WO2017170684A1 - 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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- WO2017170684A1 WO2017170684A1 PCT/JP2017/012880 JP2017012880W WO2017170684A1 WO 2017170684 A1 WO2017170684 A1 WO 2017170684A1 JP 2017012880 W JP2017012880 W JP 2017012880W WO 2017170684 A1 WO2017170684 A1 WO 2017170684A1
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- 229920001778 nylon Polymers 0.000 description 1
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- 125000002347 octyl 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])[H] 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
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- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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- 125000005372 silanol group Chemical group 0.000 description 1
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- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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.
- a liquid resist 102 is discretely dropped onto a pattern formation region on the substrate 101 by using an ink jet 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 having a pattern formed and transparent to irradiation light 106 described later (mold contact step (2), FIG. 1 (d) and (da). )).
- the droplets of the resist 102 spread over the entire gap between the substrate 101 and the mold 105 as indicated by the arrow 104 indicating the direction in which the droplets spread (FIG. 1D). This phenomenon is called spread.
- the resist 102 is also filled into the recesses on the mold 105 by capillarity as indicated by the arrows 104 indicating the direction in which the droplets spread (FIG. 1 (da)). This filling phenomenon is called fill. The time until the spread and fill are completed is called the filling time. After the filling of the resist 102 is completed, the resist 102 is cured by irradiating the irradiation light 106 (light irradiation process, FIG.
- a photocured film 107 (FIG. 1 (f)) having a predetermined pattern shape is formed on the substrate 101.
- SST-NIL a series of process units from the second lamination process (2) to the mold release process (5) is referred to as “shot”, and the mold 205 includes the curable composition (A1) 202 and the curable composition (A2). ) A region in contact with 203, that is, a region where a pattern is formed on the substrate 201 is called a “shot region”.
- shots region A region in contact with 203, that is, a region where a pattern is formed on the substrate 201 is called a “shot region”.
- the droplets of the curable composition (A2) 203 that are discretely dropped are indicated by arrows 204 indicating the direction of the droplets on the liquid film of the curable composition (A1) 202. Because it expands quickly, the filling time is short and the throughput is high. The detailed mechanism of SST-NIL will be described later.
- the curable composition (A1) 302 is laminated on the substrate 301 over an area larger than the shot region 304, for example, the entire surface of the substrate 301 by using, for example, a spin coating method.
- the curable composition (A2) 303 is limited to the shot region 304 and is laminated discretely using, for example, an inkjet method.
- Irradiation light 306 is irradiated from the back surface of mold 308 (the side not in contact with curable composition (A2) 303).
- curable composition (A1) 302 laminated outside shot region 304 is also applied.
- Leakage light 307 is irradiated.
- the curing reaction of the curable composition (A1) 302 by the leakage light 307 proceeds, and the curable composition (A1) cured by the leakage light 307. 309 was confirmed to be present. And it turned out that expansion of the droplet 310 of the curable composition (A2) 303 dripped on the curable composition (A1) 309 hardened
- An object of the present invention is to provide an SST-NIL technology that can process a plurality of shot regions of a substrate with uniform accuracy with high throughput and low cost.
- the pattern formation method includes a first lamination step (1) in which a layer made of a curable composition (A1) containing at least a component (a1) that is a polymerizable compound is laminated on the surface of a substrate. On the layer composed of the curable composition (A1), droplets of the curable composition (A2) containing at least the component (a2) which is a polymerizable compound and the component (b2) which is a photopolymerization initiator are discretely dispersed.
- a pattern forming method having The curable composition (A1) is also laminated around a region where the mold and the mixed layer are in contact with each other,
- the content of the component (b1) that is the photopolymerization initiator of the curable composition (A1) is 0 part by weight or more and 0.1 part by weight with respect to 100 parts by weight of the component (a1) that is the polymerizable compound. Is less than Illuminance 1.00mW / cm 2, the polymerization conversion ratio of a the polymerizable compound upon exposure under the conditions of exposure time 100.0 sec component (a1) is 50% or less, It is characterized by that.
- the present invention it is possible to provide a pattern forming method capable of processing a plurality of shot regions of a substrate with uniform accuracy with high throughput and low cost.
- 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 further includes a component (b) that is a photopolymerization initiator, a component (c) that is a sensitizer, a component (d) that is a non-polymerizable compound, and a component (e that is a solvent). ) May be contained.
- 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 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) is the total weight of the component (a1), the component (b1), the component (c1) and the component (d1), that is, the component which is a solvent. It is good in it being 50 to 100 weight% with respect to the total weight of the component of the curable composition (A1) except (e1). 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 blending ratio of the component (a1) which is a polymerizable compound in the curable composition (A1) is 50% by weight with respect to the total weight of the component (a1), the component (b1), the component (c1) and the component (d1).
- the blending ratio of the component (a2) that is a polymerizable compound in the curable composition (A2) is the total weight of the component (a2), the component (b2), the component (c2), and the component (d2), that is, the component that is a solvent. It is good in it being 50 weight% or more and 99.9 weight% or less with respect to the total weight of the component of the curable composition (A2) except (e2). Further, it is preferably 80% by weight or more and 99% by weight or less, and more preferably more than 90% by weight and 98% by weight or less.
- the mixing ratio of the component (a2) which is a polymerizable compound in the curable composition (A2) is 50% by weight with respect to the total weight of the component (a2), the component (b2), the component (c2) and the component (d2).
- the curable composition (A1) preferably contains the component (e1), and the component (a1) is a component of the curable composition (A1) containing the component (e1) 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.
- 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 curable composition (A1) has substantially no photoreactivity.
- the compounding ratio in the curable composition (A1) of the component (b1) which is a photopolymerization initiator is 0 part by weight or more and less than 0.1 part by weight with respect to 100 parts by weight of the component (a1). .
- it is 0 to 0.01 weight part, More preferably, it is 0 to 0.001 weight part.
- the curable composition (A1) is substantially photoreactive by setting the blending ratio of the component (b1) in the curable composition (A1) to less than 0.1 parts by weight with respect to 100 parts by weight of the component (a1). Does not have sex.
- the blending ratio in the curable composition (A2) of the component (b2) that is the photopolymerization initiator is the total weight of the component (a2), the component (b2), the component (c2), and the component (d2) described later, that is, the solvent. It is good that it is 0.1 wt% or more and 50 wt% or less with respect to the total weight of the components of the curable composition (A2) excluding the component (e2). 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 blending ratio of the component (b2) in the curable composition (A2) is 0.1% by weight or more based on the total weight of the component (a2), the component (b2), the component (c2), and the component (d2).
- the curing rate of the composition is increased, and the reaction efficiency can be improved.
- the blending ratio of the component (b2) to 50% by weight or less based on the total weight of the component (a2), the component (b2), the component (c2), and the component (d2), the cured film obtained can be obtained to some extent It can be set as the cured film which has the mechanical strength of.
- the component (c) that is a sensitizer is a compound that promotes the generation of photo radicals of the component (b) that is a photopolymerization initiator when it coexists with the component (b) that is a photopolymerization initiator.
- the component (c) alone, which is a sensitizer, is defined as a compound that has substantially no ability to initiate radical photopolymerization.
- the curable composition (A1) preferably contains a component (c1) which is a sensitizer. This is because the photo-curing property in the shot of the curable composition (A1) that substantially does not contain the component (b1) that is a photopolymerization initiator can be enhanced by the sensitization mechanism, and the adjacent shot region 305 ( This is because in FIG. 3) photocuring due to leakage light 307 (FIG. 3) does not occur.
- the photocurable sensitization mechanism in the shot of the curable composition (A1) will be described later.
- component (c) which is a sensitizer alone does not substantially initiate radical photopolymerization means “a component which does not contain component (b) which is a polymerization initiator and is a polymerizable compound”
- component (c) which is a sensitizer In the curable composition containing (a) and the component (c) which is a sensitizer, the component which is the polymerizable compound when exposed under the conditions of an illuminance of 1.00 mW / cm 2 and an exposure time of 3.2 seconds.
- the polymerization conversion rate of (a) is defined as 3% or less. A method for measuring the polymerization conversion will be described later.
- Examples of the component (c) that is a sensitizer include sensitizing dyes.
- a sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and interacts with the photopolymerization initiator that is component (b).
- the interaction described here is an energy transfer, an electron transfer, etc. from the sensitizing dye of an excited state to the photoinitiator which is a component (b).
- 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
- Examples include, but are not limited to, dyes, merocyanine dyes, quinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes.
- component (c) as the sensitizer examples include 7-diethylamino-4-methylcoumarin (Tokyo Chemical Industry), 4,4'-bis (diethylamino) benzophenone (Tokyo Chemical Industry), 2-isopropylthioxanthone ( Tokyo Chemical Industry).
- component (c) which is a sensitizer one type may be used alone, or two or more types may be mixed and used.
- the blending ratio of the component (c1) which is a sensitizer in the curable composition (A1) is the total weight of the component (a1), the component (b1), the component (c1) and the component (d1), that is, the component which is a solvent.
- the content is preferably 0.01% by weight to 10% by weight, particularly preferably 0.01% by weight to 3% by weight, based on the total weight of the components of the curable composition (A1) excluding (e1).
- the blending ratio of the component (c1), which is a sensitizer, in the curable composition (A1) is 0.01 with respect to the total weight of the component (a1), the component (b1), the component (c1), and the component (d1).
- the sensitizing effect may be insufficient.
- photopolymerization may be initiated only with the component (c1) that is a sensitizer.
