WO2023106408A1 - Plaque de réglage de couleur, module de cellule solaire, procédé de fabrication de plaque de réglage de couleur, procédé de dépôt et dispositif de dépôt - Google Patents

Plaque de réglage de couleur, module de cellule solaire, procédé de fabrication de plaque de réglage de couleur, procédé de dépôt et dispositif de dépôt Download PDF

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WO2023106408A1
WO2023106408A1 PCT/JP2022/045498 JP2022045498W WO2023106408A1 WO 2023106408 A1 WO2023106408 A1 WO 2023106408A1 JP 2022045498 W JP2022045498 W JP 2022045498W WO 2023106408 A1 WO2023106408 A1 WO 2023106408A1
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Prior art keywords
reflection
dielectric multilayer
multilayer film
color adjustment
adjustment plate
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PCT/JP2022/045498
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English (en)
Japanese (ja)
Inventor
裕之 和田
均 齋
零生 足立
聡 久保田
元輝 端無
道雄 近藤
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国立大学法人東京工業大学
国立研究開発法人産業技術総合研究所
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Publication of WO2023106408A1 publication Critical patent/WO2023106408A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • 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
    • H01L31/048—Encapsulation of modules
    • 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
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • 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

Definitions

  • the present invention relates to a color adjusting plate, a solar cell module, a method for manufacturing a color adjusting plate, a film forming method, and a film forming apparatus.
  • This application claims priority based on Japanese Patent Application No. 2021-200963 filed in Japan on December 10, 2021 and Japanese Patent Application No. 2022-102066 filed in Japan on June 24, 2022, The contents of which are incorporated herein.
  • the inventor has developed a coloring technology that can suppress the decline in conversion efficiency. Further, while studying such a coloring technique, the inventor faced the problem that even if a desired color of reflected light can be obtained by vertical reflection, the color of the reflected light changes when the incident angle changes. Therefore, as a result of further investigation, a method for reducing the incident angle dependency of reflected light was found. Furthermore, the inventors have conceived that the method can be applied to other than solar cell modules, and completed the present invention in which the incident angle dependence of reflected light is low.
  • the present invention provides the following means in order to solve the above problems.
  • Aspect 1 of the present invention comprises a substrate, and a dielectric multilayer film formed on the substrate and having high refractive index layers and low refractive index layers alternately laminated, wherein the dielectric multilayer film comprises: A color adjustment plate configured to satisfy (1-1) to (1-3) of; (1-1) White light incident from the vertical direction and reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) The plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the maximum reflectance among the reflection peaks in the wavelength range.
  • Aspect 2 of the present invention is the color adjustment plate of Aspect 1, wherein the substrate has a film forming surface on which the dielectric multilayer film is formed and a non-film forming surface on which the dielectric multilayer film is not formed.
  • One of the surfaces is formed as a diffuse reflection surface having an uneven structure.
  • Aspect 3 of the present invention is the color adjustment plate of aspect 2, wherein the non-film formed surface is formed as a diffuse reflection surface.
  • Aspect 4 of the present invention is the color adjustment plate according to aspect 3, wherein the diffuse reflection surface has a root mean square height Rq of 0.4 ⁇ m to 1.3 ⁇ m.
  • a fifth aspect of the present invention is the color adjustment plate according to any one of the first to fourth aspects, wherein the substrate is a diffusion plate.
  • a sixth aspect of the present invention is the color adjusting plate according to any one of the first to fifth aspects, wherein the plurality of reflection peaks are two reflection peaks.
  • Aspect 7 of the present invention is the color adjustment plate according to any one of aspects 1 to 5, wherein the plurality of reflection peaks are three reflection peaks.
  • Aspect 8 of the present invention is the color adjustment plate according to any one of aspects 1 to 5, wherein the plurality of reflection peaks are four reflection peaks.
  • Aspect 9 of the present invention is the color adjustment plate according to any one of Aspects 1 to 8, wherein the dielectric multilayer film further satisfies the following (1-4); (1-4) The x-coordinate and y-coordinate of the chromaticity coordinates (x, y) on the CIE-xy chromaticity diagram of the reflected light when the incident angle from the vertical direction is changed from 0° to 30° are all 0.1 or less.
  • Aspect 10 of the present invention is the color adjustment plate according to any one of Aspects 1 to 9, wherein the dielectric multilayer film further satisfies the following (1-5); (1-5) At least one of the first main reflection peak and the second main reflection peak has a full width at half maximum (FWHM) of 200 nm or less.
  • FWHM full width at half maximum
  • Aspect 11 of the present invention is the color adjustment plate according to any one of Aspects 1 to 10, wherein the dielectric multilayer film further satisfies the following (1-6): ; (1-6) Both the reflectance of the first main reflection peak and the second main reflection peak are 70% or less.
  • Aspect 12 of the present invention is the color adjustment plate according to any one of Aspects 1 to 11, wherein the dielectric multilayer film further satisfies the following (1-7): ; (1-7) the chromaticity coordinates (x, y) of the reflected light on the CIE-xy chromaticity diagram are enclosed by 0.25 ⁇ x ⁇ 0.4 and 0.25 ⁇ y ⁇ 0.4; exist within the range.
  • Aspect 13 of the present invention is the color adjustment plate of any one of Aspects 1 to 12, wherein the dielectric multilayer film further satisfies the following (1-8); (1-8) the chromaticity coordinates (x, y) of the reflected light on the CIE-xy chromaticity diagram are enclosed by 0.25 ⁇ x ⁇ 0.4 and 0.25 ⁇ y ⁇ 0.4; exists outside the range
  • Aspect 14 of the present invention includes a plurality of solar cells, and a color adjustment plate arranged on the light receiving surface side of the plurality of solar cells, the color adjustment plate being formed on a substrate and on the substrate, It has a dielectric multilayer film in which refractive index layers and low refractive index layers are alternately laminated, and the dielectric multilayer film includes the following (1-1) to (1-3) and (1-5) and (1-6), a solar cell module; (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) the plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the
  • Aspect 15 of the present invention is the solar cell module according to Aspect 14, wherein the substrate has a film forming surface on which the dielectric multilayer film is formed and a non-film forming surface on which the dielectric multilayer film is not formed.
  • One of the surfaces is formed as a diffuse reflection surface having an uneven structure.
  • a sixteenth aspect of the present invention is the color adjusting plate in the solar cell module of the fifteenth aspect, wherein the non-film-formed surface is formed as a diffuse reflection surface.
  • Aspect 17 of the present invention is the solar cell module of Aspect 16, wherein the diffuse reflection surface has a root mean square height Rq of 0.4 ⁇ m to 1.3 ⁇ m
  • Aspect 18 of the present invention is the solar cell module according to any one of aspects 14 to 17, wherein the substrate is a diffusion plate.
  • a nineteenth aspect of the present invention comprises a two-dimensional transparent substrate, and a dielectric multilayer film formed on the entire outer surface of the transparent substrate and having high refractive index layers and low refractive index layers alternately laminated.
  • the dielectric multilayer film is a color adjustment plate configured to satisfy the following (1-1) to (1-3);
  • (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less,
  • the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more;
  • the plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the maximum reflectance among the reflection peaks in the wavelength range.
  • Aspect 20 of the present invention is the color adjustment plate according to Aspect 19, wherein the substrate has a film forming surface on which the dielectric multilayer film is formed and a non-film forming surface on which the dielectric multilayer film is not formed.
  • One of the surfaces is formed as a diffuse reflection surface having an uneven structure.
  • Aspect 21 of the present invention is the color adjustment plate of aspect 20, wherein the non-film formed surface is formed as a diffuse reflection surface.
  • Aspect 22 of the present invention is the color adjusting plate according to any one of Aspects 19 to 21, wherein the transparent substrate has a size of 1 ⁇ m to 1000 ⁇ m.
  • Aspect 23 of the present invention is the color adjusting plate according to any one of aspects 19 to 22, wherein the transparent substrate is one selected from the group consisting of natural mica, artificial mica, glass, and inorganic single crystals.
  • a twenty-fourth aspect of the present invention is the color adjustment plate according to any one of aspects 19 to 23, wherein the substrate is a diffusion plate.
  • Aspect 25 of the present invention is the color adjusting plate according to any one of aspects 19 to 24, wherein the plurality of reflection peaks are two reflection peaks.
  • Aspect 26 of the present invention is the color adjusting plate according to any one of aspects 19 to 25, wherein the plurality of reflection peaks are three reflection peaks.
  • Aspect 27 of the present invention is the color adjusting plate according to any one of aspects 19 to 26, wherein the plurality of reflection peaks are four reflection peaks.
  • Aspect 28 of the present invention is the color adjustment plate according to any one of Aspects 19 to 27, wherein the dielectric multilayer film further satisfies the following (1-4); (1-4) The x-coordinate and y-coordinate of the chromaticity coordinates (x, y) on the CIE-xy chromaticity diagram of the reflected light when the incident angle from the vertical direction is changed from 0° to 30° are all 0.1 or less.
  • Aspect 29 of the present invention is the color adjustment plate according to any one of Aspects 19 to 28, wherein the dielectric multilayer film further satisfies the following (1-5); (1-5) At least one of the first main reflection peak and the second main reflection peak has a full width at half maximum (FWHM) of 200 nm or less.
  • FWHM full width at half maximum
  • Aspect 30 of the present invention is the color adjustment plate according to any one of Aspects 19 to 29, wherein the dielectric multilayer film further satisfies the following (1-6); (1-6) Both the reflectances of the first main reflection peak and the second main reflection peak are 70% or less.
  • Aspect 31 of the present invention is the color adjustment plate according to any one of Aspects 19 to 30, wherein the dielectric multilayer film further satisfies the following (1-7); (1-7) the chromaticity coordinates (x, y) of the reflected light on the CIE-xy chromaticity diagram are enclosed by 0.25 ⁇ x ⁇ 0.4 and 0.25 ⁇ y ⁇ 0.4; exist within the range.
  • Aspect 32 of the present invention is the color adjustment plate according to any one of Aspects 19 to 31, wherein the dielectric multilayer film further satisfies the following (1-8); (1-8) the chromaticity coordinates (x, y) of the reflected light on the CIE-xy chromaticity diagram are enclosed by 0.25 ⁇ x ⁇ 0.4 and 0.25 ⁇ y ⁇ 0.4; Exists outside the range.
