WO2017170625A1 - 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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- WO2017170625A1 WO2017170625A1 PCT/JP2017/012779 JP2017012779W WO2017170625A1 WO 2017170625 A1 WO2017170625 A1 WO 2017170625A1 JP 2017012779 W JP2017012779 W JP 2017012779W WO 2017170625 A1 WO2017170625 A1 WO 2017170625A1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229940066767 systemic antihistamines phenothiazine derivative Drugs 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- RLGKSXCGHMXELQ-ZRDIBKRKSA-N trans-2-styrylquinoline Chemical compound C=1C=C2C=CC=CC2=NC=1\C=C\C1=CC=CC=C1 RLGKSXCGHMXELQ-ZRDIBKRKSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
-
- 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
-
- 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
-
- 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 indicated by an arrow 104 indicating the direction of spread 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 the arrow 104 indicating the direction in which the droplet spreads (FIG. 1D). This phenomenon is called spread.
- the resist 102 is also filled into the recesses on the mold 105 by capillary action as indicated by the arrows 104 indicating the direction in which the droplets spread (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 substrate 101 is separated from the mold 105 (release step (4)). , FIG. 1F). By performing these steps, a photocured film 107 (FIG. 1F) having a predetermined pattern shape is formed on the substrate 101.
- SST-NIL short spread time nanoimprint technology
- a first lamination step (1) (FIGS. 2A and 2B) of laminating a liquid curable composition (A1) 202 on a substrate 201;
- a second lamination step (2) (FIGS.
- a series of process units from the second lamination process (2) to the release process (5) is referred to as “shot”, and the mold 205 is in contact with the curable compositions (A1) 202 and (A2) 203.
- a region where a pattern is formed on the substrate 201 is referred to as a “shot region”.
- the droplets of the curable composition (A2) 203 that are dropped in a discrete manner are indicated by arrows 204 indicating the direction in which the droplets spread on the liquid film of the curable composition (A1) 202. Therefore, the filling time is short and the throughput is high.
- the detailed mechanism of SST-NIL will be described later.
- Steps (1) to (3) in FIGS. 3A to 3C correspond to the second stacking step to the release step in FIG. 2C-2G
- step (4) in FIG. 3D corresponds to the second stacking step of the subsequent shot.
- the curable composition (A1) 302 is laminated on the substrate 301 over an area larger than the shot region, for example, the entire surface of the substrate 301 using, for example, a spin coating method.
- the curable composition (A2) 303 is limited to the first shot region 304 and is discretely stacked using, for example, an inkjet method (step (1), FIG. 3A).
- An atmosphere control gas 307 is blown from the periphery of the mold 308 in order to drive out oxygen that inhibits photocuring by irradiating the irradiation light 306 through the mold contact process to the light irradiation process (process (2), FIG. 3B). . At this time, the atmosphere control gas 307 is also blown to the curable composition (A1) 302 laminated outside the first shot region 304 such as the second shot region 305.
- the droplet of the curable composition (A2) 303 dropped in the region 309 (step (3), FIG. 3C) to which the atmosphere control gas 307 was blown. It was found that the enlargement of 310 was particularly fast (step (4), FIG. 3D). That is, the present inventors have found a problem that a uniform pattern cannot be formed due to the distribution of droplet expansion speed in the second shot region 305.
- An object of the present invention is to provide an SST-NIL technology capable of forming a uniform pattern on a substrate with high throughput.
- a first laminate is formed by laminating a layer made of a curable composition (A1) containing at least a component (a1) which is a polymerizable compound and a component (d1) which is a solvent on the surface of a substrate.
- Step (1) Second laminating step of laminating droplets of the curable composition (A2) containing at least the component (a2) which is a polymerizable compound on the layer composed of the curable composition (A1).
- a pattern forming method having The content of the component (d1) which is a solvent in the curable composition (A1) is 90% by weight or more, The content of the component (d1) that is a solvent in the curable composition (A1) in the second lamination step (2) is 10% by weight or less, The surface tension of the component (d1) as the solvent is lower than the surface tension of the composition of the component of the curable composition (A1) excluding the component (d1) as the solvent.
- a pattern forming method having high throughput and excellent uniformity can be provided.
- the curable composition (A1) according to this embodiment is a composition having at least a component (a1) that is a polymerizable compound and a component (d1) that is a solvent.
- the curable composition (A1) according to this embodiment may further contain a component (b1) that is a photopolymerization initiator and a component (c1) that is a non-polymerizable compound.
- the curable composition (A2) according to this embodiment is a composition having at least a component (a2) that is a polymerizable compound.
- the curable composition (A2) according to this embodiment may further contain a component (b2) that is a photopolymerization initiator, a component (c2) that is a non-polymerizable compound, and a component (d2) that is a solvent.
- a cured film means the film
- the shape of a cured film is not specifically limited, You may have a pattern shape on the surface.
- each component will be described in detail.
- 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. Examples of such a polymerizable compound include a radical polymerizable compound.
- 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 one or more acryloyl groups or methacryloyl groups, 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 radically polymerizable compound is composed of a plurality of types of compounds having one or more acryloyl groups or methacryloyl groups, it is preferable to include a monofunctional (meth) acryl monomer and a polyfunctional (meth) acryl monomer. This is because a cured film having high mechanical strength can be obtained by combining a monofunctional (meth) acrylic monomer and a polyfunctional (meth) acrylic monomer.
