WO2013154075A1 - 微細パターンを表面に有する物品の製造方法 - Google Patents
微細パターンを表面に有する物品の製造方法 Download PDFInfo
- Publication number
- WO2013154075A1 WO2013154075A1 PCT/JP2013/060653 JP2013060653W WO2013154075A1 WO 2013154075 A1 WO2013154075 A1 WO 2013154075A1 JP 2013060653 W JP2013060653 W JP 2013060653W WO 2013154075 A1 WO2013154075 A1 WO 2013154075A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coupling agent
- resin layer
- silane coupling
- fine pattern
- photocurable resin
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 122
- 229920005989 resin Polymers 0.000 claims abstract description 122
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 119
- 239000011342 resin composition Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 23
- -1 acryloyloxy group Chemical group 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 13
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- 239000000243 solution Substances 0.000 description 39
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- 239000010408 film Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 8
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- 125000000524 functional group Chemical group 0.000 description 6
- 238000001127 nanoimprint lithography Methods 0.000 description 6
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- 238000007607 die coating method Methods 0.000 description 5
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 238000000016 photochemical curing Methods 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 239000000178 monomer Substances 0.000 description 3
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- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
-
- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
-
- 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
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2909/00—Use of inorganic materials not provided for in groups B29K2803/00 - B29K2807/00, as mould material
- B29K2909/08—Glass
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/3086—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
Definitions
- the present invention relates to a method for producing an article having a fine pattern on the surface by a nanoimprint lithography method.
- a nanoimprint lithography method As a method for forming a resist having a predetermined pattern used as a mask during an etching process in manufacturing a semiconductor device or the like, a nanoimprint lithography method has attracted attention.
- a photoresist photocurable resin composition
- a method of forming a resist having a predetermined pattern a cured resin layer having a fine pattern on the surface of a substrate after separating the mold after curing the photoresist.
- the resist does not peel from the base material when separating the mold, and for this purpose, the adhesion between the base material and the resist is important.
- the resist is a thin film (for example, 200 nm or less)
- the reversal pattern of the mold is fine
- the reversal pattern of the mold has a high aspect ratio, or the mold has a large area, the mold is separated.
- high adhesion is required between the base material and the resist.
- a silane coupling agent solution is applied to the surface of the substrate and a primer layer is formed in advance before the photoresist is applied to the surface of the substrate.
- a primer layer is formed by applying a silane coupling agent having an epoxy group or a silane coupling agent having a (meth) acryloyloxy group to the surface of a quartz substrate (Patent Document 1)
- Patent Document 2 There is an example (Patent Document 2) in which a primer layer is formed on a surface by applying a silane coupling agent having a (meth) acryloyloxy group.
- the silane coupling agent having an epoxy group has good adhesion to the base material, the adhesion to the resist is poor, and in particular, a (meth) acrylate type photoresist (photo-curing property) that is frequently used as a resist for nanoimprinting. Since it is inferior in adhesiveness to the resin composition), it is usually not often used as a primer layer when forming a resist. Since the silane coupling agent having a (meth) acryloyloxy group has good adhesion to the substrate and the resist, it is suitably used as a primer layer when forming the resist.
- the repelling of the silane coupling agent can be suppressed by including tetraalkoxysilane in the dilute solution of the silane coupling agent having a (meth) acryloyloxy group.
- the photoresist repelling may be a thin resist (for example, 200 nm or less), or a coating method such as spin coating, die coating, dip coating, spray coating, blade coating, bar coating, roll coating, gravure. This is particularly noticeable when a thin film of photoresist such as a coating method is applied uniformly over an area of 10 mm 2 or more, or when the resist is a solution containing a solvent, and particularly needs to be dried by heating.
- the present invention provides an article having a fine pattern on the surface, in which peeling of a cured resin layer having a fine pattern is suppressed, and defects in the cured resin layer derived from repelling when a photocurable resin composition is applied are suppressed.
- a manufacturing method is provided.
- a method for producing an article having a fine pattern on a surface thereof according to the present invention comprises a substrate, a primer layer formed on the surface of the substrate, and a cured resin layer formed on the surface of the primer layer,
- a method for producing an article in which a cured resin layer has a fine pattern comprising: (a) applying a solution of a silane coupling agent to the surface of the substrate to form the primer layer; and (b) photocuring.
- a solution coupling agent characterized by using those containing a (meth) acrylate and silane coupling agent having an acryloyloxy group, a silane coupling agent having an epoxy group.
- the ratio of the coupling agent is preferably 1 to 99% by mass.
- the photocurable resin composition preferably contains 0.05 to 5% by mass of the fluorine-containing surfactant in the composition.
- the photocurable resin composition preferably contains a compound having a (meth) acryloyloxy group.
- the coating method of the photocurable resin composition is preferably a method capable of forming a photocurable resin layer in an area of 10 mm 2 or more.
- the photocurable resin composition containing a solvent is applied to the surface of the primer layer, and then heated to 60 ° C. or more to volatilize the solvent.
- the photocurable resin layer is preferably formed.
- the material of the substrate is preferably silicon, quartz or glass.
- a fine pattern or inverted pattern refers to a shape composed of one or more protrusions and / or recesses having a minimum dimension of 1 nm to 100 ⁇ m among width, length and height (ie, depth).
- the (meth) acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group.
- (Meth) acrylate refers to acrylate or methacrylate.
- the silane coupling agent has the same functional group that can react with an organic material (for example, a functional group such as a (meth) acryloyloxy group or an epoxy group) and a hydrolyzable silyl group that can form a silanol group by hydrolysis. It refers to a compound possessed in a molecule.
- An article having a fine pattern on the surface obtained by the production method of the present invention has a substrate, a primer layer formed on the surface of the substrate, and a cured resin layer formed on the surface of the primer layer.
- the cured resin layer has a fine pattern.
- FIG. 1 is a cross-sectional view showing an example of an article having a fine pattern on its surface.
- the article 10 includes a substrate 12, a primer layer 14 formed on the surface of the substrate 12, and a cured resin layer 16 formed on the surface of the primer layer 14.
- the cured resin layer 16 has a fine pattern 20 including a plurality of convex portions 22 and concave portions 24 between the convex portions 22.
- Examples of the material of the base 12 include silicon (for example, single crystal silicon, polysilicon, amorphous silicon, etc.), quartz, glass, silicon nitride, aluminum nitride, silicon carbide, sapphire, lithium niobate, lithium tantalate, metal (for example, , Aluminum, nickel, copper, etc.), metal oxides (alumina, zinc oxide, magnesium oxide, etc.), and oxide and / or metal layers (for example, chromium, aluminum, nickel, molybdenum, And tantalum, tungsten, ITO, tin oxide, gold, silver, copper, platinum, titanium, etc.) and various resins.
- silicon, quartz, or glass is preferable for the reason described later.
- the substrate 12 can be applied regardless of the thickness, from a thin and flexible substrate to a thick plate.
- the thickness of the substrate 12 is preferably 0.05 to 10 mm, and more preferably 0.10 to 6.35 mm.
- the base material 12 may be surface-treated from the point which improves the adhesiveness with the primer layer 14 further.
- Surface treatment includes ozone treatment, ultraviolet cleaning treatment, plasma treatment, corona treatment, flame treatment, itro treatment (a kind of treatment of Combustion Chemical Vapor Deposition developed by ITRO), SPM (Sulfuric Acid Hydrogen Peroxide Mixture) treatment, etc. Is mentioned.
- the primer layer 14 has a silanol group formed by applying a solution of a silane coupling agent, which will be described later, to the surface of the substrate 12, drying, and further hydrolyzing the hydrolyzable silyl group of the silane coupling agent.
- 12 is a layer formed by reacting with a functional group (such as a hydroxyl group) on 12 surfaces.
- the curable resin layer 16 is formed by applying a photocurable resin composition to be described later on the surface of the primer layer 14, curing a part or all of the photocurable compound contained in the photocurable resin composition by light irradiation, and This is a layer formed by reacting a part of the photocurable compound with a functional group ((meth) acryloyloxy group or the like) derived from the silane coupling agent on the surface of the primer layer 14.
