WO2018164015A1 - パターン形成方法、インプリント前処理コーティング材料、及び基板の前処理方法 - Google Patents
パターン形成方法、インプリント前処理コーティング材料、及び基板の前処理方法 Download PDFInfo
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- WO2018164015A1 WO2018164015A1 PCT/JP2018/008153 JP2018008153W WO2018164015A1 WO 2018164015 A1 WO2018164015 A1 WO 2018164015A1 JP 2018008153 W JP2018008153 W JP 2018008153W WO 2018164015 A1 WO2018164015 A1 WO 2018164015A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to a patterning method, a pre-imprint coating material used in the method, and a pretreatment method for a substrate using the material.
- a photocurable composition is cured in a state in which a mold (mold) having a fine uneven pattern formed on the surface is pressed against a substrate (wafer) coated with the photocurable composition (resist). Thereby, the concavo-convex pattern of the mold is transferred to the cured film of the photocurable composition to form the pattern on the substrate.
- a minute structure of several nanometers order can be formed on a substrate.
- a liquid curable composition (resist) 102 is discretely dropped onto the pattern formation region on the substrate 101 using an inkjet method (arrangement step, FIG. 1 (1)).
- the dropped droplets of the curable composition 102 spread on the substrate 101 as shown by the arrows 104 indicating the spreading direction of the droplets (FIG. 1 (1)). This phenomenon is called prespread.
- this curable composition 102 is formed into a pattern, and is molded using a mold (mold) 105 which is transparent to the irradiation light 106 described later (mold contact step, FIG. 1 (2)).
- the mold contact step droplets of the curable composition 102 spread over the entire gap between the substrate 101 and the mold 105 (FIG. 1 (2)). This phenomenon is called spread. Further, in the mold contact step, the curable composition 102 is also filled into the inside of the recess on the mold 105 by capillary action as shown by the arrow 104 indicating the spreading direction of the droplets (FIG. 1 (2)) The enlarged part of). This filling phenomenon is called a fill. The time for the spread and fill to complete is called the fill time.
- the irradiation light 106 is irradiated to cure the curable composition 102 (light irradiation step, FIG. 1 (3)) ) And let them separate (releasing process, FIG. 1 (4)).
- a cured film (photocured film) 107 having a predetermined pattern is formed on the substrate.
- Patent No. 4791357 gazette
- Patent Document 1 has a problem that the time from the start of mold contact to the completion of spread and fill (filling time) is long, and the throughput is low.
- SST-NIL Short Spread Time Nanoimprint Lithography
- Laminating step 1 (step (1)) of laminating a liquid curable composition (A1) 202 on a substrate; Layering step 2 (step (2)) in which droplets of the curable composition (A2) 203 are discretely laminated on the layer of the curable composition (A1) 202, A mold contact step (step (3)) of sandwiching a layer formed by partially mixing the curable composition (A1) 202 and the curable composition (A2) 203 between the mold 205 and the substrate 201; A light irradiation step of curing a layer consisting of the mixture 208 of the partially mixed curable composition (A1) 202 and the curable composition (A2) 203 from the mold 205 side by irradiating the irradiated light 206 at one time ( Step (4)), and releasing from the layer consisting of the curable composition after curing the mold 205 (step (5)), Is a technique for obtaining a cured film 207 having a pattern shape.
- a series of process units from step (2) to step (5) is referred to as "shot", and mold 205 is in contact with curable composition (A1) 202 and curable composition (A2) 203.
- An area, that is, an area where a pattern is formed on the substrate is referred to as a “shot area”.
- SST-NIL shown in FIG. 2 has the following problems. That is, the curable composition (A1) 202 is laminated on the substrate 201 over an area larger than the shot area, for example, the entire surface of the substrate using, for example, a spin coating method.
- the curable composition (A2) 203 is discretely laminated, for example, using an inkjet method.
- the curable composition (A1) and the curable composition (A2) are different compositions, and both are mixed before the light irradiation step after dropping of the curable composition (A2).
- the mixing of the curable composition (A1) 202 and the curable composition (A2) 203 is insufficient, the composition does not become uniform and non-uniformity of the film physical properties occurs. Therefore, there is a problem that film properties such as dry etching resistance of the cured film become nonuniform when the film is irradiated with light and cured in a state where the mixing is insufficient.
- the curable composition (A1) 202 and the curable composition (A2) 203 are mixed from the laminating step (step 2) to the light irradiation step (step 4), and the curable composition (A1) 202 and the curing property are mixed. A mixture 208 of composition (A2) 203 is formed.
- there are often differences between the dry etching resistances of the curable composition (A1) 202 and the curable composition (A2) 203 there are often differences between the dry etching resistances of the curable composition (A1) 202 and the curable composition (A2) 203. For example, when the dry etching resistance of the curable composition (A1) 202 is lower than that of the curable composition (A2) 203, mixing of the curable composition (A1) 202 and the curable composition (A2) 203 is sufficient. Regions 209 which are not formed have low dry etching resistance.
- the region with low dry etching resistance becomes a defect at the time of etching in a later step.
- the curable composition (A2) 203 In order to diffuse the curable composition (A2) 203 into the curable composition (A1) 202, the curable composition (A1) 202 and the curable composition (A2) 203 need to be in contact with each other for a long time. is there. However, if time is taken for mixing, the time taken for one shot will be long, and there is a problem that the throughput is significantly reduced.
- An object of the present invention is to provide an SST-NIL technique having high throughput and uniform physical properties in a shot area of a substrate.
- curable composition (A) The curable composition (A1) and the curable composition (A2) (hereinafter both are also referred to as “curable composition (A)”) according to the present invention contain at least component (a) which is a polymerizable compound. It is a compound which it has.
- the curable composition according to the present embodiment may further contain a component (b) which is a photopolymerization initiator, a component (c) which is a non-polymerizable compound, and a component (d) which is a solvent.
- a cured film means a film obtained by polymerizing and curing the curable composition (A) on a substrate.
- the shape of a cured film is not specifically limited, You may have a pattern shape on the surface.
- component (a) Polymerizable compound
- the component (a) which is a polymerizable compound reacts with a polymerization factor (such as a radical) generated from the component (b) which is a photopolymerization initiator, and is composed of a polymer compound by chain reaction (polymerization reaction). It is a compound that forms a film.
- a polymerization factor such as a radical
- the component (a) which is a polymeric compound may be comprised only from one type of polymeric compound, and may be comprised by multiple types of polymeric compounds.
- the radically polymerizable compound is preferably a compound having one or more of an acryloyl group or a methacryloyl group, that is, a (meth) acrylic compound. Therefore, the curable composition (A) according to the present invention preferably contains a (meth) acrylic compound as the component (a), more preferably the main component of the component (a) is the (meth) acrylic compound Most preferably, the component (a) comprises a (meth) acrylic compound. In addition, that the main component of component (a) described here is a (meth) acrylic compound shows that 90 weight% or more of component (a) is a (meth) acrylic compound.
- the radically polymerizable compound is composed of a plurality of types of compounds having one or more acryloyl groups or methacryloyl groups, it is preferable to include monofunctional (meth) acrylic monomers and polyfunctional (meth) acrylic monomers. This is because by combining a monofunctional (meth) acrylic monomer and a multifunctional (meth) acrylic monomer, a cured film having high mechanical strength can be obtained.
- 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.
- ALONIX registered trademark
- M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 all manufactured by Toagosei Co., Ltd.
- a polyfunctional (meth) acrylic compound having two or more acryloyl groups or methacryloyl groups for example, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth ) Acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylolpropane tri (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Meta) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, 1,4-butanediol di (me) acrylate
- (meth) acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto.
- the (meth) acryloyl group means a methacryloyl group having an acryloyl group or an alcohol residue equivalent thereto.
- EO represents ethylene oxide
- the EO-modified compound A is a compound in which a (meth) acrylic acid residue of compound A and an alcohol residue are linked via a block structure consisting of an ethylene oxide group oligomer or polymer Show.