- 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 generates the polymerization factor (radical) by sensing light of a predetermined wavelength.
- 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.
- the component (b) may be composed of one kind of photopolymerization initiator or may be composed of a plurality of kinds 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.
- a component (b) is an acyl phosphine oxide type
- 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 in the curable compositions (A1) and (A2) of the component (b) that is the photopolymerization initiator is the total weight of the component (a), the component (b), and the component (c) described later, that is, the solvent. It is good in it being 0.1 to 50 weight% with respect to the total weight of the component of curable composition (A1) or (A2) except a certain component (d). Further, it is preferably 0.1% by weight or more and 20% by weight or less, and more preferably 1% by weight or more and 10% by weight or less.
- the curing rate of the composition is increased and the reaction efficiency is increased. Can be improved. Further, by setting the blending ratio of the component (b) to 50% by weight or less with respect to the total weight of the component (a), the component (b), and the component (c), the cured film obtained has a certain mechanical strength. It can be set as the cured film which has.
- 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, and other additives. You may contain multiple types of the said compound as a component (c).
- a sensitizer is a compound added as appropriate for the purpose of promoting the polymerization reaction or improving the reaction conversion rate.
- 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 is an energy transfer, an electron transfer, etc. from the sensitizing dye of an excited state to the component (b) which is a photoinitiator.
- 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.
- a sensitizer may be used individually by 1 type and may be used in mixture of 2 or more types.
- 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 more reactive radical. 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 additive releasing agent can be added to the curable composition.
- the internally added type means that it is added to the curable composition in advance before the step of arranging the curable composition.
- surfactants such as silicone surfactants, fluorine surfactants, and hydrocarbon surfactants can be used.
- the internally added mold release agent is not polymerizable.
- Fluorosurfactants include polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having a perfluoroalkyl group, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyether, etc. 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).
- the internally added mold release agent may be a hydrocarbon surfactant.
- the hydrocarbon-based surfactant include an alkyl alcohol polyalkylene oxide adduct obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms.
- the alkyl alcohol polyalkylene oxide adduct 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.
- 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 blending ratio of the component (c), which is a non-polymerizable compound, in the curable compositions (A1) and (A2) is the total weight of the component (a), the component (b), and the component (c) described later, that is, the solvent. It is good in it being 0 to 50 weight% with respect to the total weight of the component of the curable composition (A1) and (A2) except a certain component (d). Further, it is preferably 0.1% by weight or more and 50% by weight or less, and more preferably 0.1% by weight or more and 20% by weight or less. Curing the resulting cured film with a certain degree of mechanical strength by adjusting the blending ratio of component (c) to 50% by weight or less with respect to the total weight of component (a), component (b) and component (c) It can be a membrane.
- the curable composition (A1) contains a component (d1) that is a solvent. 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.
- the film thickness of the curable composition (A1) is also preferably about 1 nm or more and 100 nm or less. Therefore, the content of the component (d1) as the solvent in the curable composition (A1) is preferably 90% by weight or more and 99.99% by weight or less, and particularly preferably 99% by weight or more and 99.9% by weight or less. .
- the component (d1) which is a solvent of the curable composition (A1) As the component (d1) which is a solvent of the curable composition (A1), the component (a1), the component (b1) and the component (c1) are dissolved, and the component (a1), the component (b1) and the component (c1) ), That is, a solvent having a surface tension lower than that of the component of the curable composition (A1) excluding the component (d1) which is a solvent.
- a more preferable solvent is a solvent having a boiling point of 80 ° C. or higher and 200 ° C. or lower at normal pressure.
- it is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure.
- it is a single solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, and ethyl lactate, or a mixed solvent containing at least one of these.
- the curable composition (A2) according to this embodiment may also contain a component (d2) that is a solvent.
- the component (d2) added to the curable composition (A2) is not particularly limited as long as it is a solvent in which the component (a2), the component (b2), and the component (c2) 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.
- it is a single solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, and ethyl lactate, or a mixed solvent containing at least one of these.
- 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 composition of the curable composition (A1) excluding the component (d1) which is the solvent 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 curable composition (A2) excluding the component (d2) that is the solvent according to the present 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.
- Non-Patent Document 1 Non-Patent Document 1
- the optical nanoimprint method can be performed with high throughput. Also, pattern defects due to poor filling are less likely to occur.
- the viscosity is 1 mPa ⁇ s or more
- uneven coating is less likely to occur 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 at 23 ° C. of the components of the curable compositions (A1) and (A2) excluding the component (d) which is a solvent 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 the cured film obtained by hardening
- curing a curable composition turns into a cured film which has surface smoothness by setting surface tension to 70 mN / m or less.
- 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 the 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 surface tension of the film of the curable composition (A1) is higher than the surface tension of the curable composition (A2). It is preferably 2 mN / m or higher.
- the inventors of the present invention have found that the component (d1), which is a solvent remaining in the film of the applied curable composition (A1), greatly affects the Marangoni effect.
- a solvent having a low surface tension is used for the component (d1), which is the solvent of the present invention, for spin coating uniformity. If the component (d1), which is a solvent, remains in the film of the curable composition (A1), the surface tension of the film is low and the Marangoni effect is not sufficiently exhibited.
