WO2022230871A1 - 硬化性組成物及びパターン形成方法 - Google Patents

硬化性組成物及びパターン形成方法 Download PDF

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WO2022230871A1
WO2022230871A1 PCT/JP2022/018878 JP2022018878W WO2022230871A1 WO 2022230871 A1 WO2022230871 A1 WO 2022230871A1 JP 2022018878 W JP2022018878 W JP 2022018878W WO 2022230871 A1 WO2022230871 A1 WO 2022230871A1
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component
curable composition
group
meth
acrylate
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French (fr)
Japanese (ja)
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健理 昆野
莉紗子 森
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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

Definitions

  • the present invention relates to a curable composition and a pattern forming method.
  • This application claims priority based on Japanese Patent Application No. 2021-077326 filed in Japan on April 30, 2021, the content of which is incorporated herein.
  • Lithography technology is a core technology in the manufacturing process of semiconductor devices, and along with the recent high integration of semiconductor integrated circuits (ICs), further miniaturization of wiring is progressing.
  • a shorter wavelength light source such as KrF excimer laser, ArF excimer laser, F2 laser, EUV ( extreme ultraviolet light), EB (electron beam), X-ray, etc. is used.
  • EUV extreme ultraviolet light
  • EB electron beam
  • X-ray X-ray
  • NA numerical aperture
  • Nanoimprint lithography uses a photocurable composition containing a photocurable compound that is cured by light (ultraviolet rays, electron beams).
  • a mold having a predetermined pattern is pressed against a curable film containing a photocurable compound, then light is irradiated to cure the photocurable compound, and then the mold is removed from the cured film.
  • a transfer pattern (structure) is obtained.
  • the properties required for the photocurable composition used in nanoimprint lithography include coatability when applied onto a substrate by spin coating or the like, and curability by heating or exposure. If the coatability to the substrate is poor, the film thickness of the photocurable composition coated on the substrate may vary, and pattern transferability tends to deteriorate when the mold is pressed against the curable film. Moreover, curability is an important characteristic for maintaining desired dimensions of a pattern formed by mold pressing. In addition, the photocurable composition is also required to have good mold releasability when the mold is released from the cured film.
  • titania nanoparticles titanium oxide nanoparticles
  • metal oxide nanoparticles metal oxide nanoparticles
  • titania nanoparticles have a photocatalytic action and exert a strong oxidizing action upon irradiation with ultraviolet light to decompose organic substances. Therefore, when titania nanoparticles are used, there is a problem in the light resistance of the cured film.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition capable of increasing the refractive index and forming a cured film having good light resistance, and a pattern forming method.
  • component (X) niobium oxide nanoparticles
  • component (B) a polymerizable compound
  • component (C) a polymerization initiator.
  • the content of the component (X) is 25 to 70 parts by mass relative to the total content of the component (X) and the component (B) of 100 parts by mass, and the content of the component (B) is The curable composition according to [1] or [2], which is 30 to 75 parts by mass.
  • the present invention it is possible to provide a curable composition capable of increasing the refractive index and forming a cured film with good light resistance, and a pattern forming method.
  • aliphatic is defined relative to aromatic to mean groups, compounds, etc. that do not possess aromatic character.
  • Alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
  • (Meth)acrylate means at least one of acrylate and methacrylate. When describing "may have a substituent", when replacing a hydrogen atom (-H) with a monovalent group, when replacing a methylene group (-CH 2 -) with a divalent group including both. “Exposure” is a concept that includes irradiation of radiation in general.
  • the curable composition of the first aspect of the present invention contains component (X): niobium oxide nanoparticles, component (B): polymerizable compound, and component (C): polymerization initiator.
  • the (X) component is niobium oxide nanoparticles.
  • Nanoparticle means a particle having a volume-average primary particle diameter on the order of nanometers (less than 1000 nm).
  • Niobium oxide nanoparticles are niobium oxide particles having a volume average primary particle size on the order of nanometers.
  • the volume average primary particle size is a value measured by a dynamic light scattering method.
