WO2023190168A1 - 硬化膜形成方法、インプリントモールド用基板の製造方法、インプリントモールドの製造方法、凹凸構造体の製造方法、パターン形成方法、ハードマスク形成方法、絶縁膜形成方法及び半導体装置の製造方法 - Google Patents

硬化膜形成方法、インプリントモールド用基板の製造方法、インプリントモールドの製造方法、凹凸構造体の製造方法、パターン形成方法、ハードマスク形成方法、絶縁膜形成方法及び半導体装置の製造方法 Download PDF

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Publication number
WO2023190168A1
WO2023190168A1 PCT/JP2023/011841 JP2023011841W WO2023190168A1 WO 2023190168 A1 WO2023190168 A1 WO 2023190168A1 JP 2023011841 W JP2023011841 W JP 2023011841W WO 2023190168 A1 WO2023190168 A1 WO 2023190168A1
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Prior art keywords
curable resin
substrate
forming
cured film
pattern
Prior art date
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Ceased
Application number
PCT/JP2023/011841
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English (en)
French (fr)
Japanese (ja)
Inventor
幸司 吉田
博和 小田
泰央 大川
広章 佐藤
隆治 長井
勝敏 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
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Publication date
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to JP2024512358A priority Critical patent/JPWO2023190168A1/ja
Priority to US18/852,969 priority patent/US20250282915A1/en
Priority to CN202380031542.2A priority patent/CN118974885A/zh
Priority to KR1020247035943A priority patent/KR20240172190A/ko
Publication of WO2023190168A1 publication Critical patent/WO2023190168A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/68—Organic materials, e.g. photoresists
    • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
    • B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C99/00—Subject matter not provided for in other groups of this subclass
    • B81C99/0075—Manufacture of substrate-free structures
    • B81C99/0085—Manufacture of substrate-free structures using moulds and master templates, e.g. for hot-embossing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0015—Production of aperture devices, microporous systems or stamps
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
    • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
    • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
    • H10P76/2041—Photolithographic processes

Definitions

  • 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 an uneven structure, a method for forming a pattern, a method for forming a hard mask, a method for forming an insulating film, and a method for manufacturing a semiconductor device. Regarding the method.
  • Nanoimprint lithography is known as a technology for transferring and forming fine patterns in semiconductor device manufacturing and the like.
  • an imprint mold with a finely uneven transfer pattern formed on its surface is brought into contact with a resin supplied onto a substrate to be transferred, such as a semiconductor wafer, and then the resin is cured and imprinted into the resin.
  • This is a technology that transfers the uneven shape of the transfer pattern of a print mold.
  • Nanoimprint lithography techniques include a thermal imprint method in which the uneven shape of a transfer pattern is transferred to a resin using thermal energy, and an optical imprint method in which the resin is cured by exposure to light.
  • Optical imprinting methods which are not affected by expansion or contraction due to heating, are mainly used for applications that require high alignment accuracy.
  • the main surface of the base is molded so that only a predetermined area (pattern area) in which an uneven transfer pattern is formed comes into contact with the resin supplied onto the transfer target substrate.
  • a mesa-like step structure is provided above, and a transfer pattern is formed on the upper surface of the mesa-like step structure. Note that in the imprint mold having such a configuration, the upper surface of the mesa-like step structure becomes the pattern area.
  • the height of the mesa-like step structure (the height from the main surface of the base to the top surface of the step structure) is determined by the mechanical precision of the imprint apparatus used, but is generally about 30 ⁇ m.
  • the pattern density of the transfer pattern in the imprint mold increases, the area of contact between the imprint mold and the resin increases, so when the imprint mold and the resin are released, a force that counters the frictional force between them is required. is required.
  • transfer patterns for semiconductor applications are small in size (dimensions) and have a high pattern density, so a large force is required for mold release. Therefore, by forming a recessed part on the back side of the imprint mold (the side opposite to the side on which the transfer pattern is formed), the template can be used in a predetermined area where the transfer pattern is formed (area including the pattern area).
  • the pattern area of the imprint mold is curved in a convex shape toward the transferred substrate side, and parts of the imprint mold are sequentially released from the outer edge of the transfer area. There are known methods to do this.
  • the first step of the imprint mold is A second stepped structure is formed on the structure, and a light shielding portion is provided in a non-patterned area (a different area from the transferred pattern area) on the upper surface of the first stepped structure, which is an area outside the second stepped structure. It has been proposed (see Patent Document 1).
  • an imprint mold that has a first step structure and a second step structure and a light shielding section is provided in a non-pattern area (a part different from the transfer pattern area) has a first step structure and a second step structure. It is manufactured by preparing a substrate for an imprint mold provided with a step structure of No. 2, forming a transfer pattern in a transfer pattern area, and then forming a light shielding part in a non-pattern area (see Patent Document 1). After providing a light shielding part in the non-pattern part of the imprint mold substrate having the first step structure and the second step structure, when a transfer pattern is formed in the transfer pattern area of the imprint mold substrate, the imprint mold In the etching process, cleaning process, etc.
  • the light shielding part may be damaged, so there is a possibility that the light shielding part will not be able to perform the desired function in the manufactured imprint mold.
  • a protective film on the light shielding part it is necessary to go through processes such as sputtering and patterning, and the process of forming the light shielding part is complicated.
  • the present disclosure provides a cured film forming method that can form a cured film that can be used as a protective film etc. in a simpler manner, and an imprint mold substrate using the cured film forming method.
  • An object of the present invention is to provide a method for manufacturing an imprint mold, a method for manufacturing an uneven structure, a method for forming a pattern, a method for forming a hard mask, a method for forming an insulating film, and a method for manufacturing a semiconductor device.
  • an embodiment of the present disclosure includes 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.
  • a method for forming a cured film is provided, which includes a step of forming a cured film by leaving a siloxane polymerized portion.
  • the polymerizable compound may have a spherical structure in which the polymerizable functional group extends outward from the siloxane polymerized portion.
  • the proportion of oxygen atoms bonded to silicon atoms contained in the polymerizable compound is 10 mol% or less
  • the curable resin substantially contains a solvent. and may have a viscosity of 20 cPs or less.
  • the content of the reactive crosslinking agent contained in the curable resin may be 49% by mass to 79% by mass.
  • 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 resin layer to be molded;
  • the method may include a curing step of curing the layer, and a releasing step of separating the mold from the cured resin layer to be molded.
  • the curable resin It is possible to determine the amount of the material to be supplied to the substrate.
  • Ab ct represents "the amount of decrease per unit time in the film thickness of the resin layer to be molded that changes according to the decomposition treatment time t at the initial stage of the decomposition treatment of the organic component"
  • ⁇ t represents "the amount of decrease per unit time in the film thickness of the resin layer to be molded that does not substantially change according to the decomposition treatment time t”
  • A represents "the amount of decrease per unit time in the initial stage of the decomposition treatment of the organic component”.
  • b and c are coefficients indicating an exponential decrease in the thickness of the resin layer to be formed, and b>1 and c ⁇ 0. be.
  • a cured film forming area where the cured film is formed and a cured film non-forming area where the cured film is not formed are set on the substrate, and the cured film forming area is provided with the cured film forming area based on the formula (1).
  • the curable resin is supplied in an amount determined such that the thickness T of the film exceeds 0, and the cured film thickness T is 0 or less based on the formula (1) in the non-cured film formation area. It is sufficient to supply the curable resin in an amount determined so as to satisfy the following conditions.
  • the mold has an uneven structure including depressions
  • the resin layer to be molded has a transfer structure including a projection to which the depressions of the uneven structure are transferred, and a residual film portion, and the uneven structure
  • the amount of the curable resin to be supplied to the substrate can be determined based on the depth of the recess, the thickness of the remaining film portion, and the equation (1).
  • the mold has an uneven structure with a minimum dimension of 100 nm or less, and the resin layer to be molded has a transfer structure in which the uneven structure is transferred, and the pattern has a size smaller than the minimum dimension of the uneven structure.
  • the cured film may be formed having a first surface and a second surface located on the opposite side of the first surface, and at least the first surface has a material different from that of the substrate. It has at least one material layer made of a material, and the curable resin may be supplied onto the material layer.
  • silicon (Si) atoms near the surface of the cured film are A cured film is provided that has a concentration gradient with the highest concentration of silicon (Si) atoms in the vicinity of the substrate and the lowest concentration of silicon (Si) atoms in the vicinity of the substrate.
  • the concentration distribution of carbon (C) atoms is lowest near the surface of the cured film and highest near the substrate. may have.
  • An embodiment of the present disclosure includes a base having a first surface and a second surface located on the opposite side of the first surface, a first step structure protruding from the first surface of the base, and the first step.
  • a step of preparing a multi-stage molded substrate comprising a second step structure protruding from the top surface of the structure and a light-shielding film located on the top surface of the first step structure;
  • a curable resin containing a polymerizable compound having a functional group, a polymerization initiator, and a reactive crosslinking agent is supplied onto the light shielding film and the upper surface of the second stepped structure, and a first curable resin is applied onto the light shielding film.
  • a protective film is formed on the light shielding film by subjecting the first curable resin layer and the second curable resin layer to plasma treatment or oxidation treatment to decompose the organic components contained in the curable resin and leave a siloxane polymerized portion. 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 the protective film is removed.
  • a method of manufacturing a substrate for an imprint mold is provided that is thick enough to be removed during formation.
  • a light-shielding material layer is formed on the upper surface of the second step structure of the multi-stage molded substrate, and the method may include the step of removing the light-shielding material layer by etching after removing the second curable resin layer. .
  • a first hard mask layer is formed on the protective film of the imprint mold substrate manufactured by the above method, and a second hard mask layer is formed on the upper surface of the second step structure.
  • forming a concave-convex pattern on the top surface of the second step structure by removing the first hard mask layer and etching the top surface of the second step structure using the hard mask pattern as a mask; , and a step of removing the protective film.
  • a curable resin containing a polymerizable compound having a siloxane bond in its molecule and at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent onto the core pattern.
  • a curable resin layer that covers the first surface; and performing plasma treatment or oxidation treatment on a portion of the curable resin layer that covers the side wall portion of the convex pattern, and By decomposing the organic components contained and leaving the siloxane polymerized portion, and removing the portion covering the top of the convex pattern and the portion covering the first surface exposed between adjacent convex patterns, the sidewall pattern is formed.
  • a method for manufacturing a concavo-convex structure comprising the steps of forming a core material pattern, and removing the core material pattern.