- the present inventors have come to the conclusion that the residual solvent (d1) in the applied curable composition (A1) should be reduced in advance. According to the present invention, a difference in Marangoni effect is small between a region where the atmosphere control gas 307 is sprayed and a region where the atmosphere control gas 307 is not sprayed, and a uniform pattern can be formed.
- 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 viscosity, surface tension, and contact angle of the curable compositions (A1) and (A2) according to this embodiment can be changed by adding the component (d) as a solvent, but the component (d ) Prevents the curing of the curable composition. Therefore, in this embodiment, it is preferable to set the viscosity, surface tension, and contact angle of the composition of the curable compositions (A1) and (A2) excluding the component (d) as a solvent to predetermined values. .
- 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. Therefore, it is preferable that the curable composition which concerns on this embodiment is obtained through the refinement
- 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 cured film 207 made of the curable composition 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.
- each step will be described.
- First lamination step (1) In this step (first lamination step), as shown in FIGS. 2A and 2B, the curable composition (A1) 202 according to the present embodiment described above is laminated (coated) on the substrate 201 to form a coating film.
- 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. )
- the adhesion to 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.
- the content of the component (d1) as the solvent in the curable composition (A1) 202 film is 10% by weight. % Or less.
- the component (a1), the component (b1), and the component (c1) have low volatility so as not to volatilize in the baking process.
- a known method such as an oven or a hot plate can be used for the baking process.
- Baking conditions can be performed under conditions such as 30 to 200 ° C. and 1 to 600 seconds. It is preferable to set conditions appropriately so that the component (a1), the component (b1), and the component (c1) do not volatilize while volatilizing the component (d1) that is a solvent.
- membrane of curable composition (A1) 202 changes also with the uses to be used, it is 0.1 nm or more and 10,000 nm or less, for example, Preferably they are 1 nm or more and 20 nm or less, Especially preferably. Is from 1 nm to 10 nm.
- ⁇ 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 droplets of the curable composition (A2) 203 disposed in this step have a Marangoni effect whose driving force is a difference in surface energy (surface tension).
- the droplet spreads quickly in the direction of the arrow 204 indicating the direction in which the droplet spreads (prespread) (FIG. 2D).
- the content of the component (d1) which is the solvent in the curable composition (A1) 202 film, is set to 10% by weight or less so that the atmosphere control gas 307 blown for the adjacent shot (see FIG. 3B), the Marangoni effect appears uniformly, and a uniform pattern can be formed in the second shot region 305.
- 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 transmissive resin is used as the material of 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 that the mold 205 has on the surface preferably has a pattern height of 4 nm or more and 200 nm or less.
- the lower the pattern height the lower the force to peel the mold 205 from the cured resist film 207 in the mold release process, that is, the mold release force, and the resist pattern is torn along with the mold release and remains on the mask side.
- 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. In the boundary area between the droplets of the curable composition (A2) 203, the spread is finally completed, and the concentration of the curable composition (A1) 202 is high.
- 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 inert gas is blown from the periphery of the mold 205 toward the gap between the mold 205 and the substrate 201.
- 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 the partially enlarged portion in FIG. 1D).
- 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 23 ° C., more preferably 10 ° C. to 23 ° C. If it is this range, a filling property will be further excellent.
- the vapor pressure of the condensable gas at the atmospheric temperature in the mold contact process is such that the mold 205 and the curable compositions (A1) 202 and (A2) 203 in the mold contact process are brought into contact with each other. There is no limitation as long as it is below the pressure applied to the products (A1) 202 and (A2) 203, but 0.1 to 0.4 MPa is preferable.
- 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. Among these, the irradiation light 206 is particularly preferably ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are sensitive to ultraviolet light.
- Examples of 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. Although an excimer laser etc. are mentioned, an ultrahigh pressure mercury lamp is especially preferable. Further, the number of light sources used may be one or plural. Further, when the light irradiation is performed, 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. Furthermore, the partial area A may be irradiated in the first irradiation process, and the area B different from the area A may be irradiated in the second irradiation process.
- 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
- 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.
- 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.
- 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 steps (1) to (5) may be performed collectively on the entire surface of the substrate 201.
- 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.
- pattern transfer may be performed using a processing means such as etching.
- a processing means such as etching.
- a circuit structure based on the pattern shape of the cured film 207 having a pattern shape can be formed on the substrate 201.
- the circuit board utilized by a semiconductor element etc. can be manufactured.
- 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.
- the present invention provides a curable composition (A1) that forms a liquid film as a pretreatment coating on a substrate and promotes the spread of droplet components in the substrate surface direction by applying droplets to the liquid film.
- An imprint pretreatment coating material comprising: The content of the component (d1) that is a solvent in the imprint pretreatment coating material is 90% by weight or more, The content of the component (d1), which is a solvent in the imprint pretreatment coating material at the time of application of the droplets, is 10% by weight or less, The surface tension of the component (d1) which is the solvent is lower than the surface tension of the composition of the component of the imprint pretreatment coating material excluding the component (d1) which is the solvent. Treatment coating materials.
- the surface tension of the imprint pretreatment coating is preferably higher than the surface tension of the droplet to which it is applied.
- the surface tension of the composition of the imprint pretreatment coating material component excluding the solvent is preferably higher than the surface tension of the composition of the imprint resist component excluding the solvent.
- an imprint resist is preferably provided as a combination of an imprint resist and an imprint pretreatment coating material. That is, it is provided as a set in which the surface tension of the composition of the imprint pretreatment coating material component excluding the solvent is higher than the surface tension of the composition of the imprint resist component excluding the solvent.
- a suitable imprint is realized.
- 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 or more and 25 mN / m or less 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 100 parts by weight Trimethylolpropane triacrylate (manufactured by Aldrich, abbreviated as TMPTA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component (b1) is added I didn't.
- Component (c1) Total 0 parts by weight Component (c1) 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 (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 (2-2) Component (b2): Total 3 parts by weight Lucirin TPO (manufactured by BASF): 3 parts by weight ( 2-3) Component (c2): 0.8 part in total Polyoxyethylene (13) Stearyl ether (manufactured by Kao, Emulgen 320P): 0.8 part by weight (2-4) Component (d2): Total 0 part by weight Component (d2) was not added.
- the residual ratio of the component (d1), which is a solvent, in the curable composition (A1-1) film is assumed to be 0% by weight. Since the volatility of the component (a1) is low and the influence of the volatilization of the component (d1) as a solvent is slight, the Marangoni effect is not affected by a large composition fluctuation even in the portion where the atmosphere control gas is blown for the adjacent shot. Are uniformly expressed, and a uniform pattern can be formed in the shot.
- Example 2 (1) to (3) Curable compositions (A1) and (A2) The same compositions as in Example 1 were used.
- the residual ratio of the component (d1) as a solvent in the film of the curable composition (A1-1) is assumed to be 10% by weight. Since the volatility of the component (a1) is low and the influence of the volatilization of the component (d1) as a solvent is slight, the Marangoni effect is not affected by a large composition fluctuation even in the portion where the atmosphere control gas is blown for the adjacent shot. Are uniformly expressed, and a uniform pattern can be formed in the shot.
- the residual ratio of the component (d1) as a solvent in the film of the curable composition (A1-1) is assumed to be 20% by weight. Volatilization of the component (d1), which is a solvent, progresses in the portion where the atmosphere control gas for the adjacent shot is sprayed, the surface tension of the curable composition (A1-1) is increased, and the Marangoni effect is exhibited. Spread promotion effect is obtained. On the other hand, the pre-spread promoting effect is insufficient as described above in the portion where the atmosphere control gas is not sprayed. For this reason, the uniformity of pattern formation in the shot is low.
- the residual ratio of the component (d1) as a solvent in the film of the curable composition (A1-1) is assumed to be 50% by weight. Volatilization of the component (d1), which is a solvent, progresses in the portion where the atmosphere control gas for the adjacent shot is sprayed, the surface tension of the curable composition (A1-1) is increased, and the Marangoni effect is exhibited. Spread promotion effect is obtained. On the other hand, the pre-spread promoting effect is insufficient as described above in the portion where the atmosphere control gas is not sprayed. For this reason, the uniformity of pattern formation in the shot is low.
- the pre-spread promoting effect was evaluated as a relative evaluation based on a conventional optical nanoimprint process in which the curable composition (A1) was not applied. That is, the acceleration effect was “Yes” if the speed was faster than the conventional optical nanoimprint process, and “Insufficient” if the speed was comparable.
- the pre-spreads of Examples 1 and 2 are faster than Comparative Examples 1 and 2, and the pre-spread promoting effect is recognized.
- Example 1 the pre-spread is fast and the uniformity of pattern formation is good. In Comparative Examples 1 and 2, the pre-spread is slow and the pattern formation is not uniform in the shot.
- the pattern forming method of this embodiment is excellent in high throughput and uniformity.