- the blending ratio of the component (c2) which is a sensitizer in the curable composition (A2) is the total weight of the component (a2), the component (b2), the component (c2) and the component (d2), that is, the component which is a solvent. 0.01 wt% or more and 10 wt% or less is preferable with respect to the total weight of the components of the curable composition (A2) excluding (e2), and 0.01 wt% or more and 3 wt% or less is particularly preferable.
- the blending ratio of the component (c2), which is a sensitizer, in the curable composition (A2) is 0.01 with respect to the total weight of the component (a2), the component (b2), the component (c2), and the component (d2).
- the sensitizing effect may be insufficient.
- photopolymerization may be initiated only with the component (c2) that is a sensitizer.
- Non-polymerizable compound Non-polymerizable compound
- the curable compositions (A1) and (A2) according to this embodiment have the effects of the present invention according to various purposes in addition to the components (a), (b), and (c) described above.
- the component (d), which is a non-polymerizable compound, can be further contained as long as it is not impaired.
- Such component (d) 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 thereof include a hydrogen donor, an internal release agent, a surfactant, an antioxidant, a polymer component, and other additives. You may contain multiple types of the said compound as a component (d).
- 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 release agent can be added to the curable composition for the purpose of reducing the interfacial bonding force between the mold and the resist, that is, reducing the release force in the release 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 internally added mold release agent 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 in the curable composition of the component (d) which is a non-polymerizable compound is the total weight of the component (a), the component (b), the component (c) and the component (d), that is, the curable composition excluding the solvent. It is good that it is 0 weight% or more and 50 weight% or less with respect to the total weight of the component of a thing. 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.
- the curable composition which concerns on this embodiment may contain the component (e) which is a solvent.
- the component (e) is not particularly limited as long as it is a solvent in which the component (a), the component (b), the component (c), and the component (d) 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 a component (e1). 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 (e1), which is the solvent of the curable composition (A1) according to this 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 150 mPa ⁇ s or less.
- the composition of the components excluding the component (e2) 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.
- 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 of the curable compositions (A1) and (A2) according to this embodiment is 23 ° C. for the composition of the curable compositions (A1) and (A2) except for the component (e) 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 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 surface tension of the component of the curable composition (A1) excluding the component (e1) that is the solvent is the component of the curable composition (A2) excluding the component (e2) that 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 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 (e) 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 components (a), (b), (c), (d) and (e) 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.
- a portion where the polymerization reaction of the curable composition (A1) has progressed and has been cured is not fully manifested by the Maragoni effect when the curable composition (A2) is applied, and pre-spread is not achieved. Sufficient and unfilled defects will occur.
- the inventors of the present invention have found that a very slight polymerization reaction of the curable composition (A1) substantially not containing a photopolymerization initiator is caused by light having a wavelength of 350 nm or less. It was. In particular, a (meth) acrylate having an aromatic ring has a high possibility that the polymerization reaction proceeds. On the other hand, the present inventors have found that the possibility that the polymerization reaction of the curable composition (A1) of the present invention proceeds is low when irradiated with light that does not include a wavelength of 350 nm or less, particularly 365 nm single wavelength light.
- the light used for curing the mixture of the curable compositions (A1) and (A2) used in the present invention is preferably light that does not cure the curable composition (A1), that is, light that does not include a wavelength of 350 nm or less.
- Single wavelength light of 365 nm or 375 nm is more preferable.
- Single wavelength light is defined as light having a half-value width of a peak of a spectral intensity distribution of 10 nm or less.
- the polymerization conversion rate of the curable composition used in the present invention by light irradiation can be measured using, for example, an attenuated total reflection infrared spectrometer 400 equipped with a light irradiation mechanism as shown in FIG.
- the polymerization conversion rate can be defined as the disappearance ratio of the polymerizable functional group of the component (a) accompanying the photopolymerization reaction. This ratio is synonymous with the ratio at which the polymerizable functional group was polymerized.
- the curable composition 404 is sandwiched between the diamond ATR crystal 403 and the quartz glass 405 included in the attenuated total reflection infrared spectrometer 400 shown in FIG. Arranged in a manner.
- the curable composition 404 is cured by irradiating the irradiation light 407 from the quartz glass 405 toward the curable composition 404.
- the infrared light 401 is irradiated toward the diamond ATR crystal 403.
- the detector 402 detects the evanescent wave 406 generated in the range of several ⁇ m on the diamond ATR crystal 403, and the attenuated total reflection infrared spectral spectrum of the curable composition 404 is several to several dozens per second. Get the following. Thereby, the infrared spectroscopy spectrum of the curable composition 404 during photocuring can be acquired in real time.
- the polymerization conversion rate (%) of the curable composition 404 at an arbitrary exposure amount can be calculated according to the following formula (1).
- the minimum exposure (mJ / cm 2 ) with a polymerization conversion rate exceeding 50% is defined as the half exposure (mJ / cm 2 ), and the curable composition Used as an indicator of the polymerization rate.
- the half exposure value the slower the photopolymerization, and the smaller the value, the faster the photopolymerization.
- 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 the original 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 having a pattern shape 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.
- 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 including an adhesion layer may be formed over the substrate 201.
- the adhesive layer has a pattern shape after the photopolymerization of the mixture of the curable composition (A1) 202 and the curable composition (A2) 203 by improving the adhesion between the coating film and the substrate 201. It functions to reduce the formation of defects in the cured film 207 having a pattern shape when separated from the cured film 207.
- the thickness of the adhesion layer is usually 1 nm or more and 10 nm or less. Examples of materials suitable for the adhesion layer include US Pat. Nos.
- the adhesion layer comprises ISORAD 501, CYMEL 303ULF, CYCAT 4040 or TAG 2678 (trifluoromethanesulfonic acid blocked with quaternary ammonium) and Eastman TM PM acetate (2-manufactured by Eastman Chemical Company).
- 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.
- 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 surface treatment such as silane coupling treatment, silazane treatment, or organic thin film formation, and the curable composition (A1) 202 and curability.
- the adhesiveness with the composition (A2) 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 (e1) 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 dispersed on the layer of the curable composition (A1) 202. It is preferable to arrange them dropwise. 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 indicated by the arrow 204 indicating the direction in which the droplet spreads (pre-spread) (FIGS. 2C and 2D).
- the inventors of the present invention have found that the curable composition (A1) 202 and the curable composition (A2) 203 are partially mixed in the pre-spread process.
- the component (b2) that is the photopolymerization initiator of the curable composition (A2) 203 is converted into a curable composition ( The process proceeds to A1) 202, and the curable composition (A1) 202 acquires photoreactivity for the first time.
- the curable composition (A1) 202 includes a component (c1) that is a sensitizer
- the component (b2) that is a photopolymerization initiator transferred from the curable composition (A2) 203 is sensitized. Since it is sensitized by the component (c1) which is an agent, the photocurability of the curable composition (A1) 202 in the shot is improved.
- 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 off the mold 205 from the photocured film of the resist in the mold release process, that is, the mold release force, and the resist pattern is torn off 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 curable composition (A1) 202 and the curable composition (A1) 202 and the curable composition (A1) 202 and the curable composition (A1) 202 and the curable composition are used in order to improve the peelability between the curable composition (A2) 203 and the surface of the mold 205.
- A2 Surface treatment may be performed before this step, which is a die contact step between 203 and the mold 205. Examples of 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.
- a mold 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 curable composition is used.
- the pressure applied to (A1) 202 and curable composition (A2) 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, the curable composition (A1) 202, and the curable property are used.
- the time for contacting the composition (A2) 203 can be set short. That is, one of the effects of the present invention is that many pattern forming steps can be completed in a short time and high productivity can be obtained.
- 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 a curable composition (A1) 202 and a curable composition (A2) 203 in a concave portion of a fine pattern formed on the mold 205 and a gap between the mold 205 and the substrate 201.
- the condensable gas exists as a gas in the atmosphere before the curable composition (A1) 202 and the curable composition (A2) 203 and the mold 205 come into contact with each other in the mold contact step (FIG. 1 (d) and (See (da)).
- the mold contact process is performed in a condensable gas atmosphere, the gas filled in the concave portions of the fine pattern is liquefied by the capillary pressure generated by the curable composition (A1) 202 and the curable composition (A2) 203. Since the bubbles disappear, the filling property is excellent.
- the condensable gas may be dissolved in the curable composition (A1) 202 and / or the curable composition (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 not limited as long as it is equal to or lower than the mold pressure at the time of imprinting in the mold contact process, but is preferably 0.1 to 0.4 MPa. If it is this range, a filling property will be further excellent. When 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. On the other hand, if 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, in the concave portion of the fine pattern formed on the mold 205 in the mold contact step, the gas (condensable gas and helium) together with the curable composition (A1) 202 and / or the curable composition (A2) 203 is contained. ) Is condensed, the condensable gas liquefies and helium passes through the mold 205.
- irradiation light is transmitted through a mold 205 to a mixed layer formed by partially mixing the curable composition (A 1) 202 and the curable composition (A 2) 203. 206 is irradiated. More specifically, the curable composition (A1) 202 and / or the curable composition (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 the curable composition (A2) 203 filled in the fine pattern of the mold 205 is cured by the irradiated light 206 and has a cured film 207 having a pattern shape. It becomes.