  • An embodiment of the present disclosure includes a step of preparing a substrate having a first surface and a second surface located on the opposite side of the first surface, and the first surface of the substrate has a siloxane bond in a molecule. a step of discretely dropping a curable resin containing a polymerizable compound having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; A cured film pattern is formed by curing the resin and subjecting the cured curable resin to plasma treatment or oxidation treatment to decompose organic components contained in the curable resin and leave siloxane polymerized parts.
  • a pattern forming method is provided which includes steps.
  • An embodiment of the present disclosure includes a step of preparing a substrate having a first surface and a second surface located on the opposite side of the first surface, and the first surface of the substrate has a siloxane bond in a molecule. a step of supplying a curable resin containing a polymerizable compound having at least one polymerizable functional group, a polymerization initiator, and a reactive crosslinking agent; a step of forming a molded resin layer by curing the curable resin developed between the molded resin layer, a step of separating the mold from the molded resin layer, and a step of forming a thickness on the molded resin layer.
  • a pattern forming method includes a step of forming a cured film pattern by decomposing an organic component contained in a resin and leaving a siloxane polymerized portion.
  • a method for forming a hard mask in any region on a substrate on which a metal film is formed the hard mask having a siloxane bond in the molecule and having at least one polymerized a step of supplying a curable resin containing a polymerizable compound having a functional group, a polymerization initiator, and a reactive crosslinking agent, and placing a mold close to the substrate and spreading it between the substrate and the mold.
  • a hard mask forming method is provided, which includes a step of forming a hard mask by leaving a portion of the hard mask.
  • a method for forming an insulating film on an insulating film formation region on a substrate comprising: a polymerizable compound having a siloxane bond in the molecule and at least one polymerizable functional group; A step of supplying a curable resin containing an initiator and a reactive crosslinking agent to the insulating film forming region, a step of curing the curable resin, and subjecting the cured curable resin to plasma treatment or oxidation treatment. and forming the insulating film by decomposing an organic component contained in the curable resin and leaving a siloxane polymerized portion.
  • a semiconductor layer, an insulating film, and wiring are provided on the first surface side of a substrate having a first surface and a second surface located on the opposite side of the first surface.
  • a method for forming a cured film that can form a cured film that can be used as a protective film, etc., in a simpler manner and a method for manufacturing a substrate for an imprint mold using the method for forming a cured film.
  • a method for manufacturing an imprint mold a method for manufacturing a concavo-convex structure, a method for forming a pattern, a method for forming a hard mask, a method for forming an insulating film, and a method for manufacturing a semiconductor device.
  • FIG. 1A is a cut end view schematically showing one step of a cured film forming method according to an embodiment of the present disclosure.
  • FIG. 1B is a cut end view schematically showing a step subsequent to FIG. 1A, which is one step of a cured film forming method according to an embodiment of the present disclosure.
  • FIG. 1C is a cut end view schematically showing a step following FIG. 1B, which is one step of a cured film forming method according to an embodiment of the present disclosure.
  • FIG. 1D is a cut end view schematically showing a step subsequent to FIG. 1C, which is one step of a cured film forming method according to an embodiment of the present disclosure.
  • FIG. 1A is a cut end view schematically showing one step of a cured film forming method according to an embodiment of the present disclosure.
  • FIG. 1B is a cut end view schematically showing a step subsequent to FIG. 1A, which is one step of a cured film forming method according to an embodiment of the present disclosure
  • FIG. 2A is a cut end view schematically showing one step of another aspect of the cured film forming method according to an embodiment of the present disclosure.
  • FIG. 2B is a cut end view schematically showing a step following FIG. 2A, which is one step of another aspect of the cured film forming method according to an embodiment of the present disclosure.
  • FIG. 2C is a cut end view schematically showing a step following FIG. 2B, which is one step of another aspect of the cured film forming method according to an embodiment of the present disclosure.
  • FIG. 2D is a cut end view schematically showing a step following FIG. 2C, which is one step of another aspect of the cured film forming method according to an embodiment of the present disclosure.
  • FIG. 2A is a cut end view schematically showing one step of another aspect of the cured film forming method according to an embodiment of the present disclosure.
  • FIG. 2B is a cut end view schematically showing a step following FIG. 2A, which is one step of another aspect of the cured film forming
  • FIG. 3A is a cut end view schematically showing one step of a method for manufacturing an imprint mold substrate according to an embodiment of the present disclosure.
  • FIG. 3B is a cut end view schematically showing a step subsequent to FIG. 3A, which is one step of the method for manufacturing an imprint mold substrate according to an embodiment of the present disclosure.
  • FIG. 3C is a cut end view schematically showing a step subsequent to FIG. 3B, which is one step of the method for manufacturing an imprint mold substrate according to an embodiment of the present disclosure.
  • FIG. 3D is a cut end view schematically showing a step subsequent to FIG. 3C, which is one step of the method for manufacturing an imprint mold substrate according to an embodiment of the present disclosure.
  • FIG. 3E is a cut end view schematically showing a step subsequent to FIG.
  • FIG. 3D which is one step of the method for manufacturing an imprint mold substrate according to an embodiment of the present disclosure.
  • FIG. 3F is a cut end view schematically showing a step subsequent to FIG. 3E, which is one step of the method for manufacturing an imprint mold substrate according to an embodiment of the present disclosure.
  • FIG. 4A is a cut end view schematically showing one step of a method for manufacturing an imprint mold according to an embodiment of the present disclosure.
  • FIG. 4B is a cut end view schematically showing a step subsequent to FIG. 4A, which is one step of the imprint mold manufacturing method according to an embodiment of the present disclosure.
  • FIG. 4C is a cut end view schematically showing a step subsequent to FIG. 4B, which is one step of the imprint mold manufacturing method according to an embodiment of the present disclosure.
  • FIG. 4D is a cut end view schematically showing a step subsequent to FIG. 4C, which is one step of the imprint mold manufacturing method according to an embodiment of the present disclosure.
  • FIG. 4E is a cut end view schematically showing a step subsequent to FIG. 4D, which is one step of the imprint mold manufacturing method according to an embodiment of the present disclosure.
  • FIG. 4F is a cut end view schematically showing a step subsequent to FIG. 4F, which is one step of the imprint mold manufacturing method according to an embodiment of the present disclosure.
  • FIG. 5A is a cut end view schematically showing one step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5B is a cut end view schematically showing a step subsequent to FIG.
  • FIG. 5A which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5C is a cut end view schematically showing a step subsequent to FIG. 5B, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5D is a cut end view schematically showing a step subsequent to FIG. 5C, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5E is a cut end view schematically showing a step subsequent to FIG. 5D, which is one step of a method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5C is a cut end view schematically showing a step subsequent to FIG. 5B, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5D is a
  • FIG. 6A is a plan view of the step shown in FIG. 5A, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 6B is a plan view of the step shown in FIG. 5B, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 6C is a plan view of the step shown in FIG. 5C, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 6D is a plan view of the step shown in FIG. 5D, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 5D is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 6E is a plan view of the step shown in FIG. 5E, which is one step of the method for manufacturing a concavo-convex structure according to an embodiment of the present disclosure.
  • FIG. 7A is a cut end view schematically showing one step of a pattern forming method according to an embodiment of the present disclosure.
  • FIG. 7B is a cut end view schematically showing a step following FIG. 7A, which is one step of the pattern forming method according to an embodiment of the present disclosure.
  • FIG. 8A is a cut end view schematically showing one step of another aspect of the pattern forming method according to an embodiment of the present disclosure.
  • FIG. 8B is a cut end view schematically showing a step following FIG.
  • FIG. 8A which is one step of another aspect of the pattern forming method according to an embodiment of the present disclosure.
  • FIG. 8C is a cut end view schematically showing a step following FIG. 8B, which is one step of another aspect of the pattern forming method according to an embodiment of the present disclosure.
  • FIG. 9A is a cut end view schematically showing one step of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 9B is a cut end view schematically showing a step subsequent to FIG. 9A, which is one 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.
  • the method for forming a cured film according to the present embodiment includes a step of supplying a curable resin 2 to a substrate 3 (see FIGS. 1A and 2A) and a step of curing the curable resin 2 (see FIGS. 1B, 1C, and 2B). , see FIG. 2C) and a step of forming a cured film 1 (see FIGS. 1D and 2D).
  • the curable resin 2 in this embodiment includes a polymerizable compound having an organic component and an inorganic component in the molecule.
  • the inorganic component may contain SiO x (X is 1 or more), and the polymerizable compound may have a siloxane bond as an inorganic component, and may have at least one polymerizable functional group.
  • the polymerizable compound contained in the curable resin 2 in this embodiment has a ratio of oxygen atoms bonded to a single silicon atom of 10 mol% among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound.
  • the following is sufficient.
  • polymers and oligomers having structural units of tetrafunctional silane, trifunctional silane, bifunctional silane, and monofunctional silane can be used alone or in combination of multiple types. .
  • the curable resin 2 depending on the properties desired for the curable resin 2, it is preferable to use a resin whose constituent units are mainly trifunctional silanes and difunctional silanes.
  • the ratio of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to silicon atoms contained in the polymerizable compound is preferably 10 mol% or less. is 7 mol% or less, particularly preferably 5 mol% or less.
  • 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, and an oxygen atom in which both of the two bonds of the oxygen atom are bonded to silicon. This means that it is not an oxygen atom that is bonded to an atom.
  • the other bond of the oxygen atom is not particularly limited as long as it is bonded to something other than silicon, but it is particularly preferably bonded to hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • the ratio of oxygen atoms bonded to a single silicon atom as described above that is, the ratio of oxygen atoms bonded to a single silicon atom, that is, the ratio of hydroxyl groups (-OH) and alkoxy groups (-OR, R is 1 to 1 carbon atoms)
  • the reason why the highly reactive functional groups are present in a certain proportion in the polymerizable compound is presumed to be unreacted oxygen atoms remaining during the manufacturing process of the polymerizable compound.
  • the reason why such unreacted oxygen atoms remain is that when the highly reactive functional group is an alkoxy group (-OR, R is an alkyl group having 1 to 4 carbon atoms), the alkoxy group of the raw material is hydrolyzed.
  • R is an alkoxy group having 1 to 4 carbon atoms
  • the ratio of oxygen atoms bonded to a single silicon atom refers to the proportion of oxygen atoms bonded to a single silicon atom when the number of oxygen atoms bonded to a silicon atom in the polymerizable compound is 100. It shows the number of oxygen atoms that are present. This ratio can be calculated by analyzing the spectrum using 29 Si-NMR.
  • the polymerizable compound contains a siloxane structure with a difunctional silane as a constituent unit
  • all of the two oxygen atoms bonded to silicon atoms are bonded to components that are not bonded to other silicon atoms.
  • Three peaks are observed: a component in which one of the two oxygen atoms is bonded to another silicon atom, and a component in which all of the two oxygen atoms bonded to the silicon atom are bonded to other silicon atoms. .
  • the polymerizable compound contains a siloxane structure with a tetrafunctional silane as a constituent unit, all four oxygen atoms bonded to silicon atoms are bonded to components that are not bonded to other silicon atoms, or to silicon atoms.
  • a component in which one of the four oxygen atoms bonded to another silicon atom, a component in which two of the four oxygen atoms bonded to a silicon atom are bonded to another silicon atom, a component bonded to a silicon atom Five peaks are observed: one in which three of the four oxygen atoms are bonded to other silicon atoms, and one in which all four oxygen atoms bonded to silicon atoms are bonded to other silicon atoms. .
  • the proportion (mol%) of oxygen atoms bonded to a single silicon atom can be calculated from the following formula (4). It can be calculated.
  • the above-mentioned polymerizable compound having two types of structural units, trifunctional silane and difunctional silane is contained in the above-mentioned curable resin 2, the following formula (5) shows that the polymerizable compound has two types of constituent units: a trifunctional silane and a difunctional silane. It is possible to calculate the proportion (mol%) of oxygen atoms present.
  • the weight average molecular weight (Mw) of the polymerizable compound may be within the range of 500 to 100,000, preferably within the range of 600 to 50,000, and particularly preferably within the range of 700 to 20,000.
  • the above 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 with a membrane filter with a filter pore size of 0.2 ⁇ m.
  • the above polymerizable compound has a polymerizable functional group that constitutes at least a part of the organic component.
  • the polymerizable functional group is not particularly limited as long as it is a functional group that can undergo a polymerization reaction and the polymerization reaction progresses due to external stimulation, for example, light irradiation, heat, and light irradiation.
  • An acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an oxetane group, a vinyl ether group, etc., which undergo a polymerization reaction by heat, the action of a photoacid generator, etc., can be used.
  • Such a polymerizable functional group has good stability during synthesis and storage, good reactivity during curing, and raw materials are easily available.
  • acryloyl groups and methacryloyl groups are particularly preferred from the viewpoint of curing speed and wide selection of physical properties.
  • the reactivity may change due to steric hindrance, which may affect curability.
  • the molecular weight of the group may range from 20 to 500, preferably from 25 to 400.
  • the polymerizable group refers to a group containing a polymerizable functional group. Preferred examples of such polymerizable groups include the structures shown below.
  • R 1 represents "a substituted or unsubstituted alkyl chain having 1 to 10 carbon atoms”
  • R 2 represents "a substituted or unsubstituted alkyl chain having 1 to 3 carbon atoms, or a hydrogen atom.” Further, both R 1 and R 2 may be linear or branched.
  • At least one of the polymerizable functional groups may be bonded in the structural unit of the polymerizable compound, but the present invention is not limited to this, and two or more may be bonded.
  • Examples of the structural unit having a polymerizable group of the polymerizable compound in this embodiment include the following.
  • trifunctional ones include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and vinyltrimethoxysilane.
  • difunctional sources include 3-acryloxypropyl(methyl)dimethoxysilane, 3-acryloxypropyl(methyl)diethoxysilane, 3-methacryloxypropyl(methyl)dimethoxysilane, 3-methacryloxypropyl(methyl)dimethoxysilane, and 3-methacryloxypropyl(methyl)dimethoxysilane.
  • methyl)diethoxysilane vinyl(methyl)dimethoxysilane, vinyl(methyl)diethoxysilane, allyl(methyl)dimethoxysilane, allyl(methyl)diethoxysilane, styryl(methyl)dimethoxysilane, styryl(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, dimeth
  • a structural unit that does not have a polymerizable group can also be used in combination with a structural unit that has a polymerizable group.
  • Examples of trifunctional structural units that do not have a polymerizable group include trimethoxy(methyl)silane, triethoxy(methyl)silane, methyltripropoxysilane, tributoxy(methyl)silane, methyltriphenoxysilane, and ethyltrimethoxy.
  • Silane triethoxy(ethyl)silane, ethyltripropoxysilane, tributoxy(ethyl)silane, ethyltriphenoxysilane, trimethoxy(propyl)silane, triethoxy(propyl)silane, tripropoxy(propyl)silane, tributoxy(propyl)silane, Phenoxy(propyl)silane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, tributoxy(butyl)silane, butyltriphenoxysilane, trimethoxy(phenyl)silane, triethoxy(phenyl)silane, phenyltripropoxysilane, tributoxy (Phenyl)silane, triphenoxy(phenyl)silane, cyclohexyltrimethoxysilane, cyclohe
  • Difunctional ones include dimethoxydimethylsilane, diethoxydimethylsilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, cyclohexyl(dimethoxy)methylsilane, cyclohexyldiethoxymethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxy Methylvinylsilane, diethoxymethylvinylsilane, etc. can be preferably used.
  • the structure of the polymerizable compound is not particularly limited. However, if it is a polymerizable compound having a spherical structure or a polyhedral siloxane oligomer having an incompletely condensed skeleton, which will be described later, the curable resin 2 can have a sufficiently low viscosity even if it does not substantially contain a solvent. It is preferable because it can be done. In particular, a polymerizable compound having a spherical structure is preferable from the viewpoints of thermal stability, processing uniformity, and the like.
  • a spherical structure means a structure in which polymerizable functional groups extend outward from a polymerized part with a high degree of polymerization.
  • 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. Therefore, the viscosity of the curable resin 2 can be made sufficiently low by simply adding a small amount of a solvent or a low-viscosity material.
  • Examples of the polymerizable compound having a spherical structure include those having a trifunctional silane as a constituent unit. Among these, those having only trifunctional silane as a constituent unit are preferred.
  • Examples of the polymerizable compound having such a spherical structure include one type or a mixture of two or more types of trifunctional silane hexamer to 36mer (molecular weight 1000 to 6300) having a polymerizable functional group. It will be done.
  • the molecular weight of the polymerizable compound having a spherical structure may be in the range of 2,000 or more and 6,000 or less, preferably 2,000 or more and 3,000 or less.
  • siloxane made of trifunctional silane it usually has a structure in which polymerizable functional groups extend outward from a siloxane polymerized portion having a high degree of siloxane polymerization made of SiO 3/2 units.
  • the degree of siloxane polymerization in the siloxane polymerization part can be higher than 90%, particularly 95% or higher, and even 97% or higher, so that silicon atoms contained in the polymerizable compound
  • the proportion of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to is 10 mol % or less.
  • spherical structure represented by the following formula.
  • the following formulas are schematic diagrams showing polymerizable compounds having a spherical structure, each consisting of an octamer of trifunctional silane having an acryloxypropyl group and a 3-methacryloxypropyl group as polymerizable groups. .
  • SiO 1.5 represents a siloxane polymerized portion consisting of SiO 3/2 units.
  • the polymerizable compound having a spherical structure has oxygen atoms, nitrogen atoms, phosphorus atoms, sulfur atoms, Oxygen may be present between the silicon atom (for example, the silicon atom of SiO 3/2 unit) in the siloxane polymerization part constituting the main skeleton of the spherical structure and the polymerizable functional group. Atom, nitrogen atom, phosphorus atom, or sulfur atom may not be present.
  • Examples of the bonding group between the silicon atom and the polymerizable functional group in the siloxane polymerization part include an oxygen atom, a nitrogen atom, a phosphorus atom, and a divalent hydrocarbon group that does not contain a sulfur atom, and preferably , a linear alkylene group, more preferably -(CH 2 ) n - (n is an integer from 1 to 9).
  • a polymerizable compound having a spherical structure can be obtained by subjecting a hydrolyzable silane composition containing at least a hydrolyzable silane to a hydrolytic condensation reaction under basic conditions.
  • this can be carried out by charging a solvent and silane as a raw material into a reactor, adding a basic substance as a catalyst, and adding water dropwise while stirring.
  • basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate (K 2 CO 3 ), sodium carbonate, ammonia, etc., and the pH is 8 to 13, typically room temperature to 100. Can be done at °C.
  • the silane used as the raw material may be any one or more of tetrafunctional hydrolyzable silane, trifunctional hydrolyzable silane, bifunctional hydrolyzable silane, and monofunctional hydrolyzable silane, but Preference is given to using tetrafunctional or trifunctional hydrolyzable silanes, especially trifunctional hydrolyzable silanes. Moreover, only one type of hydrolyzable silane may be used, or two or more types may be used in combination.
  • the polymerizable compound obtained by the hydrolysis condensation reaction has a high degree of condensation. Therefore, it is easy to create a polymerizable compound having a spherical structure in which the proportion of oxygen atoms bonded to a single silicon atom among the oxygen atoms bonded to silicon atoms is reduced, particularly to 10 mol% or less. can be obtained.
  • the polymerizable compound in this embodiment may be a polyhedral siloxane oligomer having an incompletely condensed skeleton. Since such polymerizable compounds have a regular structure, 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. becomes. Moreover, the viscosity of the curable resin can be made sufficiently low.
  • the polyhedral siloxane oligomer having an incompletely condensed skeleton to which a polymerizable functional group is bonded is one vertex, one edge, or one face of a polyhedral siloxane oligomer having a completely condensed skeleton.
  • An example is an incompletely condensed type that lacks.
  • the polyhedral siloxane oligomer having an incompletely condensed skeleton to which polymerizable functional groups are bonded those represented by the following formula are particularly preferred.
  • R 3 is a monovalent hydrocarbon group
  • R 4 is a -Si- polymerizable group bonded to the oxygen atom in the formula, a hydrogen atom, a metal ion such as Na or Li, or a tetraalkylammonium ion ( Examples of the alkyl group include methyl, ethyl, propyl, butyl, etc.).
  • R 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.
  • the above polymerizable compound is a polyhedral siloxane oligomer having an incompletely condensed skeleton in which a hydrogen atom, a hydroxyl group, or an organic group other than a polymerizable functional group is bonded to a silicon atom. It can be obtained by reaction.
