Mold, manufacturing method, membrane forming method, method for manufacturing article, and imprint device

Abstract

To provide a new technique related to a mold.SOLUTION: A mold having a first portion and a second portion is provided. The first portion has a first surface including a flat surface, and a second surface on the opposite side of the first surface. The second surface includes, in its center part, a recess in a concave state. The first surface includes, in its center part, a protrusion protruding from the flat surface into a convex state. The second portion has a third surface coupled to the protrusion of the first portion, and a fourth surface on the opposite side of the third surface on which a pattern to be transferred to a transfer target is formed. The first portion is formed of material having a first modulus of elasticity. The second portion is formed of material having a second modulus of elasticity lower than the first modulus of elasticity.SELECTED DRAWING: Figure 3

Description

[Technical field]

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

[0002] In optical members, recording media, semiconductor devices, MEMS, and the like, there is an increasing demand for miniaturization, and imprinting technology (photo-imprinting technology) has been attracting attention as a microfabrication technology. In the imprinting technology, a mold (type) having a fine concave-convex pattern formed on its surface is brought into contact with a curable composition supplied (applied) onto a substrate, and the curable composition is cured in that state. In this way, the pattern of the mold is transferred to a cured film of the curable composition, and a pattern is formed on the substrate. With the imprinting technology, a fine pattern (structure) on the order of several nanometers can be formed on the substrate.

[0003] The master mold used in the imprinting technology is very expensive because a fine pattern is formed on the surface of silicon, quartz glass, metal, etc. by precision machining. Therefore, a technology has been proposed in which the fine pattern of the master mold is transferred to a mold base material (e.g., quartz glass) by imprinting processing (replica imprinting) and etching processing to produce a replica mold (see Patent Document 1). A replica mold is used in the imprinting processing (device imprinting) 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 various devices, particularly optical components, foreign matter of about 1 μm to 10 μm may be present on a substrate (device substrate). When device imprinting is performed on a substrate on which foreign matter exists using a quartz glass replica mold manufactured by the technology disclosed in Patent Document 1, a non-contact area of ​​about several mm to several tens of mm is generated around the foreign matter. Here, the non-contact area is an area where the hardening composition on the substrate and the replica mold are not in contact with each other, so the pattern of the replica mold is not transferred to the non-contact area, and no pattern is formed. The non-contact area can be reduced by applying a strong force (imprinting force) to the replica mold, but the possibility of the replica mold pattern being pressed by the foreign matter and damaged increases.

[0006] The present invention has been made in view of the above problems in the conventional technology, and has an exemplary object to provide a new technology relating to molds. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, a mold as one aspect of the present invention is a mold having a first portion and a second portion, wherein the first portion has a first surface including a flat surface and a second surface opposite the first surface, the second surface including a concave recess in a central portion and a convex portion protruding from the flat surface and having a convex shape in a central portion, the second portion having a third surface joined to the convex portion of the first portion and a fourth surface opposite the third surface on which a pattern to be transferred to a transfer target is formed, the first portion being made of a material having a first elastic modulus, and the second portion being made of a material having a second elastic modulus lower than the first elastic modulus.

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

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

[0010] [Figure 1] 1A to 1C are diagrams for explaining a configuration of a replica mold according to one aspect of the present invention. [Diagram 2] 1A to 1C are diagrams for explaining a configuration of a replica mold according to one aspect of the present invention. [Diagram 3] 1A to 1C are diagrams for explaining a configuration of a replica mold according to one aspect of the present invention. [Figure 4] 10 is a flowchart illustrating a manufacturing method for manufacturing a replica mold. [Diagram 5] FIG. 2 is a diagram showing the configurations of replica molds according to Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3. [Figure 6] 1A to 1C are views for explaining a contact step in the imprint process. [Figure 7] 13 is a diagram for explaining an analytical model of the tracking behavior of a replica mold with respect to a foreign object. FIG. [Figure 8] 13 is a diagram for explaining the difference in the follow-up behavior of the replica mold with respect to a foreign substance between Example 1 and Comparative Example 2. FIG. [Figure 9] 1 is a schematic diagram showing a configuration of an imprint apparatus according to one aspect of the present invention. [Figure 10] 1A to 1C are diagrams for explaining a method for manufacturing an article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the embodiments will be described in detail with reference to the attached drawings. Note that the following embodiments do not limit the invention according to the claims. Although the embodiments describe a number of features, not all of these features are essential to the invention, and the features may be combined in any manner. Furthermore, in the attached drawings, the same reference numbers are used for the same or similar configurations, and duplicated descriptions are omitted.

