WO2013084900A1 - 積層体、及び積層体の製造方法 - Google Patents
積層体、及び積層体の製造方法 Download PDFInfo
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- WO2013084900A1 WO2013084900A1 PCT/JP2012/081418 JP2012081418W WO2013084900A1 WO 2013084900 A1 WO2013084900 A1 WO 2013084900A1 JP 2012081418 W JP2012081418 W JP 2012081418W WO 2013084900 A1 WO2013084900 A1 WO 2013084900A1
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Classifications
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- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G02F1/133502—Antiglare, refractive index matching layers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- 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
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
- H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
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- 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
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/813—Anodes characterised by their shape
-
- 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
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- G—PHYSICS
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- G06F—ELECTRIC DIGITAL DATA PROCESSING
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- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a laminate and a method for producing the laminate.
- an antireflection structure having a periodic uneven portion on its surface has been developed for display devices such as liquid crystal displays (LCDs) and solar cells (see, for example, Patent Document 1).
- the antireflection structure is a so-called “Moth ⁇ ⁇ Eye” type, and since the pitch of the convex portions is equal to or less than the wavelength of visible light, the light reflectance can be reduced and the light transmittance can be improved in a wide wavelength range.
- a laminate formed by forming a transparent conductive film on the concavo-convex portion of the antireflection structure is used for, for example, a resistance film type or electrostatic capacity type touch panel.
- the uneven part of the conventional antireflection structure has a structure in which a large number of conical protrusions are arranged on a plane.
- the protrusions are periodically arranged in a hexagonal lattice shape or a tetragonal lattice shape.
- the protrusions may be arranged such that the lower portions of the protrusions overlap each other.
- the side surface of the protrusion becomes steep, so that a transparent film is formed on the side surface of the protrusion.
- the thickness of the conductive film tends to be thin, and the conductivity may be low. Therefore, in the conventional structure, it is difficult to achieve both low reflectivity and high conductivity.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate excellent in low reflectivity and high conductivity, and a method for producing the laminate.
- a laminate according to one aspect of the present invention is provided.
- An antireflection structure having periodic irregularities on the surface;
- Arbitrary convex portions excluding the outermost convex portion and the six convex portions having the shortest sum of the distances from the arbitrary convex portions are (1) four of the six convex portions.
- each of the convex portions and the arbitrary convex portion there is a connecting portion that connects the convex portions at a position lower than the top of the convex portion and higher than the bottom point of the concave portion, and (2) the six It arrange
- the manufacturing method of the laminated body by the other aspect of this invention is as follows.
- any convex portion excluding the outermost convex portion and the six convex portions having the shortest total distance from the arbitrary convex portion are (1) of the six convex portions.
- each of the four convex portions and the arbitrary convex portion there is a connecting portion that connects the convex portions at a position lower than the vertex of the convex portion and higher than the bottom point of the concave portion, (2)
- the six convex portions are arranged such that a concave portion exists between each of the remaining two convex portions and the arbitrary convex portion.
- a laminate excellent in low reflectivity, scratch resistance and high conductivity and a method for producing the laminate are provided.
- FIG. 3 is a plan view (part 1) schematically showing irregularities on the surface of the antireflection structure of FIG. 2. It is a figure which shows the unevenness
- FIG. 10 is an explanatory diagram illustrating a method for producing an analysis model according to Comparative Example 1.
- FIG. It is a figure which shows the measurement result of the surface resistivity by Example 1 and Comparative Example 1. It is a figure which shows the measurement result of the reflectance by Example 1 and Comparative Example 1.
- FIG. 1 is a perspective view showing a part of a laminate according to the first embodiment of the present invention.
- contour lines are shown by thin lines in order to express unevenness on the surface of the laminate.
- the laminate 2 includes an antireflection structure 10 having a periodic uneven portion 20 on the surface, and a transparent conductive film 30 formed on the uneven portion 20.
- the surface shape of the transparent conductive film 30 is a shape that follows the uneven portion 20.
- a metal film (not shown) may be formed between the concavo-convex portion 20 and the transparent conductive film 30 in order to reduce the resistance.
- the thickness of the metal film may be 10 nm or less from the viewpoint of light transmittance.
- This laminated body 2 is used for, for example, a resistance film type or a capacitance type touch panel.
- FIG. 2 is a perspective view showing the antireflection structure of FIG.
- contour lines are shown by thin lines in order to express the unevenness of the surface of the antireflection structure.
- FIG. 3 is a plan view (part 1) schematically showing irregularities on the surface of the antireflection structure of FIG.
- FIG. 3A shows an array of lattices connecting the vertices of the convex portions
- FIG. 3B shows a part of FIG. In FIG.
- FIG. 4 is a view showing irregularities on the surface of the antireflection structure of FIG. 4A is unevenness in the cross section along line AA in FIG. 3,
- FIG. 4B is unevenness in the cross section along line BB in FIG. 3, and
- FIG. 4C is C in FIG.
- FIG. 4D shows unevenness in the cross section along the line DD in FIG. 3
- FIG. 4D shows unevenness in the cross section along the line DD in FIG.
- the antireflection structure 10 is of a so-called moth-eye type, and includes a base 12 and a resin layer 14 formed on the base 12 as shown in FIG.
- the base 12 and the resin layer 14 may have translucency.
- Periodic uneven portions 20 are formed on the surface of the resin layer 14.
- the antireflection structure 10 may be configured by only the resin layer 14.
- the base 12 is formed in a sheet shape, a plate shape, or a block shape, for example.
- substrate 12 is not specifically limited, For example, glass or a plastics etc. are used.
- soda lime glass for example, soda lime glass, non-alkali glass, quartz glass or the like is used.
- a glass forming method for example, a float method, a fusion method or the like is used.
- plastics include (meth) acrylic resins such as polymethyl methacrylate, methyl methacrylate and other alkyl (meth) acrylates, and copolymers of vinyl monomers such as styrene; polycarbonate, diethylene glycol bisallyl carbonate (CR-39) (Brominated) bisphenol A type di (meth) acrylate homopolymer or copolymer, (brominated) polymer of urethane-modified monomer of bisphenol A mono (meth) acrylate and copolymer Thermosetting (meth) acrylic resins such as coalescence; polyesters, especially polyethylene terephthalate, polyethylene naphthalate and unsaturated polyesters, acrylonitrile-styrene copolymers, polyvinyl chloride, polyurethane Epoxy resins, polyarylate, polyether sulfone, polyether ketone, cycloolefin polymer (trade name: ARTON, ZEONOR) and the like are prefer
- the resin layer 14 is formed by, for example, applying and curing a thermosetting or photocurable resin on the base 12.
- An uneven portion 20 is formed on the surface of the resin layer 14.
