WO2017170624A1 - パターン形成方法、加工基板の製造方法、光学部品の製造方法、回路基板の製造方法、電子部品の製造方法、インプリントモールドの製造方法 - Google Patents
パターン形成方法、加工基板の製造方法、光学部品の製造方法、回路基板の製造方法、電子部品の製造方法、インプリントモールドの製造方法 Download PDFInfo
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- 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
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- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
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- 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
- B05D3/04—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 gases
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- 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
- B05D3/12—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 mechanical means
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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
- B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
Definitions
- the present invention relates to a pattern forming method, a processed substrate manufacturing method, an optical component manufacturing method, a circuit board manufacturing method, an electronic component manufacturing method, and an imprint mold manufacturing method.
- the photocurable composition is cured in a state where a mold (mold) having a fine uneven pattern formed on the surface is pressed against a substrate (wafer) coated with the photocurable composition (resist).
- corrugated pattern of a mold is transcribe
- a fine structure of the order of several nanometers can be formed on a substrate.
- the liquid resist 102 is discretely dropped onto the pattern formation region on the substrate 101 by using an inkjet method (arrangement step (1), FIGS. 1A to 1C).
- the dropped droplet of the resist 102 spreads on the substrate 101 as shown by the arrow 104 indicating the direction of spreading of the droplet, and this phenomenon is called pre-spread (FIG. 1C).
- this resist 102 is molded using a mold (mold) 105 that is transparent to irradiation light 106 to be described later, on which a pattern is formed (mold contact step (2), FIG. 1D).
- the droplet of the resist 102 spreads over the entire gap between the substrate 101 and the mold 105 as indicated by an arrow 104 indicating the direction of the droplet spreading by capillary action (FIG. 1D). This phenomenon is called spread.
- the resist 102 is also filled into the concave portion on the mold 105 by capillary action as indicated by an arrow 104 indicating the direction in which the droplet spreads (partial enlarged portion in FIG. 1D). This filling phenomenon is called fill. The time until the spread and fill are completed is called the filling time.
- the resist 102 is cured by irradiating the irradiation light 106 (light irradiation step (3), FIG. 1E), and then the mold 105 is separated from the substrate 101 (release step (4)). FIG. 1F).
- a cured film 107 (FIG. 1F) having a predetermined pattern shape is formed on the substrate 101.
- SST-NIL Short Spread Time Nanoimprint Lithography
- the droplet of the curable composition (A2) 203 arranged in the second laminating step (2) is a direction in which the droplet spreads due to the Marangoni effect using the difference in surface energy (surface tension) as a driving force, as will be described later. Spreads quickly in the direction of the arrow 204 (pre-spread).
- the Marangoni effect is a phenomenon of free surface movement caused by a local difference in the surface tension of a liquid (Non-Patent Document 2).
- the surface tension that is, the difference in surface energy, is used as a driving force to cause diffusion such that a liquid having a low surface tension covers a wider surface. That is, if the curable composition (A1) 202 with a high surface tension is applied to the entire surface of the substrate 201 and the curable composition (A2) 203 with a low surface tension is dropped, the curable composition (A2) 203 The pre-spread is accelerated.
- the composition of the component of the curable composition (A2) 203 excluding the component (d2) as the solvent is the surface tension of the component of the curable composition (A1) 202 excluding the component (d1) as the solvent. It is preferably higher than the surface tension of the object.
- the pre-spread of the curable composition (A2) 203 is accelerated by the Marangoni effect described later (droplets spread over a wide area), and the time required for the spread during the mold contact process described later is shortened. This is because the filling time is shortened.
- the droplets of the curable composition (A2) 203 which are dropped in a discrete manner, rapidly expand on the liquid film of the curable composition (A1) 202. Throughput.
- Patent Documents 2 to 5 describe processes using two kinds of curable compositions.
- the composition on the substrate 201 side has little or no release agent, contains an adhesion improver, and has a composition on the mold 205 side.
- the product contains a lot of release agent. It is assumed that the composition on the substrate 201 side does not come into contact with the mold 205.
- the curable composition (A1) 202 that is first laminated on the substrate 201 side is also included.
- the cured film 207 having the pattern shape in the SST-NIL shown in FIG. 2G includes a cured film 2071 containing a large amount of the curable composition (A1) 202 and a cured film 2072 containing a large amount of the curable composition (A2) 203. Both are in close contact with the mold 205.
- the cured film 2071 containing a large amount of the curable composition (A1) 202 previously formed on the substrate 201 side has little or no release agent as in the case of Patent Document 2.
- the cured film 2071 containing a large amount of the curable composition (A1) 202 is damaged, and a problem arises in that the cured film 2071 ′ and the damaged cured film 2071 ′′ are separated from each other. . Similar problems also occurred when a large amount of adhesion improver was included.
- a pattern having a sufficiently high height was not formed on the substrate 201, which affected subsequent processes of the substrate 201 such as dry etching.
- a damaged cured film 2071 ′′ remains in the mold 205, which has an influence on the next imprint process.
- the same problem hardly occurs in the cured film 2072 containing a large amount of the curable composition (A2) 203 containing a release agent.
- the curable composition (A1) 202 contains a fluorine-based mold release agent that has a performance as a mold release agent and is commonly used, curing that excludes the solvent component (d1).
- the surface tension of the composition of the component of the adhesive composition (A1) 202 is low. Therefore, the above-mentioned Marangoni effect cannot be exhibited when the difference between the surface tension of the composition of the curable composition (A2) 203 excluding the component (d2) that is a solvent is small or reversed. , SST-NIL filling time shortening effect is reduced.
- An object of the present invention is to provide an SST-NIL technology with high throughput and less mold release defects.
- a layer comprising a curable composition (A1) containing at least a component (a1) which is a polymerizable compound and a component (c1) which is a surfactant is laminated on the surface of a substrate.
- a curable composition (A1) containing at least a component (a1) which is a polymerizable compound and a component (c1) which is a surfactant is laminated on the surface of a substrate.
- One lamination step (1) On the layer comprising the curable composition (A1), droplets of the curable composition (A2) containing at least the component (a2) which is a polymerizable compound and the component (c2) which is a surfactant are discretely dispersed.
- a pattern forming method having
- the curable composition (A1) contains at least 0.5% by weight or more of the component (c1), which is a surfactant, based on the total weight of the components of the curable composition (A1) excluding the solvent
- the curable composition (A2) contains at least 0.5% by weight or more of the component (c2), which is a surfactant, based on the total weight of the components of the curable composition (A2) excluding the solvent,
- the surface tension of the said curable composition (A1) is higher than the surface tension of the said curable composition (A2), It is characterized by the
- the curable compositions (A1) and (A2) according to this embodiment are compositions having at least a component (a) that is a polymerizable compound.
- the curable composition according to this embodiment may further contain a component (b) that is a photopolymerization initiator, a component (c) that is a non-polymerizable compound, and a component (d) that is a solvent.
- the cured film means a film obtained by polymerizing a curable composition on a substrate and curing it.
- shape of a cured film is not specifically limited, You may have a pattern shape on the surface.
- Component (a) is a polymerizable compound.
- the polymerizable compound means a film made of a high molecular compound by a chain reaction (polymerization reaction) by reacting with a polymerization factor (radical etc.) generated from the component (b) which is a photopolymerization initiator. It is a compound that forms.
- polymerizable compounds examples include radical polymerizable compounds.
- the component (a) which is a polymerizable compound may be composed of only one type of polymerizable compound or may be composed of a plurality of types of polymerizable compounds.
- the radical polymerizable compound is preferably a compound having at least one acryloyl group or methacryloyl group, that is, a (meth) acrylic compound. Therefore, the curable composition according to the present embodiment preferably includes a (meth) acrylic compound as the component (a), more preferably the main component of the component (a) is a (meth) acrylic compound, Most preferably, all of (a) are (meth) acrylic compounds. In addition, that the main component of the component (a) described here is a (meth) acrylic compound indicates that 90% by weight or more of the component (a) is a (meth) acrylic compound.
- the radical polymerizable compound is composed of a plurality of types of compounds having one or more acryloyl groups or methacryloyl groups
- Examples of monofunctional (meth) acrylic compounds having one acryloyl group or methacryloyl group include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, and 3-phenoxy.
- polyfunctional (meth) acrylic compounds having two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and EO-modified trimethylolpropane tri (meth).
- UV SA1002 As a commercial item of the said polyfunctional (meth) acryl compound, Iupimer (trademark) UV SA1002, SA2007 (above, Mitsubishi Chemical make), Biscote # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (above, manufactured by Osaka Organic Chemical Industry), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP- A, PE-3A, PE-4A, DPE-6A (manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120 HX-620, D-310, D-330 (Nippon Kayaku Co., Ltd.), Aronix (registered trademark) M208, M210, M215 M220, M240, M305,
- (meth) acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto.
- the (meth) acryloyl group means an acryloyl group or a methacryloyl group having an alcohol residue equivalent thereto.
- EO represents ethylene oxide
- EO-modified compound A refers to a compound in which the (meth) acrylic acid residue and alcohol residue of compound A are bonded via a block structure of an ethylene oxide group.
- PO represents propylene oxide
- PO-modified compound B refers to a compound in which the (meth) acrylic acid residue and alcohol residue of compound B are bonded via a block structure of a propylene oxide group.
- the blending ratio of the component (a1) which is a polymerizable compound in the curable composition (A1) excludes the total weight of the component (a1), the component (b1) and the component (c1), that is, the component (d1) which is a solvent. It is good in it being 50 to 100 weight% with respect to the total weight of the component of a curable composition (A1). Further, it is preferably 80% by weight or more and 100% by weight or less, more preferably more than 90% by weight and 100% by weight or less.
- the cured film obtained can be a cured film having a certain degree of mechanical strength.
- the cured film obtained can be a cured film having a certain degree of mechanical strength.
- the curable composition (A1) preferably contains the component (d1), and the component (a1) is a component of the curable composition (A1) containing the component (d1) which is a solvent. It is good that it is 0.01 weight% or more and 10 weight% or less with respect to the total weight.
- Component (b) is a photopolymerization initiator.
- the photopolymerization initiator is a compound that senses light of a predetermined wavelength and generates the polymerization factor (radical).
- the photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals by light (infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams such as X-rays, electron beams, etc., radiation). It is.
- Component (b) may be composed of one type of photopolymerization initiator, or may be composed of a plurality of types of photopolymerization initiators.
- radical generator examples include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- May have a substituent such as (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer, 4,5-triarylimidazole dimer; benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dia Benzoph
- benzoinmethy Benzoin ether derivatives such as ether, benzoin ethyl ether, benzoin phenyl ether; benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin, propyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; 9-phenylacridine, 1,7-bis (9 , 9′-acridinyl) heptane derivatives; N-phenylglycine derivatives such as N-phenylglycine; acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2- Acetophenone derivatives such as phenylacetophenone; thiophenones such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-
- Examples of commercially available radical generators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark). Examples include, but are not limited to, TPO, LR8883, LR8970 (above, manufactured by BASF), Ubekrill P36 (manufactured by UCB), and the like.
- the component (b) is preferably an acyl phosphine oxide polymerization initiator.
- acylphosphine oxide polymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.
- the blending ratio of the component (b2) that is a photopolymerization initiator in the curable composition (A2) is the total weight of the component (a2), the component (b2), and the component (c2) described later, that is, the component (d2) that is a solvent.
- the blending ratio of the component (b2) in the curable composition (A2) By setting the blending ratio of the component (b2) in the curable composition (A2) to 0.1% by weight or more based on the total weight of the component (a2), the component (b2), and the component (c2), The curing speed is increased and the reaction efficiency can be improved. Further, by setting the blending ratio of the component (b2) to 50% by weight or less with respect to the total weight of the component (a2), the component (b2), and the component (c2), the obtained cured film has a certain degree of mechanical strength. It can be set as the cured film which has.
- the compounding ratio in the curable composition (A1) of the component (b1) which is a photoinitiator is the total weight of a component (a1), a component (b1), and the component (c1) mentioned later, ie, the component which is a solvent. It is good in it being 0.1 weight% or less with respect to the total weight of the component of the curable composition (A1) except (d1).
- Non-polymerizable compound Non-polymerizable compound
- the component (c) which is a nonpolymerizable compound can be contained.
- Such a component (c) does not have a polymerizable functional group such as a (meth) acryloyl group, and has the ability to generate the polymerization factor (radical) by sensing light of a predetermined wavelength.
- No compound. Examples include sensitizers, hydrogen donors, internal release agents, surfactants, antioxidants, polymer components, adhesion improvers, and other additives. You may contain multiple types of the said representatives as a component (c).
- the sensitizer is a compound added as appropriate for the purpose of promoting the polymerization reaction or improving the reaction conversion rate.
- Examples of the sensitizer include sensitizing dyes.
- the sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and interacts with the component (b) that is a photopolymerization initiator.
- the interaction described here refers to energy transfer, electron transfer, and the like from the sensitizing dye in the excited state to the component (b) that is a photopolymerization initiator.
- sensitizing dyes include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt series Dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes, etc. It is not limited to these.
- Sensitizers may be used alone or in combination of two or more.
- the hydrogen donor is a compound that reacts with an initiation radical generated from the component (b) that is a photopolymerization initiator or a radical at a polymerization growth terminal to generate a radical having higher reactivity. It is preferable to add when the component (b) which is a photoinitiator is a photoradical generator.
- hydrogen donor examples include n-butylamine, di-n-butylamine, allylthiourea, triethylamine, triethylenetetramine, 4,4′-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid.
- the hydrogen donor one kind may be used alone, or two or more kinds may be mixed and used. Further, the hydrogen donor may have a function as a sensitizer.
- an internal release agent is added to the curable composition for the purpose of reducing the bonding force between the mold and the resist, that is, reducing the releasing force in the releasing step described later.
- the internally added type means that it is added to the curable composition in advance before the step of arranging the curable composition.
- the curable composition (A1) is cured with a component (c1) which is a surfactant that does not greatly change the surface tension, mainly a hydrocarbon surfactant.
- Component (c2) which is a surfactant that reduces the surface tension, mainly a fluorine-based surfactant can be used for the functional composition (A2).
- the internally added mold release agent is not polymerizable.
- a surfactant satisfying the following general formula (1) is preferably selected. ⁇ 5% ⁇ ⁇ ( ⁇ 1 ⁇ 2 ) / ⁇ 1 ⁇ ⁇ 5% (1)
- ⁇ 1 represents the surface tension of the curable composition (A1) at 25 ° C.
- ⁇ 2 represents the surface tension of the evaluation curable composition (A1) at 25 ° C.
- the evaluation curable composition (A1) refers to a composition having the same composition as the curable composition (A1) except that the component (c1) which is a surfactant is not included.
- Patent Document 6 there is a description of a curable composition using the same internally added mold release agent, but it is described only when one type of curable composition is used.
- a surfactant that satisfies the following general formula (2) is selected.
- ⁇ ( ⁇ 1 ⁇ 2 ) / ⁇ 1 ⁇ ⁇ 5% (2) (In Formula (2), ⁇ 1 represents the surface tension of the curable composition (A2) at 25 ° C., and ⁇ 2 represents the surface tension of the curable composition for evaluation (A2) at 25 ° C.)
- the evaluation curable composition (A2) refers to a composition having the same composition as the curable composition (A2) except that the component (c2) which is a surfactant is not included.
- Fluorosurfactants that can be preferably used in the curable composition (A2) include polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having a perfluoroalkyl group, and polyalkylenes of perfluoropolyether. Oxide (polyethylene oxide, polypropylene oxide, etc.) adducts and the like are included.
- the fluorine-based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, or the like as part of the molecular structure (for example, a terminal group).
- a commercially available product may be used as the fluorosurfactant.
- Commercially available products include, for example, MegaFace (registered trademark) F-444, TF-2066, TF-2067, TF-2068 (above, manufactured by DIC), Florard FC-430, FC-431 (above, manufactured by Sumitomo 3M) , Surflon (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (above, manufactured by Tochem Products), PF-636 , PF-6320, PF-656, PF-6520 (above, OMNOVA Solutions), Unidyne (registered trademark) DS-401, DS-403, DS-451 (above, manufactured by Daikin Industries), Footent (registered trademark) 250, 251, 222F, 208G (Neos).
- hydrocarbon surfactants that can be preferably used in the curable composition (A1) include alkyl alcohol polyalkylene oxide adducts obtained by adding alkylene oxides having 2 to 4 carbon atoms to alkyl alcohols having 1 to 50 carbon atoms. Etc. are included.
- alkyl alcohol polyalkylene oxide adduct examples include methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct / Examples thereof include propylene oxide adducts.
- the terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced by simply adding a polyalkylene oxide to an alkyl alcohol.
- This hydroxyl group may be substituted with other substituents, for example, a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group, and a silanol group, and a hydrophobic functional group such as an alkyl group and an alkoxy group.
- a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group, and a silanol group
- a hydrophobic functional group such as an alkyl group and an alkoxy group.
- alkyl alcohol polyalkylene oxide adduct a commercially available product may be used.
- examples of commercially available products include polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Yushi Kogyo, and polyoxyethylene decyl ether manufactured by Aoki Yushi Kogyo.
- (Decyl alcohol ethylene oxide adduct) FINESURF D-1303, D-1305, D-1307, D-1310), polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil & Fats Industries, Ltd.
- Stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R), BASF polyoxyethylene methyl ether (Pluriol (registered trademark) A760E), Kao polyoxyethylene alkyl ether (Emulgen series), etc. Can be mentioned.
- the internally added mold release agent is preferably an alkyl alcohol polyalkylene oxide adduct, and more preferably a long-chain alkyl alcohol polyalkylene oxide adduct.
- One type of internally added mold release agent may be used alone, or two or more types may be mixed and used.
- the compounding ratio in the curable composition of the component (c) which is an internal release agent, that is, a surfactant, is the total weight of the component (a), the component (b) and the component (c), that is, a component which is a solvent. It is good in it being 0.5 weight% or more and 50 weight% or less with respect to the total weight of the component of the curable composition except (d). Further, it is preferably 0.9% by weight or more and 50% by weight or less, and more preferably 0.9% by weight or more and 20% by weight or less.
- the blending ratio of the component (c) which is a surfactant is 0.5% by weight or more with respect to the total weight of the component (a), the component (b) and the component (c), preferably 0.8.
- the mold release performance at the time of releasing a cured film from a mold can fully be exhibited.
- the resulting cured film can be a cured film having a certain degree of mechanical strength.
- an adhesion improving agent an organometallic coupling agent is often used.
- a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, a tin coupling agent, or the like is used.
- the total weight of the component (a), the component (b) and the component (c), that is, the total weight of the components of the curable composition excluding the component (d) which is a solvent Contains from 0 to less than 0.01% by weight.
- the curable composition concerning this embodiment may contain the component (d) which is a solvent.
- the component (d) is not particularly limited as long as it is a solvent in which the component (a), the component (b), and the component (c) are dissolved.
- a preferable solvent is a solvent having a boiling point of 80 ° C. or higher and 200 ° C. or lower at normal pressure. More preferably, it is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure.
- propylene glycol monomethyl ether acetate propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, ethyl lactate, or a mixed solvent thereof.
- the curable composition (A1) according to this embodiment preferably contains the component (d1). This is because, as will be described later, a spin coating method is preferable as a method for applying the curable composition (A1) onto the substrate.
- each component is mixed and dissolved under predetermined temperature conditions. Specifically, it is performed in the range of 0 ° C. or higher and 100 ° C. or lower.
- the curable compositions (A1) and (A2) according to this embodiment are preferably liquids. This is because the spread and fill of the curable composition (A1) and / or (A2) are completed quickly, that is, the filling time is short in the mold contact step described later.
- the viscosity at 25 ° C. of the component composition excluding the component (d1) that is the solvent of the curable composition (A1) according to the present embodiment is preferably 1 mPa ⁇ s or more and 1000 mPa ⁇ s or less. Further, it is more preferably 1 mPa ⁇ s or more and 500 mPa ⁇ s or less, and further preferably 1 mPa ⁇ s or more and 100 mPa ⁇ s or less.
- the viscosity at 25 ° C. of the composition of the components excluding the component (d2) which is the solvent of the curable composition (A2) according to this embodiment is preferably 1 mPa ⁇ s or more and 100 mPa ⁇ s or less. Further, it is more preferably 1 mPa ⁇ s or more and 50 mPa ⁇ s or less, and further preferably 1 mPa ⁇ s or more and 12 mPa ⁇ s or less.
- the viscosity is set to 1 mPa ⁇ s or more, uneven coating hardly occurs when the curable compositions (A1) and (A2) are applied on the substrate. Further, when the curable compositions (A1) and (A2) are brought into contact with the mold, the curable compositions (A1) and (A2) are less likely to flow out from the end of the mold.
- the surface tension of the curable compositions (A1) and (A2) according to this embodiment is 25 ° C. with respect to the composition of the curable compositions (A1) and (A2) excluding the component (d) that is a solvent.
- the surface tension is preferably 5 mN / m or more and 70 mN / m or less. More preferably, it is 7 mN / m or more and 50 mN / m or less, More preferably, it is 10 mN / m or more and 40 mN / m or less.
- Non-Patent Document 1 As the surface tension is higher, for example, when the surface tension is 5 mN / m or more, the capillary force works strongly, so when the curable composition (A1) and / or (A2) is brought into contact with the mold, the filling (spread) And fill) are completed in a short time (Non-Patent Document 1).
- a cured film obtained by curing the curable composition becomes a cured film having surface smoothness.
- the component of the curable composition (A2) excluding the component (d2) which is the solvent has a surface tension of the component of the curable composition (A1) excluding the component (d1) which is the solvent.
- the surface tension of the composition is preferably higher.
- the Marangoni effect is a phenomenon of free surface movement caused by a local difference in the surface tension of a liquid (Non-Patent Document 2).
- the surface tension that is, the difference in surface energy, is used as a driving force to cause diffusion such that a liquid having a low surface tension covers a wider surface. That is, if the curable composition (A1) having a high surface tension is applied to the entire surface of the substrate and the curable composition (A2) having a low surface tension is dropped, the pre-spread of the curable composition (A2) is accelerated. It is done.
- the curable composition (A1) mainly contains a hydrocarbon-based surfactant as the component (c1) which is a surfactant that does not reduce the surface tension. use. It is preferable to use a material satisfying the above-described formula (1).
- a fluorosurfactant is mainly used as the component (c2) which is a surfactant that reduces the surface tension. Therefore, the surface tension of the curable composition (A1) excluding the solvent (component (d)) is maintained higher than the surface tension of the curable composition (A2) excluding the solvent (component (d)), and sufficient Marangoni The effect is demonstrated.
- the contact angles of the curable compositions (A1) and (A2) according to the present embodiment are the same as those of the components of the curable compositions (A1) and (A2) excluding the component (d) that is a solvent. And 0 ° or more and 90 ° or less with respect to both of the mold surface.
- the contact angle is larger than 90 °, the capillary force acts in the negative direction (the direction in which the contact interface between the mold and the curable composition is contracted) in the mold pattern or in the gap between the substrate and the mold and is not filled. It is particularly preferable that the angle is 0 ° or more and 30 ° or less. Since the capillary force works stronger as the contact angle is lower, the filling speed is faster (Non-Patent Document 1).
- the curable compositions (A1) and (A2) according to this embodiment contain no impurities as much as possible.
- the impurities described here mean those other than the component (a), component (b), component (c) and component (d) described above.
- the curable composition according to the present embodiment is obtained through a purification process.
- a purification step filtration using a filter or the like is preferable.
- a pore size of 0.001 ⁇ m or more and 5. It is preferable to filter with a filter of 0 ⁇ m or less. When performing filtration using a filter, it is more preferable to carry out in multiple stages or repeat many times. Moreover, you may filter the filtered liquid again. Filtration may be performed using a plurality of filters having different pore diameters.
- filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc. can be used, but are not particularly limited.
- impurities such as particles mixed in the curable composition can be removed. Thereby, it can prevent that the unevenness
- an impurity containing a metal atom (metal) in the curable composition is used so as not to hinder the operation of the product. It is preferable to avoid contamination of impurities) as much as possible.
- the concentration of the metal impurities contained in the curable composition is preferably 10 ppm or less, and more preferably 100 ppb or less.
- the pattern formation method according to the present embodiment is an embodiment of an optical nanoimprint method.
- the pattern forming method of this embodiment is A first laminating step (1) for laminating the curable composition (A1) 202 of the present embodiment described above on the substrate 201; A second lamination step (2) of laminating the curable composition (A2) 203 on the layer of the curable composition (A1) 202; A mold contact step (3) of sandwiching a mixed layer formed by partially mixing the curable composition (A1) 202 and the curable composition (A2) 203 between the mold 205 having a pattern and the substrate 201; A light irradiation step (4) for curing the mixed layer by irradiating irradiation light 206 from the mold 205 side; A mold release step (5) for separating the mold 205 from the layer made of the cured film 207 after curing, Have
- the cured film obtained by the method for producing a cured film having a pattern shape according to this embodiment is preferably a film having a pattern having a size of 1 nm or more and 10 mm or less.
- a film having a pattern having a size of 10 nm or more and 100 ⁇ m or less is more preferable.
- a pattern forming technique for producing a film having a nano-size (1 nm or more and 100 nm or less) pattern (uneven structure) using light is called an optical nanoimprint method.
- the pattern forming method according to the present embodiment uses an optical nanoimprint method.
- the component (d1) as a solvent is volatilized and the component (d1) as a solvent is present on the substrate 201. Only the composition of the component of the curable composition (A1) 202 excluding the above remains.
- the substrate 201 on which the curable composition (A1) 202 is to be placed is a substrate to be processed, and a silicon wafer is usually used.
- a layer to be processed may be formed over the substrate 201.
- Another layer may be formed between the substrate 201 and the layer to be processed. If a quartz substrate is used as the substrate 201, a replica of the quartz imprint mold (mold replica) can be produced.
- the substrate 201 is not limited to a silicon wafer or a quartz substrate.
- the substrate 201 can be arbitrarily selected from those known as semiconductor device substrates such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride. .
- the surface of the substrate 201 (substrate to be processed) or the layer to be used is subjected to curable compositions (A1) 202 and (A2) by surface treatment such as silane coupling treatment, silazane treatment, or organic thin film formation. ) Adhesion with 203 may be improved.
- the curable composition (A1) 202 on the substrate 201 or the layer to be processed
- a method of disposing the curable composition (A1) 202 on the substrate 201 or the layer to be processed for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method.
- Gravure coating method, extrusion coating method, spin coating method, slit scanning method and the like can be used.
- the spin coating method is particularly preferable.
- a baking process may be performed as necessary to volatilize the component (d) as a solvent.
- the average film thickness of the curable composition (A1) 202 varies depending on the application to be used, but is, for example, from 0.1 nm to 10,000 nm, preferably from 1 nm to 20 nm, particularly preferably 1 nm. It is 10 nm or less.
- ⁇ Second laminating step (2)> In this step (second lamination step), as shown in FIGS. 2C and 2D, droplets of the curable composition (A2) 203 are discretely dropped on the layer of the curable composition (A1) 202. It is preferable to arrange. As an arrangement method, an inkjet method is particularly preferable. The droplets of the curable composition (A2) 203 are densely deposited on the substrate 201 facing the region where the concave portions are densely present on the mold 205, and on the substrate 201 facing the region where the concave portions are sparsely present. Sparsely arranged. This makes it possible to control the remaining film, which will be described later, to a uniform thickness regardless of the density of the pattern on the mold 205.
- the curable composition (A1) 202 and the curable composition (A2) 203 formed in the previous step (first and second lamination steps) are partially mixed.
- a mold 205 having an original pattern for transferring the pattern shape is brought into contact with the liquid layer.
- the liquid formed by partially mixing the curable composition (A1) 202 and the curable composition (A2) 203 is filled (filled) into the concave portion of the fine pattern on the surface of the mold 205, and the mold 205 is filled.
- the liquid film is filled (filled) into the fine pattern.
- a mold 205 made of a light-transmitting material may be used in consideration of the next process (light irradiation process).
- the material constituting the mold 205 include light transmissive resin such as glass, quartz, PMMA, and polycarbonate resin, transparent metal vapor-deposited film, flexible film such as polydimethylsiloxane, photocured film, and metal film. Etc. are preferred.
- a light transparent resin as the material of the material constituting the mold 205, it is necessary to select a resin that does not dissolve in the components contained in the curable composition. Since the coefficient of thermal expansion is small and the pattern distortion is small, the material of the material constituting the mold 205 is particularly preferably quartz.
- the fine pattern on the surface of the mold 205 preferably has a pattern height of 4 nm or more and 200 nm or less.
- Adjacent resist patterns may come into contact with each other due to the elastic deformation of the resist pattern due to an impact when the mold 205 is peeled off, and the resist pattern may be fused or damaged. If the ratio is 2 or less, there is a high possibility that these problems can be avoided.
- the pattern height is too low, the processing accuracy of the substrate 201 (substrate to be processed) is low.
- the mold 205 includes the curable compositions (A1) 202 and (A2) 203 and the mold 205.
- Surface treatment may be performed before this step, which is the mold contact step.
- the surface treatment method include a method of applying a release agent to the surface of the mold 205 to form a release agent layer.
- a mold release agent to be applied to the surface of the mold 205 a silicone mold release agent, a fluorine mold release agent, a hydrocarbon mold release agent, a polyethylene mold release agent, a polypropylene mold release agent, a paraffin mold release agent.
- Examples thereof include a mold agent, a montan release agent, and a carnauba release agent.
- a commercially available coating mold release agent such as OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd. can be suitably used.
- a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more types. Of these, fluorine-based and hydrocarbon-based release agents are particularly preferable.
- the pressure applied to 203 is not particularly limited.
- the pressure is preferably 0 MPa or more and 100 MPa or less.
- the pressure is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and further preferably 0 MPa or more and 20 MPa or less.
- the spread of the curable composition (A2) 203 in this step is promptly Complete.
- the spread is finally completed and the concentration of the curable composition (A1) 202 is high.
- the curable composition (A1) Since the contact angle of 202 is low, the fill is completed quickly also in this region.
- the mold 205 and the curable compositions (A1) 202 and (A2) 203 are brought into contact with each other.
- the time for contact is not particularly limited, but may be, for example, 0.1 seconds to 600 seconds.
- the time is preferably 0.1 second or more and 3 seconds or less, particularly preferably 0.1 second or more and 1 second or less. If it is shorter than 0.1 seconds, spread and fill are insufficient, and defects called unfilled defects tend to occur frequently.
- this step can be performed under any conditions of air atmosphere, reduced pressure atmosphere, and inert gas atmosphere, it can prevent the influence of oxygen and moisture on the curing reaction.
- a gas atmosphere is preferable.
- Specific examples of the inert gas that can be used when this step is performed in an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbons, and a mixed gas thereof.
- a preferable pressure is 0.0001 atm or more and 10 atm or less.
- the mold contact step may be performed under an atmosphere containing a condensable gas (hereinafter referred to as “condensable gas atmosphere”).
- the condensable gas means an atmosphere together with the curable compositions (A1) 202 and (A2) 203 in the concave portions of the fine pattern formed on the mold 205 and the gap between the mold 205 and the substrate 201.
- the gas inside refers to a gas that condenses and liquefies by the capillary pressure generated during filling.
- the condensable gas exists as a gas in the atmosphere before the curable compositions (A1) 202 and (A2) 203 and the mold 205 come into contact with each other in the mold contact step (see FIG. 1D and the partially enlarged portion).
- the gas filled in the concave portions of the fine pattern is liquefied by the capillary pressure generated by the curable compositions (A1) 202 and (A2) 203, whereby the bubbles disappear. Therefore, the filling property is excellent.
- the condensable gas may be dissolved in the curable composition (A1) 202 and / or (A2) 203.
- the boiling point of the condensable gas is not limited as long as it is equal to or lower than the atmospheric temperature in the mold contact step, but is preferably ⁇ 10 ° C. to 25 ° C., more preferably 10 ° C. to 25 ° C. If it is this range, a filling property will be further excellent.
- the vapor pressure at the atmospheric temperature in the mold contact process of the condensable gas is such that the mold 205 and the curable compositions (A1) 202 and (A2) 203 are brought into contact with each other at the time of imprinting in the mold contact process.
- the vapor pressure at the atmospheric temperature is larger than 0.4 MPa, there is a tendency that the effect of eliminating the bubbles cannot be obtained sufficiently.
- the vapor pressure at the ambient temperature is less than 0.1 MPa, pressure reduction is required and the apparatus tends to be complicated.
- the atmospheric temperature in the mold contact step is not particularly limited, but is preferably 20 ° C to 25 ° C.
- the condensable gas include chlorofluorocarbon (CFC) such as trichlorofluoromethane, fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), 1,1,1,3,3-pentafluoropropane (CHF 2 CH 2 Fluorocarbons such as hydrofluorocarbon (HFC) such as CF 3 , HFC-245fa, PFP) and hydrofluoroether (HFE) such as pentafluoroethyl methyl ether (CF 3 CF 2 OCH 3 , HFE-245mc) .
- CFC chlorofluorocarbon
- FC trichlorofluoromethane
- FC fluorocarbon
- HCFC hydrochlorofluorocarbon
- CH 2 Fluorocarbons such as hydrofluorocarbon (HFC) such as CF 3 , HFC-245fa, PFP) and hydrofluoroether (HFE) such as pentafluoroethyl methyl
- 1,1,1,3,3-pentafluoropropane vapour pressure at 23 ° C., 0.14 MPa, from the viewpoint of excellent filling properties at an atmospheric temperature of 20 ° C. to 25 ° C. in the mold contact process. Boiling point 15 ° C.), trichlorofluoromethane (vapor pressure 0.1056 MPa at 23 ° C., boiling point 24 ° C.), and pentafluoroethyl methyl ether are preferred. Furthermore, 1,1,1,3,3-pentafluoropropane is particularly preferable from the viewpoint of excellent safety.
- Condensable gas may be used alone or in combination of two or more. These condensable gases may be used by mixing with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon.
- the non-condensable gas mixed with the condensable gas is preferably helium from the viewpoint of filling properties. Helium can pass through the mold 205. Therefore, the recesses of the fine pattern formed on the mold 205 in the mold contact process are filled with gas (condensable gas and helium) in the atmosphere together with the curable composition (A1) 202 and / or (A2) 203. When this occurs, the condensable gas liquefies and helium passes through the mold 205.
- irradiation light 206 is irradiated through a mold 205 to a mixed layer formed by partially mixing the curable composition (A1) 202 and the curable composition (A2) 203.
- the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205 is irradiated with the irradiation light 206 through the mold 205.
- the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205 is cured by the irradiated light 206 to be a cured film 207 having a pattern shape.
- the irradiation light 206 applied to the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205 is the sensitivity of the curable compositions (A1) 202 and (A2) 203. It is selected according to the wavelength. Specifically, it is preferable to appropriately select and use ultraviolet light having a wavelength of 150 nm to 400 nm, X-rays, electron beams, and the like.
- the irradiation light 206 is particularly preferably ultraviolet light.
- ultraviolet light is because many commercially available curing aids (photopolymerization initiators) are sensitive to ultraviolet light.
- light sources that emit ultraviolet light include high pressure mercury lamps, ultrahigh pressure mercury lamps, low pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F 2.
- an excimer laser etc. are mentioned, an ultrahigh pressure mercury lamp is especially preferable.
- the number of light sources used may be one or plural.
- the irradiation may be performed on the entire surface of the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205, or may be performed only on a partial region. Good.
- the light irradiation may be intermittently performed a plurality of times on the entire region on the substrate 201, or the entire region may be continuously irradiated.
- the component that is a photoinitiator of the curable composition (A2) 203 ( b2) is also transferred to the curable composition (A1) 202, and the curable composition (A1) 202 obtains photosensitivity, so that both the curable compositions (A1) 202 and (A2) 203 are irradiated.
- the cured film 207 having a pattern shape is cured by the irradiation light 206.
- the cured film 207 includes a 2017 containing a large amount of the curable composition (A1) 202 and a cured film 2072 containing a large amount of the curable composition (A2) 203.
- the curable composition (A1) 202 has substantially no photoreactivity.
- the curable composition (A1) 202 is cured by setting the blending ratio of the component (b1) to less than 0.1% by weight with respect to the total weight of the component (a1), the component (b1), and the component (c1).
- the curable composition (A1) 202 has substantially no photoreactivity, and the curable composition (A1) 202 laminated outside the shot is irradiated with the irradiation light 206 leaked out of the shot region. The problem of curing can be prevented.
- the cured film 207 having a pattern shape is separated from the mold 205.
- this step release step
- the cured film 207 having a pattern shape is separated from the mold 205, and the fine pattern formed on the mold 205 in the step (4) (light irradiation step).
- the cured film 207 having a pattern shape that becomes a reverse pattern is obtained in a self-supporting state.
- a cured film remains also in the recessed part of the uneven
- a curable composition (A2) is obtained by including a component (c2) which is a surfactant for reducing the amount of an internal additive release agent mainly composed of a fluorosurfactant.
- the cured film 2072 containing a large amount of 203 and the cured film 2071 containing a large amount of the curable composition (A1) 202 are not damaged, and a desired pattern is formed. Further, the damaged cured film 2071 ′′ does not remain in the mold 205 and does not affect the next shot.
- the method of separating the cured film 207 having a pattern shape from the mold 205 is not particularly limited as long as a part of the cured film 207 having the pattern shape is not physically damaged when being separated, and various conditions are not particularly limited.
- the substrate 201 substrate to be processed
- the mold 205 may be fixed and the substrate 201 may be moved away from the mold 205 to be peeled off.
- both of them may be peeled by pulling in the opposite direction.
- a cured film 207 having a desired uneven pattern shape (a pattern shape due to the uneven shape of the mold 205) at a desired position is obtained. be able to.
- the curable composition (A1) 202 is collectively laminated on most of the surface of the substrate 201 in the step (1), and the steps (2) to (5).
- a repeating unit (shot) consisting of can be repeated a plurality of times on the same substrate. Further, the steps (1) to (5) may be repeated a plurality of times on the same substrate.
- the repeating unit (shot) consisting of step (1) to step (5) or step (2) to step (5) a plurality of times, a plurality of desired irregularities are formed at a desired position on the substrate 201 (substrate to be processed).
- a cured film 207 having a pattern shape (a pattern shape resulting from the uneven shape of the mold 205) can be obtained.
- the substrate 201 (substrate to be processed) or a layer to be processed on the substrate 201 (substrate to be processed) is etched. It can be processed into a pattern using processing means. Further, after a layer to be processed is further formed on the cured film 207 having a pattern shape, pattern transfer may be performed using a processing means such as etching. In this way, a circuit structure based on the pattern shape of the cured film 207 having a pattern shape can be formed on the substrate 201. Thereby, the circuit board utilized by a semiconductor element etc. can be manufactured.
- circuit board by connecting the circuit board and a circuit control mechanism of the circuit board, electronic devices such as a display, a camera, and a medical device can be formed.
- electronic devices such as a display, a camera, and a medical device can be formed.
- the semiconductor element here include LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, and NAND flash.
- a cured film 207 having a pattern shape is produced through steps (1) to (5), and pattern transfer is performed using a processing means such as etching to produce a quartz imprint mold. Quartz replicas (mold replicas) can also be produced.
- Imprint pretreatment coating material and imprint resist set Another aspect of the present invention described above is to form a liquid film as a pretreatment coating on a substrate and apply imprint resist droplets to the liquid film to promote the spread of droplet components in the substrate surface direction.
- An imprint pretreatment coating material is provided.
- the present invention forms a liquid film as a pretreatment coating on a substrate and applies liquid droplets made of a curable component (A2) to the liquid film, thereby spreading the liquid droplet component in the substrate surface direction.
- An imprint pretreatment coating material comprising a promoting curable component (A1),
- the imprint pretreatment coating material contains at least 0.5% by weight or more of a component (c1) that is a surfactant, and the component (c1) is a component (c2) that is a surfactant contained in the droplets.
- the imprint pretreatment coating material characterized by not changing the surface tension more than
- the component (c1) that is a surfactant that does not significantly change the surface tension is preferably such that the imprint pretreatment coating material containing the component (c1) that is the surfactant satisfies the formula (1). . ⁇ 5% ⁇ ⁇ ( ⁇ 1 ⁇ 2 ) / ⁇ 1 ⁇ ⁇ 5% (1)
- ⁇ 1 represents the surface tension of the imprint pretreatment coating material at 25 ° C.
- ⁇ 2 has the same composition as the imprint pretreatment coating material except that it does not contain a surfactant. Represents the surface tension of the composition for use at 25 ° C.
- the surface tension of the imprint pretreatment coating is higher than the surface tension of the droplet to which the surface tension is applied.
- the surface tension of the composition of the imprint pretreatment coating material excluding the solvent is higher than the surface tension of the composition of the imprint resist component excluding the solvent.
- the combination in which the difference between the surface tension of the composition of the imprint pretreatment coating material excluding the solvent and the surface tension of the composition of the imprint resist component excluding the solvent is 1 mN / m to 25 mN / m It is more preferable that it is a set.
- Another aspect of the present invention provides a suitable substrate pretreatment method for imprinting by coating a substrate with an imprint pretreatment coating material.
- the present invention includes a pattern forming method for forming a pattern on a substrate.
- a pattern forming method for forming a pattern on a substrate.
- Example 1 (1) Preparation of curable composition (A1-1) Component (a1), component (b1), component (c1) and component (d1) shown below were blended, and this was added to an ultra high molecular weight of 0.2 ⁇ m. The mixture was filtered through a polyethylene filter to prepare a curable composition (A1-1) of Example 1.
- Component (a1) Total 94 parts by weight Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: IB-XA): 9 parts by weight Benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160) : 38 parts by weight Neopentyl glycol diacrylate (trade name: NP-A, manufactured by Kyoeisha Chemical Co., Ltd.): 47 parts by weight (1-2) Component (b1): Total 0 parts by weight Component (b1) was not added.
- Component (c1) 1.1 parts by weight in total Polyoxyethylene stearyl ether (EO 5 mol adduct) (manufactured by Aoki Yushi Kogyo, trade name: BLAUNON SR-705): 1.1 parts by weight (1- 4)
- Component (d1) 33,000 parts in total Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry, abbreviation PGMEA): 33000 parts by weight
- the surface tension of the composition of the curable composition (A1-1) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- curable composition (A2-1) Component (a2), component (b2), component (c2) and component (d2) shown below were blended, and this was added to an ultra high molecular weight of 0.2 ⁇ m. The mixture was filtered through a polyethylene filter to prepare a curable composition (A2-1) of Example 1.
- Component (a2) Total 94 parts by weight Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: IB-XA): 9 parts by weight Benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160) : 38 parts by weight Neopentyl glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: NP-A): 47 parts by weight (3-2)
- a curable composition (A1-1) is coated on a silicon substrate using a spin coater to form a film of the curable composition (A1-1) having a thickness of about 5 to 10 nm. Obtainable.
- 1 pL droplets of the curable composition (A2-1) can be discretely arranged using an inkjet method.
- the amount of droplets is, for example, such that the average thickness of the cured film is about 50 nm.
- the surface tension of the curable composition (A1-1) disposed in the lower layer is higher than the surface tension of the curable composition (A2-1) dropped on the upper layer, the Marangoni effect appears.
- the expansion (pre-spreading) of the droplets of the curable composition (A2-1) is rapid.
- the curable composition (A1-1) and the curable composition (A2-1) are mixed, and the component that is a photoinitiator from the curable composition (A2-1) ( When b2) shifts to the curable composition (A1-1), the curable composition (A1-1) also acquires photopolymerizability.
- the mixture of the curable composition (A1-1) and the curable composition (A2-1) is cured well.
- curable composition (A1-1) containing 0.5% by weight or more of hydrocarbon surfactant and curable composition (A2-1) containing 0.5% by weight or more of fluorosurfactant
- curable composition (A1-1) containing 0.5% by weight or more of hydrocarbon surfactant
- curable composition (A2-1) containing 0.5% by weight or more of fluorosurfactant
- Example 2 Curable composition (A1-2) Component (a1), component (b1), component (c1) and component (d1) shown below are blended, and this is added to a 0.2 ⁇ m ultrahigh molecular weight polyethylene. The mixture was filtered through a filter made to prepare the curable composition (A1-2) of Example 2. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1. (1-2) Component (b1): Total 0 parts by weight The same as in Example 1.
- Component (c1) 1.1 parts by weight in total Polyoxyethylene stearyl ether (EO 15 mol adduct) (manufactured by Aoki Yushi Kogyo, trade name: BLAUNON SR-715): 1.1 parts by weight (1- 4)
- Component (d1) 33,000 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-2) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- Curable composition (A2-2) The same composition as in Example 1 was used as the curable composition (A2-2).
- Photo-nanoimprint process As in Example 1, the surface tension of the curable composition (A1-2) disposed in the lower layer is the surface of the curable composition (A2-2) dropped onto the upper layer. Since it is higher than the tension, the Marangoni effect appears, and the expansion (pre-spread) of the droplets of the curable composition (A2-2) is rapid.
- the mixture of the curable composition (A1-2) and the curable composition (A2-2) is cured well in the light irradiation step.
- a curable composition (A1-2) containing 0.5% by weight or more of a hydrocarbon surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-2) containing 0.5% by weight or more of a hydrocarbon surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-2) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 3 Curable composition (A1-3) Component (a1), component (b1), component (c1) and component (d1) shown below are blended, and this is added to an ultrahigh molecular weight polyethylene of 0.2 ⁇ m. The mixture was filtered through a filter made to prepare a curable composition (A1-3) of Example 3. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1. (1-2) Component (b1): Total 0 parts by weight The same as in Example 1.
- Component (c1) 1.1 parts by weight in total Polyoxyethylene stearyl ether (EO 30 mol adduct) (manufactured by Aoki Yushi Kogyo, trade name: BLAUNON SR-730): 1.1 parts by weight (1- 4)
- Component (d1) 33,000 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-3) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- the mixture of the curable composition (A1-3) and the curable composition (A2-3) is cured well in the light irradiation step.
- a curable composition (A1-3) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-3) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-3) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 4 Curable composition (A1-4) Component (a1), component (b1), component (c1) and component (d1) shown below are blended, and this is added to a 0.2 ⁇ m ultrahigh molecular weight polyethylene. The mixture was filtered through a filter made to prepare the curable composition (A1-4) of Example 4. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1. (1-2) Component (b1): Total 0 parts by weight The same as in Example 1.
- Component (c1) 1.1 parts by weight in total polyoxyethylene stearyl ether (EO 50 mol adduct) (manufactured by Aoki Yushi Kogyo, trade name: BLAUNON SR-750): 1.1 parts by weight (1- 4)
- Component (d1) 33,000 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-4) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- Curable composition (A2-4) The same composition as in Example 1 was used as the curable composition (A2-4).
- the mixture of the curable composition (A1-4) and the curable composition (A2-4) is cured well in the light irradiation step.
- a curable composition (A1-4) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-4) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-4) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 5 Curable composition (A1-5) Component (a1), component (b1), component (c1) and component (d1) shown below are blended, and this is added to an ultrahigh molecular weight polyethylene of 0.2 ⁇ m. The mixture was filtered through a filter made to prepare a curable composition (A1-5) of Example 5. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1. (1-2) Component (b1): Total 0 parts by weight The same as in Example 1.
- Component (c1) 1.1 parts by weight in total Nonionic alkyl surfactant (manufactured by Aoki Yushi Kogyo, trade name: BLAUNON SA-30 / 70 2000R molecular weight 2000): 1.1 parts by weight (1 -4)
- Component (d1) 33,000 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-5) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- the mixture of the curable composition (A1-5) and the curable composition (A2-5) is cured well in the light irradiation step.
- a curable composition (A1-5) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-5) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-5) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 6 Curable composition (A1-6) Component (a1), component (b1), component (c1), and component (d1) shown below are blended, and this is added to a 0.2 ⁇ m ultrahigh molecular weight polyethylene. The mixture was filtered through a filter made to prepare a curable composition (A1-6) of Example 6. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1. (1-2) Component (b1): Total 0 parts by weight The same as in Example 1.
- Component (c1) 1.1 parts by weight in total Nonionic alkyl surfactant (manufactured by Aoki Yushi Kogyo, trade name: BLAUNON SA-50 / 50 1000R molecular weight 1000): 1.1 parts by weight (1 -4)
- Component (d1) 33,000 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-6) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- Curable composition (A2-6) The same composition as in Example 1 was used as the curable composition (A2-6).
- Photo-nanoimprint process As in Example 1, the surface tension of the curable composition (A1-6) disposed in the lower layer is the surface of the curable composition (A2-6) dropped onto the upper layer. Since it is higher than the tension, the Marangoni effect appears, and the expansion (pre-spread) of the droplets of the curable composition (A2-6) is rapid.
- the mixture of the curable composition (A1-6) and the curable composition (A2-6) is cured well in the light irradiation step.
- a curable composition (A1-6) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-6) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-6) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 7 Curable composition (A1-7) Component (a1), component (b1), component (c1) and component (d1) shown below are blended, and this is added to a 0.2 ⁇ m ultrahigh molecular weight polyethylene. The mixture was filtered through a filter made to prepare a curable composition (A1-7) of Example 7. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1. (1-2) Component (b1): Total 0 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-7) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- Curable composition (A2-7) The same composition as in Example 1 was used as the curable composition (A2-7).
- the mixture of the curable composition (A1-7) and the curable composition (A2-7) is cured well in the light irradiation step.
- a curable composition (A1-7) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-7) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-7) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 8 (1) Curable composition (A1-8) Component (a1), component (b1), component (c1) and component (d1) shown below are blended, and this is added to a 0.2 ⁇ m ultrahigh molecular weight polyethylene. The mixture was filtered through a filter made to prepare the curable composition (A1-8) of Example 8. (1-1) Component (a1): Total 94 parts by weight The same as in Example 1.
- Component (b1) Total 3 parts by weight Irgacure 651 (manufactured by BASF, abbreviation: I.651): 3 parts by weight (1-3)
- Component (c1) Total 0.9 parts by weight Polyoxyethylene stearyl ether (EO 15 mol adduct) (Aoki Yushi Kogyo Co., Ltd., trade name: BLAUNON SR-715): 0.9 parts by weight (1-4)
- Component (d1) 33,000 parts by weight The same as in Example 1.
- Curable composition (A2-8) The same composition as in Example 1 was used as the curable composition (A2-8).
- the mixture of the curable composition (A1-8) and the curable composition (A2-8) is cured well.
- a curable composition (A1-8) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-8) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-8) contains substantially the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Example 9 (1) to (2) Curable composition (A1-9) The same composition as in Example 2 was used as the curable composition (A1-9).
- curable composition (A2-9) Component (a2), component (b2), component (c2) and component (d2) shown below were blended, and this was added to an ultrahigh molecular weight of 0.2 ⁇ m. The mixture was filtered through a polyethylene filter to prepare a curable composition (A2-9) of Example 9.
- Component (a2) Total 94 parts by weight Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: IB-XA): 61.6 parts by weight (2-Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (manufactured by Osaka Organic Chemicals, trade name Medol 10): 10 parts by weight 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemicals, Abbreviation HDODA): 22.4 parts by weight (3-2)
- Component (d2) Total 0 parts by weight The same as in Example 1.
- the mixture of the curable composition (A1-9) and the curable composition (A2-9) is cured well in the light irradiation step.
- a curable composition (A1-9) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant Similar to Example 1, a curable composition (A1-9) containing 0.5% by weight or more of a hydrocarbon-based surfactant and a curable composition containing 0.5% by weight or more of a fluorosurfactant.
- the cured film made of the mixture of (A2-9) contains the same amount of the release agent, a desired pattern is formed without damaging the cured film. Further, the cured film does not remain in the mold, and the next shot is not affected. The effect by not containing an adhesion improving agent is also the same.
- Curable composition (A2-0 ′) The same composition as in Example 1 was used as the curable composition (A2-0 ′).
- the curable composition (A1-1 ′) does not contain the component (c1) which is a surfactant as an internal release agent, the calculation of the formula (1) cannot be performed.
- Curable composition (A2-1 ′) The same composition as in Example 1 was used as the curable composition (A2-1 ′).
- the mixture of the curable composition (A1-1 ′) and the curable composition (A2-1 ′) is cured well in the light irradiation step.
- curable composition (A1-2 ′) Component (a1), component (b1), component (c1) and component (d1) shown below were blended, and this was added to an ultrahigh 0.2 ⁇ m The mixture was filtered through a molecular weight polyethylene filter to prepare a curable composition (A1-2 ′) of Comparative Example 2.
- Component (a1) Total 94 parts by weight The same as in Example 1.
- Component (b1) Total 0 parts by weight The same as in Example 1.
- Component (c1) Total 1.1 parts by weight Pentadecaethylene glycol mono 1H, 1H, 2H, 2H-perfluorooctyl ether (F (CF 2 ) 6 CH 2 CH 2 (OCH 2 CH 2 ) 15 OH) (manufactured by DIC, abbreviated as DEO-15): 1.1 parts by weight (1-4) Component (d1): 33,000 parts by weight The same as in Example 1.
- the surface tension of the composition of the curable composition (A1-2 ′) excluding the component (d1) and the component (c1) as the solvent was measured and found to be 32.6 mN / m.
- Curable composition (A2-2 ′) The same composition as in Example 1 was used as the curable composition (A2-2 ′).
- Photo-nanoimprint process As in Example 1, the surface tension of the curable composition (A1-2 ′) disposed in the lower layer is such that the curable composition (A2-2 ′) is dropped onto the upper layer. The surface tension is lower, the Marangoni effect does not appear, and the expansion (pre-spread) of droplets of the curable composition (A2-2 ′) is slow.
- the mixture of the curable composition (A1-2 ′) and the curable composition (A2-2 ′) is cured well in the light irradiation step.
- the curable composition (A1-1 ′) and the curable composition (A2-1 ′) are both internally added mold release agents.
- mold release defects are observed. A small number of patterns can be formed. Further, the cured film remains in the mold and does not affect the next shot. However, the productivity and accuracy of the optical nanoimprint process are not compatible.
- curable composition (A1-3 ′) Component (a1), component (b1), component (c1) and component (d1) shown below were blended, and this was added to an ultrahigh 0.2 ⁇ m The mixture was filtered through a molecular weight polyethylene filter to prepare a curable composition (A1-3 ′) of Comparative Example 3.
- Component (a1) 100 parts by weight in total 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemicals, abbreviated as HDODA): 100 parts by weight (1-2)
- Component (b1) 0 parts by weight in total Component (b1) was not added.
- Component (c1) Total 0 parts by weight Component (c) was not added.
- Component (d1) 33,000 parts in total Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- curable composition (A1-3 ′) In the same manner as in Example 1, curable composition (A1-3 ′) excluding component (d1) which is a solvent at 25 ° C. It was 34.9 mN / m when the surface tension of the composition of the component was measured.
- the curable composition (A1-3 ′) does not contain the component (c1) which is a surfactant as an internal release agent, the calculation of the formula (1) cannot be performed.
- Curable composition (A2-3 ′) The same composition as in Example 1 was used as the curable composition (A2-3 ′).
- the mixture of the curable composition (A1-3 ′) and the curable composition (A2-3 ′) is cured well in the light irradiation step.
- a cured film composed of a mixture of the curable composition (A1-1 ′) containing no internal addition type mold release agent and the curable composition (A2-1 ′) containing a fluorine-based surfactant is a mold release agent.
- the cured film not containing the agent comes into contact with the mold, a portion where the cured film is damaged is generated, and a desired pattern cannot be formed.
- the cured film remains in the mold and affects the next shot. The productivity and accuracy of the optical nanoimprint process are not compatible.
- the pre-spread evaluation is a relative evaluation based on Comparative Example 0. That is, if the speed is faster than that of Comparative Example 0, it is “fast”, and if it is the same speed as Comparative Example 0 or slower than Comparative Example 0, it is “slow”.
- the pre-spreads of Examples 1-9 and Comparative Examples 1 and 3 are faster due to the Marangoni effect than Comparative Example 0, i.e. not using the curable composition (A1).
- the evaluation of the release force is also a relative evaluation based on Comparative Example 0. That is, if the release force was the same as that of Comparative Example 0 or smaller than that of Comparative Example 0, “good” was set. In the case of a release force higher than that of Comparative Example 0, “bad” is set.
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Abstract
Description
基板201上に、液状の硬化性組成物(A1)202を積層する第一積層工程(1)(図2A及び2B)、
前記硬化性組成物(A1)202の層上に、硬化性組成物(A2)203の液滴を離散的に滴下して積層する第二積層工程(2)(図2C及び2D)、
パターンを有するモールド205と基板201の間に硬化性組成物(A1)202と硬化性組成物(A2)203が部分的に混合してなる混合層をサンドイッチする型接触工程(3)(図2E)、
前記混合層をモールド205側から照射光206を照射することにより硬化させる光照射工程(4)(図2F)、
モールド205を硬化後の硬化性組成物(パターン形状を有する硬化膜207)からなる層から引き離す離型工程(5)(図2G)、
を有する。
すなわち、溶剤である成分(d1)を除く硬化性組成物(A1)202の成分の組成物の表面張力が、溶剤である成分(d2)を除く硬化性組成物(A2)203の成分の組成物の表面張力より高いことが好ましい。型接触工程前に、後述するマランゴニ効果により硬化性組成物(A2)203のプレスプレッドが加速され(液滴が広範囲に広がり)、後述する型接触工程中のスプレッドに要する時間が短縮され、結果として充填時間が短縮されるためである。
前記硬化性組成物(A1)からなる層の上に、少なくとも重合性化合物である成分(a2)及び界面活性剤である成分(c2)を含む硬化性組成物(A2)の液滴を離散的に滴下する第二積層工程(2)、
パターンを有するモールドと前記基板の間に前記硬化性組成物(A1)及び前記硬化性組成物(A2)が部分的に混合してなる混合層をサンドイッチする型接触工程(3)、
前記混合層をモールド側から光を照射することにより硬化させる光照射工程(4)、
前記モールドを硬化後の前記混合層から引き離す離型工程(5)、
を該順に有するパターン形成方法であって、
前記硬化性組成物(A1)は界面活性剤である成分(c1)を、溶剤を除く前記硬化性組成物(A1)の成分の合計重量に対して少なくとも0.5重量%以上含有し、前記硬化性組成物(A2)は界面活性剤である成分(c2)を、溶剤を除く前記硬化性組成物(A2)の成分の合計重量に対して少なくとも0.5重量%以上含有し、
かつ、前記硬化性組成物(A1)の表面張力が前記硬化性組成物(A2)の表面張力よりも高いことを特徴とする。
本実施形態に係る硬化性組成物(A1)及び(A2)は、少なくとも重合性化合物である成分(a)を有する組成物である。本実施形態に係る硬化性組成物はさらに、光重合開始剤である成分(b)、非重合性化合物である成分(c)、溶剤である成分(d)を含有してもよい。
成分(a)は重合性化合物である。ここで、本明細書において重合性化合物とは、光重合開始剤である成分(b)から発生した重合因子(ラジカル等)と反応し、連鎖反応(重合反応)によって高分子化合物からなる膜を形成する化合物である。
成分(b)は、光重合開始剤である。
本実施形態に係る硬化性組成物(A1)及び(A2)は、前述した、成分(a)、成分(b)の他に、種々の目的に応じ、本発明の効果を損なわない範囲で、さらに非重合性化合物である成分(c)を含有することができる。このような成分(c)としては、(メタ)アクリロイル基などの重合性官能基を有さず、かつ、所定の波長の光を感知して上記重合因子(ラジカル)を発生させる能力を有さない化合物が挙げられる。例えば、増感剤、水素供与体、内添型離型剤、界面活性剤、酸化防止剤、ポリマー成分、密着改良剤、その他添加剤等が挙げられる。成分(c)として前記化合物を複数種類含有してもよい。
-5%≦{(γ1-γ2)/γ1}≦5% (1)
(式(1)において、γ1は、25℃における硬化性組成物(A1)の表面張力を表し、γ2は、25℃における評価用硬化性組成物(A1)の表面張力を表す。ここで、評価用硬化性組成物(A1)とは、界面活性剤である成分(c1)を含まない以外は硬化性組成物(A1)と同じ組成である組成物をいう。)
{(γ1-γ2)/γ1}<-5% (2)
(式(2)において、γ1は、25℃における硬化性組成物(A2)の表面張力を表し、γ2は、25℃における評価用硬化性組成物(A2)の表面張力を表す。ここで、評価用硬化性組成物(A2)とは、界面活性剤である成分(c2)を含まない以外は硬化性組成物(A2)と同じ組成である組成物をいう。)
本実施形態に係る硬化性組成物は、溶剤である成分(d)を含有していてもよい。成分(d)としては、成分(a)、成分(b)、成分(c)が溶解する溶剤であれば、特に限定はされない。好ましい溶剤としては常圧における沸点が80℃以上200℃以下の溶剤である。さらに好ましくは、エステル構造、ケトン構造、水酸基、エーテル構造のいずれかを少なくとも1つ有する溶剤である。具体的には、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、2-ヘプタノン、γ-ブチロラクトン、乳酸エチルから選ばれる単独、あるいはこれらの混合溶剤である。
本実施形態の硬化性組成物(A1)及び(A2)を調製する際には、各成分を所定の温度条件下で混合・溶解させる。具体的には、0℃以上100℃以下の範囲で行う。
本実施形態に係る硬化性組成物(A1)及び(A2)は液体であることが好ましい。なぜならば、後述する型接触工程において、硬化性組成物(A1)及び/または(A2)のスプレッド及びフィルが速やかに完了する、つまり充填時間が短いからである。
硬化性組成物(A1)及び(A2)の粘度を100mPa・s以下とすることにより、硬化性組成物(A1)及び(A2)をモールドに接触する際に、スプレッド及びフィルが速やかに完了する(非特許文献1)。つまり、本実施形態に係る硬化性組成物を用いることで、光ナノインプリント法を高いスループットで実施することができる。また、充填不良によるパターン欠陥が生じにくい。
本実施形態に係る硬化性組成物(A1)及び(A2)の表面張力は、溶剤である成分(d)を除く硬化性組成物(A1)及び(A2)の成分の組成物について25℃での表面張力が、5mN/m以上70mN/m以下であることが好ましい。また、より好ましくは、7mN/m以上50mN/m以下であり、さらに好ましくは、10mN/m以上40mN/m以下である。ここで、表面張力が高いほど、例えば5mN/m以上であると、毛細管力が強く働くため、硬化性組成物(A1)及び/または(A2)をモールドに接触させた際に、充填(スプレッド及びフィル)が短時間で完了する(非特許文献1)。
本発明においては、内添型離型剤としては、硬化性組成物(A1)には、表面張力を低減させない界面活性剤である成分(c1)として、主には炭化水素系界面活性剤を使用する。前述した式(1)を満たすものを使用するのが好ましい。硬化性組成物(A2)には、表面張力を低減させる界面活性剤である成分(c2)として、主にはフッ素系界面活性剤を使用する。そのため、溶剤(成分(d))を除く硬化性組成物(A1)の表面張力が、溶剤(成分(d))を除く硬化性組成物(A2)の表面張力より高く維持され、十分なマランゴニ効果が発揮される。
本実施形態に係る硬化性組成物(A1)及び(A2)の接触角は、溶剤である成分(d)を除く硬化性組成物(A1)及び(A2)の成分の組成物について、基板表面及びモールド表面の双方に対して0°以上90°以下であることが好ましい。接触角が90°より大きいと、モールドパターンの内部や基板-モールドの間隙において毛細管力が負の方向(モールドと硬化性組成物間の接触界面を収縮させる方向)に働き、充填しない。0°以上30°以下であることが特に好ましい。接触角が低いほど毛細管力が強く働くため、充填速度が速い(非特許文献1)。
本実施形態に係る硬化性組成物(A1)及び(A2)は、できる限り不純物を含まないことが好ましい。ここで記載する不純物とは、前述した成分(a)、成分(b)、成分(c)及び成分(d)以外のものを意味する。
次に、本実施形態に係るパターン形成方法について、図2A-2G並びに図4A及び4Bの模式断面図を用いて説明する。
基板201上に、前述の本実施形態の硬化性組成物(A1)202を積層する第一積層工程(1)、
前記硬化性組成物(A1)202の層上に、硬化性組成物(A2)203を積層する第二積層工程(2)、
パターンを有するモールド205と基板201の間に硬化性組成物(A1)202と硬化性組成物(A2)203が部分的に混合してなる混合層をサンドイッチする型接触工程(3)、
前記混合層をモールド205側から照射光206を照射することにより硬化させる光照射工程(4)、
モールド205を硬化後の硬化膜207からなる層から引き離す離型工程(5)、
を有する。
本工程(第一積層工程)では、図2A及び2Bに示す通り、前述した本実施形態に係る硬化性組成物(A1)202を基板201上に積層(塗布)して塗布膜を形成する。硬化性組成物(A1)202を基板201上に積層(塗布)して塗布膜を形成する際に、溶剤である成分(d1)は揮発し、基板201上には溶剤である成分(d1)を除いた硬化性組成物(A1)202の成分の組成物のみ残存する。
本工程(第二積層工程)では、図2C及び2Dに示す通り、硬化性組成物(A2)203の液滴を、前記硬化性組成物(A1)202の層上に離散的に滴下して配置することが好ましい。配置方法としてはインクジェット法が特に好ましい。硬化性組成物(A2)203の液滴は、モールド205上に凹部が密に存在する領域に対向する基板201上には密に、凹部が疎に存在する領域に対向する基板201上には疎に配置される。このことにより、後述する残膜を、モールド205上のパターンの疎密によらずに均一な厚さに制御することができる。
次に、図2Eに示すように、前工程(第一及び第二積層工程)で形成された硬化性組成物(A1)202及び硬化性組成物(A2)203が部分的に混合してなる液体の層にパターン形状を転写するための原型パターンを有するモールド205を接触させる。これにより、モールド205が表面に有する微細パターンの凹部に硬化性組成物(A1)202及び硬化性組成物(A2)203が部分的に混合してなる液体が充填(フィル)されて、モールド205の微細パターンに充填(フィル)された液膜となる。
次に、図2Fに示すように、硬化性組成物(A1)202及び硬化性組成物(A2)203が部分的に混合してなる混合層に対し、モールド205を介して照射光206を照射する。より詳細には、モールド205の微細パターンに充填された硬化性組成物(A1)202及び/または(A2)203に、モールド205を介して照射光206を照射する。これにより、モールド205の微細パターンに充填された硬化性組成物(A1)202及び/または(A2)203は、照射される照射光206によって硬化してパターン形状を有する硬化膜207となる。
次に、パターン形状を有する硬化膜207とモールド205と引き離す。本工程(離型工程)では、図2Gに示すように、パターン形状を有する硬化膜207とモールド205とを引き離し、工程(4)(光照射工程)において、モールド205上に形成された微細パターンの反転パターンとなるパターン形状を有する硬化膜207が自立した状態で得られる。なお、パターン形状を有する硬化膜207の凹凸パターンの凹部にも硬化膜が残存するが、この膜のことを残膜108と呼ぶこととする(図1Fの部分拡大部参照)。
上述した本発明の別の側面は、基板上に前処理コーティングとなる液膜を形成し、液膜に対しインプリントレジストの液滴を付与することで液滴成分の基板面方向の広がりを促進するインプリント前処理コーティング材料を提供するものである。
-5%≦{(γ1-γ2)/γ1}≦5% ‥‥‥(1)
(式(1)において、γ1は、インプリント前処理コーティング材料の25℃における表面張力を表し、γ2は、界面活性剤を含まない以外はインプリント前処理コーティング材料と同じ組成である評価用組成物の25℃における表面張力を表す。)
(1)硬化性組成物(A1-1)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例1の硬化性組成物(A1-1)を調製した。
(1-1)成分(a1):合計94重量部
イソボルニルアクリレート(共栄社化学製、商品名:IB-XA):9重量部
ベンジルアクリレート(大阪有機化学工業製、商品名:V#160):38重量部
ネオペンチルグリコールジアクリレート(共栄社化学製、商品名:NP-A):47重量部
(1-2)成分(b1):合計0重量部
成分(b1)は添加しなかった。
(1-3)成分(c1):合計1.1重量部
ポリオキシエチレンステアリルエーテル(EO5モル付加物)(青木油脂工業製、商品名:BLAUNON SR-705):1.1重量部
(1-4)成分(d1):合計33000重量部
プロピレングリコールモノメチルエーテルアセテート(東京化成工業製、略称PGMEA):33000重量部
自動表面張力計DY-300(協和界面化学製)を用い、白金プレートを用いたプレート法により、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-1)の成分の組成物の表面張力を測定したところ、33.1mN/mであった。なお、測定は、測定回数5回、白金プレートのプリウェット浸漬距離0.35mmの条件で行った。1回目の測定値を除いて、2回目から5回目の測定値の平均値を表面張力とした。
下記に示される成分(a2)、成分(b2)、成分(c2)、成分(d2)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例1の硬化性組成物(A2-1)を調製した。
(3-1)成分(a2):合計94重量部
イソボルニルアクリレート(共栄社化学製、商品名:IB-XA):9重量部
ベンジルアクリレート(大阪有機化学工業製、商品名:V#160):38重量部
ネオペンチルグリコールジアクリレート(共栄社化学製、商品名:NP-A):47重量部
(3-2)成分(b2):合計3重量部
Irgacure369(BASF製、略称:I.369):3重量部
(3-3)成分(c2):合計1.1重量部
ペンタデカエチレングリコールモノ1H,1H,2H,2H-パーフルオロオクチルエーテル(F(CF2)6CH2CH2(OCH2CH2)15OH)(DIC製、略称DEO-15):1.1重量部
(3-4)成分(d2):合計0重量部
成分(d2)は添加しなかった。
硬化性組成物(A1-1)と同様の方法で硬化性組成物(A2-1)の表面張力を測定したところ、29.1mN/mであった。
スピンコーターを用いて硬化性組成物(A1-1)をシリコン基板上に塗布することで、5~10nm程度の厚さの硬化性組成物(A1-1)の膜を得ることができる。
(1)硬化性組成物(A1-2)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例2の硬化性組成物(A1-2)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
ポリオキシエチレンステアリルエーテル(EO15モル付加物)(青木油脂工業製、商品名:BLAUNON SR-715):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-2)の成分の組成物の表面張力を測定したところ、32.9mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-2)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-2)の表面張力は、その上層に滴下される硬化性組成物(A2-2)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-2)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-3)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例3の硬化性組成物(A1-3)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
ポリオキシエチレンステアリルエーテル(EO30モル付加物)(青木油脂工業製、商品名:BLAUNON SR-730):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-3)の成分の組成物の表面張力を測定したところ、33.0mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-3)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-3)の表面張力は、その上層に滴下される硬化性組成物(A2-3)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-3)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-4)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例4の硬化性組成物(A1-4)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
ポリオキシエチレンステアリルエーテル(EO50モル付加物)(青木油脂工業製、商品名:BLAUNON SR-750):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-4)の成分の組成物の表面張力を測定したところ、32.9mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-4)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-4)の表面張力は、その上層に滴下される硬化性組成物(A2-4)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-4)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-5)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例5の硬化性組成物(A1-5)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
ノニオン型アルキル系界面活性剤(青木油脂工業製、商品名:BLAUNON SA-30/70 2000R 分子量2000):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-5)の成分の組成物の表面張力を測定したところ、33.1mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-5)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-5)の表面張力は、その上層に滴下される硬化性組成物(A2-5)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-5)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-6)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例6の硬化性組成物(A1-6)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
ノニオン型アルキル系界面活性剤(青木油脂工業製、商品名:BLAUNON SA-50/50 1000R 分子量1000):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-6)の成分の組成物の表面張力を測定したところ、32.9mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-6)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-6)の表面張力は、その上層に滴下される硬化性組成物(A2-6)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-6)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-7)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例7の硬化性組成物(A1-7)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
メチルポリエチレングリコールPluriol A760E(BASF製、商品名:Pluriol A760E):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-7)の成分の組成物の表面張力を測定したところ、32.5mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-7)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-7)の表面張力は、その上層に滴下される硬化性組成物(A2-7)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-7)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-8)について
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例8の硬化性組成物(A1-8)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計3重量部
Irgacure651(BASF製、略称:I.651):3重量部
(1-3)成分(c1):合計0.9重量部
ポリオキシエチレンステアリルエーテル(EO15モル付加物)(青木油脂工業製、商品名:BLAUNON SR-715):0.9重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-8)の成分の組成物の表面張力を測定したところ、34.4mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-8)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-8)の表面張力は、その上層に滴下される硬化性組成物(A2-8)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-8)の液滴の拡大(プレスプレッド)は速やかである。
(1)~(2)硬化性組成物(A1-9)について
実施例2と同様の組成物を硬化性組成物(A1-9)として用いた。
下記に示される成分(a2)、成分(b2)、成分(c2)、成分(d2)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、実施例9の硬化性組成物(A2-9)を調製した。
(3-1)成分(a2):合計94重量部
イソボルニルアクリレート(共栄社化学製、商品名:IB-XA):61.6重量部
(2-メチル-2-エチル-1,3-ジオキソラン-4-イル)メチルアクリレート(大阪有機化学製、商品名Medol10):10重量部
1,6-へキサンジオールジアクリレート(大阪有機化学製、略称HDODA):22.4重量部
(3-2)成分(b2):合計3重量部
Lucirin TPO(BASF製、略称L.TPO):3重量部
(3-3)成分(c2):合計1.1重量部
実施例1と同様とした。
(3-4)成分(d2):合計0重量部
実施例1と同様とした。
硬化性組成物(A1-1)と同様の方法で硬化性組成物(A2-9)の表面張力を測定したところ、26.1mN/mであった。
実施例1と同様に、下層に配置されている硬化性組成物(A1-9)の表面張力は、その上層に滴下される硬化性組成物(A2-9)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-9)の液滴の拡大(プレスプレッド)は速やかである。
(1)~(2)硬化性組成物(A1-0´)について
比較例0において、硬化性組成物(A1)は使用しなかった。
実施例1と同様の組成物を硬化性組成物(A2-0´)として用いた。
硬化性組成物(A2-0´)を固体表面である基板表面に直接滴下するとマランゴニ効果は発現しない。つまり、プレスプレッドの促進効果が得られず、硬化性組成物(A2-0´)の液滴の拡大は、本発明の実施例と比較して遅い。
(1)硬化性組成物(A1-1´)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、比較例1の硬化性組成物(A1-1´)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計0重量部
成分(c)は添加しなかった。
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-1´)の成分の組成物の表面張力を測定したところ、32.6mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-1´)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-1´)の表面張力は、その上層に滴下される硬化性組成物(A2-1´)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-1´)の液滴の拡大(プレスプレッド)は速やかである。
(1)硬化性組成物(A1-2´)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、比較例2の硬化性組成物(A1-2´)を調製した。
(1-1)成分(a1):合計94重量部
実施例1と同様とした。
(1-2)成分(b1):合計0重量部
実施例1と同様とした。
(1-3)成分(c1):合計1.1重量部
ペンタデカエチレングリコールモノ1H,1H,2H,2H-パーフルオロオクチルエーテル(F(CF2)6CH2CH2(OCH2CH2)15OH)(DIC製、略称DEO-15):1.1重量部
(1-4)成分(d1):合計33000重量部
実施例1と同様とした。
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-2´)の成分の組成物の表面張力を測定したところ、28.1mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-2´)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-2´)の表面張力は、その上層に滴下される硬化性組成物(A2-2´)の表面張力より低く、マランゴニ効果が発現せず、硬化性組成物(A2-2´)の液滴の拡大(プレスプレッド)は遅い。
(1)硬化性組成物(A1-3´)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)を配合し、これを0.2μmの超高分子量ポリエチレン製フィルタでろ過し、比較例3の硬化性組成物(A1-3´)を調製した。
(1-1)成分(a1):合計100重量部
1,6-へキサンジオールジアクリレート(大阪有機化学製、略称HDODA):100重量部
(1-2)成分(b1):合計0重量部
成分(b1)は添加しなかった。
(1-3)成分(c1):合計0重量部
成分(c)は添加しなかった。
(1-4)成分(d1):合計33000重量部
プロピレングリコールモノメチルエーテルアセテート(東京化成工業製、略称PGMEA):33000重量部
実施例1と同様の方法で、25℃における溶剤である成分(d1)を除く硬化性組成物(A1-3´)の成分の組成物の表面張力を測定したところ、34.9mN/mであった。
実施例1と同様の組成物を硬化性組成物(A2-3´)として用いた。
実施例1と同様に、下層に配置されている硬化性組成物(A1-3´)の表面張力は、その上層に滴下される硬化性組成物(A2-3´)の表面張力より高いので、マランゴニ効果が発現し、硬化性組成物(A2-3´)の液滴の拡大(プレスプレッド)は速やかである。
実施例1~9及び比較例0~3の組成表を表1及び表2に、実施例1~9及び比較例0~3の結果を表3にまとめて示す。
102 レジスト
104 液滴の拡がる方向を示す矢印
105 モールド
106 照射光
107 パターン形状を有する硬化膜
108 残膜
201 基板(被加工基板)
202 硬化性組成物(A1)
203 硬化性組成物(A2)
204 液滴の拡がる方向を示す矢印
205 モールド
206 照射光
207 硬化膜
2071 硬化性組成物(A1)を多く含む硬化膜
2072 硬化性組成物(A2)を多く含む硬化膜
2071´ 2071´ 破損した硬化膜
Claims (23)
- 基板の表面に、少なくとも重合性化合物である成分(a1)及び界面活性剤である成分(c1)を含む硬化性組成物(A1)からなる層を積層する第一積層工程(1)、
前記硬化性組成物(A1)からなる層の上に、少なくとも重合性化合物である成分(a2)及び界面活性剤である成分(c2)を含む硬化性組成物(A2)の液滴を離散的に滴下して積層する第二積層工程(2)、
パターンを有するモールドと前記基板の間に前記硬化性組成物(A1)及び前記硬化性組成物(A2)が部分的に混合してなる混合層をサンドイッチする型接触工程(3)、
前記混合層を前記モールド側から光を照射することにより硬化させる光照射工程(4)、
前記モールドを硬化後の前記混合層から引き離す離型工程(5)、
を該順に有するパターン形成方法であって、
前記硬化性組成物(A1)は前記界面活性剤である成分(c1)を、溶剤を除く前記硬化性組成物(A1)の成分の合計重量に対して少なくとも0.5重量%以上含有し、前記硬化性組成物(A2)は前記界面活性剤である成分(c2)を、溶剤を除く前記硬化性組成物(A2)の成分の合計重量に対して少なくとも0.5重量%以上含有し、
かつ、前記硬化性組成物(A1)の表面張力が前記硬化性組成物(A2)の表面張力よりも高いこと
を特徴とするパターン形成方法。 - 前記界面活性剤である成分(c1)を含有する前記硬化性組成物(A1)が式(1)を満たすことを特徴とする請求項1に記載のパターン形成方法。
-5%≦{(γ1-γ2)/γ1}≦5% ‥‥‥(1)
(式(1)において、γ1は、前記硬化性組成物(A1)の25℃における表面張力を表し、γ2は、前記界面活性剤である成分(c1)を含まない以外は前記硬化性組成物(A1)と同じ組成である評価用硬化性組成物の25℃における表面張力を表す。) - 前記界面活性剤である成分(c1)と前記界面活性剤である成分(c2)が同量(重量%)含有することを特徴とする請求項1または2に記載のパターン形成方法。
- 前記硬化性組成物(A1)は前記界面活性剤である成分(c1)を少なくとも0.9重量%以上含有することを特徴とする請求項1から3のいずれか1項に記載のパターン形成方法。
- 前記硬化性組成物(A1)は密着改良剤を、溶剤を除く前記硬化性組成物(A1)の成分の合計重量に対して少なくとも0.01重量%より少なく含有することを特徴とする請求項1から4のいずれか1項に記載のパターン形成方法。
- 溶剤を除く前記硬化性組成物(A1)の成分の組成物の粘度が1mPa・s以上1000mPa・s以下であり、かつ、溶剤を除く前記硬化性組成物(A2)成分の組成物の粘度が1mPa・s以上12mPa・s以下であることを特徴とする請求項1から5のいずれか1項に記載のパターン形成方法。
- 前記モールドの表面の材質が石英であることを特徴とする請求項1から6のいずれか1項に記載のパターン形成方法。
- 前記型接触工程が、凝縮性ガスを含む雰囲気下で行われることを特徴とする、請求項1から7のいずれか1項に記載のパターン形成方法。
- 前記型接触工程が、前記凝縮性ガスと非凝縮性ガスとの混合ガスの雰囲気下で行われることを特徴とする請求項8に記載のパターン形成方法。
- 前記非凝縮性ガスが、ヘリウムであることを特徴とする請求項9に記載のパターン形成方法。
- 前記凝縮性ガスが、1,1,1,3,3-ペンタフルオロプロパンであることを特徴とする請求項8から10のいずれか1項に記載のパターン形成方法。
- 請求項1から11のいずれか1項に記載のパターンの形成方法を有することを特徴とする加工基板の製造方法。
- 請求項1から11のいずれか1項に記載のパターンの形成方法を有することを特徴とする光学部品の製造方法。
- 請求項1から11のいずれか一項に記載のパターンの形成方法を有することを特徴とする石英モールドレプリカの製造方法。
- 前記パターンが、光硬化性組成物の硬化物によるナノサイズの凹凸パターンである、請求項1から11のいずれか一項に記載のパターン形成方法。
- 基板上に前処理コーティングとなる液膜を形成し、前記液膜に対し液滴を付与することで液滴成分の基板面方向の広がりを促進するインプリント前処理コーティング材料であって、
前記インプリント前処理コーティング材料は、界面活性剤である成分(c1)を少なくとも0.5重量%以上含有し、
前記成分(c1)は、前記液滴に含まれる界面活性剤である成分(c2)よりも表面張力を大きく変えないことを特徴とするインプリント前処理コーティング材料。 - 前記界面活性剤である成分(c1)を含有する前記インプリント前処理コーティング材料が式(1)を満たすことを特徴とする請求項16に記載のインプリント前処理コーティング材料。
-5%≦{(γ1-γ2)/γ1}≦5% ‥‥‥(1)
(式(1)において、γ1は、前記インプリント前処理コーティング材料の25℃における表面張力を表し、γ2は、前記界面活性剤である成分(c1)を含まない以外は前記インプリント前処理コーティング材料と同じ組成である評価用組成物の25℃における表面張力を表す。) - 前記インプリント前処理コーティング材料の表面張力が付与される前記液滴の表面張力よりも高い請求項16または17に記載のインプリント前処理コーティング材料。
- 請求項16から18のいずれか1項に記載のインプリント前処理コーティング材料と、前記インプリント前処理コーティング材料でコーティングされた基板に滴下するためのインプリントレジストと、を有するセット。
- 溶剤を除く前記インプリント前処理コーティング材料の成分の組成物の表面張力が、溶剤を除く前記インプリントレジストの成分の組成物の表面張力より高いことを特徴とする請求項19に記載のセット。
- 請求項19または20に記載のセットに用いるインプリントレジスト。
- 基板上に硬化性組成物を配置してインプリントを行うための前処理方法であって、請求項16から18のいずれか1項に記載のインプリント前処理コーティング材料を前記基板上にコーティングすることを特徴とする基板の前処理方法。
- 基板上にパターンを形成するためのパターン形成方法であって、請求項16から18のいずれか1項に記載のインプリント前処理コーティング材料がコーティングされた前記基板上にレジストを不連続に滴下する工程を有することを特徴とするパターン形成方法。
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JP6983757B2 (ja) | 2021-12-17 |
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US10845700B2 (en) | 2020-11-24 |
TW201736087A (zh) | 2017-10-16 |
TWI629161B (zh) | 2018-07-11 |
KR20180126030A (ko) | 2018-11-26 |
US20170285466A1 (en) | 2017-10-05 |
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