WO2011070714A1 - 光電変換装置用カバーガラスおよびその製造方法 - Google Patents

光電変換装置用カバーガラスおよびその製造方法 Download PDF

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WO2011070714A1
WO2011070714A1 PCT/JP2010/006515 JP2010006515W WO2011070714A1 WO 2011070714 A1 WO2011070714 A1 WO 2011070714A1 JP 2010006515 W JP2010006515 W JP 2010006515W WO 2011070714 A1 WO2011070714 A1 WO 2011070714A1
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Prior art keywords
cover glass
glass
photoelectric conversion
surface irregularities
conversion device
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PCT/JP2010/006515
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English (en)
French (fr)
Japanese (ja)
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小用瑞穂
山本透
河津光宏
木戸優敦
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日本板硝子株式会社
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Priority to CN201080056103.XA priority Critical patent/CN102782528B/zh
Priority to JP2011545051A priority patent/JP5718825B2/ja
Priority to US13/513,972 priority patent/US9188705B2/en
Priority to EP10835645.2A priority patent/EP2511738B1/en
Priority to KR1020127017014A priority patent/KR101771757B1/ko
Publication of WO2011070714A1 publication Critical patent/WO2011070714A1/ja

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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
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
    • 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
    • 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
    • G02B1/115—Multilayers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates
    • 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
    • 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
    • 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, in an application where consideration should be given to reflected light, such as for a 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 recesses 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. When the concave portion is formed for such a purpose, 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 a fine particle-containing film is formed as a reflection suppressing film, not on a cover glass, but on the surface of a glass substrate of a so-called thin film photoelectric conversion device. It is disclosed. However, as described in this publication, float glass having a smooth surface is used for a glass substrate used in a thin film photoelectric conversion device.
  • Patent Document 1 an increase in the amount of light transmitted through a cover glass having surface irregularities has been attempted so far mainly by improving the shape of the surface irregularities. For this reason, the details of the antireflection film to be formed on the surface irregularities of the cover glass have hardly been studied so far.
  • An object of the present invention is to suppress unevenness in the appearance of a cover glass for a photoelectric conversion device provided with a glass plate having irregularities on the surface and a reflection suppressing film formed on the surface.
  • the present invention is a cover glass for a photoelectric conversion device provided with a glass plate having surface irregularities, further comprising a reflection suppressing film formed on the surface irregularities of the glass plate, wherein the reflection suppressing film comprises silica fine particles And a binder of the silica fine particles, the silica fine particles are arranged in one layer at the top of the surface unevenness, and the silica fine particles are laminated at a thickness corresponding to at least three layers at the bottom of the surface unevenness.
  • the surface irregularities of the glass plate have an average interval Sm of 0.4 mm to 2.5 mm, and an arithmetic average roughness Ra of 0.5 ⁇ m to 5 ⁇ m, and the antireflection film is formed.
  • a cover glass for a photoelectric conversion device that 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. .
  • the antireflection film basically suppresses the reflectance of light by utilizing the interference between the reflected light from the interface with the base and the reflected light from the interface with the air. And at a specific wavelength determined according to the refractive index of the film and the thickness of the film. In the cover glass of a photoelectric conversion device, this wavelength is usually set in the visible region or in the vicinity thereof. Therefore, when a reflection suppressing film is formed, a specific reflected color is easily visually recognized. Unevenness due to differences is more noticeable.
  • the cover glass according to the present invention a glass plate having a relatively large unevenness period is used, and the antireflection film is configured so that the number of laminated silica fine particles at the top and bottom of the unevenness is different, which corresponds to the visible region.
  • the reflectance curve was extremely flattened so that unevenness in the appearance of the cover glass was not easily recognized.
  • 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 0.1 mm or more and 5.0 mm or less.
  • the average interval Sm is preferably 0.2 mm or more, particularly 0.4 mm or more, particularly 1.0 mm or more, 3.0 mm or less, more preferably 2.5 mm or less, particularly 2.1 mm or less, especially 2.0 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 transcribed.
