disappearance time. On the other hand, in Comparative Examples 2, 4, 6, 1, 2, and 3, when using the hardening composition (A), theoretical calculations confirm that in a carbon dioxide environment, the thicker the average liquid film thickness, the shorter the bubble disappearance time. The reason for the difference in the qualitative behavior of bubble disappearance time relative to average liquid film thickness in helium and carbon dioxide environments is believed to be due to the different solubilities of helium and carbon dioxide in the hardening composition (A). Generally, the effect of a thicker average liquid film, which increases the bubble disappearance time due to reduced capillary force, is the opposite of the effect of a thicker average liquid film, which increases the dissolved volume of the ambient gas, thus shortening the bubble disappearance time. The time it takes for a bubble to disappear increases or decreases as the average liquid film thickness increases, depending on which of the two opposing effects is dominant. Specifically, with carbon dioxide, due to the high solubility of the hardening component (A), the effect of increasing the dissolved volume of the ambient gas by thickening the average liquid film outweighs the effect of reducing capillary force; therefore, the thicker the film, the shorter the time for the bubble to disappear. Conversely, with helium, due to the low solubility of the hardening component (A), the effect of reducing capillary force by thickening the average liquid film outweighs the effect of increasing the dissolved volume of the ambient gas; therefore, the thicker the film, the longer the time for the bubble to disappear.

[0199] When the average liquid film thickness is less than 70 nm, helium is superior to carbon dioxide because helium can diffuse toward the mold, while carbon dioxide cannot. When the average liquid film thickness is 70 nm or more, carbon dioxide is superior to helium because the effect of increasing the dissolved volume toward the hardening component (A) exceeds the effect of diffusion toward the mold.

[0200] When the average liquid film thickness exceeds 100 μm, it becomes difficult to implement the step of configuring the curable composition (A) on the substrate. Therefore, the average liquid film thickness is expected to be less than 100 μm. However, even if the average liquid film thickness exceeds 100 μm, if the curable composition (A) can be configured on the substrate, the average liquid film thickness can still exceed 100 μm.

[0201] [Comparative Example 10, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9] In the pattern forming method, the ambient gas (gas within the gap) was set to oxygen or a mixture of oxygen and carbon dioxide, and the average liquid film thickness was set to 70 nm. Then, the time until the 0.7 μm bubble at the three-phase interface of the mold, substrate, and curable component (A) disappeared when droplets of the 3.25 μm curable component (A) came into contact with each other was calculated. The weighted average based on the mole ratio of each gas was used as the input values ​​for the diffusion coefficient and solubility coefficient. Initially, the droplet diameter was set to 100 μm. The mold thickness was set to 1 mm. The calculation results for the bubble disappearance time are shown in Table 4.

[0202] [Table 4] Ambient gases Average liquid film thickness [nm] Theoretical bubble disappearance time [s] Actual bubble disappearance time [s] Comparative Example 10 100% Oxygen 70 >12 No data Example 4 Carbon dioxide 10% : Oxygen 90% 70 8.7 No data Example 5 Carbon dioxide 25% : Oxygen 75% 70 5.3 No data Example 6 Carbon dioxide 50% : Oxygen 50% 70 4.1 No data Example 7 Carbon dioxide 80% : Oxygen 20% 70 4.6 No data Example 8 Carbon dioxide 90% : Oxygen 10% 70 5.3 No data Example 9 Carbon dioxide 95% : Oxygen 5% 70 5.9 No data

[0203] The results of Comparative Examples 7, 10, 4, 5, 6, 7, 8, and 9 show that when the average liquid film thickness of the curing composition (A) is 70 nm, theoretical calculations confirm that in a mixed gas environment of oxygen and carbon dioxide with a molar ratio of carbon dioxide of 10% or more, the bubble disappearance time is shorter than in a helium environment. Here, Examples 4 to 9 are examples where the ambient gas contains carbon dioxide with a molar ratio of 10% or more and oxygen with a molar ratio of 5% or more and less than 90%. In such mixed gas environments, the bubble disappearance time is shorter than in a helium environment.

