WO2022114028A1 - Substrat de verre à film conducteur transparent et cellule solaire - Google Patents

Substrat de verre à film conducteur transparent et cellule solaire Download PDF

Info

Publication number
WO2022114028A1
WO2022114028A1 PCT/JP2021/043067 JP2021043067W WO2022114028A1 WO 2022114028 A1 WO2022114028 A1 WO 2022114028A1 JP 2021043067 W JP2021043067 W JP 2021043067W WO 2022114028 A1 WO2022114028 A1 WO 2022114028A1
Authority
WO
WIPO (PCT)
Prior art keywords
transparent conductive
conductive film
layer
glass substrate
oxide layer
Prior art date
Application number
PCT/JP2021/043067
Other languages
English (en)
Japanese (ja)
Inventor
至弘 岩田
卓 立川
亮 高橋
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Publication of WO2022114028A1 publication Critical patent/WO2022114028A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate

Definitions

  • the present invention relates to a glass substrate with a transparent conductive film and a solar cell using the glass substrate with a transparent conductive film.
  • a glass substrate with a transparent conductive film is a semiconductor such as an ITO film (tin-doped indium oxide), an FTO film (fluorine-doped tin oxide), and a TO film (tin oxide) on the surface of glass, which is an insulator. It is a glass to which conductivity is imparted by forming a thin film (transparent conductive film) of ceramics.
  • a glass substrate with a transparent conductive film is generally obtained by laminating an undercoat layer, a transparent conductive film layer, and a surface layer on a glass plate in this order.
  • Such a glass substrate with a transparent conductive film is used for a solar cell, a liquid crystal display of a personal computer, a television, a mobile phone, or the like.
  • a solar cell converts light energy into electrical energy by absorbing light in a predetermined wavelength band of sunlight.
  • solar cells such as amorphous silicon (a-Si) solar cells, cadmium telluride (CdTe) solar cells, CIS-based solar cells, and CIGS-based solar cells, depending on the difference in the absorption wavelength band.
  • a-Si amorphous silicon
  • CdTe cadmium telluride
  • CIS-based solar cells CIS-based solar cells
  • CIGS-based solar cells depending on the difference in the absorption wavelength band.
  • Each solar cell uses a glass substrate with a transparent conductive film suitable for each, and is configured by laminating a light absorption layer on the glass substrate with a transparent conductive film.
  • an alkali-containing substrate glass having a smooth surface is composed of a metal oxide base film having a crystalline thickness of 150 ⁇ or more for imparting unevenness and SiO 2 , and the unevenness of the base film.
  • An alkaline barrier continuous film having a film thickness reflecting the above and a transparent conductive film having a film thickness of 5000 ⁇ or more composed of SiO 2 doped with impurities are formed in that order, and the transparent conductive film has an adhesive force of JIS R3255-.
  • a glass substrate with a transparent conductive film having a diameter of 37 mN or more specified in 1997 "Adhesion test of a thin film using glass as a substrate" has been proposed. It is described that the glass substrate with a transparent conductive film described in Patent Document 1 is particularly useful as a substrate for an amorphous silicon solar cell.
  • a glass substrate with a transparent conductive film is required to have various characteristics according to various uses.
  • the manufactured solar cell is in addition to having high light transmission because the solar cell uses light and excellent heat resistance when forming a film of a light absorption layer. It is required to reduce the color spots of the light.
  • a semiconductor thin film of cadmium tellurium which is a light absorption layer
  • heating is performed at a high temperature of 650 ° C. or higher.
  • the undercoat layer is deteriorated by heat, the electric resistance of the glass substrate with a transparent conductive film becomes high, and the power generation efficiency of the obtained cadmium tellurium solar cell may decrease.
  • the conventional glass substrate with a transparent conductive film has a large in-plane film thickness distribution, and the cadmium telluride solar cell may have large color spots.
  • the number of situations in which solar cells are used has increased, and not only efficiency but also designability may be required. Therefore, a glass substrate with a transparent conductive film capable of suppressing color spots has been required.
  • the present invention has been made in view of the above problems, and is a glass substrate with a transparent conductive film having high light transmittance and excellent heat resistance, and further, transparent conductivity capable of suppressing variation in reflected color in the plane.
  • An object of the present invention is to provide a glass substrate with a film.
  • the present inventors have made the undercoat layer a laminated structure including a titanium oxide layer and a silicon oxide layer, and set the film thickness of each layer formed on the glass plate within a specific range. We have found that this can solve the above problems, and have arrived at the present invention.
  • the present invention relates to the following ⁇ 1> to ⁇ 9>.
  • the titanium oxide layer is located on the glass plate side
  • the silicon oxide layer is located on the transparent conductive film layer side
  • the titanium oxide layer has a film thickness of 3 to 50 nm
  • the silicon oxide layer has a film thickness of 10.
  • the thickness of the transparent conductive film layer is about 200 nm
  • the thickness of the transparent conductive film layer is 200 to 1000 nm
  • the thickness of the surface layer is 10 to 150 nm.
  • a glass substrate with a transparent conductive film that satisfies the relationships of the following formulas (1) and (2) when SiO2 is used.
  • the silicon oxide layer has a film thickness of 10 to 120 nm.