  • 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 roughness of the glass plate is 0.1 ⁇ m to 10 ⁇ m, particularly 0.5 ⁇ m to 5.0 ⁇ m, more preferably 0.5 ⁇ m to 2.0 ⁇ m, especially 0.5 ⁇ m to 1.0 ⁇ m, together with the average interval Sm in the above range. It is preferable to have an arithmetic average roughness Ra.
  • 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 indices 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 arranged so as to have a thickness corresponding to 3 layers or more, preferably 4 layers or more, at the bottom of the surface unevenness.
  • the reflection curve from the cover glass in the visible region is flattened by the film thickness distribution of the reflection suppressing film caused by the difference in the number of laminated silica fine particles, and the limited range of 1.5 to 3% in the wavelength region of 380 to 780 nm. Furthermore, the difference between the maximum value and the minimum value of the reflectance in this wavelength region can be reduced to 1% or less.
  • the average particle diameter of the silica fine particles is r, if the thickness of the antireflection film at the bottom of the surface irregularities is 3r or more, this film has a film thickness equivalent to three or more layers of silica fine particles.
  • the number of laminated silica particles and the film thickness can be confirmed by actually observing the cross section of the antireflection film using a scanning electron microscope or the like.
  • the average particle diameter r of the silica fine particles is preferably 10 nm to 1000 nm, particularly 50 nm to 300 nm, especially 70 nm to 200 nm. If the average particle size r is too small or too large, the reflectance in the visible range may not be sufficiently reduced.
  • hollow silica fine particles are also commercially available as silica fine particles, but in antireflection films formed on the cover glass for photoelectric conversion devices, wear resistance should be emphasized, so solid (non-hollow) silica The use of fine particles 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 thereof.
  • 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 converted into a binder oxide 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 coating is preferably 90:10 to 65:35, more preferably 85:15 to 65:35, and particularly preferably 80:20 to 65:35, based on the weight standard. .
  • a reflection suppressing film composed of silica fine particles and a binder having this ratio range has a void secured between the skeletons of the silica fine particles, the apparent refractive index of the film is lowered, and the reflection suppressing effect is increased.
  • 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
  • titanium oxide titanium oxide
  • TiO 2 titanium oxide
  • the content of zirconium oxide and the content of titanium oxide in the antireflection film are each 5% by weight or less. Addition of zirconium oxide or titanium oxide improves the alkali resistance of the antireflection coating.
  • the absolute value of the difference in visible light transmittance measured before and after an alkali resistance evaluation test described later is preferably 1.5% or less.
  • the additive which is zirconium oxide and / or titanium oxide is preferably contained in the antireflection film in an amount of 0.5% by weight or more, more preferably 1% by weight or more, and particularly preferably 1.5% by weight or more.
  • 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.
  • Color unevenness due to the spray method can be visually recognized regardless of whether the surface of the glass plate forming the antireflection film is smooth or uneven, but the surface unevenness is within the range defined in the present invention. As a result.
  • a method for producing a cover glass for a photoelectric conversion device comprising:
  • the cover glass further comprises a glass plate having surface irregularities and a reflection suppressing film formed on the surface irregularities of the glass plate, and the reflection suppressing film is composed of silica fine particles and a binder of the silica fine particles,
  • the silica fine particles are arranged in one layer at the top of the surface unevenness, and the silica fine particles are laminated in a thickness corresponding to at least three layers at the bottom of the surface unevenness, and the surface unevenness is zero.
  • the reflectance with respect to light incident from the side on which the antireflection film is formed has an average interval Sm of 0.4 mm to 2.5 mm and an arithmetic average roughness Ra of 0.5 ⁇ m to 5 ⁇ m.
  • the cover glass is 1.5% or more and 3% or less, Spraying a coating liquid containing the silica fine particles and a metal compound serving as a supply source of the binder onto the surface irregularities of the glass plate; Drying the coating solution sprayed onto the glass plate; And a step of producing an oxide from the metal compound contained in the dried coating solution by heating the glass plate to form the binder.