  • Aspect 33 of the present invention includes a plurality of solar cells, and a color adjustment plate disposed on the light receiving surface side of the plurality of solar cells, wherein the color adjustment plate includes a plurality of two-dimensional transparent substrates, A dielectric multilayer film formed on the entire outer surface of the transparent substrate and having high refractive index layers and low refractive index layers alternately laminated, the dielectric multilayer film comprising the following (1-1): ⁇ A solar cell module configured to satisfy (1-3), (1-5) and (1-6); (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) the plurality of reflection peaks exhibit a reflectance
  • Aspect 34 of the present invention is the solar cell module according to Aspect 33, wherein the substrate has a film forming surface on which the dielectric multilayer film is formed and a non-film forming surface on which the dielectric multilayer film is not formed.
  • One of the surfaces is formed as a diffuse reflection surface having an uneven structure.
  • a thirty-fifth aspect of the present invention is the solar cell module according to the thirty-fourth aspect, wherein the non-film-forming surface is formed as a diffuse reflection surface.
  • Aspect 36 of the present invention is the solar cell module according to any one of aspects 33 to 35, wherein the substrate is a diffusion plate.
  • Aspect 37 of the present invention is the method for manufacturing a color adjustment plate according to any one of Aspect 1, Aspect 2, or Aspect 19, comprising: A method for manufacturing a color adjustment plate, comprising a dielectric multilayer film determination step of determining at least one parameter of the layer thickness of each layer and the number of layers by optical thin film design simulation.
  • Aspect 38 of the present invention is a film forming method for forming a dielectric multilayer film in which high refractive index layers and low refractive index layers are alternately laminated on a substrate or on the entire outer surface of a transparent substrate, At least the materials of the high refractive index layer and the low refractive index layer, the layer thickness of each layer, and the number of layers, so that the dielectric multilayer film satisfies at least the following (1-1) to (1-3) A deposition method in which one parameter is determined by optical thin film design simulation; (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) The plurality
  • Aspect 39 of the present invention is a film forming apparatus for forming a dielectric multilayer film in which a high refractive index layer and a low refractive index layer are alternately laminated on a substrate or on the entire outer surface of a transparent substrate, At least the materials of the high refractive index layer and the low refractive index layer, the layer thickness of each layer, and the number of layers, so that the dielectric multilayer film satisfies at least the following (1-1) to (1-3)
  • a film forming apparatus comprising optical parameter determination means for determining one parameter by optical thin film design simulation; (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520
  • Aspect 40 of the present invention comprises a substrate and a dielectric multilayer film in which high refractive index layers and low refractive index layers are alternately laminated on at least one of the front surface and the back surface of the substrate, A color adjustment plate, wherein the dielectric multilayer film is configured to satisfy the following (1-1) to (1-3); (1-1) White light incident from the vertical direction and reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) The plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the maximum reflectance among the reflection peaks in the wavelength range.
  • Aspect 41 of the present invention is the color adjustment plate according to aspect 40, wherein the substrate is a diffusion plate.
  • Aspect 42 of the present invention includes a plurality of solar cells, and a color adjustment plate disposed on the light receiving surface side of the plurality of solar cells, wherein the color adjustment plate includes a substrate, a front surface of the substrate, and and an inorganic pigment-containing layer containing an inorganic pigment formed on at least one of the back surfaces of the substrate.
  • One of the non-film-formed surfaces is formed as a diffuse reflection surface having an uneven structure or is a diffuser plate in the solar cell module.
  • the diffuse reflection surface has a root mean square height Rq of 0.1 ⁇ m to 2.0 ⁇ m.
  • the color adjustment plate of the present invention it is possible to provide a color adjustment plate with low angle dependence.
  • FIG. 1 is a schematic cross-sectional view of a color adjustment plate according to one embodiment
  • FIG. 2 is an enlarged schematic cross-sectional view of a dielectric multilayer film portion of the color adjustment plate shown in FIG. 1
  • FIG. It is an example of the reflection spectrum of the reflected light obtained by vertical reflection of white light on the dielectric multilayer film included in the color adjustment plate.
  • FIG. 2 is a conceptual diagram showing reflection of light in a dielectric multilayer film
  • 1 is a CIE-xy chromaticity diagram
  • It is a figure for demonstrating how to see an xy chromaticity diagram.
  • FIG. 4 is a diagram for explaining dominant wavelengths;
  • (a) shows the chromaticity coordinates on the xy chromaticity diagram for the reflected light of the reflection spectrum illustrated in FIG. 3, and
  • (b) shows the parameters of the dielectric multilayer model used in the simulation.
  • (a) shows the incident angle dependence of the reflected light of white light incident on the dielectric multilayer film of the first embodiment by shifting the chromaticity coordinates on the xy chromaticity diagram, and
  • (b) shows , and are diagrams schematically showing how incident light incident at each incident angle is reflected.
  • the upper limit of the wavelength range of the reflection spectrum shown in FIG. 3 is expanded to 1200 nm.
  • FIG. 10 shows a reflection spectrum of white light vertically reflected by the dielectric multilayer film of the second embodiment.
  • FIG. (a) shows the reflection spectrum of white light incident on the dielectric multilayer film of the second embodiment at each angle of incidence; The chromaticity coordinates of the reflection peak are shown on the xy chromaticity diagram.
  • (a) is an enlarged portion of the xy chromaticity diagram of FIG.
  • FIG. 10 shows a reflection spectrum of white light vertically reflected by the dielectric multilayer film of the third embodiment.
  • FIG. The chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the third embodiment are shown on an xy chromaticity diagram.
  • FIG. 10 shows a reflection spectrum of white light vertically reflected by the dielectric multilayer film of the fourth embodiment.
  • the chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the fourth embodiment are shown on an xy chromaticity diagram.
  • FIG. 10 shows chromaticity coordinates on an xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the fifth embodiment.
  • FIG. 10 shows a reflection spectrum of white light vertically reflected by the dielectric multilayer film of the fifth embodiment.
  • FIG. The chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the fifth embodiment are shown on an xy chromaticity diagram.
  • FIG. 11 shows chromaticity coordinates on an xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the sixth embodiment.
  • FIG. FIG. 10 shows a reflection spectrum of white light vertically reflected by the dielectric multilayer film of the sixth embodiment.
  • FIG. The chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the sixth embodiment are shown on an xy chromaticity diagram.
  • (a) shows the chromaticity coordinates on the xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the seventh embodiment
  • (b) shows the dielectric multilayer used in the simulation. parameters of the membrane model. It shows the chromaticity coordinates on the xy chromaticity diagram for the reflection spectrum of the white light incident on the dielectric multilayer film of the seventh embodiment.
  • the chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the seventh embodiment are shown on an xy chromaticity diagram.
  • FIG. 12 shows chromaticity coordinates on an xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the eighth embodiment.
  • FIG. The chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the eighth embodiment are shown on an xy chromaticity diagram.
  • FIG. 21 is a schematic cross-sectional view of a color adjusting plate according to a ninth embodiment; (a) shows the chromaticity coordinates on the xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the ninth embodiment, and (b) shows the dielectric multilayer used in the simulation. parameters of the membrane model. It shows the chromaticity coordinates on the xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the ninth embodiment. The chromaticity coordinates of the reflection spectrum at each incident angle of white light incident on the dielectric multilayer film of the ninth embodiment are shown on an xy chromaticity diagram.
  • FIG. 12 shows chromaticity coordinates on an xy chromaticity diagram for the reflection spectrum of white light incident on the dielectric multilayer film of the tenth embodiment.
  • FIG. It is a cross-sectional schematic diagram showing an example of how to use the color adjustment plate according to the present invention. It is a cross-sectional schematic diagram showing an example of how to use the color adjustment plate according to the present invention.
  • FIG. 10 is a graph showing the results of measuring the rate of decrease ⁇ Jsc (%) of the short-circuit current of a solar cell module that has been exposed.
  • FIG. 43 It is an optical microscope photograph of the diffuse reflection surface of a glass substrate sandblasted with abrasive grains, (a) is #600 abrasive grains, (b) is #400 abrasive grains, and (c) is #220 abrasive grains. This is the case of using granules. Arithmetic mean roughness Ra, maximum height Ry, and root-mean-square height Rq of each XX line in FIGS. 43(a) to 43(c) are shown. It is a cross-sectional schematic diagram which shows a part of solar cell module which concerns on this invention. 4 is a graph showing the relationship between the surface roughness of the diffuse reflection surface and the reduction rate ⁇ Jsc of the short-circuit current of the solar cell module. 4 is a graph showing the relationship between the surface roughness of the diffuse reflection surface and the whiteness of the color adjustment plate of the solar cell module. FIG. 4 is a schematic cross-sectional view showing part of a solar cell module according to another embodiment of the present
  • FIG. 1 is a schematic cross-sectional view of the color adjustment plate according to this embodiment.
  • FIG. 2 is an enlarged schematic cross-sectional view of the dielectric multilayer film portion of the color adjustment plate shown in FIG.
  • FIG. 3 shows an example of the reflection spectrum of the reflected light vertically reflected when white light enters the dielectric multilayer film of the color adjustment plate from the vertical direction.
  • the color adjustment plate 10 shown in FIG. 1 includes a substrate 1 and a dielectric multilayer film 2 formed on the substrate 1 and having high refractive index layers and low refractive index layers alternately laminated. Further, the dielectric multilayer film 2 is constructed so as to satisfy the following (1-1) to (1-3); (1-1) White light incident in the vertical direction and reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics in which the reflected light has a plurality of reflection peaks in the wavelength range of 380 nm to 780 nm.
  • the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more.
  • the plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the maximum reflectance among the reflection peaks in the wavelength range.
  • the "color adjustment plate” is a plate provided with a dielectric multilayer film whose color is adjusted by the parameters of the high refractive index layer and the low refractive index layer that constitute the dielectric multilayer film, and the application is particularly limited. not.
  • the color adjustment plate can be applied to various uses.
  • the color adjustment plate can be used, for example, for coloring the appearance of the solar cell module.
  • it is necessary to color while minimizing the energy of the reflected light.
  • Various colors are required from the standpoint of maintaining the scenery of the place where the solar cell module is installed, design, etc., but arbitrary colors are possible.