- the cured resin layer 16 has a fine pattern 20 on the surface.
- the fine pattern 20 is a pattern formed by transferring a reverse pattern on the surface of the mold to be described later.
- the fine pattern 20 includes a plurality of convex portions 22 and concave portions 24 between the convex portions 22.
- Examples of the protrusions 22 include protrusions extending on the surface of the cured resin layer 16 and protrusions scattered on the surface.
- Examples of the shape of the ridge include a straight line, a curved line, a bent shape, and the like.
- a plurality of ridges may exist in parallel and have a stripe shape.
- Examples of the cross-sectional shape of the ridge in the direction orthogonal to the longitudinal direction include a rectangle, a trapezoid, a triangle, and a semicircle.
- Examples of the shape of the protrusion include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a cone, a hemisphere, and a polyhedron.
- the width of the ridge is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and particularly preferably 10 nm to 500 nm.
- the width of the ridge means the full width at half maximum in the cross section in the direction orthogonal to the longitudinal direction.
- the width of the protrusion is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and particularly preferably 10 nm to 500 nm.
- the width of the protrusion means the full width at half maximum in the cross section perpendicular to the longitudinal direction when the bottom surface is elongated, and when the bottom surface of the protrusion is not elongated, it passes through the center of gravity in the horizontal section at a position half the height of the protrusion. Means the minimum length of a line.
- the height of the convex portion 22 is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and even more preferably 10 nm to 500 nm.
- the interval between adjacent convex portions 22 is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and further preferably 10 nm to 1 ⁇ m.
- the interval between the adjacent convex portions 22 means the distance from the start end of the bottom of the cross section of the convex portion 22 to the start end of the bottom of the cross section of the adjacent convex portion 22.
- Each dimension is an average of dimensions measured at three locations.
- the minimum dimension of the convex portion 22 is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and particularly preferably 10 nm to 500 nm.
- the minimum dimension means the minimum dimension among the width, length, and height of the convex portion.
- the method for producing an article having a fine pattern on its surface is a method having the following steps (a) to (d).
- the photocurable resin layer 18 is sandwiched between the mold 30 having the reverse pattern of the fine pattern 20 described above on the surface and the primer layer 14.
- Step (a) A silanol group formed by applying a solution of a silane coupling agent to the surface of the base material 12 and drying it, and further hydrolyzing the hydrolyzable silyl group of the silane coupling agent is converted into a functional group on the surface of the base material 12 (
- the primer layer 14 is formed by reacting with a hydroxyl group or the like.
- Examples of the substrate 12 include those described above.
- silicon, quartz or glass is preferable.
- the material of the base material 12 is silicon, quartz, or glass, repelling of the silane coupling agent having a (meth) acryloyloxy group is likely to occur. Therefore, when the material of the base material 12 is silicon, quartz, or glass, the effects of the present invention are likely to appear significantly by applying the manufacturing method of the present invention.
- At least one of the substrate 12 and the mold 30 is a material that transmits 40% or more of light having a wavelength at which the photopolymerization initiator of the photocurable resin composition acts.
- silane coupling agent solution contains a silane coupling agent and a solvent, and if necessary, contains a catalyst that promotes hydrolysis of the hydrolyzable silyl group of the silane coupling agent, other silane compounds, and the like. Also good.
- a solution containing a silane coupling agent having a (meth) acryloyloxy group and a silane coupling agent having an epoxy group is used.
- the hydrolyzable silyl group of the silane coupling agent include —Si (OCH 3 ) 3 , —SiCH 3 (OCH 3 ) 2 , —Si (OCH 2 CH 3 ) 3 , —SiCl 3 , —Si (OCOCH).
- Preferred examples include at least one selected from the group consisting of 3 ) 3 and —Si (NCO) 3 .
- silane coupling agent having a (meth) acryloyloxy group examples include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyl.
- Preferred examples include at least one selected from the group consisting of diethoxysilane and 3-methacryloxypropyltriethoxysilane.
- silane coupling agent having an epoxy group examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
- a preferred example is at least one selected from the group consisting of:
- the cured resin layer 16 is compared with a case where the silane coupling agent having a (meth) acryloyloxy group is not included. Is prevented from peeling. Moreover, the silane coupling agent which has an epoxy group is not included by including the silane coupling agent which has an epoxy group with the silane coupling agent which has a (meth) acryloyloxy group in the solution of a silane coupling agent. Compared to the case, repelling of the silane coupling agent having a (meth) acryloyloxy group when applied to the surface of the substrate 12 is suppressed.
- silane coupling agent having a (meth) acryloyloxy group by adding a silane coupling agent having a (meth) acryloyloxy group to the silane coupling agent having an epoxy group, an effect of suppressing peeling of the cured resin layer 16 can be obtained. Further, by adding a slight amount of a silane coupling agent having an epoxy group to a silane coupling agent having a (meth) acryloyloxy group, the effect of suppressing repellency of the silane coupling agent can be obtained.
- the ratio of the silane coupling agent having a (meth) acryloyloxy group is the silane coupling agent having a (meth) acryloyloxy group and the silane cup having an epoxy group.
- the total amount (100% by mass) with the ring agent it may be 1 to 99% by mass, and more preferably 1 to 80% by mass.
- the optimum range of the ratio of the silane coupling agent having a (meth) acryloyloxy group for fully exhibiting the effects of the present invention is the shape of the reverse pattern of the substrate 12, the photocurable resin composition, and the mold 30. Since it varies depending on the type of the size, silane coupling agent, etc., it cannot be determined unconditionally, but 5-60 mass% is particularly preferable as a common range in which any material can sufficiently exhibit the effects of the present invention.
- the ratio of the silane coupling agent having an epoxy group in the solution of the silane coupling agent is the sum of the silane coupling agent having a (meth) acryloyloxy group and the silane coupling agent having an epoxy group (100% by mass). 1) to 99% by mass, more preferably 30 to 99% by mass.
- the optimum range of the silane coupling agent having an epoxy group for fully exhibiting the effects of the present invention is particularly preferably 40 to 95% by mass.
- 3-methacryloxypropyltrimethoxysilane and 2- (3,4-epoxy) are used from the viewpoint of the effect of suppressing repellency of the silane coupling agent due to contaminants on the glass surface. It is particularly preferred to use a combination of (cyclohexyl) ethyltrimethoxysilane.
- the solution of the silane coupling agent contains other silane coupling agents other than the silane coupling agent having a (meth) acryloyloxy group and the silane coupling agent having an epoxy group, as long as the effects of the present invention are not impaired. You may go out.
- the silane coupling agent solution preferably contains no other silane coupling agent as much as possible, and a (meth) acryloyloxy group is used as the silane coupling agent. More preferred are those containing only a silane coupling agent having an epoxy group and a silane coupling agent having an epoxy group.
- the ratio of the silane coupling agent between the silane coupling agent having a (meth) acryloyloxy group and the silane coupling agent having an epoxy group in the silane coupling agent solution is the silane coupling agent solution (100% by mass). Of these, 0.01 to 2% by mass is preferable, and 0.1 to 1% by mass is more preferable. When the ratio of the silane coupling agent is 0.01% by mass or more, the silane coupling agent can sufficiently cover the substrate 12, and adhesion can be improved. When the ratio of the silane coupling agent is 2% by mass or less, when a silane coupling agent solution is prepared, generation of aggregates in the solution can be prevented and the solution can be stabilized.
- Solvents include water, alcohols (methanol, ethanol, 2-propanol, n-propanol, butanol, pentanol, hexanol, ethylene glycol, etc.), ethers (diethyl ether, dimethyl ether, methyl ethyl ether, tetrahydrofuran, etc.), ketones (Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) and the like.
- the solvent water, methanol, ethanol, 2-propanol, and n-propanol are particularly preferable from the viewpoints of controllability and solubility of hydrolysis reaction, boiling point of the solvent, and safety to human body.