- PO represents propylene oxide
- the (meth) acrylic acid residue and the alcohol residue of compound B are bonded to the PO modified compound B via a block structure composed of an oligomer or polymer of propylene oxide group Indicates a compound.
- the mixing ratio of the polymerizable compound (a1) to the curable composition (A1) is the total weight of the components (a1), (b1) and (c1), ie, the curable composition excluding the component (d1). It is good for it to be 50 weight% or more and 100 weight% or less with respect to the total weight of the component of thing (A1). Also, it is preferably 80% by weight or more and 100% by weight or less, and more preferably more than 90% by weight and 100% by weight or less.
- the compounding ratio in the curable composition (A1) of the component (a1) which is a polymerizable compound be 50% by weight or more based on the total weight of the component (a1), the component (b1) and the component (c1)
- the obtained cured film can be a cured film having a certain degree of mechanical strength.
- the mixing ratio of the polymerizable compound (a2) to the curable composition (A2) is the total weight of the components (a2), (b2) and (c2), ie, the curable composition excluding the component (d2) It is good that it is 50 to 99.9 weight% with respect to the total weight of the component of a thing (A2).
- the curable composition (A1) preferably contains the component (d1), and the component (a1) is the total weight of the components of the curable composition (A1) containing the component (d1) It is preferable that the content is 0.01% by weight or more and 10% by weight or less.
- the component (b) which is a photoinitiator in this specification is a compound which senses the light of a predetermined
- the photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals by light (infrared, visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam such as electron beam, radiation, etc.) It is.
- the component (b) may be composed of one kind of photopolymerization initiator, or may be composed of plural kinds of photopolymerization initiators.
- radical generating agent for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- 2, which may have a substituent such as (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer 2, 4,5-Triarylimidazole dimer; benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy -4'-Dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,
- benzoin methine Benzoin ether derivatives such as diethyl 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, etc .; 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; Thioxanthones such as thioxanthone, diethylthioxanthone, 2-isopropylthi
- component (b) is preferably an acyl phosphine oxide polymerization initiator.
- the acyl phosphine oxide type polymerization initiator is 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, bis (2,6-6) Acyl phosphine oxide compounds such as dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide.
- the curable composition (A1) preferably has substantially no photoreactivity.
- the mixing ratio of the component (b1) which is a photopolymerization initiator in the curable composition (A1) is the sum of the component (a1), the component (b1) and the component (c1), that is, the component (d1) It is preferably less than 0.1% by weight based on the total weight of the components of the curable composition (A1) to be excluded. Furthermore, more preferably, it is 0.01% by weight or less.
- the curable composition (A1) is substantially obtained by setting the blending ratio of the component (b1) to less than 0.1% by weight based on the total weight of the component (a1), the component (b1) and the component (c1). It has no photoreactivity. For this reason, there is little possibility of photocuring due to leaked light, and a pattern with few unfilled defects can be obtained both in the adjacent shot area and in a short filling time.
- the curing reaction of the curable composition (A1) in the shot area will be described later.
- the compounding ratio of the component (b2) which is a photopolymerization initiator in the curable composition (A2) is the total of the component (a2), the component (b2) and the component (c2) described later, ie, curing excluding the component (d2) It is good that it is 0.1 to 50 weight% with respect to the total weight of the component of a sex composition (A1). Also, it is preferably 0.1% by weight or more and 20% by weight or less, and more preferably more than 10% by weight and 20% by weight or less.
- the composition is cured by setting the blending ratio of the component (b2) in the curable composition (A2) to 0.1% by weight or more based on the total of the component (a2), the component (b2) and the component (c2).
- the speed can be increased and the reaction efficiency can be improved.
- the obtained cured film has a certain degree of mechanical strength. It can be a cured film.
- component (c) non-polymerizable compound
- the curable compositions (A1) and (A2) according to the present embodiment can be used in addition to the components (a) and (b) described above, in accordance with various purposes, to the extent that the effects of the present invention are not impaired.
- component (c) which is a non-polymerizable compound can be contained.
- Such component (c) does not have a polymerizable functional group such as a (meth) acryloyl group, and does not have the ability to detect light of a predetermined wavelength and generate a polymerization factor (radical).
- Compounds are mentioned.
- a sensitizer, a hydrogen donor, an internally added release agent, a surfactant, an antioxidant, a polymer component, other additives and the like can be mentioned.
- a plurality of types of the above compounds may be contained as the component (c).
- the sensitizer is a compound which is appropriately added for the purpose of accelerating the polymerization reaction and improving the reaction conversion rate.
- a sensitizer a sensitizing dye etc. are mentioned, for example.
- a sensitizing dye is a compound which is excited by absorbing light of a specific wavelength and interacts with the component (b) which is a photopolymerization initiator.
- the interaction described here is an energy transfer, an electron transfer, etc. from the sensitizing dye of an excited state to the component (b) which is a photoinitiator.
- the sensitizing dye include anthracene derivative, anthraquinone derivative, pyrene derivative, perylene derivative, carbazole derivative, benzophenone derivative, thioxanthone derivative, xanthone derivative, coumarin derivative, phenothiazine derivative, camphorquinone derivative, acridine dye, thiopyrilium salt type Dyes, merocyanine dyes, quinoline dyes, styryl quinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes and the like. It is not limited to these.
- a sensitizer may be used individually by 1 type, and may be used in mixture of 2 or more types.
- the hydrogen donor is a compound which reacts with an initiating radical generated from the component (b) which is a photopolymerization initiator or a radical at the polymerization growth terminal to generate a radical having higher reactivity. It is preferable to add when the component (b) which is a photoinitiator is an optical radical generating agent.
- hydrogen donors include n-butylamine, di-n-butylamine, allylthiourea, triethylamine, triethylenetetramine, 4,4'-bis (dialkylamino) benzophenone, and N, N-dimethylaminobenzoic acid.
- the hydrogen donor may be used alone or in combination of two or more.
- the hydrogen donor may also have a function as a sensitizer.
- a mold can be added.
- the internally added type means that it has been added to the curable composition (A) in advance before the step of placing the curable composition (A).
- surfactants such as silicone surfactants, fluorine surfactants, and hydrocarbon surfactants can be used. In the present invention, it is assumed that the internally added release agent does not have polymerizability.
- polyalkylene oxide polyethylene oxide, polypropylene oxide, etc.
- adduct of alcohol having a perfluoroalkyl group polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adduct 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 in part (for example, an end group) of the molecular structure.
- a commercially available product may be used as the fluorinated surfactant.
- a commercial item for example, Megafac (registered trademark) F-444, TF-2066, TF-2067, TF-2068 (above, DIC products), Florard FC-430, FC-431 (above, Sumitomo 3M products) , Surflon (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by Tochem Products), PF-636 , PF-6320, PF-656, PF-6520 (all, manufactured by OMNOVA Solutions), Unidyne (registered trademark) DS-401, DS-403, DS-451 (manufactured by Daikin Industries, Ltd.), Futergent (registered trademark) 250, 251, 222F, 208G (made by Neos above) etc. are mentioned.
- the internally added release agent may be a hydrocarbon surfactant.
- the hydrocarbon surfactant includes, for example, 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.
- alkyl alcohol polyalkylene oxide adducts examples include methyl alcohol polyethylene oxide adduct, decyl alcohol polyethylene oxide adduct, lauryl alcohol epolythylene oxide adduct, cetyl alcohol polyethylene oxide adduct, stearyl alcohol polyethylene oxide adduct, stearyl alcohol polyethylene And oxide / polypropylene oxide adducts.
- the terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to the hydroxyl group which can be produced simply by adding a polyalkylene oxide to an alkyl alcohol.
- This hydroxyl group may be converted to another substituent, for example, a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group or a silanol group, or a hydrophobic functional group such as an alkyl group or an alkoxy group.