[0204] Hereinafter, an article manufacturing method for manufacturing articles using the above-described film forming method or pattern forming method will be described. The pattern of the hardened film or hardened material formed by the above-described film forming method or pattern forming method is used permanently on at least a portion of various articles or temporarily used during the manufacture of various articles. Examples of articles include circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Examples of circuit elements include volatile or non-volatile semiconductor memory such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensors, and FPGAs. Examples of optical elements include microlenses, light guides, waveguides, anti-reflective films, diffraction gratings, polarizing elements, color filters, light-emitting elements, displays, and solar cells. Examples of MEMS include DMDs, microfluidic circuits, and electromechanical conversion elements. Examples of recording elements include optical discs such as CDs and DVDs, magnetic discs, magneto-optical discs, and magnetic heads. Examples of sensors include magnetic sensors, light sensors, and gyroscope sensors. Examples of molds include embossing molds, etc.

[0205] The pattern of the hardened material can be used directly as at least a component of the above-mentioned article, or temporarily used as a resist mask. After etching or ion implantation in the substrate processing steps, the resist mask is removed.

[0206] Next, a method for manufacturing articles will be described, which involves forming a pattern on a substrate using an imprinting apparatus, processing the patterned substrate, and manufacturing an article from the substrate itself. As shown in FIG4A, a substrate 1z, such as a silicon wafer, on which a work material 2z, such as an insulator, is prepared. Then, an imprinting material 3z is applied to the surface of the work material 2z using an inkjet printing method or the like. Here, a plurality of imprinting materials 3z in the form of droplets are shown applied to the substrate.

[0207] As shown in Figure 4B, the embossing mold 4z, with its uneven side facing the embossing material 3z on the substrate, is placed together. As shown in Figure 4C, the substrate 1, to which the embossing material 3z has been applied, is brought into contact with the mold 4z and pressure is applied. The embossing material 3z fills the gap between the mold 4z and the workpiece 2z. When the mold 4z is irradiated with light that serves as curing energy in this state, the embossing material 3z hardens.

[0208] As shown in Figure 4D, after the embossing material 3z is hardened, when the mold 4z is pulled away from the substrate 1z, a hardened pattern of the embossing material 3z is formed on the substrate 1z. This hardened pattern is such that the concave part of the mold corresponds to the convex part of the hardened material, and the convex part of the mold corresponds to the concave part of the hardened material, that is, the concave and convex pattern of the mold 4z is transferred onto the embossing material 3z.

[0209] As shown in Figure 4E, when etching with the pattern of the hardened material as an etch-resistant mask, the portion of the workpiece 2z without hardened material or with a thin residue is removed, forming a trench 5z. As shown in Figure 4F, when the pattern of the hardened material is removed, an article with a recessed trench 5z formed on the surface of the workpiece 2z can be obtained. Although the pattern of the hardened material is removed here, it may not be removed after processing. For example, it can be used as an interlayer insulating film contained in semiconductor devices, that is, as a constituent component of the article.

[0210] Next, the manufacturing method for other articles will be explained. As shown in FIG5A, a substrate 1y such as quartz glass is prepared, and then an imprinting material 3y is applied to the surface of the substrate 1y by means of inkjet printing or the like. If necessary, other material layers such as metal or metal compounds may also be provided on the surface of the substrate 1y.

[0211] As shown in Figure 5B, the embossing mold 4y is positioned with the side having the raised and recessed pattern facing the embossing material 3y on the substrate. As shown in Figure 5C, the substrate 1y, to which the embossing material 3y has been applied, is brought into contact with the mold 4y and pressure is applied. The embossing material 3y fills the gap between the mold 4y and the substrate 1y. When light is irradiated through the mold 4y in this state, the embossing material 3y hardens.

[0212] As shown in Figure 5D, after the embossing material 3y hardens, when the mold 4y is pulled apart from the substrate 1y, a hardened pattern of the embossing material 3y is formed on the substrate 1y. Thus, an article having a hardened pattern as a constituent component is obtained. Furthermore, by etching the substrate 1y with the hardened pattern as a mask in the state shown in Figure 5D, an article with the concave and convex portions reversed relative to the mold 4y can also be obtained, such as an embossing mold.