  • the color adjustment plate is used from the viewpoint of decoration (a method of changing the appearance without changing the function), there are no particular restrictions on the application.
  • the color adjustment plate is used from the viewpoint of decoration (a method of changing the appearance without changing the function), there are no particular restrictions on the application.
  • the substrate 1 may be various glass substrates, plastic substrates made of polycarbonate resin, acrylic resin, etc., transparent inorganic material substrates other than glass, mica. (mica) or the like is used as a transparent substrate through which light in the visible light range can pass.
  • any substrate on which a dielectric multilayer film can be formed can be used without particular limitation.
  • the substrate 1 generally preferably has a flat surface (a film formation surface on which the dielectric multilayer film is formed), but has a certain degree of unevenness. Even in such a case, a substrate having unevenness on its surface can be used as long as the function as a color adjustment plate is exhibited, or if the function as a color adjustment plate can be enhanced.
  • the size of the unevenness in this case is, for example, about several tens of nanometers to several tens of micrometers.
  • the substrate 1 may be provided with an uneven structure so as to have a diffuse reflection function on the film forming surface on which the dielectric multilayer film is formed or on the non-film forming surface on which the dielectric multilayer film is not formed. can.
  • This configuration can improve the performance of the color adjustment plate. This configuration will be detailed later.
  • the surface provided with an uneven structure so as to have a diffuse reflection function may be referred to as a "diffuse reflection surface”.
  • the substrate 1 may be a diffusion plate.
  • Typical types of diffusion plates include those containing light diffusion particles and those having an uneven surface.
  • the substrate 1 is a diffusion plate having an uneven surface. Therefore, the diffuser plate is also a substrate having a diffuse reflection surface having an uneven structure.
  • commercially available frosted glass may be used as the diffuser plate having an uneven surface.
  • a ground glass diffuser plate eg, N-BK7 ground glass diffuser plate
  • a reflective diffuser plate eg, N-BK7 reflective diffuser plate
  • an engineered diffuser manufactured by THORLABS, etc. are used. be able to.
  • #120, #220, #600, and #1500 can be used as the count.
  • the dielectric multilayer film 2 is a multilayer film in which a high refractive index layer 2a and a low refractive index layer 2b are alternately laminated in order from the substrate 1 side.
  • the number of layers of the high refractive index layer 2a and the low refractive index layer 2b is not particularly limited, and can be an arbitrary number.
  • a dielectric multilayer film is a multilayer film in which high refractive index layers and low refractive index layers are alternately laminated. ), layer thickness (film thickness), and the number of layers, various spectral reflection characteristics can be obtained. In the dielectric multilayer film 2 shown in FIG.
  • a high refractive index layer 2a and a low refractive index layer 2b are alternately laminated in order from the substrate 1 side.
  • the thin layers 2a may be alternately laminated.
  • the uppermost refractive index layer may be either the high refractive index layer 2a or the low refractive index layer 2b.
  • the refractive index of the high refractive index layer 2a is, for example, 1.91 to 3.4.
  • Dielectric materials used for the high refractive index layer 2a include, for example, titanium oxide (TiO 2 , refractive index 2.33 to 2.55), niobium pentoxide (Nb 2 O 5 , refractive index 2.33), cerium oxide ( CeO 2 , refractive index 2.18-2.52), hafnium oxide (HfO 2 , refractive index 2.15), indium oxide (In 2 O 3 , refractive index 2.00), silicon (Si, refractive index 3.00).
  • silicon monoxide SiO, refractive index 2.0
  • tantalum pentoxide Ta 2 O 5 , refractive index 2.2-2.4
  • zinc oxide ZnO, refractive index 2.1
  • zinc sulfide ZnS, refractive index 2.31 to 2.38
  • zirconium oxide ZrO 2 , refractive index 1.95 to 2.05), and the like.
  • the refractive index of the low refractive index layer 2b is, for example, 1.38 to 1.9.
  • Dielectric materials used for the low refractive index layer 2b include, for example, silicon dioxide (SiO 2 , refractive index 1.46), magnesium fluoride (MgF 2 , refractive index 1.38), aluminum oxide (Al 2 O 3 , refractive index index 1.59-1.62), gadolinium oxide (Gd 2 O 3 , refractive index 1.8), magnesium oxide (MgO, refractive index 1.70-1.75), selenium trioxide (Se 2 O 3 , refractive index 1.89), yttrium oxide (Y 2 O 3 , refractive index 1.89), and the like.
  • the film thicknesses of the high refractive index layer 2a and the low refractive index layer 2b can be appropriately selected according to desired spectral reflection characteristics.
  • the film thickness of the high refractive index layer 2a can be, for example, 0.1 nm to 1000 nm.
  • the film thickness of the low refractive index layer 2b can be, for example, 0.1 nm to 1000 nm.
  • an adhesion layer may be provided to improve adhesion between the substrate 1 and the dielectric multilayer film 2 .
  • the dielectric multilayer film 2 is configured to satisfy the following (1-1) to (1-3); (1-1) White light incident in the vertical direction and reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics in which the reflected light has a plurality of reflection peaks in the wavelength range of 380 nm to 780 nm. (1-2) The plurality of reflection peaks includes at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more. (1-3) The plurality of reflection peaks of (1-1) show a reflectance of 20% or more with respect to the reflection peak showing the maximum reflectance among the reflection peaks in the above wavelength range.
  • 380 nm or more and 780 nm or less" in (1-1) may be "400 nm or more and 700 nm or less" from the viewpoint of visible light. From the same point of view, the lower limits may be 390 nm and 410 nm, and the upper limits may be 770 nm, 760 nm, 750 nm, 740 nm, 730 nm, 720 nm and 710 nm.
  • the "first main reflection peak” of (1-2) is a reflection peak with a wavelength of 380 nm or more and less than 520 nm, and the maximum reflectance It shows a reflectance of 20% or more with respect to the indicated reflection peak.
  • the number of “first main reflection peaks” is not limited to one, and may be plural.
  • the "second main reflection peak” in (1-2) is a reflection peak at a wavelength of 520 nm or more and 780 nm or less, and has a reflectance of 20% or more with respect to the reflection peak showing the maximum reflectance. is shown.
  • the number of "second main reflection peaks” is not limited to one, and may be plural.
  • the requirement of (1-3) is preferably "25% or more", more preferably "30% or more".
  • a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less 5% or less of the reflection peak showing the maximum reflectance among the reflection peaks in the above wavelength range It is preferred that no one is present, more preferably no one below 10% is present, more preferably no one below 15% is present, and most preferably no one below 20% is present.
  • (1-1) and (1-3) indicate that there are multiple dominant reflection peaks in determining the color of the reflected light of the dielectric multilayer film according to the present invention.
  • the number of this "plurality of reflection peaks" is either two, three or four.
  • (1-2) leads to suppression of blue shift of the reflected light when the incident angle is increased. Blue shift will be described later.
  • this dielectric multilayer film may be referred to as the dielectric multilayer film of the first embodiment.
  • the reflection spectrum shown in FIG. 3 has four reflection peaks p11 to p14 in the wavelength range from 380 nm to 780 nm. Of the four reflection peaks p11 to p14, the reflection peak p11 exhibits the highest reflectance.
  • the "plurality of reflection peaks" in (1-1) are limited to those exhibiting a reflectance of 20% or more with respect to the reflection peak p11, which exhibits the maximum reflectance, as defined in (1-3). Therefore, the reflection peak p12 and the reflection peak p14 are not included in the "plurality of reflection peaks" in (1-1). Therefore, the "plurality of reflection peaks" in (1-1) are only reflection peak p11 and reflection peak p13.
  • the reflection peak p11 having a reflection peak near the wavelength of 400 nm corresponds to the "first main reflection peak” of (1-2)
  • the reflection peak p13 having a reflection peak near the wavelength of 560 nm corresponds to (1-2). It corresponds to the "second main reflection peak”.
  • the configuration (1-2) is for suppressing the blue shift, as described above.
  • Blue shift is a phenomenon in which reflectance wavelength characteristics shift to the short wavelength side as the incident angle of light incident on a dielectric multilayer film increases. Blue shift will be described with reference to the drawings.
  • FIG. 4 is a conceptual diagram showing reflection of light in a dielectric multilayer film.
  • Reference numeral 2A shown in FIG. 4 is a multilayer structure in which a high refractive index layer 2Aa (thickness: d1) having a first refractive index n1 and a low refractive index layer 2Ab (thickness: d2) having a second refractive index n2 are alternately formed. It is part of the dielectric multilayer film laminated on the substrate.
  • the thickness of the two high refractive index layers 2Aa is indicated by the symbol d1, but this does not mean that the thickness is the same, and the thickness of each high refractive index layer has the desired optical properties. is determined as appropriate to have The same applies to the film thickness of the low refractive index layer.
  • the optical path length n 1 b is generated due to the deviation between the position of the reflected light and the incident position of the light reciprocating in the layer.
  • the incident angle ⁇ 1 of the incident light As the incident angle ⁇ 1 of the incident light is gradually increased, the difference in optical path length of the reflected light generated at each interface is gradually decreased, and the light with shorter wavelengths interferes and strengthens each other. Therefore, when the dielectric multilayer film 2 illuminated with white light is viewed from a more oblique angle (at an angle closer to the plane), the shorter wavelength light appears to be reflected more strongly. That is, the larger the incident angle ⁇ 1 , the more bluish the reflected light becomes. This phenomenon is called blue shift.
  • the angle of incidence is defined as the angle between the normal to the plane of incidence and the optical axis of the incident light.
  • FIG. 5 is an xy chromaticity diagram (CIE-xy chromaticity diagram) based on the CIE (International Commission on Illumination) regulations.
  • FIG. 6 is a diagram for explaining how to read the xy chromaticity diagram.
  • hue, saturation, and lightness (whiteness).
  • Hue means the type of color such as red, yellow, green, cyan, blue, and magenta, that is, the different wavelengths of light perceived by the human eye
  • saturation is the vividness of the color.
  • purity of the color high saturation approaches a pure color
  • low saturation approaches an achromatic color (white to gray)
  • lightness means the brightness of a color.
  • X, Y, and Z are called tristimulus values. It is generally represented by a chromaticity diagram using the stimulus color mixing ratio).
