Mold, manufacturing method, film forming method, article manufacturing method, and imprint device

Abstract

To provide a new technique related to a mold.SOLUTION: There is provided a mold used for imprint lithography and having a first portion formed of a material having a first modulus of elasticity and a second portion formed of a material having a second modulus of elasticity lower than the first modulus of elasticity. The first portion has a first surface including a mesa part projecting from a plane, and a second surface including a recess and on the opposite side of the first surface. The second portion has a base part including a third surface coupled to the mesa part and a fourth surface on the opposite side of the third surface, and a pattern part including a projection projecting form the fourth surface and defining a pattern. The thickness of the base part defined by the distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less. The mold has an inorganic film that covers the fourth surface of the base part and the projection of the pattern part.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a mold, a manufacturing method, a film forming method, a method for manufacturing an article, and an imprinting apparatus. [Background technology]

[0002] As demand for miniaturization of optical components, recording media, semiconductor devices, MEMS, and the like increases, imprinting technology (photoimprinting technology) has attracted attention as a microfabrication technology. In imprinting technology, a mold (die) having a fine concave-convex pattern formed on its surface is brought into contact with a curable composition placed (supplied or coated) on a substrate, and the curable composition is cured in this state. In this way, the mold pattern is transferred to a cured film of the curable composition, forming a pattern on the substrate. With imprinting technology, it is possible to form fine patterns (structures) on the order of several nanometers on a substrate.

[0003] The master molds used in imprint technology are very expensive because they are made by forming a fine pattern on the surface of silicon, quartz glass, metal, or the like through precision machining. Therefore, a technology has been proposed for producing a replica mold by transferring the fine pattern of the master mold to a mold substrate (for example, quartz glass) through an imprint process (replica imprint) and an etching process (see Patent Document 1). Replica molds are used in imprint processes (device imprint) for producing various devices. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5139421 Summary of the Invention [Problem to be solved by the invention]

[0005] When manufacturing semiconductor devices, foreign matter of approximately 0.1 μm to 1 μm may be present on a substrate (device substrate). When device imprinting is performed on a substrate containing foreign matter using a quartz glass replica mold manufactured using the technology disclosed in Patent Document 1, a non-contact area of ​​approximately several millimeters to several tens of millimeters is generated around the foreign matter. Because the non-contact area is an area where the curable composition on the substrate and the replica mold are not in contact, the replica mold pattern is not transferred to the non-contact area, and no pattern is formed. While the non-contact area can be reduced by applying a strong force (imprinting force) to the replica mold, this increases the likelihood of the replica mold pattern being compressed by the foreign matter and damaged. To prevent increased costs due to replica mold damage, it is possible to construct the replica mold from a relatively inexpensive organic material. However, this raises concerns about the adhesion of the curable composition to the replica mold.

[0006] The present invention has been made in view of the above problems in the prior art, and has as its exemplary object to provide a new technique relating to molds. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, one aspect of the present invention provides a mold for use in imprint lithography, the mold having a first portion made of a material having a first elastic modulus and a second portion made of a material having a second elastic modulus lower than the first elastic modulus, wherein the first portion has a first surface including a mesa portion protruding from a flat surface, and a second surface opposite the first surface including a recess, the second portion having a base portion including a third surface bonded to the mesa portion and a fourth surface opposite the third surface, and a pattern portion including protrusions protruding from the fourth surface and defining a pattern, the thickness of the base defined by the distance between the third surface and the fourth surface being 0.1 μm or more and 10 μm or less, and the mold has an inorganic film covering the fourth surface of the base and the protrusions of the pattern portion.

[0008] Further objects and other aspects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. [Effects of the Invention]

[0009] According to the present invention, for example, a new technique relating to a mold can be provided. [Brief explanation of the drawings]

[0010] [Figure 1] 1A and 1B are diagrams for explaining the configuration of a replica mold according to one aspect of the present invention. [Figure 2] 1A and 1B are diagrams for explaining the configuration of a replica mold according to one aspect of the present invention. [Figure 3] 1A and 1B are diagrams for explaining the configuration of a replica mold according to one aspect of the present invention. [Figure 4] 1A and 1B are diagrams for explaining the configuration of a replica mold according to one aspect of the present invention. [Figure 5] 1A to 1C are diagrams for explaining a manufacturing method for manufacturing a replica mold. [Figure 6] 1A to 1C are diagrams for explaining a manufacturing method for manufacturing a replica mold. [Figure 7] 1 is a diagram showing the configuration of replica molds of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. FIG. [Figure 8] FIG. 10 is a diagram for explaining a contact step in the imprint process. [Figure 9] 10A and 10B are diagrams for explaining an analytical model of the following behavior of a replica mold with respect to a foreign substance. [Figure 10] 10 is a diagram for explaining the difference in the follow-up behavior of the replica mold with respect to the foreign matter between Example 1 and Comparative Example 2. FIG. [Figure 11] 1 is a schematic diagram showing the configuration of an imprint apparatus according to one aspect of the present invention. [Figure 12] 1A to 1C are diagrams for explaining a method for manufacturing an article. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although multiple features are described in the embodiments, not all of these multiple features are necessarily essential to the invention, and multiple features may be combined arbitrarily. Furthermore, in the accompanying drawings, the same reference numerals are used to designate the same or similar components, and redundant explanations will be omitted.

[0012] [Replica mold] 1, 2, 3, and 4 are diagrams illustrating the configuration of a replica mold RM according to one aspect of the present invention. The replica mold RM is a mold (template, original) used in imprint lithography (an imprinting apparatus employing imprint technology), and in this embodiment, is embodied as a replica mold manufactured from a master mold. As shown in FIG. 4, the replica mold RM has a high-elasticity region 10 (first region) made of a high-elasticity material having a first elastic modulus, a low-elasticity region 31 (second region) made of a low-elasticity material having a second elastic modulus lower than the first elastic modulus, and an inorganic film 32 containing an inorganic element. FIG. 1 is a cross-sectional view schematically illustrating the high-elasticity region 10, and FIG. 2 is a plan view schematically illustrating the high-elasticity region 10. Note that FIG. 1 is a cross-sectional view taken along line AA in FIG. 2. FIG. 3 is a cross-sectional view schematically illustrating the high-elasticity region 10 and the low-elasticity region 31. FIG. 4 is a cross-sectional view that schematically shows a replica mold RM having a high elasticity region 10, a low elasticity region 31, and an inorganic film 32. As shown in FIG.

[0013] The high elasticity region 10 (high elastic modulus material) has an elastic modulus of 20 GPa or more, preferably an elastic modulus of 50 GPa or more, and particularly preferably an elastic modulus of 70 GPa or more. The higher the elastic modulus (first elastic modulus) of the high elasticity region 10, the more printing force is transmitted to the low elasticity region 31. The low elasticity region 31 (low elastic modulus material) has an elastic modulus of 10 GPa or less, preferably an elastic modulus of 3 GPa or less, and particularly preferably an elastic modulus of 1 GPa or less. The lower the elastic modulus (second elastic modulus) of the low elasticity region 31, the better the ability to follow foreign matter present on the transfer object to which the pattern of the replica mold RM is transferred.

[0014] As shown in FIGS. 1 and 2, the high elasticity region 10 is made of a replica substrate that serves as the substrate for a replica mold. As shown in FIG. 1, the high elasticity region 10 has a first surface 11 including a flat surface 11a and a second surface 12 opposite the first surface 11. The first surface 11 includes a mesa portion 14 (protrusion) that protrudes from the flat surface 11a toward the opposite side of the second surface 12, i.e., has a stepped structure that is higher than its surroundings. The mesa portion 14 is formed in the center of the first surface 11 and defines a pattern region 13 in which a pattern corresponding to a pattern to be transferred to a transfer target is formed. The mesa portion 14 has an area of, for example, 0.5% to 10% of the area of ​​the first surface 11. The mesa portion 14 has a height greater than 0 μm and less than 1000 μm. For example, the mesa portion 14 has a height from the first surface 11 of 1 μm to 1000 μm. On the other hand, as shown in FIG. 1, the second surface 12 includes a recess 15 (core-out) that is concave toward the first surface 11. The recess 15 is formed in the center of the second surface 12 so that the distance d between the flat surface 11a of the first surface 11 and the bottom surface of the recess 15 (i.e., the thickness of the bottom) is, for example, 0.1 mm or more and 3 mm or less. As shown in FIGS. 1 and 2, the recess 15 is formed on the second surface 12 so that an area (a circle indicated by a dotted line) obtained by orthogonally projecting the recess 15 onto an imaginary plane VP parallel to the first surface 11, specifically the flat surface 11a, overlaps with the mesa portion 14 (pattern region 13) formed on the first surface 11. Furthermore, the recess 15 is formed on the second surface 12 so that an area obtained by orthogonally projecting the recess 15 onto the imaginary plane VP has an area larger than the area of ​​the mesa portion 14. In other words, the mesa portion 14 is located in a region inside the outer edge of the region obtained by orthogonally projecting the recess 15 onto the imaginary plane VP. The maximum thickness of the high elasticity region 10, specifically the distance t between the plane 11a of the first surface 11 and the surface of the second surface 12 where no recess is present, is 6.35 mm±0.10 mm.

[0015] 3, the low elasticity region 31 has a base 312 including a third surface 31a that is coupled to the protrusion 14 of the high elasticity region 10 and a fourth surface 31b opposite to the third surface 31a, and a pattern portion 314 that defines a pattern and includes a protrusion 31c that protrudes from the fourth surface 31b. The low elasticity region 31 is coupled (formed) via the third surface 31a to the first surface 11 of the high elasticity region 10, specifically, to a mesa portion 14 (pattern region 13) formed on the first surface 11. An imprinting method is used to form the low elasticity region 31 in the mesa portion 14. Specifically, the imprinting method forms the base 312 in the mesa portion 14 and also forms a pattern portion 314 (protrusion 31c) that defines a pattern corresponding to the pattern to be transferred to a transfer target. In this embodiment, the thickness of the base 312, which is defined by the distance between the third surface 31a and the fourth surface 31b of the base 312, is not less than 0.1 μm and not more than 10 μm.

[0016] The low elasticity region 31 is made of, for example, a curable composition (A) for a replica mold. The curable composition (A) will be described in detail later. In this embodiment, the low elasticity region 31 is formed by photopolymerizing a non-volatile composition (A') in a state in which the solvent has been removed from the curable composition (A) by evaporation or the like.

[0017] As shown in Figure 4, the inorganic film 32 is a film that covers the low elasticity region 31, more specifically, covers the fourth surface 31b of the base 312 of the low elasticity region 31 and the convex portion 31c of the pattern portion 314 of the low elasticity region 31.

[0018] [Replica mold manufacturing method] The manufacturing method for producing the replica mold RM includes a first step of forming a low elasticity region 31 in a mesa portion 14 formed on the first surface 11 of the high elasticity region 10 using an imprint method, and a second step of forming an inorganic film 32 that covers the low elasticity region 31 using a deposition method.

[0019] The first step (imprinting method) includes a step of preparing a master mold, a step of preparing a curable composition (A) as a low elastic modulus material, a positioning step, a waiting step, a contacting step, a curing step, and a demolding step. Hereinafter, the manufacturing method for manufacturing the replica mold RM, specifically the first step of forming the low elasticity region 31, will be described with reference to Figures 5(a) to 5(h).

[0020] <Master mold preparation process> As shown schematically in FIG. 5(a), a master mold MM is prepared. The master mold MM has a fine pattern FP on its surface. The fine pattern FP is an inverted pattern of the pattern (concave and convex) to be formed on the replica mold RM. The master mold MM may be a mold made of a non-light-transmitting material or a light-transmitting material. Examples of the mold substrate for a non-light-transmitting material include silicon wafer, nickel, copper, stainless steel, titanium, SiC, and mica. Examples of the mold substrate for a light-transmitting material include glass such as quartz glass, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, and transparent fluororesin. The light-transmitting material mold may be composed of multiple materials. Note that silicon wafers and quartz wafers are preferred as the mold substrate for the master mold MM because they have a proven track record in the semiconductor industry and are available as high-quality materials.

[0021] The fine pattern FP of the master mold MM is formed using a microfabrication technique such as electron beam lithography. The fine pattern FP formed on the master mold MM has a height of, for example, 4 nm to 200 nm. The smaller the height of the fine pattern FP of the master mold MM, the smaller the force required to separate the master mold MM from the cured film of the curable composition (A) in the demolding step, i.e., the demolding force. This reduces the number of demolding defects remaining on the master mold MM when the pattern of the curable composition (A) is torn off. Furthermore, the impact generated when the master mold MM is demolded can elastically deform the pattern of the curable composition (A), causing adjacent pattern elements to come into contact with each other, resulting in adhesion or breakage. However, to avoid these problems, it is advantageous for the height of the pattern elements to be approximately twice the width of the pattern elements (aspect ratio of 2 or less). On the other hand, if the height of the pattern elements is too low, the processing accuracy of the mold substrate decreases.