[0213] Next, an article manufacturing method will be described using a film forming method for forming a mold having the aforementioned flat surface. The article manufacturing method includes a film forming step of forming a film on a substrate according to the aforementioned film forming method, and a processing step of processing the substrate on which the film has been formed, thereby manufacturing an article from the substrate through these steps. The processing step includes, for example, a step of forming a photoresist film on the film, a step of forming a latent image on the photoresist film using an exposure apparatus, and a step of developing the latent image to form a photoresist pattern. This processing step may further include a step of processing (e.g., etching, ion implantation) the substrate 1 using the photoresist pattern.

[0214] The present invention is not limited to the above-described embodiments. Various changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, the claims are attached to disclose the present invention. [Simplified Explanation of the Diagram]

[0013] The accompanying drawings are included in and form a part of this specification, illustrating embodiments of the invention and serving to explain the principles of the invention together with the description therein. [Fig. 1] is a schematic cross-sectional view showing the film formation method of this embodiment. [Fig. 2] is a schematic cross-sectional view showing the definition of average liquid film thickness. [Fig. 3] is an explanatory diagram of an approximate operation performed when calculating bubble disappearance time. [Fig. 4A] is a diagram illustrating a method of article manufacturing. [Fig. 4B] is a diagram illustrating a method of article manufacturing. [Fig. 4C] is a diagram illustrating a method of article manufacturing. [Fig. 4D] is a diagram illustrating a method of article manufacturing. [Fig. 4E] is a diagram illustrating a method of article manufacturing. [Fig. 4F] is a diagram illustrating a method of article manufacturing. [Fig. 5A] is a diagram illustrating a method of article manufacturing. [Fig. 5B] is a diagram illustrating a method of article manufacturing. [Fig. 5C] is a diagram illustrating a method of article manufacturing. [Fig. 5D] is a diagram illustrating a method of article manufacturing.

Claims

1. A film forming method, characterized by comprising the following steps: a preparation step of preparing a curable composition on a substrate; a contact step of contacting the curable composition with a film forming region of a mold after the preparation step; a curing step of curing the curable composition after the contact step; and a separation step of separating the curable composition from the mold after the curing step, wherein in the contact step, a gas is present filling the space between the substrate and the mold, the solubility coefficient of the gas for the curable composition is 0.5 kg / m³·atm or more and 10 kg / m³·atm or less, the average liquid film thickness of the curable composition divided by the area of ​​the film forming region is 70 nm or more, and the gas contains carbon dioxide of 10% or more in molar fraction and oxygen of 5% or more and 90% in molar fraction.

2. The film formation method of claim 1, wherein the aforementioned average liquid film thickness is 100 μm or less.

3. A film forming method, characterized by comprising the following steps: a preparation step of preparing a curable composition on a substrate; a contact step of contacting the curable composition with a film forming region of a mold after the preparation step; a curing step of curing the curable composition after the contact step; and a separation step of separating the curable composition from the mold after the curing step, wherein in the contact step, a gas is present filling the space between the substrate and the mold, and when the solubility coefficient of the gas for the curable composition is set as S [kg / m3‧atm], the diffusion coefficient is set as D [m2 / s], and the average liquid film thickness of the volume of the curable composition divided by the area of ​​the film forming region is set as T [nm], S‧D‧T is 1.75×10-9 or more and S is 10 or less, and the gas contains carbon dioxide of 10% or more in molar fraction and oxygen of 5% or more and 90% or less in molar fraction.

4. The membrane formation method as described in claim 3, wherein S is 0.5 or more.

5. The membrane formation method of claim 3, wherein D is 5 × 10⁻¹² or more and 1 × 10⁻⁸ or less.

6. The film forming method of claim 1, wherein the aforementioned mold has a pattern in the aforementioned film forming area, and a film with the aforementioned pattern transferred is formed by the aforementioned contact step, the aforementioned hardening step and the aforementioned separation step.

7. The film forming method of claim 1, wherein the aforementioned mold has a flat surface, and a film having a surface that becomes the aforementioned flat surface is formed by the aforementioned contact step, the aforementioned hardening step and the aforementioned separation step.

8. The film forming method of claim 1, wherein the outermost layer of the aforementioned substrate is an insulating layer comprising at least silicon atoms.

9. A method for manufacturing an article, characterized by comprising the steps of: forming a film on a substrate by any one of the film forming methods of claims 1 to 8, and processing the aforementioned substrate having the aforementioned film formed thereon to obtain an article.

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