- the concavo-convex portion 20 is formed between the predetermined convex portions 21 at a position lower than the convex portion 21, the concave portion 22, and the vertex 21 a of the convex portion 21 and higher than the bottom point 22 a of the concave portion 22.
- a connecting portion 23 for connecting the two A plurality of convex portions 21, a plurality of concave portions 22, and a plurality of connecting portions 23 are two-dimensionally arranged.
- the convex portions 21 are periodically arranged, for example, in a regular hexagonal lattice shape, a quasi-hexagonal lattice shape, a regular tetragonal lattice shape, or a quasi-tetragonal lattice shape (a regular hexagonal lattice shape in FIGS. 2 and 3).
- the convex portions 21 are preferably periodically arranged in a hexagonal lattice shape.
- a case where the convex portions 21 are periodically arranged in a hexagonal lattice shape will be described. Note that the case where the convex portions 21 are periodically arranged in a tetragonal lattice pattern will be described in the second embodiment.
- “Periodically arranged in the form of a regular hexagonal lattice” means that, as shown in FIG. 3, the arbitrary convex portions 21-1 are arranged around the arbitrary convex portions 21-1 excluding the outermost convex portions 21. This means that six convex portions 21-2 to 21-7 having the shortest distance and the same distance are arranged. The vertices of the six convex portions 21-2 to 21-7 are arranged at an equal pitch at an interval of 60 ° with the vertex of the convex portion 21-1 as the center, and constitute a regular hexagonal lattice.
- “To be periodically arranged in a quasi-hexagonal lattice shape” means to be periodically arranged in a shape according to a regular hexagonal lattice.
- the shape conforming to the regular hexagonal lattice is a shape obtained by distorting a regular hexagonal lattice such as a shape obtained by stretching a regular hexagonal lattice in a predetermined direction.
- a lattice having a shape obtained by distorting a regular hexagonal lattice may be continuously arranged in a linear shape, a curved shape, or a meandering shape.
- FIG. 3 there are six convex portions 21-1 excluding the outermost convex portion 21 and the total (sum) of the distances from the convex portions 21-1 that are the shortest.
- the convex portions 21-2 to 21-7 are arranged so as to satisfy the following conditions (1) and (2).
- (1) Between the four convex portions 21-2, 21-3, 21-5, 21-6 of the six convex portions 21-2 to 21-7 and the convex portion 21-1.
- a concave portion 22 exists between each of the remaining two convex portions 21-4 and 21-7 among the six convex portions 21-2 to 21-7 and the convex portion 21-1. .
- “Distance” is the distance between the vertices 21 a of the convex portions 21.
- convex portions along two directions (F1 direction and F2 direction) among the three directions intersecting with an arbitrary convex portion 21-1 shown in FIG. 21 and the connecting portion 23 are alternately arranged, and the convex portion 21 and the concave portion 22 are alternately arranged along the remaining one direction (F3 direction).
- the pitch P1 (see FIGS. 4A and 4B) of the protrusions 21 arranged at intervals in the F1 direction, the F2 direction, and the F3 may be set to a length equal to or shorter than the wavelength of visible light. .
- the pitch P2 (see FIG. 4C) of the protrusions 21 arranged at intervals in the direction perpendicular to the F3 direction is larger than the pitch P1.
- Concave portions 22 and connecting portions 23 are alternately arranged along a direction parallel to the F1 direction (see FIGS. 3 and 4D).
- the direction in which the convex portions 21 and the concave portions 22 are alternately arranged is different from the direction in which the convex portions 21 and the connecting portions 23 are alternately arranged. Therefore, the height difference H1 (see FIG. 4B) between the vertex 21a of the convex portion 21 and the bottom point 22a of the concave portion 22, and the vertex 21a of the convex portion 21 and the predetermined portion 23a of the connecting portion 23 (see FIG. 2).
- the height difference H2 (see FIG. 4A) can be designed independently. Therefore, the height difference H1 and the height difference H2 can be optimized independently.
- the predetermined portion 23 a of the connecting portion 23 is the lowest portion between the vertices 21 a of the convex portions 21 and is the highest portion between the bottom points 22 a of the concave portions 22.
- the range of the pitch P1 may be set.
- the pitch P1 is set to a length equal to or shorter than the wavelength of visible light, and may be, for example, 400 nm or less (preferably 300 nm or less). Further, the pitch P1 may be, for example, 50 nm or more (preferably 100 nm or more) from the viewpoint of productivity. Therefore, the pitch P1 may be 50 nm to 400 nm.
- the aspect ratio of the concavo-convex portion 20 is represented by a ratio H1 / P1 between the height difference H1 between the apex 21a of the convex portion 21 and the bottom point 22a of the concave portion 22 and the pitch P1 of the convex portion 21.
- the aspect ratio H1 / P1 is, for example, 0.5 or more (preferably 0.7 or more, more preferably 1 or more) from the viewpoint of low reflectivity of the antireflection structure 10.
- the aspect ratio H1 / P1 is, for example, 4 or less (preferably 3 or less, more preferably 2 or less) from the viewpoint of productivity.
- the aspect ratio is obtained with the shortest pitch. Since the aspect ratio H1 / P1 is 0.5 to 4, the height difference H1 may be, for example, 100 nm to 500 nm.
- a ratio H2 / H1 between the height difference H1 and the height difference H2 is set.
- the ratio H2 / H1 is, for example, 0.1 or more (preferably 0.2 or more, more preferably 0.3 or more).
- the slope becomes gentle between the apex 21a of the convex portion 21 and the predetermined portion 23a of the connecting portion 23, and the thickness of the transparent conductive film 30 becomes thicker. As a result, current flows easily.
- the ratio H2 / H1 is, for example, 0.9 or less (preferably 0.7 or less, more preferably 0.5 or less). Since the ratio H2 / H1 is 0.1 to 0.9, the height difference H2 may be, for example, 30 nm to 300 nm.
- the aspect ratio H1 / P1 and the ratio H2 / H1 can be optimized independently. Both low reflectivity and high conductivity are possible.
- the pitch P1, the height difference H1, the height difference H2, and the like are obtained from an AFM image taken with an atomic force microscope (AFM) before forming the transparent conductive film 30, and a cross-sectional profile thereof.
- AFM atomic force microscope
- the convex portions 21 and the connecting portions 23 are alternately arranged along the F1 direction and the F2 direction which are linear directions, and the convex portions 21 and the concave portions 22 are arranged along the F3 direction which is a linear direction.
- the present invention is not limited to this as long as the above conditions (1) and (2) are satisfied.
- the convex portions 21 and the connecting portions 23 may be alternately arranged along a predetermined curved direction.
- FIG. 5 is a plan view (part 2) schematically showing irregularities on the surface of the antireflection structure of FIG.
- FIG. 5A shows an array of grids connecting the bottoms of the recesses
- FIG. 5B shows a part of FIG.
- the convex portions and the connecting portions are indicated by different dot patterns
- the vertexes of the convex portions are black circles
- the bottom points of the concave portions are white circles
- the grids connecting the bottom points of the concave portions are indicated by bold lines.
- an arbitrary recess 22-1 excluding the outermost recess 22 and six recesses 22-2 to 22-7 having the shortest total (sum) of the distances from the recess 22-1 Is arranged so as to satisfy the following conditions (3) and (4).
- 23 exists.
- a convex portion 21 exists between each of the remaining two concave portions 22-4 and 22-7 among the six concave portions 22-2 to 22-7 and the concave portion 22-1.
- “Distance” is the distance between the bottom points 22 a of the recesses 22.
- the transparent conductive film 30 is formed on the concavo-convex portion 20 of the antireflection structure 10.
- the surface shape of the transparent conductive film 30 is a shape that follows the uneven portion 20 and is substantially the same as the surface shape of the uneven portion 20.
- the average thickness of the transparent conductive film 30 is, for example, 10 nm to 150 nm, preferably 30 nm to 100 nm, and more preferably 50 nm to 80 nm.
- the thickness of the transparent conductive film 30 is thick at a gentle slope portion and thin at a steep slope portion.
- the thickness of the transparent conductive film 30 is the thickest at the vertex 21 a of the convex portion 21, and the thinnest at the portion between the vertex 21 a of the convex portion 21 and the bottom point 22 a of the concave portion 22.
- the height difference H1 (see FIG. 4B) between the apex 21a of the convex portion 21 and the bottom point 22a of the concave portion 22 becomes smaller, the inclination becomes gentler and the thickness of the transparent conductive film 30 becomes thicker. , Making it easier for electricity to flow. On the other hand, if the height difference H1 is too small, sufficient low reflectivity cannot be obtained.
- the inclination of the slope is gentle like the vertex 21a of the convex portion 21, and thus the transparent conductive film 30 is thick. Therefore, current tends to flow in a net shape along the F1 direction and the F2 direction in which the convex portions 21 and the connecting portions 23 are alternately arranged.
- the inclination becomes gentler as the height difference H2 (see FIG. 4A) becomes smaller (that is, H2 / H1 becomes smaller), Since the thickness of the transparent conductive film 30 is increased, a current easily flows.
- the height difference H1 and the height difference H2 can be optimized independently, both low reflectivity and high conductivity can be achieved.
- Examples of the material of the transparent conductive film 30 include ITO (In 2 O 3 —SnO 2 : indium tin oxide), SnO 2 (tin oxide), IZO (In 2 O 3 —ZnO: indium zinc oxide), and AZO ( Aluminum doped zinc oxide), FTO (fluorine doped tin oxide), GZO (gallium doped zinc oxide), or the like is used.
- FIG. 6 and 7 are explanatory views (No. 1) and (No. 2) of the method for manufacturing a laminate according to the first embodiment of the present invention.
- FIG. 6 shows a first step of producing a stamper using the prototype
- FIG. 7 shows a second step of producing an antireflection structure (ie, replica) using the stamper.
- the manufacturing method of a laminated body has the process of manufacturing the antireflection structure 10 which has the periodic uneven
- the step includes, for example, a first step of producing a stamper 70 having a concavo-convex portion 80 on the surface of which the shape of the concavo-convex portion 60 of the prototype 50 is transferred, and a concavo-convex portion obtained by inverting and transferring the shape of the concavo-convex portion 80 of the stamper 70. And a second step of producing the antireflection structure 10 having 20 on the surface.
- the prototype 50 can be used repeatedly in the first step, and the stamper 70 can be used repeatedly in the second step.
- the first step includes, for example, a step of preparing the prototype 50 (see FIG. 6A), and a step of forming a stamper 70 by forming a metal film on the uneven portion 60 of the prototype 50 (FIG. 6B). )) And a step of peeling the stamper 70 from the master 50 (see FIG. 6C).
- the material of the stamper 70 for example, nickel (Ni) or the like is used.
- the stamper 70 is formed, for example, by forming a conductive film on the concavo-convex portion 60 of the prototype 50 and then forming a metal film such as Ni on the conductive film by electroforming.
- PVD methods such as electroless plating, sputtering, and vacuum deposition are used.
- the second step for example, a step of applying a curable resin onto the base 12 (see FIG. 7A), and the coating layer 13 is cured in a state where the uneven portion 80 of the stamper 70 is pressed against the surface of the coating layer 13. And a step of peeling the stamper 70 from the resin layer 14 formed by curing the coating layer 13 (see FIG. 7C).
- a curable resin for example, a thermosetting resin or a photocurable resin is used.
- a method for applying the curable resin for example, a general method such as a spin coating method, a die coating method, or an ink jet method is used.
- the antireflection structure 10 is manufactured. Since the uneven portion 20 of the antireflection structure 10 has a shape obtained by inverting the shape of the uneven portion 60 of the prototype 50 twice, it has substantially the same shape and substantially the same dimensions as the uneven portion 60 of the prototype 50.
- FIG. 8 is a plan view schematically showing irregularities on the surface of the prototype in FIG.
- FIG. 8A shows an array of lattices connecting the vertices of the convex portions
- FIG. 8B shows a part of FIG.
- the convex portions and the connecting portions are indicated by different dot patterns
- the vertexes of the convex portions are indicated by black circles
- the bottom points of the concave portions are indicated by white circles
- the lattices connecting the vertexes of the convex portions are indicated by bold lines.
- the concavo-convex portion 60 of the prototype 50 is similar to the concavo-convex portion 20 of the antireflection structure 10, and has a convex portion 61, a concave portion 62, and a bottom of the concave portion 62 that is lower than the apex 61 a of the convex portion 61. It has the connection part 63 which connects predetermined convex parts 61 in the position higher than the point 62a.
- a plurality of convex portions 61, a plurality of concave portions 62, and a plurality of connecting portions 63 are two-dimensionally arranged.
- the convex portions 61 are periodically arranged in, for example, a regular hexagonal lattice shape, a quasi-hexagonal lattice shape, a regular tetragonal lattice shape, or a quasi-tetragonal lattice shape (in this embodiment, a regular hexagonal lattice shape).
- the convex portions 61 are preferably arranged periodically in a hexagonal lattice shape.
- the distance from the arbitrary convex portion 61-1 around the arbitrary convex portion 61-1 except the outermost convex portion 61 is the shortest.
- equal six convex portions 61-2 to 61-7 are arranged.
- the vertices of the six convex portions 61-2 to 61-7 are arranged at an equal pitch with an interval of 60 ° around the vertex of the convex portion 61-1, and constitute a regular hexagonal lattice.
- FIG. 8 there are six arbitrary convex portions 61-1 excluding the outermost convex portion 61, and the total (sum) of the distances from the convex portions 61-1.
- the convex portions 61-2 to 61-7 are arranged so as to satisfy the following conditions (5) and (6).
- (5) Between the four convex portions 61-2, 61-3, 61-5, 61-6 of the six convex portions 61-2 to 61-7 and the convex portion 61-1.
- a concave portion 62 exists between each of the remaining two convex portions 61-4 and 61-7 among the six convex portions 61-2 to 61-7 and the convex portion 61-1. .
- convex portions along two directions (F1 direction and F2 direction) among the three directions intersecting with an arbitrary convex portion 61-1 shown in FIG. 61 and the connection part 63 are arrange
- Concave portions 62 and connecting portions 63 are alternately arranged along a direction parallel to the F1 direction.
- the direction in which the convex portions 61 and the concave portions 62 are alternately arranged differs from the direction in which the convex portions 61 and the connecting portions 63 are alternately arranged. Therefore, the height difference between the apex 61a of the convex portion 61 and the bottom point 62a of the concave portion 62, and the predetermined portion of the apex 61a of the convex portion 61 and the connecting portion 63 (corresponding to the predetermined portion 23a of the connecting portion 23 of the antireflection structure 10). It is possible to design the difference in height with respect to the portion). Therefore, in the antireflection structure 10 shown in FIGS.
- the height difference H1 between the vertex 21a of the convex portion 21 and the bottom point 22a of the concave portion 22, the vertex 21a of the convex portion 21 and the predetermined portion 23a of the connecting portion 23 can be designed independently. Therefore, since the height difference H1 and the height difference H2 can be optimized independently, both low reflectivity and scratch resistance can be achieved.
- the concavo-convex portion 20 of the antireflection structure 10 has a shape obtained by inverting the shape of the concavo-convex portion 60 of the prototype 50 twice, but the shape of the concavo-convex portion 60 of the prototype 50 is inverted one or more times.
- the coating layer 13 may be cured in a state in which the uneven portion 60 of the prototype 50 is pressed against the surface of the coating layer 13 (see FIG. 7). Regardless of the number of times of reversal transfer, the convex portion 21 of the antireflection structure 10 satisfies the above conditions (1) and (2), so that both low reflectivity and scratch resistance can be achieved.
- the method for manufacturing a laminate further includes a step (not shown) of forming a transparent conductive film 30 on the concavo-convex portion 20 of the antireflection structure 10.
- a film forming method of the transparent conductive film 30 for example, a CVD method (chemical vapor deposition method) such as thermal CVD, plasma CVD, or photo CVD, or a PVD method (physical vapor deposition method) such as vacuum vapor deposition, plasma vapor deposition, or sputtering is used.
- FIG. 9 is an explanatory diagram (part 3) of the method for manufacturing the antireflection structure according to the first embodiment of the present invention.
- FIG. 9 shows a process of manufacturing a prototype.
- the manufacturing method of a laminated body may further have the process of manufacturing the prototype 50.
- This step includes, for example, a step of forming a resist film 52 on the substrate 51 (see FIGS. 6 and 7), and a step in which the light intensity changes in the first direction (G1 direction) on the surface of the resist film 52.
- a step of exposing the stripes see FIG. 9B) and a step of developing the resist film 52 after the exposure of the first and second interference fringes.
- the substrate 51 (see FIGS. 6 and 7) is formed in, for example, a sheet shape, a plate shape, a block shape, or a roll shape.
- substrate 51 is not specifically limited, For example, a silicon
- the material of the resist film 52 a general material is used, and either a negative type or a positive type can be used. A developing solution is selected according to the material of the resist film 52.
- the first interference fringes are formed by the two-beam interference exposure method.
- a plurality of photosensitive portions 53 exposed by the first interference fringes are arranged at intervals in the first direction (G1 direction).
- a general laser oscillator such as a He—Cd laser (wavelength: 325 nm) is used.
- the second interference fringes are formed by the two-beam interference exposure method in the same manner as the first interference fringes after the resist film 52 is rotated.
- a plurality of photosensitive portions 54 exposed by the first interference fringes are arranged at intervals in the second direction (G2 direction).
- the exposure of the first interference fringes and the exposure of the second interference fringes are performed separately, but may be performed simultaneously.
- the development of the resist film 52 is performed after the exposure of the first and second interference fringes.
- a resin layer 56 (see FIG. 6A) having periodic uneven portions 60 on the surface is obtained.
- the intersection 55 between the photosensitive portion 53 and the photosensitive portion 54 becomes the convex portion 61 after development.
- the convex portion 61 is formed in a tapered shape toward the vertex 61a.
- the portions other than the intersecting portion 55 of the photosensitive portions 53 and 54 become the connecting portion 63 after development.
- a crossing portion 55 between the photosensitive portion 53 and the photosensitive portion 54 becomes a concave portion 62 after development.
- the recess 62 is formed in a tapered shape toward the bottom point 62a. The portions other than the intersecting portion 55 of the photosensitive portions 53 and 54 become the connecting portion 63 after development.
- the prototype 50 is produced.
- the angle ⁇ formed by the first direction and the second direction is 60 °
- the convex portions 61 are periodically arranged in a regular hexagonal lattice shape.
- the angle ⁇ formed by the first direction and the second direction is 90 °
- the convex portions 61 are periodically arranged in a regular tetragonal lattice shape.
- the prototype 50 of this embodiment is produced by exposing the interference fringes to the resist film 52 by the two-beam interference exposure method
- the production method of the prototype 50 is not particularly limited.
- the concavo-convex portion 60 may be formed on the surface of the substrate 51 by photolithography, electron beam (EB) drawing, laser drawing, or the like.
- FIG. 10 is a perspective view showing a part of a laminate according to the second embodiment of the present invention.
- contour lines are shown by thin lines in order to express unevenness on the surface of the laminate.
- the laminated body 102 includes an antireflection structure 110 having a periodic concavo-convex portion 120 on the surface and a transparent conductive film 130 formed on the concavo-convex portion 120, similarly to the laminated body 2 shown in FIG.
- the surface shape of the transparent conductive film 130 is a shape that follows the uneven portion 120.
- a metal film (not shown) may be formed between the concavo-convex portion 120 and the transparent conductive film 130 in order to reduce resistance.
- the antireflection structure 110 is a so-called moth-eye type, and includes, for example, a base 112 and a resin layer 114 formed on the base 112, similarly to the antireflection structure 10 shown in FIG. 2. Periodic uneven portions 120 are formed on the surface of the resin layer 114. Note that the antireflection structure 110 may be formed of only the resin layer 114.
- FIG. 11 is a perspective view showing an antireflection structure according to the second embodiment of the present invention.
- FIG. 11 in order to express the unevenness
- FIG. 12 is a plan view schematically showing irregularities on the surface of the antireflection structure of FIG. 11.
- FIG. 12A shows an array of lattices connecting the vertices of the convex portions, and
- FIG. 12B shows a part of FIG. In FIG.
- FIG. 13 is a view showing irregularities on the surface of the antireflection structure of FIG. 11.
- 13A is unevenness in the cross section along line AA in FIG. 12
- FIG. 13B is unevenness in the cross section along line BB in FIG. 12
- FIG. 13C is C in FIG. Shows irregularities in the cross section along the line -C.
- the antireflection structure 110 is of a so-called moth-eye type, and includes a base 112 and a resin layer 114 formed on the base 112 as in the first embodiment, as shown in FIG. Periodic uneven portions 120 are formed on the surface of the resin layer 114.
- the concavo-convex portion 120 includes a convex portion 121, a concave portion 122, and a connecting portion 123 that couples the predetermined convex portions 121 to each other at a position lower than the vertex 121 a of the convex portion 121 and higher than the bottom point 122 a of the concave portion 122.
- a plurality of convex portions 121, a plurality of concave portions 122, and a plurality of connecting portions 123 are two-dimensionally arranged.
- the convex portions 121 are periodically arranged in a regular tetragonal lattice shape, for example. “Periodically arranged in a tetragonal lattice shape” means that, as shown in FIG. 12, the distance from the arbitrary concave portion 122 is shortest around the arbitrary concave portion 122 except the outermost concave portion 122. It means that four equal convex portions 121 are arranged. The vertices 121a of the four convex portions 121 are arranged at equal pitches at 90 ° intervals around the bottom point 122a of the concave portion 122, and constitute a regular tetragonal lattice.
- the convex portions 121 may be periodically arranged in a quasi-tetragonal lattice shape.
- “Periodically arranged in a quasi-tetragonal lattice shape” means periodically arranged in a shape that conforms to a regular tetragonal lattice.
- the shape conforming to the tetragonal lattice is a shape obtained by distorting a regular tetragonal lattice such as a shape obtained by stretching a regular tetragonal lattice in a predetermined direction.
- a lattice having a shape obtained by distorting a regular tetragonal lattice may be continuously arranged in a linear shape, a curved shape, or a meandering shape.
- any six convex portions 121-1 excluding the outermost convex portion 121 and the six total distances (sums) from the convex portions 121-1 are the shortest.
- the convex portions (for example, convex portions 121-2 to 121-7) are arranged so as to satisfy the following conditions (7) and (8).
- (7) Between the four convex portions 121-2, 121-3, 121-5, 121-6 of the six convex portions 121-2 to 121-7 and the convex portion 121-1.
- a concave portion 122 exists between each of the remaining two convex portions 121-4 and 121-7 among the six convex portions 121-2 to 121-7 and the convex portion 121-1. .
- “Distance” is the distance between the vertices 121 a of the convex portions 121.
- the above conditions (7) and (8) are satisfied for all combinations.
- convex portions along two directions (the J1 direction and the J2 direction) among the three directions intersecting with the arbitrary convex portion 121-1 shown in FIG. 121 and the connection part 123 are arrange
- the pitch P11 (see FIG. 13A) of the convex portions 121 arranged at intervals in the J1 direction and the J2 direction may be set to a length equal to or shorter than the wavelength of visible light.
- the pitch P12 (see FIG. 13B) of the convex portions 121 arranged at intervals in the J3 direction is larger than the pitch P11.
- Concave portions 122 and connecting portions 123 are alternately arranged along a direction parallel to the J1 direction (see FIGS. 12 and 13C).
- the direction in which the convex portions 121 and the concave portions 122 are alternately arranged is different from the direction in which the convex portions 121 and the connecting portions 123 are alternately arranged. Therefore, the height difference H11 (see FIG. 13B) between the vertex 121a of the convex portion 121 and the bottom point 122a of the concave portion 122, the vertex 121a of the convex portion 121, and the predetermined portion 123a of the connecting portion 123 (see FIG. 11).
- the height difference H12 (see FIG. 13A) can be designed independently. Therefore, the height difference H11 and the height difference H12 can be optimized independently.
- the predetermined portion 123 a of the connecting portion 123 is the lowest portion between the vertices 121 a of the convex portions 121 and the highest portion between the bottom points 122 a of the concave portions 122.
- the range of the pitch P11 may be set. Since the pitch P11 is set to a length equal to or shorter than the wavelength of visible light as described above, the pitch P11 may be, for example, 400 nm or less (preferably 300 nm or less). Further, the pitch P11 may be, for example, 50 nm or more (preferably 100 nm or more) from the viewpoint of productivity. Therefore, the pitch P11 may be 50 nm to 400 nm.
- the aspect ratio of the concavo-convex portion 120 is represented by a ratio H11 / P11 between the height difference H11 between the apex 121a of the convex portion 121 and the bottom point 122a of the concave portion 122 and the pitch P11 of the convex portion 121.
- the aspect ratio H11 / P11 is, for example, 0.5 or more (preferably 0.7 or more, more preferably 1 or more) from the viewpoint of low reflectivity of the antireflection structure 110.
- the aspect ratio H11 / P11 is, for example, 4 or less (preferably 3 or less, more preferably 2 or less) from the viewpoint of productivity.
- the aspect ratio is obtained with the shortest pitch. Since the aspect ratio H11 / P11 is 0.5 to 4, the height difference H11 may be, for example, 100 nm to 500 nm.
- the ratio H12 / H11 between the height difference H11 and the height difference H12 is set.
- the ratio H12 / H11 is, for example, 0.1 or more (preferably 0.2 or more, more preferably 0.3 or more).
- the slope becomes gentle between the apex 121a of the convex portion 121 and the predetermined portion 123a of the connecting portion 123, and the thickness of the transparent conductive film 130 increases as will be described in detail later. As a result, current flows easily.
- the ratio H12 / H11 is, for example, 0.9 or less (preferably 0.7 or less, more preferably 0.5 or less). Since the ratio H12 / H11 is 0.1 to 0.9, the height difference H12 may be, for example, 30 nm to 300 nm.
- the aspect ratio H11 / P11 and the ratio H12 / H11 can be optimized independently. Both low reflectivity and high conductivity are possible.
- the convex portions 121 and the connecting portions 123 are alternately arranged along the J1 direction and the J2 direction which are linear directions, and the convex portions 121 and the concave portions 122 are along the J3 direction which is the linear direction.
- the present invention is not limited to this as long as the above conditions (7) and (8) are satisfied.
- the convex portions 121 and the connecting portions 123 may be alternately arranged along a predetermined curved direction.
- the transparent conductive film 130 is formed on the uneven portion 120 of the antireflection structure 110.
- the surface shape of the transparent conductive film 130 is a shape that follows the uneven portion 120, and is substantially the same as the surface shape of the uneven portion 120.
- the average thickness of the transparent conductive film 130 is, for example, 10 nm to 80 nm. If the average thickness is less than 10 nm, sufficient conductivity cannot be obtained. In addition, when the average thickness exceeds 80 nm, the surface shape of the transparent conductive film 130 is unlikely to follow the uneven portion 120.
- the thickness of the transparent conductive film 130 is thick at a gentle slope and thin at a steep slope.
- the thickness of the transparent conductive film 130 is the thickest at the apex 121 a of the convex portion 121 and the thinnest at the portion between the apex 121 a of the convex portion 121 and the bottom point 122 a of the concave portion 122.
- the height difference H11 (see FIG. 13B) between the apex 121a of the convex part 121 and the bottom point 122a of the concave part 122 becomes smaller, the inclination becomes gentler and the thickness of the transparent conductive film 130 becomes thinner. , Making it easier for electricity to flow. On the other hand, if the height difference H11 is too small, sufficient low reflectivity cannot be obtained.
- the transparent conductive film 130 is thick. Therefore, a current tends to flow in a net shape along the J1 direction and the J2 direction in which the convex portions 121 and the connecting portions 123 are alternately arranged.
- the height difference H12 see FIG. 13A
- the inclination becomes gentler, Since the thickness of the transparent conductive film 130 is increased, a current easily flows.
- the height difference H11 and the height difference H12 can be optimized independently, so that both low reflectivity and high conductivity can be achieved.
- Examples of the material of the transparent conductive film 30 include ITO (In 2 O 3 —SnO 2 : indium tin oxide), SnO 2 (tin oxide), IZO (In 2 O 3 —ZnO: indium zinc oxide), and AZO ( Aluminum doped zinc oxide), FTO (fluorine doped tin oxide), GZO (gallium doped zinc oxide), or the like is used.
- the manufacturing method of the stacked body 102 having the above-described configuration is the same as the manufacturing method of the stacked body 2 according to the first embodiment, and thus the description thereof is omitted.
- the laminated body may have a low-reflection treatment layer on the back surface of the antireflection structure (the surface facing the surface on which the moth-eye type irregularities are formed).
- the low reflection treatment layer has translucency.
- the low reflection treatment layer may reduce the reflectance by the interference action of light, or may reduce the reflectance by absorption of light.
- the low reflection treatment layer is formed of an organic material and / or an inorganic material.
- dry coating such as PVD method or CVD method
- wet coating such as die coating method, spray coating method, ink jet method or spin coating method is used.
- the antireflection structure is used for a touch panel, the low reflection treatment layer may be disposed on the outer side, and the moth-eye uneven portion may be disposed on the inner side.
- the laminated body may have a protective layer on a transparent conductive film.
- the protective layer has translucency.
- the protective layer absorbs the unevenness of the transparent conductive film and smoothes the surface of the laminate.
- the protective layer is formed of an organic material and / or an inorganic material.
- the protective layer may be a dielectric layer formed of, for example, SiO 2 .
- the convex part of the said embodiment is tapering toward the top, the convex part may have a flat top part.
- the “distance” in the claims is the distance between the center points of the tops of the convex portions.
- the recessed part of the said embodiment is tapered toward the bottom point, the recessed part may have a flat bottom part.
- FIG. 14 is a cross-sectional view showing an example of a display device using a laminate.
- the display device 140 includes a metal electrode layer 141, for example, a light emitting layer 142 formed of an organic light emitting diode (OLED) or an organic electroluminescence (OEL) element, a transparent electrode layer. 143, and a transparent substrate 144 formed of, for example, glass or the like is laminated.
- the transparent electrode layer 143 can be formed by, for example, the laminate 2 shown in FIG. 1 or the laminate 102 shown in FIG. By using the structure of the laminated body 2 or 102 for the transparent electrode layer 143, reflection at the interface between the transparent substrate 144 and the transparent electrode layer 143 is reduced, and light extraction efficiency is improved. Can be improved.
- FIG. 15 is a cross-sectional view showing an example of a lighting device using a laminate.
- the illumination device 150 has a configuration in which a metal electrode layer 151, for example, a light emitting layer 152 formed of an OLED or an OEL element, a transparent electrode layer 153, and a transparent substrate 154 formed of, for example, glass are stacked.
- the transparent electrode layer 153 can be formed by, for example, the laminate 2 shown in FIG. 1 or the laminate 102 shown in FIG. By using the structure of the laminated body 2 or 102 for the transparent electrode layer 153, reflection at the interface between the transparent substrate 154 and the transparent electrode layer 153 is reduced, and light extraction efficiency is improved. Can be improved.
- FIG. 16 is a cross-sectional view showing an example of a solar cell using a laminate.
- a solar cell 160 includes a metal electrode layer 161, for example, a P-type semiconductor layer 162-1 made of P-type silicon, an N-type semiconductor layer 162-2 made of, for example, N-type silicon, and a transparent electrode layer 163.
- a transparent substrate 164 made of, for example, glass or the like is laminated.
- the P-type semiconductor layer 162-1 and the N-type semiconductor layer 162-2 are examples of a power generation layer.
- the transparent electrode layer 163 can be formed by, for example, the laminate 2 shown in FIG. 1 or the laminate 102 shown in FIG. By using the structure of the laminated body 2 or 102 for the transparent electrode layer 163, reflection at the interface between the transparent substrate 164 and the transparent electrode layer 163 is reduced, and light capturing efficiency is improved. Can be improved.
- the solar panel (not shown) which is an example of a solar power generation device has the structure which has arrange
- reflection at the interface between the transparent substrate 164 and the transparent electrode layer 163 of each solar cell 160 is reduced, Since the efficiency of capturing light from the battery 160 is improved, the power generation efficiency of the solar panel can be improved.
- Example 1 an antireflection structure having periodic irregularities on the surface was prepared by the method shown in FIGS. 6, 7, and 9, and a transparent conductive film was formed on the irregularities of the antireflection structure. Thus, a laminate was produced.
- the convex portions of the concave and convex portions of the antireflection structure are periodically arranged in a regular hexagonal lattice shape.
- the original stamper was prepared by forming a resist film made of an acrylic resin on a glass substrate as a base, exposing the resist film with interference fringes twice, and then developing the resist film.
- An ArF excimer laser (wavelength 193 nm) was used as the light source for the interference fringes, and the crossing angle between the first interference fringes and the second interference fringes was set to 60 °.
- the produced prototype had irregularities on the surface.
- the dimensional shape of the original concavo-convex part is 250 nm when measured with an AFM (Seiko Instruments Inc., L-trace), the height difference between the top of the convex part and the bottom of the concave part, and the height between the top part of the convex part and the connecting part The difference is 125 nm, and the shortest pitch at the top of the convex portion is 250 nm.
- the stamper was prepared by forming a Ni layer on the concavo-convex portion of the original by electroforming and peeling the Ni layer from the original. As a result of measuring the size and shape of the surface of the stamper with the AMF, the surface of the stamper was formed with an uneven portion having a shape obtained by inverting and transferring the original uneven portion.
- the antireflection structure is formed by applying a photocurable acrylic resin on a biaxially stretched PET film as a substrate by a spin coating method, and irradiating UV light in a state where the uneven portions of the stamper are pressed against the surface of the coating layer.
- the coating layer was cured.
- the surface of the resin layer was formed with an uneven portion obtained by reversing the shape of the uneven portion of the stamper.
- the laminate was produced by forming a transparent conductive film on the uneven portion of the antireflection structure.
- a transparent conductive film an ITO film (average thickness 20 nm, 40 nm, 60 nm) formed by vacuum sputtering was used.
- the average thickness means the thickness of the transparent conductive film formed on the surface of a flat plate portion having no uneven structure when forming the film on the uneven portion.
- the surface resistance of the laminate on the transparent conductive film side was measured with a non-contact conductivity meter (Delcom Instruments, 717 Conductance Monitor, manufactured by Inc.). The measurement results are shown in FIG. In FIG. 18, the horizontal axis represents the thickness (nm) of the transparent conductive film, and the vertical axis represents the surface resistivity ( ⁇ / ⁇ ).
- the reflectance when the surface of the transparent conductive film (average thickness 60 nm) was irradiated with visible light was measured with a spectrophotometer (manufactured by JASCO Corporation, ARM-500N).
- the measurement results are shown in FIG.
- the horizontal axis represents the wavelength (nm) of incident light, and the vertical axis represents the reflectance (%).
- L1 represents the measurement result of Example 1
- L11 represents the measurement result of Comparative Example 1 described later.
- Comparative Example 1 In Comparative Example 1, an antireflection structure having a conventional concavo-convex portion on its surface was produced, and a transparent conductive film was formed on the concavo-convex portion of the antireflection structure to produce a laminate.
- the convex portions of the concave and convex portions of the antireflection structure are periodically arranged in a regular hexagonal lattice shape.
- the original stamper was prepared by forming a resist film made of an acrylic resin on a silicon substrate as a base, exposing it with an EB drawing apparatus, and developing the resist film.
- the fabricated prototype has a concavo-convex portion on the surface, and the concavo-convex portion has a structure in which a large number of conical projections 94 are arranged on a plane 92 (only five are shown in FIG. 17) as shown in FIG. Met.
- Each projection 94 has a rounded chamfer at the corner between the top surface and the side surface of the truncated cone, and has a tip formed of a part of a spherical surface.
- the lower portions of the protrusions 94 partially overlap each other so that the outer circumferences of the bottom surfaces 94a of the three adjacent protrusions 94 intersect at one point on the plane 92.
- the dimensional shape of the concavo-convex portion of the prototype is measured by AFM (manufactured by Seiko Instruments Inc., L-trace), the height H21 of the protrusion 94 is 450 nm, and the pitch P21 of the apex 94b of the protrusion 94 is 300 nm.
- the stamper was prepared by forming a Ni layer on the concavo-convex portion of the original by electroforming and peeling the Ni layer from the original.
- the surface of the stamper was formed with uneven portions having a shape obtained by inverting and transferring the original uneven portion.
- the antireflection structure is formed by applying a UV curable acrylic resin on a glass substrate as a substrate by a spin coating method, and irradiating the surface of the coating layer with UV light while pressing the uneven portions of the stamper. Was made by curing.
- the surface of the resin layer was formed with an uneven portion obtained by reversing the shape of the uneven portion of the stamper.
- the laminate was produced by forming a transparent conductive film on the uneven portion of the antireflection structure.
- a transparent conductive film an ITO film (average thickness 20 nm, 40 nm, 60 nm) formed by vacuum sputtering was used.
- the surface resistivity and reflectance (average thickness of the transparent conductive film 60 nm) of the laminate were measured in the same manner as in Example 1. The measurement results are shown in FIGS.
- Example 1 has both low reflectivity and high conductivity unlike the structure of Comparative Example 1.
- the convex portion of the reflective structure does not satisfy the above conditions (1) and (2), and the surface resistivity is high. This is because, in Comparative Example 1, the slope is steep between the convex portions of the antireflection structure.
- the present invention is suitable for a laminate that can be used for, for example, a display device, a lighting device, a solar battery, a solar panel, and the like, and a method for manufacturing the laminate.
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Abstract
Description
周期的な凹凸部を表面に有する反射防止構造体と、
前記凹凸部上に成膜される透明導電膜とを有し、
最外側の凸部を除く任意の凸部と、該任意の凸部からの距離の合計が最短である6個の凸部とは、(1)該6個の凸部のうちの4個の前記凸部のそれぞれと前記任意の凸部との間に凸部の頂点よりも低く凹部の底点よりも高い位置で凸部同士を連結する連結部が存在し、(2)該6個の凸部のうちの残りの2個の前記凸部のそれぞれと前記任意の凸部との間に凹部が存在するように、配置されることを特徴とする。
周期的な凹凸部を表面に有する原型を用いて周期的な凹凸部を表面に有する反射防止構造体を製造する工程と、
前記反射防止構造体の前記凹凸部上に透明導電膜を成膜する工程とを有し、
前記原型において、最外側の凸部を除く任意の凸部と、該任意の凸部からの距離の合計が最短である6個の凸部とは、(1)該6個の凸部のうちの4個の前記凸部のそれぞれと前記任意の凸部との間に凸部の頂点よりも低く凹部の底点よりも高い位置で凸部同士を連結する連結部が存在し、(2)該6個の凸部のうちの残りの2個の前記凸部のそれぞれと前記任意の凸部との間に凹部が存在するように、配置されることを特徴とする。
図1は、本発明の第1の実施形態による積層体の一部を示す斜視図である。図1において、積層体の表面の凹凸を表現するため、等高線を細線で示す。
(1)6個の凸部21-2~21-7のうちの4個の凸部21-2、21-3、21-5、21-6のそれぞれと、凸部21-1との間に連結部23が存在する。
(2)6個の凸部21-2~21-7のうちの残りの2個の凸部21-4、21-7のそれぞれと、凸部21-1との間に凹部22が存在する。
(3)6個の凹部22-2~22-7のうちの4個の凹部22-2、22-3、22-5、22-6のそれぞれと、凹部22-1との間に連結部23が存在する。
(4)6個の凹部22-2~22-7のうちの残りの2個の凹部22-4、22-7のそれぞれと、凹部22-1との間に凸部21が存在する。
(5)6個の凸部61-2~61-7のうちの4個の凸部61-2、61-3、61-5、61-6のそれぞれと、凸部61-1との間に連結部63が存在する。
(6)6個の凸部61-2~61-7のうちの残りの2個の凸部61-4、61-7のそれぞれと、凸部61-1との間に凹部62が存在する。
図10は、本発明の第2の実施形態による積層体の一部を示す斜視図である。図10において、積層体の表面の凹凸を表現するため、等高線を細線で示す。
(7)6個の凸部121-2~121-7のうちの4個の凸部121-2、121-3、121-5、121-6のそれぞれと、凸部121-1との間に連結部123が存在する。
(8)6個の凸部121-2~121-7のうちの残りの2個の凸部121-4、121-7のそれぞれと、凸部121-1との間に凹部122が存在する。
実施例1では、図6、図7及び図9に示す方法で周期的な凹凸部を表面に有する反射防止構造体を作製し、反射防止構造体の凹凸部上に透明導電膜を成膜して積層体を作製した。反射防止構造体の凹凸部の凸部は、正六方格子状に周期的に配置した。
比較例1では、従来の凹凸部を表面に有する反射防止構造体を作製し、反射防止構造体の凹凸部上に透明導電膜を成膜して積層体を作製した。反射防止構造体の凹凸部の凸部は、正六方格子状に周期的に配置した。
10 反射防止構造体
20 凹凸部
21 凸部
21a 頂点
22 凹部
22a 底点
23 連結部
30 透明導電膜
50 原型
51 基体
52 レジスト膜
53、54 感光部
Claims (12)
- 周期的な凹凸部を表面に有する反射防止構造体と、
前記凹凸部上に成膜される透明導電膜とを有し、
最外側の凸部を除く任意の凸部と、該任意の凸部からの距離の合計が最短である6個の凸部とは、(1)該6個の凸部のうちの4個の前記凸部のそれぞれと前記任意の凸部との間に凸部の頂点よりも低く凹部の底点よりも高い位置で凸部同士を連結する連結部が存在し、(2)該6個の凸部のうちの残りの2個の前記凸部のそれぞれと前記任意の凸部との間に凹部が存在するように、配置されることを特徴とする積層体。 - 前記任意の凸部を中心に交差する3方向のうち、2方向に沿って前記凸部と前記連結部とが交互に配置され、残りの一方向に沿って前記前記凸部と前記凹部とが交互に配置される請求項1に記載の積層体。
- 前記凸部は、正六方格子状に周期的に配置される請求項1又は2に記載の積層体。
- 前記凸部は、正四方格子状に周期的に配置される請求項1又は2に記載の積層体。
- 金属電極層、発光層、透明電極層、及び透明基板が積層された構成を有し、
前記透明電極層は、請求項1乃至4のいずれか1項に記載の積層体で形成された表示装置。 - 金属電極層、発光層、透明電極層、及び透明基板が積層された構成を有し、
前記透明電極層は、請求項1乃至4のいずれか1項に記載の積層体で形成された照明装置。 - 金属電極層、発電層、透明電極層、及び透明基板が積層された構成を有し、
前記透明電極層は、請求項1乃至4のいずれか1項に記載の積層体で形成された太陽電池。 - 周期的な凹凸部を表面に有する原型を用いて周期的な凹凸部を表面に有する反射防止構造体を製造する工程と、
前記反射防止構造体の前記凹凸部上に透明導電膜を成膜する工程とを有し、
前記原型において、最外側の凸部を除く任意の凸部と、該任意の凸部からの距離の合計が最短である6個の凸部とは、(1)該6個の凸部のうちの4個の前記凸部のそれぞれと前記任意の凸部との間に凸部の頂点よりも低く凹部の底点よりも高い位置で凸部同士を連結する連結部が存在し、(2)該6個の凸部のうちの残りの2個の前記凸部のそれぞれと前記任意の凸部との間に凹部が存在するように、配置されることを特徴とする積層体の製造方法。 - 前記任意の凸部を中心に交差する3方向のうち、2方向に沿って前記凸部と前記連結部とが交互に配置され、残りの一方向に沿って前記前記凸部と前記凹部とが交互に配置される請求項8に記載の積層体の製造方法。
- 前記原型を製造する工程をさらに有し、
該工程は、
基体上にレジスト膜を成膜する工程と、
該レジスト膜の表面に、第1の方向に沿って光強度が変化する第1の干渉縞を露光する工程と、
該レジスト膜の表面に、前記第1の方向と交差する第2の方向に沿って光強度が変化する第2の干渉縞を露光する工程と、
前記第1及び第2の干渉縞の露光後に、前記レジスト膜を現像する工程とを有する請求項8又は9に記載の積層体の製造方法。 - 前記第1の方向と前記第2の方向とのなす角が60°である請求項10に記載の積層体の製造方法。
- 前記第1の方向と前記第2の方向とのなす角が90°である請求項10に記載の積層体の製造方法。
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JP2011154338A (ja) * | 2009-09-02 | 2011-08-11 | Sony Corp | 透明導電性電極、タッチパネル、情報入力装置、および表示装置 |
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US10954157B2 (en) | 2012-10-12 | 2021-03-23 | Corning Incorporated | Articles having retained strength |
US11434166B2 (en) | 2012-10-12 | 2022-09-06 | Corning Incorporated | Articles with a low-elastic modulus layer and retained strength |
US11440837B2 (en) | 2012-10-12 | 2022-09-13 | Corning Incorporated | Articles having retained strength |
US11479501B2 (en) | 2012-10-12 | 2022-10-25 | Corning Incorporated | Articles with a low-elastic modulus layer and retained strength |
US11919803B2 (en) | 2012-10-12 | 2024-03-05 | Corning Incorporated | Articles with a low-elastic modulus layer and retained strength |
US20140293162A1 (en) * | 2013-04-01 | 2014-10-02 | Lg Electronics Inc. | Touch display unit and method for manufacturing the same |
CN104793778A (zh) * | 2014-01-21 | 2015-07-22 | 胜华科技股份有限公司 | 触控装置 |
JP2015184629A (ja) * | 2014-03-26 | 2015-10-22 | セイコーエプソン株式会社 | 液晶装置、及び電子機器 |
WO2016190247A1 (ja) * | 2015-05-25 | 2016-12-01 | 旭硝子株式会社 | 微細凹凸構造を表面に有する物品およびその製造方法 |
JP2017054713A (ja) * | 2015-09-10 | 2017-03-16 | 王子ホールディングス株式会社 | 金型、有機発光ダイオードの製造方法及び有機発光ダイオード |
Also Published As
Publication number | Publication date |
---|---|
TWI607874B (zh) | 2017-12-11 |
CN103988097A (zh) | 2014-08-13 |
US20140261677A1 (en) | 2014-09-18 |
CN103988097B (zh) | 2016-08-24 |
KR20140103264A (ko) | 2014-08-26 |
TW201331036A (zh) | 2013-08-01 |
JP6079637B2 (ja) | 2017-02-15 |
JPWO2013084900A1 (ja) | 2015-04-27 |
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