[0022] The master mold MM may be surface-treated before the placement step to improve the releasability of the master mold MM from the curable composition (A). Examples of surface treatments include applying a release agent to the surface of the master mold MM to form a release agent layer. Examples of release agents that can be applied to the surface of the master mold MM include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. Commercially available coating-type release agents, such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., can also be used. One type of release agent may be used alone, or two or more types may be used in combination. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0023] <Step of preparing curable composition (A)> A curable composition (A) is prepared as a low modulus material. The curable composition (A) is a composition containing at least a polymerizable compound (a) and a photopolymerization initiator (b). Depending on various purposes, the curable composition (A) may further contain a non-polymerizable compound (c) and a solvent (d) within a range that does not impair the effects of the present invention. The curable composition (A) is a curable composition for inkjet printing.

[0024] In this specification, the polymerizable compound (a) is a compound that reacts with a polymerization factor (such as a radical) generated from the photopolymerization initiator (b) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0025] Examples of such polymerizable compounds include radically polymerizable compounds. The polymerizable compound (a) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0026] Examples of the radically polymerizable compound include (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleyl compounds.

[0027] The (meth)acrylic compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or one methacryloyl group include, but are not limited to, the following: Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-Tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy (meth)acrylate, PO-modified phenoxy (meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate t)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pliers (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, chinoabenzyl(meth)acrylate, naphthalenemethyl(meth)acrylate, Examples of commercially available monofunctional (meth)acrylic compounds include, but are not limited to, the following: Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (all manufactured by Toagosei), MEDOL10, M IBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #19 0, #192, #193, #220, #2000, #2100, #2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A, OPP-EA (all manufactured by Kyoeisha Chemical Industry Co., Ltd.), KAYARAD (registered trademark) TC-110S, R-564, R-128H (all manufactured by Nippon Kayaku), NK Ester AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (all manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Seiyaku), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kohjin), HRD-01 (all manufactured by Nippon Shokubai) Furthermore, examples of polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m-, or p-benzenedi(meth)acrylate, o-, m-, or p-xylylenedi(meth)acrylate Examples of commercially available polyfunctional (meth)acrylic compounds include, but are not limited to, the following: Iupimer (registered trademark) UV SA1002, SA2007 (all manufactured by Mitsubishi Chemical), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (all manufactured by Osaka Organic Chemical Industry), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku), Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei), Lipoxy (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Polymer), Oxol EA-0200, Oxol EA-0300 (all manufactured by Osaka Gas Chemicals), SR295, SR355 (all manufactured by Sartomer)

[0028] In the above-mentioned compound group, (meth)acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. (Meth)acryloyl group means acryloyl group or methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are bonded via an ethylene oxide group block structure. PO represents propylene oxide, and PO-modified compound B represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are bonded via a propylene oxide group block structure.

[0029] Specific examples of styrene-based compounds include, but are not limited to, the following: Alkylstyrenes such as styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodostyrene. halogenated styrenes such as styrene; nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, divinylbiphenyl, and other compounds having a styryl group as a polymerizable functional group.

[0030] Specific examples of vinyl compounds include, but are not limited to, the following: Vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate, and acrylonitrile; conjugated diene monomers such as butadiene, isoprene, and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc.), (meth)acrylonitrile, and other compounds having a vinyl group as a polymerizable functional group. In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0031] Examples of acrylic compounds include, but are not limited to, the following: Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate

[0032] Examples of fumaric compounds include, but are not limited to, the following: Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate

[0033] Examples of maleyl compounds include, but are not limited to, the following: Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate

[0034] Examples of other radical polymerizable compounds include, but are not limited to, the following: Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, dibenzyl itaconate, etc.), N-vinylamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimide and its derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.)

[0035] When the polymerizable compound (a) is composed of multiple types of compounds having one or more polymerizable functional groups, it preferably contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound. The ratio of the polyfunctional polymerizable compound in the polymerizable compound (a) is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 40% by weight or more. This is because the combination of a monofunctional compound and a polyfunctional compound can provide a cured film with an excellent balance of properties, such as high mechanical strength, high dry etching resistance, and high heat resistance.

[0036] In this embodiment, it takes several milliseconds to several hundred seconds for multiple droplets of the curable composition (A) discretely arranged on the replica substrate (substrate) to combine with adjacent droplets to form a substantially continuous liquid film, necessitating a waiting step, as described below. During this waiting step, the solvent (d) must be evaporated while the polymerizable compound (a) must not evaporate. Therefore, the boiling point of each of the one or more polymerizable compounds contained in the polymerizable compound (a) under normal pressure is preferably 250°C or higher, more preferably 300°C or higher, and even more preferably 350°C or higher. Furthermore, in order to obtain high dry etching resistance and high heat resistance in a cured film of the curable composition (A), it is preferable that the curable composition (A) contains at least a compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that normal pressure refers to 1 atmosphere (atmospheric pressure).

[0037] The boiling point of the polymerizable compound (a) generally correlates with the molecular weight. Therefore, the molecular weight of each of the one or more polymerizable compounds contained in the polymerizable compound (a) is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. However, even if the molecular weight is 200 or less, as long as the boiling point is 250°C or higher, it can be preferably used as the polymerizable compound (a) in the present invention. Thus, it is preferable that the boiling point under normal pressure of each of the one or more polymerizable compounds contained in the polymerizable compound (a) is 250°C or higher.

[0038] The vapor pressure of the polymerizable compound (a) at 80° C. is preferably 0.001 mmHg or less. When the polymerizable compound (a) contains one or more polymerizable compounds, it is preferable that each of the one or more polymerizable compounds has a vapor pressure of 0.001 mmHg or less at 80° C. This is because, although it is preferable to heat the curable composition (A) to accelerate the evaporation of the solvent (d), which will be described later, the evaporation of the polymerizable compound (a) is suppressed during such heating.

[0039] The boiling points and vapor pressures of various organic compounds under normal pressure can be calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th Edition 5.3.04 or the like.

[0040] Dry etching rate of organic compound V, total number of atoms in the organic compound N, total number of carbon atoms in the composition N C , and the total number of oxygen atoms in the composition N O is known to be related by the following formula (1). V∝N / (Nc-No) Equation (1) Here, N / (Nc-N0) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, U.S. Patent Application Publication No. 2020 / 0286740 discloses a technology for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP.

[0041] According to formula (1), it is suggested that the more oxygen atoms there are in the molecule of an organic compound, or the fewer aromatic ring structures or alicyclic structures there are in an organic compound, the larger the OP and the faster the dry etching rate.

[0042] In the curable composition (A) of the present invention, the OP of the polymerizable compound (a) is 1.80 or more and 4.00 or less. The OP of the polymerizable compound (a) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or less. By making the OP of the polymerizable compound (a) 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. Furthermore, by making the OP of the polymerizable compound (a) 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing the underlayer using the cured film of the curable composition (A). When the polymerizable compound (a) is made of a plurality of types of polymerizable compounds a1, a2, ..., a n When the polymerizable compound (a) is composed of the above, OP is calculated as a weighted average value based on the molar fraction (molar fraction weighted average value) as shown in the following formula (2). In this way, when the polymerizable compound (a) contains one or more types of polymerizable compounds, the OP of the polymerizable compound (a) is calculated by the ratio N / (N C -N O ) values ​​are calculated as the mole fraction weighted average.

[0043]

number

[0044] Here, OP n is component a n OP of n n is component a n is the molar fraction of the total polymerizable compound (a).

[0045] In order to make the OP of the polymerizable compound (a) 1.80 or more and 2.70 or less, it is preferable to include, as at least the polymerizable compound (a), a polymerizable compound (a-1) having two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0046] The polymerizable compound (a) in the present invention may contain a polymerizable compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Furthermore, the proportion of the polymerizable compound (a-1) in the polymerizable compound (a) is preferably 65% ​​by weight or more. By setting the proportion of the polymerizable compound (a-1) to 65% by weight or more, it is possible to suppress the OP to 2.70 or less.

[0047] The cyclic structure may be an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0048] The aromatic structure preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Specific examples of the aromatic ring include the following. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring Among the aromatic rings described above, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The aromatic ring may have a structure in which multiple rings are linked together, such as a biphenyl ring or a bisphenyl ring.

[0049] The aromatic heterocyclic structure preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples of the aromatic heterocyclic ring include the following. Thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinolizine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring

[0050] The number of carbon atoms in the alicyclic structure is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. The number of carbon atoms in the alicyclic structure is preferably 22 or less, more preferably 18 or less, even more preferably 6 or less, and even more preferably 5 or less. Specific examples thereof include the following. Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, spirodecane ring, spirononane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindane ring, bornane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring

[0051] Specific examples of the polymerizable compound (a-1) having a boiling point of 250° C. or higher include, but are not limited to, the following: 3-phenoxybenzyl acrylate (mPhOBzA, OP 2.54, boiling point 367.4°C, vapor pressure at 80°C 0.0004mmHg, molecular weight 254.3),

[0052] [ka]

[0053] 1-naphthyl acrylate (NaA, OP 2.27, boiling point 317°C, vapor pressure at 80°C 0.0422mmHg, molecular weight 198),

[0054] [ka]

[0055] 2-phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2°C, vapor pressure at 80°C 0.0006mmHg, molecular weight 268.3),

[0056] [ka]

[0057] 1-Naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2),

[0058] [ka]

[0059] 2-Naphthylmethyl acrylate (Na2MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2)

[0060] [ka]

[0061] DPhPA (OP 2.38, boiling point 354.5°C, vapor pressure 0.0022mmHg at 80°C, molecular weight 266.3) shown in the formula below,

[0062] [ka]

[0063] PhBzA (OP 2.29, boiling point 350.4°C, vapor pressure 0.0022mmHg at 80°C, molecular weight 238.3) shown in the formula below,

[0064] [ka]

[0065] FLMA (OP2.20, boiling point 349.3℃, vapor pressure 0.0018mmHg at 80℃, molecular weight 250.3) shown in the following formula:

[0066] [ka]

[0067] ATMA (OP2.13, boiling point 414.9℃, vapor pressure 0.0001mmHg at 80℃, molecular weight 262.3) shown in the formula below,

[0068] [ka]

[0069] DNaMA (OP 2.00, boiling point 489.4°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 338.4) shown in the formula below,

[0070] [ka]

[0071] BPh44DA (OP 2.63, boiling point 444°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below,

[0072] [ka]

[0073] BPh43DA (OP 2.63, boiling point 439.5°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below,

[0074] [ka]

[0075] DPhEDA (OP2.63, boiling point 410℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.3) shown in the formula below,

[0076] [ka]

[0077] BPMDA (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) shown in the following formula:

[0078] [ka]

[0079] Na13MDA (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3) shown in the formula below,

[0080] [ka]

[0081] The following formula (a-1-1) (OP 2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181mmHg, molecular weight 199.2),

[0082] [ka]

[0083] The following formula (a-1-2) (OP 2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181mmHg, molecular weight 199.2),

[0084] [ka]

[0085] The following formula (a-1-3) (OP 1.86, boiling point 369.5℃, vapor pressure at 80℃ 0.0053mmHg, molecular weight 193.3),

[0086] [ka]

[0087] The following formula (a-1-4) (OP 2.85, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0088] [ka]

[0089] The following formula (a-1-5) (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0090] [ka]

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

[0092] [ka]

[0093] The following formula (a-1-7) (OP 2.87, boiling point 465.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4),

[0094] [ka]

[0095] The following formula (a-1-8) (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4),

[0096] [ka]

[0097] The following formula (a-1-9) (OP 2.50, boiling point 433.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 320.3),

[0098] [ka]

[0099] The following formula (a-1-10) (OP 2.64, boiling point 468.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 326.4),

[0100] [ka]

[0101] The following formula (a-1-11) (OP 3.25, boiling point 553.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 358.4),

[0102] [ka]

[0103] The following formula (a-1-12) (OP 2.63, boiling point 443.9°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.4),

[0104] [ka]

[0105] The following formula (a-1-13) (OP 2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4),

[0106] [ka]

[0107] The following formula (a-1-14) (OP 2.63, boiling point 450.0℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4),

[0108] [ka]

[0109] The following formula (a-1-15) (OP 3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4)

[0110] [ka]

[0111] The following formula (a-1-16) (OP 2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4)

[0112] [ka]

[0113] The following formula (a-1-17) (OP 2.36, boiling point 543.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 398.5),

[0114] [ka]

[0115] The following formula (a-1-18) (OP 3.27, boiling point 526.9 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 396.4),

[0116] [ka]