- the solution of the silane coupling agent preferably includes a catalyst that promotes hydrolysis of the hydrolyzable silyl group of the silane coupling agent.
- the catalyst include an acid catalyst and a basic catalyst.
- the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like.
- the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia, triethylamine and the like.
- the ratio of the catalyst is preferably 0.005 to 1% by mass in the silane coupling agent solution (100% by mass).
- the solution of the silane coupling agent may contain other silane compounds other than the silane coupling agent as long as the effects of the present invention are not impaired.
- examples of other silane compounds include tetraalkoxysilane (eg, tetraethoxysilane), trialkoxymonoalkylsilane, dialkoxydialkylsilane, monoalkoxytrialkylsilane, and the like.
- the silane coupling agent solution can be applied by spin coating, die coating, dip coating, spray coating, ink jet, potting, roll coating, blade coating, gravure coating, casting, bar coating. Law.
- the silane coupling agent solution is preferably subjected to filtration using a filtration filter having a small diameter of 0.1 to 5 ⁇ m immediately before application.
- the coating layer of the silane coupling agent solution is dried.
- the drying temperature of this coating layer is preferably 80 to 150 ° C, more preferably 100 to 130 ° C. If drying temperature is 80 degreeC or more, drying time will become short and reaction of a silane coupling agent and the base material 12 will advance easily. If a drying temperature is 150 degrees C or less, the thermal decomposition reaction of a silane coupling agent can be suppressed.
- the drying time is preferably 30 seconds to 20 minutes, and more preferably 2 minutes to 10 minutes.
- the primer layer 14 forms a monomolecular layer by an adsorption reaction on the surface of the substrate 12, and expresses its adhesion performance.
- the coating method in actuality, the film is often formed with a thickness equal to or larger than the monomolecular film, but when it is too thick, peeling due to cohesive failure in the primer layer 14 may occur.
- the thickness of the primer layer 14 is preferably 20 nm or less, and more preferably 10 nm or less.
- Step (b) A photocurable resin composition is applied to the surface of the primer layer 14, and when the photocurable resin composition contains a solvent, it is dried to form the photocurable resin layer 18.
- the photocurable resin composition contains a photocurable compound, and optionally contains a fluorine-containing surfactant, a photopolymerization initiator, a solvent, and other additives.
- a compound having a (meth) acryloyloxy group is preferable from the viewpoint that the curing speed is high, the transparency of the cured product is high, and the adhesiveness with the primer layer 14 is excellent.
- a compound having a (meth) acryloyloxy group hereinafter also referred to as a (meth) acrylate compound
- a compound having 1 to 15 (meth) acryloyloxy groups per molecule is preferable.
- the (meth) acrylate compound may be a relatively low molecular compound (hereinafter referred to as an acrylate monomer), and a relatively high molecular weight compound (hereinafter referred to as (meth) acrylate) having two or more repeating units. May be referred to as a system oligomer).
- Examples of the (meth) acrylate compound include one or more (meth) acrylate monomers, one or more (meth) acrylate oligomers, one or more (meth) acrylate monomers (meth) And) one or more of acrylate oligomers.
- the (meth) acrylate-based oligomer has a molecular structure (meta) having a molecular chain having two or more repeating units (for example, a polyurethane chain, a polyester chain, a polyether chain, a polycarbonate chain, etc.) and a (meth) acryloyloxy group.
- metal molecular structure having two or more repeating units (for example, a polyurethane chain, a polyester chain, a polyether chain, a polycarbonate chain, etc.) and a (meth) acryloyloxy group.
- a urethane (meth) acrylate oligomer having an acryloyloxy group is more preferable, and a urethane (meth) acrylate oligomer having a urethane bond and 6 to 15 (meth) acryloyloxy groups is more preferable.
- the ratio of the photocurable compound in the photocurable resin composition is preferably 50 to 100% by mass, preferably 60 to 100%, when the amount of the component remaining as the cured resin in the photocurable resin composition is 100% by mass.
- the mass% is more preferable.
- the ratio of the photocurable compound is 50% by mass or more, a resin having sufficient strength after curing can be obtained.
- the photocurable resin composition preferably contains a fluorine-containing surfactant from the viewpoint of flatness of the photocurable resin layer 18 and releasability between the cured resin layer 16 and the mold 30.
- a fluorine-containing surfactant having a fluorine content of 10 to 70% by mass is preferable, and a fluorine-containing surfactant having a fluorine content of 10 to 40% by mass is more preferable.
- the fluorine-containing surfactant may be water-soluble or fat-soluble.
- an anionic fluorine-containing surfactant an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, or a nonionic fluorine-containing surfactant is preferable, and a phase in the photocurable resin composition is used. From the viewpoint of solubility and dispersibility in the cured resin layer 16, a nonionic fluorine-containing surfactant is more preferable.
- the proportion of the fluorine-containing surfactant in the photocurable resin composition is preferably 0.05 to 5% by mass when the amount of the component remaining as the cured resin in the photocurable resin composition is 100% by mass, 0.1 to 5% by mass is more preferable.
- the proportion of the fluorine-containing surfactant is 0.05% by mass or more, the flatness of the photocurable resin layer 18 and the releasability between the cured resin layer 16 and the mold 30 are good. If the ratio of the fluorine-containing surfactant is 5% by mass or less, it is easy to stably maintain a uniform mixed state with other components of the photocurable resin composition, and the influence on the resin pattern shape after curing can be suppressed.
- a photocurable resin composition contains a photoinitiator from a photocurable point.
- photopolymerization initiators acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, ⁇ -aminoketone photopolymerization initiator, ⁇ -hydroxyketone photopolymerization initiator
- Polymerization initiator ⁇ -acyl oxime ester, benzyl- (o-ethoxycarbonyl) - ⁇ -monooxime, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azo Examples thereof include bisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and
- acetophenone photopolymerization initiator benzoin photopolymerization initiator, ⁇ - Aminoketone photopolymerization initiator
- benzophenone photopolymerization initiator is preferred.
- the ratio of the photopolymerization initiator in the photocurable resin composition is preferably 0.01 to 5.0% by mass when the amount of the component remaining as the cured resin in the photocurable resin composition is 100% by mass. 0.1 to 3.0% by mass is more preferable. If the ratio of the photopolymerization initiator is 0.01% by mass or more, curing can be performed with a small amount of light, and therefore the time required for the photocuring process can be shortened. If the ratio of a photoinitiator is 5.0 mass% or less, it will be easy to mix uniformly with the other component of a photocurable resin composition, and the fall of the intensity
- a photocurable resin composition contains a solvent.
- the solvent include esters, ketones, alcohols, cyclic ethers and the like.
- the ratio of the solvent in the photocurable resin composition is preferably designed so as to obtain a target film thickness after drying, depending on the coating means used.
- the viscosity of the photo-curable resin composition is reduced to make it easier to apply a thin film, and after the coating, the solvent is evaporated to reduce the film thickness, thereby making it easier to obtain a thin film. is there.
- the photo-curable resin composition is a photosensitizer, a polymerization inhibitor, a resin, metal oxide fine particles, carbon compounds, metal fine particles, other additives such as other organic compounds, as long as the effects of the present invention are not impaired. May be included.
- a coating method of the photocurable resin composition a method capable of forming the photocurable resin layer 18 with a uniform film thickness in an area of 10 mm 2 or more before the mold 30 is brought into contact is preferable.
- a photocurable resin composition is dropped into droplets of less than 10 mm 2 and spread with a mold and thinly and flatly spread.
- the method of pressing a mold after producing a substantially uniform coating film with an area of 10 mm 2 or more produces a coating film more quickly and efficiently when transferring to a large area.
- the uniformity of the film thickness can be increased over the entire surface after curing.
- a spin coating method, a die coating method, a dip coating method, a spray coating method, an ink jet method, a potting method, a roll coating method, a blade coating method, a gravure method examples thereof include a coating method, a casting method, and a bar coating method.
