Cured film forming method, method for manufacturing substrate for imprint mold, method for manufacturing imprint mold, method for manufacturing uneven structure, pattern forming method, hard mask forming method, insulating film forming method, and method for manufacturing semiconductor device

Abstract

The purpose of the present invention is to provide a cured film forming method by which a cured film that can be used as a protective film or the like can be formed in a simpler manner.　Said method comprises: a step (fig. 1A) for supplying, to a substrate (3), a curable resin (2) which contains a polymerizable compound having a siloxane bond in a molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; a step (fig. 1B) for curing the curable resin; and a step (fig. 1D) for forming a cured film (1) by subjecting the cured curable resin to a plasma treatment or an oxidation treatment, decomposing organic components contained in the curable resin, and allowing a siloxane polymerization part to remain.

Description

Cured film forming method, imprint mold substrate manufacturing method, imprint mold manufacturing method, concavo-convex structure manufacturing method, pattern forming method, hard mask forming method, insulating film forming method, and semiconductor device manufacturing method

[0001] The present disclosure relates to a method for forming a cured film, a method for manufacturing a substrate for an imprint mold, a method for manufacturing an imprint mold, a method for manufacturing a concave-convex structure, a pattern forming method, a hard mask forming method, an insulating film forming method, and a method for manufacturing a semiconductor device.

[0002] Nanoimprint lithography is known as a technique for transferring fine patterns in the manufacture of semiconductor devices and the like. Nanoimprint lithography is a technique in which an imprint mold, on whose surface a transfer pattern of fine concave and convex shapes is formed, is brought into contact with a resin supplied on a transfer substrate such as a semiconductor wafer, and the resin is then cured to transfer the concave and convex shapes of the transfer pattern of the imprint mold to the resin. Nanoimprint lithography techniques include thermal imprinting, which uses thermal energy to transfer the concave and convex shapes of the transfer pattern to the resin, and photoimprinting, which cures the resin by exposure to light. Photoimprinting, which is not affected by expansion or contraction due to heating, is mainly used for applications requiring high alignment accuracy.

[0003] In an imprint mold used in nanoimprint lithography, a mesa-shaped step structure is provided on the main surface of a base so that only a predetermined region (pattern region) where a transfer pattern having a concave and convex shape is formed comes into contact with a resin supplied onto a transfer substrate, and the transfer pattern is formed on the upper surface of the mesa-shaped step structure. Note that in an imprint mold configured in this manner, the upper surface of the mesa-shaped step structure becomes the pattern region. The step of the mesa-shaped step structure (the height from the main surface of the base to the upper surface of the step structure) is determined by the mechanical precision of the imprinting device used, but is generally about 30 μm.

[0004] Furthermore, as the pattern density of the transfer pattern in the imprint mold increases, the contact area between the imprint mold and the resin increases, and therefore, a force to counter the frictional force between the two is required to release the imprint mold from the resin. In particular, transfer patterns for semiconductor applications have small sizes (dimensions) and high pattern densities, requiring a large force for release. Therefore, a known method is to form a recess on the back side of the imprint mold (the side opposite to the surface on which the transfer pattern is formed) to reduce the thickness of the template in a predetermined region where the transfer pattern is formed (the region including the pattern region) and make it easier to bend. During release, the pattern region of the imprint mold is curved convexly toward the transfer substrate, allowing for sequential partial release from the outer edge of the transfer region.

[0005] In the optical imprinting method, in order to prevent the resin located in the non-transfer area, which is an area other than the area to which the transfer pattern is transferred, from being unintentionally hardened, it has been proposed to form a second step structure on top of the first step structure of the imprint mold, and to provide a light-shielding section in the non-pattern area (a region different from the transfer pattern area), which is an area outside the second step structure on the upper surface of the first step structure (see Patent Document 1).

[0006] JP 2018-56545 A International Publication No. 2020 / 203472 Pamphlet

[0007] An imprint mold having a first step structure and a second step structure and a light-shielding portion provided in a non-pattern portion (a portion different from the transfer pattern region) is manufactured, for example, by preparing an imprint mold substrate having a second step structure provided on the first step structure, forming a transfer pattern in the transfer pattern region, and then forming a light-shielding portion in the non-pattern portion (see Patent Document 1). If a light-shielding portion is provided in the non-pattern portion of an imprint mold substrate having a first step structure and a second step structure and then a transfer pattern is formed in the transfer pattern region of the imprint mold substrate, the light-shielding portion may be damaged during an etching process, a cleaning process, or the like in the process of manufacturing the imprint mold, and therefore the light-shielding portion may not exhibit the desired function in the manufactured imprint mold. In order to solve these problems, it is conceivable to form a protective film on the light-shielding portion to suppress damage to the light-shielding portion. However, in order to form a protective film on the light-shielding portion that is provided only in the non-patterned portion of a substrate for imprint molding, for example, processes such as sputtering and patterning must be performed, and the process of forming the light-shielding portion is therefore complicated.

[0008] In view of the above problems, an object of the present disclosure is to provide a cured film formation method that enables a cured film that can be used as a protective film or the like as described above to be formed in a simpler manner, as well as a method for manufacturing a substrate for an imprint mold, a method for manufacturing an imprint mold, a method for manufacturing a concavo-convex structure, a pattern formation method, a hard mask formation method, a method for forming an insulating film, and a method for manufacturing a semiconductor device that utilize the cured film formation method.

[0009] In order to achieve such an object, one embodiment of the present disclosure provides a method for forming a cured film, including the steps of: supplying a curable resin to a substrate, the curable resin including a polymerizable compound having a siloxane bond in the molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; curing the curable resin; and subjecting the cured curable resin to a plasma treatment or an oxidation treatment to decompose organic components contained in the curable resin and leave siloxane polymerized moieties, thereby forming a cured film.

[0010] The polymerizable compound may have a spherical structure in which the polymerizable functional groups extend outward from the siloxane polymerized portion. The proportion of oxygen atoms bonded to a single silicon atom among oxygen atoms bonded to silicon atoms contained in the polymerizable compound may be 10 mol % or less, and the curable resin may be substantially solvent-free and have a viscosity of 20 cPs or less. The content of the reactive crosslinker contained in the curable resin may be 49% by mass to 79% by mass.

[0011] The process of hardening the curable resin may include a contact process of bringing a mold close to the substrate and spreading the curable resin between the substrate and the mold to form a moldable resin layer, a hardening process of hardening the moldable resin layer, and a demolding process of pulling the mold away from the hardened moldable resin layer.

[0012] The amount of the curable resin to be supplied to the substrate can be determined based on the following formula (1), which shows the relationship between the thickness T of the resin layer to be molded, the thickness T of the cured film, and the decomposition processing time t for decomposing the organic components.

[0013] In the above formula (1), Ab ct represents "the amount of decrease per unit time in the film thickness of the molded resin layer, which changes depending on the decomposition processing time t at the beginning of the decomposition processing of the organic component", αt represents "the amount of decrease per unit time in the film thickness of the molded resin layer, which does not substantially change depending on the decomposition processing time t", A represents "the amount of decrease per unit time in the film thickness of the molded resin layer, which does not substantially change depending on the decomposition processing time t", and b and c are "coefficients indicating the exponential decrease in the film thickness of the molded resin layer", where b>1 and c<0.

[0014] A cured film formation region where the cured film is formed and a cured film non-formation region where the cured film is not formed are set on the substrate, and the curable resin is supplied to the cured film formation region in an amount determined based on the formula (1) so that the thickness T of the cured film exceeds 0, and the curable resin is supplied to the cured film non-formation region in an amount determined based on the formula (1) so that the thickness T of the cured film is 0 or less.

[0015] The mold has a concave-convex structure including recesses, and the resin layer to be molded has a transfer structure including protrusions to which the recesses of the concave-convex structure are transferred, and a residual film portion, and the amount of the curable resin to be supplied to the substrate can be determined based on the depth of the recesses of the concave-convex structure, the thickness of the residual film portion, and the formula (1).

[0016] The mold may have a concave-convex structure with a minimum dimension of 100 nm or less, the resin layer to be molded may have a transferred structure to which the concave-convex structure has been transferred, and the cured film may be formed having a pattern with dimensions smaller than the minimum dimension of the concave-convex structure. The substrate may have a first surface and a second surface located opposite the first surface, and at least one material layer made of a material different from the material of the substrate may be provided on at least the first surface, and the curable resin may be supplied onto the material layer.

[0017] As one embodiment of the present disclosure, there is provided a cured film formed by the above-described cured film formation method, wherein the cured film has a composition distribution along the thickness direction of the cured film, in which the concentration of silicon (Si) atoms is highest near the surface of the cured film and the concentration of silicon (Si) atoms is lowest near the substrate.

[0018] The cured film may have a composition distribution along its thickness direction in which the concentration of carbon (C) atoms is lowest near the surface of the cured film and highest near the substrate.

[0019] As one embodiment of the present disclosure, a method for manufacturing a multi-stage mold substrate includes the steps of: preparing a multi-stage mold substrate including a base having a first surface and a second surface located opposite to the first surface; a first step structure protruding from the first surface of the base; a second step structure protruding from an upper surface of the first step structure; and a light-shielding film located on the upper surface of the first step structure; supplying a curable resin containing a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent onto the light-shielding film and the upper surface of the second step structure, to form a first curable resin layer on the light-shielding film and a second curable resin layer on the second step structure. and forming a second curable resin layer on a surface of the light-shielding film, and curing the first curable resin layer and the second curable resin layer. The method also includes the steps of: subjecting the cured first curable resin layer and the second curable resin layer to a plasma treatment or an oxidation treatment to decompose organic components contained in the curable resin and leaving siloxane polymerized parts, thereby forming a protective film on the light-shielding film, and removing the second curable resin layer. The thickness of the second curable resin layer is smaller than the thickness of the first curable resin layer and is thick enough to be removed during the formation of the protective film.

[0020] A light-shielding material layer may be formed on the upper surface of the second step structure of the multi-stage mold substrate, and the method may include a step of removing the light-shielding material layer by etching after removing the second curable resin layer.

[0021] As one embodiment of the present disclosure, there is provided a method for manufacturing an imprint mold, including the steps of forming a first hard mask layer on the protective film of an imprint mold substrate manufactured by the above method, and forming a second hard mask layer on an upper surface of the second step structure; forming a mask pattern on the second hard mask layer; etching the second hard mask layer using the mask pattern as a mask to form a hard mask pattern on the upper surface of the second step structure and removing the first hard mask layer; and etching the upper surface of the second step structure using the hard mask pattern as a mask to form a concave-convex pattern on the upper surface of the second step structure and removing the protective film.

[0022] As one embodiment of the present disclosure, there is provided a method for manufacturing a concave-convex structure, comprising the steps of: preparing a substrate having a first surface and a second surface opposite the first surface; forming a core material pattern having a convex pattern on the first surface; supplying a curable resin onto the core material pattern, the curable resin including a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinker; contacting a template with the curable resin supplied onto the core material pattern and curing it to form a curable resin layer that covers the tops and sidewalls of the convex patterns of the core material pattern, as well as the first surface exposed between adjacent convex patterns; performing a plasma treatment or an oxidation treatment on portions of the curable resin layer that cover the sidewalls of the convex patterns, decomposing organic components contained in the curable resin to leave siloxane polymerized portions, and removing portions that cover the tops of the convex patterns and portions that cover the first surface exposed between adjacent convex patterns, to form a sidewall pattern; and removing the core material pattern.

[0023] As one embodiment of the present disclosure, there is provided a pattern formation method including the steps of: preparing a substrate having a first surface and a second surface located opposite the first surface; discretely dropping onto the first surface of the substrate a curable resin, the curable resin including a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; curing the discretely dropped curable resin; and subjecting the cured curable resin to a plasma treatment or an oxidation treatment to decompose organic components contained in the curable resin and leave siloxane polymerized moieties, thereby forming a cured film pattern.

[0024] As an embodiment of the present disclosure, there is provided a pattern forming method including the steps of: preparing a substrate having a first surface and a second surface located opposite the first surface; supplying a curable resin to the first surface of the substrate, the curable resin including a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; bringing a mold close to the substrate and curing the curable resin spread between the substrate and the mold to form a molded resin layer; separating the mold from the mold; forming a resist layer having a thickness distribution on the molded resin layer; etching the molded resin layer using the resist layer as a mask to form a resin pattern; and performing a plasma treatment or an oxidation treatment on the resin pattern to decompose organic components contained in the curable resin and leave siloxane polymerized portions, thereby forming a cured film pattern.

[0025] As one embodiment of the present disclosure, there is provided a method for forming a hard mask in an arbitrary region on a substrate on which a metal film has been formed, the hard mask formation method including the steps of: supplying, onto the metal film, a curable resin containing a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; bringing a mold close to the substrate and curing the curable resin spread between the substrate and the mold, thereby forming a moldable resin layer; and subjecting the moldable resin layer to a plasma treatment or an oxidation treatment to decompose organic components contained in the curable resin and leave siloxane polymerized portions, thereby forming a hard mask.