  • the xy chromaticity diagram has a horseshoe shape (or a bell shape) with x on the horizontal axis and y on the vertical axis.
  • the outer curve curved like a horseshoe is called a spectral locus or a monochromatic light locus, and the linear portion is called a pure purple locus.
  • hues such as yellow-red, yellow, yellow-green, green, blue-green, blue, and blue-violet are sequentially arranged counterclockwise from red on the right end of the spectrum locus.
  • Monochromatic light of each hue is arranged in the spectrum locus, and all the colors inside this spectrum locus are mixed light.
  • the color with the highest saturation among the hues is arranged on the outermost spectral locus (monochromatic light locus) and the pure purple locus.
  • ⁇ Brightness in xy chromaticity diagram> the display corresponding to the lightness (L * ) of the object color is represented by the luminous reflectance (transmittance) Y. All colors on a given xy chromaticity diagram are composed of colors with the same luminous reflectance Y value, that is, with the same lightness. In the xy chromaticity diagram, achromatic areas are often drawn white, which is the case when the luminous reflectance Y value is large (bright). As the Y value becomes smaller (darker), the entire xy chromaticity diagram becomes darker. Thus, the xy chromaticity diagram has a multi-layer structure for each luminous reflectance Y value (brightness).
  • the XYZ color system is sometimes referred to as the Yxy color system.
  • the color of light is represented by the two numbers of the x and y coordinates, but since it is not easy to associate the color from these two numbers, some accuracy is sacrificed. However, it is practical if a color can be associated with a single number.
  • a dominant wavelength is used to meet this requirement. The dominant wavelength will be explained with reference to FIG. For example, when there is a color F (0.41, 0.42) on the xy chromaticity diagram, draw a straight line from the white point W (0.333, 0.333) toward F, and then draw the straight line Suppose that the point where the spectrum locus is hit by straight extension is S.
  • the wavelength of this monochromatic light is defined as the dominant wavelength of color F. .
  • the dominant wavelength is the wavelength of monochromatic light when a certain color is produced by mixing white light and monochromatic light.
  • the spectral locus on the chromaticity diagram shows the dominant wavelength numerically. In the xy chromaticity diagram, hue corresponds to the wavelength of the dominant wavelength.
  • FIG. 8B shows parameters of the dielectric multilayer model used in the simulation. It can be seen that the reflected light of the reflection spectrum illustrated in FIG. 3 has chromaticity coordinates close to white (achromatic color).
  • FIG. 9(a) shows the reflection spectra of the dielectric multilayer film when white light is vertically incident (incident angle: 0°) and the incident angle is increased by 5° from the optical thin film design software "OptiLayer” (OptiLayer Inc.). ), and the chromaticity coordinates of the resulting reflection spectrum are shown on an xy chromaticity diagram.
  • FIG. 9B is a diagram schematically showing how light enters the dielectric multilayer film at each incident angle and is reflected at the corresponding reflection angle (direction for obtaining a reflection spectrum).
  • the symbol W indicates the chromaticity coordinates of white
  • the symbol c10 indicates the chromaticity coordinates of the reflection spectrum at normal incidence.
  • c 11 , sign c 12 , sign c 13 , sign c 14 , sign c 15 , sign c 16 are respectively an incident angle of 5°, an incident angle of 10°, an incident angle of 15°, an incident angle of 20°, an incident angle of 25°, It shows the chromaticity coordinates of the reflection spectrum when incident at an incident angle of 30°.
  • the reflection spectrum shown in FIG. 10 is obtained by extending the upper limit of the wavelength range of the reflection spectrum shown in FIG. 3 to 1200 nm.
  • FIG. 10 also shows a typical example of the wavelength dependence of the external quantum efficiency of the solar cell module.
  • the reflection spectrum shown in FIG. 10 satisfies (1-1) to (1-3) above, as described with reference to FIG.
  • the reflection peak p11 and the reflection peak p13 of the reflection spectrum have a peak wavelength of about 390 nm and a peak wavelength of about 560 nm, respectively ((1-1) is satisfied), and the wavelength of the reflection peak p11 is less than 520 nm, In addition, the wavelength of the reflection peak p13 is 520 nm or more (fulfilling (1-2)), and the reflectance of the reflection peak p13 (about 33%) exhibits the maximum reflectance of the reflection peak p11 (about 90% ) is 37% ((1-3) is satisfied).
  • both the reflection peak p11 and the reflection peak p13 have a full width at half maximum (FWHM) of 100 nm or less.
  • a narrow full width at half maximum (FWHM) of the reflection peak means that reflected light energy is suppressed when the color adjusting plate of the present invention is used in a solar cell module, and as a result, a decrease in power generation efficiency can be suppressed. Therefore, it is preferable.
  • at least one reflection peak satisfying the above (1-1) to (1-3) preferably has a full width at half maximum (FWHM) of 200 nm or less, more preferably 150 nm or less. It is preferably 100 nm or less, more preferably 100 nm or less.
  • This color adjustment plate has a dielectric multilayer film as a reflection film that exhibits a reflection spectrum having two narrow-band reflection peaks.
  • the external quantum efficiency of the solar cell module shown in FIG. 10 begins to decrease from approximately 600 nm, becomes 0.8 at approximately 480 nm, becomes 0.6 at approximately 420 nm, and becomes 0.5 at approximately 390 nm. Therefore, from the viewpoint of suppressing a decrease in power generation efficiency when the color adjustment plate of the present invention is used in a solar cell module, the "first main reflection peak" is close to 380 nm, which is the lower limit of the wavelength range of (1-1) requirements. The closer the "second main reflection peak” is to 520 nm, which is the lower limit of the wavelength range of the requirement (1-1), the better.
  • the reflectances of the "first main reflection peak” and the "second main reflection peak” are preferably 70% or less.
  • the reflectance of the "second main reflection peak” is more effective in suppressing the deterioration of the power generation efficiency than the reflectance of the "first main reflection peak”. Therefore, it is preferable that the reflectance of the "second main reflection peak” is low.
  • the reflectance of the "second main reflection peak” is preferably 60% or less, more preferably 50% or less, and even more preferably 40% or less.
  • the color adjustment plate according to the second embodiment includes a dielectric multilayer film having lower incident angle dependence than the dielectric multilayer film of the first embodiment.
  • FIG. 11A shows chromaticity coordinates c 20 (0.330, 0.330) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the second embodiment. It is a thing.
  • FIG. 11B shows parameters of the dielectric multilayer model used in the simulation.
  • FIG. 12 shows the reflection spectrum when white light is vertically incident on the dielectric multilayer film of the second embodiment.
  • the reflection spectrum shown in FIG. 12 has two reflection peaks p21 and p22 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peak p21 and the reflection peak p22 each have a peak wavelength near a wavelength of 480 nm and a wavelength near 620 nm, which are in the wavelength range of 380 nm or more and 780 nm or less, and the reflection peak p21 and the reflection peak p22 each have a wavelength of less than 520 nm.
  • the reflectance of the reflection peak p22 which is the first main reflection peak of the wavelength and the second main reflection peak of the wavelength of 520 nm or more, exhibits a reflectance of 20% or more with respect to the reflection peak p21, which shows the maximum reflectance. It is.
  • the dielectric multilayer film of the second embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that the reflection spectrum has chromaticity coordinates close to achromatic color.
  • FIG. 13(a) shows the results of a simulation using optical thin film design software for the reflection spectrum of each incident angle when the incident angle is increased by 5 degrees from normal incidence. It can be seen that there are a first main reflection peak and a second main reflection peak in both reflection spectra.
  • FIG. 13(b) shows the chromaticity coordinates of the first main reflection peak and the second main reflection peak at each incident angle on an xy chromaticity diagram.
  • FIG. 14(a) is an enlarged portion of the xy chromaticity diagram of FIG. 13(b) where the chromaticity coordinates of the first and second main reflection peaks are present.
  • FIG. 14(b) shows the chromaticity coordinates of the reflection spectrum at each incident angle on an xy chromaticity diagram.
  • both the first and second main reflection peaks are blue-shifted.
  • the chromaticity coordinates of the first main reflection peak and the second main reflection peak at each incident angle are the white (achromatic) area near W (hereinafter referred to as 0.25 ⁇ x ⁇ 0.4 on the xy chromaticity diagram, and , 0.25 ⁇ y ⁇ 0.4 is sometimes referred to as an achromatic neighborhood area. , in the achromatic neighborhood area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.31 ⁇ x ⁇ 0.34 and 0.28 ⁇ x ⁇ 0.34.
  • the dielectric multilayer film of the second embodiment has lower incident angle dependency than the dielectric multilayer film of the first embodiment, and the color of the reflected light when the incident angle is changed from 0° to 30° In degree coordinates (x, y), the change in both the x and y coordinates is 0.1 or less, the change in the x coordinate is 0.03 or less, and the change in the y coordinate is 0.06 or less.
  • the first and second main reflection peaks of the dielectric multilayer film have chromaticity coordinates on the short wavelength side and the long wavelength side across the dotted line shown in FIG.
  • the coordinates will be in the achromatic neighborhood area. If this is true for each incident angle, the incident angle dependency will be low.
  • both the reflection peak p21 and the reflection peak p22 have a full width at half maximum (FWHM) of 150 nm or less. It can be seen that the full width at half maximum (FWHM) of the reflection peak p21 is 100 nm or less.
  • a narrow full width at half maximum (FWHM) of the reflection peak means that reflected light energy is suppressed when the color adjusting plate of the present invention is used in a solar cell module, and as a result, a decrease in power generation efficiency can be suppressed. Therefore, it is preferable.
  • the reflectance of the "first main reflection peak” and the "second main reflection peak” is 70% or less, but the dielectric multilayer film of the second embodiment , the reflectances of the "first main reflection peak” and the "second main reflection peak” are 40% or less.
  • the color adjustment plate according to the third embodiment includes a dielectric multilayer film whose incident angle dependency is even lower than that of the dielectric multilayer film of the second embodiment.
  • FIG. 15A shows chromaticity coordinates c 30 (0.333, 0.327) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the third embodiment. It is a thing.
  • FIG. 15(b) shows the parameters of the dielectric multilayer model used in the simulation.
  • FIG. 16 shows the reflection spectrum when white light is vertically incident on the dielectric multilayer film of the third embodiment.
