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WO2013118897A1 - Substrat de verre pour formation de film conducteur transparent, et substrat avec film conducteur transparent - Google Patents

Substrat de verre pour formation de film conducteur transparent, et substrat avec film conducteur transparent Download PDF

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Publication number
WO2013118897A1
WO2013118897A1 PCT/JP2013/053149 JP2013053149W WO2013118897A1 WO 2013118897 A1 WO2013118897 A1 WO 2013118897A1 JP 2013053149 W JP2013053149 W JP 2013053149W WO 2013118897 A1 WO2013118897 A1 WO 2013118897A1
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WIPO (PCT)
Prior art keywords
glass substrate
transparent conductive
conductive film
glass
substrate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2013/053149
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English (en)
Japanese (ja)
Inventor
林　英明
航 西田
高橋　亮
邦明 廣松
近藤　裕己
淳 笹井
朋美 安部
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AGC Inc
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Asahi Glass Co Ltd
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Filing date
Publication date
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Publication of WO2013118897A1 publication Critical patent/WO2013118897A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
    • H10F77/247—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers comprising indium tin oxide [ITO]
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/211—SnO2
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/1525—Deposition methods from the vapour phase by cvd by atmospheric CVD

Definitions

  • the present invention relates to a glass substrate for forming a transparent conductive film used for solar cells and the like, and a substrate with a transparent conductive film, and more specifically, a glass substrate for forming a transparent conductive film from which excellent electrical characteristics such as high mobility can be obtained, And a substrate with a transparent conductive film.
  • a substrate with a transparent conductive film formed by forming a transparent conductive film such as a tin oxide film that is transparent and conductive on the surface of a glass substrate is used for solar cells and the like.
  • a method of manufacturing a substrate formed by forming such a tin oxide film As a method of manufacturing a substrate formed by forming such a tin oxide film, a method of forming a tin oxide film on the surface of a glass substrate by an atmospheric pressure CVD method using a hydrolysis reaction of tin tetrachloride is known. It has been.
  • tin oxide When tin oxide is formed by atmospheric pressure CVD, tin oxide having higher mobility can be formed as the film formation temperature (that is, the temperature of the glass substrate during film formation) is higher. Therefore, in a plate glass manufacturing process by float method (so-called on-line), a tin oxide film is formed on a glass substrate by atmospheric pressure CVD method to manufacture a substrate with a transparent conductive film. It is done. According to this film forming method, a tin oxide film can be formed in a float bath or a slow cooling furnace.
  • Patent Document 1 describes that in a plate glass manufacturing process, tin oxide is formed on the surface of a plate glass using tin tetrachloride and water (water vapor) as raw materials in a slow cooling furnace.
  • the concentration of tin tetrachloride is equivalent to a partial pressure of 2.5 ⁇ 10 ⁇ 3 to 10 ⁇ 2 atm, and the concentration of water vapor is 10 ⁇ 10 ⁇ 3 to In the slow cooling furnace, the partial pressure is 200 ⁇ 10 ⁇ 3 atm
  • the temperature of the raw material gas that is, the temperature of the injector portion from which the raw material gas is ejected
  • the glass temperature is 550 to 650 ° C.
  • tin oxide is formed on the surface of a plate glass by atmospheric pressure CVD.
  • a substrate with a transparent conductive film formed by forming a tin oxide film on the surface of a glass substrate improvement in the mobility of the tin oxide film is required.
  • the tin oxide film is formed by atmospheric pressure CVD, the higher the film formation temperature, the higher the mobility of the tin oxide film can be formed. There is a limit to improving the degree.
  • An object of the present invention is to solve the problems of the prior art, and in a substrate with a transparent conductive film formed by forming a transparent conductive film such as a tin oxide film on a glass substrate, a low resistance having high mobility.
  • a substrate with a transparent conductive film having a transparent conductive film such as a tin oxide film and to provide a glass substrate for forming a transparent conductive film from which a substrate with a transparent conductive film having high mobility can be obtained.
  • the present inventors have formed a transparent conductive film such as a tin oxide film on a glass substrate having a specific glass composition, and thus have a low mobility with high mobility. It has been found that a transparent conductive film such as a tin oxide film can be obtained.
  • This invention is made
  • a transparent conductive film-forming glass substrate having the following glass composition and substantially not containing B 2 O 3 in terms of mass% based on the following oxides.
  • SiO 2 45-80%, Al 2 O 3 : 5 to 18%, MgO: 2-8%, CaO: 0-9%, SrO: 0-8%, BaO: 0 to 10%, MgO + CaO + SrO + BaO: 3.5-27% Na 2 O: 0 to 15%, K 2 O: 0-12%, ZrO 2 : 0 to 5%, TiO 2 : 0 to 5%.