- a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group or a silanol group
- a hydrophobic functional group such as an alkyl group or an alkoxy group.
- the alkyl alcohol polyalkylene oxide adduct may be a commercially available product.
- Commercially available products include, for example, polyoxyethylene methyl ether (methyl alcohol polyethylene 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 polyethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310), Aoki Oil Co., Ltd.
- polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505 ), Polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) manufactured by Aoki Yushi Kogyo (BLAUNON CH-305, CH-310), polyoxyethylene made by Aoki Yushi Kogyo Allyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), Aoki Yushi Kogyo's random polymerization type polyoxyethylene polyoxyethylene Propylene 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 type releasing agent is preferably an alkyl alcohol polyalkylene oxide adduct, and more preferably a long chain alkyl alcohol polyalkylene oxide adduct.
- One type of internal addition type release agent may be used alone, or two or more types may be mixed and used.
- the compounding ratio of the component (c) which is a non-polymerizable compound in the curable composition (A) is the total weight of the component (a), the component (b) and the component (c), ie, the curability excluding the component (d) It is good that it is 0 to 50 weight% with respect to the total weight of the component of a composition (A). 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 cured film having a certain degree of mechanical strength is obtained by setting the blending ratio of the component (c) to 50% by weight or less based on the total weight of the component (a), the component (b) and the component (c) It can be a membrane.
- the curable composition (A) which concerns on this invention may contain the component (d) which is a solvent.
- the component (d) is not particularly limited as long as it is a solvent in which the component (a), the component (b) and the component (c) are dissolved.
- a preferable solvent is a solvent having a boiling point of 80 ° C. or more and 200 ° C. or less at normal pressure. More preferably, it is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group and an ether structure.
- it is a single solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, ethyl lactate, or a mixed solvent thereof.
- the curable composition (A1) which concerns on this embodiment contains a component (d1). It is because a spin coat method is preferable as a coating method of curable composition (A1) on a board
- ⁇ Temperature at the time of blending of the curable composition (A)> the respective components are mixed and dissolved under predetermined temperature conditions. Specifically, it is performed in the range of 0 ° C. or more and 100 ° C. or less.
- the curable compositions (A1) and (A2) according to the present invention are preferably liquids. This is because the spread and fill of the curable composition (A1) and / or (A2) are rapidly completed in the mold contact step (3) described later, that is, the filling time is short.
- the viscosity at 25 ° C. of the mixture of the components excluding the solvent (component (d1)) of the curable composition (A1) according to the present invention is preferably 20 mPa ⁇ s or more and 10000 mPa ⁇ s or less. Moreover, More preferably, they are 20 mPa * s or more and 1000 mPa * s or less. In order to shorten the filling time, it is preferable to use a liquid, but in the case of a low viscosity liquid of 20 mPa ⁇ s or less, the curable composition (A1) is affected by the flow of the atmosphere control gas 210 of FIG. Distribution tends to occur in the film thickness and composition of the liquid film of 202).
- curable composition (A1) 202 disappears due to evaporation or migration only in the affected area.
- curable composition (A1) having a high viscosity of 10000 mPa ⁇ s or more there is a problem that the effect of shortening the initial filling time is reduced.
- the viscosity at 25 ° C. of the mixture of components excluding the solvent (component (d2)) of the curable composition (A2) according to the present invention is preferably 1 mPa ⁇ s or more and less than 40 mPa ⁇ s. Moreover, More preferably, they are 1 mPa * s or more and less than 20 mPa * s.
- the viscosity of the curable composition (A2) exceeds 40 mPa ⁇ s, the residual film thickness can be made uniform by forming the droplets discretely according to the density of the desired pattern, and a high precision pattern can be formed. It becomes impossible to apply by inkjet method. If the viscosity is lower than 1 mPa ⁇ s, coating unevenness may occur due to flow when the composition is applied (arranged), or the composition may flow out from the mold end in the contact step described later. Not desirable.
- the surface tension at 23 ° C. is 5 mN / m or more and 70 mN / m or less for the composition of the components excluding the solvent (d) Is preferred. Further, more preferably, it is 7 mN / m or more and 50 mN / m or less, and still more preferably 10 mN / m or more and 40 mN / m or less.
- Non-Patent Document 1 when the surface tension is high, for example, 5 mN / m or more, the capillary force works strongly, and thus when the curable composition (A1) and / or the curable composition (A2) is brought into contact with the mold , Filling (spread and fill) is completed in a short time (Non-Patent Document 1). Further, by setting the surface tension to 70 mN / m or less, a cured film obtained by curing the curable composition becomes a cured film having surface smoothness.
- the surface tension of the curable composition (A1) excluding the solvent (d1) is higher than the surface tension of the curable composition (A2) excluding the solvent (d2). preferable.
- the prespread of the curable composition (A2) is accelerated by the Marangoni effect described later (droplets spread widely), and the time required for the spread in the mold contact step (3) described later Because the filling time is shortened.
- the Marangoni effect is a phenomenon of free surface movement caused by a local difference in surface tension of a liquid (Non-patent Document 2).
- the surface tension that is, the difference in surface energy, as a driving force
- a liquid with low surface tension diffuses to cover a wider surface. That is, if the curable composition (A1) having high surface tension is applied to the entire surface of the substrate and the curable composition (A2) having low surface tension is dropped, the prespread of the curable composition (A2) is accelerated.
- the contact angles of the curable compositions (A1) and (A2) according to the present invention are 0 ° or more and 90 ° with respect to both the substrate surface and the mold surface for the composition of the components excluding the solvent (d). It is preferable that it is the following. If the contact angle is greater than 90 °, the capillary force acts in the negative direction (in the direction of contracting the contact interface between the mold and the curable composition) in the mold pattern or in the substrate-mold gap and does not fill. Moreover, it is particularly preferable that the angle is 0 ° or more and 30 ° or less. The lower the contact angle, the stronger the capillary force, and the higher the filling speed (Non-patent Document 1).
- the curable compositions (A1) and (A2) according to the present invention preferably contain as little impurities as possible.
- the impurities described herein mean those other than the components (a), (b), (c) and (d) described above.
- the curable composition (A) which concerns on this invention is a thing obtained through the refinement
- filtration using a filter is preferable.
- the pore size is not less than 0.001 ⁇ m. It is preferable to filter with a 0 ⁇ m or less filter.
- the filtered solution may be filtered again.
- a plurality of filters with different pore sizes may be used for filtration.
- filters made of polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc. can be used, it is not particularly limited.
- the curable composition (A) which concerns on this invention for manufacturing a semiconductor integrated circuit
- a metal atom is included in a curable composition (A). It is preferable to avoid mixing of the contained impurities (metal impurities) as much as possible.
- the concentration of the metal impurity contained in the curable composition (A) is preferably 10 ppm or less, and more preferably 100 ppb or less.
- the pattern formation method according to the present invention is an embodiment of a photo nanoimprint method.
- the pattern formation method of the present invention is A laminating step (1) of laminating the curable composition (A1) 302 of the present invention on the substrate 301, A laminating step (2) of laminating a curable composition (A2) 303 on the curable composition (A1) 302 layer, A mold contact step (3) of sandwiching a layer formed by mixing the curable composition (A1) 302 and the curable composition (A2) 303 between the mold 308 and the substrate 301; A light irradiation step (4) in which a layer formed by partially mixing the curable composition (A1) 302 and the curable composition (A2) 303 is cured at one time by irradiating the irradiated light 307 from the mold 308 side ), Release step (5) for separating the mold 308 from the layer (the cured film 310 having a pattern shape) made of the curable composition after curing
- the cured film 310 having a pattern shape obtained by the manufacturing method of the present invention is preferably a film having a pattern of a size of 1 nm or more and 10 mm or less. More preferably, it is a film having a pattern of 10 nm to 100 ⁇ m in size.