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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)、
パターンを有するモールド205を硬化後の硬化性組成物からなる層(パターン形状を有する硬化膜207)から引き離す離型工程(5)(図2G)、
を有する。
前記硬化性組成物(A1)からなる層上に、少なくとも重合性化合物である成分(a2)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)中の溶剤である成分(d1)の含有率が90重量%以上であり、
前記第二積層工程(2)における前記硬化性組成物(A1)中の溶剤である成分(d1)の含有率が10重量%以下であり、
前記溶剤である成分(d1)の表面張力が、前記溶剤である成分(d1)を除いた硬化性組成物(A1)の成分の組成物の表面張力よりも低い
ことを特徴とする
本実施形態に係る硬化性組成物(A1)は、少なくとも重合性化合物である成分(a1)及び溶剤である成分(d1)を有する組成物である。本実施形態に係る硬化性組成物(A1)はさらに、光重合開始剤である成分(b1)、非重合性化合物である成分(c1)を含有してもよい。
本実施形態に係る硬化性組成物(A2)は、少なくとも重合性化合物である成分(a2)を有する組成物である。本実施形態に係る硬化性組成物(A2)はさらに、光重合開始剤である成分(b2)、非重合性化合物である成分(c2)、溶剤である成分(d2)を含有してもよい。
また、本明細書において硬化膜とは、基板上で硬化性組成物を重合させて硬化させた膜を意味する。なお、硬化膜の形状は特に限定されず、表面にパターン形状を有していてもよい。
以下、各成分について、詳細に説明する。
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。
このような重合性化合物としては、例えば、ラジカル重合性化合物が挙げられる。重合性化合物である成分(a)は、一種類の重合性化合物のみから構成されていてもよく、複数種類の重合性化合物で構成されていてもよい。
ラジカル重合性化合物が、アクリロイル基またはメタクリロイル基を1つ以上有する複数種類の化合物で構成される場合には、単官能(メタ)アクリルモノマーと多官能(メタ)アクリルモノマーを含むことが好ましい。これは、単官能(メタ)アクリルモノマーと多官能(メタ)アクリルモノマーを組み合わせることで、機械的強度が強い硬化膜が得られるからである。
また、アクリロイル基またはメタクリロイル基を2つ以上有する多官能(メタ)アクリル化合物としては、例えば、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、EO変性トリメチロールプロパントリ(メタ)アクリレート、PO変性トリメチロールプロパントリ(メタ)アクリレート、EO,PO変性トリメチロールプロパントリ(メタ)アクリレート、ジメチロールトリシクロデカンジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-へキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、1,3-アダマンタンジメタノールジ(メタ)アクリレート、トリス(2-ヒドロキシエチル)イソシアヌレートトリ(メタ)アクリレート、トリス(アクリロイルオキシ)イソシアヌレート、ビス(ヒドロキシメチル)トリシクロデカンジ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、EO変性2,2-ビス(4-((メタ)アクリロキシ)フェニル)プロパン、PO変性2,2-ビス(4-((メタ)アクリロキシ)フェニル)プロパン、EO,PO変性2,2-ビス(4-((メタ)アクリロキシ)フェニル)プロパン等が挙げられるが、これらに限定されない。
重合性化合物である成分(a1)の硬化性組成物(A1)における配合割合を、成分(a1)、成分(b1)、成分(c1)の合計重量に対して50重量%以上とすることにより、得られる硬化膜をある程度の機械的強度を有する硬化膜とすることができる。
重合性化合物である成分(a2)の硬化性組成物(A2)における配合割合を、成分(a2)、成分(b2)、成分(c2)の合計重量に対して50重量%以上とすることにより、得られる硬化膜をある程度の機械的強度を有する硬化膜とすることができる。
成分(b)は、光重合開始剤である。
本明細書において光重合開始剤は、所定の波長の光を感知して上記重合因子(ラジカル)を発生させる化合物である。具体的には、光重合開始剤は、光(赤外線、可視光線、紫外線、遠紫外線、X線、電子線等の荷電粒子線等、放射線)によりラジカルを発生する重合開始剤(ラジカル発生剤)である。
成分(b)は、一種類の光重合開始剤で構成されていてもよく、複数種類の光重合開始剤で構成されていてもよい。
光重合開始剤である成分(b)の硬化性組成物(A1)及び(A2)における配合割合は、成分(a)、成分(b)、後述する成分(c)の合計重量、すなわち溶剤である成分(d)を除く硬化性組成物(A1)または(A2)の成分の合計重量に対して、0.1重量%以上50重量%以下であるとよい。また、好ましくは、0.1重量%以上20重量%以下であり、さらに好ましくは1重量%以上10重量%以下である。
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、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。
増感色素は、特定の波長の光を吸収することにより励起され、光重合開始剤である成分(b)と相互作用する化合物である。なお、ここで記載する相互作用とは、励起状態の増感色素から光重合開始剤である成分(b)へのエネルギー移動や電子移動等である。
増感色素の具体例としては、アントラセン誘導体、アントラキノン誘導体、ピレン誘導体、ペリレン誘導体、カルバゾール誘導体、ベンゾフェノン誘導体、チオキサントン誘導体、キサントン誘導体、クマリン誘導体、フェノチアジン誘導体、カンファキノン誘導体、アクリジン系色素、チオピリリウム塩系色素、メロシアニン系色素、キノリン系色素、スチリルキノリン系色素、ケトクマリン系色素、チオキサンテン系色素、キサンテン系色素、オキソノール系色素、シアニン系色素、ローダミン系色素、ピリリウム塩系色素等が挙げられるが、これらに限定されない。
増感剤は、一種類を単独で用いてもよいし、二種類以上を混合して用いてもよい。
内添型離型剤としては、シリコーン系界面活性剤、フッ素系界面活性剤及び炭化水素系界面活性剤等の界面活性剤等を使用できる。なお、本発明において内添型離型剤は、重合性を有さないものとする。
炭化水素系界面活性剤としては、炭素数1~50のアルキルアルコールに炭素数2~4のアルキレンオキサイドを付加した、アルキルアルコールポリアルキレンオキサイド付加物等が含まれる。
アルキルアルコールポリアルキレンオキサイド付加物としては、メチルアルコールエチレンオキサイド付加物、デシルアルコールエチレンオキサイド付加物、ラウリルアルコールエチレンオキサイド付加物、セチルアルコールエチレンオキサイド付加物、ステアリルアルコールエチレンオキサイド付加物、ステアリルアルコールエチレンオキサイド/プロピレンオキサイド付加物等が挙げられる。なお、アルキルアルコールポリアルキレンオキサイド付加物の末端基は、単純にアルキルアルコールにポリアルキレンオキサイドを付加して製造できるヒドロキシル基に限定されない。このヒドロキシル基が他の置換基、例えば、カルボキシル基、アミノ基、ピリジル基、チオール基、シラノール基等の極性官能基やアルキル基、アルコキシ基等の疎水性官能基に置換されていてもよい。