[0012] [Replica mold] 1, 2 and 3 are diagrams for explaining the configuration of a replica mold RM according to one aspect of the present invention. The replica mold RM is a mold (form, template, original) used in an imprinting technique (imprinting apparatus employing the technique), and in this embodiment, is embodied as a replica mold manufactured from a master mold. As shown in FIG. 3, the replica mold RM has a high elasticity region 10 (first region) made of a high elasticity material having a first elasticity, and a low elasticity region 31 (second region) made of a low elasticity material having a second elasticity lower than the first elasticity. The high elasticity region 10 (high elasticity material) has an elasticity of 20 GPa or more, preferably an elasticity of 50 GPa or more, and particularly preferably an elasticity of 70 GPa or more. The higher the elasticity (first elasticity) of the high elasticity region 10, the more the imprinting force is transmitted to the low elasticity region 31. The low elasticity region 31 (low elasticity material) has an elasticity of 10 GPa or less, preferably 3 GPa or less, and particularly preferably 1 GPa or less. The lower the elasticity (second elasticity) of the low elasticity region 31, the better the conformability to foreign matter present on a transfer target to which the pattern of the replica mold RM is transferred. FIG. 1 is a cross-sectional view that typically shows a high elasticity region 10, and FIG. 2 is a plan view that typically shows the high elasticity region 10. Note that FIG. 1 is a cross-sectional view taken along line AA shown in FIG. 2. FIG. 3 is a cross-sectional view that typically shows a replica mold RM having a high elasticity region 10 and a low elasticity region 31.

[0013] As shown in FIG. 1 and FIG. 2, the high elasticity region 10 is made of a replica substrate that serves as a 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 to the first surface 11. The first surface 11 includes a convex portion 14 that protrudes from the flat surface 11a to the opposite side to the second surface 12 and has a convex shape, that is, a step structure (so-called mesa structure) higher than the surroundings. The convex portion 14 is formed in the center of the first surface 11 and defines a pattern region 13 in which a transfer pattern to be transferred to a transfer target is to be formed. The convex portion 14 has an area of, for example, 0.5% to 30% of the area of ​​the first surface 11. The convex portion 14 has a height of, for example, 1 μm to 1000 μm from the first surface 11. On the other hand, the second surface 12 includes a concave portion 15 that is concave on the side of the first surface 11 as shown in FIG. 1. 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 0.1 mm or more and 3 mm or less. If the distance d is shorter than 0.1 mm (the thickness of the bottom of the recess 15 is thin), the replica mold RM (high elasticity portion 10) is likely to crack. If the distance d is longer than 3 mm (the thickness of the bottom of the recess 15 is thick), a large pressure is required to deflect the recess 15 (see FIG. 6(a)). The distance d is preferably 0.5 mm or more and 2.0 mm or less, and particularly preferably 0.8 mm or more and 1.5 mm or less. As shown in Figs. 1 and 2, the recess 15 is formed on the second surface 12 such that the area (circle indicated by a dotted line) of the recess 15 orthogonally projected onto the first surface 11, specifically onto a virtual plane VP parallel to the plane 11a, overlaps with the protrusion 14 (pattern area 13) formed on the first surface 11. Furthermore, the recess 15 is formed on the second surface 12 such that the area of ​​the recess 15 orthogonally projected onto the virtual plane VP has an area larger than the area of ​​the protrusion 14. In other words, the protrusion 14 is located in an area inside the outer edge of the area of ​​the recess 15 orthogonally projected onto the virtual plane VP. Moreover, 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 portion of the second surface 12 where there is no recess, is 6.35 mm (0.25 inches) ± 0.10 mm.

[0014] As shown in FIG. 3, the low elasticity region 31 includes a third surface 31a that is coupled to the convex portion 14 of the high elasticity region 10, and a fourth surface 31b opposite to the third surface 31a. The low elasticity region 31 is coupled (formed) to the first surface 11 of the high elasticity region 10, specifically, to the convex portion 14 (pattern region 13) formed on the first surface 11, via the third surface 31a. When forming the low elasticity region 31 on the convex portion 14, an imprint method is used. Also, by the imprint method, the low elasticity region 31 is formed on the convex portion 14, and a transfer pattern to be transferred to a transfer target is formed on the fourth surface 31b of the low elasticity region 31. The low elasticity region 31 has a thickness of, for example, 0.1 μm or more and 1000 μm or less.

[0015] [Manufacturing method of replica mold] The manufacturing method for producing the replica mold RM includes a step of forming the low elasticity region 31 in the convex portion 14 formed on the first surface 11 of the high elasticity region 10 by using an imprinting method. This step (imprinting method) includes a step of preparing a master mold, a step of preparing a curable composition (A) as a low elasticity member, a positioning step, a contacting step, a curing step, and a demolding step. The manufacturing method for producing the replica mold RM will be described below with reference to Figures 4(a) to 4(h), focusing particularly on the step of forming the low elasticity region 31.

[0016] <Master mold preparation process> As shown in FIG. 4(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 recess) formed on the replica mold RM. The master mold MM may be a mold made of a non-light-transmitting material or a mold made of a light-transmitting material. Examples of the mold substrate of the non-light-transmitting material mold include silicon wafer, nickel, copper, stainless steel, titanium, SiC, mica, and the like. Examples of the mold substrate of the light-transmitting material mold include glass such as quartz glass, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, transparent fluororesin, and the like. The light-transmitting material mold may be composed of a plurality of materials. Note that silicon wafers and quartz wafers are preferable as the mold substrate of the master mold MM because they have a good track record of use in the semiconductor industry and high-quality materials are available.