[0117] The following formula (a-1-19) (OP 2.71, boiling point 333.7℃, vapor pressure 0.0302mmHg at 80℃, molecular weight 244.3),

[0118] [ka]

[0119] The following formula (a-1-20) (OP 2.73, boiling point 333.7℃, vapor pressure 0.0134mmHg at 80℃, molecular weight 258.3),

[0120] [ka]

[0121] The following formula (a-1-21) (OP 2.71, boiling point 319.2℃, vapor pressure 0.0566mmHg at 80℃, molecular weight 262.3),

[0122] [ka]

[0123] The following formula (a-1-22) (OP 2.71, boiling point 336.9°C, vapor pressure at 80°C 0.0055mmHg, molecular weight 244.3),

[0124] [ka]

[0125] The following formula (a-1-23) (OP 3.00, boiling point 370.9 ° C, vapor pressure 0.0021 mmHg at 80 ° C, molecular weight 274.4),

[0126] [ka]

[0127] The following formula (a-1-24) (OP 3.00, boiling point 376.4℃, vapor pressure at 80℃ 0.0005mmHg, molecular weight 274.4),

[0128] [ka]

[0129] The following formula (a-1-25) (OP 3.00, boiling point 379.4℃, vapor pressure at 80℃ 0.0002mmHg, molecular weight 288.4),

[0130] [ka]

[0131] The following formula (a-1-26) (OP 2.33, boiling point 360.8 ° C, vapor pressure 0.0006 mmHg at 80 ° C, molecular weight 252.3),

[0132] [ka]

[0133] The following formula (a-1-27) (OP 2.54, boiling point 371.5℃, vapor pressure 0.0003mmHg at 80℃, molecular weight 254.3),

[0134] [ka]

[0135] The following formula (a-1-28) (OP 2.57, boiling point 381.2℃, vapor pressure 0.0001mmHg at 80℃, molecular weight 268.3),

[0136] [ka]

[0137] The following formula (a-1-29) (OP 2.57, boiling point 381.8 ° C, vapor pressure at 80 ° C 0.0004 mmHg, molecular weight 268.3),

[0138] [ka]

[0139] The following formula (a-1-30) (OP 2.50, boiling point 487.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 374.4),

[0140] [ka]

[0141] The following formula (a-1-31) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0142] [ka]

[0143] The following formula (a-1-32) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0144] [ka]

[0145] The following formula (a-1-33) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0146] [ka]

[0147] The following formula (a-1-34) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0148] [ka]

[0149] The following formula (a-1-35) (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0150] [ka]

[0151] The polymerizable compound (a) in the present invention may contain a polymerizable compound (a-2) containing at least a Si atom. Furthermore, when the polymerizable compound (a) contains the polymerizable compound (a-2), the non-volatile composition (A') from which the solvent (d) has been removed preferably contains 10 wt % or more of Si atoms based on the total weight of the non-volatile composition (A').

[0152] An example of the polymerizable compound (a-2) containing at least a Si atom may be linear or branched. For example, cyclic siloxane compounds have the structures shown below. Examples of the polymerizable functional group in the group Q having a polymerizable functional group include radically polymerizable functional groups. Specific examples of the radically polymerizable functional group include a (meth)acrylic group, a (meth)acrylamide group, a vinylbenzene group, an allyl ether group, a vinyl ether group, and a maleimide group. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0153] [ka]

[0154] Other examples of the polymerizable compound (a-2) include a silsesquioxane skeleton as shown in the following chemical formula (I) and a silicone skeleton as shown in the following chemical formula (II): In chemical formula (I), m+n=8 (8≧m≧1), and R1 is a divalent organic group. In chemical formula (II), A, B, R2, and R3 are independently an alkyl group, cycloalkyl group, alkoxy group, phenyl group, or hydroxyl group having 1 to 6 carbon atoms, t is an integer of 1 to 3, and at least one of A and B is a polymerizable functional group.

[0155] [ka]

[0156] [ka]

[0157] Examples of the polymerizable functional group in the groups Q, A, and B having a polymerizable functional group include a radically polymerizable functional group. The radically polymerizable functional group may be linear or branched. Specific examples of the radically polymerizable functional group include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0158] The silicon-containing (meth)acrylate compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylate compounds having one silicon-containing acryloyl group or methacryloyl group include, but are not limited to, the following: (2-acryloylethoxy)trimethylsilane, N-(3-acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, acryloxymethyltrimethoxysilane, (acryloxymethyl)phenethyltrimethoxysilane, acryloxymethyltrimethylsilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-acryloxypropyl)methyldichlorosilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)trichlorosilane, (3-acryloxypropyl)trimethoxysilane, (3-acryloxypropyl)tris(trimethylsiloxy)silane, acryloxytriisopropylsilane, acryloxytrimethylsilane, methacryloxymethyltrimethoxysilane, 0-(methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloylpropyltriisopropoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyldimethylethoxysilane, (methacryloxymethyl)dimethylethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl silatrane, methacryloxypentamethyldisiloxane, (methacryloxymethyl)phenyldimethylsilane, methacryloxytrimethylsilane, methacryloxymethyltrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyl pentamethyldisiloxane, 0-(methacryloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propylcarbamate, methacryloxymethyltris(trimethylsiloxy)silane, methacryloxyethoxytrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyltris(vinyldimethylsiloxy)silane, methacryloxypropyltris(trimethylsiloxy)silane, 3-methacryloxypropyltriacetoxysilane, methacryloxypropylmethyldichlorosilane, methacryloxypropyltrichlorosilane, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, 3-methacryloxypropyldimethylchlorosilane, 0-methacryloxy(polyethyleneoxy)trimethylsilane, Poly(methacryloxypropylsilsesquioxane), Methacryloxypropylheptaisobutyl-T8-silsesquioxane, Methacryloxypropyltris(trimethylsiloxy)silane

[0159] Examples of commercially available silicon-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0 , SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481 .43, SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM648 6.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM6 491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, S IM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, SIM6486.65 (all manufactured by GELEST), TM-0701T, FM-0711, FM-0721, FM-0725 (all manufactured by JNC)

[0160] The silicon-containing (meth)acrylamide compound is a compound having one or more acrylamide groups or methacrylamide groups. Examples of monofunctional (meth)acrylamide compounds having one silicon-containing acrylamide group or methacrylamide group include, but are not limited to, the following: 3-Acrylamidepropyltrimethoxysilane, 3-Acrylamidepropyltris(trimethylsiloxy)silane

[0161] Examples of commercially available silicon-containing monofunctional (meth)acrylamide compounds include, but are not limited to, the following: SIA0146.0, SIA0150.0 (all manufactured by GELEST)

[0162] Furthermore, examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: A linear polydimethylsiloxane modified at both ends with acryloxypropyl groups, a linear polydimethylsiloxane modified at both ends with methacryloxypropyl groups; a cyclic siloxane modified with a plurality of acryloxypropyl groups; a cyclic siloxane modified with multiple methacryloxypropyl groups; silsesquioxane modified with multiple acryloxypropyl groups; Silsesquioxane modified with multiple methacryloxypropyl groups

[0163] Examples of commercially available silicon-containing polyfunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (all manufactured by GELEST), FM-7711, FM-7721, FM-7725 (all manufactured by JNC), X-22-2445 (Shin-Etsu Chemical), AC-SQ TA-100, MAC-SQ TM-100, AC-SQSI-20, MAC-SQ SI-20 (all manufactured by Toagosei)

[0164] In addition, for example, the following can be synthesized and / or obtained from known document 1. Linear modified polydimethylsiloxane (MA-Si-12) with both ends modified with methacryloxypropyl groups, 8-membered ring siloxane (8-ring) modified with four methacryloxypropyl groups, 10-membered ring siloxane (10-ring) modified with five methacryloxypropyl groups, Publicly known literature 1: "Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography" by Ogawa et al.

[0165] The polymerizable compound (a) in the present invention may contain a polymerizable compound (a-3) containing at least an F atom. The fluorine compound as the polymerizable compound (a-3) may be understood as a fluorine-containing polymerizable compound. In this specification, the fluorine-containing polymerizable compound is a compound that reacts with a polymerization factor (such as a radical) generated from the photopolymerization initiator (b) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0166] The fluorine-containing polymerizable compound may be, for example, a radical polymerizable compound. The polymerizable compound (a-3) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0167] Examples of the fluorine-containing radically polymerizable compound include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds.

[0168] Examples of commercially available products of the above-mentioned fluorine-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following. 2,2,2-Trifluoroethyl acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1H,1H,2H,2H-nonafluorohexyl methacrylate, 1H,1H,2H,2H-nonafluorohexyl acrylate, 1H,1H,2H,2H-nonafluorohexyl methacrylate, methacrylic acid 1H,1H,5H-Octafluoropentyl, Pentafluorophenyl Acrylate, 2,2,3,3,3-Pentafluoropropyl Methacrylate, Pentafluorobenzyl Methacrylate, 2,2,3,3-Tetrafluoropropyl Acrylate, 1H,1H,2H,2H-Tridecafluoro-n-octyl Methacrylate, 1H,1H,2H,2H-Tridecafluoro-n-octyl Acrylate, 2,2,3,3-Tetrafluoropropyl Methacrylate, 1H,1H,2H,2H-Heptadecafluorodecyl Acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl Acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl Methacrylate, Acrylic Acid 1H,1H,5H-octafluoropentyl, pentafluorophenyl methacrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.), C6 (meth)acrylate, C4 (meth)acrylate, C2 (meth)acrylate (all manufactured by Unichem), Viscoat 3F, Viscoat 4F, Viscoat 8F, Viscoat 8FM, Viscoat 13F (all manufactured by Osaka Organic Chemical Industry), 1H,1H,2H,2H-heptadecafluorodecyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, pentafluorophenyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate (all manufactured by Polysciences), Methyl-2-fluoroacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-(perfluorobutyl)ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,7H-dodecafluoroheptyl acrylate, 1H-1-(trifluoromethyl)trifluoroethyl acrylate, 1H,1H,3H-hexyl Trifluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 1H,1H,3H-tetrafluoropropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, 1H,1H,7H-dodecafluoroheptyl methacrylate, 1H-1-(trifluoromethyl)trifluoroethyl methacrylate, 1H,1H,3H-hexafluorobutyl methacrylate (all manufactured by Daikin Industries, Ltd.)

[0169] Examples of the above-mentioned fluorine-containing polyfunctional (meth)acrylate compounds that can be obtained by using the method disclosed in Japanese Patent No. 3963028 include, but are not limited to, the following. A linking group is introduced into the polyhydric alcohol moiety of trivalent trimethylolethane, tetravalent pentaerythritol, or hexavalent dipentaerythritol using a standard organic synthesis reaction, followed by a perfluorination reaction to form a core with a high fluorine content, and an acrylic group is introduced at the end.

[0170] The above-mentioned fluorine-containing polyfunctional (meth)acrylate compound may be a commercially available product.

[0171] The curable composition (A) may be a commercially available product, for example, PAK-TRAD manufactured by Toyo Gosei Kogyo Co., Ltd. or UT-UCa-368 manufactured by AGC Seimi Chemical Co., Ltd.

[0172] The blending ratio of the polymerizable compound (a) in the non-volatile composition (A') is preferably 40% by weight or more and 99% by weight or less, more preferably 50% by weight or more and 95% by weight or less, and even more preferably 60% by weight or more and 90% by weight or less. By making the blending ratio of the polymerizable compound (a) 40% by weight or more, the mechanical strength of the cured film of the curable composition (A) is increased. Furthermore, by making the blending ratio of the polymerizable compound (a) 99% by weight or less, the blending ratio of the photopolymerization initiator (b) and the non-polymerizable compound (c) can be increased, thereby achieving properties such as a fast photopolymerization rate. At least a portion of the polymerizable compound (a) containing one or more polymerizable compounds may be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, it is preferable to contain at least one structural unit represented by any of the following structures (1) to (6).

[0173] [ka]

[0174] In the structures (1) to (6), the substituents R are each independently a substituent containing a partial structure containing an aromatic ring, and R 1 is a hydrogen atom or a methyl group. In this specification, in the structural units represented by Structures (1) to (6), the portion other than R is the main chain of a specific polymer. The formula weight of the substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and even more preferably 150 or more. The upper limit of the formula weight of the substituent R is practically 500 or less.

[0175] The polymer having a polymerizable functional group is typically a compound having a weight-average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight-average molecular weight is not particularly limited, but is preferably 50,000 or less. By setting the weight-average molecular weight at or above the above-mentioned lower limit, the boiling point can be set to 250°C or higher, thereby further improving the mechanical properties after curing. Furthermore, by setting the weight-average molecular weight at or below the above-mentioned upper limit, the solubility in solvents is high, the viscosity is not too high, and the fluidity of discretely arranged droplets is maintained, thereby further improving the flatness of the liquid film surface. In the present invention, the weight-average molecular weight (Mw) refers to that measured by gel permeation chromatography (GPC), unless otherwise specified.

