WO2014020836A1 - 光電変換装置用カバーガラス - Google Patents
光電変換装置用カバーガラス Download PDFInfo
- Publication number
- WO2014020836A1 WO2014020836A1 PCT/JP2013/004247 JP2013004247W WO2014020836A1 WO 2014020836 A1 WO2014020836 A1 WO 2014020836A1 JP 2013004247 W JP2013004247 W JP 2013004247W WO 2014020836 A1 WO2014020836 A1 WO 2014020836A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fine particles
- silica fine
- glass plate
- cover glass
- average
- Prior art date
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- 239000006059 cover glass Substances 0.000 title claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 199
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 97
- 239000011521 glass Substances 0.000 claims abstract description 78
- 238000002834 transmittance Methods 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 15
- 230000001629 suppression Effects 0.000 claims abstract description 10
- 239000010419 fine particle Substances 0.000 claims description 103
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 239000011859 microparticle Substances 0.000 abstract 4
- 239000011248 coating agent Substances 0.000 description 36
- 238000000576 coating method Methods 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 35
- 239000000243 solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- -1 silicon alkoxide Chemical class 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012935 Averaging Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007372 rollout process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000006103 coloring component Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JZOLATIJRQNCPM-UHFFFAOYSA-N O.O.O.O.O.O.O.O.[Zr] Chemical compound O.O.O.O.O.O.O.O.[Zr] JZOLATIJRQNCPM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
-
- 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
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- 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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0294—Diffusing elements; Afocal elements characterized by the use adapted to provide an additional optical effect, e.g. anti-reflection or filter
-
- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- 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
- H01L31/0256—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 the material
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/20—Optical components
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/20—Optical components
- H02S40/22—Light-reflecting or light-concentrating means
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- 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
- Y02E10/52—PV systems with concentrators
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24421—Silicon containing
Definitions
- the present invention relates to a cover glass for a photoelectric conversion device, which is disposed on the light incident side of the photoelectric conversion device and transmits light to the photoelectric conversion layer in the device while protecting the photoelectric conversion device.
- a cover glass is usually disposed on the light incident side of a so-called crystalline photoelectric conversion device.
- reflected light from the cover glass may be annoying to neighboring houses. For this reason, when consideration should be given to reflected light such as installing a photoelectric conversion device on the roof of a house, a cover glass having an uneven surface is used so that the reflected light is dispersed.
- Patent Document 1 discloses a cover glass having a hemispherical recess formed on the surface.
- the shape and arrangement of the concave portions of the cover glass are designed so that the amount of light transmitted through the cover glass increases during the day and throughout the year.
- the depth of the concave portion is set deeper than that for the purpose of only anti-glare.
- a reflection suppressing film may be formed on the surface of the substrate.
- the most commonly used antireflection film is a dielectric film formed by a vacuum deposition method, a sputtering method, a chemical vapor deposition method (CVD method), or the like, but a fine particle-containing film containing fine particles such as silica fine particles is used as the antireflection film.
- the fine particle-containing film is formed by applying a coating liquid containing fine particles on a transparent substrate by dipping, flow coating, spraying, or the like.
- Patent Document 2 discloses a reflection suppressing film in which the shape of the surface irregularities of the glass plate and the number of laminated silica fine particles at the bottom of the surface irregularities and the top of the surface irregularities are adjusted.
- a cover glass for a photoelectric conversion device provided is disclosed. This cover glass has a reflectance of 1.5% or more and 3% or less over the entire wavelength range of 380 nm to 780 nm with respect to light incident from the side on which the reflection suppressing film is formed. Is suppressed.
- the cover glass for a photoelectric conversion device in which a reflection suppression film containing silica fine particles is formed on the surface irregularities of the glass plate, the average transmission of the glass plate alone from the average transmittance of the cover glass with respect to light incident from the reflection suppression film side
- the transmittance gain obtained by subtracting the rate is an important performance as a cover glass for a photoelectric conversion device.
- the cover glass described in Patent Document 2 has room for further improving the transmittance gain.
- an object of the present invention is to increase the transmittance gain of a cover glass in a cover glass for a photoelectric conversion device in which a reflection suppressing film containing silica fine particles is formed on the surface irregularities of a glass plate.
- the present invention provides the following cover glass for a photoelectric conversion device.
- the surface unevenness of the glass plate has an average interval Sm of 0.3 mm to 2.5 mm, and an arithmetic average roughness Ra of 0.3 ⁇ m to 5 ⁇ m
- the antireflection film includes silica fine particles having an average particle diameter of 50 to 200 nm and a binder of the silica fine particles, At the top of the surface irregularities, the silica fine particles are uniformly arranged in one layer so that the filling rate F defined by the following formula is 35 to 65%, From the average transmittance when light having a wavelength of 380 to 1100 nm is incident from the surface on the reflection suppression film side, the average transmittance when light of the wavelength is incident on the glass plate from the surface having the surface irregularities of the glass plate A cover glass for a photoelectric conversion device having a transmittance gain of 2.37% or
- A The number of silica fine particles contained in a square region whose side is 10 times the average particle size of the silica fine particles.
- B A sphere having the same diameter as the average particle size of the silica fine particles is the largest in the square region. The number of spheres filled, assuming a dense packing
- the average particle diameter of the silica fine particles contained in the antireflection film is 50 to 200 nm, and the silica fine particles are uniform so that the filling rate F is 35 to 65% at the top of the surface unevenness. Is arranged. For this reason, since the silica fine particles are arranged at an appropriate density on the top of the surface irregularities, the cover glass of the present invention exhibits a high transmission gain.