  • MgO + CaO + SrO + BaO contains at least one selected from the group consisting of MgO, CaO, SrO and BaO, and indicates the total amount of these components contained.
  • the glass substrate for forming a transparent conductive film according to the above (1) which has the following glass composition and does not substantially contain B 2 O 3 in terms of mass% based on the following oxide.
  • SiO 2 55 to 72%
  • Al 2 O 3 5 to 18%
  • TiO 2 : 0 to 5%.
  • the glass substrate for forming a transparent conductive film according to (2) above which is a glass substrate on which a transparent conductive film containing tin oxide as a main component is formed.
  • the glass composition of the glass substrate is expressed in mass% on the basis of the following oxide, When SiO 2 is 55% or more, the mass ratio of Al 2 O 3 / Na 2 O is 0.5 or more, When SiO 2 is less than 55%, the transparent conductive film-forming glass substrate according to (1) above, wherein the mass ratio of (SrO + BaO) / Al 2 O 3 is 1.0 or less.
  • the glass composition of the glass substrate has a mass ratio of Al 2 O 3 / Na 2 O of 0.5 or more when SiO 2 is less than 55% in the mass% display based on the following oxides. and the mass ratio of Al 2 O 3 / SiO 2 is 0.25 or more, a transparent conductive film for forming a glass substrate according to (1).
  • Glass the glass substrate, by mass% based on the following oxides, at least one of Na 2 O and K 2 O, in a total amount of Na 2 O and K 2 O, containing from 1 to 19% The glass substrate for forming a transparent conductive film according to any one of the above (1) to (6), which has a composition.
  • the glass substrate described above (1) wherein the glass substrate contains 2 to 16% of the total amount of MgO and CaO in terms of mass% based on the following oxides based on the total amount of MgO and CaO.
  • the glass substrate for forming a transparent conductive film according to any one of (7) to (7). (9) The glass substrate, by mass% based on the following oxides, at least one of SiO 2 and Al 2 O 3, in a total amount of SiO 2 and Al 2 O 3, glass containing 64 to 82%
  • the glass substrate for forming a transparent conductive film according to any one of the above (1) to (8) which has a composition.
  • a substrate with a transparent conductive film comprising a transparent conductive film having a mobility at a film thickness of 250 nm of 36 cm 2 / V ⁇ s or more on the glass substrate surface according to any one of (1) to (14).
  • a substrate with a transparent conductive film wherein a transparent conductive film having a tin oxide film is formed on the glass substrate surface according to any one of (1) to (14).
  • the tin oxide film is a tin oxide film containing fluorine as a dopant.
  • the glass substrate which can form the transparent conductive film which has high mobility can be obtained, and transparent conductive films, such as a tin oxide film, are formed into a film on the glass substrate of this specific glass composition.
  • transparent conductive films such as a tin oxide film
  • FIG. 1 shows a substrate with a transparent conductive film (hereinafter referred to as this transparent conductive film) in which a transparent conductive film (hereinafter referred to as a “TCO film”) according to an embodiment of the present invention is formed on a glass substrate.
  • the substrate is also referred to as a “TCO substrate”).
  • a substrate 10 with a transparent conductive film (hereinafter also referred to as a TCO substrate 10) shown in FIG. 1 is a transparent conductive film formed on a glass substrate 12 and the surface of the glass substrate 12 (that is, formed).
  • a tin oxide film 14 (SnO 2 film).
  • the glass substrate 12 is made of glass having the glass composition of Embodiments (1) to (4) having the following composition.
  • SiO 2 silicon oxide
  • the content of SiO 2 is preferably 57 to 72% by mass.
  • Al 2 O 3 (aluminum oxide) is a component that improves the durability of the glass, so it is contained in an amount of 5% by mass or more. However, if it exceeds 18% by mass, melting of the glass becomes extremely difficult.
  • the content of Al 2 O 3 is preferably 6 to 15% by mass, and more preferably 7.5 to 14% by mass.
  • the total amount of SiO 2 and Al 2 O 3 is preferably 64% by mass or more in order to increase the chemical durability of the glass, and the glass melt can be stabilized. In order to ensure that the high-temperature viscosity does not become too high, it is preferably 82% by mass or less.
  • Alkaline earth metal oxides that is, MgO (magnesium oxide), CaO (calcium oxide), SrO (strontium oxide) and BaO (barium oxide) improve the durability of the glass and the devitrification temperature during molding. Used to adjust viscosity. When MgO exceeds 8 mass%, devitrification temperature will rise. When CaO exceeds 9 mass%, devitrification temperature will rise. When SrO exceeds 8% by mass, the devitrification temperature rises. When BaO exceeds 10 mass%, devitrification temperature will rise. The content of CaO is preferably 8% by mass or less. Further, when the total amount of the alkaline earth metal oxide (that is, “MgO + CaO + SrO + BaO”. The total amount of these alkaline earth metal oxides also referred to as “RO”) is less than 3.5% by mass. The durability of the glass decreases, and when it exceeds 27% by mass, the devitrification temperature increases.
  • MgO magnesium oxide
  • CaO calcium
  • the generation source of Cl in the tin oxide film is a tin chloride compound (for example, SnCl 4 , SnHCl 3 , SnH 2 Cl 2) used as the Sn raw material when forming the tin oxide film by the atmospheric pressure CVD method.
  • Inorganic tin chloride compounds such as SnH 3 Cl and organic tin chloride compounds such as monobutyltin trichloride and dibutyltin dichloride).
  • the reason why the amount of Na diffused into the TCO film decreases when the RO is in the above range and the reason why the Cl concentration in the tin oxide film formed on the glass substrate decreases is as follows.
  • Heating is performed near the glass Tg temperature.
  • the RO of the glass constituting the glass substrate has a composition in the above range, the divalent R cation in the glass substrate inhibits Na diffusion.
  • the nucleation sites on the glass substrate increase and the diffusion of Na ions, which are impurities, into the film is suppressed, so that the crystallinity of the formed tin oxide film is considered to be improved.
  • the mobility of the tin oxide film increases, impurity sites such as grain boundaries in the tin oxide film decrease, and the Cl concentration decreases.
  • the RO of the glass constituting the glass substrate is outside the above range, the nucleation site on the glass substrate is reduced, and the tin oxide film is formed by increasing the amount of Na ions diffused into the film. It is thought that the degree of crystallinity of the decreases.
  • the RO of the glass constituting the glass substrate is preferably 5 to 27% by mass.
  • the alkaline earth metal oxide is reduced when the amount of Na diffusion into the tin oxide film formed on the glass substrate is reduced and the Cl concentration is reduced.
  • the influence by MgO and CaO is large. Therefore, the total amount of MgO and CaO that contains at least one of MgO and CaO (hereinafter, this total amount is also referred to as “MgO + CaO”) is preferably 2 to 16% by mass. More preferably, it is ⁇ 15% by mass.
  • Na 2 O (sodium oxide) and K 2 O (potassium oxide) are used as glass melting accelerators.
  • Na 2 O exceeds 15% by mass, the durability of the glass is lowered.
  • K 2 O is more expensive than Na 2 O, it is not preferable to exceed 12% by mass.
  • the total amount of Na 2 O and K 2 O is 19
  • the content is preferably not more than mass%, and in order to act as a glass melting accelerator, Na 2 O + K 2 O is preferably at least 1 mass%.
  • ZrO 2 zirconium oxide
  • the content of ZrO 2 is more preferably 0.5 to 5% by mass.
  • TiO 2 titanium oxide
  • TiO 2 titanium oxide
  • B 2 O 3 causes inconvenience during molding due to volatilization or the like
  • the glass constituting the glass substrate has a composition that does not substantially contain B 2 O 3 .
  • substantially free means that it is inevitably included as an impurity. For example, it means that it may be contained if it is less than 0.1%.
  • the glass constituting the glass substrate can contain 0.005 to 0.1% by mass of Fe 2 O 3 (iron oxide).
  • the content of Fe 2 O 3 is less than 0.005% by mass, the heat ray transmittance of the molten glass is increased. Therefore, during glass production, the temperature distribution in the melting tank is difficult to be attached, and the convection of the molten glass is prevented. Because it is difficult to wake up, it is difficult to obtain homogeneous glass.
  • the content of Fe 2 O 3 is more than 0.1% by mass, the heat ray transmittance of the glass is lowered, so that the battery efficiency of the solar cell produced using the substrate with a transparent conductive film is lowered, which is not preferable.
  • the content of Fe 2 O 3 is more preferably 0.007 to 0.08 mass%.
  • the mass ratio of Al 2 O 3 / Na 2 O is preferably 0.5 or more.
  • the mass ratio of Al 2 O 3 / Na 2 O is less than 0.5, the mobility of the transparent conductive film formed on the glass substrate becomes too low, which is not preferable.
  • the mass ratio of Al 2 O 3 / Na 2 O is more preferably 0.7 or more, and further preferably 0.8 or more.
  • the mass ratio of (SrO + BaO) / Al 2 O 3 is preferably 1.0 or less.
  • (SrO + BaO) includes at least one of SrO and BaO, and indicates the total amount of SrO and BaO contained.
  • the mass ratio of Al 2 O 3 / Na 2 O is 0.5 or more, and Al 2 O 3 / SiO 2 mass The ratio is preferably 0.25 or more.
  • the mass ratio of Al 2 O 3 / Na 2 O is less than 0.5, the mobility of the transparent conductive film formed on the glass substrate becomes too low, which is not preferable.
  • the mass ratio of Al 2 O 3 / Na 2 O is more preferably 0.7 or more, and further preferably 0.8 or more. Further, if the Al 2 O 3 / SiO 2 mass ratio is less than 0.25, the mobility of the transparent conductive film formed on the glass substrate becomes too low, which is not preferable.
  • the glass substrate composed of glass having the above composition preferably has a strain point of 550 ° C. or higher.
  • a transparent conductive film is formed on the glass substrate by atmospheric pressure CVD in the manufacturing process of the plate glass by the float method (on-line).
  • the film forming temperature can be increased, and the film can be formed at a high temperature and at a high speed.
  • the strain point of the glass substrate is more preferably 565 ° C. or higher.
  • the strain point is a strain point measured according to “JIS R3103-2”.
  • the glass substrate composed of the glass having the above composition preferably has an average coefficient of thermal expansion at 50 to 300 ° C. of 50 ⁇ 10 ⁇ 7 to 105 ⁇ 10 ⁇ 7 / ° C.
  • the average thermal expansion coefficient of the glass substrate at 50 to 300 ° C. is more preferably 54 ⁇ 10 ⁇ 7 to 100 ⁇ 10 ⁇ 7 / ° C.
  • the thickness of the glass substrate 12 is not particularly limited and may be appropriately determined according to the use of the TCO substrate 10 or the like, but is usually about 1.5 to 6 mm. .
  • the means for forming (that is, forming) the tin oxide film 14 as the transparent conductive film on the glass substrate 12 is not particularly limited, but preferably, as described later, This is a tin oxide film 14 formed by an atmospheric pressure CVD (Chemical Vapor Deposition) method using tin tetrachloride, water, and HF as raw materials in the manufacturing process.
  • CVD Chemical Vapor Deposition
  • a zinc oxide film formed by a CVD method using an inorganic compound may be used. In these cases, the raw material does not contain Cl, but the effect of increasing the mobility is manifested by the effect that the Na impurity in the film is reduced.
  • the film thickness of the tin oxide film 14 is not particularly limited, and may be appropriately determined according to the use of the TCO substrate 10 or the like, but is usually about 300 to 1500 nm.
  • the tin oxide film 14 is preferably a film containing fluorine as a dopant (fluorine-doped tin oxide film) in order to obtain high conductivity.
  • fluorine concentration is preferably 0.01 to 4 mol%, more preferably 0.02 to 2 mol% with respect to SnO 2 . Within the above range, the conductivity is excellent.
  • the SnO 2 ratio is preferably 90 mol% or more, and more preferably 95 mol% or more.
  • the carrier concentration is high because fluorine is doped.
  • the carrier concentration is preferably 5 ⁇ 10 19 to 4 ⁇ 10 20 cm ⁇ 3 , and more preferably 1 ⁇ 10 20 to 2.5 ⁇ 10 20 cm ⁇ 3 . It is excellent in balance with electroconductivity and absorption of near-infrared light in it being the said range.
  • the tin oxide film 14 may have a structure in which a tin oxide film not containing a dopant and a fluorine-doped tin oxide film are laminated.
  • the TCO substrate 10 of the present invention preferably has a film 14 mainly composed of a tin oxide film on a glass substrate 12, and there is no particular limitation other than that, and various configurations can be used.
  • the TCO film may be a film mainly composed of ZnO (zinc oxide).
  • the main component here means that it accounts for 80% or more of the film composition.
  • the configuration in which the tin oxide film 14 is formed on the surface of the glass substrate 12 is not limited, and between the glass substrate 12 and the tin oxide film 14 as necessary.
  • a single layer or a plurality of layers may be provided.
  • a silicon oxide film (SiO 2 film) and a titanium oxide film (TiO 2 film) are provided between the glass substrate 12 and the tin oxide film 14.
  • a configuration having at least one of the above as a base film is preferably exemplified.
  • a preferable result can be obtained in that it can be prevented from being lowered and light reflection at the interface between the glass substrate 12 and the tin oxide film 14 can be reduced (that is, the antireflection effect is improved).
  • Cl in the tin oxide film formed on the glass substrate described above is used. The effect of reducing the concentration is exhibited.
  • the thickness of the silicon oxide film is 10 to 50 nm, and the thickness of the titanium oxide film is 5 to 22 nm. It is preferable to do this.
  • FIG. 2 conceptually shows an example of a method for manufacturing the TCO substrate 10 of the present invention.
  • FIG. 2 The example shown in FIG. 2 is a so-called float glass plate production line (on-line), and is placed on a roller 20a in a slow cooling furnace (slow cooling line) 20 arranged downstream of a float bath.
  • the TCO substrate 10 is manufactured by forming a tin oxide film 14 on the surface of the glass substrate 12 that is gradually cooled while being conveyed in the y direction by an atmospheric pressure CVD method.
  • FIG. 2 shows only the atmospheric pressure CVD apparatus portion.
  • the TCO substrate 10 of the present invention (that is, the substrate with a transparent conductive film) is produced by forming a tin oxide film on the surface of the glass substrate 12 by an atmospheric pressure CVD method in such an online annealing furnace or the like.
  • the thing is not limited. That is, as a method of manufacturing the TCO substrate 10 of the present invention, a so-called off-line (off-off) method is used in which a tin oxide film is formed by an atmospheric pressure CVD method using a glass plate completed as a glass plate as a substrate instead of a plate glass manufacturing process. -Line) can also be used advantageously.
  • the glass substrate is heated with a heater to form a film, and then the glass substrate is gradually cooled in a cooling zone. This cooling zone is called a slow cooling furnace.
  • a tin oxide film is formed by atmospheric pressure CVD using tin tetrachloride (SnCl 4 ) as a main material and water (H 2 O) as an auxiliary material. Specifically, by spraying a gas and water vapor of tin tetrachloride from the injector 18 onto the glass substrate 12 conveyed in the slow cooling furnace 20, oxidation is performed on the surface of the glass substrate 12 by a hydrolysis reaction of tin tetrachloride. A tin film is formed.
  • tin tetrachloride SnCl 4
  • H 2 O water
  • tin tetrachloride (SnCl 4 ) is used as the main raw material, but other inorganic materials such as SnHCl 3 , SnH 2 Cl 2 , and SnH 3 Cl are used instead of tin tetrachloride.
  • An organic tin chloride compound such as monobutyltin trichloride or dibutyltin dichloride can also be used as the Sn raw material.
  • tin chloride compounds inorganic tin chloride compounds such as SnCl 4 , SnHCl 3 , SnH 2 Cl 2 , SnH 3 Cl and organic tin chloride compounds such as monobutyltin trichloride and dibutyltin dichloride
  • a tin chloride compound is used as the Sn raw material
  • a general stainless steel member can be used as the raw material pipe, and the vapor pressure is low enough to supply an industrially sufficient amount within the range of the heat resistant temperature of stainless steel. Because.
  • tin oxide film 14 When a fluorine-doped tin oxide film is formed as the tin oxide film 14, in addition to the above-described tin tetrachloride (SnCl 4 ) and water (H 2 O), hydrogen fluoride (HF) is used as the F raw material. It will be sprayed from the injector 18.
  • tin tetrachloride SnCl 4
  • water H 2 O
  • Such an injector 18 has a main raw material outlet 24, an auxiliary raw material outlet 26, and a suction port 28.
  • the main raw material outlet 24, the auxiliary raw material outlet 26, and the suction port 28 all extend in the width direction of the glass substrate 12 (direction perpendicular to the conveying direction of the glass substrate 12 (direction perpendicular to the paper surface of FIG. 2)). It is an existing long gas flow path.
  • the main raw material outlet 24 blows out a gas of tin tetrachloride (or a tin chloride compound other than the above-described tin tetrachloride), which is the main raw material, from the opening at the lower end of the injector 18.
  • the auxiliary raw material outlet 26 blows out water vapor (water) as an auxiliary raw material from the opening at the lower end of the injector 18.
  • Two auxiliary raw material outlets 26 are formed so as to sandwich the main raw material outlet 24 in the upstream and downstream of the conveyance direction of the glass substrate 12.
  • FIG. 1 The suction port 28 sucks the raw material gas that has not been used for the film formation of tin oxide or the hydrochloric acid gas by-produced by the film formation of tin oxide from the opening at the lower end of the injector 18 and discharges it from the film formation unit.
  • Two suction ports 28 are formed so as to sandwich the auxiliary material outlet 26 upstream and downstream in the conveyance direction of the glass substrate 12.
  • the injector 18 is provided with a supply means for supplying a gas of tin tetrachloride (or a tin chloride compound other than the above-described tin tetrachloride) to the main raw material outlet 24, and steam is supplied to the auxiliary raw material outlet 26.
  • the supply means for supplying the gas and the suction means for sucking the suction port 28 are connected.
  • supply means for supplying hydrogen fluoride (HF) to the main material outlet 24 or the auxiliary material outlet 26 is connected to the injector 18. Yes.
  • a known unit used for film formation by an atmospheric pressure CVD method using an injector may be used.
  • the manufacturing apparatus of the illustrated example sprays a gas of tin tetrachloride (or a tin chloride compound other than tin tetrachloride described above) and water vapor onto the glass substrate 12 conveyed in the slow cooling furnace 20 from the injector 18.
  • the tin oxide film 14 is formed on the surface of the glass substrate 12 by the atmospheric pressure CVD method by the hydrolysis reaction of tin tetrachloride, and the TCO substrate 10 is manufactured.
  • hydrogen fluoride (HF) is further sprayed from the injector 18.
  • the slow cooling furnace 20 shown in FIG. 2 is a slow cooling furnace of a plate glass manufacturing line made of glass having the above composition.
  • the TCO substrate 10 having a high mobility of the tin oxide film 14 can be manufactured.
  • the glass substrate 12 comprised with the glass of the composition mentioned above preferably has a strain point as high as 550 ° C. or higher, the tin oxide film 14 is formed in the plate glass manufacturing process (or offline process) by the float process. When the film is formed, the TCO substrate 10 can be manufactured at a high film formation rate and with high productivity by increasing the film formation temperature of the tin oxide film 14.
  • the conditions for forming the tin oxide film using the production apparatus of the illustrated example are not particularly limited.
  • the gas flow rate of tin tetrachloride blown from the main raw material outlet 24 is 60 to 150 cm / s, and
  • the supply amount of tin tetrachloride may be 0.3 to 2.5 vol% of the total volume of the raw material gas blown from the injector 18.
  • the quantity ratio of tin tetrachloride blown out from the main raw material outlet 24 and water vapor blown out from the auxiliary raw material outlet 26 may be 20 to 110 in terms of a molar ratio of water vapor / tin tetrachloride.
  • the temperature of the injector 18 is 200 degrees C or less. Since the temperature of the injector 18 is low, it is possible to reduce the adhesion of the tin oxide powder generated by the reaction of the raw material gas in the gas phase to the inside of the suction port 28 of the injector 18.
  • Examples 1 to 9 are shown as examples of the glass substrate for forming a transparent conductive film and the substrate with a transparent conductive film of the present invention, and Comparative Examples 1 to 3 are shown below as comparative examples.
  • the data of Examples 1 and 2 and Comparative Example 1 shown in Table 1 are based on the thickness of the tin oxide film shown in Table 1, and Examples 1, 2 and Comparative Example shown in Table 2 Each data of 1 is for the film thickness (345 nm) of a tin oxide film described later.
  • Example 1 In the manufacture of plate glass by the float process, a tin oxide film is formed on the glass substrate 12 by using an injector 18 as shown in FIG. 2 and using a slow cooling furnace 20 using tin tetrachloride, water and hydrogen fluoride as source gases. did.
  • the composition of the glass substrate 12 is expressed in terms of mass% on the basis of oxide, SiO 2 : 57.6, Al 2 O 3 : 7.0, SiO 2 + Al 2 O 3 : 64.6, MgO 2: 2.0 , CaO: 5.0, SrO: 7.0, BaO: 8.0, RO (MgO + CaO: + SrO + BaO): 22.0, MgO + CaO: 7.0, Na 2 O: 4.1, K 2 O: 6. 3, Na 2 O + K 2 O: 10.4, ZrO 2: was used which consists of 3.0 glass.
  • a 30 nm silicon oxide film was formed on the surface of the glass substrate 12 by atmospheric pressure CVD as an undercoat film upstream of the injector 18. Under such conditions, in the on-line annealing furnace 20, a fluorine-doped tin oxide film is formed as a tin oxide film 14 on the silicon oxide film of the glass substrate 12 having a 30 nm silicon oxide film on the surface, and the TCO substrate is formed. 10 was produced.
  • tin tetrachloride gas is 1.16 mol / min
  • hydrogen fluoride gas is 9.1 L / min
  • nitrogen gas is 33. 8 L / min was blown out.
  • 360 g / min of water vapor was blown out from the auxiliary material outlet 26.
  • the film thickness of the produced tin oxide film 14 (fluorine-doped tin oxide film) was 226 nm.
  • the conveyance speed of the glass substrate 12 in the slow cooling furnace 20 was 2.5 m / min.
  • region which faces the injector 18 was 590 degreeC. That is, the film forming temperature is 590 ° C.
  • Example 2 As the glass substrate 12, the composition is expressed in terms of mass% based on oxide, and SiO 2 : 60.7, Al 2 O 3 : 9.6, SiO 2 + Al 2 O 3 : 70.3, MgO: 6.9, CaO: 0.1, SrO: 0.2, BaO: 0.2, RO (MgO + CaO + SrO + BaO): 7.4, MgO + CaO: 7.0, Na 2 O: 11.6, K 2 O: 5.9, Na
  • a TCO substrate was prepared by forming a tin oxide film in the same manner as in Example 1 except that a glass composed of 2 O + K 2 O: 17.5 and ZrO 2 : 4.8 was used.
  • the film thickness of the tin oxide film 14 fluorine-doped tin oxide film
  • the TCO substrate thus fabricated was annealed at 375 ° C. for 10 minutes in a nitrogen atmosphere containing 6 ppm oxygen gas, and the sheet resistance value [ ⁇ / ⁇ of the tin oxide film 14 (fluorine-doped tin oxide film). ], Mobility [cm 2 / V ⁇ s], and carrier concentration [/ cm 3 ] were measured.
  • the sheet resistance value was measured using a Mitsubishi Leka lorester FP. Mobility and carrier concentration were measured using Nanometrics HL5500PC. Further, the Cl concentration [%] in the tin oxide film 14 (fluorine-doped tin oxide film) was measured using an XPS PHI5000 VersaProbe manufactured by ULVAC-PHI.
  • composition of the glass substrate 12 is expressed in terms of mass% based on oxides, and it is SiO 2 72.8, Al 2 O 3 1.9, SiO 2 + Al 2 O 3 74.7, MgO 3.7, CaO 8.1.
  • RO MgO + CaO + SrO + BaO
  • a tin oxide film was formed in the same manner as in Example 1 to produce a TCO substrate.
  • the film thickness of the tin oxide film 14 fluorine-doped tin oxide film) was 260 nm.
  • the glass substrate 12 is composed of glass having RO in the range of 3.5 to 27% by mass and ZrO 2 content of 2 to 5% by mass.
  • the Cl concentration in the tin oxide film was low, and the mobility of the tin oxide film was high.
  • the mobility of the tin oxide film was higher in Example 1 where the Cl concentration in the tin oxide film was lower.
  • a 30 nm silicon oxide film was formed on the surface of the glass substrate as an undercoat film by atmospheric pressure CVD upstream of the injector 18.
  • an injector 18 as shown in FIG. 2, using tin tetrachloride, water and hydrogen fluoride as raw materials, As the tin oxide film 14, a fluorine-doped tin oxide film was formed.
  • tin tetrachloride gas is 1.16 mol / min
  • hydrogen fluoride gas is 9.1 L / min
  • nitrogen gas is 33.8 L / min. min, blown out.
  • the conveyance speed of the glass substrate 12 in the off-line CVD apparatus was 2.5 m / min.
  • region which faces the injector 18 was 590 degreeC. That is, the film forming temperature is 590 ° C.
  • 360 g / min of water vapor was blown out from the auxiliary material outlet 26.
  • a TCO substrate 10 was produced by forming a tin oxide film 14 (fluorine-doped tin oxide film) on a glass substrate 12 having a 30 nm silicon oxide film on the surface in an off-line CVD apparatus.
  • the film thickness of the tin oxide film 14 (fluorine-doped tin oxide film) was 345 nm, respectively.
  • the thus fabricated TCO substrate is annealed at 375 ° C. for 10 minutes in a nitrogen atmosphere containing 6 ppm oxygen gas, and the mobility of the tin oxide film 14 (fluorine-doped tin oxide film) [cm 2 / V -S] was measured.
  • the mobility was measured using Nanometrics HL5500PC as described above.
  • the Na concentration [count / sec] in the tin oxide film 14 (fluorine-doped tin oxide film) was measured using a Dynamic SIMS ADEPT 1010 manufactured by ULVAC-PHI.
  • the Na concentration [count / sec] in the tin oxide film 14 (fluorine-doped tin oxide film: TCO film) with a SiO 2 base film was measured using a Dynamic SIMS ADEPT 1010 manufactured by ULVAC-PHI.
  • the mobility of the tin oxide film 14 [cm 2 / V ⁇ s] for the substrate with a transparent conductive film on which the tin oxide film obtained in Examples 3 to 9 and Comparative Examples 1 to 3 was formed.
  • Table 2 shows the measurement results.
  • the glass composition, mobility, and other measurement data of the glass substrates of Examples 1 and 2 are also shown.
  • the mobility data of the TCO film with the SiO 2 base film is a value obtained by measuring the mobility of the TCO film using Nanometrics HL5500PC after annealing the TCO film.
  • FIG. 3 shows the relationship between the Na concentration [count / sec] and the mobility of the tin oxide film.
  • the mobility of the tin oxide film is higher in Examples 1 to 9 than in Comparative Examples 1 to 3. Further, as can be seen from FIG. 3, it was found that the mobility of the tin oxide film was higher as the Na concentration in the SnO 2 film was lower. According to this result, it is considered that Na in SnO 2 inhibits carrier movement as an impurity, and it is necessary to reduce Na impurity in the SnO 2 film in order to obtain high mobility. I understand. From these results, the present inventors have found the glass composition of the glass substrate for reducing Na impurities in the SnO 2 film as described above.
  • the SnO 2 film is reduced when the Al 2 O 3 / Na 2 O mass ratio is decreased. It can be seen that the concentration of medium Na increases and the mobility of the tin oxide film decreases. This is described, for example, in the amount of Al 2 O 3 in the glass, as described in [MA A. Rana et al, Phys. Chem. Of Glasses, Vol. 8 (1967), No. 5, 178].
  • the present inventors have found that it is desirable that the amount of Al 2 O 3 is large and the amount of Na 2 O is small. From the result, it was found that the desired mobility can be obtained when the mass ratio of Al 2 O 3 / Na 2 O is 0.5 or more.
  • the glass substrates of Examples 8 and 9 satisfy the condition that SiO 2 is less than 55% by mass and the mass ratio of (SrO + BaO) / Al 2 O 3 is 1.0 or less.
  • the amount of Na in the SnO 2 film is small compared to From the result of FIG. 3 found by the present inventor, a linear relational expression can be derived for the mobility and the Na concentration in the SnO 2 film.
  • Examples 1 to 9 and Comparative Examples 1 to 3 were formed using a SiO 2 film alkali barrier film (underlying film). It is known from the experimental results so far that the amount of Na in the SnO 2 film is about 4.0 times when there is no alkali barrier film. Therefore, the amount of Na in the SnO 2 film without the SiO 2 base film is calculated as shown in Table 2. Further, when the mobility is calculated from Equation 1, the normal barrier film used in Comparative Example 1 is used. It is expected that a mobility similar to that in FIG.
  • substrate with a transparent conductive film of this invention can be utilized suitably for manufacture of the board
  • the entire contents of the description, claims, drawings and abstract of Japanese Patent Application No. 2012-025968 filed on February 9, 2012 are incorporated herein by reference. .
  • TCO (with transparent conductive film) substrate 12 Glass substrate 14 Tin oxide film 18 Injector 20 Slow cooling furnace 24 Main raw material outlet 26 Sub raw material outlet 28 Suction port

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PCT/JP2013/053149 2012-02-09 2013-02-08 Substrat de verre pour formation de film conducteur transparent, et substrat avec film conducteur transparent Ceased WO2013118897A1 (fr)

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WO2014112415A1 (fr) * 2013-01-16 2014-07-24 旭硝子株式会社 Procédé de fabrication d'un substrat de verre présentant un film laminé
EP3281922A4 (fr) * 2015-04-10 2018-11-21 Asahi Glass Company, Limited Feuille de verre renforcée et son procédé de fabrication
US10683231B2 (en) 2015-03-26 2020-06-16 Pilkington Group Limited Glasses
CN112703172A (zh) * 2018-09-18 2021-04-23 Ａｇｃ株式会社 玻璃基板、黑色矩阵基板和显示面板
CN115108719A (zh) * 2014-09-03 2022-09-27 日本电气硝子株式会社 支承玻璃基板及使用其的层叠体
JP7143919B1 (ja) 2021-05-07 2022-09-29 Ａｇｃ株式会社 透明導電膜付きガラス基板及びその製造方法

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WO2014112415A1 (fr) * 2013-01-16 2014-07-24 旭硝子株式会社 Procédé de fabrication d'un substrat de verre présentant un film laminé
CN115108719A (zh) * 2014-09-03 2022-09-27 日本电气硝子株式会社 支承玻璃基板及使用其的层叠体
US10683231B2 (en) 2015-03-26 2020-06-16 Pilkington Group Limited Glasses
EP3281922A4 (fr) * 2015-04-10 2018-11-21 Asahi Glass Company, Limited Feuille de verre renforcée et son procédé de fabrication
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CN112703172B (zh) * 2018-09-18 2023-03-31 Ａｇｃ株式会社 玻璃基板、黑色矩阵基板和显示面板
CN112703172A (zh) * 2018-09-18 2021-04-23 Ａｇｃ株式会社 玻璃基板、黑色矩阵基板和显示面板
JP7143919B1 (ja) 2021-05-07 2022-09-29 Ａｇｃ株式会社 透明導電膜付きガラス基板及びその製造方法
JP2022173167A (ja) * 2021-05-07 2022-11-17 Ａｇｃ株式会社 透明導電膜付きガラス基板及びその製造方法
JP2022172963A (ja) * 2021-05-07 2022-11-17 Ａｇｃ株式会社 透明導電膜付きガラス基板及びその製造方法
WO2022234811A1 (fr) * 2021-05-07 2022-11-10 Ａｇｃ株式会社 Substrat en verre pourvu d'un film conducteur transparent et procédé pour la fabrication de celui-ci
CN116395981A (zh) * 2021-05-07 2023-07-07 Ａｇｃ株式会社 带有透明导电膜的玻璃基板及其制造方法
JP7396416B2 (ja) 2021-05-07 2023-12-12 Ａｇｃ株式会社 透明導電膜付きガラス基板及びその製造方法
CN116395981B (zh) * 2021-05-07 2024-03-22 Ａｇｃ株式会社 带有透明导电膜的玻璃基板及其制造方法

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