[0026] As one embodiment of the present disclosure, there is provided a method for forming an insulating film in an insulating film formation region on a substrate, the method including the steps of: supplying a curable resin to the insulating film formation region, the curable resin including a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; curing the curable resin; and subjecting the cured curable resin to a plasma treatment or an oxidation treatment to decompose organic components contained in the curable resin and leave siloxane polymerized portions, thereby forming the insulating film.

[0027] As one embodiment of the present disclosure, there is provided a method for manufacturing a semiconductor device having a structure in which a semiconductor layer, an insulating film, and wiring are stacked in this order from the first surface side of a substrate having a first surface and a second surface located opposite the first surface, the method including the steps of: forming, on the first surface, the semiconductor layer having a channel region and source / drain regions including contact portions that contact the wiring; and forming the insulating film by the above-described method on the channel region and on a region excluding the contact portions.

[0028] According to the present disclosure, it is possible to provide a cured film formation method that enables a cured film that can be used as a protective film or the like as described above to be formed in a simpler manner, as well as a method for manufacturing an imprint mold substrate, a method for manufacturing an imprint mold, a method for manufacturing a concave-convex structure, a pattern formation method, a hard mask formation method, a method for forming an insulating film, and a method for manufacturing a semiconductor device that utilize the cured film formation method.

[0029] FIG. 1A is a cross-sectional view schematically showing a step of a method for forming a cured film according to an embodiment of the present disclosure, the step being subsequent to FIG. 1A . FIG. 1C is a cross-sectional view schematically showing a step of a method for forming a cured film according to an embodiment of the present disclosure, the step being subsequent to FIG. 1B . FIG. 1D is a cross-sectional view schematically showing a step of a method for forming a cured film according to an embodiment of the present disclosure, the step being subsequent to FIG. 1C . FIG. 2A is a cross-sectional view schematically showing a step of another aspect of the method for forming a cured film according to an embodiment of the present disclosure, the step being subsequent to FIG. 2A . FIG. 2C is a cross-sectional view schematically showing a step of another aspect of the method for forming a cured film according to an embodiment of the present disclosure, the step being subsequent to FIG. 2B . FIG. 2D is a cross-sectional view schematically showing a step of another aspect of the method for forming a cured film according to an embodiment of the present disclosure, the step being subsequent to FIG. 2C .

[0023] Figure 3A is a cross-sectional view schematically illustrating a step of a method for manufacturing a substrate for an imprint mold according to an embodiment of the present disclosure, the step continuing from Figure 3A; Figure 3B is a cross-sectional view schematically illustrating a step of a method for manufacturing a substrate for an imprint mold according to an embodiment of the present disclosure, the step continuing from Figure 3A; Figure 3C is a cross-sectional view schematically illustrating a step of a method for manufacturing a substrate for an imprint mold according to an embodiment of the present disclosure, the step continuing from Figure 3B; Figure 3D is a cross-sectional view schematically illustrating a step of a method for manufacturing a substrate for an imprint mold according to an embodiment of the present disclosure, the step continuing from Figure 3C; Figure 3E is a cross-sectional view schematically illustrating a step of a method for manufacturing a substrate for an imprint mold according to an embodiment of the present disclosure, the step continuing from Figure 3D; Figure 3F is a cross-sectional view schematically illustrating a step of a method for manufacturing a substrate for an imprint mold according to an embodiment of the present disclosure, the step continuing from Figure 3E; Figure 4A is a cross-sectional view schematically illustrating a step of a method for manufacturing an imprint mold according to an embodiment of the present disclosure. 4B is a cutaway end view that schematically illustrates a step in a method for manufacturing an imprint mold according to an embodiment of the present disclosure, the step following FIG. 4A.Fig. 4C is a cross-sectional view schematically showing a step of a method for manufacturing an imprint mold according to an embodiment of the present disclosure, the step continuing from Fig. 4B . Fig. 4D is a cross-sectional view schematically showing a step of a method for manufacturing an imprint mold according to an embodiment of the present disclosure, the step continuing from Fig. 4C . Fig. 4E is a cross-sectional view schematically showing a step of a method for manufacturing an imprint mold according to an embodiment of the present disclosure, the step continuing from Fig. 4D . Fig. 4F is a cross-sectional view schematically showing a step of a method for manufacturing an imprint mold according to an embodiment of the present disclosure, the step continuing from Fig. 4F . Fig. 5A is a cross-sectional view schematically showing a step of a method for manufacturing a concave-convex structure according to an embodiment of the present disclosure, the step continuing from Fig. 5A . Fig. 5C is a cross-sectional view schematically showing a step of a method for manufacturing a concave-convex structure according to an embodiment of the present disclosure, the step continuing from Fig. 5B . Fig. 5D is a cross-sectional view schematically showing a step of a method for manufacturing a concave-convex structure according to an embodiment of the present disclosure, the step continuing from Fig. 5C . FIG. 5E is a cross-sectional view schematically showing a step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure, the step following FIG. 5D . FIG. 6A is a plan view of a step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure, the step shown in FIG. 5A . FIG. 6B is a plan view of a step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure, the step shown in FIG. 5B . FIG. 6C is a plan view of a step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure, the step shown in FIG. 5C . FIG. 6D is a plan view of a step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure, the step shown in FIG. 5D . FIG. 6E is a plan view of a step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure, the step shown in FIG. 5E . FIG. 7A is a cross-sectional view schematically showing a step of a pattern formation method according to an embodiment of the present disclosure, the step following FIG. 7A . FIG. 8A is a cross-sectional view schematically showing a step of another aspect of a pattern formation method according to an embodiment of the present disclosure.Fig. 8B is a cross-sectional view schematically showing a step subsequent to Fig. 8A , which is a step of another aspect of the pattern formation method according to an embodiment of the present disclosure. Fig. 8C is a cross-sectional view schematically showing a step subsequent to Fig. 8B , which is a step of another aspect of the pattern formation method according to an embodiment of the present disclosure. Fig. 9A is a cross-sectional view schematically showing a step of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure. Fig. 9B is a cross-sectional view schematically showing a step subsequent to Fig. 9A , which is a step of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure. Fig. 10 is a graph showing the results of Example 1, Reference Example 1, and Reference Example 2.

[0030] Embodiments of the present disclosure will be described with reference to the drawings. In the drawings, the shape, scale, aspect ratio, and the like of each part may be shown exaggerated or modified from the actual product to facilitate understanding. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, terms such as "film," "sheet," and "plate" are not distinguished from one another based on differences in nomenclature. For example, "plate" is a concept that also includes members that may be commonly called "sheet" and "film."

[0031] [Cured Film Forming Method] The cured film forming method according to this embodiment includes a step of supplying a curable resin 2 to a substrate 3 (see FIGS. 1A and 2A), a step of curing the curable resin 2 (see FIGS. 1B, 1C, 2B, and 2C), and a step of forming a cured film 1 (see FIGS. 1D and 2D).

[0032] The curable resin 2 in this embodiment contains a polymerizable compound having an organic component and an inorganic component in the molecule. The inorganic component is SiO X (X is 1 or more), and the polymerizable compound may be any compound having a siloxane bond as an inorganic component and having at least one polymerizable functional group.

[0033] In the present embodiment, the polymerizable compound contained in the curable resin 2 may have a ratio of oxygen atoms bonded to a single silicon atom of 10 mol % or less among oxygen atoms bonded to silicon atoms contained in the polymerizable compound. As the polymerizable compound, polymers and oligomers having tetrafunctional silanes, trifunctional silanes, difunctional silanes, and monofunctional silanes as structural units can be used alone or in combination of two or more types.

[0034] In this embodiment, it is preferable to use a curable resin 2 containing mainly trifunctional silanes and bifunctional silanes as constituent units, depending on the properties desired for the curable resin 2 .

[0035] In the polymerizable compound of the present embodiment, the proportion of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound is 10 mol % or less, preferably 7 mol % or less, and particularly preferably 5 mol % or less.

[0036] An oxygen atom bonded to a single silicon atom means an oxygen atom in which one of the two bonds of the oxygen atom is bonded to silicon, but does not mean an oxygen atom in which both of the two bonds of the oxygen atom are bonded to silicon atoms. The other bond of the oxygen atom is not particularly limited as long as it is bonded to something other than silicon, but is particularly preferably bonded to hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0037] In this embodiment, by keeping the ratio of oxygen atoms bonded to a single silicon atom as described above, i.e., the ratio of highly reactive functional groups such as hydroxyl groups (-OH) and alkoxy groups (-OR, where R is an alkyl group having 1 to 4 carbon atoms) bonded to silicon atoms, within the above range, the stability of the curable resin over time can be improved and viscosity increase during storage can be suppressed. For the same reason, the reaction with the surface of the flat mold, which will be described later, can also be suppressed, thereby achieving the effect of excellent releasability from the flat mold.

[0038] The reason why the highly reactive functional group is present in a certain proportion in the polymerizable compound is presumably due to unreacted oxygen atoms remaining in the production process of the polymerizable compound. The reason why such unreacted oxygen atoms remain is thought to be that when the highly reactive functional group is an alkoxy group (-OR, where R is an alkyl group having 1 to 4 carbon atoms), hydrolysis of the alkoxy group in the raw material has not progressed, and when it is a hydroxyl group (-OH), the polymerization reaction has not progressed completely due to steric hindrance, etc.

[0039] In this embodiment, the ratio of oxygen atoms bonded to a single silicon atom refers to the number of oxygen atoms bonded to a single silicon atom when the number of oxygen atoms bonded to silicon atoms in the polymerizable compound is taken as 100. The method for measuring this ratio is as follows: 29 It can be calculated by analyzing the spectrum by Si-NMR.

[0040] Specifically, when a polymerizable compound containing a siloxane structure having a trifunctional silane as a constituent unit is analyzed by NMR, four peaks are observed: a component in which none of the three oxygen atoms bonded to the silicon atom are bonded to any other silicon atom; a component in which one of the three oxygen atoms bonded to the silicon atom is bonded to any other silicon atom; a component in which two of the three oxygen atoms bonded to the silicon atom are bonded to any other silicon atom; and a component in which all of the three oxygen atoms bonded to the silicon atom are bonded to any other silicon atom.

[0041] The integrated value of these four peaks, that is, the ratio of their areas, is T 0 ~T 3 In this case, the proportion (mol %) of oxygen atoms bonded to the single silicon atom can be calculated from the following formula (2):

[0042]

[0043] Furthermore, when the polymerizable compound contains a siloxane structure having a bifunctional silane as a constituent unit, three peaks are observed: a component in which none of the two oxygen atoms bonded to a silicon atom are bonded to another silicon atom; a component in which one of the two oxygen atoms bonded to a silicon atom is bonded to another silicon atom; and a component in which all of the two oxygen atoms bonded to a silicon atom are bonded to another silicon atom.

[0044] The integrated value of these three peaks, that is, the ratio of their areas, is D 0 ~D 2 In this case, the proportion (mol %) of oxygen atoms bonded to the single silicon atom can be calculated from the following formula (3):

[0045]

[0046] Furthermore, when the polymerizable compound contains a siloxane structure having a tetrafunctional silane as a constituent unit, five peaks are observed: a component in which none of the four oxygen atoms bonded to the silicon atom are bonded to other silicon atoms; a component in which one of the four oxygen atoms bonded to the silicon atom is bonded to other silicon atoms; a component in which two of the four oxygen atoms bonded to the silicon atom are bonded to other silicon atoms; a component in which three of the four oxygen atoms bonded to the silicon atom are bonded to other silicon atoms; and a component in which all of the four oxygen atoms bonded to the silicon atom are bonded to other silicon atoms.

[0047] The integrated value of these five peaks, that is, the ratio of each area, is Q 0 ~Q 4 In this case, the proportion (mol %) of oxygen atoms bonded to a single silicon atom can be calculated from the following formula (4):

[0048]

[0049] For example, when the above-mentioned polymerizable compound having two types of constituent units, trifunctional silane and bifunctional silane, is contained in the above-mentioned curable resin 2, the proportion (mol %) of oxygen atoms bonded to a single silicon atom can be calculated from the following formula (5).

[0050]

[0051] The weight average molecular weight (Mw) of the polymerizable compound may be in the range of 500 to 100,000, preferably in the range of 600 to 50,000, and particularly preferably in the range of 700 to 20,000.

[0052] The weight average molecular weight (Mw) is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC), and is a value measured under the following conditions after pressure filtration through a membrane filter having a pore size of 0.2 μm.

[0053] (Conditions) Apparatus: Water 2695 Sample amount: Approximately 10 mg of sample per 3 mL of solvent Injection volume: 5 μL Guard column: LF-G (Shodex) Column: GPC LF-804 x 3 (Shodex) Column temperature: 40°C Mobile phase: tetrahydrofuran Flow rate: 1.0 mL / min Detector: differential refractometer (Water 2414) Molecular weight calibration: polystyrene equivalent

[0054] The polymerizable compound has a polymerizable functional group constituting at least a part of the organic component. The polymerizable functional group is not particularly limited as long as it is a functional group capable of undergoing a polymerization reaction and the polymerization reaction proceeds in response to an external stimulus. For example, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an oxetane group, a vinyl ether group, or the like, which undergoes a polymerization reaction in response to light irradiation, heat, heat associated with light irradiation, the action of a photoacid generator, or the like, can be used. Such polymerizable functional groups have good stability during synthesis and storage, good reactivity during curing, and are easily available as raw materials.