[0017] The fine pattern FP of the master mold MM is formed by using a microfabrication technique such as an electron beam lithography technique. The fine pattern FP formed on the master mold MM has a height of, for example, 4 nm or more and 200 nm or less. The lower 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, can be. Therefore, the number of demolding defects remaining on the master mold MM after the pattern of the curable composition (A) is torn off can be reduced. In addition, the pattern of the curable composition (A) may be elastically deformed by the impact when the master mold MM is demolded, and adjacent pattern elements may come into contact with each other, causing adhesion or damage. However, it is advantageous to have the height of the pattern element be about twice or less the width of the pattern element (aspect ratio 2 or less) in order to avoid such defects. On the other hand, if the height of the pattern element is too low, the processing accuracy of the mold substrate decreases.

[0018] The master mold MM may be subjected to a surface treatment before the placement step in order to improve the releasability of the master mold MM from the curable composition (A). For example, the surface treatment may involve applying a release agent to the surface of the master mold MM to form a release agent layer. Examples of the release agent applied to the surface of the master mold MM include silicon-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. For example, commercially available coating-type release agents such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also be suitably used. The release agents may be used alone or in combination of two or more types. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0019] <Step of preparing curable composition (A)> A curable composition (A) is prepared as a low elastic modulus member. The curable composition (A) is a composition containing at least a polymerizable compound (a) and a photopolymerization initiator (b). The curable composition (A) may be a composition further containing a non-polymerizable compound (c) and a solvent (d). The curable composition (A) is a curable composition for inkjet.

[0020] The polymerizable compound (a) may further contain at least one of a component (as) which is a polymerizable silicon compound and a component (af) which is a polymerizable fluorine compound.

[0021] The silicon compound as component (as) may be understood as a silicon-containing polymerizable compound. In this specification, the silicon-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).

[0022] Examples of the silicon-containing polymerizable compound include radical polymerizable compounds. The polymerizable compound of component (as) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0023] Examples of the silicon-containing radically polymerizable compound include (meth)acrylate-based compounds, (meth)acrylamide-based compounds, vinylbenzene-based compounds, allyl ether-based compounds, vinyl ether-based compounds, and maleimide-based compounds.

[0024] The silicon-containing polymerizable compound may be linear or branched. Specific examples of the radical polymerizable functional group include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds.

[0025] 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, SIM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, SIM6486.65 (all manufactured by GELEST) TM-0701T, FM-0711, FM-0721, FM-0725 (all manufactured by JNC) Furthermore, examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Linear polydimethylsiloxane modified with acryloxypropyl groups at both ends Linear polydimethylsiloxane modified with methacryloxypropyl groups at both ends Cyclic siloxane modified with multiple acryloxypropyl groups Cyclic siloxane modified with multiple methacryloxypropyl groups Silsesquioxane modified with multiple acryloxypropyl groups Silsesquioxane modified with multiple methacryloxypropyl groups Examples of commercially available products of the above-mentioned silicon-containing polyfunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (all manufactured by GELEST) FM-7711, FM-7721, FM-7725 (all manufactured by JNC) X-22-2445 (Shin-Etsu Chemical) AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20 (all manufactured by Toagosei) The silicon-containing (meth)acrylamide compound is a compound having one or more acrylamide groups or methacrylamide groups. Examples of the silicon-containing (meth)acrylamide compound having one acrylamide group or methacrylamide group include, but are not limited to, the following: 3-Acrylamidepropyltrimethoxysilane, 3-Acrylamidepropyltris(trimethylsiloxy)silane Examples of commercially available silicon-containing (meth)acrylamide compounds include, but are not limited to, the following: SIA0146.0, SIA0150.0 (both manufactured by GELEST) The fluorine compound as component (af) 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 (radical, etc.) generated from the photopolymerization initiator (b) to form a film made of a polymer compound by a chain reaction (polymerization reaction).

[0026] The fluorine-containing polymerizable compound may be, for example, a radical polymerizable compound. The polymerizable compound, which is the component (af), may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0027] 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.

[0028] 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, 1H,1H,5H-octafluoropentyl methacrylate, pentafluorophenyl acrylate, 2,2,3,3,3-pentafluorobutyl methacrylate 1H,1H,2H,2H-Tridecafluoro-n-octyl acrylate, 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, 1H,1H,5H-octafluoropentyl acrylate, and 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 Subfluorobutyl 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.) When the method disclosed in Japanese Patent No. 3963028 is used, examples of the above-mentioned fluorine-containing polyfunctional (meth)acrylate compound include, but are not limited to, the following. A linking group is introduced to the polyhydric alcohol moiety of trimethylolethane (3), pentaerythritol (4), or dipentaerythritol (6) using a standard organic synthesis reaction, and then a core with a high fluorine content is formed by a perfluorination reaction, with an acrylic group introduced at the end. Furthermore, the curable composition (A) may be a commercially available product, for example, PAK-TRAD manufactured by Toyo Gosei Co., Ltd. or UT-UCaf68 manufactured by AGC Seimi Chemical Co., Ltd.

