WO2023054527A1 - Moule, procédé de fabrication de moule et procédé de fabrication de structure d'irrégularité fine - Google Patents

Moule, procédé de fabrication de moule et procédé de fabrication de structure d'irrégularité fine Download PDF

Info

Publication number
WO2023054527A1
WO2023054527A1 PCT/JP2022/036292 JP2022036292W WO2023054527A1 WO 2023054527 A1 WO2023054527 A1 WO 2023054527A1 JP 2022036292 W JP2022036292 W JP 2022036292W WO 2023054527 A1 WO2023054527 A1 WO 2023054527A1
Authority
WO
WIPO (PCT)
Prior art keywords
mold
uneven structure
layer
fine uneven
fine
Prior art date
Application number
PCT/JP2022/036292
Other languages
English (en)
Japanese (ja)
Inventor
大貴 清水
俊一 梶谷
Original Assignee
デクセリアルズ株式会社
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 デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority claimed from JP2022155327A external-priority patent/JP2023051846A/ja
Publication of WO2023054527A1 publication Critical patent/WO2023054527A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • 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
    • 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
    • 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
    • B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present technology relates to a mold for transfer, a method of manufacturing the mold, and a method of manufacturing a fine concavo-convex structure.
  • This application is Japanese Patent Application No. 2021-162075 filed on September 30, 2022 in Japan, and Japanese Patent Application No. 2022-155327 filed on September 28, 2022 in Japan. , which application is incorporated into this application by reference.
  • FIG. 10 is a graph showing the reflectance of a multilayer sputtered film (Multi layer AR), Moth-eye, and Bare Glass.
  • a multi-layer sputtered film which is a typical example of an antireflection film, tends to have extremely high reflectance at wavelengths other than the specific wavelength.
  • the moth-eye fine relief structure
  • a moth-eye antireflection coating for a wide band from visible light to near-infrared light is easier to achieve.
  • FIG. 11A and 11B are cross-sectional views schematically showing an example of a conventional moth-eye forming method
  • FIG. 11A is a diagram for explaining a step of forming a photocurable resin layer on a substrate film.
  • FIG. 11(B) is a diagram for explaining the step of transferring the fine uneven structure of the mold to the photocurable resin layer and curing the photocurable resin layer
  • FIG. 11(C) is a transfer product
  • FIG. 10 is a diagram for explaining a step of releasing the mold from the mold
  • UV (Ultraviolet) nanoimprinting is a representative example of the moth-eye forming method.
  • a pattern on a mold which is a mold 101, is pressed onto a UV curable resin 103 on a substrate 102, UV light is irradiated to cure the resin, and the pattern is transferred onto the substrate 102.
  • This is a method for fabricating the moth-eye 104 in the .
  • a release layer of a fluorine film is provided by wet-coating a fluorine-based organic release agent so that the substrate can be easily released from the mold during transfer (for example, Patent Document 1 , 2).
  • the present technology has been proposed in view of such conventional circumstances, and provides a mold capable of obtaining excellent releasability and transferability, a method for manufacturing the mold, and a method for manufacturing a fine concavo-convex structure. .
  • a mold according to the present technology includes a base material having a fine uneven structure on its surface, and a sputtered layer formed on the surface of the fine uneven structure and having an oxide film on the outermost surface.
  • a mold manufacturing method includes a step of forming a fine uneven structure on the surface of a base material, and a step of forming a sputter layer having an oxide film on the outermost surface of the fine uneven structure.
  • a method for manufacturing a fine uneven structure uses a mold including a base material having a fine uneven structure on its surface and a sputter layer formed on the surface of the fine uneven structure and having an oxide film on the outermost surface. and transferring the fine concave-convex structure to a photocurable resin, and curing the photocurable resin.
  • FIG. 1 is a cross-sectional view schematically showing an example of the mold according to this embodiment.
  • FIG. 2A is a cross-sectional photograph showing an example of a transfer product having a fine uneven structure with a depth of 200 nm
  • FIG. 2B is an example of a transfer product having a fine uneven structure with a depth of 320 nm. It is a cross-sectional photograph showing.
  • FIG. 3 is a graph showing an example of the reflectance Re (%) of a transfer product having a fine uneven structure with a depth of 200 nm and a transfer product having a fine uneven structure with a depth of 320 nm.
  • FIG. 4A and 4B are cross-sectional views schematically showing an example of a method for manufacturing a fine uneven structure according to the present embodiment, and FIG. 4A shows a step of forming a photocurable resin layer on a substrate film.
  • FIG. 4B is a diagram for explaining a step of transferring a fine concave-convex structure of a mold to a photocurable resin layer and curing the photocurable resin layer;
  • FIG. (C) is a diagram for explaining a step of releasing the mold from the transfer product.
  • FIG. 5 is a schematic diagram showing an example of the configuration of a transfer device that manufactures a transfer product.
  • 6A and 6B are cross-sectional views schematically showing an example of a method for producing a transfer product of the example, and FIG.