  • Niobium oxide includes niobium oxidation numbers of +5 (Nb 2 O 5 ), +4 (NbO 2 ), +3 (Nb 2 O 3 ), and +2 (NbO). The most common oxide is niobium pentoxide (Nb 2 O 5 ).
  • the volume average primary particle size of component (X) is preferably 40 nm or less.
  • the volume average primary particle size of component (X) is preferably 0.1 to 40 nm, more preferably 0.2 to 30 nm, even more preferably 0.5 to 30 nm, and 1 to 30 nm. is even more preferable, and 1 to 25 nm is particularly preferable.
  • the volume average primary particle size of the component (X) is within the preferred range, the niobium oxide nanoparticles are well dispersed in the curable composition. Also, the refractive index of the cured film is likely to be increased. In addition, the fillability of the curable composition into the mold is improved.
  • niobium oxide nanoparticles can be used as the component (X).
  • commercially available niobium oxide nanoparticles include, for example, the product name “Virar Nb-G6000” manufactured by Taki Chemical Co., Ltd., and the like.
  • the (X) component may be used alone or in combination of two or more.
  • the content of component (X) in the curable composition of the present embodiment is preferably 25 to 70 parts by mass with respect to 100 parts by mass of the total content of component (X) and component (B) described below. , more preferably 25 to 65 parts by mass, more preferably 30 to 65 parts by mass.
  • the content of component (X) is at least the lower limit of the preferred range, the refractive index of the cured film formed using the curable composition can be easily increased.
  • the content of the component (X) is equal to or less than the upper limit of the preferred range, the cured film formed using the curable composition has better light resistance.
  • the (B) component is a polymerizable compound.
  • a polymerizable compound means a compound having a polymerizable functional group.
  • a "polymerizable functional group” is a group that allows compounds to polymerize by radical polymerization or the like, and refers to a group that includes a multiple bond between carbon atoms such as an ethylenic double bond.
  • the polymerization here may be a reaction that proceeds by irradiation with light, or may be a reaction that proceeds by heating.
  • polymerizable functional groups examples include vinyl group, allyl group, acryloyl group, methacryloyl group, fluorovinyl group, difluorovinyl group, trifluorovinyl group, difluorotrifluoromethylvinyl group, trifluoroallyl group, and perfluoroallyl group.
  • trifluoromethylacryloyl group nonylfluorobutylacryloyl group, vinyl ether group, fluorine-containing vinyl ether group, allyl ether group, fluorine-containing allyl ether group, styryl group, vinylnaphthyl group, fluorine-containing styryl group, fluorine-containing vinylnaphthyl group, norbornyl groups, fluorine-containing norbornyl groups, silyl groups, and the like.
  • a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group are preferable, and an acryloyl group and a methacryloyl group are more preferable.
  • polymerizable compounds (monofunctional monomers) having one polymerizable functional group examples include isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-adamantyl (meth) acrylate, bornyl (meth) acrylate, (meth) acrylate containing an aliphatic polycyclic structure such as tricyclodecanyl (meth) acrylate; dicyclopentanyl (meth) acrylate, dicyclopentenyl ( meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acrylate containing an aliphatic monocyclic structure such as acryloylmorpholine; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( meth)acrylate, 2-hydroxybutyl
  • (Meth)acrylates containing tricyclic structures tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene Glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate; diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N,N-dimethyl (meth) ) acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethylocty
  • monofunctional monomers include, for example, Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (manufactured by Toagosei Co., Ltd.); MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscote #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (Above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, HOA (N), PO-A , P-200A, NP-4EA, NP-8EA, IB-XA, Epoxy Ester M-600A, Light Ester P-1
  • polymerizable compounds having two polymerizable functional groups include trimethylolpropane di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bis(hydroxy methyl)tricyclodecane di(meth)acrylate, 2-methacryloyloxyethyl acid phosphate and the like.