- a pattern forming technology for producing a film having a nano-sized (1 nm or more and 100 nm or less) pattern (concave and convex structure) using light is called an optical nanoimprinting method.
- the pattern formation method according to the present invention utilizes a photo nanoimprint method. Each step will be described below.
- the curable composition (A1) 302 according to the present embodiment described above is laminated (coated) on the substrate 301 to form a coating film Do.
- the substrate 301 on which the curable composition (A1) 302 is to be placed is a substrate to be processed, and a silicon wafer is usually used.
- a processed layer may be formed on the substrate 301.
- Another layer may be formed between the substrate 301 and the layer to be processed.
- a replica quartz mold replica
- a quartz imprint mold can be manufactured.
- the substrate 301 is not limited to a silicon wafer or a quartz substrate.
- the substrate 301 can be optionally selected from among known substrates for semiconductor devices such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, silicon nitride and the like. .
- the surface of the substrate 301 (substrate to be processed) to be used or the layer to be processed is curable by surface treatment such as silane coupling treatment, silazane treatment, formation of an organic thin film, etc.
- the adhesion to the composition (A2) 303 may be improved.
- the curable composition (A1) 302 as a method for disposing the curable composition (A1) 302 on the substrate 301 or the layer to be processed, for example, an inkjet method, dip coating method, air knife coating method, curtain coating method, wire bar coating method, A gravure coating method, an extrusion coating method, a spin coating method, a slit scan method, or the like can be used.
- spin coating is particularly preferred.
- a baking step may be carried out as required to volatilize the component (d1) as a solvent. .
- the average film thickness of the curable composition (A1) 302 is, for example, 0.1 nm or more and 10,000 nm or less, preferably 1 nm or more and 20 nm or less, although it varies depending on the use of the cured film. Preferably, they are 1 nm or more and 10 nm or less.
- droplets of the curable composition (A2) 303 may be discretely dropped and arranged on the layer of the curable composition (A1). preferable.
- An inkjet method is particularly preferable as the arrangement method.
- the droplets of the curable composition (A2) 303 are densely arranged on the substrate facing the area where the concaves are densely present on the mold, and sparsely arranged on the substrate facing the area where the concaves are sparsely present. Be done. By this, the residual film mentioned later can be controlled by uniform thickness irrespective of the density of the pattern on a mold.
- the droplets of the curable composition (A2) 303 disposed in this step rapidly spread (prespread) by the Marangoni effect whose driving force is a difference in surface energy (surface tension).
- the curable composition (A1) 302 has substantially no photoreactivity, as a result of mixing of the curable composition (A1) 302 and the curable composition (A2) 303, the curable composition (A2)
- the component (b2) which is a photoinitiator 303 transfers also to curable composition (A1) 302, and curable composition (A1) 302 acquires a photosensitivity for the first time.
- the mixing of the curable composition (A1) 302 and the droplets of the curable composition (A2) 303 in the shot area depends on the interdiffusion due to the composition difference, it takes several to several tens of times to achieve uniform composition. It takes a long time, such as seconds. If the diffusion time is insufficient, as shown in FIG. 2 (3), a region 209 in which the mixing of the curable composition (A1) 202 and the curable composition (A2) 203 is not sufficient occurs. For example, when the dry etching resistance of the curable composition (A1) 202 is lower than that of the curable composition (A2) 203, mixing of the curable composition (A1) 202 and the curable composition (A2) 203 is sufficient.
- Regions 209 which are not formed have low dry etching resistance.
- the region with low dry etching resistance becomes a defect at the time of etching in a later step.
- An imprint process comprising sequentially performing a mold contact process (3) to a mold release process (5) after the lamination process (2) is completed for each conventional shot area shown in FIGS. 2 (2) to 2 (5).
- a standby step (M) for stopping the step is provided to mix the curable composition (A1) 202 and the curable composition (A2) 203
- the curable composition (A1) 202 and the curable composition (A2) 203 are sufficiently mixed.
- the total required time per shot is increased by the required time of the waiting step [M], resulting in a decrease in throughput.
- the imprinting process (Im) is performed after the completion of the laminating process (2).
- the laminating step (2) and the imprinting step (Im) for example, as shown in FIG.
- the conventional one shot area can be obtained.
- the number of shot areas in the laminating step (2) to be carried out continuously is adjusted to make the laminating step per shot area
- the time interval from (2) to the mold contacting step (3) (hereinafter referred to as "mixing interval") can be sufficiently secured. Therefore, the curable composition (A1) 302 and the curable composition (A2) 303 can be sufficiently mixed.
- the mixing interval is considered to be preferably 1.5 seconds or more.
- n ⁇ Tm / Td + 1 Equation 1) (N: number of shot areas where the laminating step (2) or the mold contacting step (3) to the releasing step (5) are continuously performed, n is an integer
- Tm the laminated curable composition (A1) 302
- Td time required for the laminating step (2) per shot area
- the first plurality of shot areas (S (1), S (2),..., S (m)) (m is an integer of 2 or more) selected from the plurality of shot areas.
- the stacking step (2) is performed for the first plurality of shot areas (S (1), S (2),... S (m)) (m is an integer of 2 or more) selected from the plurality of shot areas. ) Are sequentially performed, and then the imprint process [Im] for the shot area (S (1)) and the lamination process (2) for the shot area (S (m + 1)) are alternately performed, and so on.
- the imprinting process [Im] for (S (p)) (p is an integer of 2 or more) and the laminating process (2) for the shot area (S (p + m)) are alternately performed.
- a waiting time of length can be provided.
- the implementation of the laminating step (2) and the imprinting step (Im) is performed using a single dispenser and one imprint head for a plurality of substrates. You may perform lamination
- Td and Ti are equal.
- a mold 308 made of a light transmitting material may be used in consideration of the next light irradiation step (4).
- the material of the material forming the mold 308 include glass, quartz, optically transparent resin such as PMMA and polycarbonate resin, transparent metal vapor deposited film, flexible film such as polydimethylsiloxane, photocured film, metal film Etc. is preferred.
- a light transparent resin is used as a material of the material of the mold 308, it is necessary to select a resin which does not dissolve in the components contained in the curable composition (A1) 302 and the curable composition (A2) 303.
- the material of the material of the mold 308 be quartz because the thermal expansion coefficient is small and the pattern distortion is small.
- the fine pattern that the mold 308 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 308 from the cured film 310 having a pattern shape in the release step (5), ie, the release force is lower, and the resist pattern is torn off with release.
- the number of mold release defects remaining on the mask side is small.
- Adjacent resist patterns may contact each other due to elastic deformation of the resist pattern due to impact when peeling off the mold, and the resist pattern may adhere or be damaged, but the pattern height is about 2 times or less of the pattern width (aspect ratio If it is 2 or less, there is a high possibility that those problems can be avoided.
- the pattern height is too low, the processing accuracy of the substrate to be processed is low.
- the mold 308 comprises the curable composition (A1) 302 and the curable composition.
- a surface treatment may be performed prior to the present step which is the mold contacting step (3) between 303 and the mold 308.
- a method of surface treatment there is a method of applying a mold release agent to the surface of the mold 308 to form a mold release agent layer.
- silicone type mold release agent silicone type mold release agent, fluorine type mold release agent, hydrocarbon type mold release agent, polyethylene type mold release agent, polypropylene type mold release agent, paraffin type mold release agent
- examples include mold agents, montan-based release agents, carnauba-based release agents and the like.
- commercially available coating-type mold release agents such as OPTOOL (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also 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.
- fluorine-based and hydrocarbon-based release agents are particularly preferable.
- the curable composition (A1) 302 and the curable composition (A2) 303 when the mold 308 is brought into contact with the curable composition (A1) 302 and the curable composition (A2) 303, the curable composition (A1) 302 and The pressure applied to the curable composition (A2) 303 is not particularly limited.
- the pressure may be 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 still more preferably 0 MPa or more and 20 MPa or less.