  • the transparent conductive film layer contains at least one selected from the group consisting of zinc oxide, fluorine-doped tin oxide, tin-doped indium oxide, niob-doped titanium oxide, tantalum-doped titanium oxide, and antimony-doped tin oxide.
  • ⁇ 6> The glass substrate with a transparent conductive film according to any one of ⁇ 1> to ⁇ 5>, wherein the transparent conductive film layer has a film thickness of 200 to 700 nm.
  • ⁇ 7> The glass substrate with a transparent conductive film according to any one of ⁇ 1> to ⁇ 6>, wherein the surface layer has a film thickness of 10 to 100 nm.
  • a solar cell comprising the glass substrate with a transparent conductive film according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> The solar cell according to ⁇ 8>, wherein the solar cell is a cadmium telluride solar cell.
  • the present invention it is possible to provide a glass substrate with a transparent conductive film having high light transmission and excellent heat resistance. Further, since the glass substrate with a transparent conductive film of the present invention can suppress the variation in the reflected color in the plane, the solar cell obtained by using the glass substrate with the transparent conductive film of the present invention can reduce the color unevenness.
  • FIG. 1 is a cross-sectional view of a glass substrate with a transparent conductive film as an example for explaining the configuration of the glass substrate with a transparent conductive film of the present invention.
  • FIG. 2 is a diagram showing simulation results of the relationship between the thickness of the titanium oxide layer and the silicon oxide layer and the color spots of the cadmium telluride solar cell.
  • FIG. 3 is a diagram showing a simulation result of the relationship between the thickness of the titanium oxide layer and the silicon oxide layer and the light transmittance of the glass substrate with a transparent conductive film.
  • FIG. 1 is a cross-sectional view of a glass substrate with a transparent conductive film as an example for explaining the configuration of the glass substrate with a transparent conductive film of the present invention.
  • the glass substrate 10 with a transparent conductive film of the present invention is formed by laminating an undercoat layer 3, a transparent conductive film layer 5, and a surface layer 7 on a glass plate 1 in this order.
  • the undercoat layer 3 has a laminated structure including a titanium oxide layer 31 and a silicon oxide layer 32, and the titanium oxide layer 31 is located on the glass plate 1 side and the silicon oxide layer 32 is located on the transparent conductive film layer 5 side.
  • the configuration of the glass substrate with a transparent conductive film will be specifically described by taking a solar cell as an example of the obtained product.
  • the glass plate 1 is a supporting base material for the glass substrate 10 with a transparent conductive film.
  • the same one as that conventionally used for a solar cell can be used.
  • a glass plate containing SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, CaO, SrO, BaO, ZrO 2 , Na 2 O and K 2 O as a mother composition can be mentioned. More specifically, in the oxide-based molar percentage display, SiO 2 is 60 to 75%, Al 2 O 3 is 1 to 7.5%, B 2 O 3 is 0 to 1%, and MgO is 8.5.
  • the glass plate preferably has an average transmittance of 90.3% or more, more preferably 90.4% or more, and more preferably 90. More preferably, it is 5.5% or more.
  • the glass substrate with a transparent conductive film may be heat-treated when the solar cell is manufactured, it is preferable that the glass plate has good heat resistance.
  • the glass transition temperature (Tg) is preferably 640 ° C. or higher, more preferably 645 ° C. or higher, and even more preferably 655 ° C. or higher.
  • the glass transition temperature is preferably 750 ° C. or lower, more preferably 720 ° C. or lower so as not to increase the viscosity at the time of melting too much.
  • the average coefficient of thermal expansion of the glass plate at 50 to 350 ° C. is preferably 70 ⁇ 10 -7 / ° C. or higher, preferably 80 ⁇ 10 -7 / ° C. or higher, from the viewpoint of suppressing warping of the module during modularization. Is more preferable.
  • 90 ⁇ 10 -7 / ° C. or less is preferable, and 85 ⁇ 10 -7 / ° C. or less is more preferable.
  • the thickness of the glass plate is not particularly limited, but is preferably in the range of 1 to 5 mm from the viewpoint of the balance between mechanical strength and light transmission.
  • the thickness of the glass plate is more preferably 2 mm or more, further preferably 2.5 mm or more, further preferably 4.5 mm or less, further preferably 4 mm or less, and particularly preferably 3.5 mm or less.
  • the shape of the glass plate is not particularly limited, and can be appropriately selected depending on the shape of the solar cell manufactured by using the glass substrate with the transparent conductive film of the present invention.
  • the cross-sectional shape may be a flat plate shape, a curved surface shape, or another irregular shape.
  • the undercoat layer 3 is provided to suppress reflection between the glass plate 1 and the transparent conductive film layer 5. Further, by having the undercoat layer, it is possible to prevent the diffusion of alkali from the glass plate and prevent the deterioration of the transparent conductive film layer even when the solar cell is manufactured by heat treatment.
  • the undercoat layer 3 includes at least a titanium oxide layer 31 located on the glass plate 1 side and a silicon oxide layer 32 located on the transparent conductive film layer 5 side. Since the titanium oxide layer has a higher refractive index than the transparent conductive film layer and the silicon oxide layer has a lower refractive index than the transparent conductive film layer, the undercoat layer has a laminated structure including a titanium oxide layer and a silicon oxide layer.