- the cover glass for a photoelectric conversion device includes a glass plate having surface irregularities and a reflection suppressing film formed on the surface irregularities of the glass plate.
- the average interval Sm of the surface irregularities of the glass plate is 0.3 mm or more and 2.5 mm or less.
- the average distance Sm is preferably 0.3 mm or more, particularly 0.4 mm or more, especially 0.45 mm or more, 2.5 mm or less, further 2.1 mm or less, particularly 2.0 mm or less, especially 1.5 mm or less.
- the average interval Sm is particularly preferably 0.5 mm or more and 1.5 mm or less.
- the average interval Sm means the average value of the intervals of one mountain valley obtained from the point where the roughness curve intersects the average line, and is specifically defined in JIS (Japanese Industrial Standards) B0601-1994. Value. If the average interval Sm is too small, the influence of light having a wavelength in the vicinity of the visible range from the surface irregularities is averaged, and the reflectance curve is not sufficiently flattened. On the other hand, if the average interval Sm is too large, color unevenness appears in the surface of the reflection color tone, and the requirement for appearance is not satisfied.
- a template glass produced by a roll-out method is suitable.
- the roll-out method is a method for producing a glass plate that has been conventionally used for producing a template glass mainly used as a window glass of a building.
- a molten glass raw material is sandwiched between a pair of rolls and formed into a plate shape. If irregularities are provided on the surface of the roll, the shape corresponding to the irregularities is the surface of the glass plate. Is transferred to.
- a glass plate having surface irregularities can also be obtained by roughening a glass plate having a flat surface by etching.
- a glass plate may be the same composition as normal plate glass and building plate glass, it is preferable that a coloring component is not included as much as possible.
- the content of iron oxide, which is a typical coloring component is preferably 0.06% by mass or less, particularly preferably 0.02% by mass or less in terms of Fe 2 O 3 .
- the surface irregularities of the glass plate preferably have a maximum height Ry of 0.5 ⁇ m to 10 ⁇ m, particularly 1 ⁇ m to 8 ⁇ m, with an average interval Sm in the above range.
- the surface irregularities of the glass plate have an arithmetic average roughness Ra of 0.3 ⁇ m to 5.0 ⁇ m, particularly 0.4 ⁇ m to 2.0 ⁇ m, and further 0.5 ⁇ m to 1.2 ⁇ m, with an average interval Sm in the above range. It is preferable.
- the maximum height Ry and the arithmetic average roughness Ra are defined in JIS B0601-1994 together with the average interval Sm. If the roughness represented by these indices is too small, the antiglare effect due to surface irregularities cannot be sufficiently obtained. On the other hand, if the roughness expressed by these indicators is too large, color unevenness appears in the surface of the reflection color tone, or a film is not formed on the top of the convex portion, and the reflectance increases. .
- the average inclination angle ⁇ decreases, the irregularities on the glass surface become gentler, and when the film is formed, it is difficult to form a sufficient film thickness distribution, which may cause poor appearance.
- the average inclination angle ⁇ increases, the unevenness of the glass surface becomes steeper, the film is not formed on the top of the convex part, and the glass plate may be exposed, so that the reflectance tends to increase.
- the antireflection film contains silica fine particles, and the silica fine particles constitute the skeleton of the film.
- the silica fine particles are arranged so as to be a single layer (in other words, without being stacked on each other).
- the silica fine particles are laminated so as to have a thickness corresponding to, for example, 1.5 to 2.1 times the average particle diameter of the silica fine particles at the bottom of the surface irregularities.
- the film thickness of the silica fine particles can be confirmed by actually observing the cross section of the antireflection film using a scanning electron microscope (SEM) or the like.
- the reflectance curve from the cover glass in the visible range is flattened by the difference in the thickness of the reflection suppressing film of silica fine particles. For this reason, it is possible to suppress deterioration in appearance (color unevenness) due to uneven reflection.
- the average particle diameter of the silica fine particles is, for example, 50 to 200 nm, preferably 75 to 150 nm, and more preferably 75 to 120 nm.
- the “average particle size” means a particle size (D50) corresponding to 50% volume accumulation in the particle size distribution measured by the laser diffraction particle size distribution measurement method.
- silica fine particles having an average particle diameter in the above range are uniformly arranged in a relatively sparse state. Specifically, the silica fine particles are uniformly arranged at the top of the surface irregularities so that the filling rate F defined by the following formula is 35 to 65%.
- F A / B ⁇ 100
- A Number of silica fine particles contained in a square region whose one side is 10 times the average particle size of the silica fine particles
- B A sphere having the same diameter as the average particle size of the silica fine particles in the square region The number of filled spheres when it is assumed that the spheres are packed most closely.
- the values of A and B are counted only when the entire sphere is completely included in the square area, and the spheres partially included are counted. Ask without.
- “Uniformly arranged” means that when the arrangement state of the silica fine particles of the antireflection film at the top of the surface unevenness is observed with an SEM, the distance between the silica fine particles (adjacent to each other) This refers to a state in which the silica fine particles are arranged so that a portion where the distance between the central tubes of the silica fine particles is extremely large is not observed.
- “uniformly arranged” refers to a state in which the silica fine particles are arranged so that the interval between the silica fine particles is within 1.1 to 1.6 times the average particle diameter of the silica fine particles.