[0029] <Placement process> In the disposing step, as shown diagrammatically in FIG. 4(b), droplets 102 of the curable composition (A) are discretely disposed on the master mold MM.

[0030] The inkjet method is particularly preferred as a method for arranging the droplets 102 of the curable composition (A) on the master mold MM. The droplets 102 of the curable composition (A) are densely arranged in regions where the recesses constituting the fine pattern FP of the master mold MM are densely present, and are sparsely arranged in regions where the recesses constituting the fine pattern FP of the master mold MM are sparsely present. This allows the residual film in 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.

[0031] <Standby process> The waiting step is provided after the disposing step and before the contacting step (between the disposing step and the contacting step). The waiting step is, for example, 0.1 to 600 seconds, and preferably 10 to 300 seconds. In the waiting step, the droplets 102 of the curable composition (A) spread on the master mold MM as shown in Fig. 4(c) and Fig. 4(d), and the droplets combine with each other to form a substantially continuous liquid film 103. The state of the curable composition (A) as shown in Fig. 4(d) is referred to as a "substantially continuous liquid film". In addition, when 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 in Fig. 4(e).

[0032] In the waiting step, in order to accelerate the evaporation of the solvent (d), a baking step may be performed in which the master mold MM and the curable composition (A) are heated, or the atmospheric gas around the master mold MM may be ventilated. The heating is performed, for example, at 30°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 110°C. The heating time may be 10 seconds or higher and 600 seconds or lower. The baking step may be performed using a known heater such as a hot plate or an oven.

[0033] <Contact process> In the contacting step, as shown in schematic form in Fig. 4(f), a substantially continuous liquid film 103 of the curable composition (A) on the master mold MM (the curable composition from which the solvent (d) has been removed) is brought into contact with the replica substrate 101 (protruding portion 14), which is the highly elastic member 10. The contacting step includes a step of changing a state in which the curable 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.

[0034] The replica substrate 101 preferably has a size of 152.4 mm (6 inches) square and a thickness of 6.35 mm. The material of the replica substrate 101 is preferably a high elastic modulus material having an elastic modulus of 50 GPa or more, and more specifically, quartz glass is preferable. Such quartz glass is available as a high-quality photomask substrate in the semiconductor industry and has a proven track record of use.

[0035] The contact step is preferably from 0.1 to 600 seconds, particularly preferably from 0.1 to 10 seconds. If the contact step is shorter than 0.1 seconds, the contact between the curable composition (A) on the master mold MM and the replica substrate 101 may be insufficient.

[0036] In the contact step, when the replica substrate 101 is brought into contact with the curable composition (A) on the master mold MM, the pressure applied to the curable composition (A) is not particularly limited, and is, for example, 0 MPa or more and 100 MPa or less. Note that, when the replica substrate 101 is brought into contact with the curable composition (A) on the master mold MM, the pressure applied to the curable composition (A) is preferably 0 MPa or more and 50 MPa or less. Furthermore, when the replica substrate 101 is brought into contact with the curable composition (A) on the master mold MM, the pressure applied to the curable composition (A) is more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0037] The contact step can be carried out under any of the conditions of the air atmosphere, the reduced pressure atmosphere, and the inert gas atmosphere, but it is preferable to carry out the contact step under the reduced pressure atmosphere or the inert gas atmosphere, since it can prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas used when carrying out the contact step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various fluorocarbon gases, and the like, or mixed gases thereof. When carrying out the contact step under a specific gas atmosphere, including the air atmosphere, the preferred pressure is 0.0001 atm or more and 10 atm or less.

[0038] <Curing process> In the curing step, as shown in FIG. 4(g), the liquid film 103 of the curable composition (A) is irradiated with irradiation light 107 as curing energy to cure the liquid film 103 of the curable composition (A) to form a cured film. In the curing step, for example, the liquid film 103 of the curable composition (A) is irradiated with irradiation light 107 through the replica substrate 101. More specifically, the curable composition (A) filled in the fine pattern FP of the master mold MM is irradiated with irradiation light 107 through the replica substrate 101. As a result, the curable composition (A) filled in the fine pattern FP of the master mold MM is cured to become a cured film 108 having a pattern.

[0039] The irradiation light 107 is selected according to the sensitivity wavelength of the curable composition (A). Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, or electron beams having a wavelength of 150 nm or more and 400 nm or less. It is particularly preferable that the irradiation light 107 is ultraviolet light. This is because many of the compounds commercially available as curing assistants (photopolymerization initiators) are 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, the ultra-high-pressure mercury lamp is particularly preferable as the light source that emits ultraviolet light. The number of light sources may be one or more. Furthermore, the entire area of ​​the curable 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 (protrusions 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 different from the first area of ​​the replica substrate 101 may be irradiated with light in a second irradiation process.