  • the titanium oxide layer By arranging the titanium oxide layer so as to be located on the glass plate side, the reflection between the glass plate and the transparent conductive film layer is suppressed, and the light transmission of the glass substrate with the transparent conductive film is improved. Moreover, the color unevenness of the solar cell can be suppressed.
  • the film thickness of the titanium oxide layer is 3 to 50 nm. In order to uniformly cover the surface of the glass plate, the film thickness of the titanium oxide layer should be 3 nm or more. If the film thickness exceeds one-fourth of the wavelength of visible light, new optical interference may occur in the titanium oxide layer, which may cause new color spots. Therefore, the film thickness of the titanium oxide layer should be 50 nm or less. ..
  • the film thickness of the titanium oxide layer is preferably 4 nm or more, more preferably 5 nm or more, particularly preferably 6 nm or more, preferably 30 nm or less, more preferably 25 nm or less, still more preferably 20 nm or less.
  • the film thickness of the silicon oxide layer is 10 to 200 nm. To ensure sufficient alkali barrier properties, the film thickness of the silicon oxide layer should be 10 nm or more. If the film thickness exceeds one-fourth of the wavelength of visible light, new optical interference may occur in the silicon oxide layer, which may cause new color spots. Therefore, the film thickness of the silicon oxide layer should be 200 nm or less. ..
  • the film thickness of the silicon oxide layer is preferably 12 nm or more, preferably 120 nm or less, more preferably 100 nm or less, further preferably 70 nm or less, and particularly preferably 60 nm or less.
  • the thickness (nm) of the titanium oxide layer is tTIO2 and the thickness (nm) of the silicon oxide layer is tSiO2 , the relationships of the following formulas (1) and (2) are satisfied.
  • the formula (1) affects the color spots in the solar cell obtained by using the glass substrate with the transparent conductive film of the present invention.
  • the relationship between the film thickness of the silicon oxide layer (t SiO2 ) and the film thickness of the titanium oxide layer (t TiO2 ) is in the range of 2.5t TiO2-37 ⁇ t SiO2 ⁇ 2.5t TiO2 +50, the transparent conductive film layer. Since the effect of suppressing the optical interference between the reflected light at the interface between the surface layer and the reflected light from the interface between the transparent conductive film layer and the undercoat layer can be obtained, color spots in the solar cell can be suppressed.
  • the film thickness (t SiO2 ) of the silicon oxide layer is preferably more than 2.5t TiO2-25 , more preferably more than 2.5t TiO2-12 , and more preferably less than 2.5t TiO2 +45. Less than 2.5t TiO2 +40 is more preferable, and less than 2.5t TiO2 +35 is even more preferable.
  • the formula (2) affects the light transmittance of the glass substrate with a transparent conductive film of the present invention.
  • the value of t SiO2 + 3.3t TiO2 is smaller than 158, the effect of optical absorption by the silicon oxide layer and the titanium oxide layer becomes small, so that the light transmittance of the glass substrate with a transparent conductive film can be improved.
  • the value of t SiO2 + 3.3t TiO2 is preferably less than 110, more preferably less than 100, and even more preferably less than 90.
  • the lower limit of the value of tSiO2 + 3.3t TiO2 is preferably more than 20 and more than 30 from the viewpoint of uniformly covering the surface of the glass plate with the undercoat layer and ensuring sufficient alkali barrier property. Is more preferable, and more than 40 is even more preferable.
  • the undercoat layer may include other undercoat layers as long as the effects of the present invention are not impaired.
  • the components constituting the other undercoat layer include tin oxide, silicon nitride, silicon carbide, aluminum oxide and the like.
  • the other undercoat layer may be one layer or two or more layers.
  • the position where the other undercoat layer is provided may be between the titanium oxide layer and the silicon oxide layer, between the glass plate and the titanium oxide layer, or a transparent conductive film. It may be between the layer and the silicon oxide layer, or may be a structure in which these are combined.
  • the undercoat layer is more preferably composed of a titanium oxide layer and a silicon oxide layer.
  • the film thickness of the entire undercoat layer is preferably 13 to 300 nm.
  • the total film thickness of the undercoat layer is more preferably 20 nm or more, further preferably 25 nm or more, particularly preferably 30 nm or more, further preferably 150 nm or less, further preferably 100 nm or less, and further preferably 80 nm or less. It is particularly preferable, and 70 nm or less is most preferable.
  • the transparent conductive film layer 5 is a transparent semiconductor film layer mainly containing a metal oxide.
  • mainly containing means that the metal oxide is 50% by mass or more, preferably 70% by mass or more, and more preferably 85% by mass or more with respect to the entire transparent conductive film layer. ..
  • the upper limit is not particularly limited, but when the main component is doped with a dopant (impurity metal), 99.9% by mass or less is preferable.
  • metal oxides examples include ZnO (zinc oxide), In 2 O 3 (indium oxide) and SnO 2 (tin oxide), and examples of these metal oxides include Al (aluminum).
  • Impure metals such as B (boron), Ga (gallium), In (indium), Sn (tin), Sb (antimony), and F (fluorine) may be contained.
  • Specific examples of the metal oxide containing such an impurity metal include FTO (fluorine-doped tin oxide, a metal oxide obtained by adding F to SnO 2 ) and ITO (tin-doped indium oxide, In 2 O 3 ).
  • the transparent conductive film layer preferably contains at least one selected from the group consisting of zinc oxide, fluorine-doped tin oxide, tin-doped indium oxide, niob-doped titanium oxide, tantalum-doped titanium oxide and antimonated tin oxide. From the viewpoint of electrical conductivity and productivity, FTO and ITO are more preferable.