- the filling rate F indicates a dense state of silica fine particle arrangement. If the filling rate F is larger than 65% and the silica fine particles arranged on the top of the surface irregularities are excessively dense, it is difficult to increase the transmittance gain. On the other hand, when the filling rate F is less than 35%, it is difficult to arrange the silica fine particles uniformly, and it is difficult to increase the transmittance gain.
- the filling factor F is preferably 40 to 60%, more preferably 45 to 55%.
- the transmittance gain is a glass plate on the surface having surface irregularities before forming the reflection suppressing film from the average transmittance when light having a wavelength of 380 to 1100 nm is incident on the surface of the cover glass facing the reflection suppressing film. Is a value obtained by subtracting the average transmittance when light having a wavelength of 380 to 1100 nm is incident.
- silica fine particles hollow silica fine particles are also commercially available, but in antireflection films formed on the cover glass for photoelectric conversion devices, wear resistance should be emphasized, so solid (non-hollow) silica fine particles Use is preferred.
- the antireflection film contains a binder of silica fine particles together with the silica fine particles.
- the binder is interposed between the silica fine particles and the glass plate and between the adjacent silica fine particles, and plays a role of increasing the bonding strength between them.
- metal oxides such as silicon, titanium, aluminum, zirconium, and tantalum are suitable, but silicon oxide (silica) is most suitable.
- Silicon oxide is excellent as a reinforcing agent because of its high affinity with silica fine particles and glass plates, and does not inhibit the antireflection effect of the antireflection film because of its low refractive index. Silicon is not normally classified as a metal as an element, but in accordance with common practice, here, silicon oxide (compound) is one type of metal oxide (compound).
- a hydrolyzable metal compound typified by silicon alkoxide can be used as a binder supply source.
- silicon alkoxide examples include tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.
- the hydrolyzable metal compound may be made into a binder by hydrolysis and condensation polymerization by a so-called sol-gel method.
- the hydrolysis of the hydrolyzable metal compound is preferably carried out in a solution containing silica fine particles. Because the condensation polymerization reaction between silanol groups present on the surface of silica fine particles and silanol groups generated by hydrolysis of metal compounds such as silicon alkoxide is promoted, and the ratio of the binder that contributes to improving the binding power of silica fine particles is increased. It is. Specifically, it is preferable to prepare a coating solution for the antireflection film by sequentially adding a hydrolysis catalyst and silicon alkoxide while stirring a solution containing silica fine particles.
- the ratio of the silica fine particles to the binder in the antireflection film is preferably 88:12 to 93: 7, more preferably 89:11 to 92: 8, and particularly 89:11 to 91: 9, based on weight.
- the reflection suppression film composed of the silica fine particles and the binder having this ratio range can secure an appropriate gap between the skeletons of the silica fine particles, so that the transmittance gain of the cover glass can be increased. Further, voids are secured between the skeletons of the silica fine particles, the apparent refractive index of the film is lowered, the reflection suppressing effect is increased, and the binder contributes to maintaining the strength of the skeleton of the silica fine particles. When the ratio of the binder is too high, voids between the silica fine particles are lost. On the other hand, when the binder ratio is too low, the strength of the skeleton of the silica fine particles is lowered.
- zirconium oxide (zirconia, ZrO 2 ), which is a metal oxide, is further added to the reflection suppressing film in addition to the silica fine particles and the binder.
- the content of zirconium oxide in the antireflection coating is preferably 3 to 6% by weight, more preferably 4 to 6% by weight, and particularly preferably 4.3 to 6.0% by weight.
- the addition of zirconium oxide increases the transmittance gain. The reason why the transmittance gain is improved in the specific range of the zirconium oxide content is not clear. The inventors consider that for this reason, if the binder contains zirconium oxide, the binder becomes denser, the porosity of the film increases, and the apparent refractive index of the film decreases.
- the transmittance gain can be increased to, for example, 2.37% or more, further 2.39% or more, and in some cases, 2.40% or more.
- the addition of zirconium oxide improves the alkali resistance of the antireflection film.
- the absolute value of the difference in transmittance measured before and after the alkali resistance evaluation test described later is preferably 1.5% or less. More preferably, it is 0% or less.
- the antireflection film may contain titanium oxide (titania, TiO 2 ).
- a dielectric multilayer film formed by sputtering, CVD, or the like for example, an alternating laminated film of a high refractive index film made of titanium oxide or the like and a low refractive index film made of silicon oxide or the like
- vacuum A low refractive index film formed by a vapor deposition method for example, a magnesium fluoride film formed by a vacuum vapor deposition method
- the film thickness distribution described above can be easily realized as shown in the examples described later.
- the fine particle-containing film can be formed by supplying a coating liquid containing silica fine particles and a compound serving as a binder supply source to the surface of the glass plate, and then drying and further heating.
- the coating solution can be supplied by, for example, immersing the glass plate in the coating solution (dipping), but the method of spraying the coating solution onto the glass plate is excellent in production efficiency and suitable for mass production. ing.
- the spray method is suitable for mass production in terms of production efficiency, but has a problem that non-uniformity in film thickness tends to occur when applied to mass production. This non-uniformity is caused by the overlapping of the mist-like coating liquid released from the spray gun and the distribution of the mist (spray pattern), and appears as color unevenness of a reflection color tone having a diameter of about several millimeters.
- a method for forming an antireflection film on the surface irregularities of the glass plate by the spray method will be described.
- a glass plate having surface irregularities in the above range is prepared.
- a coating liquid containing silica fine particles and a metal compound serving as a supply source of the silica fine particle binder is sprayed on the surface irregularities of the glass plate.