[0176] Specific examples of the polymerizable functional group possessed by the polymer include a (meth)acryloyl group, an epoxy group, an oxetane group, a methylol group, a methylol ether group, a vinyl ether group, etc. From the viewpoint of ease of polymerization, a (meth)acryloyl group is particularly preferred.

[0177] When a polymer having a polymerizable functional group is added as at least a part of the polymerizable compound (a), its blending ratio can be freely set as long as it falls within the viscosity specification described below. For example, it is preferably 0.1% by weight or more and 60% by weight or less, more preferably 1% by weight or more and 50% by weight or less, and even more preferably 10% by weight or more and 40% by weight or less, based on the total mass of all components excluding the solvent (d). By setting the blending ratio of the polymer having a polymerizable functional group to 0.1% by weight or more, it is possible to improve heat resistance, dry etching resistance, mechanical strength, and low volatility. Furthermore, by setting the blending ratio of the polymer having a polymerizable functional group to 60% by weight or less, it is possible to fall within the upper limit of the viscosity specification described below.

[0178] In this specification, the photopolymerization initiator (b) is a compound that senses light of a predetermined wavelength and generates the above-mentioned polymerization factor (radical). Specifically, the photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals when exposed to light (infrared rays, visible light, ultraviolet rays, far ultraviolet rays, charged particle rays such as X-rays and electron beams, or radiation). The photopolymerization initiator (b) may be composed of only one type of photopolymerization initiator, or may be composed of multiple types of photopolymerization initiators.

[0179] Examples of the radical generator include, but are not limited to, the following: 2,4,5-Triarylimidazole dimers which may have a substituent, such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone Benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, and 1,2-benz Quinones such as anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;Acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Examples of commercially available radical generators include, but are not limited to, the following: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO, LR8893, LR8970 (all manufactured by BASF), Yubecryl P36 (manufactured by UCB)

[0180] Among the above-mentioned radical generators, the photopolymerization initiator (b) is preferably an acylphosphine oxide-based polymerization initiator. Among the above-mentioned radical generators, the acylphosphine oxide-based polymerization initiator is as follows: Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide

[0181] The blending ratio of the photopolymerization initiator (b) in the non-volatile composition (A') is preferably 0.1% by weight or more and 50% by weight or less, more preferably 0.1% by weight or more and 20% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less. By blending the photopolymerization initiator (b) in a ratio of 0.1% by weight or more, the curing rate of the composition can be increased and the reaction efficiency can be improved. Furthermore, by blending the photopolymerization initiator (b) in a ratio of 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0182] In addition to the polymerizable compound (a) and the photopolymerization initiator (b), the curable composition (A) of the present invention may further contain a non-polymerizable compound (c) depending on various purposes, as long as the effects of the present invention are not impaired. Examples of such non-polymerizable compounds (c) include compounds that do not have a polymerizable functional group such as a (meth)acryloyl group and do not have the ability to sense light of a specific wavelength and generate the above-mentioned polymerization factors (radicals). Examples of non-polymerizable compounds (c) include sensitizers, hydrogen donors, surfactants (c-1), antioxidants, polymer components, and other additives. The non-polymerizable compound (c) may contain multiple types of the above-mentioned compounds.

[0183] The sensitizer is a compound that is added as needed for the purpose of accelerating the polymerization reaction and improving the reaction conversion rate. One type of sensitizer may be used alone, or two or more types may be used in combination.

[0184] Examples of sensitizers include sensitizing dyes. Sensitizing dyes are compounds that are excited by absorbing light of a specific wavelength and interact with the photopolymerization initiator (b). Here, the interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator (b). Specific examples of sensitizing dyes include, but are not limited to, the following: Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes

[0185] The hydrogen donor is a compound that reacts with the initiation radicals generated from the photopolymerization initiator (b) or the radicals at the terminal of the polymerized growth, generating radicals with higher reactivity. When the photopolymerization initiator (b) is a photoradical generator, it is preferable to add a hydrogen donor.

[0186] Specific examples of such hydrogen donors include, but are not limited to, the following: Amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanolamine, and N-phenylglycine; mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionic acid esters.

[0187] The hydrogen donor may be used alone or in combination of two or more kinds. The hydrogen donor may also function as a sensitizer.

[0188] In the present invention, a surfactant (c-1) is added to the curable composition (A) for the purpose of suppressing the extrusion and seepage of the curable composition. The surfactant (c-1) also functions as an internal mold release agent that reduces the interfacial bonding strength between the mold and the curable composition, i.e., reduces the mold release force in the mold release step described below. In this specification, "internal mold release" means that the surfactant is added to the curable composition in advance before the curable composition placement step. As the surfactant (c-1), surfactants such as silicon-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants can be used. Note that the surfactant (c-1) in the present invention is not polymerizable. The surfactant (c-1) may be used alone or in combination of two or more types.

[0189] Fluorine-based surfactants include the following: Polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols with perfluoroalkyl groups, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers

[0190] The fluorosurfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in part of its molecular structure (for example, a terminal group). For example, pentadecaethylene glycol mono 1H,1H,2H,2H-perfluorooctyl ether can be mentioned.

[0191] As the fluorine-based surfactant, commercially available products may be used. Examples of commercially available fluorine-based surfactants include the following: Megafac (registered trademark) F-444, TF-2066, TF-2067, TF-2068, abbreviated as DEO-15 (all manufactured by DIC), Fluorard FC-430, FC-431 (both 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 Tochem Products), PF-636, PF-6320, PF-656, PF-6520 (manufactured by OMNOVA Solutions), Unidyne (registered trademark) DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), Futergent (registered trademark) 250, 251, 222F, 208G (all manufactured by Neos)

[0192] The surfactant (c-1) may also be a hydrocarbon surfactant. Examples of the hydrocarbon surfactant include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides in which alkylene oxides having 2 to 4 carbon atoms are added to alkyl alcohols having 1 to 50 carbon atoms.

[0193] Examples of alkyl alcohol polyalkylene oxide adducts include the following. Methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / propylene oxide adduct

[0194] The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced simply by adding a polyalkylene oxide to an alkyl alcohol, and the hydroxyl group may be substituted with other substituents, such as polar functional groups such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or hydrophobic functional groups such as an alkyl group or an alkoxy group.

[0195] Examples of polyalkylene oxides include the following: Polyethylene glycol, polypropylene glycol, their mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monoadipate esters, monooleate esters, monostearate esters, monosuccinate esters

[0196] The alkyl alcohol polyalkylene oxide adduct may be a commercially available product. Examples of commercially available alkyl alcohol polyalkylene oxide adducts include the following: Polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), Aoki Oil & Fat Industries' random polymerization type polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R), Polyoxyethylene methyl ether (Pluriol® A760E) from BASF; Kao's polyoxyethylene alkyl ether (Emulgen series)

[0197] Alternatively, commercially available polyalkylene oxides may be used, such as BASF's ethylene oxide-propylene oxide copolymer (Pluronic PE6400).

[0198] The surfactant (c-1) may also be a silicone surfactant, such as those commercially available under the trade names SI-10 series (Takemoto Yushi Co., Ltd.), Megafac Paintad 31 (Dainippon Ink and Chemicals, Inc.), and KP-341 (Shin-Etsu Chemical Co., Ltd.).

[0199] The surfactant (c-1) may also be a surfactant containing at least both a fluorine atom and a silicon atom. Examples of surfactants containing both a fluorine atom and a silicon atom include the following: Product names: X-70-090, X-70-091, X-70-092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Product name: Megafax R-08, XRB-4 (both manufactured by Dainippon Ink and Chemicals, Inc.)

[0200] The blending ratio of the non-polymerizable compound (c), excluding surfactants, in the non-volatile composition (A') is preferably 0.01% by weight or more and 50% by weight or less. Furthermore, the blending ratio of the non-polymerizable compound (c), excluding surfactants, in the non-volatile composition (A') is more preferably 0.01% by weight or more and 50% by weight or less, and even more preferably 0.01% by weight or more and 20% by weight or less. By setting the blending ratio of the non-polymerizable compound (c), excluding surfactants, to 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0201] The curable composition (A) of the present invention contains, as the solvent (d), a solvent having a boiling point of 100°C or higher and lower than 250°C under normal pressure. Examples of the solvent (d) include solvents in which the polymerizable compound (a), the photopolymerization initiator (b), and the non-polymerizable compound (c) dissolve, such as alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. The solvent (d) can be used alone or in combination of two or more. The boiling point of the solvent (d) under normal pressure is 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of the solvent (d) under normal pressure is lower than 250°C, and preferably lower than 200°C. If the boiling point of the solvent (d) under normal pressure is less than 100°C, the evaporation rate in the waiting step described below will be too fast, and the solvent (d) may evaporate before the droplets of the curable composition (A) combine together, which may prevent the droplets of the curable composition (A) from combining together. Furthermore, if the boiling point of the solvent (d) under normal pressure is 250°C or higher, the evaporation of the solvent (d) may be insufficient in the waiting step described below, and the solvent (d) may remain in the non-volatile composition (A'). When the solvent (d) contains one or more solvents, the boiling point of each of the one or more solvents under normal pressure may be 100°C or higher and lower than 250°C (e.g., 100°C or higher and lower than 200°C).

[0202] Examples of alcohol-based solvents include the following: Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl Monoalcohol solvents such as alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyalcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0203] Examples of ketone solvents include the following: Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone

[0204] Examples of ether solvents include the following: Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran

[0205] Examples of the ester solvent include the following: Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate Ether, Diethylene Glycol Mono-n-Butyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Dipropylene Glycol Monomethyl Ether Acetate, Dipropylene Glycol Monoethyl Ether Acetate, Glycol Diacetate, Methoxytriglycol Acetate, Ethyl Propionate, n-Butyl Propionate, Isoamyl Propionate, Diethyl Oxalate, Di-n-Butyl Oxalate, Methyl Lactate, Ethyl Lactate, n-Butyl Lactate, n-Amyl Lactate, Diethyl Malonate, Dimethyl Phthalate, Diethyl Phthalate

[0206] Examples of nitrogen-containing solvents include the following: N-Methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone

[0207] Among the above-mentioned solvents, ether-based solvents and ester-based solvents are preferred, and from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a glycol structure are more preferred.

[0208] Furthermore, the following are more preferred: Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate

[0209] Furthermore, particularly preferred is propylene glycol monomethyl ether acetate. Other examples include ethyl isocyanurate di(meth)acrylate.

[0210] In the present invention, a preferred solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure, specifically, a solvent selected from propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate, either singly or in combination.

[0211] In the present invention, a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure can also be used as the solvent (d). Examples of polymerizable compounds having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure include the following. Cyclohexyl acrylate (198°C), benzyl acrylate (229°C), isobornyl acrylate (245°C), tetrahydrofurfuryl acrylate (202°C), trimethylcyclohexyl acrylate (232°C), isooctyl acrylate (217°C), n-octyl acrylate (228°C), ethoxyethoxyethyl acrylate (boiling point 230°C), divinylbenzene (193°C), 1,3-diisopropenylbenzene (218°C), styrene (145°C), α-methylstyrene (165°C)

[0212] In the present invention, when the entire curable composition (A) is taken as 100% by volume, the content of solvent (d) is greater than 5% by volume and less than 95% by volume, preferably greater than 15% by volume and less than 85% by volume, and more preferably greater than 40% by volume and less than 80% by volume. For example, the content of solvent (d) is greater than 40% by volume and less than 85% by volume. If the content of solvent (d) is less than 5% by volume, a thin film cannot be obtained after evaporation of solvent (d) under conditions that allow for a substantially continuous liquid film to be obtained. Furthermore, if the content of solvent (d) is greater than 95% by volume, a thick film cannot be obtained after evaporation of solvent (d) even when droplets are dropped in close proximity by an inkjet method.

[0213] When preparing the curable composition (A) of the present invention, at least the polymerizable compound (a), the photopolymerization initiator (b), and the solvent (d) are mixed and dissolved under a predetermined temperature condition. Specifically, the predetermined temperature condition is in the range of 0° C. or higher and 100° C. or lower. The same applies when the curable composition (A) contains the solvent (c).

[0214] The curable composition (A) in the present invention is liquid. This is because, in the disposing step described below, droplets of the curable composition (A) are discretely dropped onto the high-elasticity region by an inkjet method. The viscosity of the curable composition (A) in the present invention is 2 mPa·s or more and 60 mPa·s or less, preferably 2 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less, at 23°C and 1 atmosphere. If the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection of droplets by the inkjet method becomes unstable. Furthermore, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is not possible to form droplets with a volume of approximately 1.0 to 3.0 pL, which is preferred in the present invention.