- the prespread of the droplets of the curable composition (A2) 303 sequentially proceeds in the shot area S (1) 304, the shot area S (2) 305, and the shot area S (n) 306 Therefore, the spread in each shot area of the curable composition (A2) 303 in this step is completed quickly.
- the mold 308 and the curable composition (A1) The time for which the composition 302 and the curable composition (A2) 303 are in contact can be set short. That is, it is one of the effects of the present invention that many pattern formation steps can be completed in a short time, and high productivity can be obtained.
- the contact time is not particularly limited, but may be, for example, 0.1 seconds to 600 seconds.
- the time is preferably 0.1 seconds or more and 3 seconds or less, and particularly preferably 0.1 seconds or more and 1 second or less. If it is shorter than 0.1 seconds, the spread and fill become insufficient, and a defect called an unfilled defect tends to occur frequently.
- This process can be performed under any of the conditions of air atmosphere, reduced pressure atmosphere, and inert gas atmosphere, but since the influence on the curing reaction by oxygen and moisture can be prevented, the reduced pressure atmosphere and atmosphere control It is preferable to use an inert gas as a gas and to make an inert gas atmosphere.
- Specific examples of the inert gas that can be used when performing the present process under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbons, and the like, or a mixed gas thereof.
- the preferable pressure is 0.0001 atm or more and 10 atm or less.
- the mold contacting step (3) may be performed under an atmosphere containing a condensable gas (hereinafter referred to as a “condensable gas atmosphere”) using a condensable gas as an atmosphere control gas.
- the condensable gas refers to the curable composition (A1) 302 and the curable composition (A2) 303 in the recess of the fine pattern formed on the mold 308 and in the gap between the mold 308 and the substrate 301. Together with the gas in the atmosphere, refers to the gas that condenses and liquefies at the capillary pressure generated at the time of filling.
- the condensable gas is present as a gas in the atmosphere before the curable composition (A1) 302 and the curable composition (A2) 303 come into contact with the mold 308 in the mold contact step (3) (reference: FIG. Enlarged part of 1 (2)).
- the gas filled in the concave portions of the fine pattern is liquefied by the capillary pressure generated by the curable composition (A1) 302 and the curable composition (A2) 303. Since the air bubbles disappear by doing, the filling property is excellent.
- the condensable gas may be dissolved in the curable composition (A1) 302 and / or the curable composition (A2) 303.
- the boiling point of the condensable gas is not limited as long as it is not higher than the atmosphere temperature of the mold contact step (3), but is preferably -10 ° C to 23 ° C, and more preferably 10 ° C to 23 ° C. If it is this range, the fillability is further excellent.
- the vapor pressure of the condensable gas at the ambient temperature in the mold contacting step (3) is not limited as long as it is equal to or less than the mold pressure at the time of imprinting in the mold contacting step (3). . If it is this range, the fillability is further excellent. If the vapor pressure at ambient temperature is greater than 0.4 MPa, the effect of bubble disappearance tends to be insufficient. On the other hand, if the vapor pressure at ambient temperature is less than 0.1 MPa, decompression is required, and the apparatus tends to be complicated.
- the atmosphere temperature in the mold contacting step (3) is not particularly limited, but is preferably 20 ° C to 25 ° C.
- chlorofluorocarbon such as trichlorofluoromethane, fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), 1,1,1,3,3-pentafluoropropane (CHF 2 CH) 2
- Fluorocarbons such as hydrofluorocarbons (HFCs) such as CF 3 , HFC-245fa and PFP, and hydrofluoroethers (HFE) such as pentafluoroethyl methyl ether (CF 3 CF 2 OCH 3 , HFE-245mc).
- 1,1,1,3,3-pentafluoropropane (vapor pressure 0 ° C at 23 ° C.) from the viewpoint that the filling property at an atmosphere temperature of the mold contact step (3) is excellent at 20 ° C. to 25 ° C. 14MPa, boiling point 15 ° C), trichlorofluoromethane (vapor pressure at 23 ° C 0.1056 MPa, boiling point 24 ° C), and pentafluoroethyl methyl ether are preferred.
- 1,1,1,3,3-pentafluoropropane is particularly preferable from the viewpoint of excellent safety.
- the condensable gas may be used alone or in combination of two or more. Also, these condensable gases may be mixed with non-condensable gases such as air, nitrogen, carbon dioxide, helium, argon and the like. Helium is preferable as the non-condensable gas to be mixed with the condensable gas from the viewpoint of the filling property. Helium can permeate through the mold 205. Therefore, the gas in the atmosphere (condensable together with the curable composition (A1) 302 and / or the curable composition (A2) 303 in the recesses of the fine pattern formed on the mold 308 in the mold contact step (3) When the gas and helium are charged, the condensable gas liquefies and the helium permeates through the mold.
- non-condensable gases such as air, nitrogen, carbon dioxide, helium, argon and the like.
- Helium is preferable as the non-condensable gas to be mixed with the condensable gas from the viewpoint of the filling property
- the layer consisting of the mixture 309 of the partially mixed curable composition (A1) 302 and the curable composition (A2) 303 is irradiated through the mold 308.
- the light 307 is irradiated. More specifically, in the shot area S (1) 304, the shot area S (2) 305, and the shot area S (n) 306, the curable composition (A1) 302 and / or the filled in the fine pattern of the mold 308
- the curable composition (A2) 303 is sequentially irradiated with the irradiation light 307 through the mold 308.
- the curable composition (A1) 302 and / or the curable composition (A2) 303 filled in the fine pattern of the mold 308 is cured at one time by the irradiation light 307 and has a cured film 310 having a pattern shape. Become.
- the curable composition (A1) 302 filled in the fine pattern of the mold 308 and / or the irradiation light 307 irradiating the (A2) 303 at one time is the curable composition (A1) 302 and the one at a time (A2). ) Is selected according to the sensitivity wavelength of 303). Specifically, it is preferable to appropriately select and use ultraviolet light having a wavelength of 150 nm or more and 400 nm or less, an X-ray, an electron beam or the like.
- ultraviolet light is particularly preferable. This is because what is marketed as a curing assistant (photopolymerization initiator) has many compounds sensitive to ultraviolet light.
- a light source emitting ultraviolet light for example, high pressure mercury lamp, super high pressure mercury lamp, low pressure mercury lamp, Deep-UV lamp, carbon arc lamp, chemical lamp, metal halide lamp, xenon lamp, KrF excimer laser, ArF excimer laser, F 2 Although an excimer laser etc. are mentioned, a super-high pressure mercury lamp is especially preferable.
- the number of light sources used may be one or more.
- when light irradiation is performed it may be performed on the entire surface of the curable composition (A1) 302 and / or the curable composition (A2) 303 filled in the fine pattern of the mold 308, You may only go there.
- Light irradiation may be intermittently performed a plurality of times on the shot area on the substrate 301, or may be continuously performed on the entire area. 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 leakage light that is, the diffusion of the light to the outside of the shot area, is inevitable due to the limitations of the cost of the mold and the device.
- the photopolymerization initiator component (b1) is substantially not contained (less than 0.1% by weight)
- the curable composition (A1) alone is not cured by light irradiation.
- the curable composition (A1) on the adjacent shot area is not cured by the leaked light generated from the shot. Therefore, even in the adjacent shot, it is possible to form a pattern with few unfilled defects in a short filling time over the entire area.
- the photopolymerization initiator (b2) component of the curable composition (A2) is cured
- the curable composition (A1) is also transferred to the curable composition (A1), and the curable compositions (A1) and (A2) are both cured by the light to be irradiated so that the curable composition (A1) has photosensitivity.
- the cured film 310 is obtained.
- the cured film 310 having a pattern shape and the mold 308 are separated.
- the cured film 310 and the mold 308 having a pattern shape in the shot area S (1) 304, the shot area S (2) 305, and the shot area S (n) 306 are sequentially separated, and in the light irradiation step (4), a cured film 310 having a pattern shape that is a reverse pattern of the fine pattern formed on the mold 308 is obtained in a self-supporting state.
- this film is referred to as a residual film (see: residual film 108 in the enlarged portion of FIG. 1 (4). ).
- the mold contact step (3) is performed in a condensable gas atmosphere
- the cured film 310 and the mold 308 are separated in the mold release step (5)
- the cured film 310 having the pattern shape and the mold 308 are Condensable gas is vaporized as the pressure of the interface in contact decreases.
- the mold release force which is a force necessary to separate the cured film 310 having the pattern shape from the mold 308, tends to be reduced.
- the method for separating the cured film 310 having a pattern shape from the mold 308 is not particularly limited as long as a part of the cured film 310 having a pattern shape does not physically break when separated, and various conditions are not particularly limited.
- the substrate 301 substrate to be processed
- the mold 308 may be moved away from the substrate 301 and peeled off.
- the mold 308 may be fixed, and the substrate 301 may be moved away from the mold and peeled off.
- both of them may be pulled in opposite directions to peel off.
- Desired unevenness is obtained by a process (manufacturing process) consisting of the above-described stacking step (1), continuous execution of the stacking step (2) in multiple shot areas, and continuous execution of steps (3) to (5) in multiple shot areas.
- a cured film having a pattern shape (pattern shape resulting from the uneven shape of the mold 308) in a desired position can be obtained.
- Another aspect of the present invention is to form a liquid film to be an imprinting pre-treatment coating on a substrate, and promote spreading of droplet components in the substrate surface direction by applying droplets of imprint resist to the liquid film.
- the present invention provides an imprint pre-treatment coating material.
- a liquid film to be an imprinting pretreatment coating is formed on a substrate, and droplets of the curable composition (A2) are applied to the liquid film, whereby the substrate surface direction of the droplet component is obtained.
- a pre-imprint treatment coating material comprising a curable composition (A1) which promotes the spread of the composition, which comprises at least a component (a1) which is a polymerizable compound, and which is curable in the mold contact state
- a region where the layer formed by mixing the composition (A2) and the curable composition (A1) is to be cured is a shot region, a continuous liquid disposed so as to cover a plurality of shot regions on the surface of the substrate
- a pre-imprint treated coating material characterized in that a film is formed.
- the surface tension of the composition of the components of the imprint pre-treated coating material excluding the solvent is higher than the surface tension of the composition of the components of the imprint resist excluding the solvent.
- the surface tension of the composition of the component of the imprint pre-treatment coating material excluding the solvent is higher than the surface tension of the composition of the component of the imprint resist except the solvent, thereby providing a combined set Achieve a suitable imprint.
- a combination in which the difference between the surface tension of the composition of the imprint pre-treatment coating material excluding the solvent and the surface tension of the composition of the imprint resist excluding the solvent is 1 mN / m to 25 mN / m More preferred is a set of
- Another aspect of the present invention is also to provide a suitable substrate pretreatment method for imprinting by coating an imprint pretreatment coating material on the substrate.
- the present invention also encompasses a pattern formation method for forming a pattern on a substrate.
- a pattern formation method for forming a pattern on a substrate.
- compositions comprising the components (a1) to (d1) were mixed to prepare a curable composition.
- the measuring methods of viscosity and surface tension are as follows. The results are listed in Table 1.
- Viscosity The viscosity of the composition excluding the solvent component (d1) of the curable composition (A1) at 25 ° C. was measured using a conical plate type rotational viscometer RE-85L (manufactured by Toki Sangyo Co., Ltd.). The average of the second to fifth measurements was taken as the viscosity, excluding the first measurement.
- the composition of the curable composition (A1) at 25 ° C. excluding the solvent component (d1) was removed by a plate method using a platinum plate using an automatic surface tension meter DY-300 (manufactured by Kyowa Interface Science) The surface tension was measured. In addition, the measurement was performed on the conditions of the pre-wet immersion distance 0.35 mm of the platinum plate 5 times of measurement times. The average value of the second to fifth measurements was taken as the surface tension except for the first measurement.
- the names and manufacturers of the reagents used for the composition are as follows.
- Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as PGMEA) ⁇ Trimethylolpropane triacrylate (manufactured by Aldrich, abbreviated as TMPTA) ⁇ Dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha, abbreviated as DCPDA) ⁇ 1,3-adamantane dimethanol diacrylate (made by Idemitsu Kosan, abbreviated as ADDA) -Tetraethylene glycol diacrylate (made by Osaka Organic Chemical Industry, trade name: V # 335 HP) ⁇ Isobornyl acrylate (manufactured by Kyoeisha Chemical, trade name: IB-XA) -Benzyl acrylate (Osaka Organic Chemical Industry, trade name: V # 160) Neopentyl glyco
- Comparative Examples 1 and 2 show the time required for each step in the pattern method in which the lamination step (2) to the release step (5) are sequentially performed in the conventional one-shot region.
- the curable compositions (A1) and (A2) are sufficiently mixed as a result of securing a sufficient mixing interval regardless of the waiting step [M] being 0 seconds.
- steps (3) to (5) are shortened to 1.0 seconds because the time required for the droplets to expand after the mold contacts the curable composition (A2) is short. can do.
- the waiting step (M) is 0 seconds and high throughput, but since the mixing interval is also 0 seconds, mixing of the curable compositions (A1) and (A2) is insufficient.
- Comparative Example 2 since the waiting step [M] is secured for 1.5 seconds, the curable compositions (A1) and (A2) are uniformly mixed, but one shot cycle is as long as 3.5 seconds. Throughput is reduced.