  • the reflection spectrum shown in FIG. 16 has two reflection peaks p31 and p32 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peak p31 and the reflection peak p32 have peak wavelengths in the vicinity of a wavelength of 470 nm and a wavelength of 600 nm, respectively, which are in the wavelength range of 380 nm or more and 780 nm or less, and the reflection peak p31 and the reflection peak p32 each have a wavelength of less than 520 nm.
  • the reflectance of the reflection peak p32 which is the first main reflection peak of the wavelength and the second main reflection peak of the wavelength of 520 nm or more, exhibits a reflectance of 20% or more with respect to the reflection peak p31, which shows the maximum reflectance. It is. Although the reflection peak p33 barely satisfies the requirement (1-1), it does not satisfy the requirement (1-3), and the reflection peak p34 does not satisfy the requirement (1-1). Thus, the dielectric multilayer film of the third embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that it exhibits a reflection spectrum having chromaticity coordinates close to white light (achromatic color) to the same extent as the multilayer film.
  • FIG. 17 shows the results of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the third embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram.
  • the chromaticity coordinates of the reflection spectrum for each incident angle are all placed in the achromatic neighborhood area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.31 ⁇ x ⁇ 0.34 and 0.32 ⁇ x ⁇ 0.34.
  • the dielectric multilayer film of the third embodiment has a lower incident angle dependency than the dielectric multilayer film of the second embodiment, and the reflected light when the incident angle is changed from 0° to 30°.
  • the change in both the x-coordinate and the y-coordinate is 0.1 or less
  • the change in the x-coordinate is 0.03 or less
  • the change in the y-coordinate is 0.02 or less.
  • both the reflection peak p31 and the reflection peak p32 have a full width at half maximum (FWHM) of 150 nm or less. It can be seen that the full width at half maximum (FWHM) of the reflection peak p31 is 100 nm or less.
  • a narrow full width at half maximum (FWHM) of the reflection peak means that reflected light energy is suppressed when the color adjusting plate of the present invention is used in a solar cell module, and as a result, a decrease in power generation efficiency can be suppressed. Therefore, it is preferable.
  • the reflectance of the "first main reflection peak” and the "second main reflection peak” is 70% or less, but the dielectric multilayer film of the third embodiment , the reflectances of the "first main reflection peak” and the "second main reflection peak” are 30% or less.
  • a color adjustment plate according to the fourth embodiment includes a dielectric multilayer film having four reflection peaks satisfying the above requirements (1-1) and (1-3).
  • FIG. 18A shows the chromaticity coordinates c 40 (0.311, 0.325) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the fourth embodiment. It is.
  • FIG. 18B shows parameters of the dielectric multilayer model used in the simulation.
  • FIG. 19 shows the reflection spectrum when white light is vertically incident on the dielectric multilayer film of the fourth embodiment.
  • the reflection spectrum shown in FIG. 19 has four reflection peaks p41 to p44 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peak p41 to the reflection peak p44 respectively have peak wavelengths in the wavelength range of 380 nm or more and 780 nm or less, which are near the wavelength of 440 nm, the wavelength of 490 nm, the wavelength of 560 nm, and the wavelength of 660 nm.
  • the peak p42 is the first main reflection peak with a wavelength of less than 520 nm
  • the reflection peaks p43 and p44 are the second main reflection peaks with wavelengths of 520 nm or more
  • the reflectance of the reflection peaks p42 to p44 is It shows a reflectance of 20% or more with respect to the reflection peak p41 which shows the maximum reflectance.
  • the reflection peaks p45 and p46 do not satisfy the requirement (1-1).
  • the dielectric multilayer film of the fourth embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that the reflection spectrum has a chromaticity coordinate close to that of white light (achromatic color) to the same extent as the multilayer film.
  • FIG. 20 shows the result of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the fourth embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram.
  • the chromaticity coordinates of the reflection spectrum for each incident angle are all placed in the achromatic neighborhood area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.31 ⁇ x ⁇ 0.33 and 0.32 ⁇ x ⁇ 0.35.
  • the dielectric multilayer film of the fourth embodiment also has a low incident angle dependency to the same degree as the dielectric multilayer film of the third embodiment, and the reflected light when the incident angle is changed from 0° to 30°
  • the change in both the x and y coordinates is 0.1 or less
  • the change in the x coordinate is 0.02 or less
  • the change in the y coordinate is 0.03 or less.
  • the full width at half maximum (FWHM) of each of the reflection peaks p41 to p44 is 100 nm or less. It can be seen that the full width at half maximum (FWHM) of the reflection peak p41 and the reflection peak p43 is 70 nm or less.
  • a narrow full width at half maximum (FWHM) of the reflection peak means that the reflected light energy is suppressed when the color adjusting plate of the present invention is used in a solar cell module, and as a result, a decrease in power generation efficiency can be suppressed. Therefore, it is preferable.
  • the reflectance of the "first main reflection peak” and the “second main reflection peak” is preferably 70% or less, but the dielectric multilayer film of the fourth embodiment , the reflectances of the "first main reflection peak” and the “second main reflection peak” are 55% or less.
  • the full width at half maximum (FWHM) of at least one of the first main reflection peak and the second main reflection peak is higher than that of any of the dielectric multilayer films according to the first to fourth embodiments. It has a dielectric multilayer film with narrow characteristics.
  • FIG. 21 shows chromaticity coordinates c 50 (0.347, 0.331) on an xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the fifth embodiment.
  • the dielectric multilayer film of the fifth embodiment has 63 layers in which high refractive index layers of titanium dioxide (TiO 2 ) and low refractive index layers of silicon dioxide (SiO 2 ) are alternately laminated. It will be.
  • FIG. 21(b) shows the parameters of the dielectric multilayer model used in the simulation.
  • FIG. 22 shows the reflection spectrum when white light is vertically incident on the dielectric multilayer film of the fifth embodiment.
  • the reflection spectrum shown in FIG. 22 has three reflection peaks p51 to p53 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peaks p51 to p53 each have a peak wavelength in the wavelength range of 380 nm or more and 780 nm or less, that is, near a wavelength of 390 nm, near 480 nm, and near a wavelength of 590 nm, and the reflection peak p51 and the reflection peak p52 are less than 520 nm.
  • the dielectric multilayer film of the fifth embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment, but as shown in FIG. It can be seen that the reflection spectrum has chromaticity coordinates that are similarly close to those of white light (achromatic color).
  • FIG. 23 shows the results of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the fifth embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram.
  • the chromaticity coordinates of the reflection spectra for each incident angle are all placed in the achromatic neighborhood area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the range of 0.30 ⁇ x ⁇ 0.35 and 0.31 ⁇ x ⁇ 0.34.
  • the dielectric multilayer film of the fifth embodiment has lower incident angle dependency than the dielectric multilayer film of the second embodiment, and the chromaticity coordinates (x , y), the change in both the x and y coordinates is less than or equal to 0.1, the change in the x coordinate is less than or equal to 0.05, and the change in the y coordinate is less than or equal to 0.03.
  • the full width at half maximum (FWHM) of each of the reflection peaks p51 to p53 is 50 nm or less.
  • a narrow full width at half maximum (FWHM) of the reflection peak means that the reflected light energy is suppressed when the color adjusting plate of the present invention is used in a solar cell module, and as a result, a decrease in power generation efficiency can be suppressed. Therefore, it is preferable.
  • the color adjusting plate according to the sixth embodiment includes a dielectric multilayer film having eight layers or less, which is less than the dielectric multilayer films according to the first to fifth embodiments.
  • FIG. 24A shows chromaticity coordinates c 60 (0.324, 0.334) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the sixth embodiment. It is.
  • FIG. 24( b ) shows the parameters of the dielectric multilayer film model used in the simulation . layer with a total film thickness of 217.4 nm.
  • FIG. 25 shows the reflection spectrum when white light is vertically incident on the dielectric multilayer film of the sixth embodiment.
  • the reflection spectrum shown in FIG. 25 has two reflection peaks p61 and p62 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peak p61 and the reflection peak p62 have peak wavelengths in the vicinity of a wavelength of 460 nm and a wavelength of 610 nm, respectively, which are in the wavelength range of 380 nm or more and 780 nm or less, and the reflection peak p61 is the first main reflection with a wavelength of less than 520 nm.
  • the reflection peak p62 is the second main reflection peak with a wavelength of 520 nm or more, and the reflectances of the reflection peak p61 and the reflection peak p62 are approximately the same, about 7%.
  • the dielectric multilayer film of the sixth embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that it exhibits a reflection spectrum having chromaticity coordinates close to white light (achromatic color) to the same extent as the multilayer film.
  • FIG. 26 shows the results of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the sixth embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram.
  • the chromaticity coordinates of the reflection spectrum for each incident angle are all placed in the achromatic neighborhood area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.32 ⁇ x ⁇ 0.34 and 0.33 ⁇ x ⁇ 0.35.
  • the dielectric multilayer film of the sixth embodiment also has a low incident angle dependency to the same extent as the dielectric multilayer film of the third embodiment, and the reflected light when the incident angle is changed from 0° to 30°
  • the change in both the x and y coordinates in the chromaticity coordinates (x, y) of is 0.1 or less, the change in the x coordinate is 0.02 or less, and the change in the y coordinate is 0.02 or less.
  • a color adjustment plate according to the seventh embodiment includes a dielectric multilayer film in which the chromaticity coordinates of reflected light for normal incidence are in a range other than the achromatic neighboring area. That is, it has a dielectric multilayer film colored in a color other than whitish coloring.
  • FIG. 27(a) shows the chromaticity coordinates c70 (0.506, 0.345) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the seventh embodiment. , that is, it indicates an orange-based color.
  • FIG. 27(b) shows the parameters of the dielectric multilayer model used in the simulation.
  • FIG. 28 shows reflection spectra when white light is vertically incident on the dielectric multilayer film of the seventh embodiment.
  • the reflection spectrum shown in FIG. 28 has two reflection peaks p71 and p72 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peak p71 and the reflection peak p72 have peak wavelengths in the vicinity of a wavelength of 480 nm and a wavelength of 630 nm, respectively, which are in the wavelength range of 380 nm or more and 780 nm or less, and the reflection peak p71 is the first main reflection with a wavelength of less than 520 nm.