[0215] The viscosity of the non-volatile composition (A') in the present invention is 20 mPa·s or more and 10,000 mPa·s or less at 23°C and 1 atmosphere. The viscosity of the non-volatile composition (A') may be 30 mPa·s or more and 500 mPa·s or less at 23°C and 1 atmosphere, preferably 60 mPa·s or more and 200 mPa·s or less, and more preferably 60 mPa·s or more and 150 mPa·s or less. Note that the lower the viscosity, for example, less than 20 mPa·s, the higher the fluidity of the non-volatile composition (A'), and when the non-volatile composition (A') is brought into contact with the high elasticity region 10, the more likely the non-volatile composition (A') will flow out from the end of the mesa portion 14. Furthermore, if the viscosity is greater than 10,000 mPa·s, the fluidity of the non-volatile composition (A') is low, and when the non-volatile composition (A') is brought into contact with the high elasticity region 10, the speed at which the non-volatile composition (A') reaches the edge of the mesa portion 14 of the high elasticity region 10 is slow. Therefore, by using a curable composition (A) in which the viscosity of the non-volatile composition (A') is adjusted to 20 mPa·s or more and 10,000 mPa·s or less, the imprint process can be performed with high throughput. Furthermore, defects due to the outflow of the non-volatile composition (A') from the mesa portion 14 of the high elasticity region 10 can be suppressed.

[0216] The surface tension of the non-volatile composition (A') is preferably 5 mN / m to 70 mN / m at 23°C and 1 atmosphere, more preferably 7 mN / m to 50 mN / m, and even more preferably 10 mN / m to 40 mN / m. The higher the surface tension, for example, 5 mN / m or more, the stronger the capillary force, and therefore the shorter the time required for filling (spreading and filling) when the non-volatile composition (A') is brought into contact with the master mold MM. Furthermore, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition has a smooth surface.

[0217] The contact angle of the curable composition (A) in the present invention is preferably 0° or more and 90° or less with respect to the surface of the master mold MM. If the contact angle is greater than 90°, the droplets on the substrate do not come into contact with each other, and a continuous liquid film cannot be formed.

[0218] Furthermore, the contact angle of the curable composition (A) in the present invention is preferably between 0° and 90° with respect to both the surface of the master mold MM and the surface of the high elasticity region 10 (replica substrate). If the contact angle is greater than 90°, capillary force acts in the negative direction inside the fine pattern FP of the master mold MM and in the gap between the master mold MM and the high elasticity region 10 (replica substrate). Here, the negative direction refers to the direction in which the interface between the master mold MM and the curable composition (A) contracts, so there is a possibility that the non-volatile composition (A') will not fill the fine pattern FP of the master mold MM. The smaller the contact angle, the stronger the capillary force, and the faster the filling speed.

[0219] The curable composition (A) of the present invention preferably contains as few impurities as possible. The impurities refer to substances other than the polymerizable compound (a), the photopolymerization initiator (b), the non-polymerizable compound (c), and the solvent (d) described above. Therefore, the curable composition (A) of the present invention is preferably obtained through a purification process. Such a purification process is preferably filtration using a filter.

[0220] In the filtration using a filter, the polymerizable compound (a), photopolymerization initiator (b), and non-polymerizable compound (c) are preferably mixed and then filtered, for example, through a filter having a pore size of 0.001 μm to 5.0 μm. When performing filtration using a filter, it is more preferable to perform the filtration in multiple stages or repeatedly multiple times (circulating filtration). The liquid filtered through the filter may be filtered again, or may be filtered using multiple filters with different pore sizes. Examples of filters used for filtration include, but are not limited to, filters made of polyethylene resin, polypropylene resin, fluororesin, and nylon resin. By undergoing such a purification step, impurities such as particles mixed in the curable composition (A) can be removed. This prevents impurities mixed in the curable composition (A) from accidentally causing unevenness in the cured film obtained after curing the curable composition (A), which can result in pattern defects.

[0221] When the curable composition (A) of the present invention is used to manufacture a semiconductor integrated circuit, it is preferable to minimize the inclusion of impurities containing metal atoms (metal impurities) in the curable composition (A) so as not to impair the operation of the product. The concentration of metal impurities contained in the curable composition (A) is preferably 10 ppm or less, more preferably 100 ppb or less.

[0222] If the glass transition temperature is sufficiently higher than the temperature during demolding, the cured product will be in a strong glass state during demolding, i.e., will exhibit high mechanical strength, making it difficult for the pattern to collapse or be damaged by the impact of demolding. Therefore, when the demolding step is carried out at room temperature, the glass transition temperature of the cured product of the non-volatile composition (A') is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0223] The glass transition temperature of a cured product (photocured product) can be measured using a differential scanning calorimetry (DSC) or a dynamic viscoelasticity analyzer. For example, consider measuring the glass transition temperature using a DSC. In this case, a straight line is drawn by extending the low-temperature baseline of the DSC curve of the cured product (the portion of the DSC curve in the temperature range where no transition or reaction occurs in the test specimen) toward the high-temperature side, and a tangent is drawn at the point where the gradient of the curve in the stepwise change portion of the glass transition is maximum. The extrapolated glass transition onset temperature (Tig) is then calculated from the intersection of this straight line and this tangent, and this can be used as the glass transition temperature. Typical instruments include the STA-6000 (manufactured by Perkin Eimer). On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity analyzer, the temperature at which the loss sine (tan δ) of the cured product is maximized is defined as the glass transition temperature. Typical instruments for measuring dynamic viscoelasticity include the MCR301 (manufactured by Anton Paar).

[0224] Furthermore, the curable composition (A) may have the same composition as the curable composition for imprinting processes for producing various devices, i.e., device imprinting. By using the curable composition (A) with the same composition as the curable composition for device imprinting (using the same curable composition), the same apparatus as that used for device imprinting (imprinting apparatus) can be used in producing the replica mold RM.

[0225] <Placement process> In the disposing step, as shown schematically in FIG. 5(b), droplets 102 of the curable composition (A) are discretely disposed on the master mold MM.

[0226] The inkjet method is particularly preferred as a method for depositing droplets 102 of the curable composition (A) on the master mold MM. The droplets 102 of the curable composition (A) are deposited densely in areas where the recesses constituting the fine pattern FP of the master mold MM are densely located, and deposited sparsely in areas where the recesses constituting the fine pattern FP of the master mold MM are sparsely located. This allows the residual film of the cured film of the curable composition (A) formed on the master mold MM to be controlled to a uniform thickness, regardless of the density of the fine pattern FP of the master mold MM.

[0227] <Standby process> The waiting step is performed after the placing step and before the contacting step (between the placing step and the contacting step). The waiting step is performed for, for example, 0.1 to 600 seconds, and preferably 10 to 300 seconds.

[0228] In the waiting step, droplets 102 of the curable composition (A) spread on the master mold MM and combine to form a substantially continuous liquid film 103, as shown schematically in Figures 5(c) and 5(d). The state of the curable composition (A) as shown in Figure 5(d) is referred to as a "substantially continuous liquid film." If the curable composition (A) contains a solvent (d), the solvent (d) contained in the liquid film 103 is volatilized in the waiting step, as shown schematically in Figure 5(e).

[0229] During the waiting step, a baking step may be performed to heat the master mold MM and the curable composition (A) or to ventilate the ambient gas surrounding the master mold MM in order to accelerate the evaporation of the solvent (d). Heating is performed, for example, at a temperature of 30°C to 200°C, preferably 80°C to 150°C, and particularly preferably 90°C to 110°C. The heating time may be 10 seconds to 600 seconds. The baking step may be performed using a known heater such as a hot plate or oven.

[0230] <Contact process> In the contacting step, as shown schematically in Figure 5(f), the curable composition (A) from which the solvent (d) has been removed, i.e., a substantially continuous liquid film 103 of the non-volatile composition (A') on the master mold MM, is brought into contact with the replica substrate 101 (mesa portion 14), which is the highly elastic member 10. The contacting step includes a step of changing the state in which the non-volatile composition (A') on the master mold MM and the replica substrate 101 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other.

[0231] The replica substrate 101 preferably has a size of 152.4 mm (6 inches) square and a thickness of 6.35 mm (0.25 inches). The material for the replica substrate 101 is preferably a high-elasticity material having an elastic modulus of 50 GPa or more, and specifically, quartz glass. Such quartz glass is available as a high-quality photomask substrate in the semiconductor industry and has a proven track record of use.

[0232] The contacting step is preferably from 0.1 to 600 seconds, particularly preferably from 0.1 to 10 seconds. If the contacting step is shorter than 0.1 seconds, the contact between the non-volatile composition (A') on the master mold MM and the replica substrate 101 may be insufficient.

[0233] In the contacting step, when the replica substrate 101 is brought into contact with the non-volatile composition (A') on the master mold MM, the pressure applied to the non-volatile composition (A') is not particularly limited, and may be, for example, from 0 MPa to 100 MPa. The pressure applied to the non-volatile composition (A') when the replica substrate 101 is brought into contact with the non-volatile composition (A') on the master mold MM is preferably from 0 MPa to 50 MPa. The pressure applied to the non-volatile composition (A') when the replica substrate 101 is brought into contact with the non-volatile composition (A') on the master mold MM is more preferably from 0 MPa to 30 MPa, and even more preferably from 0 MPa to 20 MPa.

[0234] The contacting step can be carried out under any of the conditions of air, reduced pressure, and inert gas atmosphere, but a reduced pressure or inert gas atmosphere is preferred because it can prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas used when carrying out the contacting step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, and mixtures of these. When carrying out the contacting step under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0235] <Curing process> In the curing step, as shown schematically in FIG. 5( g), the liquid film 103 of the non-volatile composition (A′) is irradiated with irradiation light 107 as curing energy, thereby curing the liquid film 103 of the non-volatile composition (A′) to form a cured film. In the curing step, for example, the liquid film 103 of the non-volatile composition (A′) is irradiated with irradiation light 107 via the replica substrate 101. More specifically, the non-volatile composition (A′) filled in the fine pattern FP of the master mold MM is irradiated with irradiation light 107 via the replica substrate 101. As a result, the non-volatile composition (A′) filled in the fine pattern FP of the master mold MM is cured to form a cured film 108 having the pattern.

[0236] The irradiation light 107 is selected according to the wavelength to which the non-volatile composition (A') is sensitive. Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, electron beams, or the like having a wavelength of 150 nm or more and 400 nm or less. It is particularly preferable that the irradiation light 107 be ultraviolet light. This is because many of the commercially available curing aids (photopolymerization initiators) are compounds sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, ultra-high-pressure mercury lamps are particularly preferable as the light source that emits ultraviolet light. The number of light sources may be one or more.

[0237] Furthermore, the entire area of ​​the non-volatile composition (A') filled in the fine pattern FP of the master mold MM may be irradiated with light, or only a partial area (a limited area) may be irradiated with light. The light irradiation may be performed intermittently multiple times over the entire area of ​​the replica substrate 101 (mesa portion 14), or may be performed continuously over the entire area of ​​the replica substrate 101. Furthermore, a first area of ​​the replica substrate 101 may be irradiated with light in a first irradiation process, and a second area of ​​the replica substrate 101 different from the first area may be irradiated with light in a second irradiation process.

[0238] <Mold release process> In the demolding step, as shown schematically in FIG. 5(h), the master mold MM is separated from the cured film 108. By separating the patterned cured film 108 from the master mold MM, a cured film 108 having a pattern that is an inverse of the fine pattern FP of the master mold MM is obtained in a free-standing state on the replica substrate 101. Here, a film remains in the recesses of the cured film 108 that have a pattern corresponding to the fine pattern FP of the master mold MM. This film is called a residual film.

[0239] In this embodiment, the thickness of the residual film corresponds to the thickness of the base 312 (see FIG. 3 ), which is defined by the distance between the third surface 31a and the fourth surface 31b of the base 312, and is set to 0.1 μm or more and 10 μm or less. In other words, the cured film 108 (low-elasticity region 31) is formed so that the thickness of the residual film (the thickness of the base 312, defined by the distance between the third surface 31a and the fourth surface 31b of the base 312) is 0.1 μm or more and 10 μm or less. By setting the thickness of the residual film to 10 μm or less, the amount of distortion due to exposure heat or imprinting force is less than a few nanometers, making it usable in semiconductor applications requiring overlay and alignment accuracy of a few nanometers. Furthermore, the thickness of the residual film is preferably about 10 times the thickness of expected foreign matter; the thicker the residual film, the higher the ability to follow foreign matter during device imprinting. For example, assuming that a 10 nm foreign substance may hinder imprinting (contact between the curable composition (A) on the master mold and the replica substrate 101), the residual film preferably has a thickness of 0.1 μm or more.