  • the composition of the transparent conductive film layer can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS).
  • the transparent conductive film layer may contain these metal oxides alone or in combination of two or more. Further, the transparent conductive film layer may be composed of one layer or may have a structure in which two or more layers are laminated.
  • the film thickness of the transparent conductive film layer is 200 to 1000 nm. When the film thickness of the transparent conductive film layer is 200 nm or more, sufficient electrical conductivity can be obtained, and when it is 1000 nm or less, productivity can be guaranteed.
  • the film thickness of the transparent conductive film layer is preferably 250 nm or more, more preferably 300 nm or more, further preferably 350 nm or more, further preferably 900 nm or less, further preferably 800 nm or less, still more preferably 700 nm or less. ..
  • the film thickness of the transparent conductive film layer is preferably used in the range of, for example, 200 to 700 nm.
  • the surface layer 7 is provided to prevent recombination of optical holes generated in the solar cell and conduction carriers in the transparent conductive film, and to improve the efficiency of the solar cell.
  • the material constituting the surface layer is not particularly limited as long as it is usually used for a glass substrate with a transparent conductive film, but an oxide is preferable. Specific examples thereof include SnO 2 (tin oxide), ZnO (zinc oxide), In 2 O 3 (indium oxide), TIO 2 (titanium oxide), CdO (acid value cadmium), etc., and these are the main components. It is more preferable that the layer is made of zinc oxide.
  • the main component of the surface layer means that it is 50% by mass or more of the components constituting the surface layer, preferably 70% by mass or more, and preferably 85% by mass or more with respect to the entire surface layer. Is more preferable. Further, the upper limit is not particularly limited.
  • the main component of the surface layer is more preferably SnO 2 or ZnO, and even more preferably SnO 2 . It is also possible to use the same oxide as the main component of the transparent conductive film layer, but it is preferable that the layer does not contain a dopant. That is, SnO 2 or ZnO containing no dopant is more preferable, and SnO 2 containing no dopant is particularly preferable.
  • the composition of the surface layer can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS).
  • the surface layer may be composed of one layer or a structure composed of two or more layers.
  • the film thickness of the surface layer is 10 to 150 nm. In order for the surface layer to cover the transparent conductive film layer, the film thickness of the surface layer is 10 nm or more. On the other hand, if the film thickness of the surface layer becomes too thick, it becomes a direct resistance component for the solar cell, so the thickness is set to 150 nm or less.
  • the film thickness of the surface layer is preferably 15 nm or more, more preferably 20 nm or more, preferably 100 nm or less, more preferably 90 nm or less, still more preferably 80 nm or less.
  • the glass substrate with a transparent conductive film of the present invention can be manufactured by sequentially forming an undercoat layer, a transparent conductive film layer and a surface layer on the surface of the glass plate.
  • a melting step of heating the glass raw material to obtain molten glass a clarification step of removing bubbles from the molten glass, a molding step of forming the molten glass into a plate to obtain a glass ribbon, and slowly cooling the glass ribbon to a room temperature state. It can be obtained by a slow cooling step. Further, the molten glass may be formed into a block shape, slowly cooled, and then cut and polished to produce a glass plate.
  • conventionally known methods can be used. The manufacturing method is not limited to the embodiment, and can be appropriately modified or improved as long as the object of the present invention can be achieved.
  • the undercoat layer, the transparent conductive film layer, and the surface layer can all be formed by a CVD (Chemical Vapor Deposition) method, a sputtering method, a chemical plating method, a wet coating method, or the like.
  • the sputtering method is a method of forming a film on a made glass plate, and the chemical plating method is also used when making a mirror.
  • the CVD method includes an online CVD method and an offline CVD method.
  • the online CVD method is a method of forming a film directly on the surface of a glass plate during the manufacturing process of the glass plate on a float line. That is, instead of forming a transparent conductive film layer or the like after obtaining the glass plate, the transparent conductive film layer or the like is formed in the middle of the process of obtaining the glass plate.
  • the glass ribbon moves on the molten tin bath and then is slowly cooled to continuously manufacture the glass plate. During the movement of the glass ribbon, the glass ribbon is continuously manufactured. , The process of forming a desired layer is continuously carried out on the upper surface of the glass ribbon.
  • the gas raw material is sprayed onto the glass surface to react.
  • a glass substrate with a transparent conductive film can be obtained.
  • the online CVD method is preferable because the undercoat layer, the transparent conductive film layer and the surface layer can be formed in a series of steps for manufacturing the glass plate, and thus the manufacturing cost can be kept low.
  • the offline CVD method is a gas raw material similar to the online CVD method, in which a glass plate once manufactured by a glass manufacturing process and cut to an appropriate size is put into an electric furnace again and conveyed. It is a method of forming a desired layer by utilizing the reaction. Although there is an advantage that the transfer speed and the substrate temperature can be set according to the film formation, the manufacturing cost is higher than that of the online CVD method.
  • a desired metal thin film layer or semiconductor film layer is formed on a glass plate by injecting a very small amount of special gas into a vacuumed container and applying a voltage, with a transparent conductive film.
  • a glass substrate is obtained. Since the sputtering method forms a layer on a glass plate once made, it is possible to form a layer having various desired compositions, although the manufacturing cost is high.
  • the thickness of the undercoat layer, transparent conductive film layer, and surface layer is determined by the type of raw material, the concentration of the raw material gas, the flow rate of the raw material gas sprayed onto the glass ribbon, the substrate temperature, and the retention of the reaction gas derived from the coating beam structure. It can be controlled by time and the like. Further, in the case of the sputtering method, the thickness can be controlled by the sputtering time, voltage and the like.
  • a method for manufacturing a glass substrate with a transparent conductive film by the offline CVD method will be described.
  • a titanium oxide layer and a silicon oxide layer are formed on the surface of the glass plate to form an undercoat layer, and then an FTO film as a transparent conductive film layer and a tin oxide layer as a surface layer are formed.
  • an FTO film as a transparent conductive film layer and a tin oxide layer as a surface layer are formed.
  • examples of the raw material include tetraisopropyl orthotitamate (TTIP) and titanium tetrachloride. Of these, tetraisopropyl orthotitanium acid (TTIP) is more preferable.
  • the temperature at which the titanium oxide layer is formed is preferably 500 to 800 ° C, more preferably 550 to 700 ° C.
  • a silicon oxide layer As an undercoat layer, it is preferable to use, for example, a mixed gas containing monosilane (SiH 4 ), ethylene and carbon dioxide as a raw material.
  • the temperature at which the silicon oxide layer is formed is preferably 500 to 800 ° C, more preferably 550 to 700 ° C.
  • the transparent conductive film layer is subsequently formed.
  • an FTO film As a transparent conductive film layer, it is preferable to use, for example, a mixed gas containing monobutyltin trichloride, oxygen, water, nitrogen and trifluoroacetic acid as a raw material.
  • the temperature at which the FTO film is formed is preferably 500 to 800 ° C, more preferably 550 to 700 ° C.
  • the surface layer is subsequently formed.
  • the raw materials include, for example, monobutyltin trichloride, dimethyltin dichloride, tributyltin, trimethyltin, tin tetrachloride, oxygen, water and nitrogen. It is preferable to use a mixed gas to be used.
  • the temperature at which tin oxide is formed is preferably 400 to 800 ° C, more preferably 500 to 750 ° C.
  • the surface layer After the surface layer is formed, it is slowly cooled to obtain a glass substrate with a transparent conductive film having an undercoat layer, a transparent conductive film layer, and a surface layer formed on a glass plate.
  • the glass substrate with a transparent conductive film of the present invention preferably has a visible light transmittance of 73% or more.
  • the transmittance is 73% or more, the light conversion efficiency can be improved when the solar cell is used.
  • the transmittance is more preferably 76% or more.
  • the transmittance of the glass substrate with a transparent conductive film can be measured by an ultraviolet-visible spectrophotometer.
  • the electrical resistivity of the glass substrate with a transparent conductive film after being left in an atmosphere of 650 ° C. for 116 minutes is 1.5 times or less of the electrical resistivity before the heat treatment.
  • the rate of change (times) of the electrical resistivity after the heat treatment at 650 ° C. is within the above range, the heat resistance is excellent, so that deterioration due to high temperature treatment at the time of manufacturing the solar cell can be suppressed.
  • the electrical resistivity of the glass substrate with a transparent conductive film when left in an atmosphere of 700 ° C. for 116 minutes is 2.0 times or less of the electrical resistivity before the heat treatment.
  • the rate of change (times) of the electrical resistivity after the heat treatment at 700 ° C. is within the above range, the heat resistance is further improved, so that a solar cell having a low electrical resistance can be obtained.
  • the electrical resistivity is measured by heating a glass substrate with a transparent conductive film at 650 ° C or 700 ° C in a nitrogen atmosphere of 1 atm for 116 minutes and cooling it to room temperature using a 4-terminal electric resistance measuring device. By doing so, it is required.
  • the rate of change (times) of the electrical resistivity is obtained by dividing the electrical resistivity after the heat treatment by the electrical resistivity before the heat treatment.
  • the glass substrate with a transparent conductive film of the present invention can be used as a solar cell by forming a light absorption layer on the surface layer thereof.
  • the light absorption layer include cadmium telluride (CdTe), cadmium sulfide (CdS), CIGS (Cu / In / Ga / Se), CIS (Cu / In / Se), tin sulfide (SnS) and the like.
  • the glass substrate with a transparent conductive film of the present invention is useful for a cadmium telluride solar cell.
  • the glass substrate with a transparent conductive film of the present invention can be used as a window material used for in-vehicle windows such as in-vehicle windows, residential windows, oven windows, microwave oven windows, buildings, cooking appliances, etc., in addition to solar cells.
  • Examples 1 to 6 are examples
  • Examples 7 to 13 are comparative examples.
  • the glass plate is displayed as an oxide-based molar percentage. SiO 2 is 72%, Al 2 O 3 is 1.1%, the sum of MgO and CaO is 13.5%, and the sum of Na 2 O and K 2 O is. A glass plate containing 13.5% and a composition of Fe 2 O 3 and Fe O of 0.015% or less was used.
  • Example 1 When a thin film is formed on a glass plate by the CVD method, the film thickness varies in-plane. When a solar cell is formed on the glass plate, the optical reflection spectrum varies in the plane of the glass plate, resulting in color spots.
  • Experimental Example 1 the color spots of the solar cells laminated on various substrates having different film thicknesses were evaluated by using an optical simulation.
  • the light source was a D65 light source, and both the incident angle and the reflection angle were perpendicular to the substrate.
  • the solar cell is a cadmium telluride solar cell, and the battery structure is CdTe: 3500 nm / CdS: 50 nm / SnO 2 : 45 nm / FTO (F: SnO 2 ): 415 nm / SiO 2 : 13 ⁇ . It was assumed that 108 nm / TiO 2 : 0 to 28 nm / glass plate: 4 mm. When the film thickness of TiO 2 is between 0 and 28 nm and the film thickness of SiO 2 is between 13 and 108 nm, the film thickness of the FTO film is changed in the range of ⁇ 50 nm (365 to 465 nm) in 10 nm increments. The changes in the color coordinates (a * , b * ) in the Lab space were calculated, and the color difference variation ( ⁇ E) was evaluated. The simulation results are shown in FIG.
  • FIG. 2 shows the case where the film thickness of the FTO film is changed in the range of 365 to 465 nm in increments of 10 nm when the film thickness of the titanium oxide layer is taken on the horizontal axis and the film thickness of the silicon oxide layer is taken on the vertical axis. It is the figure which mapped the color spot of a solar cell.
  • the size of the color spots is in the range of 2.5t TiO2-37 ⁇ t SiO2 ⁇ 2.5t TiO2 +50. That is, the color difference variation ( ⁇ E) is 20 or less.
  • the color difference variation ( ⁇ E) is 18 or less in the range of 2.5t TiO2 -25 ⁇ t SiO2 ⁇ 2.5t TiO2 +45, and the color difference variation is in the range of 2.5t TiO2 -12 ⁇ t SiO2 ⁇ 2.5t TiO2 +30. ( ⁇ E) was 15 or less.
  • Example 2 the transmittance of the glass substrate with a transparent conductive film was evaluated by an optical simulation.
  • the structure of the glass substrate with a transparent conductive film depends on the composition and film thickness of the film: SnO 2 : 45 nm / FTO (F: SnO 2 : 415 nm) / SiO 2 : 13 to 108 nm / TiO 2 : 0 to 28 nm / glass plate: 4 mm was assumed.
  • the light source is a D65 light source, and when both the incident angle and the reflection angle are perpendicular to the substrate, the film thickness of TiO 2 is between 0 and 28 nm, and the film thickness of SiO 2 is between 13 and 108 nm.
  • the transmittance (%) of the attached glass substrate was evaluated. The simulation results are shown in FIG.
  • FIG. 3 is a diagram mapping the transmittance of a glass substrate with a transparent conductive film when the thickness of the titanium oxide layer is taken on the horizontal axis and the film thickness of the silicon oxide layer is taken on the vertical axis.
  • the transmittance is 73% or more when tSiO2 + 3.3t TiO2 ⁇ 158. Further, when t SiO2 + 3.3t TiO2 ⁇ 100, the transmittance was 76% or more.
  • Example 1 An undercoat layer, a transparent conductive film layer and a surface layer were formed on a glass ribbon (glass plate) having a thickness of 4 mm by using a device having a plurality of coating beams to prepare a glass substrate with a transparent conductive film.
  • Tetraisopropyl orthotitanium (TTIP) was supplied from the first coating beam located on the most upstream side where the temperature of the glass ribbon was 650 ° C., and a titanium oxide layer having a film thickness of 8 nm was formed on the glass ribbon.
  • a mixed gas composed of monosilane (SiH 4 ), ethylene, and CO 2 is supplied from the second coating beam located on the downstream side where the glass ribbon reaches 600 ° C., and the thickness is 13 nm on the titanium oxide layer.
  • a silicon oxide layer was formed.
  • a mixed gas composed of monobutyltin trichloride, oxygen, water, nitrogen and trifluoroacetic acid is supplied from a third coating beam located on the downstream side where the glass ribbon reaches 600 ° C., and the film thickness is applied on the silicon oxide layer.
  • An FTO film (SnO 2 0.2 mol%) containing SnO 2 : F at 415 nm was formed.
  • a mixed gas composed of monobutyltin trichloride, oxygen, water and nitrogen is supplied from a fourth coating beam immediately downstream thereof to form a tin oxide layer having a film thickness of 45 nm, and a glass with a transparent conductive film is formed. Obtained a substrate.
  • each substance was supplied to the mixer in a liquid phase or a gas phase state, and mixed while being heated and vaporized there to obtain a mixed gas.
  • the amount of each raw material supplied from the third coating beam when forming the transparent conductive film layer was monobutyltin trichloride 20.5 L / hour (liquid phase), oxygen 35.7 Nm 3 / hour, water 88.6 kg. / Hour, trifluoroacetic acid 4.9 L / hour (liquid phase).
  • the amount of each raw material supplied from the fourth coating beam when forming the surface layer was 5.9 L / hour (liquid phase) of monobutyltin trichloride, 1.27 Nm 3 / hour of oxygen, and 44.6 kg / hour of water. Met.
  • a cadmium sulfide layer having a thickness of 50 nm and a cadmium telluride layer having a thickness of 3500 nm were sublimated on the tin oxide layer at 440 ° C and 650 ° C, respectively.
  • cadmium chloride is sublimated and then heated at 440 ° C. to obtain CdTe (3500 nm) / CdS (50 nm) / SnO 2 (45 nm) / FTO (415 nm) / SiO.
  • a solar cell having a configuration of 2 (13 nm) / TiO 2 (8 nm) / glass plate (4 mm) was produced.
  • Examples 2-9 A glass substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the film thicknesses of the titanium oxide layer and the silicon oxide layer were changed as shown in Table 1, and a solar cell having the same configuration as in Example 1 was produced. did.
  • Example 10 A glass substrate with a transparent conductive film was produced by the same method as in Example 1.
  • a silicon oxide layer having a thickness of 33 nm was formed on the glass ribbon, a titanium oxide layer having a thickness of 8 nm was formed, and an FTO film was formed on the titanium oxide layer.
  • CdTe 3500 nm) / CdS (50 nm) / SnO 2 (45 nm) / FTO (415 nm) / TiO 2 (8 nm) / SiO 2 (33 nm) / glass plate (4 mm). ) was produced.
  • Example 11 A glass substrate with a transparent conductive film was obtained in the same manner as in Example 2 except that the titanium oxide layer was not provided, and a solar cell having the same configuration as in Example 1 was produced.
  • Example 12 An undercoat layer, a transparent conductive film layer and a surface layer were formed on a glass ribbon (glass plate) having a thickness of 4 mm (a device having a plurality of coating beams) to prepare a glass substrate with a transparent conductive film.
  • Monosilane (SiH 4 ), ethylene and CO 2 gas are supplied from the first coating beam located on the most upstream side where the temperature of the glass ribbon is 700 ° C., and a SiOC film having a thickness of 60 nm is formed on the glass ribbon. It was a film.
  • a mixed gas composed of monobutyltin trichloride, oxygen, water, nitrogen and trifluoroacetic acid is supplied from a third coating beam located on the downstream side where the glass ribbon reaches 600 ° C., and the film thickness is applied on the silicon oxide layer.
  • An FTO film (SnO 2 0.2% by mass) containing SnO 2 : F at 415 nm was formed.
  • a mixed gas composed of monobutyltin trichloride, oxygen, water and nitrogen is supplied from a fourth coating beam immediately downstream thereof to form a tin oxide layer having a film thickness of 45 nm, and a glass with a transparent conductive film is formed. Obtained a substrate. Using the obtained glass substrate with a transparent conductive film, a solar cell having the same configuration as in Example 1 was produced.
  • the amount of each raw material supplied from the third coating beam when forming the transparent conductive film layer was monobutyltin trichloride 20.5 L / hour (liquid phase), oxygen 35.7 Nm 3 / hour, water 88.6 kg. / Hour, trifluoroacetic acid 4.9 L / hour (liquid phase).
  • the amount of each raw material supplied from the fourth coating beam when forming the surface layer was 5.9 L / hour (liquid phase) of monobutyltin trichloride, 1.27 Nm 3 / hour of oxygen, and 44.6 kg / hour of water. Met.
  • Example 13 In Example 12, after forming the SiCO film and before forming the transparent conductive film layer, monosilane (SiH 4 ), ethylene, from the second coating beam located on the downstream side where the glass ribbon reaches 600 ° C. A glass substrate with a transparent conductive film was obtained in the same manner as in Example 12 except that a mixed gas composed of CO 2 was supplied and a silicon oxide layer having a film thickness of 10 nm was formed on the SiCO film. Using the obtained glass substrate with a transparent conductive film, a solar cell having the same configuration as in Example 1 was produced.
  • ⁇ Measurement of color spot size ( ⁇ E)> The size of the color spots was measured for the solar cells produced in Examples 1 to 13. In order to calculate the size of the color spots, the distribution of the reflected colors (a * , b * ) seen from the glass substrate side of the solar cell was measured.
  • the light source was a D65 light source, and both the incident angle and the reflection angle were perpendicular to the substrate. The light was emitted from the glass surface side of the substrate.
  • the spot size of the light source was adjusted to be about 1 cm 2 on the surface of the glass substrate.
  • the reflection spectra were measured at intervals of 3 cm in the plane of the glass substrate.
  • the reflection color (a * , b * ) at each measurement point was calculated from the obtained spectrum.
  • the heat resistance test was performed on the glass substrate with a transparent conductive film produced in Examples 2 and 11 to 13.
  • the glass substrate with a transparent conductive film was heated at 650 ° C. or 700 ° C. under a nitrogen atmosphere of 1 atm for 116 minutes, and after heating, it was allowed to stand in a room temperature environment for cooling.
  • the electrical resistivity was measured using a 4-terminal electric resistance measuring device (“Loresta AX MCP-T370” manufactured by Nittoseiko Analytech).
  • the electrical resistivity of the glass substrate with a transparent conductive film before the heat treatment was measured, and the electrical resistivity after the test was divided by the electrical resistivity before the test to obtain the rate of change (times).
  • the results are shown in Table 2.
  • the glass substrates with the transparent conductive film of Examples 1 to 6 had a transmittance of 77% or more. Further, in Example 2, the rate of change of the electrical resistivity of the glass substrate with a transparent conductive film at 650 ° C. is 1.5 times or less, and the rate of change of the electrical resistivity at 700 ° C. is 2.0 times or less. Was also low. Further, it was found that the solar cells obtained from the glass substrates with the transparent conductive film of Examples 1 to 6 had a color spot size ( ⁇ E) of 20 or less, and the color spots were suppressed. On the other hand, in Examples 7 to 8 and 10, the color spots of the solar cells were large, and in Example 9, the transmittance was low.
  • ⁇ E color spot size
  • Examples 12 and 13 are unsuitable for solar cells that are subjected to film formation treatment at high temperatures, such as cadmium tellurium solar cells, because the color spots of the solar cells are small but the rate of change in the electrical resistivity of the glass substrate with a transparent conductive film is high. It turned out to be.