  • the reflection peak p72 is the second main reflection peak with a wavelength of 520 nm or more, and the reflectance of the reflection peak p71 exhibits a reflectance of 20% or more with respect to the reflection peak p72, which shows the maximum reflectance. It is a thing. Note that the reflection peaks p73 and p74 do not satisfy the requirement (1-3), and the reflection peak p75 does not satisfy the requirement (1-1).
  • the dielectric multilayer film of the seventh embodiment by adopting a configuration in which the reflectances of the first main reflection peak and the reflection peak of the second main reflection peak are greatly different from each other, the chromaticity coordinates of areas other than the achromatic neighboring area are A reflected light with c 70 (0.506, 0.345) was to be produced.
  • FIG. 29 shows the result of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the seventh embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram.
  • the chromaticity coordinates of the reflection spectrum for each incident angle are all placed in the orange area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.47 ⁇ x ⁇ 0.52 and 0.33 ⁇ x ⁇ 0.36.
  • the dielectric multilayer film of the seventh embodiment which has chromaticity coordinates in the orange area under normal incidence, also has low incident angle dependence because the chromaticity coordinates only change within a narrow chromaticity coordinate range. It has become a thing.
  • a color adjustment plate according to the eighth embodiment includes a dielectric multilayer film having four reflection peaks satisfying the above requirements (1-1) and (1-3).
  • the change in the x and y coordinates of the chromaticity coordinates (x, y) of the reflected light is 0.1 or less when the incident angle dependence of the reflected light is varied over a wide range of 0° to 80°. confirmed.
  • FIG. 30(a) shows the chromaticity coordinates c80 (0.311, 0.325) on the xy chromaticity diagram of reflected light when white light is vertically incident on the dielectric multilayer film of the eighth embodiment. It is.
  • FIG. 30(b) shows the parameters of the dielectric multilayer model used in the simulation.
  • FIG. 31 shows a reflection spectrum when white light is vertically incident on the dielectric multilayer film of the eighth embodiment.
  • the reflection spectrum shown in FIG. 31 has four reflection peaks p81 to p84 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peaks p81 to p84 respectively have peak wavelengths in the wavelength range of 380 nm or more and 780 nm or less, that is, near a wavelength of 380 nm, near a wavelength of 430 nm, near a wavelength of 490 nm, and near a wavelength of 610 nm, and the reflection peaks p81 to p83.
  • the dielectric multilayer film of the fourth embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that it exhibits a reflection spectrum having chromaticity coordinates close to white light (achromatic color) to the same extent as the multilayer film.
  • FIG. 32 shows the result of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the eighth embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram. It was confirmed in a range from 0° to 80°, which is wider than the incident angle dependency of the example shown previously.
  • the chromaticity coordinates of the reflection spectrum for each incident angle are all placed in the achromatic neighborhood area.
  • the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.31 ⁇ x ⁇ 0.33 and 0.33 ⁇ x ⁇ 0.36.
  • the chromaticity coordinates (x, y), the change in both the x and y coordinates is 0.1 or less
  • the change in the x coordinate is 0.02 or less
  • the change in the y coordinate is 0.03 or less.
  • FIG. 33 is a schematic cross-sectional view of a color adjusting plate according to the ninth embodiment.
  • the color adjustment plate 20 shown in FIG. 33 includes a two-dimensional transparent substrate 21 (21A, 21B, 21C) and a high refractive index layer 22a on the entire outer surface (21a, 21b, 21c, 21d) of the transparent substrate 21. and a dielectric multilayer film 22 in which low refractive index layers 22b are alternately laminated.
  • FIG. 33 shows three color adjusting plates 20 .
  • the dielectric multilayer film 22 is configured to satisfy the following (1-1) to (1-3); (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) The plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the maximum reflectance among the reflection peaks in the wavelength range.
  • Examples of the plurality of two-dimensional transparent substrates 21 include natural mica, artificial mica, glass, and inorganic single crystals. Having two-dimensionality means that the thickness is smaller than the size in plan view, for example, 1/10 or less.
  • the dielectric multilayer film is formed on the transparent substrate by a liquid phase method such as a sol-gel method, so that the dielectric multilayer film is formed on the entire outer surface of the transparent substrate 21. .
  • the high refractive index layer 22a and the low refractive index layer 22b can be layers composed of a large number of crystal grains smaller than the wavelength of visible light.
  • a layer of crystal grains smaller than the wavelength of visible light acts optically as a film.
  • crystal grains of the materials of the high refractive index layer 2a and the low refractive index layer 2b can be used.
  • FIG. 34(a) shows chromaticity coordinates c80 (0.329, 0.322) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the ninth embodiment. It is.
  • FIG. 34(b) shows parameters of the dielectric multilayer model used in the simulation.
  • FIG. 35 shows the reflection spectrum when white light is vertically incident on the dielectric multilayer film of the ninth embodiment.
  • mica is used as the transparent substrate
  • PMMA polymethyl methacrylate resin
  • the reflection spectrum shown in FIG. 35 has two reflection peaks p91 and p92 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peaks p91 and p92 have peak wavelengths in the vicinity of a wavelength of 380 nm and a wavelength of 600 nm, respectively, which are in the wavelength range of 380 nm or more and 780 nm or less, and the reflection peak p91 is the first main reflection peak with a wavelength of less than 520 nm.
  • the reflection peak p92 is the second main reflection peak with a wavelength of 520 nm or more, and the reflectance of the reflection peak p92 shows a reflectance of 20% or more with respect to the reflection peak p91, which shows the maximum reflectance. be.
  • the dielectric multilayer film of the ninth embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that it exhibits a reflection spectrum having chromaticity coordinates close to white light (achromatic color) to the same extent as the multilayer film.
  • FIG. 36 shows the results of simulation using optical thin film design software for each reflection spectrum when the incident angle of white light on the dielectric multilayer film of the ninth embodiment is increased by 5° from normal incidence.
  • the chromaticity coordinates of the reflection spectrum are shown on the xy chromaticity diagram.
  • the chromaticity coordinates of the reflection spectrum for each incident angle are all placed in the achromatic neighborhood area. More specifically, the chromaticity coordinates of the reflection spectrum at each incident angle are in the ranges of 0.32 ⁇ x ⁇ 0.33 and 0.31 ⁇ x ⁇ 0.34.
  • the dielectric multilayer film of the ninth embodiment also has a low incident angle dependency to the same extent as the dielectric multilayer film of the above embodiments, and the reflected light when the incident angle is changed from 0° to 30°.
  • the change in both the x-coordinate and the y-coordinate is 0.1 or less
  • the change in the x-coordinate is 0.01 or less
  • the change in the y-coordinate is 0.03 or less.
  • a large number of color adjustment plates are attached to a target article such as a solar battery cell by coating or the like. It has little effect on color due to its low incident angle dependence.
  • the color adjustment plate according to the tenth embodiment also includes a plurality of two-dimensional transparent substrates, a high refractive index layer formed on the entire outer surface of the transparent substrate, and a high refractive index layer. and a dielectric multilayer film in which low refractive index layers are alternately laminated.
  • FIG. 37(a) shows chromaticity coordinates c 90 (0.325, 0.329) on the xy chromaticity diagram for reflected light when white light is vertically incident on the dielectric multilayer film of the tenth embodiment. It is a thing.
  • FIG. 37(b) shows the parameters of the dielectric multilayer model used in the simulation.
  • FIG. 38 shows reflection spectra when white light is vertically incident on the dielectric multilayer film of the tenth embodiment.
  • a simulation was performed using a model in which mica was used as a transparent substrate and PMMA (polymethyl methacrylate resin) for attaching a color adjustment plate to an article such as a solar cell was formed on a dielectric multilayer film.
  • PMMA polymethyl methacrylate resin
  • the reflection spectrum shown in FIG. 38 has two reflection peaks p101 and p102 that satisfy the above requirements (1-1) to (1-3). That is, the reflection peaks p101 and p102 have peak wavelengths in the vicinity of a wavelength of 380 nm and a wavelength of 590 nm, respectively, which are in the wavelength range of 380 nm or more and 780 nm or less, and the reflection peak p91 is the first main reflection peak with a wavelength of less than 520 nm.
  • the reflection peak p92 is the second main reflection peak with a wavelength of 520 nm or more, and the reflectance of the reflection peak p102 shows a reflectance of 20% or more with respect to the reflection peak p101, which shows the maximum reflectance. be.
  • the dielectric multilayer film of the ninth embodiment has reflection characteristics different from those of the dielectric multilayer film of the first embodiment. It can be seen that the reflection spectrum has a chromaticity coordinate close to that of white light (achromatic color) to the same extent as the multilayer film.
  • the color adjustment plate of the present invention (FIG. 39(a)) can be used by arranging other layers such as a sealing material appropriately on the dielectric multilayer film.
  • FIG. 40 illustrates the case of using it in a solar cell module, but it can be used in other products as long as it is used in the same way.
  • symbols 100A, 100B, 100C, 100D, 100E, 100F and 100G denote solar cell modules
  • symbols 10A, 10B, 10C, 10D, 10E, 10F and 10G Color adjustment plates are shown
  • solar cells are shown by reference numerals 11A, 11B, 11C, 11D, 11E, 11F, and 11G, and reference numerals 1A, 1B, 1C, 1D, 1E, 1F, and 1G.
  • FIG. 40(a) shows an example in which the color adjustment plate of the present invention is provided on the light-receiving surface side of the solar cell module, and the dielectric multilayer film is arranged facing the solar cell side;
  • (c) is an example in which the substrate side faces the solar cell side
  • (c) is an example in which a back sheet is provided on the back side of the solar cell module
  • (d) is an example of the present invention.
  • the color adjustment plate is provided on the light-receiving surface side of the solar cell module, and is a case where the solar cells are arranged in a sealed space containing a gas such as air.
  • a gas such as air
  • the surface of the substrate has unevenness
  • (e) is an example in which the color adjustment plate of the present invention is provided on the light receiving surface side of the solar cell module, and the dielectric multilayer film is arranged facing the solar cell side.
  • the color adjustment plate of the present invention is provided on the light-receiving surface side of a solar cell module, and the substrate is a solar cell.
  • (g) shows the color adjustment plate of the present invention, in which the dielectric multilayer film is formed on the surface having the unevenness on the surface of the substrate facing the atmosphere, and the substrate has unevenness on the surface facing the atmosphere.
  • the dielectric multilayer film is arranged facing the solar cell side, the surface of the substrate facing the solar cell has unevenness, and the unevenness is This is the case where a dielectric multilayer film is formed on the surface having the surface.
  • FIGS. 41(a) to 41(c) are cross-sectional schematic views of a color adjustment plate according to the present invention, in which either one of the film-formed surface and the non-film-formed surface of the substrate is a diffuse reflection surface.
  • the graph shown in FIG. 41 shows a configuration in which sandblasting is performed using abrasive grains of #600, #400, and #220 (Fujirandom A by Fuji Seisakusho Co., Ltd.) to form a diffuse reflection surface.
  • #600 has an average particle size of 20.0 ⁇ m ⁇ 1.5 ⁇ m and a maximum particle size of 53.0 ⁇ m or less
  • #400 has an average particle size of 25.0 ⁇ m ⁇ 2.0 ⁇ m and a maximum particle size of 63.0 ⁇ m
  • #220 has a median particle size of 75 to 45 ⁇ m.
  • the substrate 1 (1a, 1b, 1c, 1d) in FIGS. 41(a) to (c) is BK7 (borosilicate crown glass), and the dielectric multilayer films 2 (2a, 2b, 2c) are, in order from the substrate side, 1st layer (TiO 2 , 15.1 nm), 2nd layer (SiO 2 , 37.1 nm), 3rd layer (TiO 2 , 15.3 nm), 4th layer (SiO 2 , 44.1 nm), 5th layer Layer ( TiO2 , 84.9 nm), 6th layer (SiO2, 21.4 nm), 7th layer (TiO2 , 97.7 nm), 8th layer (SiO2 , 22.7 nm ) , 9th layer ( TiO 2 , 22.5 nm), 10th layer (SiO 2 , 22.4 nm), 11th layer (TiO 2 , 10 nm), and 12th layer (SiO 2
  • the dielectric multilayer film 2a is formed on the flat surface of the substrate 1a on the white light incident surface side, which is not sandblasted, and the diffuse reflection surface 1aa of the substrate 1a is the solar cell. It is a configuration that is placed on the side.
  • the dielectric multilayer film 2b is formed on the diffuse reflection surface 1bb of the substrate 1b on the solar cell side, and the incident surface of the white light is sandblasted. It is a configuration in which a flat surface that is not flat is arranged.
  • the color adjusting plate of FIG. 41(c) (corresponding to FIG.
  • FIG. 40(e) has a dielectric multilayer film 2b on the solar cell side of the substrate 1b, which is formed on a flat surface that is not sandblasted, and which emits white light.
  • the incident surface is the diffuse reflection surface 1cc.
  • FIG. 41(d) shows a configuration of only the substrate 1d without the dielectric multilayer film, white light is incident on the flat surface that is not sandblasted, and the diffuse reflection surface 1dd is provided on the solar cell side. Configuration.
  • the L * value is higher in the order of #220, #400, and #600 abrasive grains. That is, when sandblasting is performed with these three types of abrasive grains to form a diffuse reflection surface, the L * value is higher when coarse abrasive grains (abrasive grains with a smaller count) are used. This indicates that the scattered light can be adjusted by adjusting the size of the uneven structure on the diffuse reflection surface. This indicates that the magnitude of was suitable for increasing the L * value.
  • the dielectric multilayer film placed on the flat surface of the substrate is placed on the solar cell side, and the diffuse reflection surface is placed on the light incident side (c) Color adjustment
  • the plate (corresponding to FIG. 40(e)) has the highest L * value.
  • FIG. 42 shows the color adjustment plate having the configuration shown in FIGS. 41(a) to (c), the diffuse reflection surface of which is formed by sandblasting using abrasive grains of #600, #400, and #220.
  • the results of measurement of the rate of decrease ⁇ Jsc (%) of the short-circuit current of the solar cell module (current flowing when the external voltage applied to the solar cell is 0 V) are shown. Also shown for reference are the results of measuring the rate of decrease ⁇ Jsc (%) of the short-circuit current of the solar cell module when the substrate having the configuration shown in FIG. 41(d) was used instead of the color adjustment plate.
  • ⁇ Jsc (%) is an index for evaluating solar cell efficiency.
  • the reduction rate ⁇ Jsc of the short-circuit current is smaller in the order of abrasive grains #600, #400, and #220. That is, when sandblasting is performed with these three types of abrasive grains to form a diffuse reflection surface, ⁇ Jsc is suppressed when fine abrasive grains (abrasive grains with a large number) are used (that is, the solar cell reduction in efficiency is suppressed). This indicates that the reduction rate ⁇ Jsc of the short-circuit current can be adjusted depending on the degree of the uneven structure of the diffuse reflection surface.
  • the size of the uneven structure on the surface is suitable for suppressing the reduction rate ⁇ Jsc of the short circuit current.
  • the dielectric multilayer film placed on the flat surface of the substrate is placed on the solar cell side, and the diffuse reflection surface is placed on the light incident side. 40(e)) has the most reduced short-circuit current decrease rate ⁇ Jsc (that is, the decrease in the efficiency of the solar cell is suppressed).
  • the dielectric multilayer film arranged on the flat surface of the substrate is arranged on the solar cell side
  • the color adjustment plate of (c) (equivalent to FIG. 40(e)), in which the diffuse reflection surface is arranged on the light incident side, exhibits a high L * value and suppresses the rate of decrease ⁇ Jsc of the short circuit current most. I understand.
  • FIGS. 43(a) to 43(c) show optical micrographs of diffuse reflection surfaces of glass substrates sandblasted with abrasive grains of #600, #400, and #220, respectively.
  • FIG. 44 shows the arithmetic mean roughness Ra, maximum height Ry, and root mean square height Rq along line XX in each of FIGS. 43(a) to (c).
  • the roughness Rq of the diffuse reflection surface is preferably 0.4 ⁇ m to 1.3 ⁇ m.
  • a solar cell module includes a plurality of solar cells and a color adjustment plate disposed on the light receiving surface side of the plurality of solar cells. It has a dielectric multilayer film in which refractive index layers and low refractive index layers are alternately laminated, and the dielectric multilayer film includes the above (1-1) to (1-3), (1-5) and ( 1-6) is satisfied.
  • FIG. 45 is a schematic cross-sectional view of part of a solar cell module to which the color adjustment plate of the present invention is applied.
  • Solar cell module 100 shown in FIG. 45 includes solar cell 111, color adjusting plate 10A provided on the light receiving surface side of solar cell 111, second protective member 112 provided on the back side of solar cell 111, A sealing material 114 is provided between the first protective member 11 and the second protective member 112 to seal the solar cell 111 .
  • Sealing material 114 includes sealing material 114 a arranged between solar cell 111 and first protective member 11 and sealing material 114 b arranged between solar cell 111 and second protective member 112 . include.
  • a color adjusting plate 10A shown in FIG. 45 includes a first protective member (corresponding to the substrate 1) 11 and a dielectric plate formed on the first protective member 11 and having high refractive index layers and low refractive index layers alternately laminated. and a body multilayer film 12 .
  • a known type of solar cell can be used as the solar cell 111 .
  • either a double-sided electrode type solar cell or a back electrode type solar cell can be used.
  • the first protective member 11 for example, a member having translucency such as a glass substrate, a resin substrate, or a resin film can be used.
  • the same transparent member as the first protection member 11 may be used for the second protection member 112, or an opaque member may be used.
  • the encapsulant 114 plays a role of preventing moisture or the like from contacting the solar cell 111 . It is preferable that the resin forming the sealing material 114 has good adhesion to each protective member and the solar cell 111 and is difficult to permeate moisture.
  • the wiring members 115 are attached to the electrodes of the solar cells 111 by, for example, an adhesive.
  • a solar cell module includes a plurality of solar cells, and a color adjustment plate disposed on the light receiving surface side of the plurality of solar cells.
  • the color adjustment plate includes a plurality of two-dimensional transparent substrates. and a dielectric multilayer film in which high refractive index layers and low refractive index layers are alternately laminated on the entire outer surface of a transparent substrate, and the dielectric multilayer film has the following (1-1): ⁇ (1-3), (1-5) and (1-6) are satisfied.
  • a solar cell module includes a plurality of solar cells, and a color adjustment plate disposed on the light receiving surface side of the plurality of solar cells. and an inorganic pigment-containing layer containing an inorganic pigment formed on at least one of the back surfaces of the substrate.
  • One of the film forming surfaces is formed as a diffuse reflection surface having an uneven structure, or is a diffusion plate.
  • a pearl pigment is a pigment in which the surfaces of flaky particles (for example, particles having a longest diameter of 2 to 100 ⁇ m and a thickness of 0.01 to 10 ⁇ m) are coated with a metal or an oxide thereof.
  • flaky particles include natural mica, artificial mica, glass and inorganic single crystals.
  • the metal or oxide thereof that coats the surface of the flaky particles include titanium dioxide, iron oxide, and silver.
  • commercially available pearl pigments include TWINCLEPEARL (product name, manufactured by Nihon Koken Kogyo Co., Ltd.). For example, TWINCLEPEARL SXD (average particle size: 5-60 ⁇ m) can be used.
  • the inorganic pigment-containing layer can be formed by coating, vapor deposition, or the like.
  • the concentration is preferably about 0.125% by weight.
  • the concentration should not exceed 0.5% by weight, for example, 0.1 to 0.5% by weight, from the viewpoint of the short-circuit current reduction rate ⁇ Jsc (%) and the whiteness (L * value). can.
  • a color adjustment plate which is an inorganic pigment-containing layer
  • the surface roughness of the diffuse reflection surface corresponding to the symbol 1cc in FIG. 41(c)
  • the reduction rate ⁇ Jsc %) of the short-circuit current of the solar cell module were measured.
  • the relationship was examined and the results are shown in FIG.
  • White light was incident from the diffuse reflection surface at an incident light angle of 45° (with the direction perpendicular to the substrate surface being 0°).
  • the surface roughness was evaluated by the “contact type (stylus type)” evaluation method based on ISO25178 using the root mean square height Rq [ ⁇ m]. The measurement was performed using a stylus type surface roughness meter Dektak (manufactured by Bruker). The diffuse reflection surface was produced by sandblasting. For comparison, ⁇ Jsc was also evaluated for samples that were not subjected to sandblasting (same configuration except that sandblasting was not performed). In FIG. 46, incident light from the diffuse reflection surface is referred to as textured surface incident light, and for comparison, incident light to a non-textured surface that is not sandblasted is referred to as flat plate light incident light.
  • ⁇ Jsc increases as the surface roughness of the diffuse reflection surface increases to about 3 ⁇ m (in other words, the solar cell efficiency decreases).
  • Rq of the diffuse reflection surface it is preferable to set the surface roughness Rq of the diffuse reflection surface to 2.0 ⁇ m or less.
  • Rq of the diffuse reflection surface it is preferable to set the surface roughness Rq of the diffuse reflection surface to 1.3 ⁇ m or less.
  • FIG. 47 using the same color adjustment plate as the color adjustment plate used to obtain FIG. 46, white light is emitted from the diffuse reflection surface at an incident light angle of 45° (perpendicular to the substrate surface is 0°). The light is incident and observed at 0° to examine the relationship between the surface roughness of the diffuse reflection surface and the whiteness (L * value) of the color adjustment plate. For comparison, the whiteness (L * value) was also evaluated for those not subjected to sandblasting (the same configuration except that sandblasting was not performed). In FIG. 47, plane incidence is without sandblasting.
  • the whiteness (L * value) of the color adjustment plate increases as the surface roughness increases up to a surface roughness of about 3 ⁇ m.
  • a whiteness (L * value) of 25 or more it is preferable to set the surface roughness Rq to 0.1 ⁇ m or more.
  • a whiteness (L * value) of 35 or more it is preferable to set the surface roughness Rq to 1.5 ⁇ m or more.
  • the surface roughness Rq of the diffuse reflection surface should be 0.1 ⁇ m or more. 0 ⁇ m or less is preferable.
  • the surface roughness Rq should be 0.7 ⁇ m or more and 2.0 ⁇ m or less. preferably.
  • the surface roughness Rq should be 1.5 ⁇ m or more and 2.0 ⁇ m or less. preferably. In order to keep ⁇ Jsc within 20% and whiteness (L * value) to be 25 or more in the color adjustment plate having a diffuse reflection surface, the surface roughness Rq should be 0.1 ⁇ m or more and 1.3 ⁇ m or less. preferably. In order to keep ⁇ Jsc within 20% and whiteness (L * value) of 30 or more in the color adjustment plate having a diffuse reflection surface, the surface roughness Rq should be 0.7 ⁇ m or more and 1.3 ⁇ m or less. preferably.
  • the diffuse reflection surface is When using a substrate having a surface roughness Rq of the diffuse reflection surface is preferably 0.1 ⁇ m to 2.0 ⁇ m depending on whether the solar cell efficiency or the whiteness is more important.
  • a method for manufacturing a color adjustment plate according to the present invention is a method for manufacturing a color adjustment plate according to the present invention, comprising: and a dielectric multilayer film determination step of determining at least one parameter of the number of layers by optical thin film design simulation.
  • a film forming method according to the present invention is a film forming method for forming a dielectric multilayer film in which high refractive index layers and low refractive index layers are alternately laminated on a substrate or on the entire outer surface of a transparent substrate.
  • a known dry thin film method such as a vapor deposition method or a sputtering method can be used when forming a dielectric multilayer film on a substrate.
  • a known wet thin film method may be used.
  • a step of adjusting the size of the two-dimensional transparent substrate such as mica.
  • a mica substrate having a desired particle size distribution may be obtained by pulverizing (for example, wet pulverizing) raw mica and classifying and adjusting the particle size.
  • the titanyl sulfate method, the titanium tetrachloride method, and the sol-gel method are used when forming the dielectric multilayer film on the entire outer surface of the transparent substrate.
  • a known wet thin film forming method such as a method can be used.
  • the following chemical reactions can be used for depositing a TiO 2 layer, depositing a SiO 2 layer, and depositing a SnO 2 layer. These layers may be appropriately subjected to a crystallization process such as drying and firing.
  • a color adjustment plate formed by forming a dielectric multilayer film on a plurality of two-dimensional transparent substrates such as mica is attached to a target article such as a solar battery cell using an acrylic resin or the like (reference numeral 30 in FIG. 48). be able to.
  • a solar cell module or the like can be manufactured by mixing a color adjustment plate with a clear paint such as an acrylic resin, applying the mixture, and drying the mixture.
  • a bar coater, a doctor blade, a spray gun, an applicator, or the like can be used for the coating method.
  • the color adjustment plate 20 having a plurality of two-dimensional transparent substrates such as mica is fixed in parallel to the glass substrate when the solvent in the clear paint evaporates and solidifies, as shown in FIG.
  • the solar cell module 200 can be fabricated by bonding the two-dimensional planes parallel to the object article (for example, solar cell) 121 .
  • a technique of applying a pigment can be appropriately applied.
  • the size (two-dimensional surface direction) of a transparent substrate having two-dimensionality such as mica is not particularly specified because it is usually used by pulverizing the exfoliated substrate, but it is an irregular shape of about several ⁇ m to several hundred ⁇ m and has a thickness of about several ⁇ m. The thickness is several nm to several ⁇ m. Also, if the color adjustment plate thus produced is adhered to a transparent substrate (such as glass), it can be used in a structure completely similar to that shown in FIG.
  • the acrylic resin may be diluted with butyl acetate or the like to make it easier to apply.
  • the acrylic resin may be diluted to about 70% after drying.
  • the initial film thickness with a spray gun or applicator may be about 200 ⁇ m, and after drying shrinkage, about 30% of the resin solid content may remain, and the mica may be arranged parallel to the glass substrate.
  • the surface of the glass substrate is preferably subjected to surface treatment such as polarity so that the mica pigment or the acrylic resin adheres firmly and uniformly.
  • a film forming apparatus is a film forming apparatus for forming a dielectric multilayer film in which high refractive index layers and low refractive index layers are alternately laminated on a substrate or on the entire outer surface of a transparent substrate.
  • the materials, thicknesses, and numbers of the high-refractive-index layers and the low-refractive-index layers are selected so that the dielectric multilayer film satisfies at least the following (1-1) to (1-3): an optical parameter determining means for determining at least one parameter by optical thin film design simulation; (1-1) White light is incident in the vertical direction and the reflected light reflected in the same direction as the vertical direction exhibits spectral reflectance characteristics having a plurality of reflection peaks in the wavelength range of 380 nm or more and 780 nm or less, (1-2) the plurality of reflection peaks include at least one first main reflection peak with a wavelength of less than 520 nm and one second main reflection peak with a wavelength of 520 nm or more; (1-3) The plurality of reflection peaks exhibit a reflectance of 20% or more with respect to the reflection peak exhibiting the maximum reflectance among the reflection peaks in the wavelength range.

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  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une plaque de réglage de couleur (10) comprenant : un substrat (1) ; et un film multicouche diélectrique (2) formé sur le substrat (1) et obtenu par empilement alterné de couches à indice de réfraction élevé et de couches à faible indice de réfraction. Le film multicouche diélectrique (2) est configuré de manière à satisfaire (1-1) à (1-3). (1-1) La lumière réfléchie obtenue par la réflexion de la lumière blanche qui a été incidente depuis une direction verticale dans la même direction que la direction verticale présente une propriété de réflexion spectrale ayant une pluralité de pics de réflexion dans une plage de longueurs d'onde de 380 à 780 nm inclus. (1-2) La pluralité de pics de réflexion comprend au moins un premier pic de réflexion principal à des longueurs d'onde inférieures à 520 nm et au moins un second pic de réflexion principal à des longueurs d'onde de 520 nm ou plus. (1-3) La pluralité de pics de réflexion présentent des réflectances de 20 % ou plus par rapport à un pic de réflexion présentant une réflectance maximale parmi les pics de réflexion dans la plage de longueurs d'onde.
PCT/JP2022/045498 2021-12-10 2022-12-09 Plaque de réglage de couleur, module de cellule solaire, procédé de fabrication de plaque de réglage de couleur, procédé de dépôt et dispositif de dépôt WO2023106408A1 (fr)

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JP2021-200963 2021-12-10
JP2021200963 2021-12-10
JP2022-102066 2022-06-24
JP2022102066 2022-06-24

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WO2023106408A1 true WO2023106408A1 (fr) 2023-06-15

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JP (1) JP2023086720A (fr)
WO (1) WO2023106408A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010201644A (ja) * 2009-02-27 2010-09-16 Fujitsu Component Ltd 装飾体及びその製造方法
JP2016500799A (ja) * 2012-09-20 2016-01-14 スイスインソ・ソシエテ・アノニム 太陽エネルギーシステムに適した着色反射および高日射透過率を有する積層グレージング（ｌａｍｉｎａｔｅｄｇｌａｚｉｎｇ）
JP2021502703A (ja) * 2017-11-09 2021-01-28 ザ・リージェンツ・オブ・ザ・ユニバーシティ・オブ・ミシガンＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｍｉｃｈｉｇａｎ 高効率且つ角度に耐性のある太陽光発電デバイス用色付きフィルタ組立体
JP2021505955A (ja) * 2017-12-06 2021-02-18 ヒュー エーアイ エルエルシー 改善した装飾的外観を有する人間の色覚を向上させるための光学デバイス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010201644A (ja) * 2009-02-27 2010-09-16 Fujitsu Component Ltd 装飾体及びその製造方法
JP2016500799A (ja) * 2012-09-20 2016-01-14 スイスインソ・ソシエテ・アノニム 太陽エネルギーシステムに適した着色反射および高日射透過率を有する積層グレージング（ｌａｍｉｎａｔｅｄｇｌａｚｉｎｇ）
JP2021502703A (ja) * 2017-11-09 2021-01-28 ザ・リージェンツ・オブ・ザ・ユニバーシティ・オブ・ミシガンＴｈｅ Ｒｅｇｅｎｔｓ Ｏｆ Ｔｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｍｉｃｈｉｇａｎ 高効率且つ角度に耐性のある太陽光発電デバイス用色付きフィルタ組立体
JP2021505955A (ja) * 2017-12-06 2021-02-18 ヒュー エーアイ エルエルシー 改善した装飾的外観を有する人間の色覚を向上させるための光学デバイス

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