- the coating method is spin coating, die coating, dip coating, spray coating, blade coating, bar coating, roll coating or gravure coating, repelling occurs when a photocurable resin composition is applied Therefore, by applying the manufacturing method of the present invention, the effect of the present invention is likely to appear remarkably.
- a spin coating method, a die coating method, a dip coating, and a spray coating method are particularly preferable from the viewpoints of apparatus cost, film thickness control accuracy, and the like.
- the photocurable resin composition contains a solvent
- the drying temperature of this coating layer is preferably 60 ° C. or higher. If the drying temperature is 60 ° C. or higher, evaporation of the solvent is promoted, and drying can be performed efficiently. Moreover, when a drying temperature is 60 degreeC or more, the viscosity of a photocurable resin composition falls by heating, fluidity
- the upper limit of the drying temperature is preferably 200 ° C. from the viewpoint of suppressing the thermal decomposition of the photocurable resin composition.
- the drying time is preferably 30 seconds to 5 minutes.
- the thickness of the photocurable resin layer 18 (here, when the photocurable resin composition contains a solvent, the thickness after drying) A is preferably 200 nm or less, and more preferably 150 nm or less. When the thickness A is 200 nm or less, the thickness of the remaining film can be reduced. However, when the photocurable resin composition is applied, repelling is likely to occur, and when the mold 30 is separated, the cured resin layer 16 is formed. Easy to peel off from the primer layer 14. Therefore, when the thickness A is 200 nm or less, by applying the manufacturing method of the present invention, the effect of the present invention is likely to appear remarkably.
- the thickness A of the photocurable resin layer 18 is not more than the depth B of the reversal pattern (that is, the recess) of the mold 30 and is preferably not more than 90% of the depth B. If the thickness A is less than or equal to the depth B, the excess photocurable compound that is not filled in the reversal pattern (concave portion) is reduced, so that the thickness R of the remaining film can be reduced, and the thickness R of the remaining film can be reduced. The uniformity is further improved.
- the thickness A is such that when the entire photocurable resin layer 18 is filled in the reverse pattern (concave portion) and no remaining film is formed, the fine pattern 20 (that is, the convex portion) having a height C required as a resist pattern is formed.
- the minimum necessary thickness (theoretical film thickness) that can be formed is preferable, and 110% or more of the theoretical film thickness is more preferable from the viewpoint of forming the fine pattern 20 (convex portion) uniformly in the surface.
- the thickness A is obtained by measuring the thickness of the photocurable resin layer 18 at three locations and averaging these thicknesses.
- Step (c) The photocurable compound of the photocurable resin composition is irradiated with light with the photocurable resin layer 18 sandwiched between the mold 30 and the primer layer 14 to cure the photocurable resin layer 18.
- the cured resin layer 16 is formed by reacting a part thereof with a functional group derived from the silane coupling agent on the surface of the primer layer 14 ((meth) acryloyloxy group or the like).
- Examples of the material of the mold 30 include a non-translucent material or a translucent material.
- Examples of the non-translucent material include silicon, metal (for example, nickel, copper, stainless steel, titanium, etc.), SiC, mica, and the like.
- Examples of the light-transmitting material include quartz, glass, and various resins (for example, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, and transparent fluororesin).
- At least one of the mold 30 and the substrate 12 is made of a material that transmits 40% or more of light having a wavelength at which the photopolymerization initiator acts.
- the mold 30 has a reverse pattern on the surface.
- the reverse pattern is a reverse pattern corresponding to the fine pattern 20 on the surface of the article to be obtained.
- the reverse pattern includes a plurality of concave portions and convex portions between the concave portions. Examples of the recess include grooves extending on the surface of the mold, holes scattered on the surface, and the like.
- Examples of the shape of the groove include a straight line, a curved line, a bent shape, and the like.
- a plurality of grooves may exist in parallel and have a stripe shape.
- Examples of the cross-sectional shape of the groove in the direction orthogonal to the longitudinal direction include a rectangle, a trapezoid, a triangle, and a semicircle.
- Examples of the shape of the hole include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a cone, a hemisphere, and a polyhedron.
- the width of the groove (that is, the width of the groove when the concave portion is groove-shaped) is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and particularly preferably 10 nm to 500 nm.
- the width of the groove means the full width at half maximum in the cross section in the direction orthogonal to the longitudinal direction.
- the width of the hole (that is, the width of the hole when the concave portion is a hole) is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and particularly preferably 10 nm to 500 nm.
- the hole width means the full width at half maximum in the cross section perpendicular to the longitudinal direction when the opening is elongated, otherwise the minimum length of the line passing through the center of gravity in the horizontal cross section at half the hole depth. Means.
- the depth B of the recess is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and even more preferably 10 nm to 500 nm. Further, the ratio of the depth B of the recess to the width of the groove (the depth B of the recess / the width of the groove) or the value of the depth B of the recess and the width of the hole (the depth B of the recess / the width of the hole) is 2 or more. In this case, the adhesion between the mold 30 and the cured resin layer 16 is increased, and the cured resin layer 16 is easily peeled off from the primer layer 14 when the mold 30 is separated. Therefore, by applying the manufacturing method of the present invention when the value of (recess depth B / groove width) or (recess depth B / hole width) is 2 or more, the effect of the present invention is remarkable. It tends to appear.
- the interval between adjacent recesses is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and even more preferably 10 nm to 1 ⁇ m.
- the interval between adjacent recesses means the distance from the start end of the upper side of the cross section of the recess to the start end of the upper side of the cross section of the adjacent recess.
- Each dimension is an average of dimensions measured at three locations.
- the minimum dimension of the recess is preferably 1 nm to 100 ⁇ m, more preferably 1 nm to 10 ⁇ m, and even more preferably 10 nm to 500 nm.
- the minimum dimension means the minimum dimension among the width, length and depth of the recess.
- the pressure applied from the mold 30 to the photocurable resin layer 18 is preferably 0.05 MPa or more, and more preferably 0.3 MPa or more. When the pressure is 0.05 MPa or more, contact between the mold 30 and the photocurable resin layer 18 is promoted, and contact failure is reduced.
- the pressure applied from the mold 30 to the photocurable resin layer 18 is preferably 50 MPa or less from the viewpoint of durability of the substrate 12 and the mold 30.
- the sandwiching of the photocurable resin layer 18 between the mold 30 and the primer layer 14 may be performed under atmospheric pressure or under reduced pressure.
- a large-scale apparatus for reducing pressure is not necessary, the time for the step (c) is shortened, and volatilization of components contained in the photocurable resin layer 18 is suppressed.
- the photocurable resin layer 18 is easily filled into the holes.
- Examples of the light applied to the photocurable resin layer 18 include ultraviolet rays, visible rays, infrared rays, electron beams, and radiation.
- Examples of ultraviolet light sources include germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, and the like. Irradiation with light may be performed under normal pressure or under reduced pressure. Moreover, you may carry out in air and you may carry out in inert gas atmospheres, such as nitrogen atmosphere and a carbon dioxide atmosphere.
- the mold 30 when the mold 30 is a non-light-transmitting material, light is irradiated from the opposite surface of the base material 12 (that is, the surface opposite to the side on which the mold 30 is disposed). When the mold 30 is a light-transmitting material, light may be irradiated from either side of the substrate 12.
- Step (d) The mold 30 is separated from the cured resin layer 16 to obtain the article 10 having the fine pattern 20 made of the cured resin layer 16 on the surface.
- Examples of a method for separating the mold 30 from the cured resin layer 16 include a method in which both are fixed by vacuum suction and moved in a direction in which one is released, a method in which both are mechanically fixed and moved in a direction in which one is released. It is done. After separating the mold 30 from the cured resin layer 16, the cured resin layer 16 may be further cured. Examples of the curing method include heat treatment and light irradiation.
- Step (e) The article 10 having the fine pattern 20 obtained in the step (d) on the surface may be subjected to an etching step, that is, the following step (e) in manufacturing a semiconductor device or the like.
- etching step As shown in FIG. 3, after the step (d), etching is performed using the fine pattern 20 made of the cured resin layer 16 as a resist, and the fine pattern 20 is directly formed on the surface of the substrate 12.
- Examples of the etching method include known methods, and an etching method using a halogen-based gas is preferable. It is preferable to remove the resist remaining on the surface of the fine pattern 20 of the substrate 12 after the etching.
- Examples of the removal method include wet treatment with a stripping solution, dry treatment with oxygen plasma, and the like, and heat treatment at a temperature that promotes thermal decomposition of the resist.
- the silane coupling agent having a (meth) acryloyloxy group as a solution of the silane coupling agent for forming the primer layer 14.
- a silane coupling agent having an epoxy group is used, so that when the mold 30 is separated, peeling of the cured resin layer 16 from the primer layer 14 is suppressed, and the photocurable resin composition is used as the primer layer.
- the defect of the cured resin layer 16 derived from the repellency of the photocurable resin composition when applied to the surface of 14 is suppressed.
- the reversal pattern of the mold 30 is When it is fine (the interval between the recesses is 1 ⁇ m or less), it appears remarkably when the reversal pattern of the mold has a high aspect ratio (the aspect ratio is 2 or more).
- the aspect ratio is the ratio of the recess depth B to the groove width (recess depth B / groove width) or the recess depth B and hole width (recess depth B / hole width). It is defined by the value of
- the effect is that when the silane coupling agent is applied to the surface of the substrate 12, cissing of the silane coupling agent is generated, and as a result, the cured resin layer 16 is formed at a location where the primer layer 14 is insufficiently formed. It appears remarkably in the condition where peeling is likely to occur, that is, when the substrate is silicon, quartz or glass.
- the effect is that the photocurable resin composition is susceptible to repelling when the photocurable resin composition is applied to the surface of the primer layer 14, that is, the cured resin layer 16 is a thin film (thickness is 200 nm or less).
- the coating method is a method capable of forming the photocurable resin layer in an area of 10 mm 2 or more, the resist is a solution containing a solvent.
- the thickness of the photocurable resin layer was measured using a table thickness measurement system (Filmetrics, F20).
- KBM303 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
- KBM403 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
- KBM5103 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
- KBM503 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone).
- TEOS Tetraethoxysilane (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
- Example 1 (Process (a)) In a sample tube, 9 g of 2-propanol, 1 g of a 0.6 mass% nitric acid aqueous solution, and 100 mg of KBM403 were weighed and stirred for 1 hour to prepare a silane coupling agent solution.
- a solution of a silane coupling agent is dropped onto the surface of a circular silicon substrate having a diameter of 4 inches (SUMCO, thickness: 525 ⁇ m, ⁇ 1.0.0> surface, single-sided mirror wafer, CZ method) and 4000 rpm. Then, spin coating was performed for 20 seconds, followed by heating on a hot plate at 130 ° C. for 10 minutes to form a primer layer having a thickness of less than 10 nm. The presence or absence of repelling of the silane coupling agent was confirmed. The results are shown in Table 1.
- a quartz mold having a fine line / space pattern (line width: 60 nm, space groove width: 60 nm, groove depth: 130 nm) is applied to the photocurable resin layer by a nanoimprint apparatus (manufactured by Toshiba Machine Co., Ltd., ST50) was applied under pressure at a pressure of 3 MPa at 25 ° C. under vacuum, and irradiated with ultraviolet rays (2000 mJ / cm 2 ) in that state.
- Examples 2 to 39 A silicon substrate with a fine pattern comprising a cured resin layer in the same manner as in Example 1 except that the silane coupling agent and other silane compounds contained in the silane coupling agent solution are changed to the types and amounts shown in Table 1.
- Table 1 or Table 2 shows the presence or absence of cissing of the silane coupling agent, the presence or absence of peeling of the cured resin layer, and the presence or absence of defects in the cured resin layer derived from the repellency of the photocurable resin composition.
- Examples 40 and 41 A glass substrate with a fine pattern comprising a cured resin layer was obtained in the same manner as in Examples 1 to 39 except that the substrate was changed to 100 mm square glass (manufactured by Asahi Glass Co., Ltd., thickness: 1 mm).
- Table 2 shows the presence or absence of cissing of the silane coupling agent, the presence or absence of peeling of the cured resin layer, and the presence or absence of defects in the cured resin layer derived from the repellency of the photocurable resin composition.
- the method for manufacturing an article having a fine pattern on the surface of the present invention is used for manufacturing semiconductor devices, optical elements, antireflection members, biochips, microreactor chips, recording media, catalyst carriers, molds used in nanoimprint lithography, and the like. Useful.
- the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2012-088633 filed on April 9, 2012 are incorporated herein as the disclosure of the present invention. .
Abstract
Description
フォトレジスト(光硬化性樹脂組成物)を基材の表面に塗布し、所定のパターンの反転パターンを表面に有するモールドと基材との間にフォトレジストを挟んだ状態にて光を照射し、フォトレジストを硬化させた後、モールドを分離して、所定のパターンを有するレジスト(微細パターンを有する硬化樹脂層)を基材の表面に形成する方法。
(メタ)アクリロイルオキシ基を有するシランカップリング剤は、基材およびレジストとの密着性がよいため、レジストを形成する際のプライマ層として好適に用いられる。
しかし、(メタ)アクリロイルオキシ基を有するシランカップリング剤の希薄溶液を未洗浄のシリコン基材に塗布した場合、シランカップリング剤のハジキが発生し、プライマ層を基材の表面に均一に形成できないことが判明した。そのため、プライマ層の形成が不充分な箇所において、レジストの剥離が発生しやすい。
しかし、シランカップリング剤の希薄溶液にテトラアルコキシシランを含ませた場合、プライマ層の表面に塗布されたフォトレジストのハジキが発生し、該箇所がレジストの欠陥となる問題(基板が剥き出しとなる問題)が新たに生じた。該フォトレジストのハジキは、レジストが薄膜(たとえば200nm以下)であったり、塗布方法が、スピンコート法、ダイコート法、ディップコート法、スプレーコート、ブレードコート法、バーコート法、ロールコート法、グラビアコート法等といったフォトレジストの薄膜を10mm2以上の面積において均一に塗布する塗布方法であったり、レジストが溶媒を含む溶液で、特に加熱乾燥を必要とする場合に顕著となる。
前記光硬化性樹脂組成物は、該組成物のうち0.05~5質量%の含フッ素界面活性剤を含むことが好ましい。
前記光硬化性樹脂組成物は、(メタ)アクリロイルオキシ基を有する化合物を含むことが好ましい。
本発明の微細パターンを表面に有する物品の製造方法においては、溶媒を含む前記光硬化性樹脂組成物を前記プライマ層の表面に塗布した後、60℃以上に加熱して前記溶媒を揮発させて、前記光硬化性樹脂層を形成することが好ましい。
前記基材の材料は、シリコン、石英またはガラスであることが好ましい。
上記した数値範囲を示す「~」とは、その前後に記載された数値を下限値および上限値として含む意味で使用され、特段の定めがない限り、以下本明細書において「~」は、同様の意味をもって使用される。
微細パターンないし反転パターンとは、幅、長さおよび高さ(すなわち、深さ)のうち最小の寸法が1nm~100μmである1つ以上の凸部および/または凹部からなる形状をいう。
(メタ)アクリロイルオキシ基は、アクリロイルオキシ基またはメタクリロイルオキシ基をいう。
(メタ)アクリレートは、アクリレートまたはメタクリレートをいう。
シランカップリング剤は、有機材料と反応し得る官能基(たとえば、(メタ)アクリロイルオキシ基、エポキシ基等の官能基)と、加水分解によってシラノール基を形成し得る加水分解性シリル基とを同一分子内に有する化合物をいう。
本発明の製造方法で得られる微細パターンを表面に有する物品は、基材と、該基材の表面に形成されたプライマ層と、該プライマ層の表面に形成された硬化樹脂層とを有し、該硬化樹脂層が微細パターンを有するものである。
基材12の材料としては、シリコン(たとえば、単結晶シリコン、ポリシリコン、アモルファスシリコン等)、石英、ガラス、窒化珪素、窒化アルミニウム、シリコンカーバイド、サファイア、ニオブ酸リチウム、タンタル酸リチウム、金属(たとえば、アルミニウム、ニッケル、銅等)、金属酸化物(アルミナ、酸化亜鉛、酸化マグネシウム等)、およびこれらの基材の表面に酸化物層および/または金属層(たとえば、クロム、アルミニウム、ニッケル、モリブデン、タンタル、タングステン、ITO、酸化錫、金、銀、銅、白金、チタン等を主成分とするもの)を形成したもの、ならびに各種樹脂等が挙げられる。基材12の材料としては、後述する理由から、シリコン、石英またはガラスが好ましい。
本発明において、基材12としては、薄く可とう性のあるものから、厚い板状のものまで、厚さを問わず適用が可能である。搬送、取り扱いのしやすさの観点から、基材12の厚さとしては0.05~10mmが好ましく、0.10~6.35mmがより好ましい。
プライマ層14は、後述するシランカップリング剤の溶液を基材12の表面に塗布し、乾燥させ、さらにシランカップリング剤の加水分解性シリル基が加水分解して形成されたシラノール基を基材12の表面の官能基(水酸基等)と反応させることによって形成される層である。
硬化樹脂層16は、後述する光硬化性樹脂組成物をプライマ層14の表面に塗布し、光照射によって光硬化性樹脂組成物に含まれる光硬化性化合物の一部または全部を硬化させ、かつ光硬化性化合物の一部をプライマ層14の表面のシランカップリング剤に由来する官能基((メタ)アクリロイルオキシ基等)と反応させることによって形成される層である。
硬化樹脂層16は、表面に微細パターン20を有する。微細パターン20は、後述するモールドの表面の反転パターンを転写して形成されるパターンである。
微細パターン20は、複数の凸部22と凸部22間の凹部24とからなる。凸部22としては、硬化樹脂層16の表面に延在する凸条、表面に点在する突起等が挙げられる。
凸条の、長手方向に直交する方向の断面形状としては、長方形、台形、三角形、半円形等が挙げられる。
突起の形状としては、三角柱、四角柱、六角柱、円柱、三角錐、四角錐、六角錐、円錐、半球、多面体等が挙げられる。
突起の幅は、1nm~100μmが好ましく、1nm~10μmがより好ましく、10nm~500nmが特に好ましい。突起の幅とは、底面が細長い場合、長手方向に直交する方向の断面における半値全幅を意味し、また突起の底面が細長くない場合、突起の高さの半分の位置の水平断面における重心を通る線の最小長さを意味する。
凸部22の高さは、1nm~100μmが好ましく、1nm~10μmがより好ましく、10nm~500nmがさらに好ましい。
前記各寸法は、3箇所で測定した寸法を平均したものである。
本発明の微細パターンを表面に有する物品の製造方法は、下記の工程(a)~(d)を有する方法である。
(a)図2に示すように、シランカップリング剤の溶液を基材12の表面に塗布し、プライマ層14を形成する工程。
(b)図2に示すように、工程(a)の後、光硬化性樹脂組成物をプライマ層14の表面に塗布し、光硬化性樹脂層18を形成する工程。
(c)図2に示すように、工程(b)の後、上述した微細パターン20の反転パターンを表面に有するモールド30と、プライマ層14との間に、光硬化性樹脂層18を挟んだ状態にて光を照射し、光硬化性樹脂層18を硬化させて硬化樹脂層16とする工程。
(d)図2に示すように、工程(c)の後、硬化樹脂層16からモールド30を分離して物品10を得る工程。
基材12の表面にシランカップリング剤の溶液を塗布し、乾燥させ、さらにシランカップリング剤の加水分解性シリル基が加水分解して形成されたシラノール基を基材12の表面の官能基(たとえば、水酸基等)と反応させることによって、プライマ層14を形成する。
基材12としては、上述した材料のものが挙げられる。基材12の材料としては、シリコン、石英またはガラスが好ましい。基材12の材料がシリコン、石英またはガラスの場合、(メタ)アクリロイルオキシ基を有するシランカップリング剤のハジキが発生しやすい。よって、基材12の材料がシリコン、石英またはガラスの場合に本発明の製造方法を適用することによって、本発明による効果が顕著に現れやすい。
基材12およびモールド30のうち少なくとも一方は、光硬化性樹脂組成物の光重合開始剤が作用する波長の光を40%以上透過する材料とする。
シランカップリング剤の溶液は、シランカップリング剤と、溶媒とを含み、必要に応じてシランカップリング剤の加水分解性シリル基の加水分解を促進する触媒、他のシラン化合物等を含んでいてもよい。
シランカップリング剤の加水分解性シリル基としては、たとえば、-Si(OCH3)3、-SiCH3(OCH3)2、-Si(OCH2CH3)3、-SiCl3、-Si(OCOCH3)3、および-Si(NCO)3からなる群から選ばれる少なくとも1種が、好ましい例として挙げられる。
エポキシ基を有するシランカップリング剤としては、たとえば、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシランからなる群から選ばれる少なくとも1種が、好ましい例として挙げられる。
また、特に基材としてガラスを使用する場合について、ガラス表面の汚染物質によるシランカップリング剤のハジキを抑制する効果の観点から、3-メタクリロキシプロピルトリメトキシシランと2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランの組合せを使用することが特に好ましい。
触媒としては、酸触媒、塩基性触媒等が挙げられる。
酸触媒としては、塩酸、硝酸、酢酸、硫酸、燐酸、スルホン酸、メタンスルホン酸、p-トルエンスルホン酸等が挙げられる。
塩基性触媒としては、水酸化ナトリウム、水酸化カリウム、アンモニア、トリエチルアミン等が挙げられる。
触媒の割合は、シランカップリング剤の溶液(100質量%)のうち、0.005~1質量%が好ましい。
他のシラン化合物としては、テトラアルコキシシラン(たとえば、テトラエトキシシラン等)、トリアルコキシモノアルキルシラン、ジアルコキシジアルキルシラン、モノアルコキシトリアルキルシラン等が挙げられる。なお、テトラアルコキシシランを含む場合、プライマ層14の表面に塗布された光硬化性樹脂組成物のハジキを発生させやすいため、本発明の効果を充分に発揮させるためには、シランカップリング剤の溶液としては、他のシラン化合物をできるだけ含まないものが好ましく、他のシラン化合物を含まないものがより好ましい。
シランカップリング剤の溶液の塗布方法としては、スピンコート法、ダイコート法、ディップコート法、スプレーコート法、インクジェット法、ポッティング法、ロールコート法、ブレードコート法、グラビアコート法、キャスト法、バーコート法等が挙げられる。
シランカップリング剤の溶液については、塗布する直前に細口径0.1~5μmのろ過フィルターを使用したろ過を行うことが好ましい。
プライマ層14の表面に光硬化性樹脂組成物を塗布し、光硬化性樹脂組成物が溶媒を含む場合は乾燥させ、光硬化性樹脂層18を形成する。
光硬化性樹脂組成物は、光硬化性化合物を含み、必要に応じて含フッ素界面活性剤、光重合開始剤、溶媒、他の添加剤を含む。
(メタ)アクリロイルオキシ基を有する化合物(以下、(メタ)アクリレート系化合物とも記す。)としては、1分子あたり(メタ)アクリロイルオキシ基を1~15個有する化合物が好ましい。
(メタ)アクリレート系化合物としては、(メタ)アクリレート系モノマーの1種以上からなるもの、(メタ)アクリレート系オリゴマーの1種以上からなるもの、(メタ)アクリレート系モノマーの1種以上と(メタ)アクリレート系オリゴマーの1種以上とからなるものが挙げられる。
含フッ素界面活性剤としては、フッ素含有量が10~70質量%の含フッ素界面活性剤が好ましく、フッ素含有量が10~40質量%の含フッ素界面活性剤がより好ましい。含フッ素界面活性剤は、水溶性であってもよく、脂溶性であってもよい。
光重合開始剤としては、アセトフェノン系光重合開始剤、ベンゾイン系光重合開始剤、ベンゾフェノン系光重合開始剤、チオキサントン系光重合開始剤、α-アミノケトン系光重合開始剤、α-ヒドロキシケトン系光重合開始剤、α-アシルオキシムエステル、ベンジル-(o-エトキシカルボニル)-α-モノオキシム、アシルホスフィンオキシド、グリオキシエステル、3-ケトクマリン、2-エチルアンスラキノン、カンファーキノン、テトラメチルチウラムスルフィド、アゾビスイソブチロニトリル、ベンゾイルパーオキシド、ジアルキルパーオキシド、tert-ブチルパーオキシピバレート等が挙げられ、感度および相溶性の点から、アセトフェノン系光重合開始剤、ベンゾイン系光重合開始剤、α-アミノケトン系光重合開始剤またはベンゾフェノン系光重合開始剤が好ましい。
溶媒としては、エステル類、ケトン類、アルコール類、環式エーテル類等が挙げられる。
光硬化性樹脂組成物中の溶媒の割合は、使用する塗工手段に応じて、乾燥後に目標とする膜厚が得られるように設計することが好ましい。溶媒で希釈することで、光硬化性樹脂組成物の粘度を低減させて薄膜塗工しやすくする効果と、塗工後に溶媒を蒸発させることで膜厚減少するために薄膜を得やすくなる効果がある。
光硬化性樹脂組成物の塗布方法としては、モールド30を接触させる前の時点で光硬化性樹脂層18を10mm2以上の面積において均一な膜厚で形成可能な方法が好ましい。比較として、光硬化性樹脂組成物を10mm2未満の液滴状に滴下してモールドで押し拡げ、薄く平らに延ばす方法がある。この方法と比較して、10mm2以上の面積で実質的に均一な塗膜を作製してからモールドを押し当てる手法の方が、広い面積に転写を行う上で迅速に効率よく塗膜を作製でき、さらに硬化後に全面において膜厚の均一性が高くできるという利点がある。光硬化性樹脂層18を10mm2以上の面積において形成可能な方法としては、スピンコート法、ダイコート法、ディップコート法、スプレーコート法、インクジェット法、ポッティング法、ロールコート法、ブレードコート法、グラビアコート法、キャスト法、バーコート法等が挙げられる。塗布方法がスピンコート法、ダイコート法、ディップコート法、スプレーコート法、ブレードコート法、バーコート法、ロールコート法またはグラビアコート法の場合、光硬化性樹脂組成物を塗布した際にハジキが発生しやすいため、本発明の製造方法を適用することによって、本発明による効果が顕著に現れやすい。塗布方法としては、装置コスト、膜厚制御の精度等の観点から、スピンコート法、ダイコート法、ディップコート、スプレーコート法が特に好ましい。
厚さAは、光硬化性樹脂層18の厚さを3箇所で測定し、これら厚さを平均したものである。
モールド30とプライマ層14との間に、光硬化性樹脂層18を挟んだ状態にて光を照射し、光硬化性樹脂層18を硬化させ、かつ光硬化性樹脂組成物の光硬化性化合物の一部をプライマ層14の表面のシランカップリング剤に由来する官能基((メタ)アクリロイルオキシ基等)と反応させることによって、硬化樹脂層16を形成する。
モールド30の材料としては、非透光材料または透光材料が挙げられる。
非透光材料としては、シリコン、金属(たとえば、ニッケル、銅、ステンレス、チタン等)、SiC、マイカ等が挙げられる。
透光材料としては、石英、ガラス、各種樹脂(たとえば、ポリジメチルシロキサン、環状ポリオレフィン、ポリカーボネート、ポリエチレンテレフタレート、透明フッ素樹脂等)等が挙げられる。
モールド30および基材12のうち少なくとも一方は、光重合開始剤が作用する波長の光を40%以上透過する材料とする。
モールド30は、表面に反転パターンを有する。反転パターンは、得ようとする物品の表面の微細パターン20に対応した反転パターンである。
反転パターンは、複数の凹部と凹部間の凸部とからなる。凹部としては、モールドの表面に延在する溝、表面に点在する孔等が挙げられる。
溝の、長手方向に直交する方向の断面形状としては、長方形、台形、三角形、半円形等が挙げられる。
孔の形状としては、三角柱、四角柱、六角柱、円柱、三角錐、四角錐、六角錐、円錐、半球、多面体等が挙げられる。
孔の幅(すなわち、凹部が孔状である場合の孔の幅)は、1nm~100μmが好ましく、1nm~10μmがより好ましく、10nm~500nmが特に好ましい。孔の幅とは、開口部が細長い場合、長手方向に直交する方向の断面における半値全幅を意味し、そうでない場合、孔の深さの半分の位置の水平断面における重心を通る線の最小長さを意味する。
また、凹部の深さBと溝の幅の比率(凹部の深さB/溝の幅)もしくは凹部の深さBと孔の幅(凹部の深さB/孔の幅)の値が2以上の場合、モールド30と硬化樹脂層16の密着性が高くなり、モールド30を分離する際に硬化樹脂層16がプライマ層14から剥離しやすい。よって、(凹部の深さB/溝の幅)もしくは(凹部の深さB/孔の幅)の値が2以上の場合に本発明の製造方法を適用することによって、本発明による効果が顕著に現れやすい。
凹部の最小寸法は、1nm~100μmが好ましく、1nm~10μmがより好ましく、10nm~500nmがさらに好ましい。最小寸法とは、凹部の幅、長さおよび深さのうち最小の寸法を意味する。
モールド30から光硬化性樹脂層18に加わる圧力は、0.05MPa以上が好ましく、0.3MPa以上がより好ましい。圧力が0.05MPa以上であれば、モールド30と光硬化性樹脂層18の接触が促進され、接触不良が低減する。モールド30から光硬化性樹脂層18に加わる圧力は、基材12やモールド30の耐久性の点から、50MPa以下が好ましい。