[0240] The method for separating the master mold MM from the cured film 108 having the pattern is not particularly limited as long as a portion of the cured film 108 having the pattern is not physically damaged during separation, and various conditions are not particularly limited. For example, the replica substrate 101 may be fixed, and the master mold MM may be moved away from the replica substrate 101. Alternatively, the master mold MM may be fixed, and the replica substrate 101 may be moved away from the master mold MM. The master mold MM may be separated from the cured film 108 having the pattern by moving both the master mold MM and the replica substrate 101 in opposite directions.

[0241] The second step (deposition method) is a step of forming the low elasticity portion 31, i.e., the inorganic film 32 that covers the patterned cured film 108, as described above. The process includes a step of preparing the inorganic film 32 and a step of depositing the inorganic film 32 .

[0242] <Inorganic film preparation process> The inorganic film 32 that covers the cured film 108, which is the low elasticity region 31, can be at least one selected from metals, semiconductors, ceramics, oxide ceramics, and glass, and compounds thereof. The inorganic film 32 made of these materials inhibits adhesion or bonding between the cured film 108, which is the low elasticity region 31, and (the liquid of) the curable composition for device imprinting, thereby contributing to good separation performance. Furthermore, by protecting the cured film 108, which is the low elasticity region 31, with the inorganic film 32, the durable life of the replica mold RM can be extended.

[0243] The metal may be composed of metallic elements such as Cr, Be, Wi, Cd, Ga, In, Ir, Mg, Mn, Mo, Os, Pa, Rh, Ru, Ta, Ti, V, Zn, Sn, Zr, Cu, Ni, Co, Fe, Pt, Ag, Au, Pb, W, Al, Hf, etc. The metal may also be composed of oxides containing these elements.

[0244] The semiconductor material may be, for example, Si, Ge, α-Sn, Se, Te, B, GaP, GaAs, InP, InSb, InAs, GaSb, GaN, AlN, InN, ITO, AlxGa1-xAs, InxGa1-xN, etc. The semiconductor material may also be an oxide containing any of these.

[0245] The ceramics are composed of, for example, non-oxide ceramics (carbides, nitrides, borides, silicides), Si3N4, BN, SiC, and the like.

[0246] Oxide ceramics are composed of Al2O3, MgO, ZrO2, TiO, Ti2O3, TiO2, suboxides, etc.

[0247] The glass is made of, for example, borosilicate glass, quartz (SiO2), or the like.

[0248] The inorganic film 32 is selected from the materials described above, with SiO2, Al2O3, and HfO2 being preferred, and SiO2 being particularly preferred. However, the inorganic film 32 may be made of a material other than the materials described above. In this case, the material constituting the inorganic film 32 is preferably a transparent material or a material that is nearly transparent. Furthermore, the material constituting the inorganic film 32 is preferably conductive. Furthermore, the material constituting the inorganic film 32 is preferably conductive and transparent.

[0249] <Inorganic film deposition process> In the deposition process of the inorganic film 32, the inorganic film 32 is formed by depositing the above-mentioned material so as to cover the cured film 108, which is the low elasticity region 31. Suitable deposition methods include, for example, sputtering, chemical vapor deposition (CVD), or atomic layer deposition (ALD). In this embodiment, chemical vapor deposition (CVD) includes plasma enhanced chemical vapor deposition (PECVD). Chemical vapor deposition (CVD) also includes atmospheric pressure plasma CVD. Atmospheric pressure plasma CVD includes atmospheric pressure plasma jet (APP-Jet) and atmospheric pressure dielectric barrier discharge (AP-DBD) processes. APP-Jet is an abbreviation for atmospheric pressure plasma jet. AP-DBD is an abbreviation for atmospheric pressure dielectric barrier discharge.

[0250] Hereinafter, with reference to FIGS. 6(a) and 6(b), a manufacturing method for manufacturing the replica mold RM, specifically, the second step of forming the inorganic film 32, will be described. As shown in FIG. 6(a), using the deposition method described above, the material (constituent substance) of the inorganic film 32 is deposited on the surface of the cured film 108 (low elasticity region 31) formed on the replica substrate 101 (mesa portion 14). By continuing this process for a predetermined time, as shown in FIG. 6(b), an inorganic film 32 having a thickness of, for example, 10 nm or less is formed. The thickness of the inorganic film 32 is, for example, 10 nm or less, preferably 1 nm or more and 10 nm or less, and particularly preferably 1 nm or more and 5 nm or less. If the thickness of the inorganic film 32 is 1 nm or less, sufficient performance for protecting the replica mold RM (low elasticity region 31) cannot be obtained. Furthermore, if the thickness of the inorganic film 32 is 10 nm or more, it becomes difficult to miniaturize the pattern of the replica mold RM.

[0251] In the past, when the pattern portion 314 (cured film 108) wore away due to repeated use of a replica mold, the entire replica substrate 101 was discarded. On the other hand, with a replica mold RM, the cured film 108 and inorganic film 32 formed on the replica substrate 101 can be removed by cleaning. In other words, with a replica mold RM, the cured film 108, i.e., the pattern portion 314, can be selectively removed along with the inorganic film 32 without damaging the replica substrate 101. Therefore, the cured film 108 can be formed again on the replica substrate 101 from which the cured film 108 and inorganic film 32 have been removed, and further, the inorganic film 32 can be formed to cover the cured film 108. In this way, by repeatedly removing the cured film 108 and inorganic film 32, forming the cured film 108, and forming the inorganic film 32 on the replica substrate 101, the expensive replica substrate 101 can be reused, thereby reducing the manufacturing cost of the replica mold RM.

[0252] The replica mold RM manufactured in this manner is used, for example, in imprinting processes for manufacturing various devices, i.e., device imprinting. Here, as described above, the replica mold RM has a structure in which a cured film 108 (low elasticity region 21) and an inorganic film 32 that covers the cured film 108 are formed on a replica substrate 101 (high elasticity region 10). Therefore, the replica mold RM can reduce non-contact areas during device imprinting and suppress adhesion of the curable composition to the replica mold RM.

[0253] [Imprint method] A film formation method will be described as one aspect of the present invention. In this embodiment, the film formation method is carried out as an imprint process (imprint method) using the replica mold RM, in which a film of a curable composition is formed in the space between the replica mold RM and a substrate. The imprint process is also carried out as a pattern formation method in which a film having a pattern is formed.

[0254] [Example] To supplement the above-described embodiment, a more specific example will be described.

[0255] <Deformation analysis of foreign object tracking> It was confirmed by the method described below that the foreign matter tracking ability of the replica mold in Example 1 (replica mold RM in this embodiment) is superior to the foreign matter tracking ability of the replica molds in Comparative Examples 1, 2, 3 and 4.

[0256] (1-1) Replica mold manufacturing Replica molds were manufactured as Example 1, Comparative Example 1, Comparative Example 3, and Comparative Example 4 so as to have the configurations shown in Table 1 below.

[0257] Example 1 7(a) is manufactured as Example 1. The replica mold RMA has a high elasticity region 10, a low elasticity region 31, and an inorganic film 32.

[0258] The high elasticity region 10, which is the replica substrate, measures 152.4 mm square and 6.35 mm thick, and has a mesa portion 14 with a height of 30 μm and an area of ​​26 mm × 33 mm in the center (pattern region 13) of the first surface 11. The second surface 12 of the high elasticity region 10 overlaps with the mesa portion 14 (pattern region 13) and has a circular recess 15 (core-out) with a diameter of 60 mm that has a larger area than the mesa portion 14. The thickness of the recess 15 in the high elasticity region 10 is 1 mm. The high elasticity region 10 is synthetic quartz glass with an elastic modulus of approximately 72 GPa.

[0259] Acryloxypropyltrimethoxysilane, an acrylic group-containing silane coupling agent, is vapor-deposited on the mesa portion 14 of the high elasticity portion 10 to improve adhesion with the low elasticity portion 31 (curable composition (A)).

[0260] As the master mold MM, a mold made of a silicon wafer having a diameter of 300 mm and having a fine pattern FP formed in a central area of ​​26 mm x 33 mm is prepared.

[0261] The curable composition (A) is dropped onto the fine pattern FP portion of the master mold MM by an inkjet method to form a liquid film so that the thickness of the residual film becomes 10 μm.

[0262] The mesa portion 14 (pattern region 13) of the high elasticity portion 10, which is the replica substrate, is brought into contact with a liquid film of non-volatile composition (A') formed by volatilizing the solvent (d) from the curable composition (A) on the master mold MM. Then, ultraviolet light is irradiated through the high elasticity portion 10 to cure the non-volatile composition (A'). This forms a low elasticity portion 31 with a film thickness of 10 μm in the mesa portion 14 of the high elasticity portion 10. The elastic modulus of the low elasticity portion 31 is set to approximately 3 GPa.

[0263] Using ALD as the deposition method, SiO 2 is deposited to a thickness of 5 nm on the surface of the low elasticity portion 31 formed in the mesa portion 14 of the high elasticity portion 10, thereby forming an inorganic film 32 that covers the low elasticity portion 31.

[0264] (Comparative Example 1) As Comparative Example 1, a replica mold RMB shown in FIG. 7(b) was manufactured. The replica mold RMB did not have a low elasticity region 31 or an inorganic film 32. Synthetic quartz glass having the same structure as in Example 1 was prepared as the high elasticity region 10, which was the replica substrate. A fine pattern was formed on the mesa portion 14 of the high elasticity region 10 by electron beam lithography.

[0265] (Comparative Example 2) As Comparative Example 2, a replica mold RMC shown in FIG. 7(c) was manufactured. The replica mold RMC did not have a high elasticity region 10 or an inorganic film 32. The replica mold RMC used a low elasticity region 311 made of polycarbonate and having the same structure as the high elasticity region 10 as the replica substrate. The low elasticity region 311 had an elastic modulus of approximately 3 GPa. A fine pattern was formed in the mesa portion of the low elasticity region 311 using electron beam lithography.

[0266] (Comparative Example 3) As Comparative Example 3, a replica mold RMD shown in FIG. 7(d) was manufactured. The replica mold RMD did not have a low elasticity region 31 or an inorganic film 32. The high elasticity region 10, which was the replica substrate, had a size of 152.4 mm square and a thickness of 6.35 mm, and had a mesa portion 14 with a height of 30 μm and an area of ​​26 mm × 33 mm in the central portion (pattern region 13) of the first surface 11. The second surface 12 of the high elasticity region 10 did not have a recess 15. A fine pattern was formed on the mesa portion 14 of the high elasticity region 10 by electron beam lithography.

[0267] Comparative Example 4 As Comparative Example 4, a replica mold RMD shown in FIG. 7(e) was produced. The replica mold RMD did not have an inorganic film 32. Synthetic quartz glass having the same structure as in Example 1 was prepared as the high elasticity region 10, which was the replica substrate. As in Example 1, a liquid film was formed by dropping a curable composition (A) onto the fine pattern FP portion of the master mold MM using an inkjet method. The mesa portion 14 (pattern region 13) of the high elasticity region 10, which was the replica substrate, was brought into contact with the liquid film of a non-volatile composition (A') formed by volatilizing the solvent (d) from the curable composition (A) on the master mold MM. Ultraviolet light was then irradiated through the high elasticity region 10 to cure the non-volatile composition (A'). This formed a low elasticity region 31 in the mesa portion 14 of the high elasticity region 10. A fine pattern was then formed in the low elasticity region 31 formed in the mesa portion 14 of the high elasticity region 10 using electron beam lithography.

[0268] [Table 1]

[0269] (1-2) Device imprint An imprint process for manufacturing various devices, i.e., device imprinting, is performed using replica molds RMA (Example 1), RMB (Comparative Example 1), RMC (Comparative Example 2), RMD (Comparative Example 3), and RME (Example 4). The imprint process includes, for example, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step. The disposing step is a step of discretely disposing droplets of the curable composition for device imprinting on a device substrate. The waiting step is a step of waiting until the droplets of the curable composition for device imprinting combine with each other. The contacting step is a step of bringing the curable composition for device imprinting into contact with the replica mold. The curing step is a step of curing the curable composition for device imprinting. The demolding step is a step of separating the replica mold from the cured film of the curable composition for device imprinting. The waiting step is performed after the disposing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0270] A silicon wafer with a diameter of 300 mm is prepared as a device substrate. A curable composition for device imprinting is dropped onto one shot area (one field) of the silicon wafer by an inkjet method to form a liquid film (placement step, waiting step).