  • FIG. 6(B) is a diagram for explaining the step of transferring the fine uneven structure of the mold to the ultraviolet curable resin layer and curing the ultraviolet curable resin layer
  • FIG. 6(C) is It is a figure for demonstrating the process of releasing a mold from a transfer thing.
  • FIG. 7 is a graph showing composition changes in the depth direction by ESCA of the flat portions of the molds of Examples 1, 2, and 3.
  • FIG. 8 is a graph showing composition changes in the depth direction by ESCA of the fine relief structure portions of the molds of Examples 1, 2, and 3.
  • FIG. 9 is a graph showing the reflectance of the transfer samples of Example 1, Example 3, and Comparative Example 1.
  • FIG. 10 is a graph showing reflectance of multilayer sputtered film (Multi layer AR), moth-eye, and glass (Bare Glass).
  • 11A and 11B are cross-sectional views schematically showing an example of a conventional moth-eye forming method
  • FIG. 11A is a diagram for explaining a step of forming a photocurable resin layer on a substrate film.
  • FIG. 11(B) is a diagram for explaining the step of transferring the fine uneven structure of the mold to the photocurable resin layer and curing the photocurable resin layer
  • FIG. 11(C) is a transfer product
  • FIG. 10 is a diagram for explaining a step of releasing the mold from the mold;
  • FIG. 1 is a cross-sectional view schematically showing an example of the mold according to this embodiment.
  • the mold 1 according to the present embodiment includes a substrate 10 having a fine uneven structure on its surface, and a sputtered layer 20 formed on the surface of the fine uneven structure and having an oxide film 21 on the outermost surface.
  • a substrate 10 having a fine uneven structure on its surface and a sputtered layer 20 formed on the surface of the fine uneven structure and having an oxide film 21 on the outermost surface.
  • the mold 1 is, for example, a master plate used for imprinting by a direct pressing method or a roll-to-roll method, and can be used repeatedly. By pressing the fine concave-convex structure of the mold 1 against the material to be transferred, a reverse structure of the fine concave-convex structure of the mold 1 is formed on the transferred material.
  • the base material 10 may be, for example, a flat plate shape, a hollow cylindrical member having a cavity inside, or a solid columnar member having no cavity inside. good.
  • the substrate 10 having a cylindrical or columnar shape can be used for roll-to-roll imprinting.
  • the height (length in the axial direction) is preferably 100 mm or more, and the diameter of the bottom or top circle (outside diameter in the radial direction orthogonal to the axial direction) is preferable. diameter) is preferably 50 mm or more and 300 mm or less.
  • the thickness (thickness) in the radial direction is preferably 2 mm or more and 50 mm or less.
  • the surface roughness (arithmetic mean roughness Ra) of one surface of the substrate 10 is 1/100 of the height difference of the unevenness of the fine uneven structure. It is preferably 1/10000 or less, more preferably 1/10000 or less.
  • the surface roughness of one surface of the substrate 10 is preferably as small as possible, but from the viewpoint of the processing limit of the substrate 10, the lower limit may be 1/10000 of the height difference of the unevenness of the fine uneven structure. Thereby, the formability of a fine concavo-convex structure can be improved.
  • glass materials such as fused quartz glass, synthetic quartz glass, heat-resistant glass, white plate glass, and tempered glass, resin materials such as PET (PolyEthylene Terephthalate) and PC (PolyCarbonate), various ceramic materials, and the like can be used.
  • resin materials such as PET (PolyEthylene Terephthalate) and PC (PolyCarbonate), various ceramic materials, and the like can be used.
  • PET PolyEthylene Terephthalate
  • PC PolyCarbonate
  • AlN, C, SiC, Si, or the like can be used as the base material 10 .
  • the fine uneven structure is provided on one surface of the base material 10, and even if it is formed using thermal lithography using laser light, it is formed using UV nanoimprint that cures a UV curable resin. good too.
  • a high corrosion resistance can be obtained by forming the fine concave-convex structure with a glass material.
  • a fine relief structure is a structure in which a plurality of recesses or protrusions are arranged regularly or irregularly.
  • the average size of the planar shape of the plurality of concave portions or convex portions may be equal to or less than the wavelength of light belonging to the visible light band, and the average distance between the concave portions or convex portions may be
  • a structure in which a plurality of concave portions or convex portions are arranged regularly or irregularly so that the wavelength is equal to or less than the wavelength of light belonging to the visible light band may be used.
  • the average size and interval of the planar shape of the recesses or protrusions may be less than 1 ⁇ m, preferably 100 nm or more and 350 nm or less.
  • the fine uneven structure can function as a so-called moth-eye structure that suppresses reflection of light belonging to the visible light band.
  • the average size and interval of the planar shape of the recesses or protrusions is less than 100 nm, it may be difficult to form a fine uneven structure.
  • the average size and interval of the planar shape of the recesses or protrusions exceeds 350 nm, diffraction of visible light may occur and the function of the moth-eye structure may deteriorate.
  • the depth of the fine uneven structure may be 100 nm or more and 1000 nm or less, and the lower limit of the depth of the fine uneven structure is preferably 300 nm or more, more preferably 400 nm or more, and still more preferably 500 nm or more.