- the spraying of the coating liquid is performed, for example, using a spray gun that keeps a distance from the glass plate constant from above the horizontally held glass plate.
- the glass plate sprayed with the coating liquid is placed in an electric furnace at 400 ° C. for 46 seconds, for example, and the coating liquid is dried to remove the solvent and the like contained in the coating liquid. Further, the glass plate is placed in an electric furnace at, for example, 610 ° C. for 8 minutes to generate an oxide from the metal compound contained in the coating liquid, thereby generating a binder of silica fine particles.
- the surfactant is added to the coating solution.
- a silicon-based surfactant or a fluorine-based surfactant is suitable.
- the concentration of the surfactant in the coating liquid is preferably 0.005% by weight to 0.5% by weight, particularly 0.01% by weight to 0.3% by weight.
- the addition of a surfactant reduces the surface tension of the coating solution and promotes the aggregation of fine particles as the liquid film is concentrated when the coating solution supplied to the surface of the glass plate dries. It is considered that a preferable antireflection film is formed by depositing fine particles in the concave portion of the glass plate.
- the reflectance curve (reflection spectrum) of the surface on which the antireflection coating was formed was measured.
- the measurement was performed in accordance with JIS K5602 by making light incident from the normal direction and introducing directly reflected light having a reflection angle of 8 ° into the integrating sphere.
- the average reflectance was calculated by averaging the reflectance at wavelengths of 380 nm to 1100 nm.
- the reflectance curve of the cover glass before and after the formation of the antireflection film was measured.
- a reflectance loss was obtained by subtracting the average reflectance after forming the reflection suppressing film from the average reflectance before forming the reflection suppressing film.
- a black paint was applied to the back surface (non-measurement surface) of the glass plate to remove the reflected light from the back surface, and correction based on the reference specular reflector was performed.
- the transmittance curves (transmission spectra) of the cover glass before and after the formation of the antireflection film were measured.
- the average transmittance was calculated by averaging the transmittance at a wavelength of 380 to 1100 nm.
- a value obtained by subtracting the average transmittance before forming the reflection suppressing film from the average transmittance after forming the reflection suppressing film was defined as a transmittance gain.
- A A specific reflected color is uniformly distributed.
- ⁇ The difference in location is recognized in the reflected color tone, but the uniformity is good.
- ⁇ Reflective color tone varies depending on the location, resulting in poor uniformity.
- X The difference in reflected color tone depending on the location is quite large, and the uniformity is poor.
- the antireflection film was observed with a field emission scanning electron microscope (FE-SEM) (S-4500, manufactured by Hitachi, Ltd.).
- FE-SEM field emission scanning electron microscope
- the thickness of the reflection suppressing film in the concave portion (bottom portion) of the reflection suppressing film was measured.
- the average value of the thickness of the antireflection film in the concave portion (bottom) of the glass plate determined for the five measurement points from the FE-SEM photograph was taken as the thickness of the antireflection film.
- the alkali resistance of the obtained antireflection film was evaluated by the following method.
- the cover glass on which the antireflection film was formed was immersed in a saturated calcium hydroxide aqueous solution at a temperature of 40 ° C. for 9 hours.
- the appearance change before and after immersion was observed visually, and the transmittance before and after immersion was measured with a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the alkali resistance was evaluated by the absolute value of the difference.
- Salt spray test In order to evaluate the salt water resistance of the obtained antireflection film, a salt spray test was performed. An aqueous NaCl solution having a temperature of 35 ° C. and a concentration of 5% by mass was sprayed on the cover glass on which the antireflection coating was formed for 96 hours. The transmittance of NaCl aqueous solution before and after spraying was measured with a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the salt water resistance was evaluated based on the absolute value thereof.
- NDH2000 haze meter
- Example 1 ⁇ Preparation of coating solution> Silica fine particle dispersion (manufactured by Fuso Chemical Industry Co., Ltd., PL-7, average particle size 100 nm, solid content concentration 23 wt%) 39.1 parts by weight, ethyl cellosolve 56.4 parts by weight, 1N hydrochloric acid (hydrolysis catalyst) 1 weight Then, 3.5 parts by weight of tetraethoxysilane was added with further stirring, followed by stirring for 8 hours while keeping the temperature at 40 ° C. to obtain a stock solution. The solid concentration in this stock solution was 9% by weight, and the ratio of fine particles to binder (as oxide) in the solid was 90:10 on a weight basis. The silica fine particles were solid (in other words, not hollow) fine particles.
- a template glass (manufactured by Nippon Sheet Glass Co., Ltd., 100 mm ⁇ 300 mm, thickness 3.2 mm) made of a soda lime silicate composition was subjected to alkaline ultrasonic cleaning to prepare a substrate for forming a reflection suppressing film.
- the surface shape of this template glass was arithmetic average roughness Ra 1.1 ⁇ m of surface irregularities, maximum height Ry 4.8 ⁇ m, average interval Sm 0.79 ⁇ m, and average inclination angle ⁇ 0.32 °.
- the average reflectance was 4.5% and the average transmittance was 91.6%.
- the coating liquid was applied on the template glass by the spray method.
- the spray method was performed by spraying the coating liquid from above the template glass held horizontally using a commercially available spray gun. At this time, the spray gun was relatively moved between the spray gun and the template glass while keeping the distance from the template glass constant.
- this template glass was put into an electric furnace at 400 ° C. for 46 seconds to remove the solvent of the coating solution, and further put into an electric furnace at 610 ° C. for 8 minutes to fire the antireflection film, thereby obtaining a cover glass.