  • the polyhedral siloxane oligomer having an incompletely condensed skeleton, which is a raw material, has a hydrogen atom, a hydroxy group, or an organic group other than a polymerizable functional group bonded to the silicon atom located at the apex.
  • organic groups other than polymerizable functional groups include alkoxy groups, alkyl groups, and phenyl groups.
  • the reaction between the above-mentioned raw material and the polymerizable functional group-containing compound includes conventionally known reactions.
  • an addition reaction between a hydrogen atom directly bonded to silicon and a compound containing a polymerizable functional group having an unsaturated double bond or an addition reaction between a hydroxyl group (OH group) or an alkoxy group (OR group) directly bonded to silicon and a siloxane bond.
  • Examples include reaction with a polymerizable functional group-containing compound that can be formed.
  • the curable resin 2 in this embodiment only needs to contain a polymerization initiator.
  • the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being particularly preferred.
  • a photopolymerization initiator is a substance that generates reactive species that cause a polymerization reaction of a polymerizable compound when stimulated by light.
  • Specific examples include photoradical generators that generate radicals when stimulated by light, and photoacid generators that generate protons when stimulated by light.
  • a photoradical generator is a polymerization initiator that generates radicals using light (infrared rays, visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams such as electron beams, etc.), and is mainly used when polymerizable compounds are Used in the case of radically polymerizable compounds.
  • a photoacid generator is a polymerization initiator that generates acid (protons) when exposed to light, and is mainly used when the polymerizable compound is a cationically polymerizable compound.
  • photoradical generators examples include 2,4,6-trimethyldiphenylphosphine oxy, 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, 2-hydroxy-2-methyl-1-phenyl-propan-1 -on, etc., but are not limited to these. Note that these photoradical generators may be used alone or in combination of two or more.
  • photoacid generator examples include, but are not limited to, onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, and diazomethane compounds.
  • the thermal polymerization initiator is a compound that generates the above polymerization factors (radicals, cations, etc.) by heat.
  • examples of the thermal polymerization initiator include a thermal radical generator that generates radicals when heated, a thermal acid generator that generates protons (H + ) when heated, and the like.
  • the thermal radical generator is mainly used when the polymerizable compound is a radically polymerizable compound.
  • a thermal acid generator is mainly used when the polymerizable compound is a cationically polymerizable compound.
  • thermal radical generators include organic peroxides and azo compounds.
  • organic peroxides include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxy-3,5,5-trimethylhexanoate.
  • peroxy esters such as oxyisopropyl carbonates, peroxy ketals such as 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane
  • diacyl peroxides such as lauroyl peroxide. However, it is not limited to these.
  • examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), etc.
  • examples include, but are not limited to, azonitrile.
  • thermal acid generator examples include known iodonium salts, sulfonium salts, phosphonium salts, ferrocenes, and the like. Specific examples include diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, and triphenylsulfonium hexafluoroborate. It is not limited to these.
  • the content of the polymerization initiator in the curable resin 2 is not particularly limited, and can be within the range of 0.5% by mass to 20% by mass, and 1% by mass to 20% by mass, based on the polymerizable compound. It can be within the range of 10% by mass.
  • the curable resin 2 in this embodiment does not need to substantially contain a solvent.
  • substantially not containing a solvent it is possible to suppress deterioration in flatness and poor curing due to the solvent floating to the surface during curing.
  • substantially free of solvent means that it does not contain any solvent other than the solvent that is unintentionally included, such as impurities. That is, for example, the content of the solvent in the curable resin 2 is preferably 0.01% by mass or less, and more preferably 0.001% by mass or less, based on the entire curable resin 2.
  • the solvent means a solvent used in general resin compositions, photoresists, and the like. That is, 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.
  • the curable resin 2 may contain a reactive crosslinking agent.
  • the reactive crosslinking agent has a polymerizable functional group, and includes, for example, one having two or more polymerizable functional groups.
  • the polymerizable functional group include ethylenically unsaturated bond-containing groups, epoxy groups, and the like, and preferably ethylenically unsaturated bond-containing groups.
  • the ethylenically unsaturated bond-containing group include a (meth)acrylic group and a vinyl group, with a (meth)acrylic group being more preferred and an acrylic group being even more preferred.
  • 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 groups.
  • photopolymerizable monomers (bifunctional monomers) having two polymerizable functional groups include trimethylolpropane di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol.
  • bifunctional monomers include, for example, light acrylates 3EG-A, 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EAL, BP-4PA (manufactured by Kyoeisha Chemical Co., Ltd.), etc. can be mentioned. Further, from the viewpoint of compatibility, polyfunctional monomers having a siloxane structure are preferred.
  • the content of the reactive crosslinking agent is not particularly limited, and can be within the range of 0% to 99% by mass, especially within the range of 5% to 80% by mass in the curable resin 2. It is preferably within the range of 49% by mass to 79% by mass.
  • the curable resin 2 may contain other components in addition to the above-mentioned polymerizable compound, polymerization initiator, and reactive crosslinking agent.
  • Other components include, for example, surfactants, mold release agents, silane coupling agents, photosensitizers, antioxidants, organometallic coupling agents, polymerization inhibitors, ultraviolet absorbers, and photostabilizers as necessary. , anti-aging agents, plasticizers, adhesion promoters, photobase generators, colorants, elastomer particles, photoacid multipliers, basic compounds, other components such as flow regulators, antifoaming agents, dispersants, etc. Can be mentioned.
  • the content of other components is not particularly limited, but is preferably 5% by mass or less, particularly preferably 3% by mass or less in the curable resin 2.
  • 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.
  • the lower limit of the viscosity is not particularly limited, but can be 1 cPs or more, preferably 1.5 cPs or more. Since the curable resin 2 has a very low viscosity, it can be applied onto the uneven structure with good filling properties while suppressing the generation of bubbles. Further, such a low viscosity allows application by an inkjet method.
  • the viscosity of the curable resin 2 was determined by dropping the curable resin 2 onto a disc plate using an AR-G2 manufactured by T.A. Instruments in a measurement environment of 25°C and 40% RH. This is the value at 25° C. and 1000 (1/s) when the shear rate of a standard steel cone with a diameter of 40 mm is varied from 10 to 1000 (1/s).
  • the curable resin 2 exhibits a contact angle with respect to the surface of the standard resist of 20° or less, more preferably 15° or less.
  • the contact angle is determined by dropping the curable resin 2 onto the surface of the standard resist layer under normal pressure atmosphere with a temperature of 25°C and a humidity of 33%, and then 5 seconds later using a contact angle measuring device (Kyowa Interface Science). It can be measured using an automatic contact angle meter DM-501 (manufactured by Co., Ltd.).
  • the standard resist layer may be one formed using, for example, an acrylic-styrene copolymer (organic resist resin) as a base resin.
  • the curable resin 2 when used as an inversion layer material in an inversion process, for example, it will have good wettability to the core material pattern formed from the resist composition, so it will have better filling properties. Can be applied.
  • the curable resin 2 exhibits the above contact angle with respect to the standard resist, it exhibits good wettability even if the composition of the organic resist material actually used as the core pattern is different from the composition of the standard resist. .
  • the surface free energy of the curable resin 2 is preferably 20 mJ/m 2 or more and 70 mJ/m 2 or less, particularly preferably 25 mJ/m 2 or more and 50 mJ/m 2 or less.
  • the above range is preferable because, for example, compatibility with the core material pattern made of an organic resist material can be suppressed, and the material can sufficiently wet and spread over the core material pattern.
  • the substrate 3 to which the curable resin 2 is supplied is not particularly limited, and examples thereof include a quartz glass substrate, a soda glass substrate, a fluorite substrate, a calcium fluoride substrate, and a magnesium fluoride substrate.
  • glass substrates such as alkali-free glass substrates such as barium borosilicate glass, aminoborosilicate glass, aluminosilicate glass; transparent resin substrates such as polycarbonate substrates, polypropylene substrates, polyethylene substrates, polymethyl methacrylate substrates, polyethylene terephthalate substrates, etc.
  • Semiconductor substrates such as silicon substrates, GaAs substrates, InP substrates, GaN substrates, GaP substrates, and SiC substrates; metal-based substrates such as stainless steel substrates, aluminum substrates, copper substrates, iron substrates; and gold. It may also be a metal vapor-deposited substrate in which a metal such as silver, copper, ITO, or chromium is vapor-deposited on the surface of a glass substrate or the like. Alternatively, it may be a laminated substrate formed by laminating two or more substrates arbitrarily selected from the above. Note that in the present embodiment, "transparent" means that the transmittance of light with a wavelength of 300 nm to 450 nm is 70% or more, preferably 90% or more.
  • 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 of 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 discretely supplied to the first surface 3A of the substrate 3 by an inkjet method. Alternatively, 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.
  • 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 developed between the substrate 3 and the mold 4 to form the resin layer 5 to be molded (contact). process, see Figures 1B and 2B).
  • the mold 4 is made of, for example, a quartz glass substrate, a soda glass substrate, a fluorite substrate, a calcium fluoride substrate, a magnesium fluoride substrate, a glass substrate such as acrylic glass, a resin such as a polycarbonate substrate, a polypropylene substrate, a polyethylene substrate, a polyethylene terephthalate substrate, etc. It may be formed of a substrate, a transparent substrate such as a laminated substrate formed by laminating two or more substrates arbitrarily selected from these substrates, or the like.
  • the mold 4 has a first surface 4A and a second surface 4B located on the opposite side thereof, and may be a flat plate mold in which the first surface 4A is a flat surface (see FIG. 1A), and includes a recess 42.
  • the uneven structure 41 may be formed on the first surface 4A (see FIG. 2A).
  • the shape of the uneven structure 41 formed on the first surface 4A of the mold 4 is not particularly limited, and examples include a space shape, a hole shape, and the like.
  • the dimensions of the uneven structure 41 are not particularly limited either; for example, in the case of a space-like uneven structure 41, the length of the recess 42 in the transverse direction may be about 10 nm to 100 nm; In this case, the maximum diameter of the recess 42 may be approximately 10 nm to 100 nm. Note that the maximum diameter of the hole-shaped recess 42 is, for example, the diameter of the circle when the recess 42 is circular in plan view, and the length of the diagonal of the rectangle when the recess 42 is rectangular. It is.
  • the dimensions of the plurality of recesses 42 included in the uneven 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.
  • the resin layer 5 to be molded is cured (curing step).
  • the method for curing the resin layer 5 to be molded may be appropriately selected depending on the curing type of the curable resin 2 constituting the resin layer 5 to be molded.
  • the curable resin 2 is a photocurable type
  • the molded resin layer 5 (curable resin 2) may be irradiated with light (for example, ultraviolet rays, electron beams, etc.) through the mold 4.
  • the curable resin 2 is a thermosetting type
  • heat may be applied to the molded resin layer 5 (curable resin 2).
  • the mold 4 may be brought into contact with the heated and softened resin layer 5 to be molded, and the resin layer 5 to be molded may be hardened by cooling the resin layer 5 as it is.
  • the thickness of the cured resin layer 5 to be molded is important in forming the cured film 1 (see FIGS. 1D and 2D). As will be described later, by performing an etching treatment on the cured resin layer 5 to be molded (curable resin 2), organic components in the resin layer 5 to be molded (curable resin 2) are decomposed and siloxane polymerization is performed.
  • the cured film 1 is formed by leaving and concentrating the inorganic components mainly containing By etching the resin layer 5 to be molded, the inorganic components are bonded to each other and at the same time, the inorganic components are separated. If the thickness of the resin layer 5 to be molded is relatively thin, most of the inorganic components will be detached, making it difficult to form the cured film 1. By being thick, inorganic components bonded to each other can be concentrated, and a cured film 1 having a desired thickness can be formed.
  • the thickness of the cured resin layer 5 to be molded may be appropriately set to such an extent that a cured film 1 having a desired thickness can be formed.
  • the following mathematical formula (1) shows the relationship between the film thickness T 0 of the cured resin layer 5 to be molded, the film thickness T of the cured film 1 to be formed, and the decomposition treatment time t for decomposing the organic component. Based on this, the amount of curable resin 2 to be supplied to the first surface 3A of the substrate 3 may be determined, and the molded resin layer 5 having a predetermined thickness T 0 may be formed.
  • Ab ct represents "the amount of decrease per unit time in the film thickness of the resin layer 5 to be molded that changes according to the decomposition treatment time t at the initial stage of the decomposition treatment of organic components"
  • ⁇ t represents " A represents the amount of decrease per unit time in the thickness of the resin layer 5 to be molded that does not substantially change depending on the decomposition treatment time t, and A represents the amount of decrease in the thickness of the resin layer to be molded per unit time at the initial stage of the decomposition treatment of organic components.
  • b and c are "coefficients indicating an exponential decrease in the thickness of the resin layer 5", and b>1 and c ⁇ 0.
  • each of the coefficients b and c changes depending on the conditions for decomposing the organic component of the resin layer 5 to be molded, and can be appropriately set according to the conditions.
  • the above formula (1) includes a component in which the thickness of the resin layer 5 to be molded changes exponentially and a component in which it changes linearly.
  • This exponentially changing component can be said to represent a state in which the inorganic components bonded to each other are concentrated, and the inorganic components remain as the decomposition treatment time t elapses.
  • the component that changes linearly can be said to represent a state in which the thickness of the resin layer 5 to be molded decreases due to physical etching in substantially proportion to the decomposition treatment time t. .
  • the "initial stage of the decomposition treatment of organic components” is determined by the type of organic component contained in the resin layer 5 to be molded (curable resin 2), the etching conditions for the resin layer 5 to be molded, etc.
  • the process may be carried out within 10 seconds to 300 seconds after the start of the etching process for the resin layer 5 to be molded, preferably between 10 seconds and 60 seconds after the start of the etching process. be.
  • the resin layer 5 to be molded (curable resin 2) is subjected to an etching process to cure the resin layer 5.
  • a film 1 is formed (see FIGS. 1D and 2D).
  • the etching process performed on the resin layer 5 to be molded uses oxygen gas, nitrogen gas, argon gas, chlorine gas, or a mixture of two or more thereof in a discharge plasma atmosphere in a vacuum chamber.
  • etching treatment in which the resin layer 5 to be molded is etched by etching
  • oxidation treatment in which the resin layer 5 to be molded is etched by contacting an etching solution such as sulfuric acid or hydrogen peroxide solution with oxidizing power.
  • a cured film forming region 31 where the cured film 1 is formed and a cured film non-forming region where the cured film 1 is not formed are formed on the first surface 3A of the substrate 3.
  • the curable resin 2 is supplied to the cured film forming area 31 in an amount determined based on the above formula (1) so that the thickness T of the cured film 1 exceeds 0, and the cured film is not formed.
  • the forming region 32 is supplied with the curable resin 2 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, and the resin layer 5 to be molded is formed. good. For example, as shown in FIGS.
  • the projections 51 of the resin layer 5 to be molded are formed in the recesses 42.
  • the concave portions (residual film portions) 52 of the resin layer 5 to be molded are formed corresponding to the convex portions between the adjacent concave portions 42 . Therefore, the region where the convex portion 51 of the resin layer 5 to be molded is to be located is set as the cured film forming region 31, and the region where the recessed portion (remaining film portion) 52 is to be located is set as the cured film non-forming region 32.
  • the height of the convex portion 51 of the resin layer 5 to be molded and the thickness of the concave portion (remaining film portion) 52 of the resin layer 5 to be molded are determined based on the above formula (1), and the height of the convex portion 51 of the resin layer 5 to be molded is determined based on the above formula (1).
  • the resin layer 5 to be molded is formed such that the resin layer 51 remains as the cured film 1 and the recessed portion (residual film portion) 52 of the resin layer 5 to be molded disappears. Thereby, a patterned cured film 1 as shown in FIG. 2D can be formed.
  • the cured film 1 thus formed mainly contains an inorganic component, and more specifically, mainly contains SiO x (X is 1 or more).
  • the above-mentioned "mainly contains” means that the cured film 1 may contain an organic component.
  • the content ratio of the inorganic component in the cured film 1 is higher than that of the inorganic component in the curable resin 2. This includes the concept that the content ratio is greater than the content ratio of
  • the thickness T of the cured film 1 is thinner than the thickness T 0 of the resin layer 5 to be molded. 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 inorganic components to be eliminated. Therefore, the dimensions of the patterned cured film 1 shown in FIG. 2D (dimensions of the convex pattern) are smaller than the dimensions (dimensions of the convex pattern) of the patterned resin layer 5 to be molded (see FIG. 2C).
  • the cured film forming method 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 is provided on the first surface 3A of the substrate 3 on which the cured film 1 is formed.
  • the cured film 1 may be formed on the material layer.
  • the material layer is not particularly limited, but includes, for example, a hard mask layer made of metal chromium or the like, a P-type semiconductor such as boron-doped silicon, or a P-type semiconductor such as arsenic-doped silicon. Examples include a semiconductor layer made of ITO, a conductive film layer made of ITO, and the like.
  • the base 11 has a first surface 11A and a second surface 11B located on the opposite side of the first surface 11A, and a first step structure 12 protruding from the first surface 11A of the base 11. , the second step structure 13 protruding from the upper surface portion 12A of the first step structure 12, the light shielding film 14 located on the upper surface portion 12A of the first step structure 12, and the curing as the protective film 15 located on the light shielding film 14.
  • the method for manufacturing the imprint mold substrate 10 including the film 1 will be exemplified, the present invention is not limited to the method for manufacturing the imprint mold substrate 10 of this embodiment.
  • a multi-stage molded substrate 10' is prepared (see FIG. 3A).
  • the multi-stage molded substrate 10' includes a base 11 having a first surface 11A and a second surface 11B located on the opposite side of the first surface 11A, and a first step structure 12 protruding from the first surface 11A of the base 11.
  • the second step structure 13 protrudes from the top surface 12A of the first step structure 12, and the light shielding is located on the first surface 11A of the base 11, the top surface 12A of the first step structure 12, and the top surface 13A of the second step structure 13.
  • a membrane 14 is provided.
  • a recess 16 is formed in the second surface 11B of the base 11 and has a size that can physically accommodate the outer edge of the first stepped structure 12 in plan view.
  • the base 11 is made of a material commonly used as a substrate for imprint molding, such as a quartz glass substrate, a soda glass substrate, a fluorite substrate, a calcium fluoride substrate, a magnesium fluoride substrate, a barium borosilicate glass, an aminoborosilicate glass, or an aluminosilicate glass substrate.
  • a glass substrate such as an alkali-free glass substrate such as acid glass, a resin substrate such as a polycarbonate substrate, a polypropylene substrate, a polyethylene substrate, a polymethyl methacrylate substrate, a polyethylene terephthalate substrate, and two or more substrates arbitrarily selected from these are laminated. Any transparent substrate such as a laminated substrate formed by the above may be used.
  • the shape of the base 11 in plan view is not particularly limited, and includes, for example, a substantially rectangular shape.
  • the shape of the base 11 in plan view is usually approximately rectangular.
  • the size of the base 11 is also 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 x 152 mm. Further, the thickness of the base portion 11 may be appropriately set, for example, in a range of approximately 300 ⁇ m to 10 mm, taking into consideration strength, handling suitability, and the like.
  • the first step structure 12 protruding from the first surface 11A of the base 11 is provided approximately at the center of the base 11 in plan view.
  • the first stepped structure 12 has an upper surface portion 12A, and a light shielding film 14 is located on the upper surface portion 12A.
  • imprinting using the imprint mold 20 (see FIG. 4F) manufactured from the imprint mold substrate 10 is possible. In the process, only the resin onto which the concavo-convex pattern 21 of the imprint mold 20 has been transferred (the resin immediately below the second step structure 13) can be cured.
  • the second step structure 13 protruding from the upper surface portion 12A of the first step structure 12 is provided approximately at the center of the base 11 (first step structure 12) in plan view.
  • the second step structure 13 has an upper surface portion 13A, and a light shielding film 14 is located on the upper surface portion 13A.
  • the light shielding film 14 will be removed in a later step.
  • the upper surface portion 13A of the second step structure 13 constitutes a pattern area in which the concavo-convex pattern 21 is formed in the imprint mold 20 (see FIG. 4F).
  • 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 approximately rectangular.
  • the size of the upper surface portion 13A of the second step structure 13 is suitable for products manufactured through imprint processing using an imprint mold 20 (see FIG. 4F) made from the imprint mold substrate 10. It is set as appropriate depending on the size, and is set to, for example, about 30 mm x 25 mm.
  • the outer size (size) of the upper surface portion 12A of the first step structure 12 may be larger than the size (size) of the upper surface portion 13A of the second step structure 13 by about 10 ⁇ m to 4000 ⁇ m. That is, the width W 12A of the upper surface portion 12A of the first stepped structure 12 may be set to approximately 5 ⁇ m to 2000 ⁇ m.
  • the protrusion height T 12 of the first step structure 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 As long as the manufactured imprint mold substrate 10 can fulfill the purpose of providing the first step structure 12, the thickness is not particularly limited, and may be set to about 10 ⁇ m to 30 ⁇ m, for example.
  • the length T 13 (projection height T 13 of the second step structure 13) parallel to the thickness direction of the base 11 between the top surface portion 12A of the first step structure 12 and the top surface portion 13A of the second step structure 13 is Although not particularly limited, it may be set to about 1 ⁇ m to 5 ⁇ m, for example.
  • a recess 16 of a predetermined size is formed on the second surface 11B of the base 11.
  • the formation of the recessed portion 16 makes it particularly difficult to interact with the imprint resin during imprint processing using the imprint mold 20 (see FIG. 4F) manufactured from the imprint mold substrate 10 manufactured according to this embodiment.
  • the base 11, especially the upper surface portion 13A of the second step structure 13 can be curved.
  • the unevenness formed on the first upper surface portion 311 of the convex structure portion 3 is brought into contact with the imprint resin. It is possible to prevent gas from being trapped between the uneven pattern 21 and the imprint resin, and it is also possible to easily remove the imprint mold 20 from the transfer pattern in which the uneven pattern 21 is transferred to the imprint resin. Can be peeled off.
  • the recessed portion 16 has a substantially circular shape in plan view.
  • the approximately circular shape allows the imprint mold to be easily removed during imprint processing, especially when bringing the upper surface portion 13A of the second step structure 13 into contact with the imprint resin or when peeling the imprint mold 20 from the imprint resin.
  • the upper surface portion 13A of the second step structure 13 of 20 can be curved substantially uniformly within its plane.
  • the size of the recess 16 in plan view is not particularly limited as long as it is large enough to include the first step structure 12 within the projection area of the recess 16 projected onto the first surface 11A of the base 11. It is not something that will be done. If the projection area has a size that cannot include the first step structure 12, there is a possibility that the entire surface of the upper surface portion 13A of the second step structure 13 of the imprint mold 20 cannot be effectively curved.
  • the light shielding film 14 blocks light (for example, UV light, etc.) irradiated onto the imprint mold 20 during imprint processing using the imprint mold 20 (see FIG. 4F) produced from the imprint mold substrate 10.
  • Possible materials e.g. metals such as chromium, titanium, tantalum, silicon, aluminum; chromium-based compounds such as chromium nitride, chromium oxide, chromium oxynitride, tantalum oxide, tantalum oxynitride, tantalum boron oxide, boron oxynitride It may be made of a tantalum compound such as tantalum, titanium nitride, silicon nitride, silicon oxynitride, or the like. Further, the thickness of the light shielding film 14 is not particularly limited as long as it is thick enough to block the light. Note that the light shielding film 14 may be formed by a conventionally known method, such as a sputtering method.
  • the 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 multi-stage molded substrate 10' and on the light shielding film 14 located on the upper surface 13A of the second step structure 13.
  • the first curable resin layer 18 is formed on the light shielding film 14 located on the upper surface portion 12A of the first stepped structure 12.
  • a second curable resin layer 19 is formed on the light shielding film 14 located on the upper surface portion 13A of the second stepped structure 13 (see FIG. 3C).
  • the template 17 is separated from the cured first curable resin layer 18 and second curable resin layer 19 (see FIG. 3D).
  • the first curable resin layer 18 is for forming the cured film 1 as the protective film 15 in a later step.
  • the second curable resin layer 19 is removed without remaining in the subsequent step of forming the cured film 1.
  • the first curable resin layer 18 is formed with a thickness that allows formation of the cured film 1 as the protective film 15, while the second curable resin layer 19 is formed to such a degree that it disappears by etching treatment in a later step. It is formed with a film thickness of . That is, the curable resin 2 is supplied so that the thickness of the second curable resin layer 19 is smaller than the thickness of the first curable resin layer 18, and the first curable resin layer 18 and the second curable resin layer 18 are A synthetic resin layer 19 is formed. Specifically, according to the above formula (1), the amount of curable resin 2 supplied to the upper surface portion 12A of the first step structure 12 and the amount of curable resin 2 supplied to the upper surface portion 12A of the second step structure 13 are calculated. All you have to do is decide.
  • the method of curing the first curable resin layer 18 and the second curable resin layer 19 depends on the curing type of the curable resin 2 constituting the first curable resin layer 18 and the second curable resin layer 19. You can select it as appropriate. 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) are exposed to light (for example, ultraviolet rays, electron beams, etc.) through 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).
  • the template 17 has a convex portion 171 that is rectangular annular in plan view and a concave portion 172 surrounded by the convex portion 171.
  • the convex portion 171 corresponds to the upper surface portion 12A of the first step structure 12 of the multi-stage molded substrate 10'
  • the concave portion 172 surrounded by the convex portion 171 corresponds to the upper surface of the second step structure 13 of the multi-stage molded substrate 10'. This corresponds to part 13A.
  • the protrusion height of the convex portion 171 may be appropriately set so that the first curable resin layer 18 and the second curable resin layer 19 are each formed with a predetermined thickness.
  • the etching process is a dry etching process (plasma process) that uses 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.
  • plasma process a dry etching process
  • 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.
  • it may be wet etching treatment (oxidation treatment) in which the first curable resin layer 18 and the second curable resin layer 19 are etched by contacting with an etching solution such as sulfuric acid or hydrogen peroxide solution. Good too.
  • the film thickness of the first curable resin layer 18 is determined by the etching process, which allows organic components to be decomposed and inorganic components to combine and concentrate.
  • the temperature is set to such an extent that a cured film 1 mainly containing the components can be formed.
  • the thickness of the second curable resin layer 19 is set to such an extent that it can be eliminated by the etching process. Therefore, through the etching process described above, the cured film 1 is formed on the light shielding film 14 located on the upper surface portion 12A of the first step structure 12.
  • the second curable resin layer 19 is removed from above the light shielding film 14 located on the upper surface portion 13A of the second step structure 13, and the light shielding film 14 is exposed.
  • 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 portion 13A of the second step structure 13 are dry etched using, for example, chlorine-based (Cl 2 +O 2 ) gas. It is removed by treatment etc. (see FIG. 3F).
  • a cured film 1 as a protective film 15 mainly containing SiO x (X is 1 or more) is formed on the light shielding film 14 located on the upper surface portion 12A of the first step structure 12. Since the cured film 1 has low reactivity to chlorine-based (Cl 2 +O 2 ) gas that can etch the light shielding film 14, it can protect the light shielding film 14 located on the upper surface portion 12A of the first step structure 12. . Therefore, according to the present embodiment, it is possible to manufacture the 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 portion 12A of the first step structure 12.
  • the imprint mold substrate 10 is manufactured using the multi-stage mold substrate 10' in which the light shielding film 14 is located on the upper surface portion 13A of the second step structure 13. It is not limited to.
  • 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 portion 13A of the second stepped structure 13. In this case, it is not necessary to form the second curable resin layer 19 on the upper surface portion 13A of the second stepped structure 13.
  • 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 portion 13 ⁇ /b>A of the second step structure 13 , and a first hard mask layer 222 formed on the top surface portion 13 ⁇ /b>A of the second step structure 13 . It includes a third hard mask layer 223 formed on surface 11A.
  • 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 oxide, tantalum oxynitride, and boron oxide.
  • Examples include tantalum compounds such as tantalum oxide and tantalum oxynitride boride, titanium nitride, silicon nitride, and silicon oxynitride, and these can be used alone or in combination of two or more arbitrarily selected types.
  • the second hard mask layer 222 is for forming a mask pattern used when performing an etching process to form the uneven pattern 21 on the upper surface portion 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 constituent material of the hard mask layer 22 may be selected in accordance with the constituent material of the base portion 11 and in consideration of etching selectivity and the like. For example, when the base portion 11 is made of quartz glass, chromium oxide or the like may be suitably selected as the material constituting the hard mask layer 22.
  • the thickness of the hard mask layer 22 is appropriately set in consideration of the etching selectivity depending on the constituent material of the base 11.
  • the thickness of the hard mask layer 22 can be appropriately set within a range of about 0.5 nm to 200 nm.
  • the method for forming the hard mask layer 22 is not particularly limited, and examples include sputtering, PVD (Physical Vapor Examples of known film forming methods include the CVD (Chemical Vapor Deposition) method and the CVD (Chemical Vapor Deposition) method.
  • droplets of the imprint resin 23 are discretely supplied onto the second hard mask layer 222 by an inkjet method (see FIG. 4B).
  • imprint resin 23 is dropped onto third hard mask layer 223 (see FIG. 4B).
  • the droplets of the imprint resin 23 are distributed on the upper surface 13A of the second step structure 13 ( second hard mask layer 222).
  • 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 formed on the first surface 11A of the base 11.
  • the uneven pattern formed on the pattern surface 24A of the master mold 24 is brought into contact with the imprint resin 23 supplied on the second hard mask layer 222, and the pattern surface 24A of the master mold 24 and the upper surface of the second step structure 13 are brought into contact with each other. 13A (second hard mask layer 222), imprint resin 23 is developed.
  • the imprint resin 23 is cured. Thereby, the uneven pattern of the master mold 24 can be transferred to the imprint resin 23 on the second hard mask layer 222 to form the resin pattern 231, and the resist pattern 232 can be formed on the third hard mask layer 223. (See Figure 4C).
  • the imprint resin 23 (resist material) is not particularly limited, and resin materials commonly used in imprint processing (for example, ultraviolet curable resins, thermosetting resins, etc.) can be used.
  • the imprint resin 23 includes a mold release agent to easily separate the master mold 24, and improves adhesion to the upper surface portion 13A (second hard mask layer 222) of the second step structure 13 of the imprint mold substrate 10. It may also contain an adhesive or the like for adhesion.
  • a resin pattern 231 is formed by separating the master mold 24 from the cured imprint resin 23, and if necessary, the remaining film portion of the resin pattern 231 is removed (see FIG. 4D). In this way, the resin pattern 231 to which the uneven 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.
  • the grooves are formed on the upper surface portion 13A of the second step structure 13 of the imprint mold substrate 10 by dry etching using, for example, a chlorine-based (Cl 2 +O 2 ) etching gas.
  • 2 hard mask layer 222 to form a hard mask pattern 22P1 (see FIG. 4E).
  • the third hard mask layer 223 is etched using the resist pattern 232 as a mask to form a hard mask pattern 22P2 (see FIG. 4E).
  • the first hard mask layer 221 located on the upper surface portion 12A of the first step structure 12 is removed by etching, and the protective film 15 is exposed (see FIG. 4E).
  • Dry etching is performed on the imprint mold substrate 10 using the hard mask patterns 22P 1 and 22P 2 as a mask to form an uneven pattern 21 on the upper surface 13A of the second step structure 13 and on the first surface 11A of the base 11.
  • Imprint mold 20 is manufactured by forming alignment mark 23 (see FIG. 4F).
  • the protective film 15 mainly composed of SiO x (X is 1 or more) is etched and removed at the same time as the imprint mold substrate 10 .
  • Dry etching of the imprint mold substrate 10 may be performed by selecting an etching gas as appropriate depending on the type of constituent material of the imprint mold substrate 10.
  • the etching gas for example, a fluorine gas or the like can be used.
  • the method for manufacturing a concavo-convex structure in this embodiment is a method for manufacturing a concave-convex structure constituted by a line-and-space sidewall pattern formed along the sidewall of a resist pattern. This is a method of manufacturing.
  • a sidewall material film is formed on the sidewall of a resist pattern serving as a core material by ALD method or the like, and a sidewall pattern is formed by etching the sidewall material film.
  • the sidewall pattern formed along the sidewall of the core material is loop-shaped (annular in plan view), so in order to form a line-and-space sidewall pattern, a process called loop cutting is required. is necessary.
  • the method for manufacturing a concavo-convex structure according to the present embodiment is characterized in that the process called loop cutting is not necessary.
  • a substrate 31 is prepared, which has a first surface 31A and a second surface 31B located on the opposite side thereof, and a resist pattern is provided on the first surface 31A.
  • the resist pattern can be formed, for example, by imprint lithography using a mold, electron beam lithography using an electron beam lithography device, photolithography using a photomask having a predetermined opening and a light shielding portion, or the like.
  • the resist pattern serves as a core material pattern 32 for forming a sidewall pattern 36 to be described later.
  • the height (thickness) of the sidewall pattern 36 depends on the etching selection of the materials constituting each of the sidewall pattern 36 and the substrate 31. Depending on the ratio, etc., the height (thickness) is required to be such that the sidewall pattern 36 does not disappear during the etching process of the substrate 31.
  • the height (thickness) of the core material pattern 32 is smaller than the height (thickness) of the resist pattern. becomes lower (thinner). Therefore, the height (thickness) of the resist pattern is higher (thicker) than the height (thickness) required for the sidewall pattern 36, taking into consideration the amount of slimming in the process of forming a core pattern, which will be described later. It is necessary to do so.
  • the resist pattern formed on the first surface 31A of the substrate 31 is subjected to a slimming process to form a core material pattern 32 in which the resist pattern is thinned.
  • the resist pattern slimming process may be performed by, for example, a wet etching method, a dry etching method, a combination thereof, or the like.
  • droplets of the sidewall material 33 are dropped onto the core material pattern 32 (see FIGS. 5A and 6A).
  • the curable resin 2 in this embodiment is used as the side wall material 33.
  • the position and number of droplets of the sidewall material 33 to be dropped, as well as the size of the droplet (one droplet amount), are determined by the position and number of droplets of the sidewall material 33, and the size of the droplet (one droplet amount), when the mold 34 and the core material pattern 32 are brought into contact with the sidewall material 33 in a later step.
  • the side wall material 33 that is developed during this period may be set so that it does not completely cover the core pattern 32 and does not reach at least both longitudinal ends of the core pattern 32 in plan view.
  • the mold 34 having the convex pattern 341 is brought into contact with the droplet of the side wall material 33 dropped onto the core material pattern 32, the side wall material 33 is expanded between the mold 34 and the core material pattern 32, and in this state, the side wall material 33 is By curing the material 33, a sidewall material film 35 is formed (see FIGS. 5B and 6B). Thereafter, the mold 34 is separated from the cured sidewall material film 35 (see FIGS. 5C and 6C).
  • the convex pattern 341 of the mold 34 has a size that allows it to be inserted between adjacent core patterns 32 and to form a predetermined gap with the side wall of the core pattern 32 (length in the short direction in plan view). It is sufficient if the applicant has the following. By inserting the convex pattern 341 having such dimensions between adjacent core patterns 32 and bringing the mold 34 and the side wall material 33 into contact and curing, the side walls and top of the core pattern 32, and A sidewall material film 35 can be formed to cover the first surface 31A of the substrate 31 exposed between adjacent core patterns 32.
  • the side wall material film 35 is etched (dry etching using oxygen gas, nitrogen gas, argon gas, chlorine gas, or a mixture of two or more of these gases) to remove the core.
  • a sidewall pattern 36 is formed on the sidewall of the material pattern 32 (see FIGS. 5D and 6D).
  • the sidewall material film 35 disappears because the portion located on the top of the core pattern 32 is a relatively thin film.
  • the sidewall material film 35 also disappears from the portion located on the first surface 31A of the substrate 31 exposed between adjacent core material patterns 32.
  • the portion along the sidewall of the core material pattern 32 is relatively thick, the organic component is decomposed and the inorganic component is combined and concentrated, forming the cured film 1 as the sidewall pattern 36. It turns out.
  • the core pattern 32 on which the sidewall pattern 36 is formed is removed by ashing (plasma ashing using oxygen-containing gas, etc.) (see FIGS. 5E and 6E).
  • ashing plasma ashing using oxygen-containing gas, etc.
  • the sidewall pattern 36 can remain on the first surface 31A of the substrate 31.
  • the uneven structure 30 in which the line-and-space sidewall pattern 36 is formed on the first surface 31A of the substrate 31 can be manufactured.
  • the sidewall pattern 36 may be formed on a hard mask layer (not shown) formed on the first surface 31A of the substrate 31 and made of Cr or the like.
  • a pattern forming method in this embodiment will be explained. 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 explained as examples. It is not limited to this embodiment.
  • the method for manufacturing the convex lens substrate 60 includes preparing a base material 61 having a first surface 61A and a second surface 61B located on the opposite side, and applying droplets of the curable resin 2 to the first surface 61A of the base material 61. (see Figure 7A). Since each droplet of the curable resin 2 that is dropped constitutes a convex lens 62 on the convex lens substrate 60, the dropping arrangement and size (amount of one drop) of the droplet of the curable resin 2 are determined according to the convex lens to be manufactured. It may be set as appropriate depending on the arrangement and size of the convex lens 62 required on the substrate 60.
  • the droplets of the curable resin 2 are 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 as an etching gas, or sulfuric acid). (wet etching treatment using an etching solution such as hydrogen peroxide or hydrogen peroxide solution).
  • This etching treatment can decompose the organic components in the curable resin 2 and cause the bonding and concentration of the inorganic components, thereby forming a convex lens 62 mainly containing the inorganic components (see FIG. 7B).
  • the convex lens substrate 60 having the convex lenses 62 as the cured film 1 can be manufactured.
  • a method for manufacturing a Fresnel lens substrate includes preparing a base material 71 having a first surface 71A and a second surface 71B located on the opposite side, and applying a hardened resin 2 to the first surface 71A of the base material 71.
  • a synthetic resin layer 72 is formed.
  • 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, while bringing a mold (not shown) having a flat surface into contact with the droplets of the curable resin 2. It can be formed by curing the curable resin 2.
  • a photoresist layer is formed on the curable resin layer 72, and a resin layer 73 having a thickness distribution (for example, a resin layer having a sawtooth cross section) is formed by forming a photoresist layer on the curable resin layer 72 and subjecting the photoresist layer to gradation exposure at a predetermined number of gradations. 73) (see FIG. 8A).
  • a resin layer 73 having a thickness distribution for example, a resin layer having a sawtooth cross section
  • the shape of the resin layer 73 is transferred to the curable resin layer 72 (see FIG. 8B).
  • a curable resin layer 72 having a sawtooth cross section is formed. This etching may be, for example, dry etching using a fluorine gas or the like.
  • 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 thereof as an etching gas, or by dry etching using sulfuric acid or etching gas.
  • Wet etching is performed using hydrogen oxide water or the like as an etching solution.
  • This etching process can decompose the organic components in the curable resin 2 and cause the binding and concentration of the inorganic components, making it possible to form a Fresnel lens 74 mainly containing inorganic components (see FIG. 8C). .
  • the Fresnel lens substrate 70 having the Fresnel lens 74 as the cured film 1 can be manufactured.
  • a method for manufacturing a semiconductor device in this embodiment will be described.
  • a semiconductor layer, an insulating film, and wiring are arranged in this order from the first surface side on the first surface side of a substrate having a first surface and a second surface located on the opposite side. It has a laminated structure.
  • This method of manufacturing a semiconductor device includes a step of forming a semiconductor layer 82 having a channel region 821 and a source/drain region 822 including a contact portion that contacts wiring on the first surface 81A side of the substrate 81 (see FIG. 9A). ) and a step of forming an insulating film 83 on an insulating film formation region including the channel region 821 and a region excluding the contact portion (see FIG. 9B).
  • the step of forming the insulating film 83 includes a step of supplying the curable resin 2 to the insulating film forming area, a step of curing the curable resin 2, and a step of decomposing the organic component in the cured curable resin 2 and removing the inorganic component. This includes a step of forming an insulating film 83 by leaving the insulating film 83.
  • the curable resin 2 supplied to the insulating film forming area is cured, and the curable resin 2 is subjected to a predetermined etching treatment (oxygen gas, nitrogen gas, argon gas, chlorine gas, or
  • a predetermined etching treatment oxygen gas, nitrogen gas, argon gas, chlorine gas, or
  • the insulating film 83 can be formed by a simple method by performing dry etching treatment or wet etching treatment using a gas mixture of two or more of the above.
  • the cured film forming method according to the above embodiment is a hard mask forming method for forming a cured film 1 functioning as a hard mask layer on a metal film such as a quartz glass substrate on which a metal film such as a Cr film is formed. You may use it.
  • a hard mask forming method includes, for example, a step of supplying the curable resin 2 to the metal film, and a step of bringing a flat plate mold (for example, mold 4 shown in FIG. 1B) into contact with the curable resin 2 and curing it.