[0055] In this embodiment, acryloyl groups and methacryloyl groups are particularly preferred because of the wide range of curing speed and physical properties available.

[0056] In a polymerizable compound, if the polymerizable group directly bonded to the silicon atom is bulky, steric hindrance may change the reactivity, affecting curability, etc. In consideration of this, the molecular weight of the polymerizable group directly bonded to the silicon atom may be in the range of 20 to 500, preferably in the range of 25 to 400. In this embodiment, the polymerizable group refers to a group containing a polymerizable functional group. Preferred examples of such polymerizable groups include the structures shown below.

[0057]

[0058] R1 represents a "substituted or unsubstituted alkyl chain having 1 to 10 carbon atoms," and R2 represents a "substituted or unsubstituted alkyl chain having 1 to 3 carbon atoms, or a hydrogen atom." Both R1 and R2 may be linear or branched.

[0059] At least one polymerizable functional group may be bonded to the structural unit of the polymerizable compound, but this is not limitative, and two or more polymerizable functional groups may be bonded.

[0060] Examples of the structural unit having a polymerizable group of the polymerizable compound in this embodiment include the following.

[0061] Examples of trifunctional silanes include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-[3'-(trimethoxysilyl)propyl]methyloxetane, 3-ethyl-3-[3'-(triethoxysilyl)propyl]methyloxetane, and 3-ethyl-3-[3'-(triethoxysilyl)propyl]methyloxetane. Among these, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-[3'-(trimethoxysilyl)propyl]methyloxetane, 3-ethyl-3-[3'-(triethoxysilyl)propyl]methyloxetane, and the like can be preferably used.

[0062] Examples of bifunctional silanes include 3-acryloxypropyl(methyl)dimethoxysilane, 3-acryloxypropyl(methyl)diethoxysilane, 3-methacryloxypropyl(methyl)dimethoxysilane, 3-methacryloxypropyl(methyl)diethoxysilane, vinyl(methyl)dimethoxysilane, vinyl(methyl)diethoxysilane, allyl(methyl)dimethoxysilane, allyl(methyl)diethoxysilane, styryl(methyl)dimethoxysilane, styryl(methyl)diethoxysilane, 3-glycidylsilane, Examples of the silane include dimethylpropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)diethoxysilane, 3-ethyl-3-[3'-(methyldimethoxysilyl)propyl]methyloxetane, 3-ethyl-3-[3'-(methyldiethoxysilyl)propyl]methyloxetane, dimethoxymethylvinylsilane, and diethoxymethylvinylsilane. Of these, 3-acryloxypropyl(methyl)dimethoxysilane, 3-acryloxypropyl(methyl)diethoxysilane, 3-methacryloxypropyl(methyl)dimethoxysilane, 3-methacryloxypropyl(methyl)diethoxysilane, vinyl(methyl)dimethoxysilane, vinyl(methyl)diethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)diethoxysilane, 3-ethyl-3-[3'-(methyldimethoxysilyl)propyl]methyloxetane, 3-ethyl-3-[3'-(methyldiethoxysilyl)propyl]methyloxetane, and the like can be preferably used.

[0063] A structural unit having a polymerizable group can also be used in combination with a structural unit having no polymerizable group. As a structural unit having no polymerizable group, trifunctional ones include trimethoxy(methyl)silane, triethoxy(methyl)silane, methyltrippropoxysilane, tributoxy(methyl)silane, methyltriphenoxysilane, ethyltrimethoxysilane, triethoxy(ethyl)silane, ethyltrippropoxysilane, tributoxy(ethyl)silane, ethyltriphenoxysilane, trimethoxy(propyl)silane, triethoxy(propyl)silane, tripropoxy(propyl)silane, tributoxy(propyl)silane, triphenoxy(propyl)silane, Silane, butyltrimethoxysilane, butyltriethoxysilane, butyltrippropoxysilane, tributoxy(butyl)silane, butyltriphenoxysilane, trimethoxy(phenyl)silane, triethoxy(phenyl)silane, phenyltrippropoxysilane, tributoxy(phenyl)silane, triphenoxy(phenyl)silane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrippropoxysilane, cyclohexyltributoxysilane, cyclohexyltriphenoxysilane, etc. can be used. Among these, trimethoxy(methyl)silane, triethoxy(methyl)silane, ethyltrimethoxysilane, triethoxy(ethyl)silane, trimethoxy(phenyl)silane, triethoxy(phenyl)silane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, etc. can be preferably used.

[0064] As bifunctional silanes, dimethoxydimethylsilane, diethoxydimethylsilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, cyclohexyl(dimethoxy)methylsilane, cyclohexyldiethoxymethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, and the like can be preferably used.

[0065] In this embodiment, the structure of the polymerizable compound is not particularly limited. However, polymerizable compounds having a spherical structure, as described below, and polyhedral siloxane oligomers having an incompletely condensed skeleton are preferred because they can provide a curable resin 2 with a sufficiently low viscosity even if they do not substantially contain a solvent. In particular, polymerizable compounds having a spherical structure are preferred from the viewpoints of thermal stability, processing uniformity, and the like.

[0066] The spherical structure means a structure in which polymerizable functional groups extend outward from a polymerized portion with a high degree of polymerization at the center. For example, in the case of a polymerizable compound having a spherical structure such as a dendrimer, the proportion of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound is 10 mol % or less, and the viscosity of the curable resin 2 can be sufficiently reduced by simply adding a small amount of solvent or low-viscosity material.

[0067] Examples of polymerizable compounds having a spherical structure include those containing trifunctional silane as a constituent unit. Among these, those containing only trifunctional silane as a constituent unit are preferred. Examples of polymerizable compounds having such a spherical structure include one or a mixture of two or more hexamers to 36amers (molecular weight of 1000 or more and 6300 or less) of trifunctional silanes having polymerizable functional groups. The molecular weight of the polymerizable compound having a spherical structure may be in the range of 2000 or more and 6000 or less, and preferably in the range of 2000 or more and 3000 or less.

[0068] In the case of a siloxane consisting of a trifunctional silane, SiO 3 / 2 The polymerizable compound has a structure in which polymerizable functional groups extend outward from a siloxane polymerization portion having a high degree of siloxane polymerization, which is composed of units. In such a polymerizable compound having a spherical structure, the degree of siloxane polymerization in the siloxane polymerization portion can be made higher than 90%, particularly 95% or higher, and even 97% or higher, so that the proportion of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound is 10 mol % or less.

[0069] This is presumably due to the following reason: When the hydrolysis reaction of trifunctional silane is carried out under basic conditions, OH groups are formed on the Si atom. - A nucleophilic reaction occurs. When one hydrolyzable group (alkoxy group) is hydrolyzed, the steric hindrance of the Si atom decreases, increasing the hydrolysis reaction rate, and all three hydrolyzable groups (alkoxy groups) are hydrolyzed to produce -Si(OH)3. Because all OH groups in -Si(OH)3 are capable of condensation polymerization, a three-dimensional siloxane structure with high density and high degree of polymerization is formed.

[0070] Specifically, it has a spherical structure represented by the following formula: The following formula is a schematic diagram showing a polymerizable compound having a spherical structure, which is composed of an octamer of trifunctional silanes having an acryloxypropyl group and a 3-methacryloxypropyl group as the polymerizable group.

[0071] In the formula, SiO 1.5 is SiO 3 / 2 The siloxane polymerized moiety is composed of units.

[0072] In the present disclosure, the polymerizable compound having the spherical structure may be one that does not have an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom in the bonding group between the siloxane polymerized portion constituting the main skeleton of the spherical structure and the polymerizable functional group, and may be one that does not have a silicon atom (for example, SiO 3 / 2 The unit may not have an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom between the silicon atom and the polymerizable functional group.

[0073] The bonding group between the silicon atom and the polymerizable functional group in the siloxane polymerization moiety is, for example, a divalent hydrocarbon group that does not contain an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom, preferably a linear alkylene group, and more preferably -(CH2) n - (n is an integer from 1 to 9).

[0074] The polymerizable compound having a spherical structure can be obtained by subjecting a hydrolyzable silane composition containing at least a hydrolyzable silane to a hydrolysis and condensation reaction under basic conditions.

[0075] Specifically, the reaction can be carried out by placing a solvent and the silane raw material in a reactor, adding a basic catalyst, and then adding water dropwise while stirring. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate (K2CO3), sodium carbonate, and ammonia. The reaction can be carried out at a pH of 8 to 13, typically at room temperature to 100°C.

[0076] The silane used as the raw material may be one or more of tetrafunctional hydrolyzable silane, trifunctional hydrolyzable silane, bifunctional hydrolyzable silane, and monofunctional hydrolyzable silane, but it is preferable to use tetrafunctional hydrolyzable silane or trifunctional hydrolyzable silane, especially trifunctional hydrolyzable silane. Furthermore, only one type of hydrolyzable silane may be used, or two or more types may be used in combination.

[0077] By using a basic catalyst in the synthesis step, the polymerizable compound obtained by the hydrolysis and condensation reaction has a high degree of condensation, and therefore it is possible to easily obtain a polymerizable compound having a spherical structure in which the proportion of oxygen atoms bonded to a single silicon atom is reduced, particularly to 10 mol % or less, among the oxygen atoms bonded to silicon atoms.

[0078] The polymerizable compound in this embodiment may be a polyhedral siloxane oligomer having an incompletely condensed skeleton. Such a polymerizable compound has a regular structure, so that the proportion of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound is 10 mol % or less. Furthermore, the viscosity of the curable resin can be sufficiently reduced.

[0079] The polyhedral siloxane oligomer having an incompletely condensed skeleton to which a polymerizable functional group is bonded may be an incompletely condensed type polyhedral siloxane oligomer having a completely condensed skeleton, in which one vertex, one side, or one face is missing.The polyhedral siloxane oligomer having an incompletely condensed skeleton to which a polymerizable functional group is bonded is particularly preferably one represented by the following formula:

[0080]

[0081] In the formula, R 3 is a monovalent hydrocarbon group, and R 4 R is a -Si-polymerizable group bonded to an oxygen atom in the formula, a hydrogen atom, a metal ion such as Na or Li, or a tetraalkylammonium ion (the alkyl group is methyl, ethyl, propyl, butyl, etc.). 3 is a monovalent hydrocarbon group, preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group, specifically an ethyl group, a butyl group, or a phenyl group.

[0082] The polymerizable compound can be obtained by reacting a polyhedral siloxane oligomer having an incompletely condensed skeleton in which a hydrogen atom, a hydroxy group, or an organic group other than a polymerizable functional group is bonded to a silicon atom, with a polymerizable functional group-containing compound.

[0083] The starting polyhedral siloxane oligomer with an incompletely condensed skeleton has silicon atoms at its vertices bonded to hydrogen atoms, hydroxyl groups, or organic groups other than polymerizable functional groups, such as alkoxy groups, alkyl groups, and phenyl groups.

[0084] The reaction between the raw material and the polymerizable functional group-containing compound may be a conventionally known reaction, such as an addition reaction between a hydrogen atom directly bonded to silicon and a polymerizable functional group-containing compound having an unsaturated double bond, or a reaction between a hydroxyl group (OH group) or an alkoxy group (OR group) directly bonded to silicon and a polymerizable functional group-containing compound capable of forming a siloxane bond.

[0085] In this embodiment, the curable resin 2 may contain a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, with a photopolymerization initiator being particularly preferred.

[0086] A photopolymerization initiator is a substance that generates reactive species that cause a polymerization reaction of a polymerizable compound upon light stimulation. Specific examples include photoradical generators that generate radicals upon light stimulation and photoacid generators that generate protons upon light stimulation. A photoradical generator is a polymerization initiator that generates radicals upon light (radiation, such as infrared rays, visible light, ultraviolet rays, far ultraviolet rays, charged particle rays such as X-rays and electron beams) and is mainly used when the polymerizable compound is a radically polymerizable compound. On the other hand, a photoacid generator is a polymerization initiator that generates acid (protons) upon light stimulation and is mainly used when the polymerizable compound is a cationically polymerizable compound.

[0087] Examples of photoradical generators include, but are not limited to, 2,4,6-trimethyldiphenylphosphine oxide, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one. These photoradical generators may be used alone or in combination of two or more.

[0088] Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, and diazomethane compounds.

[0089] The thermal polymerization initiator is a compound that generates the above-mentioned polymerization factors (radicals, cations, etc.) by heat. Specifically, the thermal polymerization initiator includes a thermal radical generator that generates radicals by heat, a compound that generates protons (H + Thermal radical generators are mainly used when the polymerizable compound is a radical polymerizable compound. On the other hand, thermal acid generators are mainly used when the polymerizable compound is a cationically polymerizable compound.