- the above-mentioned characteristics were evaluated for the cover glass thus obtained.
- the evaluation results are shown in Table 1.
- FIG. 1 (top) and FIG. 2 (bottom) show the results of observing the cross section of the produced antireflection film using FE-SEM.
- Example 2 to Example 8 Covers according to Comparative Examples 2 to 8 in the same manner as in Example 1, with the ratio of each raw material and the conditions (drying conditions and firing conditions) for forming the antireflection coating when preparing the stock solution and coating solution as shown in Table 2. Glass was obtained. As shown in Table 2, in Example 3 and Example 4, “CoatOSil3505” manufactured by Momentive Performance Materials Japan was used as the silicon surfactant. The above characteristics were evaluated for the cover glasses according to Examples 2 to 8 obtained as described above. The evaluation results are shown in Table 1.
- silica fine particles were uniformly arranged on the top of the surface irregularities of the glass plate of Example 1.
- the filling rate (filling rate) of silica fine particles at the top of the surface irregularities of Example 1 was 49.4%.
- the silica fine particles were arranged in a denser state than Example 1 at the top of the surface irregularities of the glass plate of Comparative Example 1.
- the filling rate of Comparative Example 1 was 67.2%.
- the silica fine particles were arranged in a sparser state than Example 1 at the top of the surface irregularities of the glass plate of Comparative Example 2.
- the filling rate of Comparative Example 2 was 29.9%.
- corrugation was seen in some places.
- the silica fine particles were not uniformly arranged on the top of the surface irregularities of the glass plate of Comparative Example 2.
- the transmittance gain of Example 1 was 2.46, whereas the transmittance gain of Comparative Example 1 was 2.05, and the transmittance gain of Comparative Example 2 was 2.35. Met. This suggests that a cover glass having a silica fine particle filling rate in the range of 35 to 65% at the top of the surface irregularities of the glass plate exhibits a high transmittance gain of 2.40% or more.
- the thickness of the antireflection film at the bottom of the surface irregularities of Comparative Example 1 is 3.6 times the average particle size of 100 nm of the silica fine particles
- the thickness of the antireflection film at the bottom of the surface irregularities of Comparative Example 3 is The thickness was 2.3 times the average particle size of the silica fine particles.
- the thickness of the antireflection film at the bottom of the surface irregularities of Comparative Example 8 was 1.2 times the average particle diameter of the silica fine particles.
- the thickness of the antireflection film at the bottom of the surface irregularities of Examples 1 to 8 was in the range of 1.5 to 2.1 times the average particle diameter of 100 nm of silica fine particles.
- the transmittance gains according to Comparative Example 1 and Comparative Example 8 are lower than the transmittance gains according to Examples 1 to 8, for example.
- the silica fine particles are preferably laminated at a height corresponding to 1.5 to 2.1 times the average particle diameter of the silica fine particles at the bottom of the surface unevenness. It was done.
- Comparative Example 4 did not contain ZrO 2 .
- the amount of ZrO 2 added in Comparative Example 5 was 2.44% by weight, which was smaller than the amount of ZrO 2 added in Examples 1 to 8.
- the transmittance gains of Comparative Example 4 and Comparative Example 5 were smaller than those of Examples 1-8.
- ZrO 2 contained in the antireflection film of the cover glass has been suggested that preferably not less than 3 wt%.
- Comparative Example 6 and Comparative Example 7 contained more ZrO 2 than Examples 1 to 8, but the transmittance gains of Comparative Examples 6 and 7 were the same as those of Examples 1 to 8. It was smaller than the rate gain.
- ZrO 2 contained in the reflection suppression film of the cover glass is preferably 6% by weight or less. From the above, in order for the cover glass to exhibit a high transmittance gain, ZrO 2 contained in the antireflection coating is preferably 3 to 6% by weight, more preferably 4 to 6% by weight, and 4.3 to 6.0% by weight. % Was particularly preferred.
- the ratio between the silica fine particles and the binder was 90:10 on a weight basis.
- Comparative Example 1 and Comparative Example 2 the ratio between the silica fine particles and the binder was 85:15 on a weight basis.
- the transmittance gains of Comparative Examples 1 and 2 are smaller than the transmittance gains of Examples 1 to 8. Therefore, in order for the cover glass to exhibit a high transmittance gain, the ratio of the silica fine particles to the binder in the antireflection coating is preferably 88:12 to 93: 7, and 89:11 to 92: 8 on a weight basis. It was suggested that 89:11 to 91: 9 is more preferable.
- the absolute value of the transmittance change of the cover glasses of Examples 1 to 4 is 1% or less, and the cover glasses of Examples 1 to 4 show practical salt water resistance. It was.
- the absolute value of the transmittance change of the cover glasses of Examples 1 to 6 and Example 8 is 1% or less as a result of the evaluation of alkali resistance, and the cover glasses of Examples 1 to 6 and Example 8 Showed practical alkali resistance.
- the average reflectance of the cover glasses according to Examples 1 to 8 was smaller than 2.0%. Further, the reflectance loss of the cover glasses according to Examples 1 to 8 was larger than 2.50%.
- a cover glass for a photoelectric conversion device exhibiting a high transmittance gain can be provided.