成分(c)の配合割合を成分(a)、成分(b)、成分(c)の合計重量に対して50重量%以下とすることにより、得られる硬化膜をある程度の機械的強度を有する硬化膜とすることができる。
本実施形態に係る硬化性組成物(A1)は、溶剤である成分(d1)を含有する。後述するように、基板上への硬化性組成物(A1)の塗布方法としてスピンコート法が好ましいためである。本発明の光ナノインプリント法により1nm以上100nm以下のパターンを形成するためには、硬化性組成物(A1)の膜厚も1nm以上100nm以下程度であることが好ましい。このため、溶剤である成分(d1)の硬化性組成物(A1)中の含有率は、90重量%以上99.99重量%以下が好ましく、99重量%以上99.9重量%以下が特に好ましい。硬化性組成物(A1)の溶剤である成分(d1)としては、成分(a1)、成分(b1)、成分(c1)が溶解し、かつ成分(a1)、成分(b1)、成分(c1)からなる混合物、すなわち溶剤である成分(d1)を除く硬化性組成物(A1)の成分の組成物、よりも表面張力が低い溶剤を用いる。溶剤である成分(d1)の表面張力が低いほど、スピンコート法で均一な膜が得られる。さらに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、あるいはこれらのうち少なくとも1種類以上を含有する混合溶剤である。
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。
また、粘度を1mPa・s以上とすることにより、硬化性組成物(A1)及び(A2)を基板上に塗布する際に塗りムラが生じにくくなる。さらに、硬化性組成物(A1)及び(A2)をモールドに接触する際に、モールドの端部から硬化性組成物(A1)及び(A2)が流出しにくくなる。
本実施形態に係る硬化性組成物(A1)及び(A2)において、溶剤である成分(d)を除く硬化性組成物(A1)及び(A2)の成分の組成物の23℃での表面張力は、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)。
また、表面張力を70mN/m以下とすることにより、硬化性組成物を硬化して得られる硬化膜が表面平滑性を有する硬化膜となる。
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と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。
したがって、本実施形態に係る硬化性組成物は、精製工程を経て得られたものであることが好ましい。このような精製工程としては、フィルタを用いた濾過等が好ましい。
このような精製工程を経ることで、硬化性組成物に混入したパーティクル等の不純物を取り除くことができる。これにより、パーティクル等の不純物によって、硬化性組成物を硬化した後に得られる硬化膜に不用意に凹凸が生じてパターンの欠陥が発生することを防止することができる。
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を硬化後の硬化性組成物からなる硬化膜207から引き離す離型工程(5)、
を有する。
以下、各工程について説明する。
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。
なお、使用される基板201(被加工基板)あるいは被加工層の表面は、シランカップリング処理、シラザン処理、有機薄膜の成膜、等の表面処理によって硬化性組成物(A1)202及び(A2)203との密着性が向上されていてもよい。
ベーク工程は、オーブンやホットプレートなど、既知の方法を用いることができる。ベーク条件は、30~200℃、1~600秒などの条件で行うことができる。溶剤である成分(d1)を揮発させつつ、成分(a1)、成分(b1)、成分(c1)が揮発しないよう、適切に条件を設定することが好ましい。
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。
パターン高さが低いほど、離型工程においてモールド205をレジストの硬化膜207から引き剥がす力、すなわち離型力が低く、また、離型に伴ってレジストパターンがひきちぎられてマスク側に残存する離型欠陥数が少ない。モールド205を引き剥がす際の衝撃によるレジストパターンの弾性変形で隣接レジストパターン同士が接触し、レジストパターンが癒着あるいは破損する場合があるが、パターン幅に対してパターン高さが2倍程度以下(アスペクト比2以下)であると、それらの不具合を回避できる可能性が高い。一方、パターン高さが低過ぎると、基板201(被加工基板)の加工精度が低い。
凝縮性ガス雰囲気下で型接触工程を行うと、微細パターンの凹部に充填されたガスが硬化性組成物(A1)202及び(A2)203により発生する毛細管圧力により液化することで気泡が消滅するため、充填性が優れる。凝縮性ガスは、硬化性組成物(A1)202及び/または(A2)203に溶解してもよい。
凝縮性ガスの型接触工程の雰囲気温度での蒸気圧は、型接触工程で押印するときのモールド205と硬化性組成物(A1)202及び(A2)203とを接触させる際に、硬化性組成物(A1)202及び(A2)203に加える圧力以下であれば制限がないが、0.1~0.4MPaが好ましい。この範囲であれば、充填性がさらに優れる。雰囲気温度での蒸気圧が0.4MPaより大きいと、気泡の消滅の効果を十分に得ることができない傾向がある。一方、雰囲気温度での蒸気圧が0.1MPaよりも小さいと、減圧が必要となり、装置が複雑になる傾向がある。
これらのうち、型接触工程の雰囲気温度が20℃~25℃での充填性が優れるという観点から、1,1,1,3,3-ペンタフルオロプロパン(23℃での蒸気圧0.14MPa、沸点15℃)、トリクロロフルオロメタン(23℃での蒸気圧0.1056MPa、沸点24℃)、及びペンタフルオロエチルメチルエーテルが好ましい。さらに、安全性が優れるという観点から、1,1,1,3,3-ペンタフルオロプロパンが特に好ましい。
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。
これらの中でも、照射光206は、紫外光が特に好ましい。これは、硬化助剤(光重合開始剤)として市販されているものは、紫外光に感度を有する化合物が多いからである。ここで紫外光を発する光源としては、例えば、高圧水銀灯、超高圧水銀灯、低圧水銀灯、Deep-UVランプ、炭素アーク灯、ケミカルランプ、メタルハライドランプ、キセノンランプ、KrFエキシマレーザ、ArFエキシマレーザ、F2エキシマレーザ等が挙げられるが、超高圧水銀灯が特に好ましい。また使用する光源の数は1つでもよいしまたは複数であってもよい。また、光照射を行う際には、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の全面に行ってもよく、一部領域にのみ行ってもよい。
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)。
本実施形態のパターン形状を有する膜の製造方法では、工程(1)で基板201表面の大部分に硬化性組成物(A1)202を一括して積層し、工程(2)~工程(5)からなる繰り返し単位(ショット)を、同一基板上で繰り返して複数回行うことができる。また、工程(1)~工程(5)を同一基板上で繰り返して複数回行ってもよい。工程(1)~工程(5)あるいは工程(2)~工程(5)からなる繰り返し単位(ショット)を複数回繰り返すことで、基板201(被加工基板)の所望の位置に複数の所望の凹凸パターン形状(モールド205の凹凸形状に因むパターン形状)を有する硬化膜207を得ることができる。また、工程(1)~工程(5)を基板201全面に対して一括して行っても良い。
工程(1)~工程(5)を経て得られた、パターン形状を有する硬化膜207をマスクとして、基板201(被加工基板)あるいは基板201(被加工基板)上の被加工層をエッチングなどの加工手段を用いてパターン状に加工することができる。また、パターン形状を有する硬化膜207上にさらに被加工層を成膜した後に、エッチングなどの加工手段を用いてパターン転写を行っても良い。このようにして、パターン形状を有する硬化膜207のパターン形状に基づく回路構造を基板201上に形成することができる。これにより、半導体素子等で利用される回路基板を製造することができる。また、この回路基板と回路基板の回路制御機構などとを接続することにより、ディスプレイ、カメラ、医療装置などの電子機器を形成することもできる。ここでいう半導体素子とは、例えば、LSI、システムLSI、DRAM、SDRAM、RDRAM、D-RDRAM、NANDフラッシュ等が挙げられる。
工程(1)~工程(5)を経て得られた、パターン形状を有する硬化膜207を回折格子や偏光板などの光学部材(光学部材の一部材として用いる場合を含む)として利用し、光学部品を得ることもできる。このような場合、少なくとも、基板201と、この基板201上のパターン形状を有する硬化膜207と、を有する光学部品とすることができる。
また、基板201として石英基板を用いて、工程(1)~工程(5)を経てパターン形状を有する硬化膜207を作製し、エッチングなどの加工手段を用いてパターン転写を行って石英インプリントモールドの石英レプリカ(モールドレプリカ)を作製することもできる。
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、液膜に対し硬化性組成物(A2)からなる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(硬化性組成物(A1))を提供するものである。
前記インプリント前処理コーティング材料中の溶剤である成分(d1)の含有率が90重量%以上であり、
前記液滴の付与の際の前記インプリント前処理コーティング材料中の溶剤である成分(d1)の含有率が10重量%以下であり、
前記溶剤である成分(d1)の表面張力が、前記溶剤である成分(d1)を除いた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よりも低い
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、を包含する。
特に、溶剤を除く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が好ましい。
これにより、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が促進され、好適なインプリントを実現することができる。
すなわち、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、という関係で組み合わせたセットとして提供することで、好適なインプリントを実現する。
(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100重量部
トリメチロールプロパントリアクリレート(アルドリッチ製、略称TMPTA):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(c1)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
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。
(2-1)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
(2-2)成分(b2):合計3重量部
Lucirin TPO(BASF製):3重量部
(2-3)成分(c2):合計0.8重量部
ポリオキシエチレン(13)ステアリルエーテル(花王製、エマルゲン320P):0.8重量部
(2-4)成分(d2):合計0重量部
成分(d2)は添加しなかった。
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、36.0mN/mであった。また、溶剤である成分(d1)の表面張力を測定したところ、27.2mN/mであった。硬化性組成物(A2-1)の表面張力を測定したところ、32.7mN/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。
硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を0重量%と仮定する。硬化性組成物(A1-1)膜の表面張力は36.0mN/mであり、硬化性組成物(A2-1)の32.7mN/mより2mN/m以上高いため、プレスプレッド促進効果を強く得ることができる。
同様に、硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を0重量%と仮定する。成分(a1)の揮発性は低く、溶剤である成分(d1)の揮発の影響も軽微であるため、隣接ショットのために雰囲気制御気体が吹き付けられた部分でも大きな組成変動を受けずにマランゴニ効果が均一に発現し、当該ショット内で均一なパターン形成が可能である。
(1)~(3)硬化性組成物(A1)及び(A2)について
実施例1と同様の組成物を用いた。
硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を10重量%と仮定する。この場合、硬化性組成物(A1-1)膜の表面張力は35.1mN/mであり、硬化性組成物(A2-1)の32.7mN/mより2mN/m以上高いため、プレスプレッド促進効果を強く得ることができる。
同様に、硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を10重量%と仮定する。成分(a1)の揮発性は低く、溶剤である成分(d1)の揮発の影響も軽微であるため、隣接ショットのために雰囲気制御気体が吹き付けられた部分でも大きな組成変動を受けずにマランゴニ効果が均一に発現し、当該ショット内で均一なパターン形成が可能である。
(1)~(3)硬化性組成物(A1)及び(A2)について
実施例1と同様の組成物を用いた。
硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を20重量%と仮定する。この場合、硬化性組成物(A1-1)膜の表面張力は34.2mN/mであり、硬化性組成物(A2-1)の32.7mN/mとの差が2mN/m以下であることから、プレスプレッド促進効果は不十分である。