[0090] Examples of thermal radical generators include organic peroxides and azo compounds. Examples of organic peroxides include peroxyesters such as t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxyisopropyl carbonates; peroxyketals such as 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane; and diacyl peroxides such as lauroyl peroxide, but are not limited to these. Examples of azo compounds include azonitriles such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexane-1-carbonitrile), but are not limited to these.

[0091] Examples of thermal acid generators include known iodonium salts, sulfonium salts, phosphonium salts, ferrocenes, etc. Specific examples include, but are not limited to, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, and triphenylsulfonium hexafluoroborate.

[0092] The content of the polymerization initiator in the curable resin 2 is not particularly limited, and can be in the range of 0.5% by mass to 20% by mass, or in the range of 1% by mass to 10% by mass, relative to the polymerizable compound.

[0093] In this embodiment, the curable resin 2 may be substantially free of solvent. By being substantially free of solvent, it is possible to prevent deterioration of flatness and poor curing due to the solvent floating to the surface during curing. Here, "substantially free of solvent" means that the curable resin 2 does not contain any solvent other than impurities or other solvents that are unintentionally contained. That is, for example, the solvent content of the curable resin 2 is preferably 0.01% by mass or less, and more preferably 0.001% by mass or less, relative to the entire curable resin 2. The solvent refers to a solvent used in general resin compositions, photoresists, and the like. In other words, the type of solvent is not particularly limited as long as it dissolves and uniformly disperses the curable resin 2 and does not react with the curable resin 2.

[0094] The curable resin 2 may contain a reactive crosslinking agent. The reactive crosslinking agent may have a polymerizable functional group, for example, one having two or more polymerizable functional groups. Examples of the polymerizable functional group include an ethylenically unsaturated bond-containing group and an epoxy group, and the ethylenically unsaturated bond-containing group is preferred. Examples of the ethylenically unsaturated bond-containing group include a (meth)acrylic group and a vinyl group, and the (meth)acrylic group is more preferred, and the acrylic group is even more preferred. Furthermore, the (meth)acrylic group is preferably a (meth)acryloyloxy group. One molecule may contain two or more types of polymerizable groups, or may contain two or more of the same type of polymerizable group.

[0095] Examples of photopolymerizable monomers (bifunctional monomers) having two polymerizable functional groups include trimethylolpropane di(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, and bis(hydroxymethyl)tricyclodecane di(meth)acrylate. Commercially available bifunctional monomers include Light Acrylate 3EG-A, 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EAL, and BP-4PA (all manufactured by Kyoeisha Chemical Co., Ltd.). Furthermore, from the viewpoint of compatibility, polyfunctional monomers having a siloxane structure are preferred.

[0096] The content of the reactive crosslinking agent in the curable resin 2 is not particularly limited, and can be within a range of 0% by mass to 99% by mass, preferably within a range of 5% by mass to 80% by mass, and particularly preferably within a range of 49% by mass to 79% by mass.

[0097] The curable resin 2 may contain other components in addition to the polymerizable compound, polymerization initiator, and reactive crosslinker described above. Examples of other components include surfactants, release agents, silane coupling agents, photosensitizers, antioxidants, organometallic coupling agents, polymerization inhibitors, UV absorbers, light stabilizers, antiaging agents, plasticizers, adhesion promoters, photobase generators, colorants, elastomer particles, photoacid amplifiers, basic compounds, and other components such as flow adjusters, antifoamers, and dispersants, as needed. The content of the other components is not particularly limited, but is preferably 5% by mass or less, and particularly preferably 3% by mass or less, of the curable resin 2.

[0098] The viscosity of the curable resin 2 may be 20 cPs or less, preferably 10 cPs or less, and more preferably 7 cPs or less. On the other hand, the lower limit of the viscosity is not particularly limited, but may be 1 cPs or more, preferably 1.5 cPs or more. Because the curable resin 2 has a very low viscosity, it can be applied to the concave-convex structure with good filling properties while suppressing the generation of air bubbles. Furthermore, such a low viscosity allows application using an inkjet method. The viscosity of the curable resin 2 was measured at 25°C and 1000 (1 / s) using an AR-G2 manufactured by TA Instruments, Inc., in a measurement environment of 25°C and 40% RH. The curable resin 2 was dropped onto a disk plate, and a standard steel cone with a diameter of 40 mm was subjected to a shear rate of 10 to 1000 (1 / s).

[0099] The contact angle of the curable resin 2 with respect to the surface of the standard resist is preferably 20° or less, and more preferably 15° or less. Specifically, the contact angle can be measured 5 seconds after dropping the curable resin 2 onto the surface of the standard resist layer in atmospheric air at a temperature of 25°C and humidity of 33%, using a contact angle measuring device (automatic contact angle meter DM-501, manufactured by Kyowa Interface Science Co., Ltd.). The standard resist layer may be formed using, for example, an acrylic-styrene copolymer (organic resist resin) as the base resin.

[0100] If the curable resin 2 has a contact angle with the standard resist layer, when it is used as a reversal layer material in a reversal process, for example, it will have good wettability with respect to the core pattern formed from the resist composition, and will be able to be applied with better filling properties. When the curable resin 2 has the above contact angle with the standard resist, it will exhibit good wettability even if the composition of the organic resist material actually used for the core pattern is different from the composition of the standard resist.

[0101] The surface free energy of the curable resin 2 is 20 mJ / m 2 70mJ / m or more 2 It is preferable that the fluence is 25 mJ / m or less, and particularly 25 mJ / m 2 50mJ / m or more 2Within the above range, for example, compatibility with the core pattern made of an organic resist material can be suppressed, and the resin can be sufficiently wetted and spread over the core pattern, which is preferable.

[0102] In the cured film forming method according to this embodiment, the substrate 3 to which the curable resin 2 is supplied is not particularly limited and may be a transparent substrate such as a glass substrate, such as a quartz glass substrate, a soda glass substrate, a fluorite substrate, a calcium fluoride substrate, a magnesium fluoride substrate, an alkali-free glass substrate such as barium borosilicate glass, amino borosilicate glass, or aluminosilicate glass; a resin substrate, such as a polycarbonate substrate, a polypropylene substrate, a polyethylene substrate, a polymethyl methacrylate substrate, or a polyethylene terephthalate substrate; a semiconductor substrate, such as a silicon substrate, a GaAs substrate, an InP substrate, a GaN substrate, a GaP substrate, or a SiC substrate; a metal-based substrate, such as a stainless steel substrate, an aluminum substrate, a copper substrate, or an iron substrate; or a metal-deposited substrate in which a metal such as gold, silver, copper, ITO, or chromium is vapor-deposited on the surface of a glass substrate. Alternatively, the substrate may be a laminated substrate formed by laminating two or more substrates arbitrarily selected from the above. In this embodiment, "transparent" means that the transmittance of light having a wavelength of 300 nm to 450 nm is 70% or more, preferably 90% or more.

[0103] The substrate 3 has a first surface 3A and a second surface 3B located on the opposite side thereof, and the curable resin 2 is supplied to the first surface 3A of the substrate 3 (see FIGS. 1A and 2A ). The method for supplying the curable resin 2 to the first surface 3A of the substrate 3 is not particularly limited, and for example, the curable resin 2 may be supplied discretely to the first surface 3A of the substrate 3 by an inkjet method, or the curable resin 2 may be applied to the first surface 3A of the substrate 3 using a coating machine such as a spin coater or a spray coater.

[0104] The mold 4 is brought close to the curable resin 2 supplied to the first surface 3A of the substrate 3, and the curable resin 2 is spread between the substrate 3 and the mold 4 to form a molded resin layer 5 (contact process, see Figures 1B and 2B).

[0105] The mold 4 may be made of a transparent substrate such as a glass substrate such as a quartz glass substrate, a soda glass substrate, a fluorite substrate, a calcium fluoride substrate, a magnesium fluoride substrate, or an acrylic glass substrate, a resin substrate such as a polycarbonate substrate, a polypropylene substrate, a polyethylene substrate, or a polyethylene terephthalate substrate, or a laminated substrate formed by laminating two or more substrates arbitrarily selected from the above.

[0106] The mold 4 has a first surface 4A and a second surface 4B located on the opposite side thereof. The first surface 4A may be a flat plate mold in which the first surface 4A is a flat surface (see FIG. 1A), or may have a concave-convex structure 41 including recesses 42 formed on the first surface 4A (see FIG. 2A). The shape of the concave-convex structure 41 formed on the first surface 4A of the mold 4 is not particularly limited, and examples thereof include a space-like structure, a hole-like structure, and the like. The dimensions of the concave-convex structure 41 are also not particularly limited. For example, in the case of a space-like concave-convex structure 41, the length of the short side of the recesses 42 may be approximately 10 nm to 100 nm, and in the case of a hole-like concave-convex structure, the maximum diameter of the recesses 42 may be approximately 10 nm to 100 nm. Note that the maximum diameter of the hole-like concaves 42 is, for example, the diameter of the circle when the planar shape of the concaves 42 is circular, or the length of the diagonal of the rectangle when the planar shape is rectangular. The dimensions of the plurality of recesses 42 included in the relief structure 41 of the mold 4 may be different, and in this case, the smallest dimension (minimum dimension) of the plurality of recesses 42 may be 100 nm or less.

[0107] The moldable resin layer 5 (curable resin 2) is cured while the mold 4 is in contact with the moldable resin layer 5 (curing step). The method for curing the moldable resin layer 5 may be selected appropriately depending on the curing type of the curable resin 2 constituting the moldable resin layer 5. For example, if the curable resin 2 is a photocurable type, light (e.g., ultraviolet light, electron beam, etc.) may be irradiated onto the moldable resin layer 5 (curable resin 2) via the mold 4. If the curable resin 2 is a thermosetting type, heat may be applied to the moldable resin layer 5 (curable resin 2). If the curable resin 2 is a thermoplastic type, the moldable resin layer 5 may be softened by heating and brought into contact with the mold 4, and then cooled to harden the moldable resin layer 5.

[0108] The film thickness of the cured moldable resin layer 5 is important in forming the cured film 1 (see FIGS. 1D and 2D ). As will be described later, by subjecting the cured moldable resin layer 5 (curable resin 2) to an etching treatment, the organic components in the moldable resin layer 5 (curable resin 2) are decomposed, and the inorganic components containing siloxane polymerized moieties as a main component are left and concentrated, thereby forming the cured film 1. The etching treatment of the moldable resin layer 5 causes the inorganic components to bond together and at the same time, the inorganic components are detached. If the moldable resin layer 5 is relatively thin, most of the inorganic components will be detached, making it difficult to form the cured film 1. However, if the moldable resin layer 5 is relatively thick, the inorganic components that have bonded together will be concentrated, and a cured film 1 having the desired film thickness can be formed.

[0109] Therefore, the film thickness of the cured moldable resin layer 5 may be appropriately set to such an extent that a cured film 1 having a desired film thickness can be formed. For example, the amount of curable resin 2 supplied to the first surface 3A of the substrate 3 may be determined based on the following mathematical formula (1) which shows the relationship between the film thickness T0 of the cured moldable resin layer 5, the film thickness T of the cured film 1 to be formed, and the decomposition processing time t for decomposing the organic components, and a moldable resin layer 5 having a predetermined film thickness T0 may be formed.

[0110] In the above formula (1), Ab ct represents "the amount of decrease per unit time in the film thickness of the molded resin layer 5, which changes according to the decomposition processing time t in the early stage of the decomposition processing of the organic components," αt represents "the amount of decrease per unit time in the film thickness of the molded resin layer 5, which does not substantially change according to the decomposition processing time t," A represents "the amount of decrease per unit time in the film thickness of the molded resin layer 5, which does not change according to the decomposition processing time t," and b and c are "coefficients indicating the exponential decrease in the film thickness of the molded resin layer 5," where b > 1 and c < 0. As the absolute values ​​of the coefficients b and c increase, the amount of decrease per unit time in the film thickness of the molded resin layer 5, which changes according to the decomposition processing time 5, increases. The coefficients b and c each change depending on the conditions for decomposing the organic components of the molded resin layer 5, and can be set appropriately according to those conditions.

[0111] The above formula (1) includes a component in which the thickness of the molded resin layer 5 changes exponentially and a component in which it changes linearly. The exponentially changing component can be said to represent a state in which the inorganic components bonded to each other are concentrated and remain as the decomposition treatment time t passes. On the other hand, the linearly changing component can be said to represent a state in which the thickness of the molded resin layer 5 decreases due to physical etching in substantial proportion to the decomposition treatment time t.

[0112] The "initial stage of the decomposition process of the organic components" is determined by the type of organic components contained in the molded resin layer 5 (curable resin 2) and the conditions of the etching process on the molded resin layer 5, and is, for example, approximately 10 to 300 seconds after the start of the etching process on the molded resin layer 5, and preferably approximately 10 to 60 seconds after the start of the etching process.