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Abstract
Description
表面凹凸を有するガラス板と、
前記ガラス板の前記表面凹凸上に形成された反射抑制膜と、を備え、
前記ガラス板の前記表面凹凸は、0.3mm以上2.5mm以下の平均間隔Sm、及び0.3μm~5μmの算術平均粗さRaを有し、
前記反射抑制膜が、平均粒径が50~200nmであるシリカ微粒子と前記シリカ微粒子のバインダーとを含み、
前記表面凹凸の頂部において、前記シリカ微粒子は、1層に、かつ、以下の式で定義される充填率Fが35~65%となるように、均一に配置されており、
前記反射抑制膜側の面から波長380~1100nmの光を入射したときの平均透過率から前記ガラス板の前記表面凹凸を有する面から前記ガラス板に前記波長の光を入射したときの平均透過率を差し引いた透過率ゲインが2.37%以上である、光電変換装置用カバーガラス。
F=A/B×100
A:1辺が前記シリカ微粒子の平均粒径の10倍である正方領域に含まれている前記シリカ微粒子の個数
B:前記正方領域に前記シリカ微粒子の平均粒径と同一の直径の球を最密に充填したと仮定したときの当該球の充填数
F=A/B×100
A:1辺が前記シリカ微粒子の平均粒径の10倍である正方領域に含まれている前記シリカ微粒子の個数
B:上記の正方領域に前記シリカ微粒子の平均粒径と同一の直径の球を最密に充填したと仮定したときの当該球の充填数
ここで、A及びBの値は、正方領域に球の全体が完全に含まれるもののみをカウントし、部分的に含まれる球をカウントせずに求める。
非接触三次元形状測定装置(三鷹光器株式会社製、NH-3N)を用い、JIS B0601-1994に準じて、評価長さ5.0mm、カットオフ値2.5mmとして、基板として用いた型板ガラスの表面凹凸の算術平均粗さRa、最大高さRy、平均間隔Smを測定点10点における値を平均して求めた。また、算術平均粗さRa及び平均間隔Smを用いて、平均傾斜角θを求めた。
分光光度計(島津製作所社製、UV-3100)を用い、反射抑制膜を形成した面の反射率曲線(反射スペクトル)を測定した。測定は、JIS K5602に準拠し、法線方向から光を入射させ、反射角8°の直接反射光を積分球に導入して行った。平均反射率は、波長380nm~1100nmにおける反射率を平均化して算出した。また、反射抑制膜の形成前後におけるカバーガラスの反射率曲線を測定した。反射抑制膜を形成する前の平均反射率から反射抑制膜を形成した後の平均反射率を差し引いたものを反射率ロスとした。なお、測定に際しては、ガラス板裏面(非測定面)に黒色塗料を塗布して裏面からの反射光を除き、基準鏡面反射体に基づく補正を行った。
上記分光光度計を用い、反射抑制膜の形成前後におけるカバーガラスの透過率曲線(透過スペクトル)をそれぞれ測定した。平均透過率は、波長380~1100nmにおける透過率を平均化して算出した。反射抑制膜を形成した後の平均透過率から、反射抑制膜を形成する前の平均透過率を差し引いた値を透過率ゲインとした。
目視により、反射抑制膜を形成したカバーガラスの外観を下記基準で評価した。
◎ :特定の反射色が均一に分布している。
○ :反射色調に場所の違いは認められるが、均一性は良好である。
△ :場所によって反射色調が異なり、均一性に劣る。
× :場所による反射色調の差がかなり大きく、均一性は不良である。
反射抑制膜を電界放射型走査型電子顕微鏡(FE-SEM)(日立製作所社製、S-4500)によって観察した。また、反射抑制膜の凹部の30°斜め上方からの断面におけるFE-SEM写真から、反射抑制膜の凹部(底部)における反射抑制膜の厚みを測定した。FE-SEM写真から測定点5点について求めたガラス板の凹部(底部)における反射抑制膜の厚みの平均値を反射抑制膜の厚みとした。さらに、反射抑制膜の凸部(頂部)における真上からのFE-SEM写真において、1辺がシリカ微粒子の平均粒径の10倍である正方形を当てはめ、その正方形内に完全に含まれているシリカ微粒子の数をカウントした。直径がシリカ微粒子の平均粒径と同一の直径を有する球をその正方形内に最密に充填すると、その球を105個充填することができる。この最密充填した場合の球の充填数に対する上述のカウントしたシリカ微粒子の数の百分率を、反射抑制膜の凹部(底部)におけるシリカ微粒子の充填率とした。
得られた反射抑制膜の耐アルカリ性を、以下の方法により評価した。反射抑制膜を形成したカバーガラスを、温度40℃、水酸化カルシウム飽和水溶液に9時間浸漬した。浸漬前後の外観変化を目視により観察するとともに、浸漬前後の透過率をヘイズメータ(日本電色工業社製、NDH2000)により測定し、それらの差の絶対値によって耐アルカリ性を評価した。
得られた反射抑制膜の耐塩水性を評価するため、ソルトスプレーテストを実施した。反射抑制膜を形成したカバーガラスに、温度35℃、濃度5質量%のNaCl水溶液をミスト状にして96時間噴霧した。NaCl水溶液の噴霧前後の透過率をヘイズメータ(日本電色工業社製、NDH2000)により測定し、それらの絶対値によって耐塩水性を評価した。
<コーティング液の調製>
シリカ微粒子分散液(扶桑化学工業社製、PL-7、平均粒径100nm、固形分濃度23重量%)39.1重量部、エチルセロソルブ56.4重量部、1N塩酸(加水分解触媒)1重量部を撹拌混合し、さらに撹拌しながらテトラエトキシシラン3.5重量部を添加し、引き続き40℃に保温しながら8時間撹拌して原液を得た。この原液における固形分濃度は9重量%であり、固形分中の微粒子とバインダー(酸化物換算)との比率は、重量基準で90:10であった。なお、上記シリカ微粒子は、中実の(言い換えれば中空ではない)微粒子であった。
ソーダライムシリケート組成からなる型板ガラス(日本板硝子社製、100mm×300mm、厚さ3.2mm)をアルカリ超音波洗浄し、反射抑制膜を形成するための基板として準備した。この型板ガラスの表面形状は、表面凹凸の算術平均粗さRa1.1μm、最大高さRy4.8μm、平均間隔Sm0.79μm、平均傾斜角θ0.32°であった。なお、この型板ガラスの反射及び透過特性を上述の方法により測定したところ、平均反射率4.5%、平均透過率91.6%であった。
原液及びコーティング液を調製するときの各原料の比率、反射抑制膜を形成する条件(乾燥条件及び焼成条件)を表2の通りとし、実施例1と同様にして比較例2~8に係るカバーガラスを得た。表2に示す通り、実施例3及び実施例4において、シリコン系界面活性剤として、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製、「CoatOSil3505」を用いた。このようにして得た実施例2~8に係るカバーガラスに対して上記特性を評価した。評価結果を表1に示す。