  • bifunctional monomer examples include, for example, Light Acrylate 3EG-A, 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EAL, BP-4PA, Light Ester P-2M (above, Kyoeisha Chemical Co., Ltd.); APG-100, APG-200, APG-400, APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • Polymerizable compounds having three or more polymerizable functional groups include polymerizable siloxane compounds, polymerizable silsesquioxane compounds, polyfunctional monomers having three or more polymerizable functional groups, and the like.
  • polymerizable siloxane compounds examples include compounds having an alkoxysilyl group and a polymerizable functional group in the molecule.
  • Commercially available products of the polymerizable siloxane compound include, for example, Shin-Etsu Chemical Co., Ltd. product names "KR-513", “X-40-9296", “KR-511”, “X-12-1048”, “X-12-1050” and the like.
  • the main chain skeleton is composed of Si—O bonds and has the following chemical formula: [(RSiO 3/2 ) n ] (wherein R represents an organic group and n represents a natural number ) and the compounds represented by R represents a monovalent organic group, and the monovalent organic group includes a monovalent hydrocarbon group which may have a substituent.
  • the hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and 2-ethylhexyl group. , an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
  • the aromatic hydrocarbon group includes aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, benzyl group, tolyl group and styryl group.
  • substituents that the monovalent hydrocarbon group may have include a (meth)acryloyl group, a hydroxy group, a sulfanyl group, a carboxy group, an isocyanato group, an amino group, and a ureido group.
  • -CH 2 - contained in the monovalent hydrocarbon group may be replaced with -O-, -S-, carbonyl group or the like.
  • the polymerizable silsesquioxane compound has three or more polymerizable functional groups. Examples of the polymerizable functional group here include a vinyl group, an allyl group, a methacryloyl group, an acryloyl group, and the like.
  • the compound represented by the chemical formula: [(RSiO 3/2 ) n ] may be of cage type, ladder type or random type.
  • the cage-type silsesquioxane compound may be a complete cage or an incomplete cage such that a part of the cage is open.
  • polyfunctional monomers having three or more polymerizable functional groups examples include ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (3) trimethylolpropane trimethacrylate, and ethoxylated (6) trimethylolpropane triacrylate.
  • ethoxylated (9) trimethylolpropane triacrylate, ethoxylated (15) trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, propoxylated (3) glyceryl Triacrylate, Propoxylated (3) Glyceryl Triacrylate, Propoxylated (5.5) Glyceryl Triacrylate, Propoxylated (3) Trimethylolpropane Triacrylate, Propoxylated (6) Trimethylolpropane Triacrylate, Trimethylolpropane Triacrylate , trimethylolpropane trimethacrylate, tris-(2-hydroxyethyl)-isocyanurate triacrylate, tris-(2-hydroxyethyl)-isocyanurate trimethacrylate, ⁇ -caprolactone-modified tris-(2-acryloxyethyl) iso
  • the (B) component may be a polymerizable sulfur compound (hereinafter also referred to as the (BS) component).
  • a "polymerizable sulfur compound” is a polymerizable compound containing a sulfur atom in the molecule. That is, the polymerizable sulfur compound is a monomer containing a sulfur atom and having a polymerizable functional group.
  • BS components include, for example, compounds having a diarylsulfide skeleton.
  • Examples of compounds having a diarylsulfide skeleton include compounds represented by the following general formula (bs-1).
  • R 11 to R 14 and R 21 to R 24 each independently represent a hydrogen atom, an alkyl group or a halogen atom, and R 5 represents a polymerizable functional group.
  • R 11 to R 14 and R 21 to R 24 each independently represent a hydrogen atom, an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group is preferably linear or branched.
  • Linear alkyl groups include methyl, ethyl, n-propyl and n-butyl groups.
  • the branched chain alkyl group includes isopropyl group, sec-butyl group, tert-butyl group and the like. Among them, the alkyl group is preferably a methyl group or an ethyl group, more preferably a methyl group.
  • the halogen atoms for R 11 to R 14 and R 21 to R 24 include fluorine, chlorine, bromine and iodine atoms.
  • a chlorine atom is preferable as the halogen atom.
  • R 11 to R 14 and R 21 to R 24 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom.
  • R 5 represents a polymerizable functional group.
  • the polymerizable functional group include those similar to those listed above. Among them, the polymerizable functional group is preferably a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and more preferably an acryloyl group or a methacryloyl group.
  • R5 is preferably an acryloyl group or a methacryloyl group, more preferably an acryloyl group or a methacryloyl group.
  • (BS) components include, for example, bis(4-methacryloylthiophenyl) sulfide and bis(4-acryloylthiophenyl) sulfide. Among them, bis(4-methacryloylthiophenyl)sulfide is preferable as the (BS) component.
  • the component (B) may be used singly or in combination of two or more.
  • Component (B) preferably contains a photopolymerizable compound.
  • the component (B) more preferably contains a polyfunctional photopolymerizable compound, and more preferably contains a polyfunctional monomer having three or more polymerizable functional groups.
  • the polyfunctional photopolymerizable compound when forming a cured film using the curable composition, curing is further accelerated, and the strength stress resistance of the cured film can be easily increased.
  • a combination of a polyfunctional photopolymerizable compound and a monofunctional monomer may be used as the component (B). By using these in combination, when forming a cured film using the curable composition, curing is further accelerated, and the stress resistance of the cured film can be easily increased.
  • the content of component (B) in the curable composition of the present embodiment is preferably 30 to 75 parts by mass with respect to 100 parts by mass of the total content of component (X) and component (B), It is more preferably 35 to 75 parts by mass, even more preferably 35 to 70 parts by mass.
  • the content of component (B) is at least the lower limit of the preferred range, the cured film formed using the curable composition has better light resistance. Moreover, the strength of the cured film is enhanced.
  • the content of the component (B) is equal to or less than the upper limit of the preferred range, the refractive index of the cured film formed using the curable composition can be easily increased. In addition, the stress resistance of the cured film is improved.
  • the total content of the component (X) and the component (B) is 100 parts by mass, and the component (X) is 25 to 70 parts by mass, and the content of the component (B) is preferably 30 to 75 parts by mass, the content of the component (X) is 25 to 65 parts by mass, And it is more preferable that the content of the component (B) is 35 to 75 parts by mass, the content of the component (X) is 30 to 65 parts by mass, and the content of the component (B) is 35 More preferably, it is up to 70 parts by mass.
  • Component is a polymerization initiator.
  • Component (C) is a compound that initiates or promotes the polymerization of component (B) by exposure or heating.
  • Component (C) includes, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy-2-methyl-1-phenylpropanone), 1- [4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2 -methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ethanone-1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-c
  • 1-hydroxycyclohexylphenyl ketone 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy-2-methyl-1-phenylpropanone), 2-methyl-1- (4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl) )-phenylphosphine oxide, 2,2-dimethoxy-2-phenylacetophenone are preferred.
  • component (C) A commercial item can be obtained and used for a component.
  • Commercially available products of component (C) include BASF's product name "IRGACURE 907", BASF's product name “IRGACURE 369", BASF's product name “IRGACURE 819”; V. product names "Omnirad 184", “Omnirad 651”, “Omnirad 819”, and “Omnirad 1173" manufactured by the company.
  • the component (C) preferably has a smaller molecular weight. When the molecular weight of component (C) is small, haze tends to be further reduced.
  • the molecular weight of component (C) is, for example, preferably 500 or less, more preferably 400 or less, still more preferably 350 or less, and particularly preferably 300 or less. Although the lower limit of the molecular weight of component (C) is not particularly limited, it may be 100 or more, 150 or more, or 200 or more.
  • Component (C) has a molecular weight of, for example, 100 to 500, preferably 150 to 500, more preferably 150 to 400, still more preferably 150 to 350, and particularly preferably 150 to 300.
  • the component (C) may be used singly or in combination of two or more.
  • the component (C) is preferably a radical photopolymerization initiator because it is suitable for nanoimprint lithography.
  • the content of component (C) in the curable composition of the present embodiment is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total content of component (X) and component (B). , more preferably 2 to 15 parts by mass, more preferably 5 to 15 parts by mass. If the content of component (C) is within the above preferred range, a good cured film can be formed.
  • the curable composition of the embodiment may contain components (optional components) in addition to the components (X), (B) and (C).
  • Such optional components include, for example, metal oxide nanoparticles other than the (X) component ((X2) component), solvents ((S) component), miscible additives ((E) component: for example, interface activators, anti-color separation agents, anti-deterioration agents, release agents, diluents, antioxidants, heat stabilizers, flame retardants, plasticizers and other additives for improving the properties of the cured film), etc. mentioned.
  • the curable composition of the present embodiment may contain metal oxide nanoparticles (component (X2)) other than the component (X).
  • the volume average primary particle size of component (X2) is preferably 100 nm or less.
  • component (X2) commercially available metal oxide nanoparticles can be used.
  • Metal oxides include, for example, oxide particles of titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn), or magnesium (Mg).
  • titania nanoparticles include, for example, Ishihara Sangyo Co., Ltd. TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, V series (TTO-S-1, TTO-S -2, TTO-V-3, etc.); Titania Sol LDB-014-35 manufactured by Ishihara Sangyo Co., Ltd.; NS405; ELECOM V-9108 manufactured by Nikki Shokubai Kasei Co., Ltd.; STR-100A-LP manufactured by Sakai Chemical Industry Co., Ltd.; Examples of commercially available zirconia nanoparticles include UEP (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.), UEP-100 (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.); PCS (manufactured
  • the component (X2) may be used singly or in combination of two or more.
  • titania (TiO 2 ) nanoparticles or zirconia (ZrO 2 ) nanoparticles are preferable as the component (X2) from the viewpoint of refractive index.
  • the content of the (X2) component is preferably adjusted in consideration of the light resistance of the cured film.
  • the curable composition of the present embodiment may contain a solvent ((S) component).
  • the (S) component is used to dissolve or disperse and mix the (X) component, (B) component, (C) component and desired optional components.
  • Component (S) includes, for example, water; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-pentyl alcohol, s-pentyl alcohol, t-pentyl alcohol, isopentyl alcohol, 2-methyl-1-propanol, 2-ethylbutanol, neopentyl alcohol, n-butanol, s-butanol, t-butanol, 1-propanol, n-hexanol, 2-heptanol, 3-heptanol, 2-methyl-1-butanol, 2-methyl-2 -butanol, 4-methyl-2-pentanol, 1-butoxy-2-propanol, propylene glycol monopropyl ether, 5-methyl-1-hexanol, 6-methyl-2-heptanol, 1-octanol, 2-octanol, Chain structure alcohols such as 3-octanol, 4-oct
  • the (S) component may be used singly or in combination of two or more.
  • water, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME) are preferable as the (S) component.
  • the amount of component (S) to be used is not particularly limited, and may be appropriately set according to the coating film thickness of the curable composition. For example, it can be used in an amount of about 100 to 1000 parts by mass per 100 parts by mass of the total content of the component (X) and the component (B).
  • the curable composition of the present embodiment may contain a surfactant in order to adjust applicability and the like.
  • surfactants include silicone-based surfactants and fluorine-based surfactants.
  • silicone surfactants include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK -323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355 , BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 (manufactured by
  • fluorine-based surfactants include F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F -446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484 , F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF -1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (manufactured by DIC Corporation); Polyfox series PF-636, PF-6320, PF-656, PF-6520 (manufactured by Omnova Co., Ltd.) and the like can be used
  • surfactants may be used singly or in combination of two or more.
  • the content of the surfactant is 0.5 parts per 100 parts by mass of the total content of the component (X) and the component (B). 01 to 3 parts by mass, more preferably 0.02 to 1 part by mass, and even more preferably 0.03 to 0.5 parts by mass.
  • the content of the surfactant is within the above preferred range, the coating properties of the curable composition are improved.