Abstract
Description
基板上に、液状の硬化性組成物(A1)202を積層する積層工程1(工程(1))、
前記硬化性組成物(A1)202層上に、硬化性組成物(A2)203の液滴を離散的に積層する積層工程2(工程(2))、
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(工程(3))、
前記部分的に混合した硬化性組成物(A1)202と硬化性組成物(A2)203の混合物208からなる層をモールド205側から照射光206を照射することにより一度に硬化させる光照射工程(工程(4))、及び
モールド205を硬化後の硬化性組成物からなる層から引き離す離型工程(工程(5))、
を有する、パターン形状を有する硬化膜207を得る技術である。
基板の表面の複数のショット領域のそれぞれに対し、
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積層工程(1)、
前記硬化性組成物(A1)からなる層の上に、少なくとも重合性化合物である成分(a2)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積層工程(2)、
モールドと前記基板の間に、前記積層工程(2)を実施することにより形成される、前記硬化性組成物(A1)と前記硬化性組成物(A2)と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)、
前記硬化性組成物(A1)と前記硬化性組成物(A2)とが部分的に混合してなる層を、前記モールドの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)、及び
硬化後の前記硬化性組成物(A1)及び前記硬化性組成物(A2)からなる層から前記モールドを引き離す離型工程(5)、
をこの順に実施することからなり、
前記型接触工程(3)から前記離型工程(5)までの工程を合わせてインプリント工程[Im]とよぶとき、
前記複数のショット領域から選択される少なくとも1つのショット領域において、前記積層工程(2)が終了した後前記インプリント工程[Im]が開始されるまでの間に、該選択された少なくとも1つのショット領域とは別のショット領域に対して、前記積層工程(2)または前記インプリント工程[Im]を実施することを特徴とするパターン形成方法が提供される。
以下、本発明の第1実施形態について適宜図面を参照しながら詳細に説明する。ただし、本発明は以下に説明する実施形態に限定されるものではない。また、本発明においては、その趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下に説明する実施形態に対して適宜変更、改良等が加えられたものについても本発明の範囲に含まれる。なお、硬化性組成物(A1)に含まれる成分(a)を成分(a1)と表記し、硬化性組成物(A2)に含まれる成分(a)を成分(a2)と表記する。成分(b)から成分(d)についても同様である。
本発明に係る硬化性組成物(A1)及び硬化性組成物(A2)(以下、両者を「硬化性組成物(A)」とも称する。)は、少なくとも重合性化合物である成分(a)を有する化合物である。本実施形態に係る硬化性組成物はさらに、光重合開始剤である成分(b)、非重合性化合物である成分(c)、溶剤である成分(d)を含有してもよい。
<成分(a):重合性化合物>
本明細書において重合性化合物である成分(a)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。
重合性化合物である成分(a1)の硬化性組成物(A1)における配合割合を、成分(a1)、成分(b1)、成分(c1)の合計重量に対して50重量%以上とすることにより、得られる硬化膜をある程度の機械的強度を有する硬化膜とすることができる。
重合性化合物である成分(a2)の硬化性組成物(A2)における配合割合は、成分(a2)、成分(b2)、成分(c2)の合計重量、すなわち成分(d2)を除く硬化性組成物(A2)の成分の合計重量に対して、50重量%以上99.9重量%以下であるとよい。また、好ましくは、80重量%以上99重量%以下であり、さらに好ましくは90重量%より大きく98重量%以下である。
重合性化合物である成分(a2)の硬化性組成物(A2)における配合割合を、成分(a2)、成分(b2)、成分(c2)の合計重量に対して50重量%以上とすることにより、得られる硬化膜をある程度の機械的強度を有する硬化膜とすることができる。
また、後述するように、硬化性組成物(A1)は、成分(d1)を含有することが好ましく、成分(a1)は成分(d1)を含む硬化性組成物(A1)の成分の合計重量に対して、0.01重量%以上10重量%以下であるとよい。
本明細書において光重合開始剤である成分(b)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。
本実施形態に係る硬化性組成物(A1)及び(A2)は、前述した、成分(a)、成分(b)の他に、種々の目的に応じ、本発明の効果を損なわない範囲で、さらに非重合性化合物である成分(c)を含有することができる。このような成分(c)としては、(メタ)アクリロイル基などの重合性官能基を有さず、かつ、所定の波長の光を感知して重合因子(ラジカル)を発生させる能力を有さない化合物が挙げられる。例えば、増感剤、水素供与体、内添型離型剤、界面活性剤、酸化防止剤、ポリマー成分、その他添加剤等が挙げられる。成分(c)として前記化合物を複数種類含有してもよい。
本発明に係る硬化性組成物(A)は、溶剤である成分(d)を含有していてもよい。成分(d)としては、成分(a)、成分(b)、成分(c)が溶解する溶剤であれば、特に限定はされない。好ましい溶剤としては常圧における沸点が80℃以上200℃以下の溶剤である。さらに好ましくは、エステル構造、ケトン構造、水酸基、エーテル構造のいずれかを少なくとも1つ有する溶剤である。具体的には、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、2-ヘプタノン、γ-ブチロラクトン、乳酸エチルから選ばれる単独、あるいはこれらの混合溶剤である。
本実施形態の硬化性組成物(A1)及び(A2)を調製する際には、各成分を所定の温度条件下で混合・溶解させる。具体的には、0℃以上100℃以下の範囲で行う。
本発明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(3)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。
本発明に係る硬化性組成物(A1)及び(A2)の表面張力は、溶剤である成分(d)を除く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/または硬化性組成物(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。
本発明に係る硬化性組成物(A1)及び(A2)の接触角は、溶剤である成分(d)を除く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。また、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)。
本発明に係る硬化性組成物(A1)及び(A2)は、できる限り不純物を含まないことが好ましい。ここで記載する不純物とは、前述した成分(a)、成分(b)、成分(c)及び成分(d)以外のものを意味する。
次に、本発明に係るパターン形成方法について、図3の模式断面図を用いて説明する。
基板301上に、前述の本発明の硬化性組成物(A1)302を積層する積層工程(1)、
前記硬化性組成物(A1)302層上に、硬化性組成物(A2)303を積層する積層工程(2)、
モールド308と基板301の間に硬化性組成物(A1)302と硬化性組成物(A2)303が混合してなる層をサンドイッチする型接触工程(3)、
前記硬化性組成物(A1)302と前記硬化性組成物(A2)303が部分的に混合してなる層をモールド308側から照射光307を照射することにより一度に硬化させる光照射工程(4)、
モールド308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310)から引き離す離型工程(5)、
を有し、積層工程(2)の所要時間Tdと、型接触工程(3)、光照射工程(4)、及び離型工程(5)の合計所要時間Tiが等しく、
複数のショット領域に対して積層工程(2)を連続して実施した後に、型接触工程(3)、光照射工程(4)、離型工程(5)を、積層工程(2)が実施済みのそれぞれの前記ショット領域に対して、積層工程(2)が実施された順番に実施することを特徴とする。
本工程(積層工程(1))では、図3(1)に示す通り、前述した本実施形態に係る硬化性組成物(A1)302を基板301上に積層(塗布)して塗布膜を形成する。
積層工程(2)では、図3(2)に示す通り、硬化性組成物(A2)303の液滴を、前記硬化性組成物(A1)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)303の液滴は、モールド上に凹部が密に存在する領域に対向する基板上には密に、凹部が疎に存在する領域に対向する基板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。
n≧Tm/Td+1 (式1)
(n:積層工程(2)または型接触工程(3)から離型工程(5)を連続して行うショット領域の数。nは整数。Tm:積層された前記硬化性組成物(A1)302と前記硬化性組成物(A2)303の混合にかかる時間。Td:1ショット領域あたりの積層工程(2)の所要時間。)
すなわち、前記複数のショット領域から選択される一のショット領域に対する積層工程(2)と、該複数のショット領域のうち既に積層工程(2)が実施された他のショット領域に対するインプリント工程[Im]とを、同時に実施する。具体的には、前記複数のショット領域から選択される第1の複数のショット領域(S(1),S(2),・・・,S(m))(mは2以上の整数)に対して積層工程(2)を順次実施した後に、前記複数のショット領域から同数選択される第2の複数のショット領域(S(m+1)、S(m+2),・・・,S(2m))に対する積層工程(2)と前記第1の複数のショット領域(S(1),S(2),・・・,S(m))に対するインプリント工程[Im]とを同時並行的に順次実施する。
前記複数のショット領域から選択される第1の複数のショット領域(S(1),S(2),・・・S(m))(mは2以上の整数)に対して積層工程(2)を順次実施した後に、ショット領域(S(1))に対するインプリント工程[Im]とショット領域(S(m+1))に対する積層工程(2)とを交互に実施し、以下、同様にショット領域(S(p))(pは2以上の整数)に対する前記インプリント工程[Im]とショット領域(S(p+m))に対する前記積層工程(2)とを交互に実施する。 ショット領域に対する積層工程(2)を実施してから次のショット領域に対する積層工程(2)を実施するまでの間に、一のショット領域に対するインプリント工程[Im]の実施に必要な時間と同じ長さの待機時間を設けることができる。
次に、図3(3)に示すように、前工程(積層工程(1)及び積層工程(2))で形成された硬化性組成物(A1)302及び硬化性組成物(A2)303の混合物309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308を接触させる。これにより、モールド308が表面に有する微細パターンの凹部に部分的に混合した硬化性組成物(A1)302及び硬化性組成物(A2)303の混合物309が充填(フィル)されて、モールドの微細パターンに充填(フィル)された液膜となる。
次に、図3(3)に示すように、部分的に混合した硬化性組成物(A1)302及び硬化性組成物(A2)303の混合物309からなる層に対し、モールド308を介して照射光307を照射する。より詳細には、ショット領域S(1)304、ショット領域S(2)305、ショット領域S(n)306において、モールド308の微細パターンに充填された硬化性組成物(A1)302及び/または硬化性組成物(A2)303に、モールド308を介して照射光307を順番に照射する。これにより、モールド308の微細パターンに充填された硬化性組成物(A1)302及び/または硬化性組成物(A2)303は、照射光307によって一度に硬化してパターン形状を有する硬化膜310となる。
次に、パターン形状を有する硬化膜310とモールド308と引き離す。本工程では、図3(3)に示すように、ショット領域S(1)304、ショット領域S(2)305、ショット領域S(n)306において、パターン形状を有する硬化膜310とモールド308とを順番に引き離し、光照射工程(4)において、モールド308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310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310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と呼ぶこととする(参考:図1(4)の拡大部の残膜108)。
本発明の別の態様は、基板上にインプリント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。
以下に使用される「部」及び「%」は特に示さない限りすべて重量基準である。
円錐平板方式回転型粘度計RE-85L(東機産業製)を用いて25℃における硬化性組成物(A1)の溶剤成分(d1)を除く組成物の粘度を測定した。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粘度とした。
自動表面張力計DY-300(協和界面科学製)を用い、白金プレートを用いたプレート法により、25℃における硬化性組成物(A1)の溶剤成分(d1)を除く組成物の表面張力を測定した。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。
・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)
・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)
・ジメチロールトリシクロデカンジアクリレート(共栄社製、略称DCPDA)
・1,3-アダマンタンジメタノールジアクリレート(出光興産製、略称ADDA)
・テトラエチレングリコールジアクリレート(大阪有機化学工業製、商品名:V#335HP)
・イソボルニルアクリレート(共栄社化学製、商品名:IB-XA)
・ベンジルアクリレート(大阪有機化学工業製、商品名:V#160)
・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)
・Irgacure369(BASF製、略称:I.369)
・ペンタデカエチレングリコールモノ1H,1H,2H,2H-パーフフルオロオクチルエーテル(F(CF2)6CH2CH2(OCH2CH2)15OH)(DIC製、略称:DEO-15)
なお、比較例1~2は、従来の1ショット領域に積層工程(2)~離型工程(5)を順次行うパターン方法で行う際の各工程の所要時間を示す。
102 硬化性組成物
104 液滴の拡がる方向
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
202 硬化性組成物(A1)
203 硬化性組成物(A2)
204 液滴の拡がる方向
205 モールド
206 照射光
207 パターン形状を有する硬化膜
208 硬化性組成物(A1)と硬化性組成物(A2)の混合物
209 硬化性組成物(A1)と硬化性組成物(A2)の混合が十分に混合されていない領域
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1(ショット領域S(1))
305 ショット領域2(ショット領域S(2))
306 ショット領域n(ショット領域S(2))
307 照射光
308 モールド
309 硬化性組成物(A1)と(A2)の混合物
310 パターン形状を有する硬化膜
Claims (17)
- 光ナノインプリントプロセスを用いたパターン形成方法であって、
基板の表面の複数のショット領域のそれぞれに対し、
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積層工程(1)、
前記硬化性組成物(A1)からなる層の上に、少なくとも重合性化合物である成分(a2)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積層工程(2)、
モールドと前記基板の間に、前記積層工程(2)を実施することにより形成される、前記硬化性組成物(A1)と前記硬化性組成物(A2)と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)、
前記硬化性組成物(A1)と前記硬化性組成物(A2)とが部分的に混合してなる層を、前記モールドの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)、及び
硬化後の前記硬化性組成物(A1)及び前記硬化性組成物(A2)からなる層から前記モールドを引き離す離型工程(5)、
をこの順に実施することからなり、
前記型接触工程(3)から前記離型工程(5)までの工程を合わせてインプリント工程[Im]とよぶとき、
前記複数のショット領域から選択される少なくとも1つのショット領域において、前記積層工程(2)が終了した後前記インプリント工程[Im]が開始されるまでの間に、該選択された少なくとも1つのショット領域とは別のショット領域に対して、前記積層工程(2)または前記インプリント工程[Im]を実施することを特徴とするパターン形成方法。 - 前記積層工程(2)を、前記複数のショット領域から選択される複数のショット領域(S(1),S(2),・・・,S(n))(nは2以上の整数)に対して順次実施した後に、前記インプリント工程[Im]を、該選択された複数のショット領域(S(1),S(2),・・・,S(n))に対して前記積層工程(2)と同じ順に実施することを特徴とする請求項1に記載のパターン形成方法。
- 前記複数のショット領域から選択される一のショット領域に対する前記積層工程(2)と、該複数のショット領域のうち既に前記積層工程(2)が実施された他のショット領域に対する前記インプリント工程[Im]とを、同時に実施することを特徴とする請求項1に記載のパターン形成方法。
- 前記複数のショット領域から選択される第1の複数のショット領域(S(1),S(2),・・・,S(m))(mは2以上の整数)に対して前記積層工程(2)を順次実施した後に、前記複数のショット領域から同数選択される第2の複数のショット領域(S(m+1)、S(m+2),・・・,S(2m))に対する前記積層工程(2)と前記第1の複数のショット領域(S(1),S(2),・・・,S(m))に対する前記インプリント工程[Im]とを同時並行的に順次実施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。
- 前記複数のショット領域から選択される第1の複数のショット領域(S(1),S(2),・・・S(m))(mは2以上の整数)に対して前記積層工程(2)を順次実施した後に、前記ショット領域(S(1))に対する前記インプリント工程[Im]とショット領域(S(m+1))に対する前記積層工程(2)とを交互に実施し、以下、同様にショット領域(S(p))(pは2以上の整数)に対する前記インプリント工程[Im]とショット領域(S(p+m))に対する前記積層工程(2)とを交互に実施することを特徴とする請求項1に記載のパターン形成方法。
- 前記積層工程を前記複数のショット領域(S(1),S(2),・・・S(m))(mは2以上の整数)に対して順次実施するに際し、一のショット領域に対する前記積層工程(2)を実施してから次のショット領域に対する前記積層工程(2)を実施するまでの間に、一のショット領域に対する前記インプリント工程[Im]の実施に必要な時間と同じ長さの待機時間を設けることを特徴とする請求項5に記載のパターン形成方法。
- 複数の前記基板に対して1つのディスペンサと1つのインプリントヘッドを用いて前記積層工程(2)及び前記インプリント工程[Im]を実施し、第1の基板上の一のショット領域に対する前記積層工程(2)と同時に、第2の基板上の一のショット領域に対する前記インプリント工程[Im]を実施することを特徴とする請求項3または4のいずれか1項に記載のパターン形成方法。
- 前記積層工程(2)に必要な時間Tdと、前記インプリント工程[Im]に必要な時間Tiとが、等しいことを特徴とする請求項1から7のいずれか1項に記載のパターン形成方法。
- 前記硬化性組成物(A1)の光重合開始剤(b1)含有量が、前記重合性化合物(a1)100重量部に対して0重量部以上0.1重量部未満であることを特徴とする請求項1から8のいずれか1項に記載のパターン形成方法。
- 溶剤を除く前記硬化性組成物(A1)の表面張力が、溶剤を除く前記硬化性組成物(A2)の表面張力より大きいことを特徴とする請求項1から9のいずれか1項に記載のパターン形成方法。
- 溶剤を除く前記硬化性組成物(A1)の25℃における粘度が20mPa・s以上10000mPa・s未満であり、前記硬化性組成物(A2)の25℃における粘度が1mPa・s以上40mPa・s未満である請求項1から10のいずれか1項に記載のパターン形成方法。
- 基板上にインプリント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、
前記硬化性組成物(A1)が重合性化合物である成分(a1)を少なくとも有しており、
モールドを接触させた状態で前記硬化性組成物(A2)と前記硬化性組成物(A1)とが混合してなる層を硬化させる領域をショット領域としたとき、
前記基板の表面の複数のショット領域を覆うように配置された連続した液膜が形成される、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。 - 請求項12に記載のインプリント前処理コーティング材料と、該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前記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12に記載のセット。
- 請求項13または14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インプリント前処理方法であって、
請求項12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、基板のインプリント前処理方法。 - 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13に記載のインプリント前処理方法が、インプリント前処理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さらに有することを特徴とするパターン形成方法。
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