[0271] In the contact step, as shown schematically in FIG. 8( a), the recess 15 of the replica mold RMA is sealed to form a sealed space, and nitrogen gas is supplied into the sealed space to set the pressure in the sealed space to 1.5 atmospheres. This deflects the recess 15, causing the replica mold RMA (the mesa portion 14, the low-elasticity portion 31 formed on the mesa portion 14, and the inorganic film 32) to bend (deform) convexly toward the device substrate. An example of a sealing mechanism for forming the recess 15 into a sealed space is a holding unit that holds the replica mold RMA. The holding unit may include a sealing member such as seal glass to form the recess 15 into a sealed space. Next, as shown schematically in FIG. 8( b), the replica mold RMA is lowered in the bent state, so that only the mesa portion 14, the low-elasticity portion 31 formed on the mesa portion 14, and the central portion of the inorganic film 32 are brought into contact with the curable composition on the device substrate. Furthermore, as shown schematically in Figure 8(c), the replica mold RMA is gradually brought into contact with the curable composition on the device substrate from the center toward the outer periphery of the replica mold RMA while applying an imprinting force of up to 42 N.

[0272] Thus, in the contacting step, the low elasticity region 31 and the central portion of the inorganic film 32 are brought into contact with the liquid film of the curable composition on the device substrate by bending the recess 15 of the high elasticity region 10. After the low elasticity region 31 and the central portion of the inorganic film 32 are brought into contact with the liquid film of the curable composition, the bending of the recess 15 is released to bring the entire surfaces of the low elasticity region 31 and the inorganic film 32 into contact with the liquid film of the curable composition on the device substrate.

[0273] In the curing step, ultraviolet light is irradiated as curing energy through the replica mold RMA to cure the curable composition on the device substrate.

[0274] In the demolding step, the replica mold RMA is separated from the cured film of the curable composition on the device substrate, thereby forming a cured film on the device substrate having a pattern that is the inverse of the pattern of the replica mold RMA.

[0275] 8, device imprinting has been explained using the replica mold RMA as an example, but the same process is also carried out for device imprinting using each of the replica molds RMB, RMC, RMD, and RME. However, since the replica mold RMD does not have a recess 15 formed therein, the replica mold RMD is brought into contact with the curable composition on the device substrate without being curved.

[0276] (Analysis of tracking behavior against foreign objects) Referring to Figure 8, an analytical model for the replica mold's tracking behavior with respect to a foreign particle present on a device substrate is described. A liquid film of a curable composition with an average thickness of 50 nm is formed in a 26 mm x 33 mm shot area on a silicon wafer with a diameter of 300 mm and an elastic modulus of 190 GPa as the device substrate. A cylindrical foreign particle with a diameter of 1 μm and a height of 1 μm is present in the center of the liquid film on the shot area of ​​the device substrate. The replica mold was brought into contact with the shot area with an imprinting force of 42 N, and the tracking behavior (deformation) of each of the replica molds in Example 1, Comparative Example 1, and Comparative Example 2 was analyzed. The meniscus pressure due to the liquid film sandwiched between the replica mold and the silicon wafer was calculated to be 1.18 MPa. Because the meniscus pressure attracts the replica mold toward the silicon wafer, its effect was also taken into consideration. In the analytical model, the radius of the non-contact area generated between the replica mold and the silicon wafer due to the presence of the foreign particle was calculated. The smaller the radius of the non-contact area, the better the ability to follow the foreign object.The analysis was performed using Abaqus, a finite element analysis software from Dassault Systèmes.

[0277] In Example 1, device imprinting was possible without sandwiching atmospheric gas between the replica mold RMA and the silicon wafer. The radius of the non-contact area formed around the foreign particle was 16 μm.

[0278] In Comparative Example 1, device imprinting was possible without sandwiching atmospheric gas between the replica mold RMB and the silicon wafer. The radius of the non-contact area formed around the foreign particle was 54 μm.

[0279] In Comparative Example 2, device imprinting was possible without sandwiching atmospheric gas between the replica mold RMC and the silicon wafer. The radius of the non-contact area formed around the foreign particle was 22 μm.

[0280] Here, with reference to FIG. 10 , the difference in the replica mold's behavior in response to foreign matter between Example 1 and Comparative Example 2 will be described. In Comparative Example 2, the entire replica mold RMC is made of a low-elasticity material with a modulus of elasticity of approximately 3 GPa, so the imprinting force is consumed in deforming the recesses of the replica mold RMC. On the other hand, in Example 1, the recesses 15 (replica substrate) of the replica mold RMA are made of a high-elasticity material with a modulus of elasticity of approximately 72 GPa, so less imprinting force is consumed in deforming the recesses 15, and the imprinting force is transmitted to the mesa portion 14. Therefore, the low-elasticity region 31 and inorganic film 32 formed on the mesa portion 14 of the replica mold RMA have improved ability to follow foreign matter compared to Comparative Example 2.

[0281] In Comparative Example 3, atmospheric gas was sandwiched between the replica mold RMD and the silicon wafer during device imprinting. This was because synthetic silica glass with a thickness of 6.35 mm could not be curved at 1.5 atmospheres. Analysis of the conformal behavior to foreign matter was not performed.

[0282] In Comparative Example 4, the low elasticity region 31 and the curable composition for device imprinting were bonded by irradiation with ultraviolet light during device imprinting. This resulted in problems such as the low elasticity region 31 peeling off from the high elasticity region 10 and the curable composition for device imprinting peeling off from the device substrate. Analysis of the behavior of the device in response to foreign matter was not performed.

[0283] <Thermal and stress distortion analysis> It was confirmed by the method described below that the resistance to thermal deformation of the replica molds in Examples 1 and 2 (replica mold RM in this embodiment) was superior to the resistance to thermal deformation of the replica molds in Comparative Examples 1, 2, 3 and 4.

[0284] (2-1) Replica mold manufacturing Replica molds were manufactured as Example 1, Example 2, Comparative Example 1, Comparative Example 3, and Comparative Example 4 so as to have the configurations shown in Table 2 below.

[0285] (Example 1, Example 2, Comparative Example 2, Comparative Example 3) In Examples 1 and 2 and Comparative Examples 2 and 3, the high elasticity region 10, which is the replica substrate, is 152.4 mm square and 6.35 mm thick, and has a mesa portion 14 with a height of 30 μm and an area of ​​26 mm × 33 mm in the center (pattern region 13) of the first surface 11. The second surface 12 of the high elasticity region 10 overlaps with the mesa portion 14 (pattern region 13) and has a circular recess 15 (core-out) with a diameter of 60 mm that has a larger area than the mesa portion 14. The thickness of the recess 15 in the high elasticity region 10 is 1 mm. The high elasticity region 10 is synthetic quartz glass with an elastic modulus of approximately 72 GPa.

[0286] Acryloxypropyltrimethoxysilane, an acrylic group-containing silane coupling agent, is vapor-deposited on the mesa portion 14 of the high elasticity portion 10 to improve adhesion with the low elasticity portion 31 (curable composition (A)).

[0287] A mold consisting of a 300 mm diameter silicon wafer with a fine pattern FP formed in a central area of ​​26 mm x 33 mm was prepared as the master mold MM. A liquid film was formed by dripping the curable composition (A) onto the fine pattern FP portion of the master mold MM using an inkjet method, so that the residual film thickness was 10 μm in Example 1 and 20 μm in Example 2. Furthermore, a liquid film was formed by dripping the curable composition (A) onto the fine pattern FP portion of the master mold MM using an inkjet method, so that the residual film thickness was 30 μm in Comparative Example 2 and 100 μm in Comparative Example 3.

[0288] The mesa portion 14 (pattern region 13) of the high elasticity portion 10, which is the replica substrate, is brought into contact with a liquid film of non-volatile composition (A') formed by volatilizing the solvent (d) from the curable composition (A) on the master mold MM. Then, ultraviolet light is irradiated through the high elasticity portion 10 to cure the non-volatile composition (A'). This forms low elasticity portions 31 of various film thicknesses in the mesa portion 14 of the high elasticity portion 10. The elastic modulus of the low elasticity portion 31 is set to approximately 3 GPa.

[0289] Using ALD as the deposition method, SiO 2 is deposited to a thickness of 5 nm on the surface of the low elasticity portion 31 formed in the mesa portion 14 of the high elasticity portion 10, thereby forming an inorganic film 32 that covers the low elasticity portion 31.

[0290] (Comparative Example 1) As Comparative Example 1, a replica mold was produced that did not have the low elasticity region 31, the low elasticity region 31, and the inorganic film 32. Synthetic quartz glass having the same structure as in Example 1 was prepared as the high elasticity region 10, which was the replica substrate.

[0291] Comparative Example 4 As Comparative Example 4, a replica mold was produced that did not have the high elasticity region 10 or the inorganic film 32. In Comparative Example 4, polycarbonate having the same structure as the high elasticity region 10 was used as the replica substrate. Polycarbonate has an elastic modulus of approximately 3 GPa.

[0292] (2-2) Analysis of thermal deformation behavior To evaluate the deformation of the replica mold (pattern) due to UV radiation heat (exposure heat), we used a typical irradiation energy of 10,000 W / m for device imprinting. 2 The thermal deformation of the replica mold was analyzed for an irradiation time of 0.1 seconds. If the amount of deformation of the replica mold was 1 nm or less, it was rated as good (○), if the amount of deformation of the replica mold was 1 nm to 5 nm, it was rated as fair (△), and if the amount of deformation of the replica mold was 5 nm or more, it was rated as poor (×).

[0293] [Table 2]

[0294] In Examples 1 and 2, because they were restricted by synthetic quartz glass as the replica substrate, the amount of deformation was similar to that of Comparative Example 1, which was a conventional replica mold.

[0295] In Comparative Examples 2 and 3, although the replica substrate was bound by synthetic quartz glass, the residual film was thick and the deformation was not sufficient for semiconductor applications.

[0296] In Comparative Example 4, the replica substrate was made of polycarbonate instead of synthetic quartz glass, and therefore the amount of deformation was greater than in the other Examples and Comparative Examples.

[0297] As described above, this embodiment can provide a replica mold with improved conformability to foreign matter. Therefore, even when foreign matter is present on the substrate, the non-contact area where the curable composition on the substrate does not come into contact with the replica mold is reduced, allowing the transfer pattern of the replica mold to be transferred with high precision. Furthermore, since there is no need to apply a strong imprinting force to the replica mold, the possibility of the transfer pattern of the replica mold being compressed by foreign matter and damaged can be reduced. Furthermore, in this embodiment, an inorganic film is formed to cover the low-elasticity regions of the replica mold, thereby suppressing adhesion of the curable composition to the replica mold.

[0298] [Imprinting device] 11 is a schematic diagram showing the configuration of an imprint apparatus IMP according to one aspect of the present invention. The imprint apparatus IMP is a lithography apparatus that forms a pattern on a substrate. The imprint apparatus IMP brings a curable composition (imprint material) arranged on the substrate into contact with a replica mold, and applies energy for curing to the curable composition, thereby forming a pattern in the cured product to which the pattern of the replica mold has been transferred.

[0299] The imprint apparatus IMP has a holder HU that holds the replica mold RM and a substrate stage SS that holds the substrate SB. The imprint apparatus IMP also has a supply unit that includes a dispenser for disposing (supplying) the curable composition onto the substrate, a bridge surface plate for holding the holder HU, and a base surface plate for holding the substrate stage SS.

[0300] The replica mold RM is a mold for molding a curable composition on a substrate. As described above, the replica mold RM has a high elasticity region 10 including a mesa portion 14 and a recess 15, a low elasticity region 31 bonded to (formed on) the mesa portion 14, and an inorganic film 32 covering the low elasticity region 31.

[0301] The holding unit HU is a holding mechanism that holds the replica mold RM. The holding unit HU includes, for example, a chuck that vacuum- or electrostatically adsorbs the replica mold RM and a mold driver that drives the chuck. The mold driver drives (moves) the chuck that adsorbs the replica mold RM, i.e., the replica mold RM, in the X, Y, Z, and θZ directions.

[0302] The substrate stage SS is a holding mechanism that holds the substrate SB onto which the transfer pattern of the replica mold RM is transferred. The substrate stage SS, for example, vacuum- or electrostatically adsorbs the substrate SB via a chuck, and is driven by a substrate driver. The substrate driver drives the substrate stage SS that holds the substrate SB, i.e., the substrate SB, in the X, Y, Z, and θZ directions.

[0303] In the imprint apparatus IMP, while the curable composition on the substrate and the replica mold RM are in contact with each other, ultraviolet light is irradiated from above the apparatus to cure the curable composition, thereby curing the curable composition on the substrate. After that, by separating the replica mold RM, a cured film (cured product) of the curable composition onto which the transfer pattern of the replica mold RM has been transferred is formed on the substrate.