  • the spraying of the coating liquid is performed using a spray gun that maintains a constant distance from the glass plate from above the horizontally held glass plate.
  • a surfactant is added to the coating solution.
  • a silicone surfactant or a fluorine surfactant is suitable.
  • the concentration of the surfactant in the coating solution is preferably 0.005% by weight to 0.5% by weight, particularly 0.01% by weight to 0.1% by weight.
  • 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 400 nm to 1100 nm.
  • 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 400 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.
  • the alkali resistance of the obtained antireflection film was evaluated according to JIS R3221.
  • the cover glass on which the antireflection film was formed was immersed in an aqueous sodium hydroxide solution at a temperature of 23 ° C. and a concentration of 1 kmol / m 3 (1 N) for 24 hours.
  • the appearance change before and after immersion was observed visually, the transmittance before and after immersion was measured with a haze meter (Nippon Denshoku, NDH2000), and the alkali resistance was evaluated by the absolute value of the difference.
  • the alkali resistance was evaluated according to the following criteria. ⁇ : No change in appearance ⁇ : Reflection color changes slightly, but the film remains on the whole surface ⁇ : Reflection color tone changes greatly ⁇ : The film is peeled off
  • Example 1 Preparation of coating solution> Silica fine particle dispersion (Fuso Chemical Co., Ltd., PL-7, average particle size 100 nm, solid content concentration 23 wt%) 36.96 parts by weight, ethyl cellosolve 56.84 parts by weight, 1N hydrochloric acid (hydrolysis catalyst) 1 0.0 part by weight was mixed with stirring, and further 5.2 parts by weight of tetraethoxysilane was added with 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 is 10% by weight, and the ratio of the fine particles to the binder (as oxide) in the solid is 85:15 on a weight basis.
  • the silica fine particles are solid (in other words, not hollow) fine particles.
  • a template glass having a soda lime silicate composition (manufactured by Nippon Sheet Glass, 100 mm ⁇ 300 mm, thickness 3.2 mm) 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 0.76 ⁇ m of surface irregularities, maximum height Ry 4.54 ⁇ m, average interval Sm 1120 ⁇ m, and average inclination angle ⁇ 0.156 degrees.
  • the average reflectance was 4.54% and the average transmittance was 91.68%.
  • 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.
  • the template glass was placed in an electric furnace at 300 ° C. for 1 minute to remove the solvent of the coating solution, and further placed in an electric furnace at 610 ° C. for 8 minutes to fire the antireflection film, thereby obtaining a cover glass.
  • the above 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 The ratio of each raw material when preparing the stock solution was changed to 30.43 parts by weight of silica fine particle dispersion, 58.17 parts by weight of ethyl cellosolve, 1.0 part by weight of concentrated hydrochloric acid, and 10.4 parts by weight of tetraethoxysilane.
  • a stock solution was obtained.
  • the concentration of the solid content of this stock solution is 10% by weight, and the ratio of the fine particles to the binder (as oxide) in the solid content is 70:30 on a weight basis.
  • the ratio of each raw material when preparing the coating solution was as follows: stock solution 17.0 parts by weight, propylene glycol 5.0 parts by weight, 2-propanol 77.95 parts by weight, silicone surfactant 0.05 parts by weight.
  • a coating solution was obtained in the same manner as in Example 1 except that. However, CoatOSil 3505 by Momentive Performance Materials Japan GK was used as the silicone surfactant.
  • the solid concentration in this coating solution is 1.7% by weight, and the surfactant concentration is 0.05% by weight.
  • a cover glass was obtained in the same manner as in Example 1. The above characteristics were evaluated for the cover glass thus obtained. The evaluation results are shown in Table 1.
  • Example 3 A cover glass was obtained in the same manner as in Example 1 using the template glass having the surface shape shown in Table 1 and the coating liquid prepared as shown in Table 1. Each characteristic was evaluated about the cover glass of each Example obtained in this way. The evaluation results are shown in Table 1.
  • Example 9 A cover glass was obtained in the same manner as in Example 1 using a template glass having the surface shape shown in Table 2 and a coating solution prepared as shown in Table 2. However, a fluorosurfactant was used as the surfactant in the coating solution. Specifically, in each Example, F444 by DIC Corporation, Footage 251 by Neos Corporation, and 215M by Neos Corporation were used, respectively. Each characteristic was evaluated about the cover glass of each Example obtained in this way. The evaluation results are shown in Table 2.
  • Example 12 and 13 A cover glass was obtained in the same manner as in Example 1 using a template glass having the surface shape shown in Table 2 and a coating solution prepared as shown in Table 2.
  • ZrO 2 is added to the antireflection films of Examples 12 and 13.
  • zirconium oxychloride octahydrate (special grade, Kanto Chemical Co., Inc.) was used.
  • the coating liquid was obtained by stirring and mixing the raw materials in the ratios shown in Table 3.
  • the stock solution was prepared as in Example 2.
  • the ratio in terms of oxides of SiO 2 and ZrO 2 in the solid content is 100: 3 on a weight basis in Example 12, and 100: 5 on a weight basis in Example 13.
  • the ratio between the fine particles and the binder (as oxide) in the solid content was 70:30 on a weight basis in any of the examples.
  • Each characteristic was evaluated about the cover glass of each Example obtained in this way.
  • the evaluation results are shown in Table 2.
  • FIG. 3 (top) and FIG. 4 (bottom) show the results of observing the cross section of the antireflection film prepared in Example 12 using FE-SEM.
  • Example 14 and 15 A cover glass was obtained in the same manner as in Example 1 using a template glass having the surface shape shown in Table 2 and a coating solution prepared as shown in Table 2. TiO 2 is added to the antireflection films of Examples 14 and 15. ORGATICS TC-401 (Matsumoto Co., Ltd., titanium acetylacetonate, solid content concentration 65% by weight, 2-propanol solution) was used as a starting material for TiO 2 .
  • the coating liquid was obtained by stirring and mixing the raw materials in the ratios shown in Table 3.
  • the stock solution was prepared as in Example 2.
  • the ratio in terms of oxides of SiO 2 and TiO 2 in the solid content is 100: 3 on a weight basis in Example 14, and 100: 5 on a weight basis in Example 15.
  • the ratio between the fine particles and the binder (as oxide) in the solid content was 70:30 on a weight basis in any of the examples.
  • Each characteristic was evaluated about the cover glass of each Example obtained in this way. The evaluation results are shown in Table 2.
  • Example 16 A cover glass was obtained in the same manner as in Example 1 using a template glass having the surface shape shown in Table 2 and a coating solution prepared as shown in Table 2. In the same manner as in Example 12, the coating liquid was obtained so that each raw material had the ratio shown in Table 3. As the surfactant, Fluorent surfactant 251 was used. The above characteristics were evaluated for the cover glass thus obtained. The evaluation results are shown in Table 2. In addition, FIG. 5 (top) and FIG. 6 (bottom) show the results of observing the cross section of the produced antireflection film using FE-SEM.
  • Example 17 A cover glass was obtained in the same manner as in Example 1 using a template glass having the surface shape shown in Table 2 and a coating solution prepared as shown in Table 2.
  • the ratio of the fine particles to the binder (as oxide) in the solid content of the stock solution is 95: 5 on a weight basis
  • the solid content concentration in the coating solution is 1.3% by weight
  • the agent concentration is 0.02% by weight. The above characteristics were evaluated for the cover glass thus obtained. The evaluation results are shown in Table 2.
  • Example 1 A stock solution was prepared in the same manner as in Example 1, and the ratio of each raw material when preparing the coating solution was 13.0 parts by weight of the stock solution, 5.0 parts by weight of propylene glycol, and 82.0 parts by weight of 2-propanol. Except for this, a coating solution was obtained in the same manner as in Example 1. However, no surfactant is added. The solid concentration in this coating solution is 1.3% by weight. Subsequently, a cover glass was obtained in the same manner as in Example 1. The above characteristics were evaluated for the cover glass thus obtained. Table 4 shows the evaluation results. In addition, FIG. 7 (top) and FIG. 8 (bottom) show the results of observing the cross section of the produced antireflection film using FE-SEM.
  • Example 2 A stock solution was prepared in the same manner as in Example 2, and the ratio of each raw material when preparing the coating solution was 17.0 parts by weight of the stock solution, 5.0 parts by weight of propylene glycol, and 78.0 parts by weight of 2-propanol. Except for this, a coating solution was obtained in the same manner as in Example 1. However, no surfactant is added. The solid content concentration in this coating solution is 1.7% by weight. Subsequently, a cover glass was obtained in the same manner as in Example 1. The above characteristics were evaluated for the cover glass thus obtained. Table 4 shows the evaluation results.
  • Example 7 A cover glass was obtained in the same manner as in Example 1 using a template glass having the surface shape shown in Table 4 and a coating solution prepared as shown in Table 4.
  • the surfactant used in the coating liquid of each comparative example is SN wet L by San Nopco Co., which is a fatty acid ester surfactant, SN wet 970 by San Nopco Co., which is a sulfonic acid surfactant, It was set to Tween80 by Sigma Aldrich Japan Co., Ltd. which is a sorbitan monooleate surfactant.
  • Table 4 shows the evaluation results.
  • the antireflection film has a skeleton composed of silica fine particles arranged in one layer at the top of the concavo-convex portion of the template glass (FIGS. 1, 3 and 5).
  • the antireflection film has a skeleton composed of a laminate in which silica fine particles are laminated in about 3 to 6 layers (FIGS. 2, 4, and 6).
  • the number of layers of the antireflection coating decreases as it approaches the top, and the number of layers increases as it approaches the bottom, at the slope between the top and bottom of the unevenness of the template glass. I was able to confirm.
  • the film thickness of the antireflection film continuously changed along the irregularities on the surface of the template glass.
  • silica fine particles were arranged in a single layer at the top and about 4 to 5 layers of silica fine particles at the bottom. And arranged in layers.
  • the antireflection film has a skeleton composed of silica fine particles arranged in one or two layers.
  • the film thickness of the antireflection film at the top and bottom of the unevenness is almost the same.
  • the antireflection film produced in Comparative Example 2 also had the same film structure as the antireflection film produced in Comparative Example 1.
  • FIG. 9 shows the reflectance curves (reflection spectra) of the cover glasses produced in Examples 1 and 2 and Comparative Examples 1 and 2. From the cover glasses of Examples 1 and 2, the reflectance at a wavelength of 380 nm to 780 nm is in a range of 1.5 to 3% (in Example 2, a range of 2.5 to 3%; both of Examples 1 and 2 have a wavelength of 380 nm to A reflectance curve having a difference between the maximum reflectance and the minimum reflectance at 780 nm of 1% or less was obtained. On the other hand, the reflectance curve of the cover glass of Comparative Example 1 has a large peak near the wavelength of 400 nm.
  • the reflectance curve of the cover glass of Comparative Example 2 is flatter than that of Comparative Example 1, but a small peak is present near the wavelength of 400 nm to 500 nm, so that it is not sufficiently flat and the maximum reflectance is 3%. It was more than.
  • the appearance evaluation of the cover glass produced in Comparative Example 3 was ⁇ , and the appearance evaluation of the cover glass produced in Comparative Example 6 was ⁇ , but these were not practical because the average reflectance was too high.
  • the cover glasses produced in Comparative Examples 7 to 9 do not use a silicone-based surfactant or a fluorine-based surfactant, and thus it is considered that a preferable antireflection film was not formed.
  • the upper limit of the reflectance when light having a wavelength of 380 nm to 780 nm is incident is 3% or less, and the lower limit of the reflectance is 1.5% or more. Therefore, it can be said that a preferable antireflection film is formed on the cover glass of all the examples. Moreover, in the cover glass of all the examples, since average reflectance is 3% or less, it can be said that reflected light can fully be suppressed.
  • the silica fine particles are arranged in one layer at the top, and the silica fine particles have a thickness corresponding to at least three layers at the bottom. It was confirmed that they were stacked.
  • a cover glass for a photoelectric conversion device with improved appearance can be provided.

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PCT/JP2010/006515 2009-12-11 2010-11-05 光電変換装置用カバーガラスおよびその製造方法 WO2011070714A1 (ja)

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US13/513,972 US9188705B2 (en) 2009-12-11 2010-11-05 Cover glass for photoelectric conversion devices and method for producing the same
EP10835645.2A EP2511738B1 (en) 2009-12-11 2010-11-05 Cover glass for photoelectric converter and process for producing same
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JP2014006443A (ja) * 2012-06-26 2014-01-16 Jgc Catalysts & Chemicals Ltd 反射防止膜付基材の製造方法および光電気セル
WO2014020836A1 (ja) 2012-08-01 2014-02-06 日本板硝子株式会社 光電変換装置用カバーガラス
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
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
JP2017040937A (ja) * 2016-11-04 2017-02-23 大日本印刷株式会社 光学積層体、偏光板及び画像表示装置
US9874658B2 (en) 2013-01-31 2018-01-23 Nippon Sheet Glass Company, Limited Low reflection coating glass sheet and method for producing the same
JP2023014241A (ja) * 2017-03-10 2023-01-26 キヤノン株式会社 光学部材及び光学部材の製造方法

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CN103130420B (zh) * 2011-11-25 2017-08-01 三菱综合材料株式会社 带抗反射膜的玻璃基材
JP2014006443A (ja) * 2012-06-26 2014-01-16 Jgc Catalysts & Chemicals Ltd 反射防止膜付基材の製造方法および光電気セル
CN103515457B (zh) * 2012-06-26 2017-08-25 日挥触媒化成株式会社 带防反射膜的基材的制造方法及光电池
TWI572045B (zh) * 2012-06-26 2017-02-21 日揮觸媒化成股份有限公司 附抗反射膜基材的製造方法及光電單元
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US9664822B2 (en) 2012-08-01 2017-05-30 Nippon Sheet Glass Company, Limited Cover glass for photoelectric conversion device
KR101939871B1 (ko) 2012-08-01 2019-01-17 니혼 이타가라스 가부시키가이샤 광전 변환 장치용 커버 유리
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CN104508518A (zh) * 2012-08-01 2015-04-08 日本板硝子株式会社 光电转换装置用玻璃盖片
JP2014032248A (ja) * 2012-08-01 2014-02-20 Nippon Sheet Glass Co Ltd 光電変換装置用カバーガラス
EP2881765A4 (en) * 2012-08-01 2016-03-02 Nippon Sheet Glass Co Ltd COVER GLASS FOR PHOTOELECTRIC CONVERSION DEVICE
US9874658B2 (en) 2013-01-31 2018-01-23 Nippon Sheet Glass Company, Limited Low reflection coating glass sheet and method for producing the same
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
JPWO2016051750A1 (ja) * 2014-09-30 2017-08-31 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
US10600923B2 (en) 2014-09-30 2020-03-24 Nippon Sheet Glass Company, Limited Low-reflection coating, glass sheet, glass substrate, and photoelectric conversion device
JP2017040937A (ja) * 2016-11-04 2017-02-23 大日本印刷株式会社 光学積層体、偏光板及び画像表示装置
JP2023014241A (ja) * 2017-03-10 2023-01-26 キヤノン株式会社 光学部材及び光学部材の製造方法

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