同様に、硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を20重量%と仮定する。隣接ショットのための雰囲気制御気体が吹き付けられた部分では溶剤である成分(d1)の揮発が進行し、硬化性組成物(A1-1)の表面張力が高くなり、マランゴニ効果が発現し、プレスプレッド促進効果が得られる。一方で、雰囲気制御気体が吹き付けられなかった部分では、前述のようにプレスプレッド促進効果が不十分である。このため、当該ショット内のパターン形成の均一性が低い。
(1)~(3)硬化性組成物(A1)及び(A2)について
実施例1と同様の組成物を用いた。
硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を50重量%と仮定する。この場合、硬化性組成物(A1-1)膜の表面張力は31.6mN/mであり、硬化性組成物(A2-1)の32.7mN/mより低いことから、プレスプレッド促進効果は不十分である。
同様に、硬化性組成物(A1-1)膜中の溶剤である成分(d1)残存率を50重量%と仮定する。隣接ショットのための雰囲気制御気体が吹き付けられた部分では溶剤である成分(d1)の揮発が進行し、硬化性組成物(A1-1)の表面張力が高くなり、マランゴニ効果が発現し、プレスプレッド促進効果が得られる。一方で、雰囲気制御気体が吹き付けられなかった部分では、前述のようにプレスプレッド促進効果が不十分である。このため、当該ショット内のパターン形成の均一性が低い。
実施例1~2及び比較例1~2の組成表を表1及び表2に、結果を表3にまとめて示す。
102 レジスト
104 液滴の広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光硬化膜
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 液滴の広がる方向を示す矢印
205 モールド
206 照射光
207 硬化膜
301 基板
302 硬化性組成物(A1)
303 硬化性組成物(A2)
304 第一ショット領域
305 第二ショット領域
306 照射光
307 雰囲気制御気体
308 モールド
309 雰囲気制御気体が吹きつけられた領域
310 雰囲気制御気体が吹きつけられた領域(A1)に滴下された硬化性組成物(A2)の液滴
Claims (20)
- 基板の表面に、少なくとも重合性化合物である成分(a1)及び溶剤である成分(d1)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)からなる層上に、少なくとも重合性化合物である成分(a2)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)中の前記溶剤である成分(d1)の含有率が90重量%以上であり、
前記第二積層工程(2)における前記硬化性組成物(A1)中の前記溶剤である成分(d1)の含有率が10重量%以下であり、
前記溶剤である成分(d1)の表面張力が、前記溶剤である成分(d1)を除いた前記硬化性組成物(A1)の成分の組成物の表面張力よりも低い
ことを特徴とするパターン形成方法。 - 前記溶剤である成分(d1)が、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、シクロヘキサノンから選ばれる単独、あるいはこれらのうち少なくとも1種類以上を含有する混合溶剤であることを特徴とする請求項1に記載のパターン形成方法。
- 前記溶剤である成分(d1)を除く前記硬化性組成物(A1)の成分の組成物の表面張力が、溶剤を除く前記硬化性組成物(A2)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1または2に記載のパターン形成方法。
- 前記溶剤である成分(d1)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、前記溶剤を除く前記硬化性組成物(A2)の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3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4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5のいずれか1項に記載のパターン形成方法。
- 前記第二積層工程が、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6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7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6から8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9のいずれか1項に記載のパターン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9のいずれか1項に記載のパターン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9のいずれか一項に記載のパターン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、前記硬化性組成物(A1)及び(A2)の光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9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中の溶剤である成分(d1)の含有率が90重量%以上であり、
前記液滴の付与の際の前記インプリント前処理コーティング材料中の前記溶剤である成分(d1)の含有率が10重量%以下であり、
前記溶剤である成分(d1)の表面張力が、前記溶剤である成分(d1)を除いた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よりも低い
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14に記載のインプリント前処理コーティング材料。
- 請求項14または15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16に記載のセット。
- 請求項16または17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14または15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14または15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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KR1020187030398A KR102209277B1 (ko) | 2016-03-31 | 2017-03-29 | 패턴 형성 방법, 가공 기판의 제조 방법, 광학 부품의 제조 방법, 회로 기판의 제조 방법, 전자 부품의 제조 방법, 임프린트 몰드의 제조 방법 |
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