[0304] The pattern of the cured product formed using the imprinting apparatus IMP can be used permanently on at least a portion of various articles, or temporarily when manufacturing various articles. Examples of articles include electrical circuit elements, optical elements, MEMS, recording elements, sensors, and molds. Examples of electrical circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSIs, CCDs, image sensors, and FPGAs. Examples of molds include imprinting molds. Examples of optical elements include quantum dot structures, subwavelength antireflection structures, light extraction structures for LEDs and the like, photonic crystals, ultraviolet wire-grid polarizers, structural birefringence wave plates, diffraction gratings, and metalenses.

[0305] The pattern of the cured product may be used as it is as at least a part of a component of the above-mentioned article, or may be used temporarily as a resist mask, which is removed after etching or ion implantation is performed in a substrate processing step.

[0306] [Production method] A specific method for manufacturing the article will now be described. As shown in Figure 11(a), a substrate such as a silicon wafer having a workpiece such as an insulator formed on its surface is prepared, and then a curable composition is applied to the surface of the workpiece by an inkjet method or the like. Here, the state in which multiple droplets of the curable composition have been applied to the substrate is shown.

[0307] As shown in Figure 11(b), the replica mold is placed with the side on which the concave-convex pattern is formed facing the curable composition on the substrate. As shown in Figure 11(c), the replica mold is brought into contact with the substrate on which the curable composition has been applied, and pressure is applied. The curable composition fills the gap between the replica mold and the workpiece. In this state, when light is irradiated through the replica mold as curing energy, the curable composition cures.

[0308] 11(d), when the replica mold and the substrate are separated after the curable composition is cured, a pattern of the curable composition is formed on the substrate. In this cured product pattern, the recesses of the transfer pattern on the replica mold correspond to the protrusions of the cured product, and the protrusions of the transfer pattern on the replica mold correspond to the recesses of the cured product. In other words, the transfer pattern of the replica mold is transferred to the curable composition.

[0309] As shown in Figure 11(e), when etching is performed using the cured material pattern as an etching-resistant mask, the portions of the surface of the workpiece where no cured material is present or where only a thin layer remains are removed, forming grooves. As shown in Figure 11(f), when the cured material pattern is removed, an article with grooves formed on the surface of the workpiece can be obtained. Here, the cured material pattern was removed, but it may also be used as an interlayer insulating film included in semiconductor devices, i.e., a component of an article, without being removed after processing.

[0310] The disclosure of the present specification includes the following mold, manufacturing method, film forming method, article manufacturing method, and imprinting apparatus.

[0311] (Item 1) 1. A mold for use in imprint lithography, comprising: a first portion made of a material having a first modulus of elasticity; and a second portion made of a material having a second modulus of elasticity lower than the first modulus of elasticity, the first portion has a first surface including a mesa portion protruding from a plane, and a second surface opposite to the first surface including a recess; the second portion has a base portion including a third surface coupled to the mesa portion and a fourth surface opposite to the third surface, and a pattern portion including a protrusion protruding from the fourth surface and defining a pattern, a thickness of the base defined by the distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less; an inorganic film that covers the fourth surface of the base and the convex portions of the pattern portion; A mold characterized by:

[0312] (Item 2) 2. The mold according to item 1, wherein the inorganic film includes at least one selected from metals, semiconductors, ceramics, oxide ceramics, and glass.

[0313] (Item 3) 3. The mold according to item 1 or 2, wherein the mesa portion is located in a region inside an outer edge of a region obtained by orthogonally projecting the recess onto an imaginary plane parallel to the plane.

[0314] (Item 4) the first elastic modulus is 20 GPa or more; The second elastic modulus is 10 GPa or less. 4. The mold according to any one of items 1 to 3, characterized in that:

[0315] (Item 5) 5. The mold according to any one of items 1 to 4, wherein the distance between the flat surface of the first surface and the surface of the portion of the second surface where the recess is not present is 6.35 mm±0.10 mm.

[0316] (Item 6) 6. The mold according to any one of items 1 to 5, wherein the distance between the flat surface of the first surface and the bottom surface of the recess is 0.1 mm or more and 3 mm or less.

[0317] (Item 7) 7. The mold according to any one of items 1 to 6, wherein the mesa portion has a height greater than 0 μm and equal to or less than 1000 μm.

[0318] (Item 8) the material having the second elastic modulus is composed of a curable composition including a polymerizable compound, a photopolymerization initiator, and a solvent; the curable composition has a viscosity of 2 mPa·s or more and 60 mPa·s or less at 23°C and 1 atmosphere, The content of the solvent in the entire curable composition is greater than 5% by volume and less than 95% by volume, The boiling point of the solvent is less than 250°C at 1 atmosphere, a composition obtained by removing the solvent from the curable composition has a viscosity of 20 mPa·s or more and 10,000 mPa·s or less at 23°C and 1 atmosphere; 8. The mold according to any one of items 1 to 7, characterized in that:

[0319] (Item 9) 9. The mold according to any one of items 1 to 8, wherein the mold includes a replica mold.

[0320] (Item 10) A manufacturing method for manufacturing a mold having a first portion made of a material having a first elastic modulus, a second portion made of a material having a second elastic modulus lower than the first elastic modulus, and an inorganic film, comprising: a first step of forming, by imprinting, the second portion, in the mesa portion of the first portion, the mesa portion having a first surface including a mesa portion protruding from a plane and a second surface including a recess and opposite the first surface, the second portion having a base portion including a third surface coupled to the mesa portion and a fourth surface opposite the third surface, and a pattern portion defining a pattern including a protrusion protruding from the fourth surface; a second step of forming the inorganic film by using a deposition method, the inorganic film covering the fourth surface of the base and the convex portions of the pattern portion; and In the first step, the second portion is formed so that the thickness of the base defined by the distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less. A manufacturing method characterized by:

[0321] (Item 11) Item 11. The manufacturing method according to item 10, wherein the inorganic film contains at least one selected from metals, semiconductors, ceramics, oxide ceramics, and glass.

[0322] (Item 12) Item 11. The manufacturing method according to item 10, wherein the inorganic film contains Al2O3, SiO2 or HfO2.

[0323] (Item 13) 13. The manufacturing method according to any one of items 10 to 12, wherein the deposition method includes atomic layer deposition.

[0324] (Item 14) a third step of removing the inorganic film and the second portion; a fourth step of forming the second portion in the mesa portion by using an imprint method after the third step; a fifth step of forming the inorganic film by a deposition method after the fourth step, the inorganic film covering the fourth surface of the base and the convex portions of the pattern portion; and In the fifth step, the second portion is formed so that the thickness of the base defined by the distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less. 14. The manufacturing method according to any one of items 10 to 13,

[0325] (Item 15) Item 15. The method for producing a semiconductor device according to item 14, wherein the third step, the fourth step, and the fifth step are repeated.

[0326] (Item 16) A film forming method for forming a film of a curable composition in a space between the mold and a substrate using the mold according to any one of items 1 to 9, a disposing step of discretely disposing a plurality of droplets of the curable composition on the substrate; a waiting step of waiting until the plurality of droplets combine with adjacent droplets to form a liquid film; a contacting step of contacting the mold with the liquid film after the waiting step; and In the contacting step, a recess on a second surface of the first portion of the mold is bent to bring a central portion of the pattern portion in the second portion of the mold into contact with the liquid film, and after the pattern portion is brought into contact with the liquid film, the bending of the recess is released to bring the entire surface of the pattern portion into contact with the liquid film. A film forming method comprising:

[0327] (Item 17) A forming step of forming a film of a curable composition on a substrate using the film forming method according to item 16; a processing step of processing the substrate on which the film has been formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

[0328] (Item 18) An imprint apparatus for forming a pattern of a curable composition on a substrate, comprising: A holder that holds the mold according to any one of items 1 to 9; An imprinting apparatus comprising:

[0329] The invention is not limited to the above-described embodiments, and various changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention. [Explanation of symbols]

[0330] RM: replica mold 10: high elasticity portion 11: first surface 11a: flat surface 12: second surface 14: mesa portion 15: recessed portion 31: low elasticity portion 31a: third surface 31b: fourth surface 31c: protrusion portion 312: base portion 314: pattern portion

Claims

1. 1. A mold for use in imprint lithography, comprising: a first portion made of a material having a first modulus of elasticity; and a second portion made of a material having a second modulus of elasticity lower than the first modulus of elasticity, the first portion has a first surface including a mesa portion protruding from a plane, and a second surface opposite to the first surface including a recess; the second portion has a base portion including a third surface coupled to the mesa portion and a fourth surface opposite to the third surface, and a pattern portion including a protrusion protruding from the fourth surface and defining a pattern, a thickness of the base defined by the distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less; an inorganic film that covers the fourth surface of the base and the convex portions of the pattern portion; A mold characterized by:

2. The mold according to claim 1 , wherein the inorganic film contains at least one selected from the group consisting of metal, semiconductor, ceramic, oxide ceramic, and glass.

3. 2. The mold according to claim 1, wherein the mesa portion is located in a region inside an outer edge of a region obtained by orthogonally projecting the recess onto an imaginary plane parallel to the plane.

4. the first elastic modulus is 20 GPa or more; The second elastic modulus is 10 GPa or less. The mold of claim 1 .

5. 2. The mold according to claim 1, wherein the distance between the flat surface of the first surface and the surface of the portion of the second surface where the recess is not present is 6.35 mm±0.10 mm.

6. The mold according to claim 1 , wherein the distance between the flat surface of the first surface and the bottom surface of the recess is 0.1 mm or more and 3 mm or less.

7. The mold of claim 1 , wherein the mesa portion has a height greater than 0 μm and less than or equal to 1000 μm.

8. the material having the second elastic modulus is composed of a curable composition including a polymerizable compound, a photopolymerization initiator, and a solvent; the curable composition has a viscosity of 2 mPa·s or more and 60 mPa·s or less at 23°C and 1 atmosphere, the content of the solvent relative to the entire curable composition is greater than 5% by volume and less than 95% by volume; The boiling point of the solvent is less than 250°C at 1 atmosphere, a composition obtained by removing the solvent from the curable composition has a viscosity of 20 mPa·s or more and 10,000 mPa·s or less at 23°C and 1 atmosphere; The mold of claim 1 .

9. The mold of claim 1 , wherein the mold comprises a replica mold.

10. A manufacturing method for manufacturing a mold having a first portion made of a material having a first elastic modulus, a second portion made of a material having a second elastic modulus lower than the first elastic modulus, and an inorganic film, comprising: a first step of forming, by imprinting, the second portion, in the mesa portion of the first portion, the mesa portion having a first surface including a mesa portion protruding from a plane and a second surface including a recess and opposite the first surface, the second portion having a base portion including a third surface coupled to the mesa portion and a fourth surface opposite the third surface, and a pattern portion defining a pattern including a protrusion protruding from the fourth surface; a second step of forming the inorganic film by using a deposition method, the inorganic film covering the fourth surface of the base and the convex portions of the pattern portion; and In the first step, the second portion is formed so that a thickness of the base portion defined by a distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less. A manufacturing method characterized by:

11. 11. The manufacturing method according to claim 10, wherein the inorganic film contains at least one selected from the group consisting of metal, semiconductor, ceramic, oxide ceramic, and glass.

12. The inorganic film is Al ２ O ３ , SiO ２ or HfO ２ The method of claim 10, comprising:

13. The method of claim 10 , wherein the deposition method comprises atomic layer deposition.

14. a third step of removing the inorganic film and the second portion; a fourth step of forming the second portion in the mesa portion by using an imprint method after the third step; a fifth step of forming the inorganic film by a deposition method after the fourth step, the inorganic film covering the fourth surface of the base and the convex portions of the pattern portion; and In the fifth step, the second portion is formed so that a thickness of the base portion defined by a distance between the third surface and the fourth surface is 0.1 μm or more and 10 μm or less. The method of claim 10 .

15. The manufacturing method according to claim 14, wherein the third step, the fourth step, and the fifth step are repeated.

16. A film forming method for forming a film of a curable composition in a space between the mold and a substrate using the mold according to claim 1, comprising: a disposing step of discretely disposing a plurality of droplets of the curable composition on the substrate; a waiting step of waiting until the plurality of droplets combine with adjacent droplets to form a liquid film; a contacting step of contacting the mold with the liquid film after the waiting step; and In the contacting step, a recess in a second surface of the first portion of the mold is bent to bring a central portion of the pattern portion in the second portion of the mold into contact with the liquid film, and after the pattern portion is brought into contact with the liquid film, the bending of the recess is released to bring the entire surface of the pattern portion into contact with the liquid film. A film forming method comprising:

17. a forming step of forming a film of a curable composition on a substrate using the film forming method according to claim 16; a processing step of processing the substrate on which the film has been formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

18. An imprint apparatus for forming a pattern of a curable composition on a substrate, comprising: A holder that holds the mold according to claim 1 ; An imprinting apparatus comprising:

Images