  • a low reflectance can be obtained in the wavelength range of 400 to 1000 nm (visible to near-infrared wavelength band).
  • the optical body which is a transfer material, is used as a sensor, it can be used not only in the visible light range used for normal image imaging, but also in the near field used for sensing such as position and space recognition.
  • the depth of the fine concave-convex structure is the average of the distances from the bottom of the concave portion to the apex of the convex portion, and can be obtained, for example, by measuring the height of concave portions at five or more locations and calculating the average.
  • the aspect ratio of the fine uneven structure is preferably set in the range of 0.81 to 1.46, more preferably in the range of 0.94 to 1.28. If the aspect ratio is less than 0.81, the reflection properties and transmission properties tend to be deteriorated. There is a tendency for the microrelief structure to break.
  • the aspect ratio of the fine uneven structure is the ratio of the average of the depth of the pattern formed by etching and the interval between the recesses or protrusions, or the average ratio of the planar size of the recesses or protrusions. The smaller the average depth and the larger the depth, the higher the aspect ratio. In other words, the aspect ratio can also be defined by Equation (1) below.
  • Aspect ratio H/P (1)
  • H is the depth of the fine uneven structure (or the height of the fine uneven structure)
  • P is the average arrangement pitch (average period) of the fine uneven structure.
  • FIG. 2A is a cross-sectional photograph showing an example of a transfer product having a fine uneven structure with a depth of 200 nm
  • FIG. 2B is an example of a transfer product having a fine uneven structure with a depth of 320 nm. It is a cross-sectional photograph showing.
  • FIG. 3 is a graph showing an example of the reflectance Re (%) of a transfer product having a fine uneven structure with a depth of 200 nm and a transfer product having a fine uneven structure with a depth of 320 nm.
  • FIGS. 2 and 3 by setting the depth of the fine concave-convex structure to 320 nm, low reflectance can be obtained in the infrared wavelength range of 780 nm or longer.
  • the planar shape of the concave portion or convex portion may be substantially circular, elliptical, or polygonal.
  • the arrangement of the concave portions or the convex portions in the fine concave-convex structure may be any of a close-packed arrangement, a tetragonal lattice arrangement, a hexagonal lattice arrangement, or a staggered lattice arrangement. The arrangement can be appropriately selected according to the function of the transfer product to which the fine uneven structure is transferred.
  • the sputtered layer 20 is a precise film formed by sputtering, which is dense and has few defects.
  • the average surface roughness (Ra) of the sputtered layer 20 is preferably 1.0 nm or less, more preferably 0.8 nm or less, still more preferably 0.6 nm or less. This makes it possible to obtain excellent releasability and transferability.
  • the average surface roughness (Ra) of the sputtered layer can be measured by measuring the flat portion of the sputtered layer using an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the thickness of the sputtered layer 20 may be 3 nm or more and 30 nm or less, and the upper limit of the thickness of the sputtered layer 20 is preferably 25 nm or less, more preferably 20 nm or less, and still more preferably 15 nm or less. As a result, it is possible to improve the transferability of transferring while maintaining the shape of the fine concavo-convex structure.
  • the thickness of the sputtered layer can be measured by step measurement using a stylus-type surface roughness meter.
  • the sputtered layer 20 is not particularly limited as long as it is a deposition material that can be sputtered and an oxide film can be formed on the outermost surface, and is composed of a metal, an alloy, a metal oxide, or the like.
  • the sputter layer is preferably made of one selected from the group consisting of Cr, Ni, Cu, HfO2 , Ti, Ta, Al, Mo and Si. As a result, excellent releasability between the mold and the transfer product can be obtained.
  • the degree of oxidation of the sputtered layer 20 on the outermost layer side may be different from that on the substrate side. That is, the degree of oxidation of the oxide film 21 on the outermost surface of the sputter layer 20 may be different from the degree of oxidation of the inside of the sputter layer 20 .
  • the degree of oxidation of the sputtered layer 20 can be, for example, the oxygen bonding ratio measured by ESCA (Electron Spectroscopy for Chemical Analysis).
  • the oxide film 21 is a part of the sputtered layer 20 formed on the outermost surface of the sputtered layer 20.
  • the oxide film 21 may be the same as in the sputtered layer 20 .
  • the oxygen binding ratio can be measured by ESCA (Electron Spectroscopy for Chemical Analysis). If the bonding ratio of oxygen in the oxide film 21 is the same as in the inside of the sputtered layer 20, for example, if the sputtered layer 20 is a metal oxide, the bonding ratio between metal and oxygen is the same even if it becomes deeper from the outermost surface. be.
  • the thickness of the oxide film 21 may be the same as the thickness of the sputtered layer 20 .
  • the thickness of the oxide film 21 is preferably 10 nm or less, more preferably 8 nm or less, and even more preferably 5 nm or less.
  • the thickness of the oxide film 21 can be measured by ESCA based on the composition change in the depth direction. For example, when the sputtered layer 20 is made of metal, the bonding ratio between the metal and oxygen decreases continuously as the depth increases from the outermost surface, reaching a constant bonding ratio at a predetermined depth.
  • the bonding ratio of oxygen in the oxide film 21 having a thickness of 2 nm is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more in the fine uneven structure portion. As a result, excellent releasability between the mold and the transfer product can be obtained.
  • the method for manufacturing a mold according to the present embodiment includes a step (A) of forming a fine uneven structure on the surface of a substrate, and a step of forming a sputter layer having an oxide film on the outermost surface of the fine uneven structure ( B). Thereby, a mold having excellent releasability and transferability can be obtained.
  • step (A) thermal lithography using a laser beam may be used, or UV nanoimprint for curing a UV curable resin may be used.
  • a method of forming a fine uneven structure on the outer peripheral surface of a cylindrical substrate using thermal lithography using laser light will be described below.
  • the method for forming this fine uneven structure includes a resist film forming step of forming a resist layer on the outer peripheral surface of the cylindrical base material, an exposure step of forming a latent image on the resist layer, and a development of the resist layer on which the latent image is formed. and an etching step of etching using the pattern of the developed resist layer as a mask to form a fine uneven structure on the outer peripheral surface of the cylindrical substrate.
  • a resist layer is formed on the outer peripheral surface of a cylindrical substrate made of quartz glass, for example.
  • a material of the resist layer for example, either an organic resist or an inorganic resist may be used.
  • the organic resist for example, a novolac resist or a chemically amplified resist can be used.
  • the inorganic resist for example, a metal oxide composed of one or more transition metals such as tungsten and molybdenum can be used.
  • an exposure device is used to rotate the cylindrical substrate and irradiate the resist layer with laser light (exposure beam).
  • exposure beam laser light
  • the entire surface of the resist layer is exposed by intermittently irradiating the laser beam while moving the laser beam in the height direction (direction parallel to the central axis) of the cylindrical substrate.
  • a latent image corresponding to the trajectory of the laser beam is formed over the entire surface of the resist layer at a pitch approximately equal to the wavelength of visible light, for example.
  • the resist layer by developing the resist layer, a pattern corresponding to the latent image is formed in the resist layer.
  • the resist layer can be developed with an alkaline solution such as a TMAH (TetraMethylAmmonium Hydroxide) aqueous solution.
  • TMAH TetraMethylAmmonium Hydroxide
  • etching process Next, the surface of the cylindrical substrate is etched using a resist layer pattern (resist pattern) formed with a pattern corresponding to the fine concave-convex structure as a mask. Thereby, a fine concavo-convex structure can be formed on the surface of the cylindrical substrate.
  • a resist layer pattern resist pattern
  • As an etching method dry etching using fluorocarbon gas or wet etching using hydrofluoric acid or the like may be used. By using dry etching, a glass master having a depth three times or more that of the resist layer (selection ratio of 3 or more) can be produced, and a high aspect ratio of the fine concave-convex structure can be achieved. After etching, an ashing process may be performed to remove the remaining resist layer. As described above, a fine concavo-convex structure can be formed on the outer peripheral surface of the cylindrical substrate.
  • step (B) for example, a sputtered layer is formed on the surface of the fine unevenness structure by sputtering with a DC (direct current) power supply or an RF (radio frequency) power supply.
  • the sputtered layer is a metal or alloy
  • the surface of the sputtered layer is oxidized.
  • the method for manufacturing a fine uneven structure according to the present embodiment uses a mold that includes a substrate having a fine uneven structure on the surface and a sputtered layer formed on the surface of the fine uneven structure and having an oxide film on the outermost surface. Then, the fine uneven structure is transferred to the photocurable resin, and the photocurable resin is cured. As a result, it is possible to obtain a transfer product in which the fine concavo-convex structure is transferred while maintaining the shape of the fine concavo-convex structure of the mold.
  • FIG. 4A and 4B are cross-sectional views schematically showing an example of a method for manufacturing a fine uneven structure according to the present embodiment, and FIG. 4A shows a step of forming a photocurable resin layer on a substrate film.
  • FIG. 4B is a diagram for explaining a step of transferring a fine concave-convex structure of a mold to a photocurable resin layer and curing the photocurable resin layer;
  • FIG. (C) is a diagram for explaining a step of releasing the mold from the transfer product.
  • the base film 2 include PET.
  • the fine uneven structure provided on the base material surface of the mold 1 is pressed against the photocurable resin layer 3, and the photocurable resin layer 3 is irradiated with light from a metal halide lamp or the like. .
  • the photocurable resin composition is cured to form the transfer layer 4 on the substrate film 2 by transferring the fine concavo-convex structure.
  • FIG. 4C by releasing the mold 1 from the transfer layer 4, it is possible to obtain a fine concavo-convex structure as a transferred product.
  • FIG. 5 is a schematic diagram showing an example of the configuration of a transfer device that manufactures a transfer product.
  • This transfer device includes a cylindrical master 11 , a substrate supply roll 31 , a take-up roll 32 , guide rolls 33 and 34 , a nip roll 35 , a peel roll 36 , a coating device 37 and a light source 38 .
  • the base material supply roll 31 is, for example, a roll in which a sheet-like base material 41 is wound into a roll shape, and the take-up roll 32 winds up a transfer product in which a resin layer 42 to which the fine concavo-convex structure 12 is transferred is laminated. is a roll. Further, the guide rolls 33 and 34 are rolls for conveying the sheet-like base material 41 before and after transfer.
  • the nip roll 35 is a roll that presses the sheet-like substrate 41 on which the resin layer 42 is laminated against the master 11, and the peel roll 36 transfers the fine concavo-convex structure 12 to the resin layer 42, and then the resin layer 42 is laminated. It is a roll for peeling off the sheet-like base material 41 from the master 11 .
  • the coating device 37 includes coating means such as a coater, and coats the sheet-like substrate 41 with the photocurable resin composition to form the resin layer 42 .
  • the coating device 37 may be, for example, a gravure coater, a wire bar coater, or a die coater.
  • the light source 38 is a light source that emits light having a wavelength capable of curing the photocurable resin composition, and may be, for example, an ultraviolet lamp. Further, the light source 38 may be arranged outside the outer periphery of the master 11, or may be arranged inside the cylinder when the master 11 is transparent.
  • a photocurable resin composition is a resin that cures when irradiated with light of a predetermined wavelength.
  • the photocurable resin composition may be an ultraviolet curable resin containing a (meth)acrylate monomer and a photopolymerization initiator.
  • (meth)acrylate includes acrylate and methacrylate.
  • the photocurable resin composition may contain fillers, functional additives, solvents, inorganic materials, pigments, antistatic agents, sensitizing dyes, and the like, if necessary.
  • the sheet-like base material 41 is continuously delivered from the base material supply roll 31 through the guide rolls 33 .
  • the resin layer 42 is laminated on the sheet-like substrate 41 by applying the photocurable resin composition to the sent sheet-like substrate 41 by the coating device 37 .
  • the sheet-like base material 41 laminated with the resin layer 42 is pressed against the master 11 by the nip rolls 35 .
  • the fine concavo-convex structure 12 formed on the outer peripheral surface of the master 11 is transferred to the resin layer 42 .
  • the resin layer 42 onto which the fine concavo-convex structure 12 has been transferred is cured by irradiation of light from the light source 38 .
  • the sheet-like substrate 41 to which the fine uneven structure 12 has been transferred is peeled off from the master 11 by the peel roll 36, sent to the take-up roll 32 via the guide roll 34, and taken up. According to such a transfer apparatus, it is possible to efficiently and continuously manufacture a transferred product in which the fine concave-convex structure 12 formed on the outer peripheral surface of the master 11 is transferred.
  • Example> a moth-eye film having a moth-eye (fine uneven structure) formed on a film substrate was produced by UV nanoimprinting, and a sputtered layer was formed on the fine uneven structure of the moth-eye film to produce a mold. Then, a mold was used to transfer the fine concave-convex structure to an ultraviolet curable resin, and mold releasability evaluation and optical characteristic evaluation were performed. Note that the present technology is not limited to these examples.
  • a film of about 50 nm to 60 nm of tungsten oxide was formed by a sputtering method on the outer peripheral surface of a substrate made of cylindrical quartz glass to form a resist layer.
  • thermal lithography was performed using the laser light to form a latent image on the resist layer, followed by exposure.
  • a predetermined latent image was formed on the resist layer by modulating a control signal for controlling the output of laser light.
  • TMAH manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • TMAH manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • CHF 3 gas 30 sccm
  • reactive ion etching RIE: Reactive Ion Etching
  • a master A was manufactured in which a fine concave-convex structure having a depth of about 320 nm was formed on the outer peripheral surface. Also, in the same manner, a master B having a fine concave-convex structure with a depth of about 500 nm formed on the outer peripheral surface was manufactured.
  • the fine concavo-convex structure of master A or master B is transferred to the UV-curable resin layer formed on the base film, and irradiated with UV rays of 1000 mJ/cm 2 for 1 minute from a metal halide lamp.
  • the UV-curable resin layer was cured to produce a moth-eye film.
  • PET Toyobo PET A4360, thickness 125 ⁇ m
  • the fine relief structure of the moth-eye film using master A had a pitch of 150 to 230 nm and a depth of about 320 nm.
  • the fine uneven structure of the moth-eye film using master B had a pitch of 150 to 230 nm and a depth of about 500 nm.
  • FIG. 6A and 6B are cross-sectional views schematically showing an example of a method for producing a transfer product of the example
  • FIG. 6(B) is a diagram for explaining the step of transferring the fine uneven structure of the mold to the ultraviolet curable resin layer and curing the ultraviolet curable resin layer
  • FIG. 6(C) is It is a figure for demonstrating the process of releasing a mold from a transfer thing.
  • a transfer sample 54 was produced by UV imprinting the fine uneven structure of the mold sample 51 onto an ultraviolet curable resin layer 53 formed on a film substrate 52 (Toyobo PET A4360, thickness 50 ⁇ m). Then, the transfer sample 54 was cut out with a width of 25 mm, and as shown in FIG. was performed, and the peel strength (N) was measured.
  • the UV-curable resin layer is composed of 39 parts by mass of hexanediol diacrylate (HDDA, "Miramer M200” manufactured by Toyo Chemicals Co., Ltd.) and 24 parts by mass of trimethylolpropane triacrylate (TMPTA, "Miramer M300” manufactured by Toyo Chemicals Co., Ltd.). part, 34 parts by mass of dicyclopentanyl methacrylate (“FA-513M” manufactured by Showa Denko Materials Co., Ltd.), and a photopolymerization initiator (“Irgacure 184” manufactured by IGM Resins B.V.) 3 parts by mass. It is a layer made up of things.
  • HDDA hexanediol diacrylate
  • TMPTA trimethylolpropane triacrylate
  • F-513M dicyclopentanyl methacrylate
  • Irgacure 184 manufactured by IGM Resins B.V.
  • a transfer sample was produced by UV imprinting the fine uneven structure of the mold sample onto an ultraviolet curable resin layer formed on a slide glass. After attaching a black tape to the back of the transfer sample, using a spectral reflectometer (manufactured by JASCO Corporation, V770), the reflectance (wavelength band of visible light to near infrared rays) of the fine uneven structure at a wavelength of 400 to 1000 nm ( %) was measured.
  • a spectral reflectometer manufactured by JASCO Corporation, V770
  • Example 1 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (high frequency) power source to form a sputtered layer of Cr with a thickness of 15 nm, and exposed to normal temperature air for 11 days to prepare a mold. Then, the releasability evaluation and the optical property evaluation were performed. As shown in Table 1, the peel force for peeling the mold sample from the transfer sample of Example 1 was 0.08 N, and excellent releasability was obtained.
  • RF radio frequency
  • FIG. 7 is a graph showing composition changes in the depth direction by ESCA of the flat portions of the molds of Examples 1, 2, and 3, and
  • FIG. 10 is a graph showing the composition change in the depth direction of the fine relief structure portion of the mold of Example 3 by ESCA.
  • FIG. 9 is a graph showing the reflectance of transfer samples of Examples 1, 3, and Comparative Example 1.
  • FIG. 9 the transfer sample of Example 1 had a reflectance of 0.70% at a wavelength of 800 nm, and excellent transferability was obtained.
  • Example 2 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (high frequency) power source to form a sputtered layer of Cr with a thickness of 15 nm, and exposed to normal temperature air for 3 days to prepare a mold. Then, the releasability evaluation and the optical property evaluation were performed. As shown in Table 1, the peel force for peeling the mold sample from the transfer sample of Example 2 was 0.16 N, and excellent releasability was obtained.
  • RF radio frequency
  • Example 3 A sputtered Cr layer with a thickness of 15 nm was formed on a moth-eye film having a fine uneven structure with a depth of 320 nm by sputtering with an RF (high frequency) power source, and exposed to room temperature air for 1 day to prepare a mold. Then, the releasability evaluation and the optical property evaluation were performed.
  • RF radio frequency
  • the reflectance of the transfer sample of Example 3 at a wavelength of 800 nm was 0.80%. Further, as shown in Table 1, the peeling force for peeling the mold sample from the transfer sample of Example 3 was 0.24 N, and excellent releasability was obtained.
  • Example 4 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (high frequency) power source to form a sputtered layer of Si with a thickness of 15 nm, and exposed to normal temperature air for 11 days to prepare a mold. Then, the releasability evaluation and the optical property evaluation were performed. As shown in Table 1, the peel force for peeling the mold sample from the transfer sample of Example 4 was 0.49 N, and excellent releasability was obtained. Further, the reflectance of the transfer sample of Example 4 at a wavelength of 800 nm was 0.88%, and excellent transferability was obtained.
  • a 15 nm-thick sputtered layer made of Si was formed by sputtering with an RF (high frequency) power source on a moth-eye film having a fine uneven structure with a depth of about 320 nm. After being exposed to the inside, it was treated with oxygen plasma and coated with a fluorine release agent (Novec 1720 manufactured by 3M) to prepare a mold. Then, one day after coating with the fluorine release agent, evaluation of releasability and evaluation of optical properties were performed. As shown in Table 1, the peel force for peeling the mold sample from the transfer sample of Comparative Example 1 was 0.10N. Further, as shown in FIG. 9, the reflectance of the transfer sample of Comparative Example 1 at a wavelength of 800 nm was 0.92%.
  • Examples 1 to 4 by forming a sputtered layer without coating with a fluorine release agent as in Comparative Example 1, the fine concave-convex structure of the mold can be transferred while maintaining its shape. I was able to get the reflectivity. Further, according to Examples 1 to 4, a reflectance of 0.90% or less could be obtained if the peel force in the 90 degree peel test was 0.5 N or less. Therefore, in the following, only the releasability evaluation is performed, and the optical characteristic evaluation is omitted.
  • Example 5 A sputtered Cr layer with a thickness of 5 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 320 nm by sputtering with an RF (high frequency) power source, and exposed to normal temperature air for 11 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 2, the peeling force for peeling the mold sample from the transfer sample of Example 5 was 0.10 N, and excellent releasability was obtained.
  • Example 6 A sputtered layer with a thickness of 25 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 320 nm by sputtering with an RF (radio frequency) power source, and exposed to normal temperature air for 11 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 2, the peel force for peeling the mold sample from the transfer sample of Example 6 was 0.10 N, and excellent releasability was obtained.
  • Example 7 A sputtered Cr layer with a thickness of 5 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 500 nm by sputtering with an RF (high frequency) power source, and exposed to normal temperature air for 6 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 2, the peel force for peeling the mold sample from the transfer sample of Example 7 was 0.26 N, and excellent releasability was obtained.
  • Example 8 A sputtered Cr layer with a thickness of 15 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 500 nm by sputtering with an RF (high frequency) power source, and exposed to normal temperature air for 6 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 2, the peel force for peeling the mold sample from the transfer sample of Example 8 was 0.27 N, and excellent releasability was obtained.
  • Example 9 A sputtered layer of Cr with a thickness of 25 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 500 nm by sputtering with an RF (high frequency) power source, and exposed to room temperature air for 6 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 2, the peel force for peeling the mold sample from the transfer sample of Example 9 was 0.27 N, and excellent releasability was obtained.
  • Example 10 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (high frequency) power source to form a sputtered Ni layer with a thickness of 15 nm, and exposed to normal temperature air for 14 days to prepare a mold. Then, the releasability was evaluated. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 10 was 0.08 N, and excellent releasability was obtained.
  • RF radio frequency
  • Example 11 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (high frequency) power source to form a sputtered layer of Cu with a thickness of 15 nm, and exposed to normal temperature air for 14 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 11 was 0.11 N, and excellent releasability was obtained.
  • Example 12 A sputtered layer of HfO 2 with a thickness of 15 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 320 nm by sputtering with an RF (high frequency) power source, and exposed to normal temperature air for 14 days to prepare a mold. . Then, the releasability evaluation was performed. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 12 was 0.15 N, and excellent releasability was obtained.
  • Example 13 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (radio frequency) power source to form a sputtered layer of Ti with a thickness of 15 nm, and exposed to normal temperature air for 14 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 13 was 0.21 N, and excellent releasability was obtained.
  • RF radio frequency
  • Example 14 A sputtered Ta layer with a thickness of 15 nm was formed on a moth-eye film having a fine uneven structure with a depth of about 320 nm by sputtering with an RF (high frequency) power source, and exposed to normal temperature air for 14 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 14 was 0.22 N, and excellent releasability was obtained.
  • Example 15 A 15 nm-thick Al sputtered layer was formed on a moth-eye film having a fine uneven structure with a depth of about 320 nm by sputtering with an RF (high frequency) power source, and exposed to normal temperature air for 14 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 15 was 0.23 N, and excellent releasability was obtained.
  • Example 16 A moth-eye film having a fine uneven structure with a depth of about 320 nm was sputtered with an RF (high frequency) power source to form a sputtered Mo layer with a thickness of 15 nm, and exposed to normal temperature air for 14 days to prepare a mold. Then, the releasability evaluation was performed. As shown in Table 3, the peel force for peeling the mold sample from the transfer sample of Example 16 was 0.40 N, and excellent releasability was obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne un moule ayant une excellente aptitude au démoulage et une excellente aptitude au transfert, un procédé de fabrication d'un moule et un procédé de fabrication d'une structure d'irrégularité fine. Un moule (1) est pourvu d'un matériau de base (10) ayant une structure d'irrégularité fine sur une surface de celui-ci, et une couche pulvérisée (20) formée sur la surface de la structure d'irrégularité fine et ayant un film d'oxyde (21) sur sa surface la plus externe. La couche pulvérisée (20) ayant le film d'oxyde (21) formé sur sa surface la plus externe confère au moule (1) une excellente aptitude au démoulage et une excellente aptitude au transfert.
PCT/JP2022/036292 2021-09-30 2022-09-28 Moule, procédé de fabrication de moule et procédé de fabrication de structure d'irrégularité fine WO2023054527A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021162075 2021-09-30
JP2021-162075 2021-09-30
JP2022-155327 2022-09-28
JP2022155327A JP2023051846A (ja) 2021-09-30 2022-09-28 モールド、モールドの製造方法および微細凹凸構造体の製造方法

Publications (1)

Publication Number Publication Date
WO2023054527A1 true WO2023054527A1 (fr) 2023-04-06

Family

ID=85780714

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/036292 WO2023054527A1 (fr) 2021-09-30 2022-09-28 Moule, procédé de fabrication de moule et procédé de fabrication de structure d'irrégularité fine

Country Status (2)

Country Link
TW (1) TW202330233A (fr)
WO (1) WO2023054527A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230882A1 (en) * 2004-04-19 2005-10-20 Molecular Imprints, Inc. Method of forming a deep-featured template employed in imprint lithography
KR100663263B1 (ko) * 2005-08-17 2007-01-02 삼성전기주식회사 임프린트 몰드의 이형처리방법 및 이에 의해 형성된 배선기판
JP2007144995A (ja) * 2005-10-25 2007-06-14 Dainippon Printing Co Ltd 光硬化ナノインプリント用モールド及びその製造方法
JP2008217845A (ja) * 2007-02-28 2008-09-18 Bridgestone Corp スタンパ、その製造方法、成形体、その成形方法、及び光情報記録媒体
WO2012018048A1 (fr) * 2010-08-06 2012-02-09 綜研化学株式会社 Moule en résine pour nano-impression et procédé de fabrication de celui-ci
JP2016523449A (ja) * 2013-06-20 2016-08-08 エーファウ・グループ・エー・タルナー・ゲーエムベーハー モールド構造物を有するモールドならびにその製造のための装置および方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230882A1 (en) * 2004-04-19 2005-10-20 Molecular Imprints, Inc. Method of forming a deep-featured template employed in imprint lithography
KR100663263B1 (ko) * 2005-08-17 2007-01-02 삼성전기주식회사 임프린트 몰드의 이형처리방법 및 이에 의해 형성된 배선기판
JP2007144995A (ja) * 2005-10-25 2007-06-14 Dainippon Printing Co Ltd 光硬化ナノインプリント用モールド及びその製造方法
JP2008217845A (ja) * 2007-02-28 2008-09-18 Bridgestone Corp スタンパ、その製造方法、成形体、その成形方法、及び光情報記録媒体
WO2012018048A1 (fr) * 2010-08-06 2012-02-09 綜研化学株式会社 Moule en résine pour nano-impression et procédé de fabrication de celui-ci
JP2016523449A (ja) * 2013-06-20 2016-08-08 エーファウ・グループ・エー・タルナー・ゲーエムベーハー モールド構造物を有するモールドならびにその製造のための装置および方法

Also Published As

Publication number Publication date
TW202330233A (zh) 2023-08-01

Similar Documents

Publication Publication Date Title
TWI417181B (zh) The manufacturing method of seamless mold
US8840258B2 (en) Antireflection structure formation method and antireflection structure
JP6725097B2 (ja) フィルムマスク、その製造方法、これを用いたパターンの形成方法およびこれを用いて形成されたパターン
US8408895B2 (en) Transferring mold and production process of transferring mold
JP4575154B2 (ja) 多段リソグラフィックテンプレート、その製造方法、及び当該テンプレートを用いるデバイス作成方法
JP5909046B2 (ja) 近接場露光方法
US8896923B2 (en) Corrugated pattern forming sheet, and methods for manufacturing antireflector, retardation plate, original process sheet plate, and optical element
WO2012077738A1 (fr) Stratifié à structure fine, procédé de préparation d'un stratifié à structure fine et procédé de production d'un stratifié à structure fine
WO2009148138A1 (fr) Moule pour nano-impression, procédé pour sa fabrication et procédés pour produire une résine moulée ayant une structure à fine rugosité sur une surface et pour produire un polariseur à grille métallique
KR101691157B1 (ko) 나노임프린트용 스탬프 제조방법
JP5499668B2 (ja) インプリント用モールドおよび該モールドを用いたパターン形成方法
JP5532854B2 (ja) パターン形成方法、パターン形成装置、ナノインプリントモールド及びナノインプリントモールドの製造方法
JP5773024B2 (ja) ナノインプリントによるパターン形成装置
JP6208924B2 (ja) 微細構造転写用モールド、微細構造転写用モールドの製造方法及び表面微細構造部材の製造方法
WO2023054527A1 (fr) Moule, procédé de fabrication de moule et procédé de fabrication de structure d'irrégularité fine
JP2023051846A (ja) モールド、モールドの製造方法および微細凹凸構造体の製造方法
TW201518765A (zh) 防眩膜
Haslinger et al. Antireflective moth-eye structures on curved surfaces fabricated by nanoimprint lithography
JP2007035998A (ja) インプリント用モールド
US20140246797A1 (en) Transfer mold and manufacturing method for structure
JP2019145578A (ja) ブランクス基材、インプリントモールド、インプリントモールドの製造方法及びインプリント方法
JP2014240994A (ja) 近接場露光用マスク、レジストパターン形成方法、デバイスの製造方法、近接場露光方法、パターン形成方法、近接場光リソグラフィ部材、および近接場ナノインプリント方法
Nakamatsu et al. Room-temperature nanoimprint lithography using photosensitive dry film
JP2020167268A (ja) 被加工基板及びインプリント方法
TW201424998A (zh) 輥之製造方法及圖案形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22876393

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE