WO2013161454A1 - 微細パターン転写用のモールドの製造方法及びそれを用いた凹凸構造を有する基板の製造方法、並びに該凹凸構造を有する基板を有する有機ｅｌ素子の製造方法 - Google Patents

微細パターン転写用のモールドの製造方法及びそれを用いた凹凸構造を有する基板の製造方法、並びに該凹凸構造を有する基板を有する有機ｅｌ素子の製造方法 Download PDF

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Publication number
WO2013161454A1
WO2013161454A1 PCT/JP2013/057851 JP2013057851W WO2013161454A1 WO 2013161454 A1 WO2013161454 A1 WO 2013161454A1 JP 2013057851 W JP2013057851 W JP 2013057851W WO 2013161454 A1 WO2013161454 A1 WO 2013161454A1
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WIPO (PCT)
Prior art keywords
substrate
mold
concavo
block copolymer
unevenness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/057851
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English (en)
French (fr)
Japanese (ja)
Inventor
隆史 關
聡 増山
真林 福田
涼 西村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
JX Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Oil and Energy Corp filed Critical JX Nippon Oil and Energy Corp
Priority to AU2013253941A priority Critical patent/AU2013253941B2/en
Priority to CN201380021957.8A priority patent/CN104254438B/zh
Priority to CA2870426A priority patent/CA2870426C/en
Priority to IN9101DEN2014 priority patent/IN2014DN09101A/en
Priority to EP13781178.2A priority patent/EP2842721B1/en
Priority to JP2014512423A priority patent/JP5695799B2/ja
Priority to KR1020147019842A priority patent/KR20140106704A/ko
Publication of WO2013161454A1 publication Critical patent/WO2013161454A1/ja
Priority to US14/513,622 priority patent/US20150028325A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3807—Resin-bonded materials, e.g. inorganic particles
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • B29C33/3857—Manufacturing moulds, e.g. shaping the mould surface by machining by making impressions of one or more parts of models, e.g. shaped articles and including possible subsequent assembly of the parts
    • B29C33/3878—Manufacturing moulds, e.g. shaping the mould surface by machining by making impressions of one or more parts of models, e.g. shaped articles and including possible subsequent assembly of the parts used as masters for making successive impressions
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • B29C45/263—Moulds with mould wall parts provided with fine grooves or impressions, e.g. for record discs
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/10—Moulds; Masks; Masterforms
    • 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
    • G03F7/165—Monolayers, e.g. Langmuir-Blodgett
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • B29C2033/385—Manufacturing moulds, e.g. shaping the mould surface by machining by laminating a plurality of layers
    • 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
    • B29C2059/023—Microembossing
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0058—Liquid or visquous
    • B29K2105/0061—Gel or sol
    • 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
    • B29K2825/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as mould material
    • B29K2825/04—Polymers of styrene
    • B29K2825/08—Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene
    • 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
    • B29K2833/00—Use of polymers of unsaturated acids or derivatives thereof as mould material
    • B29K2833/04—Polymers of esters
    • B29K2833/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms

Definitions

  • the present invention relates to a mold for transferring a fine pattern, a substrate having an uneven structure, and an organic EL element.
  • Lithography is known as a method for forming a fine pattern such as a semiconductor integrated circuit.
  • the resolution of the pattern formed by the lithography method depends on the wavelength of the light source and the numerical aperture of the optical system.
  • a light source having a shorter wavelength is desired.
  • short wavelength light sources are expensive, and their development is not easy, and development of optical materials that transmit such short wavelength light is also necessary.
  • manufacturing a large-area pattern by a conventional lithography method requires a large optical element, and is difficult both technically and economically. Therefore, a new method for forming a desired pattern having a large area has been studied.
  • a nanoimprint method is known as a method for forming a fine pattern without using a conventional lithography apparatus.
  • the nanoimprint method is a technology that can transfer a nanometer order pattern by sandwiching a resin between a mold (mold) and a substrate. Basically, i) application of a resin layer, ii) press by a mold, iii) It consists of four steps of pattern transfer and iv) mold release, and is excellent in that nano-size processing can be realized by such a simple process. Moreover, since the equipment to be used is simple, large-area processing is possible, and high throughput can be expected, practical application is expected not only in semiconductor devices but also in many fields such as storage media, optical members, and biochips. ing.
  • a mold for transferring a pattern having a line width of several tens of nanometers can basically expose and develop a resist pattern on a silicon substrate using a lithography apparatus. is necessary.
  • a metal current seed layer is formed on the resist pattern.
  • the pattern definition becomes 100 nm or less, the coverage of the current seed layer formed on the resist pattern by sputtering decreases, and at the top, side walls, and bottom of the resist pattern (the substrate exposed portion of the pattern recess, that is, the trench).
  • the thickness of the current seed layer obtained is different.
  • the formation of the current seed layer proceeds preferentially, which causes a problem that the trench opening is narrowed. For this reason, when holes or trenches and ridges are formed on the substrate using a resist layer, the current seed layer is unlikely to deposit metal at the bottom of the holes or trenches, resulting in overhangs on top of the resist layer ridge. There was a problem.
  • the laminate is electroformed using such a current seed layer, the electroformed film is joined above the hole or the trench due to overhang, and a void is left inside the trench.
  • the mold obtained by electroforming has a problem of low mechanical strength and causes defects such as deformation of the mold and pattern loss.
  • Patent Document 1 discloses a process of forming a resist layer having a concavo-convex pattern on a substrate having a conductive surface and exposing the conductive surface in a concave portion of the pattern of the resist layer in order to solve the above problem; A step of performing electroforming on the conductive surface exposed in the concave portion of the pattern of the resist layer to form an electroformed film having a thickness larger than the thickness of the resist layer; a substrate having a conductive surface and the resist layer A method for producing a mold for nanoimprinting, comprising In this method, the electroformed film can be grown unidirectionally upward from the conductive surface at the bottom of the resist pattern without using a current seed layer, so that there is no void in the nanoimprint mold. Has been. However, even if this method is used, the mold used in the nanoimprint method still has to rely on the lithography method.
  • JP 2010-017865 A WO2011 / 007878A1 JP 2010-056256 A
  • the inventor of the present application applies a block copolymer solution containing a block copolymer and a solvent satisfying a predetermined condition on a base material, and dries it to cause microphase separation of the block copolymer.
  • Disclosed is a method of obtaining a mother mold (mold) in which a fine and irregular concavo-convex pattern is formed by forming a structure.
  • a matrix used for nanoimprinting or the like can be obtained using a phenomenon in which a block copolymer is self-assembled without using a lithography method.
  • a liquid mixture of a silicone polymer and a curing agent is dropped onto the obtained matrix and cured to obtain a transfer pattern
  • a glass substrate coated with a curable resin is pressed against the transfer pattern, and the curable resin is applied by ultraviolet rays.
  • a diffraction grating in which the transfer pattern is duplicated is produced.
  • An organic EL element (organic light emitting diode) obtained by laminating a transparent electrode, an organic layer and a metal electrode on the diffraction grating has a sufficiently high luminous efficiency and a sufficiently high external extraction efficiency. It has been confirmed that the wavelength dependency and directivity of light emission are sufficiently low and the power efficiency is sufficiently high.
  • a step of removing one polymer constituting the block copolymer by etching treatment is required.
  • one polymer is removed on the surface of the base material, and the portion where the base material is exposed and the other polymer remain to form a convex portion, but the remaining convex portion is in contact with the base material. Since the area is small, it is easy to peel off from the substrate surface. Further, with the etching process, foreign substances may adhere to the surface of the base material or the convex portion, and the diffraction grating manufactured from the mother mold or the mother mold through the transfer process may be contaminated.
  • Patent Document 2 the manufacturing method of the diffraction grating that can be achieved in the above-mentioned prior patent application (Patent Document 2) of the present inventor is further advanced, and the manufacturing is more suitable for mass production of products such as organic EL elements. It was desired to provide a method.
  • Patent Document 3 discloses that a polymer layer containing a relatively low molecular weight block copolymer is phase-separated to form a columnar microdomain structure or a lamellar microdomain structure. The polymer is removed by etching or the like.
  • an object of the present invention is to provide a method for producing a mold for transferring a fine pattern, which is suitable for mass production of a substrate having a concavo-convex structure such as a diffraction grating used for general-purpose products such as organic EL elements, and obtained. It is to provide a method for producing a substrate having a concavo-convex structure using a mold and a method for producing an organic EL element using a substrate having such a concavo-convex structure.
  • a further object of the present invention is to produce a mold for transferring a fine pattern, a substrate having a concavo-convex structure, and an organic EL element with high throughput using these production methods.
  • a method for producing a mold for transferring a fine pattern wherein a solution containing at least a block copolymer comprising first and second polymer segments and a polyalkylene oxide is applied to the surface of a substrate.
  • the volume ratio of the first polymer and the second polymer in the block copolymer is 4: 6 to 6: 4 in order to create a horizontal cylinder structure.
  • the polyalkylene oxide is preferably contained in an amount of 5 to 70 parts by mass with respect to 100 parts by mass of the block copolymer in order to obtain a sufficient height (groove depth) of the concavo-convex structure.
  • the number average molecular weight of the block copolymer is preferably 500,000 or more.
  • the first polymer constituting the block copolymer may be polystyrene
  • the second polymer may be polymethyl methacrylate
  • the organic solvent is chloroform, acetone, dichloromethane, and It may be a kind selected from the group consisting of a carbon disulfide / acetone mixed solvent.
  • the time for phase separation of the block copolymer in the presence of organic solvent vapor may be 6 to 168 hours.
  • the mold manufacturing method of the present invention even if the first or second polymer segment is formed in one or two stages in the cylinder structure, a concavo-convex structure appears on the surface.
  • the average value of the unevenness depth distribution is in the range of 20 to 200 nm, preferably in the range of 30 to 150 nm, and the standard deviation of the unevenness depth is in the range of 10 to 100 nm, preferably 15 to 75 nm. It is desirable to be a mold for a substrate having a concavo-convex structure such as a diffraction grating.
  • a primer layer is formed on the surface of the base material before applying a solution containing at least a block copolymer composed of first and second polymer segments and a polyalkylene oxide. It is preferable.
  • the molecular weight distribution (Mw / Mn) of the block copolymer is preferably 1.5 or less, and the difference in solubility parameter between the first polymer and the second polymer is 0.1 to 10 (cal / cm 3). ) It is preferable that it is 1/2 .
  • the mold obtained by the mold manufacturing method is pressed onto the substrate on which the unevenness forming material is applied to cure the unevenness forming material, and the mold is removed to remove the mold.
  • a method of manufacturing a diffraction grating for forming a diffraction grating having an uneven structure is provided.
  • the mold obtained by the method for producing a mold is pressed onto a substrate coated with a concavo-convex forming material to cure the concavo-convex forming material, and the mold is removed to remove the mold.
  • a diffraction grating having a concavo-convex structure made of a sol-gel material is prepared by pressing the structure onto a substrate coated with a sol-gel material to cure the sol-gel material and removing the structure.
  • a method of manufacturing a diffraction grating to be formed is provided.
  • an organic EL device is manufactured by sequentially laminating a transparent electrode, an organic layer, and a metal electrode on the concavo-convex structure of the diffraction grating manufactured by the method for manufacturing a diffraction grating.
  • a method for manufacturing an EL device is provided.
  • a mold for transferring a fine pattern manufactured by the mold manufacturing method is provided.
  • a diffraction grating manufactured by the method for manufacturing a diffraction grating and having an uneven structure on the surface.
  • the average pitch of the unevenness of the uneven structure is preferably 100 to 1500 nm, and more preferably 200 to 1200 nm.
  • the cross-sectional shape of the concavo-convex structure is a waveform, and the planar shape of the concavo-convex structure is subjected to a two-dimensional fast Fourier transform process on the concavo-convex analysis image obtained by analysis using an atomic force microscope to obtain a Fourier transform image.
  • the Fourier transform image shows an annular pattern substantially centered at the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the annular pattern has an absolute value of the wave number of 10 ⁇ m ⁇ It is desirable to exist in a region that is 1 or less. Further, it is desirable that the kurtosis of the cross-sectional shape of the concavo-convex structure of the diffraction grating is ⁇ 1.2 or more, and further ⁇ 1.2 to 1.2.
  • an organic EL element produced by the method for producing an organic EL element.
  • a concavo-convex structure is obtained by pressing the mold obtained by the mold manufacturing method onto a substrate coated with the concavo-convex forming material, curing the concavo-convex forming material, and removing the mold.
  • a method for manufacturing a substrate having a diffractive concavo-convex structure is provided.
  • the mold obtained by the method for producing a mold is pressed onto a substrate coated with a concavo-convex forming material to cure the concavo-convex forming material, and then removed from the mold.
  • a structure having a concavo-convex structure is prepared by pressing the structure onto a substrate coated with a sol-gel material, curing the sol-gel material, and removing the structure.