紫外線の光源としては、殺菌灯、紫外線用蛍光灯、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧または高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、自然光等が挙げられる。
光の照射は、常圧下で行ってもよく、減圧下で行ってもよい。また、空気中で行ってもよく、窒素雰囲気、二酸化炭素雰囲気等の不活性ガス雰囲気で行ってもよい。
なお、モールド30が非透光材料の場合には、基材12の反対面(すなわち、モールド30が配される側と反対面)側から光が照射される。モールド30が透光材料の場合には、基材12のどちらの面側から光を照射してもよい。
硬化樹脂層16からモールド30を分離して、硬化樹脂層16からなる微細パターン20を表面に有する物品10を得る。
硬化樹脂層16からモールド30を分離した後、硬化樹脂層16をさらに硬化させてもよい。硬化の方法としては、加熱処理、光照射等が挙げられる。
工程(d)で得られた微細パターン20を表面に有する物品10は、半導体デバイス等の製造においては、エッチング工程、すなわち下記の工程(e)に供される場合がある。
(e)図3に示すように、工程(d)の後、硬化樹脂層16からなる微細パターン20をレジストとしてエッチングを行い、基材12の表面に微細パターン20を直接形成する工程。
エッチングの後、基材12の微細パターン20の表面に残ったレジストを除去することが好ましい。除去方法としては、剥離液等によるウエット処理、酸素プラズマ等によるドライ処理、レジストの熱分解を促す温度での熱処理等が挙げられる。
以上説明した本発明の微細パターンを表面に有する物品10の製造方法にあっては、プライマ層14を形成するためのシランカップリング剤の溶液として、(メタ)アクリロイルオキシ基を有するシランカップリング剤と、エポキシ基を有するシランカップリング剤とを含むものを用いるため、モールド30を分離する際に硬化樹脂層16のプライマ層14からの剥離が抑えられ、かつ光硬化性樹脂組成物をプライマ層14の表面に塗布した際の光硬化性樹脂組成物のハジキに由来する硬化樹脂層16の欠陥が抑えられる。
例5~35、40、41は実施例であり、例1~4、36~39は比較例である。
光硬化性樹脂層の厚さを、卓上膜厚測定システム(フィルメトリクス社製、F20)を用いて測定した。
基材の表面にプライマ層を形成した直後のプライマ層を顕微鏡および目視で観察し、シランカップリング剤のハジキの有無を下記の基準にて官能評価した。
◎:顕微鏡で観察してもシランカップリング剤のハジキは見られない。
○:顕微鏡で観察した場合、シランカップリング剤のハジキが見られるが、目視で観察した場合、シランカップリング剤のハジキは見られない。
×:目視で観察してシランカップリング剤のハジキが見られる。
プライマ層の表面に光硬化性樹脂層を形成し、ナノインプリント法によって微細パターンを形成した後の硬化樹脂層を目視で観察し、硬化樹脂層の剥離の有無を下記の基準にて官能評価した。
◎:5つのサンプルで試験を行った時、硬化樹脂層の剥離が1つも見られない。
○:5つのサンプルで試験を行った時、硬化樹脂層の剥離が見られたサンプルが2つ以下。
×:5つのサンプルで試験を行った時、硬化樹脂層の剥離が見られたサンプルが3つ以上。
プライマ層の表面に光硬化性樹脂層を形成し、ナノインプリント法によって微細パターンを形成した後の硬化樹脂層を目視で観察し、光硬化性樹脂組成物のハジキに由来する硬化樹脂層の欠陥の有無を下記の基準にて官能評価した。
◎:目視で観察して光硬化性樹脂組成物のハジキに由来する硬化樹脂層の欠陥は見られない。
×:目視で観察して光硬化性樹脂組成物のハジキに由来する硬化樹脂層の欠陥が見られる。
KBM303:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン(信越シリコーン社製)、
KBM403:3-グリシドキシプロピルトリメトキシシラン(信越シリコーン社製)、
KBM5103:3-アクリロキシプロピルトリメトキシシラン(信越シリコーン社製)、
KBM503:3-メタクリロキシプロピルトリメトキシシラン(信越シリコーン社製)。
TEOS:テトラエトキシシラン(東京化成工業社製試薬)。
(工程(a))
サンプル管に、2-プロパノールの9g、0.6質量%の硝酸水溶液の1g、KBM403の100mgをはかりとり、1時間撹拌し、シランカップリング剤の溶液を調製した。
U-6H(新中村化学工業社製、ウレタンアクリレート系オリゴマー)の5質量%、IRGACURE907(BASFジャパン社製、光重合開始剤)の3質量%、サーフロンS-650(AGCセイミケミカル社製、ノニオン性含フッ素界面活性剤)の3質量%および酢酸イソブチルからなる光硬化性樹脂組成物を、プライマ層の表面に滴下し、3000rpmで20秒間のスピンコートを行い、その後、ホットプレート上にて70℃で1分間の加熱を行い、厚さ120nmの光硬化性樹脂層を形成した。
光硬化性樹脂層に対して、ライン/スペースの微細パターンを有する石英モールド(ラインの線幅:60nm、スペースの溝幅:60nm、溝深さ:130nm)を、ナノインプリント装置(東芝機械社製、ST50)を用い、真空下、25℃にて、3MPaの圧力で押し付けて密着させ、その状態のまま紫外線(2000mJ/cm2)を照射した。
石英モールドを垂直方向に0.1mm/秒の速度で剥がし取り、硬化樹脂層からなる微細パターン付きシリコン基材を得た。硬化樹脂層の剥離、光硬化性樹脂組成物のハジキに由来する硬化樹脂層の欠陥の有無を確認した。結果を表1に示す。
シランカップリング剤の溶液に含まれるシランカップリング剤、他のシラン化合物を、表1に示す種類、量に変更した以外は、例1と同様にして硬化樹脂層からなる微細パターン付きシリコン基材を得た。シランカップリング剤のハジキの有無、硬化樹脂層の剥離の有無、光硬化性樹脂組成物のハジキに由来する硬化樹脂層の欠陥の有無を表1または表2に示す。
〔例40,41〕
基材を100mm角のガラス(旭硝子社製、厚さ:1mm)に変更した以外は、例1~39と同様にして硬化樹脂層からなる微細パターン付きガラス基材を得た。シランカップリング剤のハジキの有無、硬化樹脂層の剥離の有無、光硬化性樹脂組成物のハジキに由来する硬化樹脂層の欠陥の有無を表2に示す。
なお、2012年4月9日に出願された日本特許出願2012-088633号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
12 基材
14 プライマ層
16 硬化樹脂層
18 光硬化性樹脂層
20 微細パターン
22 凸部
24 凹部
30 モールド
Claims (9)
- 基材と、該基材の表面に形成されたプライマ層と、該プライマ層の表面に形成された硬化樹脂層とを有し、該硬化樹脂層が微細パターンを有する物品を製造する方法であって、
(a)シランカップリング剤の溶液を前記基材の表面に塗布し、前記プライマ層を形成する工程と、
(b)光硬化性樹脂組成物を前記プライマ層の表面に塗布し、光硬化性樹脂層を形成する工程と、
(c)前記微細パターンの反転パターンを表面に有するモールドと、前記プライマ層との間に、前記光硬化性樹脂層を挟んだ状態にて光を照射し、前記光硬化性樹脂層を硬化させて前記硬化樹脂層とする工程と、
(d)前記硬化樹脂層から前記モールドを分離して前記物品を得る工程と、
を有し、
前記シランカップリング剤の溶液として、(メタ)アクリロイルオキシ基を有するシランカップリング剤と、エポキシ基を有するシランカップリング剤とを含むものを用いる、微細パターンを表面に有する物品の製造方法。 - 前記シランカップリング剤の溶液における(メタ)アクリロイルオキシ基を有するシランカップリング剤とエポキシ基を有するシランカップリング剤との合計量を100質量%としたとき、(メタ)アクリロイルオキシ基を有するシランカップリング剤の割合が、1~99質量%である、請求項1に記載の微細パターンを表面に有する物品の製造方法。
- 前記光硬化性樹脂層の厚さが、200nm以下である、請求項1または2に記載の微細パターンを表面に有する物品の製造方法。
- 前記光硬化性樹脂組成物が、該組成物のうち0.05~5質量%の含フッ素界面活性剤を含む、請求項1~3のいずれか一項に記載の微細パターンを表面に有する物品の製造方法。
- 前記光硬化性樹脂組成物が、(メタ)アクリロイルオキシ基を有する化合物を含む、請求項1~4のいずれか一項に記載の微細パターンを表面に有する物品の製造方法。
- 前記光硬化性樹脂組成物の塗布方法が、光硬化性樹脂層を10mm2以上の面積において形成可能な方法である、請求項1~5のいずれか一項に記載の微細パターンを表面に有する物品の製造方法。
- 溶媒を含む前記光硬化性樹脂組成物を前記プライマ層の表面に塗布した後、60℃以上に加熱して前記溶媒を揮発させて、前記光硬化性樹脂層を形成する、請求項1~6のいずれか一項に記載の微細パターンを表面に有する物品の製造方法。
- 前記基材の材料が、シリコン、石英またはガラスである、請求項1~7のいずれか一項に記載の微細パターンを表面に有する物品の製造方法。
- 前記(d)工程の後に、前記硬化樹脂層からなる微細パターンをレジストとしてエッチングを行い、基材の表面に微細パターンを形成する、請求項1~8のいずれか一項に記載の微細パターンを表面に有する物品の製造方法。
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KR20147024363A KR20150003158A (ko) | 2012-04-09 | 2013-04-08 | 미세 패턴을 표면에 갖는 물품의 제조 방법 |
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