[0113] After the mold 4 is separated from the cured resin layer 5 (mold release step, see FIGS. 1C and 2C), the resin layer 5 (curable resin 2) is subjected to an etching process to form a cured film 1 (see FIGS. 1D and 2D). The etching process performed on the resin layer 5 may be a dry etching process (plasma process) in which etching is performed using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a mixture of two or more of these gases in a discharge plasma atmosphere in a vacuum chamber, or a wet etching process (oxidation process) in which etching is performed by contacting the resin layer 5 with an oxidizing etchant such as sulfuric acid or hydrogen peroxide solution. These etching processes can decompose organic components and bond and concentrate inorganic components. As a result, a cured film 1 containing mainly inorganic components can be formed.

[0114] When forming the cured film 1 on the first surface 3A of the substrate 3, a cured film formation region 31 where the cured film 1 is formed and a cured film non-formation region 32 where the cured film 1 is not formed are set on the first surface 3A of the substrate 3, and the curable resin 2 is supplied to the cured film formation region 31 in an amount determined based on the above formula (1) so that the film thickness T of the cured film 1 exceeds 0, and the curable resin 2 is supplied to the cured film non-formation region 32 in an amount determined based on the above formula (1) so that the film thickness T of the cured film 1 is 0 or less, thereby forming the moldable resin layer 5. For example, as shown in Figures 2A to 2D, when the moldable resin layer 5 is formed using a mold 4 having a concave-convex structure 41 including recesses 42, the convex portions 51 of the moldable resin layer 5 are formed corresponding to the recesses 42, and the recesses (residual film portions) 52 of the moldable resin layer 5 are formed corresponding to the convex portions between adjacent recesses 42. Therefore, the region where the convex portions 51 of the moldable resin layer 5 should be located is set as the cured film formation region 31, and the region where the concave portions (residual film portions) 52 should be located is set as the cured film non-formation region 32. Then, the height of the convex portions 51 of the moldable resin layer 5 and the thickness of the concave portions (residual film portions) 52 of the moldable resin layer 5 are determined based on the above mathematical formula (1), and the moldable resin layer 5 is formed so that the convex portions 51 of the moldable resin layer 5 remain as the cured film 1 and the concave portions (residual film portions) 52 of the moldable resin layer 5 disappear. This makes it possible to form a patterned cured film 1 as shown in FIG. 2D .

[0115] The cured film 1 thus formed mainly contains inorganic components, more specifically, SiO X (X is 1 or more). The term "mainly containing" means that the cured film 1 may contain an organic component, in other words, it includes the concept that the content of the inorganic component in the cured film 1 is greater than the content of the inorganic component in the curable resin 2.

[0116] The film thickness T of the cured film 1 is thinner than the film thickness T of the molded resin layer 5. This is because the etching process for forming the cured film 1 decomposes the organic components in the molded resin layer 5 (curable resin 2) and also causes the detachment of inorganic components. Therefore, the dimensions of the patterned cured film 1 shown in FIG. 2D (the dimensions of the convex pattern) are smaller than the dimensions of the patterned molded resin layer 5 (see FIG. 2C) (the dimensions of the convex pattern). In other words, by forming the cured film 1 using a mold 4 having a concave-convex structure 41, it is possible to form a cured film 1 including a convex pattern whose dimensions are smaller than the minimum dimension of the recesses 42 of the concave-convex structure 41 of the mold 4.

[0117] In the cured film forming method according to the present embodiment, at least one material layer made of a material different from the material constituting the substrate 3 may be provided on the first surface 3A of the substrate 3 on which the cured film 1 is formed, and the cured film 1 may be formed on the material layer. The material layer is not particularly limited, and examples thereof include a hard mask layer made of metallic chromium or the like, a semiconductor layer made of a P-type semiconductor such as boron-doped silicon or arsenic-doped silicon, and a conductive film layer made of ITO or the like.

[0118] [Method for Manufacturing Imprint Mold Substrate] A method for manufacturing an imprint mold substrate according to this embodiment will be described. Note that this embodiment will cite as an example a method for manufacturing an imprint mold substrate 10 including a base 11 having a first surface 11A and a second surface 11B located on the opposite side of the first surface 11A, a first step structure 12 protruding from the first surface 11A of the base 11, a second step structure 13 protruding from an upper surface 12A of the first step structure 12, a light-shielding film 14 located on the upper surface 12A of the first step structure 12, and a cured film 1 as a protective film 15 located on the light-shielding film 14. However, the method for manufacturing an imprint mold substrate 10 according to this embodiment is not limited to this embodiment.

[0119] In this embodiment, first, a multi-level molded substrate 10′ is prepared (see FIG. 3A ). The multi-level molded substrate 10′ includes a base 11 having a first surface 11A and a second surface 11B located opposite the first surface 11A, a first step structure 12 protruding from the first surface 11A of the base 11, a second step structure 13 protruding from an upper surface 12A of the first step structure 12, and a light-shielding film 14 located on the first surface 11A of the base 11, the upper surface 12A of the first step structure 12, and the upper surface 13A of the second step structure 13. A recess 16 having a size large enough to physically encompass the outer edge of the first step structure 12 in a plan view is formed on the second surface 11B of the base 11.

[0120] The base 11 may be a transparent substrate such as a typical substrate for an imprint mold, for example, a glass substrate such as a quartz glass substrate, a soda glass substrate, a fluorite substrate, a calcium fluoride substrate, a magnesium fluoride substrate, an alkali-free glass substrate such as barium borosilicate glass, amino borosilicate glass, or aluminosilicate glass; a resin substrate such as a polycarbonate substrate, a polypropylene substrate, a polyethylene substrate, a polymethyl methacrylate substrate, or a polyethylene terephthalate substrate; or a laminated substrate formed by laminating two or more substrates arbitrarily selected from the above.

[0121] The shape of the base 11 in plan view is not particularly limited, and may be, for example, a substantially rectangular shape, etc. When the base 11 is made of a quartz glass substrate that is generally used for photoimprinting, the shape of the base 11 in plan view is usually a substantially rectangular shape.

[0122] The size of the base 11 (size in a plan view) is not particularly limited, but when the base 11 is made of the above-mentioned quartz glass substrate, the size of the base 11 is, for example, about 152 mm × 152 mm. The thickness of the base 11 can be appropriately set, for example, in the range of about 300 μm to 10 mm, taking into consideration strength, handling suitability, etc.

[0123] The first step structure 12 protruding from the first surface 11A of the base 11 is provided approximately in the center of the base 11 in a plan view. The first step structure 12 has an upper surface 12A, and a light-shielding film 14 is located on the upper surface 12A. In this embodiment, since the light-shielding film 14 is located on the upper surface 12A of the first step structure 12, in an imprint process using an imprint mold 20 (see FIG. 4F ) manufactured from the imprint mold substrate 10, it is possible to harden only the resin to which the concave-convex pattern 21 of the imprint mold 20 has been transferred (the resin directly below the second step structure 13).

[0124] The second step structure 13 protruding from the upper surface 12A of the first step structure 12 is provided approximately in the center of the base 11 (first step structure 12) in a plan view. The second step structure 13 has an upper surface 13A, and a light-shielding film 14 is located on the upper surface 13A. The light-shielding film 14 will be removed in a later process. The upper surface 13A of the second step structure 13 forms a pattern region in which a concave-convex pattern 21 is formed in the imprint mold 20 (see FIG. 4F ).

[0125] In a plan view, the outer shape of the upper surface portion 12A of the first step structure 12 and the outer shape of the upper surface portion 13A of the second step structure 13 are substantially rectangular. The size of the upper surface portion 13A of the second step structure 13 is set appropriately depending on the product to be manufactured through an imprint process using an imprint mold 20 (see FIG. 4F ) made from the imprint mold substrate 10, and is set to, for example, about 30 mm x 25 mm. The outer size of the upper surface portion 12A of the first step structure 12 may be approximately 10 μm to 4000 μm larger than the size of the upper surface portion 13A of the second step structure 13. That is, the width W of the upper surface portion 12A of the first step structure 12 is set to, for example, about 30 mm x 25 mm. 12A can be set to about 5 μm to 2000 μm.

[0126] The protrusion height T of the first step structure 12 12(The length parallel to the thickness direction of the base 11 between the first surface 11A of the base 11 and the upper surface 12A of the first step structure 12) is not particularly limited as long as the imprint mold substrate 10 manufactured in this embodiment can achieve the purpose of having the first step structure 12, and can be set, for example, to approximately 10 μm to 30 μm.

[0127] The length T between the upper surface 12A of the first step structure 12 and the upper surface 13A of the second step structure 13 in the thickness direction of the base 11 13 (The protrusion height T of the second step structure 13 13 ) is not particularly limited, but can be set to, for example, about 1 μm to 5 μm.

[0128] A recess 16 of a predetermined size is formed on the second surface 11B of the base 11. The formation of the recess 16 allows the base 11, and particularly the top surface 13A of the second step structure 13, to be curved during an imprint process using an imprint mold 20 (see FIG. 4F ) fabricated from the imprint mold substrate 10 manufactured according to this embodiment, particularly upon contact with an imprint resin or upon peeling off the imprint mold 20. As a result, when the top surface 13A of the second step structure 13 (the concave-convex pattern 21 formed on the top surface 13A) is brought into contact with the imprint resin, it is possible to prevent gas from being trapped between the concave-convex pattern 21 formed on the first top surface 311 of the convex structure 3 and the imprint resin, and also allows the imprint mold 20 to be easily peeled off from the transfer pattern in which the concave-convex pattern 21 is transferred to the imprint resin.

[0129] The shape of the recess 16 in plan view is preferably substantially circular. The substantially circular shape allows the upper surface 13A of the second step structure 13 of the imprint mold 20 to be curved substantially uniformly within its plane during the imprinting process, particularly when the upper surface 13A of the second step structure 13 is brought into contact with the imprint resin or when the imprint mold 20 is peeled off from the imprint resin.

[0130] The size of the recess 16 in a plan view is not particularly limited as long as the first step structure 12 is included within the projection area of ​​the recess 16 projected onto the first surface 11A of the base 11. If the projection area is too large to include the first step structure 12, it may not be possible to effectively curve the entire top surface 13A of the second step structure 13 of the imprint mold 20.

[0131] The light-shielding film 14 may be made of a material capable of blocking light (e.g., UV light) irradiated onto the imprint mold 20 (see FIG. 4F ) produced from the imprint mold substrate 10 during an imprint process using the imprint mold 20, such as metals such as chromium, titanium, tantalum, silicon, and aluminum; chromium compounds such as chromium nitride, chromium oxide, and chromium oxynitride; tantalum compounds such as tantalum oxide, tantalum oxynitride, tantalum oxide boride, and tantalum oxynitride boride; titanium nitride, silicon nitride, and silicon oxynitride. The film thickness of the light-shielding film 14 is not particularly limited as long as it is thick enough to block the light. The light-shielding film 14 may be formed by a conventionally known method, such as sputtering.

[0132] Next, a curable resin 2 is supplied onto the light-shielding film 14 located on the upper surface 12A of the first step structure 12 of the multistage mold substrate 10′ and onto the light-shielding film 14 located on the upper surface 13A of the second step structure 13 (see FIG. 3B ). The curable resin 2 is brought into contact with a predetermined template 17 and cured, thereby forming a first curable resin layer 18 on the light-shielding film 14 located on the upper surface 12A of the first step structure 12 and a second curable resin layer 19 on the light-shielding film 14 located on the upper surface 13A of the second step structure 13 (see FIG. 3C ). The template 17 is then separated from the cured first curable resin layer 18 and second curable resin layer 19 (see FIG. 3D ).

[0133] The first curable resin layer 18 is intended to form a cured film 1 as the protective film 15 in a later process. On the other hand, the second curable resin layer 19 is intended to be removed without remaining in the later process of forming the cured film 1. By subjecting the layer made of the curable resin 2 to an etching process, the inorganic components contained in the curable resin 2 bond together and simultaneously detach the inorganic components. If the layer made of the curable resin 2 is relatively thin, most of the inorganic components will detach, making it difficult to form the cured film 1. However, if the layer is relatively thick, the inorganic components that have bonded together will be concentrated, allowing the formation of a cured film 1 having the desired thickness. Therefore, the first curable resin layer 18 is formed to a thickness that allows the cured film 1 as the protective film 15 to be formed, while the second curable resin layer 19 is formed to a thickness that will disappear by the etching process in a later process. That is, the curable resin 2 is supplied to form the first curable resin layer 18 and the second curable resin layer 19 so that the film thickness of the second curable resin layer 19 is smaller than the film thickness of the first curable resin layer 18. Specifically, the amount of curable resin 2 supplied to the upper surface 12A of the first step structure 12 and the amount of curable resin 2 supplied to the upper surface 12A of the second step structure 13 can be determined by the above formula (1).

[0134] The method for curing the first curable resin layer 18 and the second curable resin layer 19 may be selected appropriately depending on the curing type of the curable resin 2 constituting the first curable resin layer 18 and the second curable resin layer 19. For example, if the curable resin 2 is a photocurable type, the first curable resin layer 18 and the second curable resin layer 19 (curable resin 2) may be irradiated with light (e.g., ultraviolet light, electron beam, etc.) via the template 17. If the curable resin 2 is a thermosetting type, heat may be applied to the first curable resin layer 18 and the second curable resin layer 19 (curable resin 2).

[0135] The template 17 has a convex portion 171 that is a square ring in plan view, and a concave portion 172 that is surrounded by the convex portion 171. The convex portion 171 corresponds to the upper surface 12A of the first step structure 12 of the multi-stage molded substrate 10′, and the concave portion 172 that is surrounded by the convex portion 171 corresponds to the upper surface 13A of the second step structure 13 of the multi-stage molded substrate 10′. The protruding height of the convex portion 171 may be set appropriately so that the first curable resin layer 18 and the second curable resin layer 19 are each formed to a predetermined film thickness.

[0136] Subsequently, the first curable resin layer 18 and the second curable resin layer 19 (curable resin 2) are subjected to an etching treatment to remove the second curable resin layer 19 and to form a cured film 1 as a protective film 15 on the light-shielding film 14 located on the upper surface portion 12A of the first step structure 12 (see FIG. 3E ). The etching treatment may be a dry etching treatment (plasma treatment) in which etching is performed using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a gas containing a mixture of two or more of these in a discharge plasma atmosphere in a vacuum chamber, or a wet etching treatment (oxidation treatment) in which etching is performed by bringing the first curable resin layer 18 and the second curable resin layer 19 into contact with an etching solution such as sulfuric acid or hydrogen peroxide water.

[0137] As described above, the film thickness of the first curable resin layer 18 is set to a level that allows the etching process to decompose the organic components and bond and concentrate the inorganic components, thereby forming a cured film 1 that mainly contains inorganic components. On the other hand, the film thickness of the second curable resin layer 19 is set to a level that allows it to be eliminated by the etching process. Therefore, through the etching process, the cured film 1 is formed on the light-shielding film 14 located on the upper surface 12A of the first step structure 12. On the other hand, the second curable resin layer 19 is removed from the light-shielding film 14 located on the upper surface 13A of the second step structure 13, exposing the light-shielding film 14.

[0138] Finally, the light-shielding film 14 located on the first surface 11A of the base 11 and the light-shielding film 14 located on the upper surface 13A of the second step structure 13 are removed by dry etching using, for example, chlorine-based (Cl + O) gas (see FIG. 3F). X (X is 1 or more) is formed as the protective film 15. The cured film 1 has low reactivity with chlorine-based (Cl + O) gas that can etch the light-shielding film 14, and is therefore able to protect the light-shielding film 14 located on the upper surface 12A of the first step structure 12. Therefore, according to this embodiment, it is possible to manufacture an imprint mold substrate 10 in which the light-shielding film 14 and the protective film 15 are laminated in this order on the upper surface 12A of the first step structure 12.

[0139] In the above embodiment, an example has been given in which the imprint mold substrate 10 is manufactured using a multi-stage mold substrate 10' in which the light-shielding film 14 is located on the upper surface 13A of the second step structure 13, but the present invention is not limited to this example. For example, the imprint mold substrate 10 may be manufactured using a multi-stage mold substrate 10' in which the light-shielding film 14 is not present on the upper surface 13A of the second step structure 13. In this case, it is not necessary to form the second curable resin layer 19 on the upper surface 13A of the second step structure 13.

[0140] [Method of Manufacturing Imprint Mold] A method of manufacturing an imprint mold in this embodiment will be described. First, an imprint mold substrate 10 manufactured as shown in Figures 3A to 3F is prepared, and a hard mask layer 22 is formed on the first surface 11A of the base 11 of the imprint mold substrate 10, the protective film 15 located on the upper surface 12A of the first step structure 12, and the upper surface 13A of the second step structure 13 (Figure 4A). The hard mask layer 22 includes a first hard mask layer 221 formed on the protective film 15, a second hard mask layer 222 formed on the upper surface 13A of the second step structure 13, and a third hard mask layer 223 formed on the first surface 11A of the base 11.

[0141] Examples of materials constituting the hard mask layer 22 include metals such as chromium, titanium, tantalum, silicon, and aluminum; chromium-based compounds such as chromium nitride, chromium oxide, and chromium oxynitride; tantalum compounds such as tantalum oxide, tantalum oxynitride, tantalum oxide boride, and tantalum oxynitride; titanium nitride, silicon nitride, and silicon oxynitride; and these may be used alone or in combination of two or more arbitrarily selected types.

[0142] The second hard mask layer 222 is for forming a mask pattern used when performing an etching process to form the concave-convex pattern 21 on the upper surface 13A of the second step structure 13. The third hard mask layer 223 is for forming a mask pattern used when performing an etching process to form the alignment mark 23 on the first surface 11A of the base 11. Therefore, the material for the hard mask layer 22 can be selected in consideration of the etching selectivity and the like depending on the material for the base 11. For example, when the base 11 is made of quartz glass, chromium oxide or the like can be suitably selected as the material for the hard mask layer 22.

[0143] The thickness of the hard mask layer 22 is set appropriately taking into consideration the etching selectivity and the like according to the constituent material of the base 11. For example, when the base 11 is made of quartz glass and the hard mask layer 22 is made of chromium oxide, the thickness of the hard mask layer 22 can be set appropriately within the range of about 0.5 nm to 200 nm.

[0144] The method for forming the hard mask layer 22 (the first hard mask layer 221, the second hard mask layer 222, and the third hard mask layer 223) is not particularly limited, and examples thereof include known film formation methods such as a sputtering method, a PVD (Physical Vapor Deposition) method, and a CVD (Chemical Vapor Deposition) method.

[0145] Next, droplets of imprint resin 23 are discretely supplied onto the second hard mask layer 222 by an inkjet method (see FIG. 4B ). At the same time, the imprint resin 23 is dropped onto the third hard mask layer 223 (see FIG. 4B ). The droplets of imprint resin 23 are arranged on the upper surface 13A (second hard mask layer 222) of the second step structure 13 according to the pattern density of the concave-convex pattern of the master mold 24 used to form the resin pattern 231 on the second hard mask layer 222, etc. The imprint resin 23 dropped onto the third hard mask layer 223 is arranged according to the position and size of the alignment mark 23 to be formed on the first surface 11A of the base 11.

[0146] The concave-convex pattern formed on the pattern surface 24A of the master mold 24 is brought into contact with the imprint resin 23 supplied onto the second hard mask layer 222, and the imprint resin 23 is spread between the pattern surface 24A of the master mold 24 and the upper surface portion 13A (second hard mask layer 222) of the second step structure 13. The imprint resin 23 between the pattern surface of the master mold 24 and the upper surface portion 13A (second hard mask layer 222) of the second step structure 13, and the imprint resin 23 on the first surface 11A (third hard mask layer 223) of the base 11 are cured. This allows the concave-convex pattern of the master mold 24 to be transferred to the imprint resin 23 on the second hard mask layer 222 to form a resin pattern 231, and also allows a resist pattern 232 to be formed on the third hard mask layer 223 (see FIG. 4C ).

[0147] The imprint resin 23 (resist material) is not particularly limited, and may be a resin material generally used in imprint processing (e.g., ultraviolet-curable resin, thermosetting resin, etc.). The imprint resin 23 may contain a release agent for easily separating the master mold 24, an adhesion agent for improving adhesion to the upper surface 13A (second hard mask layer 222) of the second step structure 13 of the imprint mold substrate 10, etc.

[0148] Next, the master mold 24 is separated from the cured imprint resin 23 to form a resin pattern 231, and the remaining film portion of the resin pattern 231 is removed as needed (see FIG. 4D ). In this way, the resin pattern 231 to which the concave-convex pattern of the master mold 24 is transferred can be formed on the second step structure 13 (second hard mask layer 222) of the imprint mold substrate 10.

[0149] Using the resin pattern 231 as a mask, the second hard mask layer 222 formed on the upper surface 13A of the second step structure 13 of the imprint mold substrate 10 is etched by dry etching using, for example, a chlorine-based (Cl + O) etching gas, to form a hard mask pattern 22P (see FIG. 4E). At the same time, the third hard mask layer 223 is etched using the resist pattern 232 as a mask, to form a hard mask pattern 22P (see FIG. 4E). Note that the first hard mask layer 221 located on the upper surface 12A of the first step structure 12 is removed by etching, exposing the protective film 15 (see FIG. 4E).

[0150] The imprint mold substrate 10 is subjected to dry etching using the hard mask patterns 22P1 and 22P2 as a mask, forming a concave-convex pattern 21 on the upper surface 13A of the second step structure 13 and an alignment mark 23 on the first surface 11A of the base 11, thereby manufacturing the imprint mold 20 (see FIG. 4F). X (X is 1 or more) as a main component, the protective film 15 is etched and removed simultaneously with the imprint mold substrate 10. Dry etching of the imprint mold substrate 10 can be performed by selecting an etching gas appropriate for the type of constituent material of the imprint mold substrate 10. As the etching gas, for example, a fluorine-based gas or the like can be used.

[0151] [Method for manufacturing a concave-convex structure] A method for manufacturing a concave-convex structure in this embodiment will be described. The method for manufacturing a concave-convex structure in this embodiment is a method for manufacturing a concave-convex structure configured with a line-and-space sidewall pattern formed along the sidewall of a resist pattern, and is a method for manufacturing a concave-convex structure by a so-called sidewall method. Generally, when manufacturing a concave-convex structure by the sidewall method, a sidewall material film is formed on the sidewall of a resist pattern that serves as a core material by an ALD method or the like, and the sidewall pattern is formed by etching the sidewall material film. In this case, the sidewall pattern formed along the sidewall of the core material has a loop shape (annular in plan view), so a process called loop cutting is required to form a line-and-space sidewall pattern. The method for manufacturing a concave-convex structure in this embodiment is characterized in that the process called loop cutting is not required.

[0152] First, a substrate 31 is prepared, which has a first surface 31A and an opposite second surface 31B, with a resist pattern provided on the first surface 31A. The resist pattern can be formed by, for example, imprint lithography using a mold, electron beam lithography using an electron beam lithography device, or photolithography using a photomask having predetermined openings and light-shielding portions. The resist pattern serves as a core pattern 32 for forming a sidewall pattern 36, which will be described later.

[0153] When the sidewall pattern 36 serves as an etching mask for etching the substrate 31, the height (thickness) of the sidewall pattern 36 is required to be such that the sidewall pattern 36 does not disappear during the etching process of the substrate 31, depending on the etching selectivity of the materials constituting the sidewall pattern 36 and the substrate 31, etc.

[0154] On the other hand, since the mandrel pattern 32 is formed by slimming the resist pattern by etching, the height (thickness) of the mandrel pattern 32 is lower (thinner) than the height (thickness) of the resist pattern. Therefore, the height (thickness) of the resist pattern needs to be higher (thicker) than the height (thickness) required for the sidewall pattern 36, taking into account the amount of slimming in the process of forming the mandrel pattern, which will be described later.

[0155] Next, the resist pattern formed on the first surface 31A of the substrate 31 is subjected to a slimming process to thin the resist pattern to form a core pattern 32. The slimming process of the resist pattern can be performed by, for example, a wet etching method, a dry etching method, a combination thereof, or the like.

[0156] Next, droplets of sidewall material 33 are dropped onto the core pattern 32 (see FIGS. 5A and 6A ). The curable resin 2 in this embodiment is used as the sidewall material 33. The positions and number of the dropped droplets of sidewall material 33, as well as the size of the droplets (amount of one droplet), may be set so that when a mold 34 is brought into contact with the sidewall material 33 in a later step, the sidewall material 33 spreading between the mold 34 and the core pattern 32 does not completely cover the core pattern 32 and does not reach at least both longitudinal ends of the core pattern 32 in a plan view.

[0157] A mold 34 having a convex pattern 341 is brought into contact with the droplets of sidewall material 33 dropped on the core pattern 32, and the sidewall material 33 is spread between the mold 34 and the core pattern 32. The sidewall material 33 is then hardened in this state to form a sidewall material film 35 (see FIGS. 5B and 6B). Then, the mold 34 is separated from the hardened sidewall material film 35 (see FIGS. 5C and 6C).

[0158] The convex patterns 341 of the mold 34 may be inserted between adjacent core patterns 32 and may have a size (length in the short direction in a plan view) large enough to form a predetermined gap between the convex patterns 341 and the sidewalls of the core patterns 32. By inserting the convex patterns 341 having such dimensions between the adjacent core patterns 32 and bringing the mold 34 into contact with the sidewall material 33 to harden, a sidewall material film 35 can be formed that covers the sidewalls and tops of the core patterns 32 and the first surface 31A of the substrate 31 exposed between the adjacent core patterns 32.

[0159] Next, the sidewall material film 35 is subjected to an etching process (dry etching process using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a mixture of two or more of these gases) to form sidewall patterns 36 on the sidewalls of the core pattern 32 (see FIGS. 5D and 6D ). When the curable resin 2 constituting the sidewall material film 35 is subjected to an etching process, the sidewall material film 35 disappears because the portion located on the top of the core pattern 32 is relatively thin. Similarly, the sidewall material film 35 disappears from the portion located on the first surface 31A of the substrate 31 exposed between adjacent core patterns 32. On the other hand, the portion along the sidewall of the core pattern 32 is relatively thick, so the organic components are decomposed and the inorganic components are combined and concentrated, resulting in the formation of a cured film 1 as the sidewall pattern 36.

[0160] Thereafter, the core pattern 32 with the sidewall pattern 36 formed thereon is removed by ashing (such as plasma ashing using an oxygen-containing gas) (see FIGS. 5E and 6E ). This removes only the core pattern 32, leaving the sidewall pattern 36 on the first surface 31A of the substrate 31. In this manner, a concave-convex structure 30 can be manufactured in which the line-and-space sidewall pattern 36 is formed on the first surface 31A of the substrate 31. The sidewall pattern 36 may be formed on a hard mask layer (not shown) made of Cr or the like that is formed on the first surface 31A of the substrate 31.

[0161] [Pattern Forming Method] The pattern forming method in this embodiment will be described below. Note that, as the pattern forming method in this embodiment, a method for manufacturing a convex lens substrate (see FIGS. 7A to 7B) and a method for manufacturing a Fresnel lens substrate (see FIGS. 8A to 8C) will be described as examples, but the pattern forming method is not limited to these modes.

[0162] [Method for manufacturing convex lens substrate] The method for manufacturing the convex lens substrate 60 involves preparing a base material 61 having a first surface 61A and a second surface 61B located on the opposite side thereof, and dripping droplets of curable resin 2 onto the first surface 61A of the base material 61 (see FIG. 7A ). Each droplet of the dripped curable resin 2 constitutes a convex lens 62 in the convex lens substrate 60, and therefore the drip arrangement and size (amount of one droplet) of the droplets of curable resin 2 may be appropriately set according to the arrangement and size of the convex lenses 62 required in the convex lens substrate 60 to be manufactured.

[0163] Next, the droplets of curable resin 2 are subjected to an etching process (dry etching using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a mixture of two or more of these as an etching gas, or wet etching using an etching solution such as sulfuric acid or hydrogen peroxide solution). This etching process decomposes the organic components in the curable resin 2 and causes the inorganic components to bond and concentrate, forming convex lenses 62 containing mainly inorganic components (see FIG. 7B). In this way, a convex lens substrate 60 having convex lenses 62 as the cured film 1 can be manufactured.

[0164] [Method of Manufacturing Fresnel Lens Substrate] A method of manufacturing a Fresnel lens substrate includes preparing a base material 71 having a first surface 71A and a second surface 71B located opposite to the first surface 71A, and forming a curable resin layer 72 made of a curable resin 2 on the first surface 71A of the base material 71. The curable resin layer 72 can be formed, for example, by dropping droplets of the curable resin 2 onto the first surface 71A of the base material 71, and curing the curable resin 2 while bringing a mold (not shown) having a flat surface into contact with the droplets of the curable resin 2.

[0165] A photoresist layer is formed on the curable resin layer 72, and a resin layer 73 having a thickness distribution (e.g., a resin layer 73 having a sawtooth cross section) is formed by, for example, subjecting the photoresist layer to gradation exposure at a predetermined number of gradations (see FIG. 8A).

[0166] Next, the curable resin layer 72 is etched using the resin layer 73 as a mask, thereby transferring the shape of the resin layer 73 to the curable resin layer 72 (see FIG. 8B ). In this embodiment, the curable resin layer 72 has a sawtooth cross section. This etching may be, for example, dry etching using a fluorine-based gas or the like.

[0167] Finally, the curable resin layer 72 having a sawtooth cross section is subjected to dry etching using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a mixture of two or more of these as an etching gas, or wet etching using sulfuric acid, hydrogen peroxide solution, or the like as an etching solution. This etching process decomposes the organic components in the curable resin 2 and causes the inorganic components to bond and concentrate, thereby forming a Fresnel lens 74 containing mainly inorganic components (see FIG. 8C ). In this way, a Fresnel lens substrate 70 having the Fresnel lens 74 as the cured film 1 can be manufactured.

[0168] [Method of Manufacturing Semiconductor Device] A method of manufacturing a semiconductor device in this embodiment will be described. The semiconductor device manufactured in this embodiment has a structure in which a semiconductor layer, an insulating film, and wiring are stacked in this order from the first surface side of a substrate having a first surface and a second surface located opposite the first surface. The method of manufacturing this semiconductor device includes the steps of forming a semiconductor layer 82 having a channel region 821 and source / drain regions 822 including contact portions that contact the wiring on the first surface 81A side of a substrate 81 (see FIG. 9A ), and forming an insulating film 83 on an insulating film formation region that includes the channel region 821 and a region excluding the contact portions (see FIG. 9B ).

[0169] The process of forming the insulating film 83 includes a process of supplying the curable resin 2 to the insulating film formation region, a process of curing the curable resin 2, and a process of decomposing the organic components in the cured curable resin 2 and leaving the inorganic components to form the insulating film 83. According to this embodiment, the insulating film 83 can be formed by a simple method by curing the curable resin 2 supplied to the insulating film formation region and performing a predetermined etching process on the curable resin 2 (a dry etching process or a wet etching process using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a gas containing a mixture of two or more of these).

[0170] The above-described embodiments have been described to facilitate understanding of the present invention, and are not intended to limit the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention.

[0171] The hardened film forming method according to the above embodiment may be used as a hard mask forming method for forming a hardened film 1, which functions as a hard mask layer, on a metal film, such as a Cr film, formed on a quartz glass substrate or the like. Such a hard mask forming method may include, for example, a step of supplying the hardened resin 2 to the metal film, a step of bringing a flat mold (e.g., mold 4 shown in FIG. 1B ) into contact with the hardened resin 2 and hardening it to form a moldable resin layer 5, and a step of performing a predetermined etching process on the moldable resin layer 5 to decompose organic components and combine and concentrate inorganic components to form the hardened film 1.

[0172] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0173] Example 1: A curable resin 2 was applied to a quartz glass substrate and cured while a flat mold was pressed against it from above, forming a moldable resin layer 5 with a thickness of 150 nm. The moldable resin layer 5 was then subjected to a dry etching process using chlorine-based (Cl + O) gas (etching time: 1555 seconds) to form a cured film 1 with a thickness of 95 nm. FIG. 10 shows the relationship between etching time and the thickness (nm) of the moldable resin layer 5. In the graph shown in FIG. 10, black circles (●) represent the results of Example 1, open diamonds (◇) represent the results of Reference Example 1, and open circles (○) represent the results of Reference Example 2, which will be described later. As shown in FIG. 10, after approximately 300 seconds of etching, almost no exponential fluctuation in film thickness was observed. These results confirm that forming a moldable resin layer 5 having a predetermined initial thickness using a curable resin 2 and then subjecting the moldable resin layer 5 to a predetermined etching process decomposes the organic components and bonds and concentrates the inorganic components, thereby forming a cured film 1 primarily containing inorganic components. The organic components contained in the moldable resin layer 5 are decomposed by the dry etching process, whereas the inorganic components are not. It is believed that the organic components are primarily decomposed in the early stages of the dry etching process (e.g., within 300 seconds of the start of the dry etching process). At this time, the inorganic components are bonded and concentrated, but some of the inorganic components are thought to be physically etched. Therefore, the amount of film thickness reduction per unit time of the moldable resin layer 5 in the early stages of the dry etching process is relatively large (see FIG. 10 ). On the other hand, after most of the organic components contained in the moldable resin layer 5 are decomposed (after 300 seconds of the start of the dry etching process), it is believed that the inorganic components continue to bond and concentrate, while some of the inorganic components are physically etched. Therefore, the amount of decrease in the film thickness of the resin layer 5 per unit time becomes relatively small (see FIG. 10).

[0174] The relationship between the initial thickness T0 of the molded resin layer 5 and the thickness T of the cured film 1 is expressed as follows: Ab ctWhen the amount of film thickness reduction per unit time of the moldable resin layer 5, which does not substantially change with the decomposition treatment time t, is defined as αt, A, which is the amount of film thickness reduction per unit time in the initial stage of the decomposition treatment of the organic components, can be calculated as the amount of change per unit time from the amount of film thickness change of the moldable resin layer 5 when the moldable resin layer 5 is subjected to an etching treatment for a short period of time, for example, 30 seconds or less. Furthermore, α can be calculated as the amount of change per unit time by continuing the etching treatment of the moldable resin layer 5 and measuring the amount of change in film thickness of the moldable resin layer 5 after the amount of film thickness reduction per unit time of the moldable resin layer 5 with the decomposition treatment time t no longer changes substantially. The coefficients b and c, which indicate the exponential behavior of the film thickness of the moldable resin layer 5, can be derived by appropriately adjusting the values ​​to fit the change in film thickness of the moldable resin layer 5. However, since the values ​​change depending on the decomposition treatment conditions, the above formula (1) can be derived appropriately depending on the material of the moldable resin layer 5 (curable resin 2), the etching treatment conditions, etc.

[0175] In Example 1 above, a composition containing 20% ​​by mass of a polymerizable compound having a spherical structure shown below, a reactive crosslinker (dimethylsiloxane-containing bifunctional acrylate, 79% by mass), and a photopolymerization initiator (Omnirad 907, 1% by mass) was used as the curable resin 2. In a measurement environment of 25°C and 40% RH, an AR-G2 manufactured by TA Instruments was used to drop the curable resin onto a disk plate, and a standard steel cone with a diameter of 40 mm was used to change the shear rate from 10 to 1000 (1 / s). The viscosity of the curable resin at 25°C and 1000 (1 / s) was 6.4 cPs, indicating that the resin could be applied by inkjet printing.

[0176] In the formula, SiO 1.5 is SiO 3 / 2 The siloxane polymerized moiety is composed of units.

[0177] The above polymerizable compound was synthesized as follows. 11.7 g of 3-acryloxypropyltrimethoxysilane was dissolved in 93.9 g of acetone and heated to 50°C. A mixed solution of 13.5 g of ion-exchanged water and 0.07 g of potassium carbonate (K2CO3) was added dropwise thereto, and the mixture was stirred at 50°C for 5 hours. The resulting reaction solution was washed and extracted with saturated saline and chloroform. The volatile components were removed, and the above polymerizable compound having a spherical structure was obtained.

[0178] [Reference Example 1] An attempt was made to form a cured film 1 in the same manner as in Example 1, except that the film thickness of the molded resin layer 5 was changed to 40.5 nm. When the etching time of the dry etching process was 330 seconds, it was confirmed that the molded resin layer 5 disappeared (see FIG. 10).

[0179] [Reference Example 2] An attempt was made to form a cured film 1 in the same manner as in Example 1, except that the film thickness of the molded resin layer 5 was changed to 27.3 nm. When the etching time of the dry etching process was 120 seconds, it was confirmed that the molded resin layer 5 disappeared (see Figure 10).

[0180] Reference Example 3 An attempt was made to form a cured film 1 in the same manner as in Example 1, except that a composition containing 35% by mass of the above-mentioned polymerizable compound having a spherical structure, a reactive crosslinker (dimethylsiloxane-containing bifunctional acrylate, 64% by mass), and a photopolymerization initiator (Omnirad 907, 1% by mass) was used as the curable resin. The variation in film thickness decreased more quickly than in Example 1, and no variation in film thickness was observed over time (not shown). The viscosity of the curable resin measured in the same manner as in Example 1 was 20 cPs, and it was possible to apply it by inkjet.

[0181] Reference Example 4 An attempt was made to form a cured film 1 in the same manner as in Example 1, except that a composition containing 50% by mass of the above-mentioned polymerizable compound having a spherical structure, a reactive crosslinker (dimethylsiloxane-containing bifunctional acrylate, 49% by mass), and a photopolymerization initiator (Omnirad 907, 1% by mass) was used as the curable resin. As a result, the variation in film thickness decreased even more rapidly than in Reference Example 3, and no variation in film thickness was observed over time (not shown). The viscosity of the curable resin measured in the same manner as in Example 1 was 54 cPs, and since application by inkjet was impossible, application by spin coating was performed.

[0182] Example 2 Manufacturing Example of Imprint Mold A multi-stage mold substrate 10' made of a quartz glass substrate as shown in Figure 3A was prepared, and the curable resin 2 used in Example 1 was applied to the upper surface portion 12A of the first step structure 12 and the upper surface portion 13A of the second step structure 13. A template 17 shown in Figure 3C was pressed against the curable resin 2, and the curable resin 2 was irradiated with ultraviolet light to harden it, thereby forming a first curable resin layer 18 and a second curable resin layer 19. The supply amount of the curable resin 2 was adjusted based on the above formula (1) so that the film thickness of the first curable resin layer 18 was 80 nm and the film thickness of the second curable resin layer 19 was 30 nm.

[0183] Next, the first curable resin layer 18 and the second curable resin layer 19 were subjected to a dry etching process (etching time: 300 seconds) using chlorine-based (Cl+O) gas to remove the second curable resin layer 19, and a cured film 1 (film thickness: 40 nm) was formed as a protective film 15 on the light-shielding film 14 located on the upper surface portion 12A of the first step structure 12, thereby producing an imprint mold substrate 10.

[0184] Next, a hard mask layer 22 made of metal Cr was formed on the first surface 11A of the base 11 of the imprint mold substrate 10, the protective film 15 located on the upper surface 12A of the first step structure 12, and the upper surface 13A of the second step structure 13 (see FIG. 4A ). Droplets of imprint resin 23 were discretely supplied onto the second hard mask layer 222 by an inkjet method (see FIG. 4B ). The concavo-convex pattern of the master mold 24 was then transferred to the imprint resin 23 supplied onto the second hard mask layer 222 to form a resin pattern 231. The second hard mask layer 222 was then etched using the resin pattern 231 as a mask to form a hard mask pattern 22P1. The imprint mold substrate 10 was then subjected to a dry etching process using the hard mask pattern 22P1 as a mask to form a concavo-convex pattern 21 on the upper surface 13A of the second step structure 13, thereby producing the imprint mold 20.

[0185] Example 3 Example of manufacturing a concave-convex structure by the sidewall method A synthetic quartz glass substrate having an outer shape of 6 inches square and a thickness of 0.25 inches was prepared as a substrate having a first surface 31A and a second surface 31B located on the opposite side thereof. An electron beam sensitive resist was applied to the first surface 31A of the quartz glass substrate by spin coating, and this resist layer was subjected to electron beam lithography and development to form a line and space shaped resist pattern having a pattern width of 48 nm, a height of 59 nm, a half pitch of 52 nm, and a line length of 10 μm.

[0186] Next, the resist pattern was slimmed by dry etching with oxygen plasma to form a core pattern 32 with a pattern width of 26 nm and a height of 48 nm, and droplets of curable resin 2 were dropped onto the core pattern 32 as a sidewall material 33. The curable resin 2 used in Example 1 was used.

[0187] A mold 34 having a convex pattern 341 with a pattern width of 26 nm and a height of 55 nm was brought into contact with the droplets of curable resin 2 dropped on the core material pattern 32, and the curable resin 2 was spread between the mold 34 and the core material pattern 32 and cured by irradiation with ultraviolet light to form a sidewall material film 35 (see FIGS. 5B and 6B). Thereafter, the mold 34 was separated from the cured sidewall material film 35 (see FIGS. 5C and 6C).

[0188] Subsequently, the sidewall material film 35 was subjected to an etching process (dry etching process using chlorine-based (Cl + O) gas (etching time: 300 seconds)) to decompose the organic components and combine and concentrate the inorganic components, thereby forming a sidewall pattern 36 having a pattern width of 26 nm and a height of 23 nm on the sidewall of the core pattern 32 (see FIGS. 5D and 6D). Thereafter, the core pattern 32 on which the sidewall pattern 36 was formed was removed by plasma ashing using an oxygen-containing gas (see FIGS. 5E and 6E), thereby producing a concavo-convex structure 30 having a line-and-space sidewall pattern 36.

[0189] [Example 4] Surface composition analysis by XPS A cured film 1 was formed in the same manner as in Example 1, except that the film thickness of the moldable resin layer 5 was changed to 39 nm and dry etching was performed until the film thickness reached 24 nm, and surface composition analysis was performed on the cured film 1 by X-ray photoelectron spectroscopy (XPS). In addition, surface composition analysis was also performed on the moldable resin layer 5 before the dry etching process by X-ray photoelectron spectroscopy (XPS). As a result, the composition ratios (%) of elements in the cured film 1 and the moldable resin layer 5 were as shown in Table 1 below.

[0190]

[0191] From the results shown in Table 1, it was confirmed that the cured film formed through the dry etching treatment has a concentration gradient in which the concentration of silicon (Si) atoms is high near the surface of the cured film and decreases toward the inside of the cured film along the thickness direction of the cured film. It was also confirmed that the cured film formed through the dry etching treatment has a concentration gradient in which the concentration of carbon (C) atoms is low near the surface of the cured film and increases toward the inside of the cured film along the thickness direction of the cured film.

[0192] REFERENCE SIGNS LIST 1... Cured film 2... Curable resin 10... Substrate for imprint mold 20... Imprint mold 30... Concave-convex structure 60... Convex lens substrate 70... Fresnel lens substrate

Claims

1. A step of supplying a curable resin containing a polymerizable compound having a siloxane bond in the molecule and at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent to a substrate; curing the curable resin; a step of subjecting the cured resin to a plasma treatment or an oxidation treatment to decompose an organic component contained in the curable resin and leave a siloxane polymerized portion to form a cured film; A method for forming a cured film comprising the steps of:

2. The polymerizable compound has a spherical structure in which the polymerizable functional groups extend outward from the siloxane polymerized portion. The method for forming a cured film according to claim 1 .

3. Among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound, the ratio of oxygen atoms bonded to a single silicon atom is 10 mol % or less, The curable resin is substantially free of solvent and has a viscosity of 20 cPs or less. The method for forming a cured film according to claim 1 or 2.

4. The content of the reactive crosslinking agent in the curable resin is 49% by mass to 79% by mass. The method for forming a cured film according to claim 1 or 2.

5. The step of curing the curable resin includes a contact step of bringing a mold close to the substrate and spreading the curable resin between the substrate and the mold to form a molded resin layer, a curing step of curing the molded resin layer, and a demolding step of separating the mold from the cured molded resin layer. The method for forming a cured film according to claim 1 or 2.

6. The thickness T of the resin layer to be molded ０ The amount of the curable resin to be supplied to the substrate is determined based on the following formula (1) which shows the relationship between the thickness T of the cured film and the decomposition processing time t for decomposing the organic components: The method for forming a cured film according to claim 5 . [0010] In the above formula (1), Ab ｃｔ represents "the amount of reduction in the film thickness of the molded resin layer per unit time which changes according to the decomposition processing time t in the early stage of the decomposition processing of the organic component", αt represents "the amount of reduction in the film thickness of the molded resin layer per unit time which does not substantially change according to the decomposition processing time t", A represents "the amount of reduction in the film thickness of the molded resin layer per unit time in the early stage of the decomposition processing of the organic component", and b and c are "coefficients indicating the exponential reduction in the film thickness of the formed resin layer", where b>1 and c<0.

7. A cured film forming region in which the cured film is formed and a cured film non-forming region in which the cured film is not formed are provided on the substrate; The curable resin is supplied to the cured film formation region in an amount determined based on the formula (1) so that the thickness T of the cured film exceeds 0, and the cured resin is supplied to the cured film non-formation region in an amount determined based on the formula (1) so that the thickness T of the cured film is 0 or less. The method for forming a cured film according to claim 6 .

8. The mold has a concave-convex structure including a concave portion, the molded resin layer has a transfer structure including a convex portion to which a concave portion of the concave-convex structure is transferred, and a residual film portion; The amount of the curable resin to be supplied to the substrate is determined based on the depth of the recesses of the uneven structure, the thickness of the remaining film portion, and the formula (1). The method for forming a cured film according to claim 6 .

9. the mold has a relief structure with a minimum dimension of 100 nm or less, the molded resin layer has a transfer structure to which the concave-convex structure is transferred, The cured film is formed having a pattern with dimensions smaller than the minimum dimension of the relief structure. The method for forming a cured film according to claim 5 .

10. the substrate has a first surface and a second surface opposite to the first surface, and at least one material layer on at least the first surface, the material layer being made of a material different from that of the substrate; Providing the hardenable resin on the material layer The method for forming a cured film according to claim 1 or 2.

11. A cured film formed by the method for forming a cured film according to claim 1 or 2, In the composition distribution along the thickness direction of the cured film, the cured film has a concentration gradient in which the concentration of silicon (Si) atoms is highest near the surface of the cured film and the concentration of silicon (Si) atoms is lowest near the substrate.

12. In the composition distribution along the thickness direction of the cured film, the concentration of carbon (C) atoms is lowest in the vicinity of the surface of the cured film, and the concentration of carbon (C) atoms is highest in the vicinity of the substrate. The cured film according to claim 11.

13. A step of preparing a multi-stage mold substrate including a base having a first surface and a second surface located opposite to the first surface, a first step structure protruding from the first surface of the base, a second step structure protruding from an upper surface of the first step structure, and a light-shielding film located on the upper surface of the first step structure; supplying a curable resin containing a polymerizable compound having a siloxane bond in a molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent onto the light-shielding film and an upper surface of the second step structure, forming a first curable resin layer on the light-shielding film and forming a second curable resin layer on the upper surface of the second step structure, and curing the first curable resin layer and the second curable resin layer; a step of performing a plasma treatment or an oxidation treatment on the cured first curable resin layer and the cured second curable resin layer to decompose an organic component contained in the curable resin and leave a siloxane polymerized portion to form a protective film on the light-shielding film, and removing the second curable resin layer; Including, A method for manufacturing a substrate for an imprint mold, wherein the thickness of the second curable resin layer is smaller than the thickness of the first curable resin layer and is thick enough to be removed during formation of the protective film.

14. a light-shielding material layer is formed on an upper surface of the second step structure of the multi-step mold substrate; and removing the light-shielding material layer by etching after removing the second hardening resin layer. The method for producing a substrate for an imprint mold according to claim 13.

15. forming a first hard mask layer on the protective film of the imprint mold substrate manufactured by the method according to claim 13 or 14, and forming a second hard mask layer on an upper surface of the second step structure; forming a mask pattern on the second hard mask layer; forming a hard mask pattern on an upper surface of the second step structure by etching the second hard mask layer using the mask pattern as a mask, and removing the first hard mask layer; forming a concave-convex pattern on the upper surface of the second step structure by etching the upper surface of the second step structure using the hard mask pattern as a mask, and removing the protective film; A method for manufacturing an imprint mold comprising:

16. providing a substrate having a first side and a second side opposite the first side; forming a core pattern having a convex pattern on the first surface; supplying a curable resin onto the core pattern, the curable resin including a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; a step of contacting a template with the curable resin supplied onto the core pattern and curing the curable resin to form a curable resin layer that covers the tops and sidewalls of the protruding patterns of the core pattern and the first surface exposed between adjacent protruding patterns; a step of performing a plasma treatment or an oxidation treatment on a portion of the curable resin layer that covers a sidewall portion of the protruding pattern, thereby decomposing an organic component contained in the curable resin, leaving a siloxane polymerized portion, and removing a portion that covers the top portion of the protruding pattern and a portion that covers the first surface exposed between adjacent protruding patterns, thereby forming a sidewall pattern; removing the core pattern; A method for producing a concave-convex structure having the above structure.

17. providing a substrate having a first side and a second side opposite the first side; A step of discretely dropping a curable resin onto the first surface of the substrate, the curable resin including a polymerizable compound having a siloxane bond in a molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; curing the discretely dropped curable resin; a step of subjecting the cured resin to a plasma treatment or an oxidation treatment to decompose an organic component contained in the curable resin and leave a siloxane polymerized portion, thereby forming a cured film pattern; The pattern forming method includes the steps of:

18. providing a substrate having a first side and a second side opposite the first side; supplying a curable resin onto the first surface of the substrate, the curable resin including a polymerizable compound having a siloxane bond in a molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; a step of bringing a mold close to the substrate and curing the curable resin spread between the substrate and the mold to form a molded resin layer; a step of separating the mold from the resin layer; forming a resist layer having a thickness distribution on the resin layer to be molded; forming a resin pattern by etching the resin layer to be molded using the resist layer as a mask; a step of subjecting the resin pattern to a plasma treatment or an oxidation treatment to decompose an organic component contained in the curable resin and leave a siloxane polymerized portion, thereby forming a cured film pattern; The pattern forming method includes the steps of:

19. A method for forming a hard mask in an arbitrary region on a substrate on which a metal film is formed, comprising the steps of: supplying a curable resin on the metal film, the curable resin including a polymerizable compound having a siloxane bond in a molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; a step of bringing a mold close to the substrate and curing the curable resin spread between the substrate and the mold to form a molded resin layer; a step of subjecting the resin layer to a plasma treatment or an oxidation treatment to decompose an organic component contained in the curable resin and leave a siloxane polymerized portion to form a hard mask; The hard mask forming method includes the steps of:

20. A method for forming an insulating film in an insulating film formation region on a substrate, comprising the steps of: supplying a curable resin containing a polymerizable compound having a siloxane bond in its molecule and having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent to the insulating film formation region; curing the curable resin; a step of subjecting the cured resin to a plasma treatment or an oxidation treatment to decompose an organic component contained in the curable resin and leave a siloxane polymerized portion to form the insulating film; The insulating film forming method includes the steps of:

21. A method for manufacturing a semiconductor device having a structure in which a semiconductor layer, an insulating film, and wiring are laminated in this order from a first surface side of a substrate having a first surface and a second surface located opposite to the first surface, the method comprising the steps of: forming the semiconductor layer on the first surface, the semiconductor layer having a channel region and source / drain regions including contact portions in contact with the wiring; forming the insulating film on the channel region and a region other than the contact portion by the method according to claim 20; A method for manufacturing a semiconductor device comprising the steps of:

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