  • a method for manufacturing a substrate having a concavo-convex structure is provided.
  • a substrate having a concavo-convex structure on the surface produced by the method for producing a diffraction grating.
  • the substrate having this concavo-convex structure preferably has an average pitch of the concavo-convex of 100 to 1500 nm, and more preferably 200 to 1200 nm.
  • the block copolymer is self-organized by phase-separating the solution containing the block copolymer with an organic solvent, and the surface has a smooth corrugated uneven structure and the cross-sectional structure is A block copolymer film having a horizontal cylinder structure is obtained. Therefore, the etching process required for forming the concavo-convex structure is not required, the manufacturing process can be simplified, and the possibility of dirt and foreign matter adhering to the mold through the manufacturing process can be reduced. it can. As for the surface property of the metal layer of the obtained mold, smooth irregularities are distributed substantially uniformly, and it is suppressed that the resin remains on the mold side when the block copolymer and the substrate are peeled from the mold.
  • FIG. 8A It is the photograph which observed the cross section of the thin film after solvent annealing obtained in Example 1 with the transmission electron microscope, and shows the one-step horizontal cylinder structure. It is an enlarged photograph of the photograph of FIG. 8C.
  • FIG. 2 is a photograph showing a concavity and convexity analysis image by an atomic force microscope on the surface of the thin film concavity and convexity obtained in Example 1.
  • FIG. 9A It is a photograph which shows the unevenness
  • FIG. 9B It is a photograph which shows the Fourier-transform image obtained based on the unevenness
  • FIG. 10A It is a photograph which shows the unevenness
  • the mold manufacturing method mainly includes a block copolymer solution preparation process, a block copolymer solution coating process, a drying process, a solvent annealing process, a seed layer forming process, an electroforming process.
  • a process and a peeling process are included.
  • each process of the manufacturing method of a mold and a subsequent process are demonstrated, referring also to the conceptual diagram of FIG.1 and FIG.2.
  • a diffraction grating substrate will be described as an example of a substrate having a concavo-convex structure.
  • the substrate having a concavo-convex structure of the present invention is not limited to an optical substrate such as a diffraction grating substrate as described later, It can be applied to a substrate having the following uses.
  • the block copolymer used in the present invention has at least a first polymer segment composed of a first homopolymer and a second polymer segment composed of a second homopolymer different from the first homopolymer.
  • the second homopolymer desirably has a solubility parameter that is 0.1 to 10 (cal / cm 3 ) 1/2 higher than the solubility parameter of the first homopolymer.
  • the difference between the solubility parameters of the first and second homopolymers is less than 0.1 (cal / cm 3 ) 1/2, it is difficult to form a regular microphase separation structure of the block copolymer, and the difference is 10 When it exceeds (cal / cm 3 ) 1/2 , it is difficult to prepare a uniform solution of the block copolymer.
  • Examples of the monomer that can be used as the first homopolymer and the second homopolymer as a raw material for the homopolymer include styrene, methylstyrene, propylstyrene, butylstyrene, hexylstyrene, octylstyrene, methoxystyrene, ethylene, Propylene, butene, hexene, acrylonitrile, acrylamide, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, buty
  • styrene methyl methacrylate, ethylene oxide, butadiene, isoprene, vinyl pyridine, and lactic acid from the viewpoint that phase-separation formation easily occurs and unevenness is easily formed by etching.
  • styrenic polymer more preferably polystyrene
  • polyalkyl methacrylate more preferably polymethyl methacrylate
  • polyethylene oxide polybutadiene
  • polyisoprene polyvinyl pyridine
  • two combinations selected from the group consisting of polylactic acid are two combinations selected from the group consisting of polylactic acid.
  • a combination of methyl methacrylate, a combination of styrenic polymer and polyisoprene, a combination of styrenic polymer and polybutadiene is particularly preferred. More preferred is a combination of polystyrene (PS) and polymethyl methacrylate (PMMA) from the viewpoint of obtaining a preferred number average molecular weight (Mn) of the block copolymer.
  • the number average molecular weight (Mn) of the block copolymer is preferably 500,000 or more, more preferably 1,000,000 or more, and particularly preferably 1,000,000 to 5,000,000.
  • the domain size of block copolymers increases with molecular weight.
  • the average pitch of the unevenness formed by the microphase separation structure of the block copolymer becomes small, and the average pitch of the unevenness of the resulting diffraction grating becomes insufficient.
  • the average pitch is preferably 100 to 1500 nm, and more preferably 200 to 1200 nm. From this point, the number average molecular weight (Mn) of the block copolymer is preferably 500,000 or more.
  • the molecular weight distribution (Mw / Mn) of the block copolymer is preferably 1.5 or less, more preferably 1.0 to 1.35. When such molecular weight distribution exceeds 1.5, it becomes difficult to form a regular microphase separation structure of the block copolymer.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the block copolymer are values measured by gel permeation chromatography (GPC) and converted to the molecular weight of standard polystyrene.
  • the volume ratio of the first polymer segment to the second polymer segment (first polymer segment: second polymer segment) in the block copolymer creates a horizontal cylinder structure described later by self-assembly. Therefore, it is in the range of 4: 6 to 6: 4, and more preferably about 5: 5.
  • the volume ratio is out of the above range, it becomes difficult to form a concavo-convex pattern due to the horizontal cylinder structure described later, and a spherical or vertical cylinder structure tends to appear.
  • the block copolymer solution used in the present invention is prepared by dissolving the block copolymer in a solvent.
  • solvents include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ethers such as diethyl ether, tetrahydrofuran, and dioxane.
  • Ketones such as acetone, methyl ethyl ketone, isophorone and cyclohexanone; ether alcohols such as butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol and benzyloxyethanol; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triglyme, propylene glycol monomethyl Glycol ethers such as ether and propylene glycol monomethyl ether acetate; ethyl acetate, ethyl lactate, ⁇ Esters such as butyrolactone; phenols such as phenol and chlorophenol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; chloroform, methylene chloride, tetrachloroethane, monochlorobenzene, di Halogen-based solvents such as chlorobenzene; hetero-
  • the block copolymer solution may contain other homopolymer (a homopolymer other than the first homopolymer and the second homopolymer in the block copolymer contained in the solution: for example, block copolymer
  • a homopolymer other than the first homopolymer and the second homopolymer in the block copolymer contained in the solution for example, block copolymer
  • the combination of the first homopolymer and the second homopolymer in the combination is a combination of polystyrene and polymethyl methacrylate
  • it may be a homopolymer of a type other than polystyrene and polymethyl methacrylate.
  • polyalkylene oxide a homopolymer other than the first homopolymer and the second homopolymer in the block copolymer contained in the solution: for example, block copolymer
  • block copolymer When the combination of the first homopolymer and the second homopolymer in the combination is a combination of polystyrene and
  • the depth of the unevenness formed by the microphase separation structure of the block copolymer can be made deeper.
  • polyalkylene oxide polyethylene oxide and polypropylene oxide are more preferable, and polyethylene oxide is particularly preferable.
  • polyethylene oxide the following formula: HO— (CH 2 —CH 2 —O) n —H [Wherein, n represents an integer of 10 to 5000 (more preferably an integer of 50 to 1000, still more preferably an integer of 50 to 500). ] The thing represented by these is preferable.
  • the number average molecular weight (Mn) of the polyalkylene oxide is preferably 460 to 220,000, and more preferably 2200 to 46000. When such a number average molecular weight is less than the lower limit, the molecular weight is too low, it is liquid at room temperature, and is likely to separate and precipitate, and those exceeding the upper limit are difficult to synthesize.
  • the molecular weight distribution (Mw / Mn) of the polyalkylene oxide is preferably 1.5 or less, more preferably 1.0 to 1.3. If the molecular weight distribution exceeds the above upper limit, it is difficult to maintain the uniformity of the microphase separation shape.
  • Such number average molecular weight (Mn) and weight average molecular weight (Mw) are values measured by gel permeation chromatography (GPC) and converted to the molecular weight of standard polystyrene.
  • the combination of the first homopolymer and the second homopolymer in the block copolymer is preferably a combination of polystyrene and polymethyl methacrylate (polystyrene-polymethyl methacrylate).
  • polystyrene-polymethyl methacrylate polystyrene-polymethyl methacrylate
  • polyalkylene oxide such as polyethylene oxide
  • the content of the polyalkylene oxide is preferably 1 to 100 parts by mass, more preferably 5 to 100 parts by mass, with respect to 100 parts by mass of the block copolymer. More preferably, it is 5 to 70 parts by mass.
  • the content of the polyalkylene oxide is less than 5 parts by mass, the effect obtained by containing the polyalkylene oxide becomes poor.
  • the content of the polyalkylene oxide exceeds 100 parts by mass with respect to 100 parts by mass of the block copolymer, the uneven pattern formed by phase separation of the block copolymer tends to collapse, and when the content exceeds 70 parts by mass. Polyalkylene oxide may precipitate.
  • the total content of polyalkylene oxide and other homopolymers in the block copolymer solution is preferably 0.1 to 15% by mass in the block copolymer solution, and 0.3 to 5 More preferably, it is mass%.
  • the total content is less than the lower limit, it is not easy to uniformly apply the solution with a sufficient film thickness in order to obtain a required film thickness. Is relatively difficult to prepare.
  • the block copolymer solution may further contain a homopolymer other than polyalkylene oxide, a surfactant, an ionic compound, an antifoaming agent, a leveling agent, and the like.
  • the block copolymer When other homopolymer is contained, it can be contained in a proportion of 1 to 100 parts by mass with respect to 100 parts by mass of the block copolymer, as in the case of polyalkylene oxide. Moreover, when using the said surfactant, it is preferable that the content is 10 mass parts or less with respect to 100 mass parts of said block copolymers. Furthermore, when using the said ionic compound, it is preferable that the content is 10 mass parts or less with respect to 100 mass parts of said block copolymers.
  • the block copolymer solution prepared as described above is applied onto the substrate 10 to form the thin film 30.
  • resin substrates such as a polyimide, polyphenylene sulfide (PPS), polyphenylene oxide, polyether ketone, polyethylene naphthalate, polyethylene terephthalate, polyarylate, triacetyl cellulose, polycycloolefin; Glass, octadecyldimethylchlorosilane (ODS) treated glass, octadecyltrichlorosilane (OTS) treated glass, organosilicate treated glass, glass treated with a silane coupling agent, inorganic substrates such as silicon substrates; metal substrates such as aluminum, iron and copper Is mentioned.
  • the base material 10 may be subjected to a surface treatment such as an orientation treatment.
  • a surface treatment such as an orientation treatment.
  • an organosilicate-treated glass is prepared by applying a methyl isobutyl ketone (MIBK) solution of methyltrimethoxysilane (MTMS) and 1,2-bis (trimethoxysilyl) ethane (BTMSE) to the glass and heat-treating it.
  • MIBK methyl isobutyl ketone
  • MTMS methyltrimethoxysilane
  • BTMSE 1,2-bis (trimethoxysilyl) ethane
  • the octadecyldimethylchlorosilane-treated glass and octadecyltrichlorosilane-treated glass can be produced by a method of immersing the glass in a heptane solution of those silanes and washing away unreacted components later.
  • the substrate surface of glass or the like may be surface-treated with a primer layer such as octadecyldimethylchlorosilane or organosilicate, or a block copolymer substrate by performing a silane coupling treatment with a general silane coupling agent.
  • Adhesion to can be improved. If the adhesion is insufficient, it peels off during electroforming, which hinders the production of a transfer mold.
  • the method for applying the block copolymer solution is not particularly limited.
  • spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress printing, die coating, A curtain coating method or an ink jet method can be employed.
  • the thickness of the thin film 30 of the block copolymer is preferably 10 to 3000 nm, more preferably 50 to 500 nm, as described later.
  • the thin film 30 made of the block copolymer solution is applied on the base material 10
  • the thin film 30 on the base material 10 is dried. Drying can be performed in an air atmosphere.
  • the drying temperature is not particularly limited as long as the solvent can be removed from the thin film 30, but is preferably 10 to 200 ° C, and more preferably 20 to 100 ° C.
  • corrugation may be seen on the surface of the thin film 30 when the said block copolymer begins to form a micro phase-separation structure by drying.
  • the thin film 30 is subjected to solvent annealing (solvent phase separation) in an organic solvent vapor atmosphere to form a block copolymer phase separation structure in the thin film 30.
  • solvent annealing solvent phase separation
  • the self-assembly of the block copolymer proceeds, and the block copolymer is microphase-separated into the first polymer segment 32 and the second polymer segment 34 as shown in FIG. It becomes a horizontal cylinder structure.
  • the “horizontal cylinder structure” means that the first polymer segment or the second polymer segment extends in a cylinder shape (orientation) in a direction along the surface of the base material to which the block copolymer solution is applied.
  • the “vertical cylinder structure” means that the first polymer segment or the second polymer segment extends in a cylinder shape (orientation) in a direction substantially perpendicular to the surface of the substrate to which the block copolymer solution is applied. It means self-organization.
  • These structures can be confirmed by dyeing a polymer with ruthenium oxide, osmium oxide or the like and observing the cross-sectional structure by electron microscope measurement or the like. Small-angle X-ray scattering (SAXS) measurement is also effective in identifying their orientation structure.
  • SAXS Small-angle X-ray scattering
  • the solvent annealing treatment can be performed, for example, by bringing a vapor atmosphere of an organic solvent into a sealable container such as a desiccator and exposing the thin film 30 as an object in this atmosphere.
  • concentration of the organic solvent vapor is preferably higher in order to promote the phase separation of the block copolymer, desirably a saturated vapor pressure, and concentration management is relatively easy.
  • the saturated vapor amount is known to be 0.4 g / l to 2.5 g / l at room temperature (0 ° C. to 45 ° C.).
  • the annealing time for the organic solvent such as chloroform is too long, polyethylene oxide is deposited on the surface of the coating film or the phase-separated uneven shape (pattern) tends to be broken (rounded).
  • the treatment time of the solvent annealing treatment can be 6 hours to 168 hours, preferably 12 hours to 48 hours, and more preferably 12 hours to 36 hours. If the treatment time is too long, the concavo-convex shape is broken (smoothed), and if it is too short, the groove of the concavo-convex structure is shallow, and when a diffraction grating is produced using a mold, the diffraction effect becomes insufficient.
  • an organic solvent having a boiling point of 20 ° C. to 120 ° C. is preferable.
  • chloroform, dichloromethane, toluene, tetrahydrofuran (THF), acetone, carbon disulfide, a mixed solvent thereof or the like is used. Can do. Among these, chloroform, dichloromethane, acetone, and a mixed solvent of acetone / carbon disulfide are preferable.
  • the ambient temperature of the solvent annealing is preferably 0 ° C. to 45 ° C. When the temperature is higher than 45 ° C., the uneven structure formed in the thin film becomes loose and easily collapses. In an environment lower than 0 ° C., the organic solvent is difficult to evaporate, and phase separation of the block copolymer is difficult to occur.
  • the block copolymer is phase-separated into a horizontal cylinder structure by the solvent annealing treatment.
  • the mixing ratio of the first homopolymer and the second homopolymer constituting the block copolymer is equal (5: 5) or close to it, a lamellar phase separation structure appears by thermal annealing. It is generally known that a cylindrical structure appears at about 7 and a spherical structure appears at about 2: 8.
  • the solvent annealing treatment according to the present invention is performed, even if the mixing ratio of the first homopolymer and the second homopolymer composing the block copolymer is 40:60 to 60:40, the cylinder structure is formed in the horizontal direction.
  • the first homopolymer 32 extends in a cylinder shape in a direction substantially parallel to the surface of the substrate 10 in the layer of the second homopolymer 34.
  • the orientation is as follows.
  • the surface layer portion of the second homopolymer 34 in which the first homopolymer 32 is present rises smoothly to form a waveform.
  • the cylinder-like arrangement in which the first homopolymer 32 extends in a cylinder shape in a direction substantially parallel to the surface of the substrate 10 has a plurality of layers (a plurality of steps) in the direction perpendicular to the surface of the substrate 10 (height direction). (See FIGS. 8A and 8B described later).
  • the raised corrugated structure can be directly used as an uneven pattern of an optical substrate such as a diffraction grating. For this reason, unlike the case of phase separation by thermal annealing, it is not necessary to remove one homopolymer by etching after phase separation.
  • a part of the horizontal cylinder structure may include a vertical cylinder or a spherical structure.
  • the patterning process of the mold can be simplified.
  • the etching process usually involves the following problems, but such a problem does not occur in the mold manufacturing method of the present invention. That is, when the etching process is performed, protrusions are likely to occur in the remaining homopolymer pattern, the numerical value of kurtosis described later is reduced, and an overhang cross-sectional shape is also likely to occur. For this reason, in the subsequent electroforming process, the plated metal is likely to be drawn to the convex portion or protruding corner of the object, and is difficult to be drawn to the concave portion or the recessed portion.
  • the seed layer applied before the electroforming process is less likely to adhere to such a complicated structure. For these reasons, pattern defects are likely to occur due to the etching process. Further, in the etching process, dirt and dust are easily generated on the mold by using an etching solution and removing one of the homopolymers.
  • the use of the solvent annealing process eliminates the need for an etching process, which eliminates the problems associated with etching as described above, and a mold having a reliable concavo-convex pattern and less adhesion of foreign matter, and a mold made therefrom.
  • An optical substrate such as a diffraction grating can be obtained. Therefore, an optical substrate such as a diffraction grating can be manufactured with a high throughput and a simple process.
  • the surface shape defined by the polymer segment 34 by the solvent annealing treatment is a relatively smooth inclined surface as conceptually shown in FIG. Is referred to as a “waveform structure” as appropriate).
  • a corrugated structure there is no overhang, and the metal layer deposited on the corrugated structure 38 is replicated in its reverse pattern and is therefore easily peeled off.
  • the base material 10 having the corrugated structure 38 thus obtained can be used as a transfer master (mold) in a subsequent process.
  • the average pitch of the irregularities representing the corrugated structure 38 is preferably in the range of 100 to 1500 nm, and more preferably in the range of 200 to 1200 nm. If the average pitch of the irregularities is less than the lower limit, the pitch is too small with respect to the wavelength of visible light, so that it is difficult to cause visible light diffraction in a diffraction grating obtained using such a matrix, and exceeds the upper limit. The diffraction angle of the diffraction grating obtained by using such a matrix becomes small, and the function as the diffraction grating cannot be fully exhibited.
  • corrugation means the average value of the pitch of an unevenness
  • the average value of the pitch of the unevenness is obtained by analyzing the unevenness of the surface using a scanning probe microscope (for example, product name “E-sweep” manufactured by SII NanoTechnology Co., Ltd.). Is measured, 100 or more intervals between adjacent adjacent convex portions or adjacent concave portions in the unevenness analysis image are measured, and a value calculated by calculating the average is adopted.
  • the average value of the depth distribution of the unevenness representing the corrugated structure 38 is preferably in the range of 20 to 200 nm, and more preferably in the range of 30 to 150 nm. If the average depth distribution is less than the lower limit, the height is insufficient with respect to the wavelength of visible light, resulting in insufficient diffraction. If the upper limit is exceeded, the resulting diffraction grating is extracted from the organic EL device. When used as an optical element on the mouth side, the electric field distribution inside the organic layer becomes non-uniform, and the element is easily destroyed due to heat generated by the concentration of the electric field at a specific location, and the life is likely to be shortened.
  • the average value (m) of the uneven depth distribution is represented by the following formula (I):
  • N represents the total number of measurement points (total number of pixels), i represents any of integers from 1 ⁇ N, x i is the i-th measurement point uneven depth Data is shown, m shows the average value of the uneven
  • the heating temperature can be, for example, not less than the glass transition temperature of the first and second polymer segments 32, 34, for example, not less than the glass transition temperature of those homopolymers and not more than 70 ° C. higher than the glass transition temperature. can do.
  • the heat treatment can be performed in an air atmosphere using an oven or the like.
  • a seed layer 40 to be a conductive layer for the subsequent electroforming process is formed on the surface of the master corrugated structure 38 obtained as described above.
  • the seed layer 40 can be formed by electroless plating, sputtering, or vapor deposition.
  • the thickness of the seed layer 40 is preferably 10 nm or more, more preferably 20 nm or more in order to make the current density uniform in the subsequent electroforming process and to make the thickness of the metal layer deposited by the subsequent electroforming process constant. is there.
  • seed layer materials include nickel, copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chromium, gold / cobalt alloy, gold / nickel alloy, boron / nickel alloy, solder, copper / nickel / chromium An alloy, a tin-nickel alloy, a nickel-palladium alloy, a nickel-cobalt-phosphorus alloy, or an alloy thereof can be used.
  • a metal layer 50 is deposited on the seed layer 40 by electroforming (electroplating).
  • the thickness of the metal layer 50 can be set to a total thickness of 10 to 3000 ⁇ m including the thickness of the seed layer 40, for example.
  • Any of the above metal species that can be used as the seed layer 40 can be used as the material of the metal layer 50 deposited by electroforming. From the viewpoint of wear resistance as a mold, peelability, etc., nickel is preferable. In this case, it is preferable to use nickel also for the seed layer 40.
  • the current density in electroforming can be set to, for example, 0.03 to 10 A / cm 2 from the viewpoint of shortening the electroforming time while suppressing the bridge to form a uniform metal layer.
  • the formed metal layer 50 has an appropriate hardness and thickness in view of the ease of processing such as pressing, peeling and cleaning of the subsequent resin layer.
  • the surface of the metal layer may be subjected to diamond-like carbon (DLC) treatment or Cr plating treatment.
  • the metal layer may be further heat treated to increase its surface hardness.
  • the metal layer 50 including the seed layer obtained as described above is peeled from the base material having the concavo-convex structure to obtain a mold that becomes a father.
  • the peeling method may be physically peeled off, and the first homopolymer and the remaining block copolymer are removed by dissolving them using an organic solvent such as toluene, tetrahydrofuran (THF) or chloroform. May be.
  • ⁇ Washing process> When the mold is peeled from the substrate 10 having the corrugated structure 38 as described above, a part of the polymer 60 may remain in the mold as shown in FIG. In such a case, those remaining portions 60 can be removed by washing.
  • wet cleaning or dry cleaning can be used.
  • the wet cleaning can be removed by cleaning with an organic solvent such as toluene or tetrahydrofuran, a surfactant, or an alkaline solution.
  • ultrasonic cleaning may be performed. Further, it may be removed by electrolytic cleaning.
  • As the dry cleaning it can be removed by ashing using ultraviolet rays or plasma.
  • a combination of wet cleaning and dry cleaning may be used. After such washing, rinsing with pure water or purified water may be performed, followed by ozone irradiation after drying. In this way, a mold 70 having a desired uneven structure as shown in FIG.
  • the mold 70 may be subjected to a mold release treatment in order to improve the mold release from the resin.
  • a mold release treatment a prescription for lowering the surface energy is generally used, and there is no particular limitation.
  • the method include coating the surface 70a, treating with a fluorine-based silane coupling agent, and forming a diamond-like carbon film on the surface.
  • the concavo-convex structure (pattern) of the mold is transferred to a concavo-convex forming material layer made of an organic material such as a resin or an inorganic material such as a sol-gel material. Or a mother mold).
  • the shape of the mold 70 may be changed to a shape suitable for transfer at the time of transfer. For example, when performing roll transfer, the mold 70 can be wound around the outer periphery of a cylindrical body to form a roll-shaped mold (a transfer process using the roll-shaped mold will be described later).
  • the unevenness forming material layer to be transferred is a resin layer
  • a transfer processing method as shown in FIG. 2B, for example, a curable resin is applied to the support substrate 90, and then the resin layer 80 is cured while pressing the uneven structure of the mold 70 against the resin layer 80.
  • a base material made of a transparent inorganic material such as glass; polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), Base material made of resin such as polystyrene (PS); gas barrier layer made of inorganic material such as SiN, SiO 2 , SiC, SiO x N y , TiO 2 , Al 2 O 3 is formed on the surface of the base material made of these resins A laminated substrate formed by alternately laminating a substrate made of these resins and a gas barrier layer made of these inorganic substances.
  • the thickness of the support substrate 90 can be in the range of 1 to 500 ⁇ m.
  • the support substrate 90 is desirably transparent depending on the application. However, when the resin layer 80 to which the concavo-convex structure is transferred is used again as a mold (matrix), the support substrate 90 does not need to be transparent. .
  • the unevenness forming material examples include curable resins such as various UV curable resins such as epoxy resins, acrylic resins, urethane resins, melamine resins, urea resins, polyester resins, phenol resins, and cross-linked liquid crystal resins.
  • the thickness of the curable resin is preferably in the range of 0.5 to 500 ⁇ m. If the thickness is less than the lower limit, the height of the irregularities formed on the surface of the cured resin layer tends to be insufficient, and if the thickness exceeds the upper limit, the influence of the volume change of the resin that occurs during curing increases and the irregular shape is well formed. It may not be possible.
  • the unevenness forming material 84 such as a curable resin
  • the conditions for curing the unevenness forming material 84 vary depending on the type of resin used.
  • the curing temperature is in the range of room temperature to 250 ° C.
  • the curing time is 0.5 minutes to It is preferably in the range of 3 hours.
  • a method of curing by irradiating energy rays such as ultraviolet rays or electron beams may be used. In that case, the irradiation amount is preferably in the range of 20 mJ / cm 2 to 5 J / cm 2 .