原液及びコーティング液を調製するときの各原料の比率、反射抑制膜を形成する条件(乾燥条件及び焼成条件)を表3の通りとし、実施例1と同様にして比較例1~8に係るカバーガラスを得た。このようにして得た比較例1~8に係るカバーガラスに対して上記特性を評価した。評価結果を表4に示す。また、比較例1に係るカバーガラスの反射抑制膜をFE-SEMを用いて断面観察をした結果を図3(頂部)、図4(底部)に示す。さらに、比較例2に係るカバーガラスの反射抑制膜をFE-SEMを用いて断面観察した結果を図5(頂部)、図6(底部)に示す。
Claims (6)
- 表面凹凸を有するガラス板と、
前記ガラス板の前記表面凹凸上に形成された反射抑制膜と、を備え、
前記ガラス板の前記表面凹凸は、0.3mm以上2.5mm以下の平均間隔Sm、及び0.3μm~5μmの算術平均粗さRaを有し、
前記反射抑制膜が、平均粒径が50~200nmであるシリカ微粒子と前記シリカ微粒子のバインダーとを含み、
前記表面凹凸の頂部において、前記シリカ微粒子は、1層に、かつ、以下の式で定義される充填率Fが35~65%となるように、均一に配置されており、
前記反射抑制膜側の面から波長380~1100nmの光を入射したときの平均透過率から前記ガラス板の前記表面凹凸を有する面から前記ガラス板に前記波長の光を入射したときの平均透過率を差し引いた透過率ゲインが2.37%以上である、光電変換装置用カバーガラス。
F=A/B×100
A:1辺が前記シリカ微粒子の平均粒径の10倍である正方領域に含まれている前記シリカ微粒子の個数
B:前記正方領域に前記シリカ微粒子の平均粒径と同一の直径の球を最密に充填したと仮定したときの当該球の充填数 - 前記ガラス板の前記表面凹凸は、0.5μm~1.0μmの算術平均粗さRaを有する請求項1に記載の光電変換装置用カバーガラス。
- 前記ガラス板の前記表面凹凸は、0.05~1.0度の平均傾斜角θを有する請求項1又は請求項2に記載の光電変換装置用カバーガラス。
- 前記表面凹凸の底部において、前記シリカ微粒子の平均粒径の1.5~2.1倍に相当する高さに前記シリカ微粒子が積層されている、請求項1に記載の光電変換装置用カバーガラス。
- 前記シリカ微粒子と前記バインダーとの比が、重量基準で、88:12~93:7である、請求項1に記載の光電変換装置用カバーガラス。
- 前記反射抑制膜はジルコニウム酸化物を3~6質量%含む、請求項1に記載の光電変換装置用カバーガラス。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015137196A1 (ja) * | 2014-03-14 | 2015-09-17 | 日本電気硝子株式会社 | ディスプレイのカバー部材及びその製造方法 |
EP2955553A3 (de) * | 2014-05-20 | 2016-03-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Lichtstreuendes schichtsystem, verfahren zu seiner herstellung und verwendung des schichtsystems |
US20180251398A1 (en) * | 2015-09-11 | 2018-09-06 | Nippon Electric Glass Co., Ltd. | Display cover member and production method therefor |
US20180292577A1 (en) * | 2015-10-01 | 2018-10-11 | Nippon Sheet Glass Company, Limited | Coated glass sheet and method for producing same |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2812613T3 (es) | 2014-06-30 | 2021-03-17 | Nippon Sheet Glass Co Ltd | Sustrato provisto de un recubrimiento de baja reflexión, método para su producción y dispositivo de conversión fotoeléctrica que lo contiene |
WO2016051750A1 (ja) * | 2014-09-30 | 2016-04-07 | 日本板硝子株式会社 | 低反射コーティング、ガラス板、ガラス基板、及び光電変換装置 |
WO2016051718A1 (ja) * | 2014-09-30 | 2016-04-07 | 日本板硝子株式会社 | 低反射コーティング、低反射コーティング付ガラス板、低反射コーティングを有するガラス板、ガラス基板、および光電変換装置 |
MY183280A (en) | 2015-01-29 | 2021-02-18 | Nippon Sheet Glass Co Ltd | Low-reflection coated glass sheet, method for producing low-reflection coated substrate, and coating liquid for forming low-reflection coating of low-reflection coated substrate |
US9903982B2 (en) * | 2015-03-04 | 2018-02-27 | Fujifilm Corporation | Antireflection article, polarizing plate, cover glass and image display device, and manufacturing method of antireflection article |
WO2016143297A1 (ja) | 2015-03-06 | 2016-09-15 | 日本板硝子株式会社 | コーティング膜付きガラス板及びその製造方法 |
JP6491934B2 (ja) * | 2015-04-13 | 2019-03-27 | 富士フイルム株式会社 | 反射防止物品の製造方法、及び反射防止物品 |
JP6650368B2 (ja) * | 2016-07-28 | 2020-02-19 | 日本板硝子株式会社 | 低反射コーティング付ガラス板、低反射コーティング付基材を製造する方法、及び低反射コーティング付基材の低反射コーティングを形成するためのコーティング液 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003243689A (ja) | 2001-12-13 | 2003-08-29 | Asahi Glass Co Ltd | 太陽電池用カバーガラス、その製法及び該カバーガラスを使用した太陽電池モジュール |
JP2009088503A (ja) * | 2007-09-14 | 2009-04-23 | Mitsubishi Chemicals Corp | 太陽電池用積層カバー基板、太陽電池、並びに、太陽電池用積層カバー基板の製造方法 |
WO2011070714A1 (ja) | 2009-12-11 | 2011-06-16 | 日本板硝子株式会社 | 光電変換装置用カバーガラスおよびその製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01164073A (ja) * | 1987-09-11 | 1989-06-28 | Canon Inc | 光電変換装置 |
EP1167313B1 (en) | 1999-12-13 | 2015-09-23 | Nippon Sheet Glass Co., Ltd. | Low-reflection glass article |
JP4527272B2 (ja) * | 1999-12-13 | 2010-08-18 | 日本板硝子株式会社 | 低反射ガラス物品 |
US6512170B1 (en) | 2000-03-02 | 2003-01-28 | Nippon Sheet Glass Co., Ltd. | Photoelectric conversion device |
JP5160574B2 (ja) * | 2000-03-02 | 2013-03-13 | 日本板硝子株式会社 | 光電変換装置 |
WO2003003076A1 (en) * | 2001-06-29 | 2003-01-09 | Nippon Sheet Glass Co., Ltd. | Light scattering reflection substrate-use photosensitive resin composition, light scattering reflection substrate, and production methods therefor |
JP2003124491A (ja) | 2001-10-15 | 2003-04-25 | Sharp Corp | 薄膜太陽電池モジュール |
CN100391011C (zh) * | 2001-12-13 | 2008-05-28 | 旭硝子株式会社 | 用于太阳能电池的防护玻璃罩 |
KR20110079107A (ko) * | 2009-12-31 | 2011-07-07 | 주식회사 효성 | 박막 태양전지 기판용 글라스 및 그를 포함하는 박막 태양전지의 제조방법 |
-
2012
- 2012-08-01 JP JP2012171266A patent/JP6039962B2/ja active Active
-
2013
- 2013-07-09 KR KR1020157003280A patent/KR101939871B1/ko active IP Right Grant
- 2013-07-09 WO PCT/JP2013/004247 patent/WO2014020836A1/ja active Application Filing
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- 2013-07-09 US US14/418,791 patent/US9664822B2/en active Active
- 2013-07-09 CN CN201380040559.0A patent/CN104508518B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003243689A (ja) | 2001-12-13 | 2003-08-29 | Asahi Glass Co Ltd | 太陽電池用カバーガラス、その製法及び該カバーガラスを使用した太陽電池モジュール |
JP2009088503A (ja) * | 2007-09-14 | 2009-04-23 | Mitsubishi Chemicals Corp | 太陽電池用積層カバー基板、太陽電池、並びに、太陽電池用積層カバー基板の製造方法 |
WO2011070714A1 (ja) | 2009-12-11 | 2011-06-16 | 日本板硝子株式会社 | 光電変換装置用カバーガラスおよびその製造方法 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015137196A1 (ja) * | 2014-03-14 | 2015-09-17 | 日本電気硝子株式会社 | ディスプレイのカバー部材及びその製造方法 |
JP2016153914A (ja) * | 2014-03-14 | 2016-08-25 | 日本電気硝子株式会社 | ディスプレイのカバー部材及びその製造方法 |
JPWO2015137196A1 (ja) * | 2014-03-14 | 2017-04-06 | 日本電気硝子株式会社 | ディスプレイのカバー部材及びその製造方法 |
EP2955553A3 (de) * | 2014-05-20 | 2016-03-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Lichtstreuendes schichtsystem, verfahren zu seiner herstellung und verwendung des schichtsystems |
US20180251398A1 (en) * | 2015-09-11 | 2018-09-06 | Nippon Electric Glass Co., Ltd. | Display cover member and production method therefor |
US11884576B2 (en) * | 2015-09-11 | 2024-01-30 | Nippon Electric Glass Co., Ltd. | Display cover member and production method therefor |
US20180292577A1 (en) * | 2015-10-01 | 2018-10-11 | Nippon Sheet Glass Company, Limited | Coated glass sheet and method for producing same |
US10908320B2 (en) * | 2015-10-01 | 2021-02-02 | Nippon Sheet Glass Company, Limited | Coated glass sheet and method for producing same |
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