  • the process includes a step of forming a molded resin layer 5, and a step of performing a predetermined etching treatment on the molded resin layer 5 to decompose organic components and combine and concentrate inorganic components to form a cured film 1. It's fine if you have one.
  • Example 1 A curable resin 2 was applied onto a quartz glass substrate, and cured while a flat mold was pressed against it from above to form a resin layer 5 to be molded with a thickness of 150 nm.
  • the resin layer 5 to be molded was subjected to dry etching treatment (etching time: 1555 seconds) using chlorine-based (Cl 2 +O 2 ) gas, thereby forming a cured film 1 with a thickness of 95 nm.
  • FIG. 10 shows the relationship between the etching time and the thickness (nm) of the resin layer 5 to be molded. In the graph shown in FIG.
  • the black circles ( ⁇ ) are the results of Example 1
  • the open diamonds ( ⁇ ) are the results of Reference Example 1, which will be described later
  • the white circles ( ⁇ ) are the results of Reference Example 2, which will be described later. It is.
  • FIG. 10 after about 300 seconds of etching time, almost no exponential film thickness variation was observed. From this result, by forming a molded resin layer 5 having a predetermined initial film thickness using the curable resin 2 and performing a predetermined etching treatment on the molded resin layer 5, the organic components can be decomposed and It was confirmed that it is possible to form a cured film 1 mainly containing inorganic components by binding and concentrating the inorganic components.
  • the organic components contained in the molded resin layer 5 are decomposed by the dry etching process, whereas the inorganic components are not decomposed by the dry etching process.
  • the inorganic components are mainly decomposed.
  • the inorganic components are combined 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 resin layer 5 to be molded at the initial stage of the dry etching process becomes relatively large (see FIG. 10).
  • the relational expression between the initial film thickness T 0 of the resin layer 5 to be molded and the film thickness T of the cured film 1 is expressed as follows:
  • the amount of decrease is Ab ct and the amount of decrease per unit time in the film thickness of the resin layer 5 that does not substantially change depending on the decomposition treatment time t is ⁇ t
  • the amount per unit time at the initial stage of the decomposition treatment of the organic component is A, which is the amount of decrease in the thickness of the resin layer to be molded, is calculated from the amount of change in the thickness of the resin layer to be molded 5 when the resin layer to be molded 5 is subjected to an etching treatment in a short time of, for example, 30 seconds or less. It can be calculated as the amount of change per unit time.
  • ⁇ is a value of ⁇ after the etching process of the resin layer 5 to be molded is continued and the amount of decrease per unit time in the thickness of the resin layer 5 to be molded according to the decomposition treatment time t does not substantially change.
  • Coefficients b and c which indicate an exponential phenomenon of the thickness of the resin layer 5 to be molded, can be derived by appropriately adjusting the numerical values to fit changes in the thickness of the resin layer 5 to be molded.
  • the above formula (1) may be derived as appropriate depending on the material of the resin layer 5 to be molded (curable resin 2), the etching process conditions, etc.
  • the curable resin 2 includes 20% by mass of a polymerizable compound having a spherical structure shown below, a reactive crosslinking agent (dimethylsiloxane-containing bifunctional acrylate, 79% by mass), and a photopolymerization initiator (Omnirad 907 , 1% by mass) was used.
  • a curable resin was dropped onto a disc plate, and a standard steel cone with a diameter of 40 mm was set at a shear rate.
  • the viscosity of the curable resin when changed from 10 to 1000 (1/s) at 25°C and 1000 (1/s) was 6.4 cPs, making it possible to apply by inkjet. Ta.
  • SiO 1.5 represents a siloxane polymerized portion consisting of SiO 3/2 units.
  • 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 (K 2 CO 3 ) 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 brine and chloroform. The volatile components were removed to obtain the above polymerizable compound having a spherical structure.
  • a curable resin As a curable resin, a composition containing 35% by mass of the above polymerizable compound having a spherical structure, a reactive crosslinking agent (dimethylsiloxane-containing bifunctional acrylate, 64% by mass), and a photopolymerization initiator (Omnirad 907, 1% by mass).
  • a reactive crosslinking agent dimethylsiloxane-containing bifunctional acrylate, 64% by mass
  • a photopolymerization initiator Omnirad 907, 1% by mass
  • a curable resin As a curable resin, a composition containing 50% by mass of the above polymerizable compound having a spherical structure, a reactive crosslinking agent (dimethylsiloxane-containing bifunctional acrylate, 49% by mass), and a photopolymerization initiator (Omnirad 907, 1% by mass).
  • a reactive crosslinking agent dimethylsiloxane-containing bifunctional acrylate, 49% by mass
  • a photopolymerization initiator Omnirad 907, 1% by mass
  • Example 2 Example of manufacturing an imprint mold A multi-stage mold substrate 10' made of a quartz glass substrate as shown in FIG. 13A, apply the curable resin 2 used in Example 1, press the template 17 shown in FIG. A curable resin layer 18 and a second curable resin layer 19 were formed. The supply amount of the curable resin 2 was adjusted based on the above formula (1) so that the first curable resin layer 18 had a thickness of 80 nm and the second curable resin layer 19 had a thickness of 30 nm. .
  • the first curable resin layer 18 and the second curable resin layer 19 are subjected to a dry etching process (etching time: 300 seconds) using chlorine-based (Cl 2 +O 2 ) gas, thereby performing a second curing process.
  • etching time: 300 seconds etching time: 300 seconds
  • chlorine-based (Cl 2 +O 2 ) gas thereby performing a second curing process.
  • the cured film 1 film thickness: 40 nm
  • the protective film 15 is formed on the light shielding film 14 located on the upper surface portion 12A of the first stepped structure 12, and the imprint mold substrate 10 is removed. Created.
  • a metal Cr is applied 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, a metal Cr is applied.
  • a hard mask layer 22 was formed (see FIG. 4A), and droplets of imprint resin 23 were discretely supplied onto the second hard mask layer 222 by an inkjet method (see FIG. 4B).
  • the uneven pattern of the master mold 24 is transferred to the imprint resin 23 supplied onto the second hard mask layer 222 to form a resin pattern 231, and the second hard mask layer 222 is etched using the resin pattern 231 as a mask.
  • a hard mask pattern 22P1 was thus formed.
  • the imprint mold 20 was manufactured by dry etching the imprint mold substrate 10 using the hard mask pattern 22P 1 as a mask and forming the uneven pattern 21 on the upper surface portion 13A of the second step structure 13. .
  • Example 3 Manufacturing example of a concavo-convex structure by the sidewall method
  • a synthetic quartz glass with an external diameter of 6 inches square and a thickness of 0.25 inches was used as a substrate having a first surface 31A and a second surface 31B located on the opposite side.
  • the substrate was prepared.
  • An electron beam sensitive resist is applied to the first surface 31A of the quartz glass substrate by a spin coating method, and this resist layer is subjected to electron beam drawing and development to form a pattern with a width of 48 nm, a height of 59 nm, a half pitch of 52 nm, and a line.
  • a line and space resist pattern with a length of 10 ⁇ m was formed.
  • the resist pattern is 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. was dripped.
  • the curable resin 2 that used in Example 1 was used.
  • a mold 34 having a convex pattern 341 with a pattern width of 26 nm and a height of 55 nm is brought into contact with the droplets of the curable resin 2 dropped onto the core material pattern 32, and a curable resin is formed between the mold 34 and the core material pattern 32.
  • the side wall material film 35 was formed by developing the resin 2 and curing it by irradiating it with ultraviolet rays (see FIGS. 5B and 6B). Thereafter, the mold 34 was separated from the cured sidewall material film 35 (see FIGS. 5C and 6C).
  • the sidewall material film 35 is subjected to etching treatment (dry etching treatment using chlorine-based (Cl 2 + O 2 ) gas (etching time: 300 seconds)) to decompose the organic components and remove the inorganic components.
  • etching treatment dry etching treatment using chlorine-based (Cl 2 + O 2 ) gas (etching time: 300 seconds)
  • etching time 300 seconds
  • a sidewall pattern 36 having a pattern width of 26 nm and a height of 23 nm was formed on the sidewall of the core material pattern 32 (see FIGS. 5D and 6D).
  • the core material pattern 32 with the sidewall pattern 36 formed thereon is removed by plasma ashing using an oxygen-containing gas (see FIGS. 5E and 6E) to form the uneven structure 30 having the line-and-space sidewall pattern 36.
  • Example 4 Surface composition analysis by XPS
  • the cured film 1 was prepared in the same manner as in Example 1, except that the thickness of the resin layer 5 to be molded was changed to 39 nm, and the dry etching treatment was performed until the film thickness reached 24 nm.
  • the cured film 1 was subjected to surface composition analysis using X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • the cured film formed through the dry etching process has a high concentration of silicon (Si) atoms near the surface of the cured film, and moves toward the inside of the cured film along the thickness direction. It was confirmed that there was a concentration gradient in which the concentration of silicon (Si) atoms decreased.
  • the cured film formed through the dry etching process has a low concentration of carbon (C) atoms near the surface of the cured film, and the concentration of carbon (C) atoms decreases toward the inside of the cured film along the thickness direction of the cured film. It was confirmed that there is a concentration gradient in which the concentration of atoms increases.

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PCT/JP2023/011841 2022-03-31 2023-03-24 硬化膜形成方法、インプリントモールド用基板の製造方法、インプリントモールドの製造方法、凹凸構造体の製造方法、パターン形成方法、ハードマスク形成方法、絶縁膜形成方法及び半導体装置の製造方法 Ceased WO2023190168A1 (ja)

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US18/852,969 US20250282915A1 (en) 2022-03-31 2023-03-24 Method for forming cured film, method for manufacturing imprint mold substrate, method for manufacturing imprint mold, method for manufacturing relief structure, method for forming pattern, method for forming hard mask, method for forming insulating film, and method for manufacturing semiconductor device
CN202380031542.2A CN118974885A (zh) 2022-03-31 2023-03-24 固化膜形成方法、压印模具用基板的制造方法、压印模具的制造方法、凹凸结构体的制造方法、图案形成方法、硬掩模形成方法、绝缘膜形成方法和半导体装置的制造方法
KR1020247035943A KR20240172190A (ko) 2022-03-31 2023-03-24 경화막 형성 방법, 임프린트 몰드용 기판의 제조 방법, 임프린트 몰드의 제조 방법, 요철 구조체의 제조 방법, 패턴 형성 방법, 하드마스크 형성 방법, 절연막 형성 방법, 및 반도체 장치의 제조 방법

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