  • the mold 70 is removed from the cured resin layer 80 after curing.
  • the method for removing the mold 70 is not limited to the mechanical peeling method, and any known method can be adopted.
  • a peeling roll can be used. In this way, as shown in FIG. 2C, a resin film structure 100 having a cured resin layer in which irregularities are formed on the support substrate 90 can be obtained.
  • the resin film structure 100 can be used as it is as a diffraction grating.
  • the resin film structure 100 is further used as a mold to produce a diffraction grating made of an organic material such as a resin or a structure made of an inorganic material such as a sol-gel material and used as the diffraction grating. You can also.
  • the mold manufacturing method of the present invention can be used not only for manufacturing a diffraction grating provided on the light extraction port side of an organic EL element but also for manufacturing an optical component having a fine pattern used in various devices.
  • an optical component having a fine pattern used in various devices .
  • a wire grid polarizer, an antireflection film, a liquid crystal display, a touch panel, or an optical element for providing a light confinement effect inside a solar cell by being installed on the photoelectric conversion surface side of the solar cell is used for manufacturing. be able to.
  • the resin film structure 100 having a desired pattern can be obtained.
  • the reverse pattern of the resin film structure 100 is used as a diffraction grating, the resin film structure obtained through the above-described mold transfer process.
  • a curable resin layer 82 is applied on another transparent support base 92 as shown in FIG.
  • the resin film structure 100 is pressed against the curable resin layer 82 to cure the curable resin layer 82.
  • the resin film structure 100 is peeled from the cured curable resin layer 82, whereby a replica 110 which is another resin film structure as shown in FIG. 2E can be obtained.
  • the above-described transfer process may be performed using the replica 110 as a master to manufacture a reverse pattern replica of the replica 110, and the transfer process may be repeated again using the reverse pattern as a master to form a child replica. Also good.
  • the roll process apparatus 170 shown in FIG. 4 manufactures the film-like substrate 180a by forming a concavo-convex pattern on the film covered with the long substrate film 180.
  • the roll process apparatus 170 includes a transport system 186 for a substrate film (base material) 180, a die coater 182 for applying an unevenness forming material to the substrate film 180 being transported, and a metal that is located downstream of the die coater 182 and transfers a pattern.
  • a roll 190 and an irradiation light source 185 for irradiating the substrate film 180 with UV light are mainly provided to face the metal roll 190 with the substrate film 180 interposed therebetween.
  • the transport system 186 for the substrate film 180 includes a film feed roll 172 that feeds the substrate film 180, a nip roll 174 and a release roll 176 that are arranged on the upstream and downstream sides of the metal roll 190 and bias the substrate film to the metal roll 190, respectively.
  • a winding roll 187 that winds up the substrate film 180a to which the pattern has been transferred, and a plurality of transport rolls 178 that transport the substrate film 180.
  • the metal roll 190 can be a roll-shaped mold formed by winding the previously prepared mold 70 (see FIG. 1F) around the outer periphery of a cylindrical body.
  • a film-like substrate to which the pattern of the metal roll 190 is transferred is obtained by the following process.
  • the substrate film 180 that has been wound around the film feeding roll 172 in advance is fed downstream by the rotation of the film feeding roll 172 and the film winding roll 187.
  • the unevenness forming material 184 is applied to one surface of the substrate film 180 by the die coater 182 to form a coating film having a predetermined thickness.
  • the coating film of the substrate film 180 is pressed against the outer peripheral surface of the metal roll 190 by the nip roll 174, and the pattern on the outer peripheral surface of the metal roll 190 is transferred to the coating film.
  • the coating film is irradiated with UV light from the irradiation light source 185 and the unevenness forming material 184 is cured.
  • the wavelength of the UV light varies depending on the unevenness forming material 184, but is generally 200 to 450 nm, and the irradiation amount can be 10 mJ / cm 2 to 5 J / cm 2 .
  • the concavo-convex pattern can be retransferred to a curable resin or a sol-gel material using the long film-like substrate 180a as a mold.
  • a long film-like substrate 180a is obtained in a form wound in a roll shape, it is suitable for a mass production process of an optical substrate (diffraction grating substrate) using the film-like substrate as a mold. It is also suitable for conveyance to an apparatus that performs a mass production process of substrates.
  • storage and an aging process can be performed by producing a film-like substrate and winding it once in a roll shape.
  • the method for forming a substrate having a concavo-convex pattern using a sol-gel material is mainly a solution preparation step S1 for preparing a sol solution, a coating step S2 for applying the prepared sol solution to a substrate, a substrate Drying step S3 for drying the coating film of the sol solution applied to the substrate, transfer step S4 for pressing the mold on which the transfer pattern is formed, peeling step S5 for peeling the mold from the coating film, and main firing step for firing the coating film S6.
  • a solution preparation step S1 for preparing a sol solution
  • a coating step S2 for applying the prepared sol solution to a substrate
  • a substrate Drying step S3 for drying the coating film of the sol solution applied to the substrate
  • transfer step S4 for pressing the mold on which the transfer pattern is formed
  • peeling step S5 for peeling the mold from the coating film
  • main firing step for firing the coating film S6 main firing the coating film S6.
  • a sol solution used to form a coating film to which a pattern is transferred is prepared by a sol-gel method (step S1 in FIG. 5).
  • a sol solution of a metal alkoxide sica precursor
  • tetramethoxysilane MTES
  • tetraethoxysilane TEOS
  • tetra-i-propoxysilane tetra-n-propoxysilane
  • tetra-i-butoxysilane tetra-n-butoxysilane
  • tetra-n-butoxysilane tetra-n-butoxysilane
  • tetra- Tetraalkoxide monomers such as sec-butoxysilane and tetra-t-butoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane Ethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane
  • metal acetylacetonate metal carboxylate, oxychloride, chloride, a mixture thereof and the like can be mentioned, but not limited thereto.
  • the metal species include, but are not limited to, Ti, Sn, Al, Zn, Zr, In, and a mixture thereof in addition to Si. What mixed suitably the precursor of the said metal oxide can also be used.
  • the mixing ratio can be 1: 1, for example, in a molar ratio.
  • This sol solution produces amorphous silica by performing hydrolysis and polycondensation reactions.
  • an acid such as hydrochloric acid or an alkali such as ammonia is added.
  • the pH is preferably 4 or less or 10 or more.
  • the amount of water to be added can be 1.5 times or more in molar ratio with respect to the metal alkoxide species.
  • a material other than silica can be used as the sol-gel material.
  • a Ti-based material, an ITO (indium-tin-oxide) -based material, Al 2 O 3 , ZrO 2 , ZnO, or the like can be used.
  • solvent for the sol solution examples include alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane, benzene, toluene, xylene, mesitylene, and the like.
  • alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane, benzene, toluene, xylene, mesitylene, and the like.
  • Aromatic hydrocarbons such as diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, isophorone and cyclohexanone, ethers such as butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol and benzyloxyethanol Alcohols, glycols such as ethylene glycol and propylene glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Glycol ethers such as recall monomethyl ether acetate, esters such as ethyl acetate, ethyl lactate and ⁇ -butyrolactone, phenols such as phenol and chlorophenol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Amides such as pyrrolidone, halogen-based solvents such as chloroform,
  • Sol solution additives include polyethylene glycol, polyethylene oxide, hydroxypropyl cellulose, polyvinyl alcohol for viscosity adjustment, alkanolamines such as triethanolamine, which are solution stabilizers, ⁇ -diketones such as acetylacetone, and ⁇ -ketoesters. , Formamide, dimethylformamide, dioxane and the like can be used.
  • the sol solution prepared as described above is applied on the substrate (step S2 in FIG. 5). From the viewpoint of mass productivity, it is preferable to apply the sol solution to the substrate at a predetermined position while continuously transporting the plurality of substrates.
  • a coating method any coating method such as a bar coating method, a spin coating method, a spray coating method, a dip coating method, a die coating method, and an ink jet method can be used, but the sol solution is uniformly applied to a relatively large area substrate.
  • the die coating method, the bar coating method, and the spin coating method are preferred because the coating can be completed quickly before the sol solution is gelled.
  • Substrates made of inorganic materials such as glass, quartz and silicon substrates, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), polystyrene Resin substrates such as (PS), polyimide (PI), and polyarylate can be used.
  • the substrate may be transparent or opaque, but it is relatively hard if the sol-gel material layer is formed on this substrate, and further the functional layer is further formed on the optical substrate when it is incorporated into the device.
  • a substrate is preferred.
  • substrate provided with heat resistance, weather resistance with respect to UV light etc. is desirable.
  • a substrate made of an inorganic material such as glass, quartz, or silicon substrate is more preferable, and the substrate made of these inorganic materials can be divided into a substrate and a sol-gel material if the applied sol-gel material is an inorganic material. It is also preferable in that the difference in refractive index between the layers is small and unintended refraction and reflection in the optical substrate can be prevented.
  • a surface treatment or an easy-adhesion layer may be provided on the substrate, or a gas barrier layer may be provided for the purpose of preventing the ingress of gases such as moisture and oxygen.
  • a gas barrier layer may be provided for the purpose of preventing the ingress of gases such as moisture and oxygen.
  • the substrate is held in the atmosphere or under reduced pressure to dry the solvent in the coated film (hereinafter also referred to as “sol-gel material layer” as appropriate) (step S3 in FIG. 5). If this holding time is short, the viscosity of the coating film is too low to transfer the pattern in the subsequent transfer step, and if the holding time is too long, the polymerization reaction of the precursor proceeds so much that transfer cannot be performed in the transfer step. In the case of mass production of an optical substrate, the holding time can be managed by the substrate transport time from the application of the sol solution to the subsequent transfer process using the film-like substrate.
  • the substrate holding temperature in this drying step is preferably a constant temperature in the range of 10 to 100 ° C., and more preferably in the range of 10 to 30 ° C.
  • the holding temperature is higher than this range, the gelation reaction of the coating film proceeds rapidly before the transfer process, which is not preferable.
  • the holding temperature is lower than this range, the gelation reaction of the coating film before the transfer process is slow. This is not preferable because productivity decreases.
  • the evaporation of the solvent proceeds and the polymerization reaction of the precursor also proceeds, and the physical properties such as the viscosity of the sol solution change in a short time.
  • the amount of evaporation of the solvent also depends on the amount of solvent used at the time of preparing the sol solution (sol solution concentration).
  • the sol solution is a silica precursor
  • hydrolysis / condensation polymerization of the silica precursor occurs as a gelation reaction
  • alcohol is generated in the sol solution through a dealcoholization reaction.
  • a volatile solvent such as alcohol is used as a solvent in the sol solution. That is, the sol solution contains alcohol generated in the hydrolysis process and alcohol present as a solvent, and the sol-gel reaction proceeds by removing them in the drying step. Therefore, it is desirable to adjust the holding time and holding temperature in consideration of the gelation reaction and the solvent used.
  • the drying process since the solvent in the sol solution evaporates simply by holding the substrate as it is, it is not always necessary to perform an aggressive drying operation such as heating or blowing, and the substrate on which the coating film has been formed is left as it is for a predetermined time. It can be left alone or transported for a predetermined time for a subsequent process. In this respect, the drying process is not essential.
  • the film-like substrate 180a as a mold obtained by the roll process apparatus 170 shown in FIG. 4 is pressed against the coating film by a press roll (laminate roll) to thereby form the film-like substrate.
  • the uneven pattern is transferred to the coating film on the substrate (step S4 in FIG. 5).
  • the film-like substrate 180 a is fed between the pressing roll 122 and the substrate 140 conveyed immediately below it, so that the concavo-convex pattern of the film-like substrate 180 a is applied to the coating film (sol solution) on the substrate 140. 142).
  • the film-like substrate 180a when the film-like substrate 180a is pressed against the substrate 140 by the pressing roll 122, the film-like substrate 180a is coated on the surface of the coating film 142 of the substrate 140 while the film-like substrate 180a and the substrate 140 are conveyed synchronously. At this time, the film-like substrate 180a and the substrate 140 are in close contact with each other by rotating while pressing the pressing roll 122 against the back surface of the film-like substrate 180a (the surface opposite to the surface on which the concavo-convex pattern is formed). In order to feed the long film-like substrate 180a toward the pressing roll 140, the film-like substrate 180a is unwound as it is from the take-up roll 187 (see FIG. 4) on which the long film-like substrate 180a is wound. It is advantageous to use.
  • Hard molds made of metal, quartz, etc. can be cleaned and repaired (defect repaired) when defects are found in the concavo-convex pattern, thereby transferring the defects to the sol-gel side. It is possible to prevent defects due to being performed. However, in the case of a film mold (soft mold), such cleaning and repair is not easy.
  • a mold made of metal, quartz or the like is in a roll shape, and when a defect occurs due to clogging or the like, the transfer device must be stopped immediately to replace the mold.
  • the desired substrate can be obtained by selecting a material suitable for each process, which is divided into two processes, a process for producing a film mold from a metal mold and a process for transferring the film mold to the sol-gel side.
  • a desired material can be used, and not only necessary characteristics but also pattern transfer can be performed with no pattern defect and good releasability.
  • the roll process using the above-described pressing roll has the following advantages compared to the press type. i) Since the time for contact between the mold and the coating film is short, it is possible to prevent the pattern from being damaged due to the difference in thermal expansion coefficient between the mold, the substrate and the stage on which the substrate is installed. ii) Productivity is improved due to the roll process, and further productivity can be further improved by using a long film substrate (film mold). iii) It is possible to prevent gas bubbles from being generated in the pattern or gas marks from remaining due to bumping of the solvent in the gel solution. iv) Since it is in line contact with the substrate (coating film), the transfer pressure and the peeling force can be reduced, and it is easy to cope with an increase in area.
  • the film substrate may be pressed against the coating film while heating the coating film.
  • the heating may be performed through a pressing roll, or the coating film may be heated directly or from the substrate side.
  • a heating means may be provided inside the pressure roll (transfer roll), and any heating means can be used.
  • a heater provided with a heater inside the pressing roll is suitable, but a heater separate from the pressing roll may be provided. In any case, any pressing roll may be used as long as pressing is possible while heating the coating film.
  • the pressing roll is preferably a roll having a coating of a resin material such as ethylene-propylene-diene rubber (EPDM), silicone rubber, nitrile rubber, fluororubber, acrylic rubber, chloroprene rubber, etc. having heat resistance on the surface.
  • a supporting roll may be provided so as to sandwich the substrate facing the pressing roll, or a supporting table for supporting the substrate may be installed.
  • the heating temperature of the coating film at the time of transfer can be 40 ° C. to 150 ° C.
  • the heating temperature of the pressing roll can be similarly 40 ° C. to 150 ° C. it can.
  • the coating film may be temporarily fired.
  • Pre-baking promotes gelation of the coating film, solidifies the pattern, and makes it difficult to collapse during peeling.
  • pre-baking it is preferably heated in the atmosphere at a temperature of 40 to 150 ° C.
  • the film-like substrate is peeled from the coating film (sol-gel material layer) after the transfer process or the pre-baking process (process S5 in FIG. 5). Since the roll process is used as described above, the peel force may be smaller than that of the plate-type mold used in the press method, and the mold can be easily peeled off from the coating film without remaining on the mold (film substrate). can do. In particular, since the coating film is transferred while being heated, the reaction easily proceeds, and the mold is easily peeled off from the coating film immediately after the transfer. Furthermore, you may use a peeling roll for the improvement of the peelability of a mold. As shown in FIG.
  • the peeling roll 123 is provided on the downstream side of the pressing roll 122, and the film-like substrate 180a is turned into the coating film by rotating and supporting the film-like substrate 180a against the coating film 142 by the peeling roll 123.
  • the attached state can be maintained only for the distance between the pressing roll 122 and the peeling roll 123 (a fixed time).
  • substrate 180a is peeled from the coating film 142 by changing the course of the film-like board
  • the above-described pre-baking or heating of the coating film may be performed while the film-like substrate 180a is attached to the coating film 142.
  • the peeling roll 123 it is possible to further facilitate the peeling of the coating film by peeling while heating at 40 to 150 ° C., for example.
  • the coating film 142 is subjected to main baking (step S6 in FIG. 5).
  • the main baking is preferably performed at a temperature of 200 to 1200 ° C. for about 5 minutes to 6 hours.
  • the coating film is cured to obtain a substrate having a concavo-convex pattern film corresponding to the concavo-convex pattern of the film substrate 180a, that is, a substrate (diffraction grating) in which a sol-gel material layer having a concavo-convex pattern is directly formed on a flat substrate. It is done. At this time, when the sol-gel material layer is silica, it becomes amorphous or crystalline, or a mixed state of amorphous and crystalline depending on the firing temperature and firing time.
  • replicating the replica 110 (or sol-gel structure) using the resin film structure 100, or using the obtained replica 110 (or sol-gel structure) another replica is used.
  • a film may be laminated on the surface of the resin film structure 100 or the replica 110 (or sol-gel structure) on which the concavo-convex pattern is formed by a vapor phase method such as a vapor deposition method or a sputtering method.
  • a deposited film examples include metals such as aluminum, gold, silver, platinum, and nickel, and metal oxides such as aluminum oxide.
  • the thickness of such a film is preferably 5 to 500 nm. If the thickness is less than the lower limit, it is difficult to obtain a uniform film, and the effect of sufficiently reducing the adhesiveness is reduced. If the thickness exceeds the upper limit, the shape of the matrix tends to be distorted.
  • post curing may be appropriately performed by irradiating ultraviolet light again after the resin is cured.
  • the curable resins 80 and 82 are applied to the support substrates 90 and 92, respectively, but directly on the surface of the mold 70 or the cured resin layer 80 which is a matrix.
  • a matrix that is applied with a curable resin and removed after curing may be used.
  • a concave / convex film of a cured resin obtained by pressing the mother die against the resin coating and curing the resin may be used as the mother die.
  • the substrate is washed with a brush or the like, and organic substances and the like are removed with an alkaline cleaner and an organic solvent.
  • the transparent electrode 93 is laminated on the sol-gel material layer 142 of the substrate 140 so that the uneven structure formed on the surface of the sol-gel material layer (coating film) 142 is maintained.
  • the material of the transparent electrode 93 for example, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) that is a composite thereof, gold, platinum, silver, and copper are used. Among these, ITO is preferable from the viewpoints of transparency and conductivity.
  • the thickness of the transparent electrode 93 is preferably in the range of 20 to 500 nm. If the thickness is less than the lower limit, the conductivity tends to be insufficient, and if it exceeds the upper limit, the transparency may be insufficient and the emitted EL light may not be sufficiently extracted to the outside.
  • a known method such as a vapor deposition method, a sputtering method, or a spin coating method can be appropriately employed.
  • the sputtering method is preferable from the viewpoint of improving adhesion, and after that, a photoresist is applied and exposed with an electrode mask pattern, and then etched with a developer to obtain a transparent electrode having a predetermined pattern. . Note that the substrate is exposed to a high temperature of about 300 ° C. during sputtering. It is desirable to clean the obtained transparent electrode with a brush, remove organic matter with an alkaline cleaner and an organic solvent, and then perform UV ozone treatment.
  • Such an organic layer 94 shown in FIG. 7 is laminated on the transparent electrode 93.
  • Such an organic layer 94 is not particularly limited as long as it can be used for the organic layer of the organic EL element, and a known organic layer can be appropriately used.
  • Such an organic layer 94 may be a laminate of various organic thin films. For example, a laminate comprising a hole transport layer 95, a light emitting layer 96, and an electron transport layer 97 as shown in FIG. It may be.
  • phthalocyanine derivatives As a material of the hole transport layer 95, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′- Aromatic diamine compounds such as diamine (TPD) and 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene Derivatives, pyrazoline derivatives, tetrahydroimidazole, polyarylalkanes, butadiene, 4,4 ′, 4 ′′ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), It is not limited to these.
  • TPD diamine
  • ⁇ -NPD
  • the light emitting layer 96 is provided to recombine the holes injected from the transparent electrode 93 and the electrons injected from the metal electrode 98 to emit light.
  • Materials that can be used for the light emitting layer 96 include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, aluminum Organometallic complexes such as quinolinol complex (Alq3), tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivatives, pyran, quinacridone, rubrene, distyryl Benzene derivatives, distyrylarylene derivatives,
  • the light emitting material selected from these compounds suitably.
  • a material system that emits light from a spin multiplet for example, a phosphorescent material that emits phosphorescence, and a compound that includes a portion formed of these in a part of the molecule can be preferably used.
  • the phosphorescent material preferably contains a heavy metal such as iridium. Even if the above-mentioned light emitting material is doped as a guest material in a host material having high carrier mobility, light can be emitted by utilizing dipole-dipole interaction (Felster mechanism) and electron exchange interaction (Dexter mechanism). good.
  • the material for the electron transport layer 97 includes nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane. And organometallic complexes such as anthrone derivatives, oxadiazole derivatives, aluminum quinolinol complexes (Alq3), and the like.
  • a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the hole transport layer 95 or the electron transport layer 97 may also serve as the light emitting layer 96.
  • the organic layer between the transparent electrode 93 and the metal electrode 98 is two layers.
  • a metal fluoride such as lithium fluoride (LiF) or Li 2 O 3 or a metal oxide is used as an electron injection layer between the organic layer 94 and the metal electrode 98.
  • a layer made of a highly active alkaline earth metal such as Ca, Ba, or Cs, an organic insulating material, or the like may be provided.
  • a triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative as a hole injection layer between the organic layer 94 and the transparent electrode 93, Pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, or conductive polymer oligomers
  • a layer made of a thiophene oligomer or the like may be provided.
  • the organic layer 94 is a stacked body including the hole transport layer 95, the light emitting layer 96, and the electron transport layer 97
  • the thickness of the hole transport layer 95, the light emitting layer 96, and the electron transport layer 97 is 1 respectively.
  • a range of ⁇ 200 nm, a range of 5 to 100 nm, and a range of 5 to 200 nm are preferable.
  • a method for laminating the organic layer 94 a known method such as an evaporation method, a sputtering method, a spin coating method, or a die coating method can be appropriately employed.
  • a metal electrode 98 is then laminated on the organic layer 94 as shown in FIG.
  • a material of the metal electrode 98 a substance having a small work function can be used as appropriate, and is not particularly limited, and examples thereof include aluminum, MgAg, MgIn, and AlLi.
  • the thickness of the metal electrode 98 is preferably in the range of 50 to 500 nm. If the thickness is less than the lower limit, the conductivity tends to decrease, and if the thickness exceeds the upper limit, it may be difficult to repair when a short circuit occurs between the electrodes.
  • the metal electrode 98 can be laminated by employing a known method such as vapor deposition or sputtering. Thus, an organic EL element 200 having a structure as shown in FIG. 7 is obtained.
  • an organic EL element is manufactured using a diffraction grating formed from a sol-gel material, it is advantageous in comparison with a diffraction grating in which a concavo-convex pattern is formed from a curable resin as described below.
  • a sol-gel material is excellent in mechanical strength, scratches, adhesion of foreign matter, protrusions on the transparent electrode, etc. are unlikely to occur even if the concavo-convex pattern surface is washed after forming the substrate and the transparent electrode in the manufacturing process of the organic EL element. , Device defects caused by them can be suppressed.
  • the organic EL element obtained by the method of the present invention is superior to the case of using a curable resin substrate in terms of the mechanical strength of the substrate having a concavo-convex pattern.
  • a substrate formed from a sol-gel material is excellent in chemical resistance. Therefore, it is relatively corrosion resistant to the alkaline liquid and organic solvent used in the cleaning process of the substrate and the transparent electrode, and various cleaning liquids can be used. Further, as described above, an alkaline developer may be used when patterning the substrate, and the developer is also resistant to corrosion. This is advantageous compared to a curable resin substrate having a relatively low resistance to an alkaline solution. Furthermore, the substrate formed from the sol-gel material is excellent in heat resistance.
  • a substrate formed from a sol-gel material is excellent in UV resistance and weather resistance as compared with a curable resin substrate. For this reason, it has tolerance also to the UV ozone cleaning process after transparent electrode formation.
  • the organic EL element produced by the method of the present invention When the organic EL element produced by the method of the present invention is used outdoors, deterioration due to sunlight can be suppressed as compared with the case of using a curable resin substrate. Further, the cured resin as described above may deteriorate when left for a long period of time due to heat generated during light emission, and may cause yellowing or generation of gas. Although it is difficult to use, deterioration is suppressed in an organic EL element including a substrate manufactured using a sol-gel material.
  • Block copolymers 1 to 11 (referred to as “BCP-1” to “BCP-11” as appropriate) manufactured by Polymer Source, which are used in Examples 1 and 2 were prepared. All of these block copolymers have polystyrene (hereinafter abbreviated as “PS” where appropriate) as the first polymer segment and polymethyl methacrylate (hereinafter abbreviated as “PMMA” where appropriate) as the second polymer segment.
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • Table 1 also shows the volume ratio (PS: PMMA) and molecular weight distribution (Mw / Mn) of the PS segment and the PMMA segment, and the Tg of the PS segment and the PMMA segment.
  • the volume ratio of the first and second polymer segments in the block copolymer is such that the density of polystyrene is 1.05 g / cm 3 and the density of polymethyl methacrylate is It was calculated as 1.19 g / cm 3 .
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer segment or polymer are gel permeation chromatography (manufactured by Tosoh Corporation, model number “GPC-8020”, TSK-GEL SuperH1000, SuperH2000, SuperH3000, and SuperH4000 in series. Measured by using a device connected to The glass transition point (Tg) of the polymer segment was determined by using a differential scanning calorimeter (manufactured by Perkin-Elmer, product name “DSC7”) at a temperature increase rate of 20 ° C./min in the temperature range of 0 to 200 ° C. Measurement was performed while raising the temperature.
  • the solubility parameters of polystyrene and polymethylmethacrylate are 9.0 and 9.3, respectively (see Chemical Handbook, Application, 2nd revised edition).
  • Table 1 shows the physical properties of the block copolymer 1 (hereinafter abbreviated as BCP-1 as appropriate).
  • the block copolymer solution was filtered through a membrane filter having a pore size of 0.5 ⁇ m to obtain a block copolymer solution.
  • a mixed solution of 1 g of KBM-5103 manufactured by Shin-Etsu Silicone Co., Ltd., 1 g of ion-exchanged water, 0.1 ml of acetic acid, and 19 g of isopropyl alcohol was spin-coated on a glass substrate (after 10 seconds at a rotation speed of 500 rpm, followed by For 45 seconds at 800 rpm). It processed at 130 degreeC for 15 minute (s), and the silane coupling process glass was obtained.
  • the obtained block copolymer solution was applied on a silane coupling-treated glass as a base material with a film thickness of 150 to 170 nm by spin coating.
  • the spin coating was performed at a rotational speed of 200 rpm for 10 seconds, and subsequently at 300 rpm for 30 seconds.
  • FIG. 8B show an observation photograph of the thin film cross section. Since the PS portion is preliminarily RuO4 stained, as shown in FIG. 8B, the PS portion is dark (dark gray) and the PMMA portion is thin (light gray). From this observation photograph, it can be seen that the circular cross-sections of the PS portion are arranged in two steps in the direction (height direction) perpendicular to the substrate surface while being separated from each other in the direction parallel to the substrate surface. When considered together with an analysis image of an atomic force microscope described later, it can be seen that the PS portion is phase-separated from the PMMA portion into a horizontal cylinder structure. The PS part is a core (island), and the PMMA part surrounds it (sea).
  • the solvent chloroform is a good solvent for both PS and PMMA, it is a better solvent for PMMA. Therefore, it is considered that PMMA swelled more and the volume ratio deviated from 5: 5. Further, it can be seen that the surface of the thin film has a waveform shape reflecting the presence of the PS portion isolated with the PMMA portion interposed therebetween.
  • the concentration of the block copolymer 1 in the block copolymer solution is reduced to 0.5%
  • a thin film was formed on the substrate in the same manner as described above, and a solvent annealing treatment was performed.
  • the cross-sectional structure of this thin film observed with a transmission electron microscope is shown in FIG. 8C and FIG. 8D which is an enlarged view thereof.
  • the horizontal cylinder structure was maintained by the decrease in the block copolymer concentration, but the block copolymer was arranged in one step in the height direction. Also in FIG.
  • the surface of the thin film has a waveform shape reflecting the presence of the PS portion isolated with the PMMA portion interposed therebetween.
  • the portion that appears as dark black on the surface of the thin film shows the shade of the protective film applied to cut the thin film, and is not a component of the thin film itself.
  • a thin nickel layer of about 20 nm was formed as a current seed layer on the surface of the thin film corrugated by the solvent annealing treatment by sputtering.
  • the substrate with the thin film was placed in a nickel sulfamate bath, and electrocasting (maximum current density 0.05 A / cm 2 ) was performed at a temperature of 50 ° C. to deposit nickel until the thickness reached 250 ⁇ m.
  • the substrate with a thin film was mechanically peeled from the nickel electroformed body thus obtained.
  • the nickel electroformed body is immersed in a tetrahydrofuran solvent for 2 hours, and then partially coated on the surface of the electroformed body by repeating the application and curing of an acrylic UV curable resin three times.
  • the polymer component that had been removed was removed. Then, it immersed in Nippon CB Chemical's Chemisole 2303, and it wash
  • the nickel electroformed body was immersed in HD-2101TH manufactured by Daikin Chemicals Sales Co., Ltd. for about 1 minute, dried, and allowed to stand overnight.
  • the nickel electroformed body was immersed in HDTH manufactured by Daikin Chemicals Sales Co., Ltd. and subjected to ultrasonic treatment for about 1 minute.
  • a nickel mold subjected to the release treatment was obtained.
  • a fluorine-based UV curable resin is applied onto a PET substrate (Toyobo Co., Ltd., Cosmo Shine A-4100), and irradiated with ultraviolet rays at 600 mJ / cm 2 while pressing a nickel mold, the fluorine-based UV curable resin.
  • a PET substrate Toyobo Co., Ltd., Cosmo Shine A-4100
  • the fluorine-based UV curable resin was cured.
  • the nickel mold was peeled off from the cured resin. In this way, a diffraction grating composed of a PET substrate with a resin film onto which the surface shape of the nickel mold was transferred was obtained.
  • Measurement mode Dynamic force mode Cantilever: SI-DF40P2 (material: Si, lever width: 40 ⁇ m, tip diameter: 10 nm) Measurement atmosphere: in the air Measurement temperature: 25 ° C.
  • FIG. 9A An unevenness analysis image of the thin film surface is shown in FIG. 9A.
  • corrugation analysis image of the cross section (The cross section along the line in FIG. 9A) of the thin film surface vicinity is shown to FIG. 9B. From the cross-sectional structure of FIG. 9B, it can be seen that smooth irregularities are formed on the surface. The full scale of the vertical axis is 160 nm (the same applies to the unevenness analysis images of other cross sections).
  • the Fourier transform image, the average pitch of the unevenness, the average value of the unevenness depth distribution, the standard deviation of the unevenness depth, and the kurtosis of the unevenness are as follows. It asked for by the method.
  • ⁇ Fourier transform image> An irregularity analysis image is obtained as described above by measuring an arbitrary measurement area of 3 ⁇ m square (vertical 3 ⁇ m, horizontal 3 ⁇ m) of the diffraction grating. The obtained unevenness analysis image was subjected to flat processing including primary inclination correction, and then subjected to two-dimensional fast Fourier transform processing to obtain a Fourier transform image. The obtained Fourier transform image is shown in FIG. As is clear from the results shown in FIG.
  • the Fourier transform image shows an annular pattern substantially centered at the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the annular pattern was confirmed to be present in a region where the absolute value of the wave number falls within the range of 10 ⁇ m ⁇ 1 or less.
  • the circular pattern of the Fourier transform image is a pattern that is observed when bright spots are gathered in the Fourier transform image.
  • “Circular” as used herein means that the pattern of bright spots appears to be almost circular, and is a concept that includes a part of the outer shape that appears to be convex or concave. .
  • a pattern in which bright spots are gathered may appear to be almost circular, and this case is expressed as “annular”.
  • annular includes those in which the outer circle of the ring and the inner circle appear to be substantially circular, and the outer circle of the ring and a part of the outer shape of the inner circle are convex or concave. It is a concept including what appears to be.
  • the term “present in” means that 30% or more (more preferably 50% or more, even more preferably 80% or more, particularly preferably 90% or more) of luminescent spots constituting the Fourier transform image have wavenumbers. It means that the absolute value is within a range of 10 ⁇ m ⁇ 1 or less (more preferably 1.25 to 10 ⁇ m ⁇ 1 , more preferably 1.25 to 5 ⁇ m ⁇ 1 ).
  • the two-dimensional fast Fourier transform processing of the unevenness analysis image can be easily performed by electronic image processing using a computer equipped with two-dimensional fast Fourier transform processing software.
  • ⁇ Average pitch of unevenness> An irregularity analysis image is obtained as described above by measuring an arbitrary measurement area of 3 ⁇ m square (vertical 3 ⁇ m, horizontal 3 ⁇ m) of the diffraction grating. In such an unevenness analysis image, 100 or more intervals between any adjacent convex portions or adjacent concave portions are measured, and the average is calculated as the average pitch of the unevenness. From the analysis image obtained in this example, the average pitch of the concavo-convex pattern was 73.5 nm.
  • An unevenness analysis image is obtained by measuring a measurement region of an arbitrary 3 ⁇ m square (3 ⁇ m in length and 3 ⁇ m in width) of the thin film.
  • region are each calculated
  • 65536 points 256 vertical points ⁇ 256 horizontal points
  • the measurement point P having the highest height from the surface of the substrate is obtained.
  • a plane including the measurement point P and parallel to the surface of the substrate is defined as a reference plane (horizontal plane), and a depth value from the reference plane (a height value from the substrate at the measurement point P is determined at each measurement point).
  • the difference obtained by subtracting the height from the substrate is determined as the depth data.
  • Such unevenness depth data can be automatically calculated by the software in E-sweep, and the automatically calculated value can be obtained as the unevenness depth data.
  • the average value (m) of the unevenness depth distribution can be determined by calculating using the above-described equation (I).
  • the average value (m) of the uneven depth distribution of the diffraction grating obtained in this example was 20.6 nm.
  • N denotes the total number of measurement points (total number of pixels)
  • x i denotes the data of the i-th uneven depth measuring points
  • m represents the average value of the depth distribution of the irregularities .
  • the standard deviation ( ⁇ ) of the unevenness depth of the thin film was 18.2 nm.
  • N represents the total number of measurement points (total number of pixels)
  • x i denotes the data of the i-th uneven depth measuring points
  • m represents the average value of the depth distribution of the irregularities
  • ⁇ indicates the value of the standard deviation of the unevenness depth.
  • the kurtosis of the irregularities formed on the surface of the thin film is preferably ⁇ 1.2 or more, more preferably ⁇ 1.2 to 1.2, and ⁇ 1. 2 to 1 is more preferable, and ⁇ 1.1 to 0.0 is particularly preferable from the previous experiments of the present application (see, for example, Applicants' WO2011 / 007878A1). . If the kurtosis is less than the lower limit, it tends to be difficult to sufficiently suppress the occurrence of leakage current when used in an organic EL element. On the other hand, if the upper limit is exceeded, the thin film has a cross-sectional shape.
  • the unevenness is almost eliminated and there are sparse protrusions or depressions, the light extraction efficiency that is a feature of the uneven structure cannot be sufficiently improved (a sufficient diffraction effect cannot be obtained).
  • the electric field tends to concentrate on the protrusion, and a leak current tends to occur.
  • the kurtosis (k) is -1.2 or more, the cross-sectional shape of the structure has no extreme cusp regardless of the height, pitch, and surface shape of the corrugations.
  • the organic layer is deposited on the surface of the unevenness by using this for the production of an organic EL device, the thickness of a part of the organic layer can be sufficiently prevented. It is considered that the organic layer can be laminated with a sufficiently uniform film thickness.
  • the distance between the electrodes can be made sufficiently uniform, and the concentration of the electric field can be sufficiently suppressed. Further, in the organic EL element, it is considered that the generation of leakage current can be more sufficiently suppressed because the gradient of the potential distribution at the inclined portion of the corrugated structure has a gentle slope.
  • the kurtosis of the unevenness of the diffraction grating obtained in Example 1 was ⁇ 0.67.
  • Example 2 In this example, how the uneven structure of the thin film after the solvent annealing treatment is changed by changing the number average molecular weight (Mn) of the block copolymer and the ratio of the PS portion and the PMMA portion constituting the block copolymer. Observed about what to do.
  • the block copolymer block copolymers 1 (BCP-1) to 11 (BCP-11) having physical properties as shown in Table 1 are used, and the amount of polyethylene oxide added is 100 parts by mass of the block copolymer. Except having changed to 30 mass parts, it carried out similarly to Example 1, the block copolymer solution was apply
  • Block copolymer 1 (BCP-1): The block copolymer 1 is the same as in Example 1, but the polyethylene oxide content in the block copolymer solution is higher than in Example 1. From the unevenness analysis image (not shown) near the cross section of the thin film obtained by the solvent annealing treatment, it was found that the shape of the unevenness was clearer than that in Example 1. Although it is thought that this is due to the difference in the content of polyethylene oxide, the influence of the content of polyethylene oxide on the unevenness height will be described in detail in Example 5.
  • the average value of the depth distribution of the unevenness on the thin film surface calculated by E-sweep based on the unevenness analysis image is 78.1 nm, the average pitch of the unevenness is 305 nm, and the standard deviation of the unevenness depth is 24.7 nm. there were.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.63.
  • Block copolymer 2 (BCP-2): Although the number average molecular weight (Mn) of the block copolymer 2 exceeds 500,000, the number average molecular weight (Mn) of the PS portion and the PMMA portion constituting the block copolymer 2 is considerably larger than that of Example 1. Low, 270,000 and 289,000, respectively, and the ratio PS: PMMA of PS part to PMMA part is 51:49. From the unevenness analysis image (not shown) of the cross section near the surface of the thin film obtained by the solvent annealing treatment, it was found that the height of the unevenness was considerably lower than that of the block copolymer 1.
  • the average value of the depth distribution of the unevenness on the thin film surface calculated by E-sweep based on the unevenness analysis image is 22.5 nm, the average pitch of the unevenness is 162 nm, and the standard deviation of the unevenness depth is 10.1 nm. there were.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area.
  • the kurtosis of the unevenness was ⁇ 1.01.
  • Block copolymer 3 (BCP-3): The number average molecular weight (Mn) of the block copolymer 3 is 1,010,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 3 are 510,000 and 500,000, respectively.
  • the ratio PS: PMMA between the PS portion and the PMMA portion is 54:46, which is the same as in the first embodiment. From the unevenness analysis image (not shown) of the cross section in the vicinity of the thin film surface obtained by the solvent annealing treatment, it was found that the unevenness on the surface was as smooth as in Example 1.
  • the average value of the unevenness distribution on the surface of the thin film calculated by E-sweep based on the unevenness analysis image is 47.1 nm, the average pitch of the unevenness is 258 nm, and the standard deviation of the unevenness depth is 18.0 nm. there were.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.95.
  • Block copolymer 4 (BCP-4): The number average molecular weight (Mn) of the block copolymer 4 is 1,160,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 4 are 590,000 and 570, respectively.
  • the ratio PS: PMMA between the PS portion and the PMMA portion is 54:46, which is the same as in the first embodiment. From the unevenness analysis image (not shown) of the cross section in the vicinity of the thin film surface obtained by the solvent annealing treatment, it was found that the unevenness on the surface was generally smooth although there was a part protruding.
  • the average value of the depth distribution of the unevenness on the thin film surface calculated by E-sweep based on the unevenness analysis image is 80.1 nm, the average pitch of the unevenness is 278 nm, and the standard deviation of the unevenness depth is 31.2 nm. there were.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 1.06.
  • Block copolymer 5 (BCP-5): The number average molecular weight (Mn) of the block copolymer 5 is 1,600,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 5 are 700,000 and 900,000, respectively. 000, and the ratio PS: PMMA between the PS portion and the PMMA portion is 47:53. From the unevenness analysis image (not shown) of the cross section near the surface of the thin film obtained by the solvent annealing treatment, it was found that the unevenness on the surface was smooth.
  • the average value of the depth distribution of the unevenness on the thin film surface calculated by E-sweep based on the unevenness analysis image is 53.7 nm, the average pitch of the unevenness is 315 nm, and the standard deviation of the unevenness depth is 18.0 nm. there were.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.33.
  • Block copolymer 6 (BCP-6): The number average molecular weight (Mn) of the block copolymer 6 is 1,725,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 6 are 868,000 and 857, respectively.
  • the ratio PS: PMMA of the PS portion and the PMMA portion is 53:47. From the unevenness analysis image (not shown) of the cross section near the surface of the thin film obtained by the solvent annealing treatment, it was found that the unevenness on the surface was smooth.
  • the average value of the depth distribution of the unevenness on the thin film surface calculated by E-sweep based on the unevenness analysis image is 72.9 nm, the average pitch of the unevenness is 356 nm, and the standard deviation of the unevenness depth is 19.9 nm. there were.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.09.
  • Block copolymer 7 (BCP-7):
  • the number average molecular weight (Mn) of the block copolymer 7 is 1,120,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 7 are 700,000 and 420, respectively.
  • the ratio PS: PMMA of the PS portion and the PMMA portion is 65:35. According to the unevenness analysis image (not shown) of the cross section in the vicinity of the thin film surface obtained by the solvent annealing treatment, the surface unevenness hardly appeared.
  • the average value of the unevenness distribution of the thin film surface calculated by E-sweep based on the unevenness analysis image was as extremely low as 5.0 nm, and the standard deviation of the unevenness depth was 1.4 nm.
  • the average pitch of the irregularities was not measurable.
  • the Fourier transform image shows a circular pattern whose center is the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the circular pattern falls within the range where the absolute value of the wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area.
  • the kurtosis of the unevenness was ⁇ 0.33.
  • Block copolymer 8 (BCP-8): The number average molecular weight (Mn) of the block copolymer 8 is 1,350,000, and the number average molecular weight (Mn) of the PS portion and the PMMA portion constituting the block copolymer 8 is 1,200,000 and The ratio PS: PMMA of the PS portion and the PMMA portion is 90:10.
  • the unevenness analysis image (not shown) of the cross section near the thin film surface obtained by the solvent annealing treatment, the unevenness appeared slightly on the surface of the thin film.
  • the average value of the unevenness distribution of the thin film surface calculated by E-sweep based on the unevenness analysis image was 36.9 nm, and the standard deviation of the unevenness depth was 5.6 nm.
  • the average pitch of the irregularities was not measurable.
  • the Fourier transform image shows a circular pattern whose center is the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the circular pattern falls within the range where the absolute value of the wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area.
  • the kurtosis of the irregularities was 2.29.
  • Block copolymer 9 (BCP-9): The number average molecular weight (Mn) of the block copolymer 9 is 1,700,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 9 are 556,000 and 120,000, respectively.
  • the ratio PS: PMMA of the PS portion and the PMMA portion is 34:66.
  • the unevenness analysis image (not shown) of the cross section near the thin film surface obtained by the solvent annealing treatment, the unevenness appeared slightly on the surface of the thin film.
  • the average value of the unevenness distribution of the thin film surface calculated by E-sweep based on the unevenness analysis image was 35.7 nm, and the standard deviation of the unevenness depth was 14.5 nm.
  • the average pitch of the irregularities was not measurable.
  • the Fourier transform image shows a circular pattern whose center is the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the circular pattern falls within the range where the absolute value of the wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was 0.03.
  • Block copolymer 10 (BCP-10): The number average molecular weight (Mn) of the block copolymer 10 is 995,000, and the number average molecular weights (Mn) of the PS portion and the PMMA portion constituting the block copolymer 10 are 315,000 and 680,000, respectively. In addition, the ratio PS: PMMA of the PS portion and the PMMA portion is 34:66. According to the unevenness analysis image (not shown) of the cross section near the thin film surface obtained by the solvent annealing treatment, the unevenness appeared slightly on the surface of the thin film.
  • the average value of the unevenness depth distribution on the thin film surface calculated by E-sweep based on the unevenness analysis image was 31.3 nm, and the standard deviation of the unevenness depth was 8.5 nm.
  • the average pitch of the irregularities was not measurable.
  • the Fourier transform image shows a circular pattern whose center is the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the circular pattern falls within the range where the absolute value of the wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area.
  • the kurtosis of the unevenness was ⁇ 0.13.
  • Block copolymer 11 (BCP-11): The number average molecular weight (Mn) of the block copolymer 11 is 263,000, and the number average molecular weight (Mn) of the PS portion and the PMMA portion constituting the block copolymer 10 is 133,000 and 139,000, respectively. Yes, and the ratio PS: PMMA of the PS portion to the PMMA portion is 54:46. From the unevenness analysis image (not shown) of the cross section near the surface of the thin film obtained by the solvent annealing treatment, it was found that the unevenness on the surface was small.
  • the average value of the unevenness depth distribution on the thin film surface calculated by E-sweep based on the unevenness analysis image is 17.7 nm, the average pitch of the unevenness is 87 nm, and the standard deviation of the unevenness depth is 4.8 nm. there were. Unevenness does not appear on the surface of the thin film.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of the wave number is 15 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the irregularities was 1.4.
  • the number average molecular weight of the block copolymer is less than 500,000. It is understood that the uneven surface hardly appears and the number average molecular weight is preferably at least 500,000, and the number average molecular weight of the block copolymer is particularly preferably 1,000,000 or more in view of the height of the unevenness. It can also be seen that when the ratio PS: PMMA of the PS part to the PMMA part is outside the range of 40:60 to 60:40 as in the case of the block copolymers 7 to 10, the height of the unevenness is lowered.
  • Example 3 it was observed how the uneven structure of the thin film was changed by changing the processing time of the solvent annealing.
  • the block copolymer used was the block copolymer 1 (BCP-1) used in Example 1, except that the treatment time was changed to 1, 3, 6, 12, 48 and 168 hours.
  • the block copolymer solution was applied to a silane coupling-treated glass substrate, dried, and then subjected to a solvent annealing treatment with chloroform.
  • An analysis image of the uneven shape on the surface of the thin film after the solvent annealing treatment was observed with an atomic force microscope under the same analysis conditions as in Example 1.
  • Table 2 shows the average value of the depth distribution of the unevenness on the thin film surface (average unevenness), the standard deviation of the unevenness depth, and the kurtosis calculated by E-sweep based on these analysis images.
  • the Fourier transform image shows an annular pattern whose center is the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 in any processing time film, and the annular pattern has an absolute value of the wave number. It was confirmed that it was present in a region within a range of 10 ⁇ m ⁇ 1 or less. Note that 6 to 168 hours are preferable based on the average value of the uneven depth distribution.
  • Example 4 changes in the shape of the unevenness due to the type of solvent used in the solvent annealing treatment were observed.
  • Silane coupling treatment of the block copolymer solution (block copolymer BCP-1) was conducted in the same manner as in Example 1 except that a mixed solvent of carbon disulfide and acetone (75:25) was used instead of chloroform as the solvent. It was applied to a glass substrate, dried, and then subjected to a solvent annealing treatment. An analysis image of the uneven shape on the surface of the thin film after the solvent annealing treatment was observed with an atomic force microscope under the same analysis conditions as in Example 1.
  • the average value of the unevenness distribution of the thin film surface calculated by E-sweep based on the analysis image and the standard deviation of the unevenness depth were 50.5 nm and 20.0 nm, respectively.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area.
  • the kurtosis of the unevenness was ⁇ 0.27.
  • block copolymer solution (block copolymer BCP-1) was treated with silane coupling in the same manner as above except that the mixing ratio of carbon disulfide and acetone was changed to 50:50 instead of chloroform as a solvent. It was applied to a glass substrate, dried, and then subjected to a solvent annealing treatment.
  • the average value of the unevenness distribution of the thin film surface and the standard deviation of the unevenness depth calculated by E-sweep based on the unevenness analysis image of the film surface and the unevenness analysis image of the cross section near the surface were 23.6 nm, respectively. And 10.3 nm. It can be seen that the height of the unevenness decreases as the mixing ratio of acetone increases.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was -0.98.
  • a block copolymer solution (block copolymer BCP-1) was applied to a silane coupling treated glass substrate in the same manner as above except that dichloromethane was used as a solvent, dried, and then subjected to a solvent annealing treatment. went.
  • the average value of the unevenness distribution of the thin film surface and the standard deviation of the unevenness depth calculated by E-sweep based on the unevenness analysis image of the film surface and the unevenness analysis image of the cross section near the surface are 45.0 nm, respectively. And 15.0 nm.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.51.
  • a block copolymer solution (block copolymer BCP-1) was applied to a silane coupling treated glass substrate in the same manner as above except that toluene was used as a solvent, dried, and then subjected to a solvent annealing treatment. went.
  • the unevenness analysis image of the film surface and the unevenness analysis image (not shown) of the cross section near the surface the unevenness was not so clear and the pitch seemed to be widened.
  • the average value of the depth distribution of the unevenness on the thin film surface and the standard deviation of the unevenness depth calculated by E-sweep based on the unevenness analysis image were 33.0 nm and 10.3 nm, respectively.
  • the Fourier transform image shows a circular pattern whose center is the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 , and the circular pattern falls within the range where the absolute value of the wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.17.
  • a block copolymer solution (block copolymer BCP-1) was applied to the silane coupling treated glass substrate in the same manner as above except that acetone alone was used as a solvent, dried, and then solvent annealed Processed.
  • the average value of the unevenness distribution of the thin film surface and the standard deviation of the unevenness depth calculated by E-sweep based on the unevenness analysis image of the film surface and the unevenness analysis image of the cross section near the surface are 52.1 nm, respectively. And 16.3 nm.
  • the Fourier transform image shows an annular pattern whose center is the origin whose absolute value of wave number is 0 ⁇ m ⁇ 1 , and the annular pattern falls within the range where the absolute value of wave number is 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. The kurtosis of the unevenness was ⁇ 0.6.
  • Example 5 the change in the shape of the irregularities after the solvent annealing treatment was observed when the amount of polyethylene oxide (PEO) added to the block copolymer solution was changed.
  • the mass parts (% notation) of polyethylene oxide with respect to 100 parts by mass of the block copolymer were changed to 0%, 5%, 15%, 25%, 30%, 35%, and 70%, and the same as in Example 1.
  • the block copolymer solution (block copolymer BCP-1) was applied to a silane coupling-treated glass substrate, dried, and then subjected to a solvent annealing treatment.
  • An analysis image of the uneven shape on the surface of the thin film after the solvent annealing treatment was observed with an atomic force microscope under the same analysis conditions as in Example 1. Based on these unevenness analysis images, the average value of the unevenness distribution of the surface of the thin film calculated by E-sweep (and the standard deviation of the unevenness depth) was obtained. The results are shown in Table 3 together with the kurtosis.
  • the Fourier transform image shows an annular pattern with the origin at which the absolute value of the wave number is 0 ⁇ m ⁇ 1 for all the films with different PEO addition amounts, and the annular pattern is the absolute value of the wave number.
  • the annular pattern is the absolute value of the wave number.
  • Example 6 the change in the concavo-convex shape was observed depending on the presence or absence of heat treatment (heat annealing) after the solvent annealing treatment and the heating temperature.
  • a block copolymer was used in the same manner as in Example 1 except that the block copolymer 1 (BCP-1) was used as the block copolymer and the content of polyethylene oxide in the block copolymer was changed to 30%.
  • the solution was applied to a silane coupling treated glass substrate, dried, and then subjected to a solvent annealing treatment. After the solvent annealing treatment, a sample that was not heated, a sample that was heat-treated at 40 ° C. for 1 hour, a sample that was heat-treated at 50 ° C.
  • FIG. 1 The average value of the depth distribution of the unevenness on the surface of the thin film, the standard deviation of the unevenness depth, and the kurtosis calculated by E-sweep based on the unevenness analysis image are shown in the following table.
  • the average value of the unevenness depth distribution was 71.3 nm, but by heating at 40 ° C. for 1 hour, the average value of the unevenness depth distribution was reduced to 55.8 nm. .
  • the heating temperature was raised to 50 ° C.
  • the average value of the uneven depth distribution was further reduced to 40.4 nm.
  • the heating temperature is increased to 60 ° C.
  • the average value of the uneven depth distribution is further decreased to 27.1 nm.
  • the height of the unevenness is sufficient only by the solvent annealing treatment and the kurtosis is -0.75, and a smooth uneven waveform is obtained. Therefore, it can be seen that the thermal annealing after patterning (solvent annealing) is basically unnecessary except in special cases such as when the height of the unevenness is required.
  • this base material was heated in an oven at 160 ° C. for 3 hours (annealing treatment). Concavities and convexities were formed on the thin film on the substrate surface after heating, and it was observed that the block copolymer was microphase-separated.
  • the heated thin film was etched as follows. After irradiating with ultraviolet rays at an irradiation intensity of 30 J / cm 2 using a high-pressure mercury lamp, it was immersed in acetone, washed with ion-exchanged water, and then dried. By this etching process, PMMA on the substrate was selectively removed to obtain a thin film on which a fine concavo-convex pattern was formed.
  • FIG. 10A The obtained unevenness analysis image of the thin film surface is shown in FIG. 10A, and the unevenness analysis image of the cross section near the thin film surface is shown in FIG. 10B.
  • FIG. 10B From the cross-sectional structure of FIG. 10B, since it has a vertical cross-sectional structure, it is considered that PS and PMMA are aligned in a vertical lamella. 10A and 10B, the Fourier transform image, the average pitch of the unevenness, the average value of the unevenness depth distribution, and the standard deviation of the unevenness depth were obtained in the same manner as in Example 1. However, the average value of the uneven depth distribution was 75.8 nm, the standard deviation of the uneven depth was 47.2 nm, and the kurtosis was ⁇ 1.63. As shown in FIG.
  • the Fourier transform image shows a circular pattern whose center is the origin, and the annular pattern has an absolute value of the wave number of 10 ⁇ m ⁇ 1 or less. It was confirmed to exist in the area. From these results, even when a block polymer having the same composition as in Example 1 was used, the microphase separation structure caused by the self-organization of the block copolymer was different due to the different annealing method, and according to the present invention. It can be seen that a horizontal cylinder structure can only appear by solvent phase separation (solvent annealing). In addition, it can be seen that in the solvent phase separation according to the present invention, a corrugated uneven structure with a smooth surface is obtained.
  • Example 7 In this example, a mold is manufactured according to the method of the present invention, a diffraction grating is manufactured using the mold, and an organic EL element is manufactured using the obtained diffraction grating.
  • Block copolymer 1 (BCP-1) was used as the block copolymer and polyethylene oxide was used at 30 parts by mass with respect to 100 parts by mass of the block copolymer
  • the block copolymer was A polymer solution was prepared, applied to a silane coupling treated glass substrate, dried, and then subjected to a solvent annealing treatment.
  • Corrugated irregularities were generated on the surface of the thin film by the solvent annealing.
  • a thin nickel layer of about 20 nm was formed as a current seed layer on the surface of the thin film by sputtering.
  • This substrate with a thin film was placed in a nickel sulfamate bath, and was subjected to electroforming (maximum current density 0.05 A / cm 2 ) at a temperature of 50 ° C. to deposit nickel until the thickness reached 250 ⁇ m.
  • the substrate with a thin film was mechanically peeled from the nickel electroformed body thus obtained.
  • the nickel electroformed body is immersed in a tetrahydrofuran solvent for 2 hours, and then partially coated on the surface of the electroformed body by repeating the application and curing of an acrylic UV curable resin three times.
  • the polymer component that had been removed was removed.
  • a UV ozone treatment was applied to the nickel electroformed body for 10 minutes.
  • the shape of the irregularities on the surface of the nickel electroformed body was analyzed using the atomic force microscope used in Example 1, and an analysis image was obtained.
  • the analysis image was observed with an atomic force microscope under the same analysis conditions as in Example 1, and the average height of the unevenness on the thin film surface and the standard deviation of the unevenness depth calculated by E-sweep based on the analysis image were respectively 45.7 and 22.4 nm.
  • a resin substrate with an uneven pattern was produced as follows.
  • a fluorine-based UV curable resin on a PET substrate (Toyobo Co., Ltd., easy-adhesion PET film, Cosmo Shine A-4100) and irradiating it with UV light at 600 mJ / cm 2 while pressing the mold.
  • a fluorine-based UV curable resin was cured.
  • the mold was peeled off from the cured resin.
  • a resin substrate with a concavo-convex pattern to which the surface shape of the mold was transferred was obtained.
  • This resin substrate with a concavo-convex pattern can be used as a diffraction grating as it is, but in this example, the resin substrate with a concavo-convex pattern was used again as a mold (diffraction grating mold) to produce a diffraction grating as follows. .
  • TEOS tetraethoxysilane
  • MTES methyltriethoxysilane
  • This doctor blade was designed to have a coating film thickness of 5 ⁇ m, but an imide tape with a thickness of 35 ⁇ m was attached to the doctor blade so that the coating film thickness was adjusted to 40 ⁇ m. After 60 seconds had elapsed after coating, the diffraction grating mold was pressed against the coating film on the glass plate with a pressing roll by the method described below.
  • the surface on which the pattern of the diffraction grating mold was formed was pressed against the coating film on the glass substrate while rotating a press roll at 23 ° C. from one end of the glass substrate toward the other end.
  • the substrate was moved onto a hot plate, and the substrate was heated at 100 ° C. (preliminary firing). After heating was continued for 5 minutes, the substrate was removed from the hot plate, and the diffraction grating mold was manually peeled from the edge from the substrate. Peeling was performed so that the angle (peeling angle) of the diffraction grating mold with respect to the substrate was about 30 °.
  • the substrate was baked by heating at 300 ° C. for 60 minutes using an oven. In this way, a diffraction grating having a concavo-convex pattern made of a sol-gel material was obtained.
  • the obtained transparent electrode was washed with a brush, organic substances and the like were removed with an alkaline detergent and an organic solvent, and then subjected to UV ozone treatment.
  • the luminous efficiency of the organic EL device obtained in this example was measured by the following method. A voltage is applied to the obtained organic EL element, and the applied voltage V and the current I flowing through the organic EL element are measured with an applied measuring instrument (manufactured by ADC Co., Ltd., R6244), and the total luminous flux L is measured with Spectra Corp. It measured with the manufactured total luminous flux measuring apparatus.
  • FIG. 11 shows a change in current efficiency with respect to luminance applied to the organic EL element.
  • FIG. 12 shows the change in power efficiency with respect to the luminance applied to the organic EL element.
  • an organic EL element was produced by the same method as described above using a glass substrate (flat substrate) having no unevenness, and current efficiency and power efficiency with respect to voltage were shown in FIG. 11 and FIG. .
  • the organic EL device of this example showed a current efficiency of about 1.5 times at a luminance of 1000 cd / m 2 as compared with an organic EL device having no unevenness on the glass substrate.
  • the organic EL element of this example showed about 1.7 times the power efficiency at a luminance of 1000 cd / m 2 as compared with the organic EL element having no unevenness on the glass substrate. Therefore, the organic EL device of the present invention has sufficient light extraction efficiency.
  • the directivity of light emission of the organic EL element obtained in this example was evaluated by the following method.
  • the emitted organic EL element was visually observed from all directions (direction of 360 degrees around the entire circumference). Even when observed from any direction of 360 ° around the entire circumference, a particularly bright place or a particularly dark place was not observed, and uniform brightness was exhibited in all directions. Thus, it was confirmed that the organic EL element of the present invention has sufficiently low directivity of light emission.
  • the organic EL element obtained by forming the concave / convex pattern on the substrate through the solvent annealing treatment as described above and using the mold and the diffraction grating has sufficient light extraction efficiency.
  • the concavo-convex pattern of the diffraction grating manufactured in this example is formed from a sol-gel material, it has excellent mechanical strength, chemical resistance, and heat resistance. Can withstand the atmosphere and chemicals.
  • the organic EL element as a device manufactured by the method of the present invention is excellent in weather resistance, heat resistance and corrosion resistance and has a long life.
  • a diffraction grating substrate (optical substrate) has been described as an example of the “substrate having a concavo-convex pattern”, the present invention is not limited to this and can be applied to substrates having various uses.
  • optical elements such as microlens arrays, nanoprism arrays, optical waveguides, optical components such as lenses, solar cells, antireflection films, semiconductor chips, patterned media, data storage, electronic paper, LSI manufacturing, paper manufacturing
  • the present invention can also be applied to substrates used in applications in the bio field such as food production, immunoassay chips, and cell culture sheets.
  • a concave / convex pattern can be formed through self-organization by solvent annealing of a block copolymer, and an etching process is not required. Therefore, a substrate having a concave / convex structure such as a diffraction grating and the like are used.
  • a useful device such as an organic EL element can be manufactured with a simple process and high throughput. Therefore, the method of the present invention is excellent in mass productivity and contributes significantly to the development of the optical device industry in Japan.

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PCT/JP2013/057851 2012-04-26 2013-03-19 微細パターン転写用のモールドの製造方法及びそれを用いた凹凸構造を有する基板の製造方法、並びに該凹凸構造を有する基板を有する有機ｅｌ素子の製造方法 Ceased WO2013161454A1 (ja)

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AU2013253941A AU2013253941B2 (en) 2012-04-26 2013-03-19 Method for producing mold for transferring fine pattern, method for producing substrate having uneven structure using same, and method for producing organic el element having said substrate having uneven structure
CN201380021957.8A CN104254438B (zh) 2012-04-26 2013-03-19 微细图案转印用模具的制造方法以及使用该模具的具有凹凸结构的基板的制造方法、以及具备具有该凹凸结构的基板的有机电致发光元件的制造方法
CA2870426A CA2870426C (en) 2012-04-26 2013-03-19 Method for producing mold for transferring fine pattern, method for producing substrate having uneven structure using same, and method for producing organic el element having saidsubstrate having uneven structure
IN9101DEN2014 IN2014DN09101A (https=) 2012-04-26 2013-03-19
EP13781178.2A EP2842721B1 (en) 2012-04-26 2013-03-19 Method for producing mold for transferring fine pattern, method for producing substrate having uneven structure using same, and method for producing organic el element having said substrate having uneven structure
JP2014512423A JP5695799B2 (ja) 2012-04-26 2013-03-19 微細パターン転写用のモールドの製造方法及びそれを用いた凹凸構造を有する基板の製造方法、並びに該凹凸構造を有する基板を有する有機ｅｌ素子の製造方法
KR1020147019842A KR20140106704A (ko) 2012-04-26 2013-03-19 미세 패턴 전사용 몰드의 제조 방법 및 이것을 사용한 요철 구조를 가지는 기판의 제조 방법, 및 상기 요철 구조를 가지는 기판을 가지는 유기 el 소자의 제조 방법
US14/513,622 US20150028325A1 (en) 2012-04-26 2014-10-14 Method for producing mold for transferring fine pattern, method for producing substrate having concave-convex structure using same, and method for producing organic el element having said substrate having concave-convex structure

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CA2870426A1 (en) 2013-10-31
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TW201402297A (zh) 2014-01-16
IN2014DN09101A (https=) 2015-05-22
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