- the irradiation light 206 for irradiating the curable composition (A1) 202 and / or the curable composition (A2) 203 filled in the fine pattern of the mold 205 is the curable composition (A1) 202 and the curable composition. It is selected according to the sensitivity wavelength of the composition (A2) 203. Specifically, light that does not cure the curable composition (A1) 202, that is, light that does not include a wavelength of 350 nm or less is preferably selected and used, and single wavelength light of 365 nm or 375 nm is more preferable. Among these, the irradiation light 206 is particularly preferably ultraviolet light.
- UV 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, a laser diode (for example, L375P70MLD (manufactured by THORLABS)) and the like can be mentioned, and an ultrahigh pressure mercury lamp is particularly preferable. Further, 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 the curable composition (A2) 203 filled in the fine pattern of the mold 205, and in a partial region. You may only go.
- 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 diffusion of the leaked light that is, the light outside the shot region is inevitable due to the cost restrictions of the mold 205 and the apparatus.
- the curable composition (A1) 202 alone is not cured by light irradiation.
- the curable composition (A1) 202 on the adjacent shot region is not cured by the leakage light generated from the shot. For this reason, it is possible to form a pattern with few unfilled defects in a short filling time in the entire adjacent shot.
- the photopolymerization initiator of the curable composition (A2) 203 is obtained.
- the component (b2) is also transferred to the curable composition (A1) 202, and the curable composition (A1) 202 obtains photoreactivity, so that the curable composition (A1) 202 and the curable composition ( All of A2) 203 are cured by the irradiated light 206 to be a cured film 207 having a pattern shape.
- the cured film 207 having a pattern shape is separated from the mold 205.
- this step (release step) as shown in FIG. 2G, the cured film 207 having a pattern shape is separated from the mold 205, and formed on the mold 205 in the step (4) (light irradiation step). Further, the cured film 207 having a pattern shape to be a reverse pattern of the fine pattern is obtained in a self-supporting state. Note that the cured film remains in the concave portions of the uneven pattern of the cured film 207 having a pattern shape, and this film is referred to as a remaining film 108 (see FIG. 1 (fa)).
- 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.
- 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 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.
- a processed substrate can be obtained by processing into a pattern using a processing means.
- 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.
- 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. That is, the present invention forms a liquid film as a pretreatment coating on a substrate, and applies droplets made of the curable composition (A2) to the liquid film, thereby spreading droplet components in the substrate surface direction.
- an imprint pretreatment coating material comprising the curable composition (A1) that promotes the polymerization, and has at least the component (a1) that is a polymerizable compound, and the content of the component (b1) that is the photopolymerization initiator is When the exposure is performed under the conditions of 0 part by weight or more and less than 0.1 part by weight with respect to 100 parts by weight of the polymerizable compound component (a1), an illuminance of 1.00 mW / cm 2 and an exposure time of 100.0 seconds. And the imprint pretreatment coating material characterized in that the polymerization conversion of the component (a1) which is the polymerizable compound is less than 50%.
- 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 Preparation of curable composition (A1-1) The following components (a1), (b1), (c1), (d1) and (e1) were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight 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) Total 0 parts by weight Component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the area intensity of the peak at 810 cm ⁇ 1 derived from the acrylic group of component (a1) is greater than 50% of the initial value immediately after the start of light irradiation at an exposure time of 100.0 seconds, that is, the polymerization conversion is 50 % (Half-exposure exposure is greater than 100 mJ / cm 2 ). From this, it was found that the curable composition (A1-1) had low reactivity to UV light, and the curable composition (A1-1) alone was not cured by leakage light.
- curable composition (A2-1) Component (a2), component (b2), component (c2), component (d2) and component (e2) shown below were blended, and The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight 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 (5-2)
- Component (b2) Total 3 parts by weight Irgacure 651 (manufactured by BASF): 3 parts by weight (5 -3)
- Component (c2) Total 0 parts by weight Component (c2) was not added.
- Component (d2) Total 0 parts by weight Component (d2) was not added.
- Component (e2) Total 0 parts by weight Component (e2) was not added.
- a curable composition (A1-1) having a thickness of about 5 to 10 nm is formed by applying the curable composition (A1-1) onto a silicon substrate using a spin coater. 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 photopolymerization initiator component (b2) is mixed from the curable composition (A2-1).
- the curable composition (A1-1) 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.
- the optical nanoimprint process can be performed in the adjacent shot region with the same productivity and accuracy as the shot region.
- Example 2 (1) to (4) Curable composition (A1-2)
- the same composition as in Example 1 was used as the curable composition (A1-2).
- curable composition (A2-2) Component (a2), component (b2), component (c2), component (d2) and component (e2) shown below were blended, and The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A2-1) of Example 2.
- Component (a2) 94 parts by weight in total The same as in Example 1.
- Component (b2) Total 3 parts by weight Irgacure 907 (manufactured by BASF): 3 parts by weight
- Component (c2) Total 0 parts by weight The same as in Example 1.
- Component (d2) Total 0 parts by weight The same as in Example 1.
- Component (e2) Total 0 parts by weight The same as in Example 1.
- 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.
- Example 3 (1) to (4) Curable composition (A1-3)
- the same composition as in Example 1 was used as the curable composition (A1-3).
- curable composition (A2-3) The following components (a2), (b2), (c2), (d2) and (e2) were blended, and The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A2-3) of Example 3.
- Component (a2) 94 parts by weight in total The same as in Example 1.
- Component (b2) Total 3 parts by weight Irgacure 369 (manufactured by BASF): 3 parts by weight
- Component (c2) Total 0 parts by weight The same as in Example 1.
- Component (d2) Total 0 parts by weight The same as in Example 1.
- Component (e2) Total 0 parts by weight The same as in Example 1.
- the mixture of the curable composition (A1-3) and the curable composition (A2-3) is cured well in the light irradiation step.
- the curing of the curable composition (A1-3) in the adjacent portion due to the leaked light generated from the imprint shot does not proceed. That is, the optical nanoimprint process can be performed in the adjacent shot region with the same productivity and accuracy as the shot region.
- Example 4 Preparation of curable composition (A1-4) The following components (a1), (b1), (c1), (d1) and (e1) were blended, and The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-4) of Example 4.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (c1) Total 0 parts by weight Component (c1) was not added.
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) 33,000 parts by weight in total Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry, abbreviation PGMEA): 33000 parts by weight
- curable composition (A2-4) The following components (a2), (b2), (c2), (d2) and (e2) were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight 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 (5-2) Component (b2): 3 parts by weight in total Darocur (registered trademark) TPO (manufactured by BASF, abbreviated name) TPO): 3 parts by weight (5-3) Component (c2): Total 0 parts by weight Component (c2) was not added. (5-4) Component (d2): Total 0 parts by weight Component (d2) was not added. (5-5) Component (e2): Total 0 parts by weight Component (e2) was not added.
- the mixture of the curable composition (A1-4) and the curable composition (A2-4) is cured well in the light irradiation step.
- the curing of the curable composition (A1-4) in the adjacent portion due to the leakage light generated from the imprint shot does not proceed. That is, the optical nanoimprint process can be performed in the adjacent shot region with the same productivity and accuracy as the shot region.
- Example 5 Preparation of curable composition (A1-5) The following components (a1), (b1), (c1), (d1) and (e1) were blended, and The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-5) of Example 5.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b1) was not added.
- Component (1-3) Component (c1): Total 0.5 parts by weight 7-Diethylamino-4-methylcoumarin (Tokyo Chemical Industry, abbreviation EAMC): Total 0.5 parts by weight (1-4)
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the curable composition (A1-5) has low reactivity to UV light, and the curable composition (A1-5) alone is not cured by leakage light.
- Simulated curable composition (A1 ′′) Component (a1) which is the polymerizable compound except the component (c1) which is a sensitizer and the component (e1) which is a solvent from the curable composition (A1-5) ) 0.5 parts by weight of TPO was added as a component (b2) which is a photopolymerization initiator to 100 parts by weight.
- the value obtained by subtracting the polymerization conversion rate of the curable composition (A1 ′′) from the polymerization conversion rate of the curable composition (A1 ′) was defined as the value of the sensitizing effect. Note that an increase in the value of the sensitizing effect in the positive direction means that the sensitizing action is working more strongly.
- component (b2) which is a photoinitiator is from curable composition (A2) when curable composition (A1) and (A2) were laminated
- the polymerization conversion rates of the curable compositions (A1 ′) and (A1 ′′) were evaluated. However, the exposure time was 3.2 seconds. The polymerization conversion rate of the curable composition (A1 ′) was 25%, and the polymerization conversion rate of the curable composition (A1 ′′) was 0%. It was +25 points when the sensitizing effect was calculated from this result. This confirmed that EAMC has a sensitizing effect in the curable composition (A1-5).
- Curable composition (A2-5) The same composition as in Example 4 was used as the curable composition (A2-5).
- the mixture of the curable composition (A1-5) and the curable composition (A2-5) is cured well in the light irradiation step.
- Example 6 (1) Preparation of curable composition (A1-6) The following components (a1), (b1), (c1), (d1) and (e1) were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-6) of Example 6.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b1) was not added.
- Component (1-3) Component (c1): 0.5 parts by weight in total 4,4′-bis (diethylamino) benzophenone (Tokyo Chemical Industry, abbreviated EAB): 0.5 parts by weight (1-4)
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the exposure time 100.0 sec the polymerization conversion rate was found to be less than 50% (half decay exposure is greater than 100mJ / cm 2). From this, it was found that the curable composition (A1-6) has low reactivity to UV light, and the curable composition (A1-6) alone is not cured by leakage light.
- Curable composition (A2-6) The same composition as in Example 4 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.
- Example 7 (1) Preparation of curable composition (A1-7) Component (a1), component (b1), component (c1), component (d1) and component (e1) shown below were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-7) of Example 7.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b1) was not added.
- Component (1-3) Component (c1): Total 0.5 parts by weight 2-Isopropylthioxanthone (Tokyo Chemical Industry, abbreviated as ITX): 0.5 parts by weight (1-4)
- Component (d1) Total 0 parts by weight Component ( d1) was not added.
- Component (e1) 33,000 parts by weight in total Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry, abbreviation PGMEA): 33000 parts by weight
- the exposure time 100.0 sec the polymerization conversion rate was found to be less than 50% (half decay exposure is greater than 100mJ / cm 2). From this, it was found that the curable composition (A1-7) has low reactivity to UV light, and the curable composition (A1-7) alone is not cured by leakage light.
- Curable composition (A2-7) The same composition as in Example 4 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.
- the curing of the curable composition (A1-7) in the adjacent portion due to the leaked light generated from the imprint shot does not proceed. That is, the optical nanoimprint process can be performed in the adjacent shot region with the same productivity and accuracy as the shot region.
- Example 8 (1) Preparation of curable composition (A1-8) The following components (a1), (b1), (c1), (d1), and (e1) were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-8) of Example 8.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b1) was not added.
- Component (1-3) Component (c1): Total 1 part by weight 7-Diethylamino-4-methylcoumarin (Tokyo Chemical Industry, abbreviation EAMC): 1 part by weight (1-4)
- Component (d1) Total 0 part by weight Component ( d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the curable composition (A1-8) has low reactivity to UV light, and the curable composition (A1-8) alone is not cured by leakage light.
- Curable composition (A2-8) The same composition as in Example 4 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 in the light irradiation step.
- Example 9 (1) Preparation of curable composition (A1-9) The following components (a1), (b1), (c1), (d1) and (e1) were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-9) of Example 9.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b) was not added.
- Component (1-3) Component (c1): Total 3 parts by weight 7-Diethylamino-4-methylcoumarin (Tokyo Chemical Industry, abbreviation EAMC): 3 parts by weight (1-4)
- Component (d1) Total 0 parts by weight Component ( d) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the curable composition (A1-9) has low reactivity to UV light, and the curable composition (A1-9) alone is not cured by leakage light.
- Curable composition (A2-9) The same composition as in Example 4 was used as the curable composition (A2-9).
- the mixture of the curable composition (A1-9) and the curable composition (A2-9) is cured well in the light irradiation step.
- Example 10 (1) Preparation of curable composition (A1-10) Component (a1), component (b1), component (c1), component (d1) and component (e1) shown below were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-10) of Example 10.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b1) was not added.
- Component (1-3) Component (c1): 0.1 part by weight in total 4,4′-bis (diethylamino) benzophenone (Tokyo Chemical Industry, abbreviated as EAB): 0.1 part by weight (1-4)
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) 33,000 parts by weight in total Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry, abbreviation PGMEA): 33000 parts by weight
- the curable composition (A1-10) has low reactivity to UV light, and the curable composition (A1-10) alone is not cured by leakage light.
- Curable composition (A2-10) The same composition as in Example 4 was used as the curable composition (A2-10).
- the mixture of the curable composition (A1-10) and the curable composition (A2-10) is cured well in the light irradiation step.
- Example 11 (1) Preparation of curable composition (A1-11) Component (a1), component (b1), component (c1), component (d1) and component (e1) shown below were blended, and The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-11) of Example 11.
- Component (a1) Total 100 parts by weight Dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., abbreviated as DCPDA): 100 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component ( b1) was not added.
- Component (c1) Total 0.05 parts by weight 4,4′-bis (diethylamino) benzophenone (Tokyo Chemical Industry, abbreviated EAB): Total 0.05 parts by weight (1-4)
- Component (d1) 0 parts by weight in total No component (d1) was added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the exposure time 100.0 sec the polymerization conversion rate was found to be less than 50% (half decay exposure is greater than 100mJ / cm 2). From this, it was found that the curable composition (A1-11) has low reactivity to UV light, and the curable composition (A1-11) alone is not cured by leakage light.
- Curable composition (A2-11) The same composition as in Example 4 was used as the curable composition (A2-11).
- the mixture of the curable composition (A1-11) and the curable composition (A2-11) is cured well in the light irradiation step.
- Example 12 (1) Preparation of curable composition (A1-12) The same composition as in Example 1 was used as the curable composition (A1-12).
- the exposure amount necessary for the polymerization conversion rate to be 3% was 14000 mJ / cm 2 or more, that is, the polymerization reaction Was confirmed not to proceed substantially. From this, it was found that the curable composition (A1-12) has low reactivity to 365 nm UV light, and the curable composition (A1-12) alone is not cured by leakage light.
- Curable composition (A2-12) The same composition as in Example 4 was used as the curable composition (A2-12).
- the mixture of the curable composition (A1-12) and the curable composition (A2-12) is cured well in the light irradiation step.
- Example 13 (1) Preparation of curable composition (A1-13) The same composition as in Example 4 was used as the curable composition (A1-13).
- the exposure necessary for the polymerization conversion rate to be 3% was 14000 mJ / cm 2 or more. That is, it was confirmed that the polymerization reaction did not substantially proceed. From this, it was found that the curable composition (A1-13) has low reactivity to 365 nm UV light, and the curable composition (A1-13) alone is not cured by leakage light.
- Curable composition (A2-13) The same composition as in Example 4 was used as the curable composition (A2-13).
- the mixture of the curable composition (A1-13) and the curable composition (A2-13) is cured well in the light irradiation step.
- the curing of the curable composition (A1-13) in the adjacent portion due to the leaked light generated from the imprint shot does not proceed. That is, the optical nanoimprint process can be performed in the adjacent shot region with the same productivity and accuracy as the shot region.
- Example 14 (1) Preparation of curable composition (A1-14) Component (a1), component (b1), component (c1), component (d1) and component (e1) shown below were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-14) of Example 14.
- Component (a1) Total 100 parts by weight Polyethylene glycol # 200 diacrylate (Shin Nakamura Kogyo Co., Ltd., abbreviated as 4EGDA): 100 parts by weight (1-2)
- Component (b1): Total 0 parts by weight Component ( b1) was not added.
- Component (c1) Total 0 parts by weight Component (c1) was not added.
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the exposure necessary for the polymerization conversion rate to be 3% was 14000 mJ / cm 2 or more. That is, it was confirmed that the polymerization reaction did not substantially proceed. From this, it was found that the curable composition (A1-14) has low reactivity to 365 nm UV light, and the curable composition (A1-14) alone is not cured by leakage light.
- Curable composition (A2-14) The same composition as in Example 4 was used as the curable composition (A2-14).
- the mixture of the curable composition (A1-14) and the curable composition (A2-14) is cured well in the light irradiation step.
- Example 15 (1) Preparation of curable composition (A1-15) Component (a1), component (b1), component (c1), component (d1) and component (e1) shown below were blended, The mixture was filtered through a 2 ⁇ m ultrahigh molecular weight polyethylene filter to prepare a curable composition (A1-15) of Example 15.
- Component (a1) Total 100 parts by weight Polyethylene glycol # 200 diacrylate (manufactured by Shin-Nakamura Chemical, abbreviated 4EGDA): 75 parts by weight dimethylol tricyclodecane diacrylate (manufactured by Shin-Nakamura Chemical, abbreviated DCPDA): 25 parts by weight (1-2)
- Component (b1) Total 0 parts by weight Component (b1) was not added.
- Component (c1) Total 0 parts by weight Component (c1) was not added.
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- the exposure necessary for the polymerization conversion rate to be 3% was 14000 mJ / cm 2 or more. That is, it was confirmed that the polymerization reaction did not substantially proceed. From this, it was found that the curable composition (A1-15) has low reactivity to 365 nm UV light, and the curable composition (A1-15) alone is not cured by leakage light.
- Curable composition (A2-15) The same composition as in Example 4 was used as the curable composition (A2-15).
- the mixture of the curable composition (A1-15) and the curable composition (A2-15) is cured well in the light irradiation step.
- the curing of the curable composition (A1-15) in the adjacent portion due to the leakage light generated from the imprint shot does not proceed. That is, the optical nanoimprint process can be performed in the adjacent shot region with the same productivity and accuracy as the shot region.
- Curable composition (A2-0 ′) The same composition as in Example 1 was used as the curable composition (A2-0 ′).
- the substrate surface which is a solid surface, is not reactive to UV light, it is possible to perform the optical nanoimprint process with the same accuracy even in adjacent parts without being affected by the leakage light generated from the imprint shot. is there.
- 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) 3 parts by weight in total Irgacure 369 (manufactured by BASF): 3 parts by weight (1-3)
- Component (c1) Total 0 parts by weight Component (c1) was not added.
- Component (d1) A total of 0 parts by weight of component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- Curable composition (A1-1 ′) excluding component (e1) which is a solvent in the same manner as curable composition (A1-1) It was 5.91 mPa * s when the viscosity in 25 degreeC of the composition of this component was measured.
- 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.
- the curable composition (A1-1 ′) in the adjacent portion is cured by the leakage light generated from the imprint shot.
- the curable composition (A1-1 ′) is a solid film in the portion irradiated with the leaking light in the adjacent portion.
- the Marangoni effect does not appear with respect to the composition (A2-1 ′), and the expansion of the droplets is slow.
- the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- 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) 3 parts by weight in total Irgacure 907 (manufactured by BASF): 3 parts by weight (1-3)
- Component (c1) Total 0 parts by weight Component (c1) was not added.
- Component (d1) A total of 0 parts by weight of component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- Curable composition (A1-2 ′) excluding component (e1) which is a solvent in the same manner as curable composition (A1-1) It was 5.91 mPa * s when the viscosity in 25 degreeC of the composition of this component was measured.
- Curable composition (A2-2 ′) The same composition as in Example 1 was used as the curable composition (A2-2 ′).
- 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 (A1-2 ′) in the adjacent portion is cured by the leaked light generated from the imprint shot.
- the curable composition (A1-2 ′) is a solid film in the portion irradiated with the leaking light in the adjacent portion.
- the Marangoni effect does not appear with respect to the composition (A2-2 ′), and the expansion of the droplets is slow.
- the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- curable composition (A1-3 ′) Component (a1), component (b1), component (c1), component (d1) and component (e1) shown below were blended, and this was changed to 0 The mixture was filtered through a 2 ⁇ m ultrahigh 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) 3 parts by weight in total Irgacure 651 (manufactured by BASF): 3 parts by weight (1-3)
- Component (c1) Total 0 parts by weight Component (c1) was not added.
- Component (d1) Total 0 parts by weight Component (d1) was not added.
- Component (e1) Total 33000 parts by weight Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry, abbreviated as PGMEA): 33000 parts by weight
- Curable composition (A1-3 ′) excluding component (e1) which is a solvent in the same manner as curable composition (A1-1) It was 5.91 mPa * s when the viscosity in 25 degreeC of the composition of this component was measured.
- 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.
- the curable composition (A1-3 ′) in the adjacent portion is cured by the leakage light generated from the imprint shot.
- the curable composition (A1-3 ′) is a solid film in the portion irradiated with the leaking light in the adjacent portion.
- the Marangoni effect does not appear with respect to the composition (A2-3 ′), and the expansion of the droplets is slow.
- the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- the curable composition (A1-4 ′) has higher reactivity to UV light of 313 nm than 365 nm, and the curable composition (A1-4 ′) is cured by leak light alone. It turns out that the possibility is high.
- Curable composition (A1-4 ′) excluding component (e1) as a solvent in the same manner as curable composition (A1-1) It was 84.7 mPa * s when the viscosity in 25 degreeC of the composition of the component of this was measured.
- Curable composition (A2-4 ′) The same composition as Comparative Example 0 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.
- the curable composition (A1-4 ′) in the adjacent portion is cured by the leakage light generated from the imprint shot.
- the curable composition (A1-4 ′) when imprinting is performed in an adjacent shot, the curable composition (A1-4 ′) is a solid film in the portion irradiated with leakage light in the adjacent portion.
- the Marangoni effect does not appear with respect to the composition (A2-4 ′), and the expansion of the droplets is slow. For this reason, the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- the curable composition (A1-5 ′) has a higher reactivity to UV light of 313 nm than 365 nm, and the curable composition (A1-5 ′) is cured by leak light alone. It turns out that the possibility is high.
- Curable composition (A1-5 ′) excluding component (e1) which is a solvent in the same manner as curable composition (A1-1) It was 126 mPa * s when the viscosity in 25 degreeC of the composition of the component of this was measured.
- Curable composition (A2-5 ′) The same composition as Comparative Example 0 was used as the curable composition (A2-5 ′).
- the mixture of the curable composition (A1-5 ′) and the curable composition (A2-5 ′) is cured well in the light irradiation step.
- the curable composition (A1-5 ′) in the adjacent portion is cured by the leakage light generated from the imprint shot.
- the curable composition (A1-5 ′) is a solid film in the portion irradiated with leakage light in the adjacent portion.
- the Marangoni effect does not appear with respect to the composition (A2-5 ′), and the expansion of the droplets is slow.
- the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- the curable composition (A1-6 ′) has higher reactivity with respect to 313 nm UV light than 365 nm, and the curable composition (A1-6 ′) is cured by leak light alone. I understood it.
- Curable composition (A1-6 ′) excluding component (e1) as a solvent in the same manner as curable composition (A1-1) It was 17.7 mPa * s when the viscosity at 25 degrees C of the composition of this component was measured.
- Curable composition (A2-6 ′) The same composition as Comparative Example 0 was used as the curable composition (A2-6 ′).
- the mixture of the curable composition (A1-6 ′) and the curable composition (A2-6 ′) is cured well in the light irradiation step.
- the curable composition (A1-6 ′) in the adjacent portion is cured by the leakage light generated from the imprint shot. That is, when imprinting is performed in an adjacent shot, the curable composition (A1-6 ′) is a solid film in the portion irradiated with the leaking light in the adjacent portion. The Marangoni effect does not appear with respect to the composition (A2-6 ′), and the expansion of the droplets is slow. For this reason, the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- the curable composition (A1-7 ′) has a higher reactivity to UV light of 313 nm than 365 nm, and the curable composition (A1-7 ′) is cured by leak light alone. I understood it.
- Curable composition (A2-7 ′) The same composition as Comparative Example 0 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.
- the curable composition (A1-7 ′) in the adjacent portion is cured by the leakage light generated from the imprint shot.
- the curable composition (A1-7 ′) when imprinting is performed in an adjacent shot, the curable composition (A1-7 ′) is a solid film in the portion irradiated with the leaking light in the adjacent portion.
- the Marangoni effect does not appear with respect to the composition (A2-7 ′), and the expansion of the droplets is slow. For this reason, the adjacent shot affected by the leaked light has a portion where the filling time is long depending on the location, and the productivity and / or accuracy of the optical nanoimprint process is low.
- the pre-spread evaluation was a relative evaluation based on Comparative Example 0. That is, if the speed is faster than 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 to 11 and Comparative Examples 1 to 3 are faster due to the Marangoni effect than Comparative Example 0, that is, the case where the curable composition (A1) is not used.
- Comparative Example 1 In Examples 1 to 11 and Comparative Example 0, there is no influence of leakage light on adjacent shots. Comparative Examples 1 to 3 have an effect and cause problems such as many unfilled defects and a long filling time. As described above, in Examples 1 to 11, it was shown that a high-speed pre-spread can be obtained without affecting the adjacent shots.
- Examples 5 to 11 in which the component (c1) as the sensitizer was added to the curable composition (A1) were compared with the compositions excluding the component (c1) as the sensitizer. It was shown that the polymerization conversion rate was increased.
- an optical nanoimprint pattern can be formed with high throughput and high accuracy by using the method of this embodiment.
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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)、
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)、
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層をサンドイッチする型接触工程(3)、
前記2種の硬化性組成物が部分的に混合してなる層をモールド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)、
を有する。
SST-NILにおいては、離散的に滴下された硬化性組成物(A2)203の液滴が、硬化性組成物(A1)202の液膜上において液滴の方向を示す矢印204で示すように速やかに拡大するため、充填時間が短く、高スループットである。SST-NILの詳しいメカニズムは後述する。
ここで、ショット領域304に隣接する隣接ショット領域305の一部において、漏れ光307による硬化性組成物(A1)302の硬化反応が進行し、漏れ光307で硬化した硬化性組成物(A1)309が存在することが確認された。そして、漏れ光307で硬化した硬化性組成物(A1)309上に滴下された硬化性組成物(A2)303の液滴310の拡大が遅くなることがわかった。本発明者らは、一部の液滴の拡大が遅いことで、隣接ショット領域305において未充填欠陥が生じるか、あるいは、未充填欠陥を発生させないために充填時間を長くする必要が生じ、結果として生産性が低下する、という課題を見出した。
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)及び光重合開始剤である成分(b2)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工程(5)、
を該順に有するパターン形成方法であって、
前記モールドと前記混合層とが接触する領域の周囲にも前記硬化性組成物(A1)が積層されており、
前記硬化性組成物(A1)の前記光重合開始剤である成分(b1)の含有量が、前記重合性化合物である成分(a1)100重量部に対して0重量部以上0.1重量部未満であり、
照度1.00mW/cm2、露光時間100.0秒の条件で露光した際に前記重合性化合物である成分(a1)の重合転化率が50%以下である、
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)、増感剤である成分(c)、非重合性化合物である成分(d)、溶剤である成分(e)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。
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)、成分(d1)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)、成分(d2)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。
硬化性組成物(A1)における成分(b1)の配合割合を成分(a1)100重量部に対して0.1重量部未満とすることにより、硬化性組成物(A1)は実質的に光反応性を有さない。このため、前述のような漏れ光307(図3)による光硬化が生じず、隣接ショット領域305(図3)においても短い充填時間でも未充填欠陥が少ないパターンが得られるのである。当該ショットにおける硬化性組成物(A1)の硬化反応については、後述する。
硬化性組成物(A2)における成分(b2)の配合割合を成分(a2)、成分(b2)、成分(c2)、成分(d2)の合計重量に対して0.1重量%以上とすることにより、組成物の硬化速度が速くなり、反応効率を良くすることができる。また、成分(b2)の配合割合を成分(a2)、成分(b2)、成分(c2)、成分(d2)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。
本明細書において増感剤である成分(c)は、光重合開始剤である成分(b)と共存した場合には光重合開始剤である成分(b)の光ラジカル発生を促進させる化合物であり、かつ増感剤である成分(c)単独では実質的に光ラジカル重合を開始する能力を有さない化合物と定義する。
増感剤である成分(c2)の硬化性組成物(A2)における配合割合は、成分(a2)、成分(b2)、成分(c2)、成分(d2)の合計重量、すなわち溶剤である成分(e2)を除く硬化性組成物(A2)の成分の合計重量、に対して0.01重量%以上10重量%以下が好ましく、0.01重量%以上3重量%以下が特に好ましい。増感剤である成分(c2)の硬化性組成物(A2)における配合割合が、成分(a2)、成分(b2)、成分(c2)、成分(d2)の合計重量に対して0.01重量%より少ないと増感効果が不十分な場合があり、10重量%より多いと増感剤である成分(c2)だけで光重合を開始する場合がある。
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)、成分(c)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(d)を含有することができる。このような成分(d)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、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(d)として前記化合物を複数種類含有してもよい。
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(d)の配合割合を成分(a)、成分(b)、成分(c)、成分(d)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は、溶剤である成分(e)を含有していてもよい。成分(e)としては、成分(a)、成分(b)、成分(c)、成分(d)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。
本実施形態に係る硬化性組成物(A2)の溶剤である成分(e2)を除く成分の組成物の25℃での粘度は、1mPa・s以上100mPa・s以下であることが好ましい。また、より好ましくは、1mPa・s以上50mPa・s以下であり、さらに好ましくは、1mPa・s以上12mPa・s以下である。
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)の表面張力は、溶剤である成分(e)を除く硬化性組成物(A1)及び(A2)の成分の組成物について23℃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)。
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(e)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)、成分(d)及び成分(e)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。
前記マランゴニ効果は、本発明の前記硬化性組成物(A1)及び(A2)が液体状態で接触することで十分に効果を発現する。しかしながら前記硬化性組成物(A1)を前記基板全面に塗布した後、前記硬化性組成物(A2)を部分的に塗布し光照射を行う際に、漏れ光により、つまり当該ショット領域外へ光が拡散し、当該ショット領域外に塗布された前記硬化性組成物(A1)の重合反応が進行してしまう場合がある。この重合反応は、前記硬化性組成物(A1)が前記光重合開始剤を実質的に含有していなくても極めてわずかに起こる。前記硬化性組成物(A1)の重合反応が進行し、硬化してしまった箇所は、前記硬化性組成物(A2)を塗布した際に、マラゴンニ効果が十分に発現せず、プレスプレッドが不十分で未充填欠陥が生じてしまう。
本発明で用いる硬化性組成物の、光照射による重合転化率は、例えば、図4に示すような光照射機構を備えた減衰全反射赤外分光測定装置400を用いて測定することができる。ここで、重合転化率は、光重合反応に伴う成分(a)の重合性官能基の消失割合として定義することができる。なお、この割合は、重合性官能基が重合した割合と同義である。
〔重合転化率(%)〕=100×(1-P2/P1) (1)
(式(1)において、P1は、光照射開始直後における成分(a)の重合性官能基に由来するピークのピーク強度(初期強度)を表し、P2は、任意の時間で露光した後における成分(a)の重合性官能基に由来するピークのピーク強度(初期強度)を表す。)
次に、本実施形態に係るパターン形成方法について、図2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)、
原型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)、
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2(a)及び(b)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(e1)は揮発し、基板201上には溶剤である成分(e1)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。
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及び硬化性組成物(A2)203との密着性を向上されていてもよい。
本工程(第二積層工程)では、図2(c)及び(d)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。
ここで、硬化性組成物(A1)202が増感剤である成分(c1)を含む場合、硬化性組成物(A2)203から移行してきた光重合開始剤である成分(b2)が増感剤である成分(c1)により増感されるため、当該ショットにおける硬化性組成物(A1)202の光硬化性が向上する。
次に、図2(e)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をレジストの光硬化膜から引き剥がす力、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及び硬化性組成物(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/または硬化性組成物(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2(f)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/または硬化性組成物(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/または硬化性組成物(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、レーザーダイオード(例えばL375P70MLD(THORLABS製))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/または硬化性組成物(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。
本発明においては、重合開始剤成分(b1)を実質的に含有しない(0.1重量%未満)ため、硬化性組成物(A1)202は単独では光照射によって硬化しない。このため、当該ショットから発生した漏れ光によって隣接ショット領域上の硬化性組成物(A1)202が硬化することはない。このため、隣接ショットにおいてもその全域で短い充填時間で未充填欠陥の少ないパターンを形成することができるのである。
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2(g)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(図1(fa)参照)と呼ぶこととする。
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)を有する硬化膜を得ることができる。
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。
すなわち、本発明は、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硬化性組成物(A1)からなるインプリント前処理コーティング材料であって、重合性化合物である成分(a1)を少なくとも有し、前記光重合開始剤である成分(b1)含有量が、前記重合性化合物である成分(a1)100重量部に対して0重量部以上0.1重量部未満であり、照度1.00mW/cm2、露光時間100.0秒の条件で露光した際に前記重合性化合物である成分(a1)の重合転化率が50%未満である、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。
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)、成分(e1)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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
溶剤である成分(e1)を除く硬化性組成物(A1-1)の成分の組成物、すなわち成分(a1)、成分(b1)、成分(c1)、及び成分(d1)の混合物、を調製した。その組成物を約10μLとり、これを減衰全反射赤外分光装置上のダイヤモンドATR結晶上に滴下して塗布膜を形成した。次に、厚さ1mmの石英ガラスを、形成した塗布膜上にかぶせた。
円錐平板方式回転型粘度計RE-85L(東機産業製)を用いて、溶剤である成分(e1)を除く硬化性組成物(A1-1)の成分の組成物の25℃における粘度を測定したところ、84.7mPa・sであった。
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(e1)を除く硬化性組成物(A1-1)の成分の組成物の表面張力の測定を行ったところ、35.5mN/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)、成分(e2)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。
(5-1)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
(5-2)成分(b2):合計3重量部
Irgacure651(BASF製):3重量部
(5-3)成分(c2):合計0重量部
成分(c2)は添加しなかった。
(5-4)成分(d2):合計0重量部
成分(d2)は添加しなかった。
(5-5)成分(e2):合計0重量部
成分(e2)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)の重合転化率を評価した。露光時間8.9秒で重合転化率が50%以上となる(半減露光量が8.9mJ/cm2)ことがわかった。
硬化性組成物(A1-1)と同様の方法で硬化性組成物(A2-1)の表面張力の測定を行ったところ、33.4mN/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)~(4)硬化性組成物(A1-2)について
実施例1と同様の組成物を硬化性組成物(A1-2)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)、成分(e2)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(A2-1)を調製した。
(5-1)成分(a2):合計94重量部
実施例1と同様とした。
(5-2)成分(b2):合計3重量部
Irgacure907(BASF製):3重量部
(5-3)成分(c2):合計0重量部
実施例1と同様とした。
(5-4)成分(d2):合計0重量部
実施例1と同様とした。
(5-5)成分(e2):合計0重量部
実施例1と同様とした。
実施例1と同様に硬化性組成物(A2-2)の重合転化率を評価した。露光時間8.3秒で重合転化率が50%以上となる(半減露光量が8.3mJ/cm2)ことがわかった。
実施例1と同様に硬化性組成物(A2-2)の表面張力の測定を行ったところ、33.4mN/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(A1-2)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)~(4)硬化性組成物(A1-3)について
実施例1と同様の組成物を硬化性組成物(A1-3)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)、成分(e2)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(A2-3)を調製した。
(5-1)成分(a2):合計94重量部
実施例1と同様とした。
(5-2)成分(b2):合計3重量部
Irgacure369(BASF製):3重量部
(5-3)成分(c2):合計0重量部
実施例1と同様とした。
(5-4)成分(d2):合計0重量部
実施例1と同様とした。
(5-5)成分(e2):合計0重量部
実施例1と同様とした。
実施例1と同様に硬化性組成物(A2-3)の重合転化率を評価した。露光時間2.4秒で重合転化率が50%以上となる(半減露光量が2.4mJ/cm2)ことがわかった。
実施例1と同様に硬化性組成物(A2-3)の表面張力の測定を行ったところ、33.4mN/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(A1-3)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)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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と同様の方法で硬化性組成物(A1-4)の重合転化率の評価を行った。重合転化率が50%未満である(半減露光量が100mJ/cm2より大きい)ことがわかった。このことから、硬化性組成物(A1-4)はUV光に対する反応性が低く、硬化性組成物(A1-4)は単独では漏れ光では硬化しないことがわかった。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-4)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-4)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
下記に示される成分(a2)、成分(b2)、成分(c2)、成分(d2)、成分(e2)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。
(5-1)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
(5-2)成分(b2):合計3重量部
Darocur(登録商標)TPO(BASF製、略称TPO):3重量部
(5-3)成分(c2):合計0重量部
成分(c2)は添加しなかった。
(5-4)成分(d2):合計0重量部
成分(d2)は添加しなかった。
(5-5)成分(e2):合計0重量部
成分(e2)は添加しなかった。
実施例1と同様の方法で硬化性組成物(A2-4)の重合転化率を評価した。露光時間3.7秒で重合転化率が50%以上となる(半減露光量が3.7mJ/cm2)ことがわかった。
実施例1と同様の方法で硬化性組成物(A2-4)の表面張力の測定を行ったところ、33.4mN/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(A1-4)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)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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0.5重量部
7-ジエチルアミノ-4-メチルクマリン(東京化成工業、略称EAMC):合計0.5重量部
(1-4)成分(d1):合計0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例1と同様に硬化性組成物(A1-5)の重合転化率の評価を行った。ただし、露光時間は、3.2秒及び100.0秒の2通りを行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、EAMCは硬化性組成物(A1-5)において実質的に光重合を開始する能力を有さないことが確認された。
増感効果の評価は、以下に示す模擬硬化性組成物(A1’)及び模擬硬化性組成物(A1’’)の重合転化率を比較評価することで行った。
模擬硬化性組成物(A1’):増感剤である成分(c1)を有する前記硬化性組成物(A1-5)から溶剤である成分(e1)を除き前記重合性化合物である成分(a1)100重量部に対して光重合開始剤である成分(b2)としてTPO0.5重量部を添加した。
模擬硬化性組成物(A1’’):前記硬化性組成物(A1-5)から増感剤である成分(c1)と溶剤である成分(e1)を除き前記重合性化合物である成分(a1)100重量部に対して光重合開始剤である成分(b2)としてTPO0.5重量部を添加した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-5)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-5)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4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)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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0.5重量部
4,4’-ビス(ジエチルアミノ)ベンゾフェノン(東京化成工業、略称EAB):0.5重量部
(1-4)成分(d1):合計0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例5と同様の方法で硬化性組成物(A1-6)の重合転化率の評価を行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、EABは硬化性組成物(A1-6)において実質的に光重合を開始する能力を有さないことが確認された。
実施例5と同様の方法で硬化性組成物(A1-6)に含有される増感剤の増感効果の評価を行った。模擬硬化性組成物(A1’)の重合転化率は28%であり、模擬硬化性組成物(A1’’)の重合転化率は0%であった。この結果から増感効果を計算したところ+28ポイントであった。このことにより、EABが硬化性組成物(A1-6)において増感効果を有することが確認された。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-6)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-6)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4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)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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0.5重量部
2-イソプロピルチオキサントン(東京化成工業、略称ITX):0.5重量部
(1-4)成分(d1):合計0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例5と同様の方法で硬化性組成物(A1-7)の重合転化率の評価を行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、ITXは硬化性組成物(A1-7)において実質的に光重合を開始する能力を有さないことが確認された。
実施例5と同様の方法で硬化性組成物(A1-7)に含有される増感剤の増感効果の評価を行った。模擬硬化性組成物(A1’)の重合転化率は26%であり、模擬硬化性組成物(A1’’)の重合転化率は0%であった。この結果から増感効果を計算したところ+26ポイントであった。このことにより、ITXが硬化性組成物(A1-7)において増感効果を有することが確認された。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-7)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-7)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4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)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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1重量部
7-ジエチルアミノ-4-メチルクマリン(東京化成工業、略称EAMC):1重量部
(1-4)成分(d1):合計0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例5と同様の方法で硬化性組成物(A1-8)の重合転化率の評価を行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、EAMCは硬化性組成物(A1-8)において実質的に光重合を開始する能力を有さないことが確認された。
実施例5と同様の方法で硬化性組成物(A1-8)に含有される増感剤の増感効果の評価を行った。模擬硬化性組成物(A1’)の重合転化率は26%であり、模擬硬化性組成物(A1’’)の重合転化率は0%であった。この結果から増感効果を計算したところ+26ポイントであった。このことにより、EAMCが硬化性組成物(A1-8)において増感効果を有することが確認された。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-8)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-8)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4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)硬化性組成物(A1-9)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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(A1-9)を調製した。
(1-1)成分(a1):合計100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):100重量部
(1-2)成分(b1):合計0重量部
成分(b)は添加しなかった。
(1-3)成分(c1):合計3重量部
7-ジエチルアミノ-4-メチルクマリン(東京化成工業、略称EAMC):3重量部
(1-4)成分(d1):合計0重量部
成分(d)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例5と同様の方法で硬化性組成物(A1-9)の重合転化率の評価を行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、EAMCは硬化性組成物(A1-9)において実質的に光重合を開始する能力を有さないことが確認された。
実施例5と同様の方法で硬化性組成物(A1-9)に含有される増感剤の増感効果の評価を行った。模擬硬化性組成物(A1’)の重合転化率は28%であり、模擬硬化性組成物(A1’’)の重合転化率は0%であった。この結果から増感効果を計算したところ+28ポイントであった。このことにより、EAMCが硬化性組成物(A1-9)において増感効果を有することが確認された。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-9)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-9)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-9)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(A1-9)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)硬化性組成物(A1-10)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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10の硬化性組成物(A1-10)を調製した。
(1-1)成分(a1):合計100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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0.1重量部
4,4’-ビス(ジエチルアミノ)ベンゾフェノン(東京化成工業、略称EAB):0.1重量部
(1-4)成分(d1):合計0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例5と同様の方法で硬化性組成物(A1-10)の重合転化率の評価を行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、EABは硬化性組成物(A1-10)において実質的に光重合を開始する能力を有さないことが確認された。
実施例5と同様の方法で硬化性組成物(A1-10)に含有される増感剤の増感効果の評価を行った。模擬硬化性組成物(A1’)の重合転化率は25%であり、模擬硬化性組成物(A1’’)の重合転化率は0%であった。この結果から増感効果を計算したところ+25ポイントであった。このことにより、EABが硬化性組成物(A1-10)において増感効果を有することが確認された。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-10)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-10)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-10)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(A1-10)の表面張力は、その上層に滴下される硬化性組成物(A2-10)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(A2-10)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(A1-11)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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11の硬化性組成物(A1-11)を調製した。
(1-1)成分(a1):合計100重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):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0.05重量部
4,4’-ビス(ジエチルアミノ)ベンゾフェノン(東京化成工業、略称EAB):合計0.05重量部
(1-4)成分(d1):合計0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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
(2-1)隣接ショットにおける光硬化性の評価
実施例5と同様の方法で硬化性組成物(A1-11)の重合転化率の評価を行った。露光時間3.2秒では、重合転化率は3%未満であることがわかった。このことにより、EABは硬化性組成物(A1-11)において実質的に光重合を開始する能力を有さないことが確認された。
実施例4と同様の方法で硬化性組成物(A1-11)に含有される増感剤の増感効果の評価を行った。模擬硬化性組成物(A1’)の重合転化率は9%であり、模擬硬化性組成物(A1’’)の重合転化率は0%であった。この結果から増感効果を計算したところ+9ポイントであった。このことにより、EABが硬化性組成物(A1-11)において増感効果を有することが確認された。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-11)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-11)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-11)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(A1-11)の表面張力は、その上層に滴下される硬化性組成物(A2-11)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(A2-11)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(A1-12)の調製
実施例1と同様の組成物を硬化性組成物(A1-12)として用いた。
溶剤である成分(e1)を除く硬化性組成物(A1-12)の成分の組成物を調製した。この組成物を約10μLとり、これを減衰全反射赤外分光装置上のダイヤモンドATR結晶上に滴下して塗布膜を形成した。次に、厚さ1mmの石英ガラスを、形成した塗布膜上にかぶせた。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-12)の成分の組成物の25℃における粘度を測定したところ、84.7mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-12)の成分の組成物の表面張力の測定を行ったところ、35.5mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-12)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(A1-12)の表面張力は、その上層に滴下される硬化性組成物(A2-12)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(A2-12)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(A1-13)の調製
実施例4と同様の組成物を硬化性組成物(A1-13)として用いた。
実施例12と同様に溶剤である成分(e1)を除く硬化性組成物(A1-13)の成分の組成物の波長365nmでの露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-13)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-13)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-13)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(A1-13)の表面張力は、その上層に滴下される硬化性組成物(A2-13)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(A2-13)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(A1-14)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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14の硬化性組成物(A1-14)を調製した。
(1-1)成分(a1):合計100重量部
ポリエチレングリコール#200ジアクリレート(新中村工業株式会社、略称4EGDA):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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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12と同様に溶剤である成分(e1)を除く硬化性組成物(A1-14)の成分の組成物の波長365nmでの露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-14)の成分の組成物の25℃における粘度を測定したところ、17.7mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-14)の成分の組成物の表面張力の測定を行ったところ、39.7mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-14)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(A1-14)の表面張力は、その上層に滴下される硬化性組成物(A2-14)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(A2-14)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(A1-15)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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15の硬化性組成物(A1-15)を調製した。
(1-1)成分(a1):合計100重量部
ポリエチレングリコール#200ジアクリレート(新中村化学製、略称4EGDA):75重量部
ジメチロールトリシクロデカンジアクリレート(新中村化学製、略称DCPDA):25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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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12と同様に溶剤である成分(e1)を除く硬化性組成物(A1-15)の成分の組成物の波長365nmでの露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-15)の成分の組成物の25℃における粘度を測定したところ、22.5mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-15)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
実施例4と同様の組成物を硬化性組成物(A2-15)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(A1-15)の表面張力は、その上層に滴下される硬化性組成物(A2-15)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(A2-15)の液滴の拡大(プレスプレッド)は速やかである。
実施例1と同様に、当該インプリントショットから発生した漏れ光による隣接部分の硬化性組成物(A1-15)の硬化が進まない。つまり、隣接ショット領域においても光ナノインプリントプロセスを当該ショット領域と同様の生産性と精度で実施することが可能である。
(1)~(3)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)、成分(e1)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3重量部
Irgacure369(BASF製):3重量部
(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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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と同様に硬化性組成物(A1-1´)の重合転化率を評価した。露光時間0.6秒で重合転化率が50%以上となる(半減露光量が0.6mJ/cm2)ことがわかった。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-1´)の成分の組成物の25℃における粘度を測定したところ、5.91mPa・sであった。
実施例1と同様に溶剤である成分(e1)を除く硬化性組成物(A1-1´)の成分の組成物の表面張力の測定を行ったところ、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(A2-1´)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)、成分(e1)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3重量部
Irgacure907(BASF製):3重量部
(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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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と同様に硬化性組成物(A1-2´)の重合転化率を評価した。露光時間1.2秒で重合転化率が50%以上となる(半減露光量が1.2mJ/cm2)ことがわかった。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-2´)の成分の組成物の25℃における粘度を測定したところ、5.91mPa・sであった。
実施例1と同様に溶剤である成分(e1)を除く硬化性組成物(A1-2´)の成分の組成物の表面張力の測定を行ったところ、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(A2-2´)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´)の調製
下記に示される成分(a1)、成分(b1)、成分(c1)、成分(d1)、成分(e1)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3重量部
Irgacure651(BASF製):3重量部
(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0重量部
成分(d1)は添加しなかった。
(1-5)成分(e1):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と同様に硬化性組成物(A1-3´)の重合転化率を評価した。露光時間7.5秒で重合転化率が50%以上となる(半減露光量が7.5mJ/cm2)ことがわかった。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-3´)の成分の組成物の25℃における粘度を測定したところ、5.91mPa・sであった。
実施例1と同様に溶剤である成分(e1)を除く硬化性組成物(A1-3´)の成分の組成物の表面張力の測定を行ったところ、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。
(1)硬化性組成物(A1-4´)の調製
実施例1と同様の組成物を硬化性組成物(A1-4´)として用いた。
干渉フィルタをHG0313(朝日分光株式会社)に変更し波長を313mにし、照度を74.0mW/cm2に変更した以外は、実施例12と同様に溶剤である成分(e1)を除く硬化性組成物(A1-4´)の成分の組成物の露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-4´)の成分の組成物の25℃における粘度を測定したところ、84.7mPa・sであった。
実施例1と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-4´)の成分の組成物の表面張力の測定を行ったところ、35.5mN/mであった。
比較例0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´)の調製
実施例4と同様の組成物を硬化性組成物(A1-5´)として用いた。
比較例4と同様に溶剤である成分(e1)を除く硬化性組成物(A1-5´)の成分の組成物の波長313nmで露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-5´)の成分の組成物の25℃における粘度を測定したところ、126mPa・sであった。
実施例4と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-5´)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
比較例0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´)の調製
実施例14と同様の組成物を硬化性組成物(A1-6´)として用いた。
比較例4と同様に溶剤である成分(e1)を除く硬化性組成物(A1-6´)の成分の組成物の波長313nmで露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-6´)の成分の組成物の25℃における粘度を測定したところ、17.7mPa・sであった。
実施例4と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-6´)の成分の組成物の表面張力の測定を行ったところ、39.7mN/mであった。
比較例0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´)の調製
実施例15と同様の組成物を硬化性組成物(A1-7´)として用いた。
比較例4と同様に溶剤である成分(e1)を除く硬化性組成物(A1-7´)の成分の組成物の波長313nmで露光量を評価した。
硬化性組成物(A1-1)と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-7´)の成分の組成物の25℃における粘度を測定したところ、22.5mPa・sであった。
実施例4と同様の方法で溶剤である成分(e1)を除く硬化性組成物(A1-7´)の成分の組成物の表面張力の測定を行ったところ、39.2mN/mであった。
比較例0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。
実施例1~15及び比較例0~7の組成表を表1及び表2に、実施例及び比較例の結果を表3から表5にまとめて示す。
以上のように、実施例1~11において、高速なプレスプレッドを隣接ショットへの影響なしに得られることが示された。
表4において実施例12~15、比較例4~7ついて実施例1~11と同様にプレスプレッド及び隣接ショットへの影響を評価した。実施例12~15では、プレスプレッド及び隣接ショットへの影響も良好であることが示された。対して比較例4~7は、プレスプレッドは良好ながら、隣接ショットへの漏れ光の影響があることが示された。
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 パターン形状を有する硬化膜
301 基板
302 硬化性組成物(A1)
303 硬化性組成物(A2)
304 ショット領域
305 隣接ショット領域
306 照射光
307 漏れ光
308 モールド
309 漏れ光で硬化した硬化性組成物(A1)
310 漏れ光で硬化した硬化性組成物(A1)上に滴下された硬化性組成物(A2)の液滴
400 減衰全反射赤外分光測定装置
401 赤外光
402 検出器
403 ダイヤモンドATR結晶
404 硬化性組成物
405 石英ガラス
406 エバネッセント波
407 照射光
Claims (27)
- 基板の表面に、少なくとも重合性化合物である成分(a1)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)及び光重合開始剤である成分(b2)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、
前記モールドと前記混合層とが接触する領域の周囲にも前記硬化性組成物(A1)が積層されており、
前記硬化性組成物(A1)の光重合開始剤である成分(b1)の含有量が、前記重合性化合物である成分(a1)100重量部に対して0重量部以上0.1重量部未満であり、
照度1.00mW/cm2、露光時間100.0秒の条件で露光した際に前記重合性化合物である成分(a1)の重合転化率が50%以下である、
ことを特徴とするパターン形成方法。 - 前記硬化性組成物(A1)が少なくとも増感剤である成分(c1)を含む、または少なくとも非重合性化合物である成分(d1)として水素供与体を含むことを特徴とする請求項1に記載のパターン形成方法。
- 溶剤である成分(e1)を除く前記硬化性組成物(A1)の成分の組成物の重合転化率が、照度1.00mW/cm2、露光時間3.2秒の露光条件で露光した際に、3%以下であることを特徴とする請求項2に記載のパターン形成方法。
- 前記硬化性組成物(A1)が、前記増感剤である成分(c1)として、ベンゾフェノン誘導体、チオキサントン誘導体、クマリン誘導体、からなる群より選択される少なくとも1種類の増感剤を含有することを特徴とする請求項3に記載のパターン形成方法。
- 前記硬化性組成物(A1)が、前記増感剤である成分(c1)として、7-ジエチルアミノ-4-メチルクマリン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2-イソプロピルチオキサントンから選択される少なくとも1種類の増感剤を含有することを特徴とする請求項3に記載のパターン形成方法。
- 前記増感剤である成分(c1)を有する前記硬化性組成物(A1)において溶剤である成分(e1)を除き前記重合性化合物である成分(a1)100重量部に対して前記光重合開始剤である成分(b2)0.5重量部を添加した硬化性組成物(A1’)と、前記硬化性組成物(A1)において前記増感剤である成分(c1)と前記溶剤である(e1)を除き前記重合性化合物である成分(a1)100重量部に対して前記光重合開始剤である成分(b2)0.5重量部を添加した硬化性組成物(A1’’)の重合転化率が、照度1.00mW/cm2、露光時間3.2秒で露光した際に、硬化性組成物(A1’)の重合転化率から硬化性組成物(A1’’)の重合転化率を引いた値が正の値とな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。
- 溶剤である成分(e1)を除く前記硬化性組成物(A1)の成分の合計重量に対して、前記増感剤である成分(c1)の配合割合が0.01重量%以上3重量%以下であることを特徴とする請求項2に記載のパターン形成方法。
- 基板の表面に、少なくとも重合性化合物である成分(a1)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)及び光重合開始剤である成分(b2)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)、
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、
前記モールドと前記混合層とが接触する領域の周囲にも前記硬化性組成物(A1)が積層されており、
前記硬化性組成物(A1)中の前記光重合開始剤である成分(b1)の含有量が、前記重合性化合物である成分(a1)100重量部に対して0重量部以上0.1重量部未満であり、
前記光照射工程(4)において照射される前記光が波長350nm以下の光を含まないことを特徴とするパターン形成方法。 - 前記光が波長365nmまたは375nmの単一波長光であ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。
- 前記重合性化合物である成分(a1)の重合転化率が3%となる露光量が14000mJ/cm2以上とな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。
- 前記重合性化合物である成分(a1)が、少なくとも単官能性(メタ)アクリルモノマー及び多官能性(メタ)アクリルモノマーのいずれか一方であることを特徴とする請求項8~10に記載のパターン形成方法。
- 溶剤である成分(e1)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、溶剤である成分(e2)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から11のいずれか1項に記載のパターン形成方法。
- 溶剤である成分(e1)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、溶剤である成分(e2)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12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13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14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15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15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15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)の混合物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15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、
重合性化合物である成分(a1)を少なくとも有し、
前記光重合開始剤である成分(b1)の含有量が、前記重合性化合物である成分(a1)100重量部に対して0重量部以上0.1重量部未満であり、
照度1.00mW/cm2、露光時間100.0秒の条件で露光した際に前記重合性化合物(a1)の重合転化率が50%以下である、
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が、増感剤として、ベンゾフェノン誘導体、チオキサントン誘導体、クマリン誘導体、からなる群より選択される少なくとも1種類の増感剤を含有することを特徴とする請求項20に記載の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が、増感剤として、7-ジエチルアミノ-4-メチルクマリン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2-イソプロピルチオキサントンから選択される少なくとも1種類の増感剤を含有することを特徴とする請求項20に記載のインプリント前処理コーティング材料。
- 請求項20から22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、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23に記載のセット。
- 請求項23または24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20から22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20から22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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CN108885975A (zh) | 2018-11-23 |
US10754244B2 (en) | 2020-08-25 |
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CN108885975B (zh) | 2023-12-26 |
TW201736984A (zh) | 2017-10-16 |
JPWO2017170684A1 (ja) | 2019-02-14 |
KR102211415B1 (ko) | 2021-02-03 |
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