  • the cured film formed using the curable composition of the present embodiment preferably has a refractive index of 1.50 or more at a wavelength of 530 nm, more preferably 1.55 or more, and the refractive index is It is more preferably 1.60 or more. Since the curable composition of the present embodiment can form a cured film with an increased refractive index in this way, applications requiring a high refractive index such as 3D sensors and AR waveguides of AR (augmented reality) glasses It can also be suitably used for The refractive index of the cured film can be measured with a spectroscopic ellipsometer.
  • the curable composition of the present embodiment described above contains component (X): niobium oxide nanoparticles, component (B): polymerizable compound, and component (C): polymerization initiator.
  • component (X) niobium oxide nanoparticles
  • component (B) polymerizable compound
  • component (C) polymerization initiator.
  • niobium oxide which does not have photocatalytic activity in the visible light region, is used as the metal oxide, and its nanoparticles are utilized.
  • the refractive index of the cured film can be increased, and a cured film having good light resistance can be formed.
  • the curable composition of the present embodiment has good fine pattern transferability during pattern formation. That is, such a curable composition is useful as a material for forming a fine pattern on a substrate by imprint technology, and is particularly suitable for optical imprint lithography. In particular, it has an advantageous effect in applications that require high refractive index and light resistance, such as 3D sensors for automatic driving and AR waveguides for AR (augmented reality) glasses.
  • the curable composition of the present embodiment is also useful as a material for antireflection films, for example.
  • the pattern forming method of the second aspect of the present invention comprises a step of forming a curable film on a substrate using the curable composition of the first aspect described above (hereinafter referred to as “step (i)”); A step of pressing a mold having an uneven pattern against the curable film to transfer the uneven pattern to the curable film (hereinafter referred to as “step (ii)”); and pressing the mold against the curable film. Meanwhile, a step of curing the curable film to which the uneven pattern has been transferred to form a cured film (hereinafter referred to as “step (iii)”), and a step of peeling the mold from the cured film (hereinafter referred to as “step ( iv)”);
  • FIG. 1 is a schematic process diagram explaining one embodiment of the pattern forming method.
  • step (i) a curable film is formed on a substrate using the curable composition of the first aspect described above.
  • a substrate 1 is coated with the curable composition of the first aspect described above to form a curable film 2 .
  • the mold 3 is arranged above the curable film 2 .
  • the substrate 1 can be selected according to various uses, and examples thereof include substrates for electronic components, substrates having predetermined wiring patterns formed thereon, and the like. More specifically, metal substrates such as silicon, silicon nitride, copper, chromium, iron, and aluminum, glass substrates, and the like are included. Materials for the wiring pattern include, for example, copper, aluminum, nickel, and gold. Further, the shape of the substrate 1 is not particularly limited, and may be plate-like or roll-like. Further, as the substrate 1, a light-transmitting or non-light-transmitting substrate can be selected depending on the combination with the mold.
  • Examples of methods for applying the curable composition to the substrate 1 include spin coating, spraying, ink jetting, roll coating, spin coating, and the like. Since the curable film 2 functions as a mask in the etching process of the substrate 1 that may be performed later, it is preferable that the film thickness when applied to the substrate 1 is uniform. From this point of view, the spin coating method is suitable for applying the curable composition to the substrate 1 .
  • the film thickness of the curable film 2 may be appropriately selected depending on the application, and may be, for example, about 0.05 to 30 ⁇ m.
  • step (ii) a mold having an uneven pattern is pressed against the hardening film to transfer the uneven pattern to the hardening film.
  • a mold 3 having a fine uneven pattern on its surface is pressed against a substrate 1 on which a curable film 2 is formed, facing the curable film 2 .
  • the curable film 2 is deformed according to the uneven structure of the mold 3 .
  • the pressure on the curable film 2 when the mold 3 is pressed is preferably 10 MPa or less, more preferably 5 MPa or less, and particularly preferably 1 MPa or less.
  • the concave-convex pattern of the mold 3 can be formed according to desired processing accuracy by photolithography, electron beam drawing, or the like, for example.
  • the mold 3 is preferably a light transmissive mold.
  • the material of the light-transmitting mold is not particularly limited as long as it has predetermined strength and durability. Specific examples include glass, quartz, light-transparent resin films such as polymethyl methacrylate and polycarbonate resin, transparent metal deposition films, flexible films such as polydimethylsiloxane, photocured films, metal films, and the like.
  • step (iii) the curable film having the uneven pattern transferred thereto is cured while pressing the mold against the curable film to form a cured resin film.
  • the hardening film 2 onto which the uneven pattern has been transferred is exposed while the mold 3 is pressed against the hardening film 2 .
  • the curable film 2 is irradiated with electromagnetic waves such as ultraviolet rays (UV). Due to the exposure, the curable film 2 is cured while the mold 3 is pressed, and a cured film (cured pattern) is formed on which the uneven pattern of the mold 3 is transferred.
  • the mold 3 in FIG. 1C has transparency to electromagnetic waves.
  • the light used to cure the curable film 2 is not particularly limited, and examples thereof include light or radiation with wavelengths in regions such as high-energy ionizing radiation, near-ultraviolet rays, far-ultraviolet rays, visible rays, and infrared rays.
  • the radiation for example, microwaves, EUV, LED, semiconductor laser light, or laser light used in semiconductor microfabrication, such as 248 nm KrF excimer laser light or 193 nm ArF excimer laser light, can be suitably used.
  • Monochromatic light may be used for these lights, or light with different wavelengths (mixed light) may be used.
  • step (iv) the mold is separated from the cured film. As shown in FIG. 1(D), the mold 3 is separated from the cured film. As a result, a pattern 2 ′ (cured pattern) made of a cured film to which the uneven pattern is transferred is patterned on the substrate 1 .
  • a curable composition containing the above-described components (X), (B) and (C) is used. Since such a curable composition is used, the refractive index of the cured film can be increased, and a cured film having good light resistance can be formed.
  • a release agent may be applied to the surface 31 of the mold 3 that is in contact with the curable film 2 (FIG. 1(A)).
  • release agents here include silicone-based release agents, fluorine-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. stencil agents and the like.
  • fluorine-based release agents are preferred.
  • a commercially available coating-type release agent such as OPTOOL DSX manufactured by Daikin Industries, Ltd. can be suitably used.
  • the release agent may be used alone or in combination of two or more.
  • an organic layer may be provided between the substrate 1 and the curable film 2 . Accordingly, by etching the substrate 1 using the curable film 2 and the organic layer as a mask, a desired pattern can be easily and reliably formed on the substrate 1 .
  • the film thickness of the organic layer may be appropriately adjusted according to the depth of processing (etching) of the substrate 1, and is preferably 0.02 to 2.0 ⁇ m, for example.
  • the material of the organic layer preferably has lower etching resistance to oxygen-based gas than the curable composition and higher etching resistance to halogen-based gas than the substrate 1 .
  • a method for forming the organic layer is not particularly limited, but examples thereof include a sputtering method and a spin coating method.
  • the pattern forming method of the second aspect may further include other steps (optional steps) in addition to steps (i) to (iv).
  • steps (optional steps) include an etching step (step (v)) and a step of removing a cured film (cured pattern) after etching treatment (step (vi)).
  • step (v) for example, the substrate 1 is etched using the pattern 2' obtained in the above steps (i) to (iv) as a mask.
  • the substrate 1 on which the pattern 2' is formed is irradiated with at least one of plasma and reactive ions (indicated by arrows), thereby exposing the substrate to the pattern 2' side.
  • One portion is removed by etching to a predetermined depth.
  • the plasma or reactive ion gas used in step (v) is not particularly limited as long as it is a gas commonly used in the field of dry etching.
  • step (vi) the cured film remaining after the etching treatment in step (v) is removed. As shown in FIG. 2F, this is a step of removing the cured film (pattern 2') remaining on the substrate 1 after the substrate 1 has been etched.
  • a method for removing the cured film (pattern 2′) remaining on the substrate 1 is not particularly limited, but an example thereof includes a process of washing the substrate 1 using a solution that dissolves the cured film.
  • ⁇ (X) component (niobium oxide nanoparticles) (X)-1 Niobium oxide nanoparticles, manufactured by Taki Chemical Co., Ltd., product name “Virar Nb-G6000”, water solvent, concentration 6.68% by mass. Volume average primary particle diameter 23 nm.
  • X2 component metal oxide nanoparticles
  • (X2)-1 Titanium oxide nanoparticles, manufactured by Ishihara Sangyo Co., Ltd., product name "LDB-014-35", PGME solvent, concentration 35% by mass. Volume average primary particle diameter 55 nm.
  • (X2)-2 Titanium oxide nanoparticles, manufactured by Nikki Shokubai Kasei Co., Ltd., product name "ELECOM V-9108", PGME solvent, concentration 35% by mass. Volume average primary particle diameter 15 nm.
  • (B) component (polymerizable compound) (B)-1: Polyfunctional acrylate, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., product name "SA-TE60”; solution.
  • C component (polymerization initiator)
  • C)-1 2-Hydroxy-2-methyl-1-phenylpropanone, IGM Resins B.I. V. company, product name "Omnirad 1173”.
  • C)-2 2,2-dimethoxy-2-phenylacetophenone, IGM Resins B.I. V. company, product name "Omnirad 651”.
  • E)-1 Anti-color separation agent, manufactured by Kyoeisha Chemical Co., Ltd., product name "Floren GW-1500”.
  • E)-2 Fluorinated surfactant, manufactured by OMNOVA, product name "PolyFox PF656”.
  • Each curable composition of Examples 1 to 3 and Comparative Example 1 was spin-coated onto a silicon substrate at a spin speed of 2000 rpm. Next, pre-baking is performed at 60° C. for 1 minute, and an imprinting apparatus ST-200 manufactured by Toshiba Machine Co., Ltd. is used to perform photocuring treatment with an exposure amount of 5 J/cm 2 (under a vacuum atmosphere of 200 Pa) to obtain a cured film having a thickness of 200 nm. got Further, each curable composition of Comparative Examples 2 and 3 was spin-coated onto a silicon substrate at a spin speed of 1000 rpm. Next, pre-baking is performed at 100° C. for 1 minute, and an imprinting apparatus ST-200 manufactured by Toshiba Machine Co., Ltd.
  • the refractive index at a wavelength of 530 nm was measured using a spectroscopic ellipsometer M2000 manufactured by Woollam.
  • the refractive indices measured here were defined as the refractive index after 0.1 hour of the light resistance test and the refractive index after 150 hours of the light resistance test, respectively. Then, the difference between the refractive index after 0.1 hour of the light resistance test and the refractive index after 150 hours of the light resistance test was determined, and the light resistance was evaluated according to the following evaluation criteria.
  • the curable composition of Example 3 was spin-coated onto a silicon substrate at a spin speed of 2000 rpm. Next, prebaking is performed at 60° C. for 1 minute, and a transfer test is performed using an imprinting apparatus ST-200 manufactured by Toshiba Machine Co., Ltd. under a pressing condition of 0.5 kN for 150 seconds and an exposure amount of 5 J/cm 2 (in a vacuum atmosphere of 200 Pa). Then, the transferability and filling property of the fine pattern were evaluated. As a mold, a standard film mold LSP70-140 (70 nm Line & Space) manufactured by Soken Kagaku Co., Ltd. was used.
  • the curable compositions of Examples to which the present invention was applied can increase the refractive index and form a cured film having good light resistance. Moreover, it was confirmed that the curable compositions of Examples to which the present invention was applied had good pattern transferability and were suitable materials for photoimprint lithography.

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WO2010071134A1 (ja) * 2008-12-15 2010-06-24 旭硝子株式会社 光硬化性材料の製造方法、光硬化性材料および物品
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