[0040] <Mold release process> In the demolding step, as shown in FIG. 4(h), the master mold MM is separated from the cured film 108. By separating the patterned cured film 108 from the master mold MM, the cured film 108 having a pattern that is an inversion of the fine pattern FP of the master mold MM is obtained in a self-supporting state on the replica substrate 101. Here, a film remains in the recesses of the cured film 108 having a pattern corresponding to the fine pattern FP of the master mold MM. Such a film is called a residual film.

[0041] The thickness of the residual film is 0.1 μm or more and 1000 μm or less. The thickness of the low elasticity portion 31 is defined as the total thickness of the thickness of the residual film and the height of the pattern. The thicker the residual film, the higher the followability to foreign matter present on the device substrate in the imprint process (device imprint) for manufacturing various devices. The residual film preferably has a thickness of about 10 times that of the foreign matter assumed to be present on the device substrate. For example, when the height of the foreign matter present on the device substrate is assumed to be about 0.1 μm, the residual film preferably has a thickness of 1 μm or more. Also, when the height of the foreign matter present on the device substrate is assumed to be about 1 μm, the residual film preferably has a thickness of 10 μm or more. Also, when the height of the foreign matter present on the device substrate is assumed to be about 10 μm, the residual film preferably has a thickness of 100 μm or more.

[0042] The method of separating the master mold MM from the cured film 108 having the pattern is not particularly limited as long as a part of the cured film 108 having the pattern is not physically damaged during the separation. For example, the replica substrate 101 may be fixed, and the master mold MM may be moved away from the replica substrate 101. 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.

[0043] [Imprint processing] A film forming method according to one aspect of the present invention will be described. In this embodiment, the film forming method is carried out as an imprinting process (imprinting method) using a replica mold by forming a film of a curable composition in a space between a replica mold and a substrate. The imprinting process is also carried out as a pattern forming method for forming a film having a pattern.

[0044] First, before carrying out the imprint process, a replica mold shown in each of the following Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 is manufactured (prepared).

[0045] Example 1 As Example 1, a replica mold RMA shown in FIG. 5(a) is manufactured. The high elasticity region 10, which is a replica substrate, has a size of 152.4 mm square and 6.35 mm thick, and has a convex 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 has a circular concave portion 15 with a diameter of 60 mm that overlaps with the convex portion 14 (pattern region 13) and has an area larger than that of the convex portion 14. The thickness of the concave portion 15 of the high elasticity region 10 is 1 mm. The high elasticity region 10 is synthetic quartz glass having an elastic modulus of about 72 GPa.

[0046] On the protrusions 14 of the high elasticity region 10, acryloxypropyltrimethoxysilane, which is an acrylic group-containing silane coupling agent, is vapor-deposited in order to improve adhesion with the curable composition (A).

[0047] 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 the center of an area of ​​26 mm x 33 mm is prepared.

[0048] A curable composition (A) containing a fluorine-containing polymerizable compound (af) is dropped by an inkjet method onto the fine pattern FP of the master mold MM so that the residual film has a thickness of 100 μm to form a liquid film.

[0049] The convex portion 14 (pattern region 13) of the high elasticity portion 10, which is the replica substrate, is brought into contact with the liquid film of the curable composition (A) on the master mold MM, and the curable composition (A) is cured by irradiating ultraviolet light through the high elasticity portion 10. As a result, a low elasticity portion 31 having a film thickness of 100 μm is formed on the convex portion 14 of the high elasticity portion 10. The elastic modulus of the low elasticity portion 31 is set to about 3 GPa.

[0050] Comparative Example 1 As Comparative Example 1, a replica mold RMB shown in Fig. 5(b) is manufactured. The replica mold RMB does not have a low elasticity region 31. As the high elasticity region 10, which is a replica substrate, synthetic quartz glass having the same structure as in Example 1 is prepared. A fine pattern is formed on the convex portion 14 of the high elasticity region 10 by electron beam lithography.

[0051] Comparative Example 2 As Comparative Example 2, a replica mold RMC shown in FIG. 5(c) is manufactured. In the replica mold RMC, both the portion 10C, which has the same shape as the high elasticity portion 10, and the low elasticity portion 31 have the second elastic modulus. Polycarbonate having the same structure as in Example 1 is prepared as the portion 10C and the low elasticity portion 31, which are replica substrates. A fine pattern is formed on the convex portion (mesa structure) of the low elasticity portion 31 (polycarbonate) by electron beam lithography. The second elastic modulus is set to about 3 GPa.

[0052] Comparative Example 3 As Comparative Example 3, a replica mold RMD shown in FIG. 5(d) is manufactured. The replica mold RMD does not have a recess 15. The high elasticity region 10, which is the replica substrate, has a size of 152.4 mm square and a thickness of 6.35 mm, and has a protrusion 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 does not have a recess 15. A fine pattern is formed on the protrusion 14 of the high elasticity region 10 by electron beam drawing technology.

[0053] (Device Imprint) Using replica molds RMA (Example 1), RMB (Comparative Example 1), RMC (Comparative Example 2), and RMD (Comparative Example 3), an imprint process (device imprint) for manufacturing various devices is performed. The imprint process includes, for example, a placement step, a waiting step, a contact step, a curing step, and a demolding step. The placement step is a step of discretely placing droplets for device imprinting on a device substrate. The waiting step is a step of waiting until the droplets for device imprinting are bonded to each other. The contact step is a step of contacting a curable composition for device imprinting with a replica mold. The curing step is a step of curing the curable composition for device imprinting. The demolding step is a step of detaching the replica mold from a cured film of the curable composition for device imprinting. The waiting step is performed after the placement step, the contact step is performed after the waiting step, the curing step is performed after the contact step, and the demolding step is performed after the curing step.

[0054] 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).

[0055] In the contact step, as shown in FIG. 6(a), the concave portion 15 of the replica mold is sealed to form a sealed space, and nitrogen gas is supplied to the sealed space to set the pressure of the sealed space to 1.5 atmospheres. This causes the concave portion 15 to bend, and the replica mold (the convex portion 14 and the low elasticity portion 31 formed on the convex portion 14) is curved (deformed) in a convex shape toward the device substrate. An example of a sealing mechanism for making the concave portion 15 into a sealed space is a holding portion that holds the replica mold. The holding portion may include a sealing member such as seal glass for making the concave portion 15 into a sealed space. Next, as shown in FIG. 6(b), the replica mold is lowered in a curved state, and only the center portion of the replica mold (the convex portion 14 and the low elasticity portion 31 formed on the convex portion 14) is brought into contact with the curable composition on the device substrate. As shown in Fig. 6(c), the replica mold is gradually brought into contact with the curable composition on the device substrate from the center to the outer periphery of the replica mold while applying an imprinting force of up to 42 N. Then, as shown in Fig. 6(d), when the entire replica mold (pattern region 13) comes into contact with the curable composition on the device substrate, the pressure in the sealed space is released to atmospheric pressure (1 atm) to eliminate the deflection of the replica mold.

[0056] Thus, in the contact step, the recess 15 of the high elasticity region 10 is deflected to bring the center of the fourth surface 31b of the low elasticity region 31 into contact with the liquid film of the curable composition on the device substrate. Then, after the center of the fourth surface 31b of the low elasticity region 31 is brought into contact with the liquid film of the curable composition, the deflection of the recess 15 is released to bring the entire surface of the fourth surface 31b of the low elasticity region 31 into contact with the liquid film of the curable composition on the device substrate.

[0057] In the curing step, the curable composition on the device substrate is cured by irradiating it with ultraviolet light as curing energy through the replica mold.

[0058] In the demolding step, the replica mold 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.

[0059] (Analysis of tracking behavior against foreign objects) With reference to FIG. 7, an analytical model of the replica mold's follow-up behavior with respect to a foreign object present on a device substrate will be described. A liquid film of a curable composition with an average thickness of 50 nm is formed in a shot area of ​​26 mm×33 mm on a silicon wafer having a diameter of 300 mm and an elastic modulus of 190 GPa as a device substrate. A cylindrical foreign object with a diameter of 10 μm and a height of 10 μm is present in the center of the liquid film on the shot area of ​​the device substrate. When the replica mold is brought into contact with the shot area with an imprinting force of 42 N, the follow-up behavior (deformation) of each of the replica molds in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 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. The meniscus pressure draws the replica mold toward the silicon wafer, so the effect of this pressure 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 sandwiching of the foreign object was calculated. The smaller the radius of the non-contact area, the higher the ability to follow the foreign object. The analysis was performed using Abaqus, a finite element analysis software from Dassault Systèmes.

[0060] In Example 1, device imprinting (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 object was 163 μm.

[0061] 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 object was 540 μm.

[0062] In Comparative Example 2, device imprinting (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 object was 220 μm.

[0063] Here, the difference in the replica mold's behavior in response to foreign matter between Example 1 and Comparative Example 2 will be described with reference to Fig. 8. In Comparative Example 2, the entire replica mold RMC is made of a low elasticity material of about 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 of about 72 GPa, so less imprinting force is consumed in deforming the recesses 15, and the imprinting force is transmitted to the protrusions 14. Therefore, the low elasticity regions 31 formed on the protrusions 14 of the replica mold RMA have improved ability to follow foreign matter compared to Comparative Example 2.

[0064] In Comparative Example 3, in device imprinting, an atmospheric gas was sandwiched between the replica mold RMD and the silicon wafer. This is because the synthetic quartz glass with a thickness of 6.35 mm cannot be curved at 1.5 atm. Analysis of the conforming behavior to foreign matter was not performed.

[0065] Thus, according to the present embodiment, a replica mold with improved conformability to foreign matter can be provided. Therefore, even if foreign matter is present on the substrate, the non-contact area where the curable composition on the substrate and the replica mold are not in contact is reduced, and the transfer pattern of the replica mold can be transferred with high accuracy. In addition, since there is no need to apply a strong imprinting force to the replica mold, the possibility that the transfer pattern of the replica mold will be damaged by being pressed by the foreign matter can be reduced.

[0066] [Imprint device] 9 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 of a cured material to which the pattern of the replica mold is transferred.

[0067] The imprint apparatus IMP has a holding part 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 part including a dispenser for disposing (supplying) the curable composition onto the substrate, a bridge surface plate for holding the holding part HU, a base surface plate for holding the substrate stage SS, and the like.

[0068] The replica mold RM is a mold for forming a curable composition on a substrate. As described above, the replica mold RM has the high elasticity region 10 including the convex portion 14 and the concave portion 15, and the low elasticity region 31 bonded (formed) to the convex portion 14 and having a transfer pattern formed thereon.

[0069] 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 driving unit that drives the chuck. The mold driving unit drives (moves) the chuck that adsorbs the replica mold RM, i.e., the replica mold RM, in the X direction, Y direction, Z direction, and θZ direction.

[0070] 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 driving unit. The substrate driving unit drives the substrate stage SS that holds the substrate SB, i.e., the substrate SB, in the X-, Y-, Z-, and θZ-directions.

[0071] 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. This cures the curable composition on the substrate, and then the replica mold RM is separated to form a cured film (cured product) of the curable composition onto which the transfer pattern of the replica mold RM is transferred, on the substrate.

[0072] The pattern of the cured product formed by using the imprinting apparatus IMP is used permanently on at least a part of various articles, or temporarily when manufacturing various articles. The article is an electric circuit element, an optical element, a MEMS, a recording element, a sensor, or a mold. Examples of the electric circuit element include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensor, and FPGA. Examples of the mold include a mold for imprinting. Examples of the optical element include a quantum dot structure, a subwavelength antireflection structure, a light extraction structure such as an LED, a photonic crystal, a wire grid type polarizing plate for ultraviolet light, a structural birefringent wave plate, a diffraction grating, and a metalens.

[0073] The pattern of the cured product may be used as it is as at least a part of the 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.

[0074] [Production method] A specific method for manufacturing the article will be described. As shown in Fig. 10(a), a substrate such as a silicon wafer with 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 the curable composition in the form of multiple droplets is applied onto the substrate is shown.

[0075] As shown in Fig. 10(b), the replica mold is placed so that the side on which the concave-convex pattern is formed faces the curable composition on the substrate. As shown in Fig. 10(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. When light is irradiated through the replica mold in this state as energy for curing, the curable composition is cured.

[0076] 10(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 of the replica mold correspond to the protruding parts of the cured product, and the protruding parts of the transfer pattern of the replica mold correspond to the recesses of the cured product, i.e., the transfer pattern of the replica mold is transferred to the curable composition.

[0077] As shown in Fig. 10(e), when etching is performed using the pattern of the cured material as an etching-resistant mask, the portions of the surface of the workpiece where there is no cured material or where only a thin portion remains are removed, forming grooves. As shown in Fig. 10(f), when the pattern of the cured material is removed, an article having grooves formed on the surface of the workpiece can be obtained. Here, the pattern of the cured material is removed, but it may be used as an interlayer insulating film included in a semiconductor element, i.e., a component of an article, without being removed after processing.

[0078] The disclosure of the present specification includes the following mold, manufacturing method, film formation method, article manufacturing method, and imprint apparatus.

[0079] (Item 1) A mold having a first portion and a second portion, The first portion has a first surface including a flat surface and a second surface opposite to the first surface, The second surface includes a concave recess in a central portion, The first surface includes a convex portion at a central portion thereof that protrudes from the flat surface and has a convex shape, the second portion has a third surface coupled to the convex portion of the first portion, and a fourth surface opposite to the third surface, on which a pattern to be transferred to a transfer target is formed; the first portion is made of a material having a first elastic modulus; The second portion is made of a material having a second elastic modulus lower than the first elastic modulus. A mold comprising:

[0080] (Item 2) 2. The mold according to item 1, wherein the convex portion is located in an area inside an outer edge of an area obtained by orthogonally projecting the concave portion onto a virtual plane parallel to the plane.

[0081] (Item 3) The first elastic modulus is 20 GPa or more, The second elastic modulus is 10 GPa or less. 3. The mold according to item 1 or 2, characterized in that

[0082] (Item 4) A mold described in any one of items 1 to 3, characterized in that the distance between the plane of the first surface and the surface of the portion of the second surface that does not have the recess is 6.35 mm ± 0.10 mm.

[0083] (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 bottom surface of the recess is 0.1 mm or more and 3 mm or less.

[0084] (Item 6) 6. The mold according to any one of items 1 to 5, wherein the convex portion has a height greater than 0 μm and less than or equal to 1000 μm.

[0085] (Item 7) 7. The mold according to any one of claims 1 to 6, wherein the second portion has a thickness of 0.1 μm or more and 1000 μm or less.

[0086] (Item 8) 8. The mold according to any one of items 1 to 7, wherein the convex portion has an area of ​​0.5% to 30% of the area of ​​the first surface.

[0087] (Item 9) 9. The mold according to any one of claims 1 to 8, wherein the mold comprises a replica mold.

[0088] (Item 10) A method for manufacturing a mold having a first portion and a second portion, comprising the steps of: forming the second portion in the convex portion of the first portion, the first portion having a first surface including a flat surface and a second surface opposite to the first surface, the second surface including a concave portion in a central portion thereof that is concave, and the first surface including a convex portion in a central portion thereof that protrudes from the flat surface and is convex; having In the step, a pattern to be transferred to a transfer target is also formed on a fourth surface of the second portion opposite to a third surface coupled to the convex portion of the first portion, the first portion is made of a material having a first elastic modulus; The second portion is made of a material having a second elastic modulus lower than the first elastic modulus. A manufacturing method comprising the steps of:

[0089] (Item 11) A film forming method for forming a film of a curable composition in a space between the mold and a substrate by using the mold according to claim 1, comprising the steps of: 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; having In the contacting step, a recess in a second surface of a first portion of the mold is deflected to bring a central portion of a fourth surface in the second portion of the mold into contact with the liquid film, and after the central portion is brought into contact with the liquid film, the deflection of the recess is released to bring the entire surface of the fourth surface into contact with the liquid film. A film forming method comprising the steps of:

[0090] (Item 12) A forming step of forming a film of a curable composition on a substrate by using the film forming method according to item 11; a processing step of processing the substrate on which the film is formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for producing an article, comprising the steps of:

[0091] (Item 13) An imprint apparatus for forming a pattern of a curable composition on a substrate, comprising: A holder for holding the mold according to any one of items 1 to 9; 1. An imprint apparatus comprising:

[0092] The invention is not limited to the above-described embodiments, and various modifications and variations are possible 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]

[0093] RM: replica mold 10: high elasticity area 11: first surface 11a: flat surface 12: second surface 14: convex portion 15: concave portion 31: low elasticity area 31a: third surface 31b: fourth surface

Claims

1. A mold having a first portion and a second portion, The first portion has a first surface including a flat surface and a second surface opposite to the first surface, The second surface includes a concave recess in a central portion, The first surface includes a convex portion at a central portion thereof that protrudes from the flat surface and has a convex shape, the second portion has a third surface coupled to the convex portion of the first portion, and a fourth surface opposite to the third surface, on which a pattern to be transferred to a transfer target is formed; the first portion is made of a material having a first elastic modulus; The second portion is made of a material having a second elastic modulus lower than the first elastic modulus. A mold comprising:

2. The mold according to claim 1 , wherein the convex portion is located in an area inside an outer edge of an area obtained by orthogonally projecting the concave portion onto an imaginary plane parallel to the plane.

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

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

5. The mold according to claim 1 , wherein a distance between the flat surface of the first surface and a bottom surface of the recess is not less than 0.1 mm and not more than 3 mm.

6. The mold according to claim 1 , wherein the protrusions have a height greater than 0 μm and less than or equal to 1000 μm.

7. The mold of claim 1 , wherein the second portion has a thickness of 0.1 μm to 1000 μm.

8. The mold according to claim 1 , wherein the protrusion has an area that is 0.5% to 30% of an area of ​​the first surface.

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

10. 1. A method for manufacturing a mold having a first portion and a second portion, comprising the steps of: forming the second portion on the convex portion of the first portion, the first portion having a first surface including a flat surface and a second surface opposite to the first surface, the second surface including a concave portion at a central portion thereof that is concave, and the first surface including a convex portion at a central portion thereof that protrudes from the flat surface and is convex; having In the step, a pattern to be transferred to a transfer target is also formed on a fourth surface of the second portion opposite to a third surface coupled to the convex portion of the first portion, the first portion is made of a material having a first elastic modulus; The second portion is made of a material having a second elastic modulus lower than the first elastic modulus. A manufacturing method comprising the steps of:

11. A film forming method for forming a film of a curable composition in a space between the mold and a substrate by using the mold according to claim 1, comprising the steps of: 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; having In the contacting step, a recess in a second surface of a first portion of the mold is deflected to bring a central portion of a fourth surface in the second portion of the mold into contact with the liquid film, and after the central portion has been brought into contact with the liquid film, the deflection of the recess is released to bring the entire surface of the fourth surface into contact with the liquid film. A film forming method comprising the steps of:

12. A forming step of forming a film of a curable composition on a substrate by using the film forming method according to claim 11; a processing step of processing the substrate on which the film is formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for producing an article, comprising:

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

Images