Abstract

La présente invention concerne un substrat de verre avec un film conducteur transparent qui présente une transparence à la lumière élevée et une résistance à la chaleur élevée et avec lequel une cellule solaire dans laquelle une irrégularité de couleur est supprimée peut être fournie. Un substrat de verre avec un film conducteur transparent selon la présente invention comporte une sous-couche, une couche de film conducteur transparent, et une couche de surface stratifiée dans cet ordre sur une plaque de verre. La sous-couche est pourvue d'une couche d'oxyde de titane et d'une couche d'oxyde de silicium. La couche d'oxyde de titane est située plus près de la plaque de verre, et la couche d'oxyde de silicium est située plus près de la couche de film conducteur transparent. La couche d'oxyde de titane a une épaisseur de 3 à 50 nm, la couche d'oxyde de silicium a une épaisseur de 10 à 200 nm, la couche de film conducteur transparent a une épaisseur de 200 à 1000 nm, et la couche de surface a une épaisseur de 10 à 150 nm. Le substrat de verre avec un film conducteur transparent satisfait les relations suivantes : Expression (1) : 2.5tTiO2 – 37 < tSiO2 < 2.5tTiO2 + 50 ; et Expression (2) : tSiO2 + 3.3tTiO2 < 158, l'épaisseur de la couche d'oxyde de titane étant tTiO2, et l'épaisseur de la couche d'oxyde de silicium étant tSiO2.
PCT/JP2021/043067 2020-11-30 2021-11-24 Substrat de verre à film conducteur transparent et cellule solaire WO2022114028A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020198736 2020-11-30
JP2020-198736 2020-11-30

Publications (1)

Publication Number Publication Date
WO2022114028A1 true WO2022114028A1 (fr) 2022-06-02

Family

ID=81755566

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/043067 WO2022114028A1 (fr) 2020-11-30 2021-11-24 Substrat de verre à film conducteur transparent et cellule solaire

Country Status (1)

Country Link
WO (1) WO2022114028A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000082831A (ja) * 1998-06-30 2000-03-21 Canon Inc 光起電力素子
JP2001007363A (ja) * 1999-06-18 2001-01-12 Nippon Sheet Glass Co Ltd 太陽電池用透明電極付きガラス
JP2004362842A (ja) * 2003-06-02 2004-12-24 Nippon Sheet Glass Co Ltd 透明導電膜付き透明基体、その製造方法、および光電変換素子用基板ならびに光電変換素子
CN203883019U (zh) * 2014-05-15 2014-10-15 湖南师范大学 一种具有石墨烯导电膜与二氧化锡过渡层的碲化镉薄膜太阳电池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000082831A (ja) * 1998-06-30 2000-03-21 Canon Inc 光起電力素子
JP2001007363A (ja) * 1999-06-18 2001-01-12 Nippon Sheet Glass Co Ltd 太陽電池用透明電極付きガラス
JP2004362842A (ja) * 2003-06-02 2004-12-24 Nippon Sheet Glass Co Ltd 透明導電膜付き透明基体、その製造方法、および光電変換素子用基板ならびに光電変換素子
CN203883019U (zh) * 2014-05-15 2014-10-15 湖南师范大学 一种具有石墨烯导电膜与二氧化锡过渡层的碲化镉薄膜太阳电池

Similar Documents

Publication Publication Date Title
US6380480B1 (en) Photoelectric conversion device and substrate for photoelectric conversion device
US6362414B1 (en) Transparent layered product and glass article using the same
US6444898B1 (en) Transparent layered product and glass article using the same
JP5330400B2 (ja) 改良された抵抗率を有する層で被覆したガラス基板
KR101567615B1 (ko) 박막 광전지 애플리케이션용 투명 전도성 산화물 코팅 및 이의 제조 방법
US20130333752A1 (en) Photovoltaic Solar Cell With High-Haze Substrate
JP2002260448A (ja) 導電膜、その製造方法、それを備えた基板および光電変換装置
JP2022123516A (ja) 太陽電池用ガラス基板及び太陽電池
JP5841074B2 (ja) 向上した機械的強度の層でコーティングしたガラス基材
KR20140064713A (ko) 광전지용 기판
JP4272534B2 (ja) 透明導電膜を備えたガラス基板の製造方法、透明導電膜を備えたガラス基板、およびそれを用いた光電変換装置
JP4468894B2 (ja) 透明導電性基板とその製造方法、および光電変換素子
JP7020458B2 (ja) 膜付きガラス基板及びその製造方法
WO2022114028A1 (fr) Substrat de verre à film conducteur transparent et cellule solaire
JP4430193B2 (ja) 導電膜付きガラス板の製造方法
JP2001060707A (ja) 光電変換装置
JP2001035262A (ja) 導電膜付きガラス板とその製造方法、およびこれを用いた光電変換装置
JP2004362842A (ja) 透明導電膜付き透明基体、その製造方法、および光電変換素子用基板ならびに光電変換素子
JP3984404B2 (ja) 導電膜付きガラス板とその製造方法、およびこれを用いた光電変換装置
US20110020621A1 (en) Glass-type substrate coated with thin layers and production method
JP7306502B2 (ja) 膜付きガラス基板及びその製造方法
JP4516657B2 (ja) 光電変換装置用基板とその製造方法、およびこれを用いた光電変換装置
JP2017001924A (ja) コーティング膜つきガラス板
WO2022114027A1 (fr) Substrat de verre avec film, et procédé de fabrication de celui-ci
JP7160232B1 (ja) 透明電極基板及び太陽電池

Legal Events

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

Ref document number: 21898000

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21898000

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP