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WO2012176899A1 - Procédé de fabrication de substrat ayant un film d'oxyde conducteur transparent - Google Patents

Procédé de fabrication de substrat ayant un film d'oxyde conducteur transparent Download PDF

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Publication number
WO2012176899A1
WO2012176899A1 PCT/JP2012/066056 JP2012066056W WO2012176899A1 WO 2012176899 A1 WO2012176899 A1 WO 2012176899A1 JP 2012066056 W JP2012066056 W JP 2012066056W WO 2012176899 A1 WO2012176899 A1 WO 2012176899A1
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Prior art keywords
substrate
oxide
transparent substrate
transparent
oxide film
Prior art date
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PCT/JP2012/066056
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English (en)
Japanese (ja)
Inventor
直樹 岡畑
章 宇惠野
邦明 廣松
航 西田
剛志 角田
純一 宮下
高橋　亮
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AGC Inc
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Asahi Glass Co Ltd
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Publication of WO2012176899A1 publication Critical patent/WO2012176899A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
    • 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
    • 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
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H10F77/707—Surface textures, e.g. pyramid structures of the substrates or of layers on substrates, e.g. textured ITO layer on a glass substrate
    • 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
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • 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
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface

Definitions

  • the present invention relates to a method for producing a substrate with a transparent conductive oxide film.
  • Thin film solar cells that are photoelectric conversion elements include amorphous silicon (a-Si) and polycrystalline silicon depending on the type of power generation layer. These thin film silicon solar cells have an incident light side.
  • a transparent conductive oxide film is used as an electrode. This transparent conductive oxide film is required to have low resistance and high transparency and high light scattering performance in order to increase photoelectric conversion efficiency.
  • Patent Documents 1 and 2 list a “substrate with a transparent conductive oxide film in which a conductive oxide film is provided on a substrate”.
  • a substrate with a transparent conductive oxide film is formed by forming a discontinuous hill portion made of a first oxide on a transparent substrate by an atmospheric pressure CVD method, and then forming a second ridge on the discontinuous ridge portion. It is manufactured by forming a continuous layer made of an oxide by an atmospheric pressure CVD method.
  • a first CVD process for forming nuclei with a mass thickness of 1 to 20 nm and a second CVD process for forming small ridges with a mass thickness of 100 to 1000 nm are performed on a transparent substrate. A small mountain is formed.
  • Patent Document 2 the first CVD process and the second CVD process described above are performed to form the small ridges, whereby the pitch between the small ridges can be easily set to about 0.7 to 1.2 ⁇ m as a linear distance. It is said that.
  • the reason for this is that, in Patent Document 2, in the transport-type atmospheric pressure CVD apparatus shown in FIG. 3 of the same document, the source gas supply part and the exhaust part are in the front-rear direction in the glass substrate traveling direction. This is considered to be because the influence of turbulent flow generated at the lower part of the exhaust port can be minimized when the core of the part is formed.
  • the substrate with a transparent conductive oxide film described in Patent Document 2 has a C light source haze ratio of 30 to 90% when the C light source haze ratio is measured with a haze meter over the entire transparent substrate, and the C light source haze ratio varies. That is, the value obtained by dividing the difference between the maximum value and the minimum value of the C light source haze ratio (maximum value ⁇ minimum value) by about an average value is about 55%, but the photoelectric conversion efficiency of the thin-film solar cell is further improved. Therefore, the transparent conductive oxide film used as the incident light side electrode of the thin-film solar cell is required to further reduce variation in the C light source haze ratio.
  • the present invention provides a substrate with a transparent conductive oxide film having a large light scattering performance and a sufficiently small variation in C light source haze ratio, specifically, the entire surface of the substrate.
  • An object of the present invention is to provide a method for producing a substrate with a transparent conductive oxide film, which can obtain a substrate with a transparent conductive oxide film having a small variation in the C light source haze ratio when measuring the C light source haze rate. To do.
  • the present invention has been made on the basis of the above knowledge, and a plurality of crests are provided on a transparent substrate so as to be separated from each other, and one surface of the transparent substrate is composed of a plurality of crests and a plurality of flat portions.
  • the surface of the peak and the flat portion has a number of microscopic projections continuously, the bottom surface diameter of the projections is 0.1 to 0.3 ⁇ m, and the height of the projections /
  • a method for producing a substrate with a transparent conductive oxide film in which a transparent conductive oxide film having a bottom diameter ratio of 0.7 to 1.2 is provided on a transparent substrate On the transparent substrate, a procedure for forming a discontinuous mound portion made of the first oxide using a transfer type atmospheric pressure CVD apparatus using a transfer type atmospheric pressure CVD apparatus, and, A step of forming a continuous layer made of a second oxide on the transparent substrate on which the small ridges and the small ridges are not formed using a transfer-type atmospheric pressure CVD apparatus;
  • the steps for forming the ridges include a first CVD process for forming nuclei having a height of 100 to 400 nm, and a ridge having a height of 0.2 to 2.0 ⁇ m starting from the nuclei.
  • the flow direction of the source gas ejected from the injector is the same as the transport direction of the transparent substrate
  • the flow direction of the source gas ejected from the injector is two directions that are the same as and opposite to the transport direction of the transparent substrate.
  • the first oxide and the second oxide are made of an oxide containing SnO 2 as a main component.
  • the second oxide is preferably composed of a conductive oxide mainly composed of SnO 2 containing fluorine or antimony as a dopant.
  • a carrier-type atmospheric pressure CVD apparatus is provided between a small hill portion made of the first oxide and a continuous layer made of the second oxide.
  • the method further includes a step of forming an oxide layer made of an oxide having a composition different from that of the first oxide and the second oxide.
  • the procedure for forming the oxide layer made of the different oxide includes an injector in which the flow of the raw material gas on the transparent substrate is in the same direction and in the opposite direction to the transport direction of the transparent substrate (that is, a double flow structure). It is preferable to use an injector.
  • the oxide having a composition different from that of the first oxide and the second oxide is preferably composed of an oxide containing SiO 2 as a main component.
  • the main component of SiO 2 means that SiO 2 is contained by 50 mol% or more in terms of mol%.
  • the C light source haze ratio is measured on the substrate with a transparent substrate, specifically, the entire surface of the transparent substrate, a substrate with a transparent conductive oxide film having a small variation in the C light source haze ratio can be obtained. Further, since the variation in the C light source haze ratio is small, it is possible to prevent the appearance of the entire solar cell panel from deteriorating due to the haze unevenness when the solar cell is produced using this substrate, and to improve the design. .
  • FIG. 1 is a partially cutaway cross-sectional view showing the shape and configuration of a substrate with a transparent conductive oxide film produced by the method of one embodiment of the present invention.
  • FIG. 2 is a diagram schematically illustrating an example of a single-flow injector used in the first CVD process of one embodiment of the present invention.
  • FIG. 3 is a diagram schematically illustrating an example of a double-flow injector used in the second CVD process according to an aspect of the present invention and the procedure for forming a continuous layer.
  • FIG. 1 is a partially cutaway cross-sectional view showing the shape and configuration of a substrate with a transparent conductive oxide film produced by the method of one embodiment of the present invention.
  • the transparent conductive oxide film 14 formed on the transparent substrate 11 has a plurality of discontinuous layers. And a plurality of flat portions 13 filled between the ridges (texture), and a plurality of flat portions 13 filled between the ridges.
  • the surface of the peak portion 12 and the flat portion 13 has a large number of irregularities (textures) of “microscopic” (herein, “microscopic” is also simply referred to as “micro”).
  • a double texture structure By forming the transparent conductive oxide film 14 formed on the transparent substrate 11 to have a double texture structure, that is, the outer surfaces of the ridges 12 and the flat portions 13 are made uneven by the ridges (macro unevenness). ) Smaller than (), it is possible to strongly scatter light having a short wavelength and effectively scatter light in a wide area as a whole. That is, since long wavelength light can be scattered by a large peak part and short wavelength light can be scattered by a small convex part, high light-scattering property can be achieved as a whole.
  • the transparent conductive oxide film 14 shown in FIG. 1 is a continuous layer made of a discontinuous hill portion 15 made of a first oxide and a second oxide formed thereon, and the continuous layer And a continuous layer 16 having a large number of micro-convex portions 17 on the surface thereof.
  • the continuous layer 16 made of the second oxide is continuously formed on the small ridge 15 and on the transparent substrate 11 where the small ridge 15 is not formed.
  • the substrate with a transparent conductive oxide film produced by the method of the present invention is not particularly limited as long as it has the above-described configuration, but the dimensions of each part preferably satisfy the conditions described below.
  • the height of the small mountain portion 15 is preferably 0.2 to 2.0 ⁇ m, more preferably 0.2 to 1.0 ⁇ m, and further preferably 0.25 to 0.5 ⁇ m.
  • the bottom diameter of the small mountain portion 15 is preferably 0.05 to 2.0 ⁇ m, and more preferably 0.2 to 1.5 ⁇ m.
  • the pitch between the adjacent small ridges 15 is 0.1 to 2.5 ⁇ m as a linear distance on the transparent substrate 11, and after forming the continuous layer made of the second oxide, the C light source haze ratio is 30 to 30 ⁇ m. 90%, which is preferable because it is easy to reduce variation in the C light source haze ratio, and is more preferably 0.2 to 1.6 ⁇ m.
  • the distance of the flat portion between the adjacent small hill portions 15 (hereinafter, also simply referred to as “interval between small ridge portions”) is preferably 0.1 to 2.3 ⁇ m in a linear distance, preferably 0.1 to More preferably, it is 1.5 ⁇ m.
  • the thickness of the continuous layer 16 on the small ridge 15 is preferably 0.5 to 1.0 ⁇ m, and more preferably 0.5 to 0.7 ⁇ m.
  • the thickness of the continuous layer 16 on the transparent substrate 11 is preferably 0.5 to 1.0 ⁇ m, and more preferably 0.5 to 0.7 ⁇ m.
  • the shape of the small hill portion is not limited to a substantially conical shape, a cone having an elliptical shape on the bottom surface, or a pyramid formed from a plane.
  • the height of the small ridge means the height difference between the surface where the small ridge is formed (that is, the surface of the base, or the surface of the base film when the base film is formed on the surface of the transparent base) and the apex of the small hill.
  • the bottom surface diameter of the small mountain portion refers to the diameter when the bottom surface is circular, and the diameter when converted into a circle having the same bottom area when the bottom surface is not circular.
  • the height of the convex portions 17 existing on the surface of the continuous layer 16 is preferably 0.05 to 0.2 ⁇ m, and more preferably 0.1 to 0.2 ⁇ m.
  • the height of a convex part is called the height of a convex part the largest height difference in the height difference of the vertex of a convex part from the trough part formed with a some adjacent convex part.
  • the vertex-to-vertex distance between adjacent convex portions 17 is preferably a linear distance of 0.1 to 0.3 ⁇ m, preferably 0.1 to More preferably, it is 0.2 ⁇ m.
  • the bottom diameter of the convex portion 17 is preferably 0.1 to 0.3 ⁇ m, more preferably 0.15 to 0.3 ⁇ m, and the ratio of the height / bottom diameter of the convex portion 17 is 0.00. It is preferably 7 to 1.2, and more preferably 0.7 to 1.0.
  • the bottom face diameter of a convex part means the diameter when a bottom face is circular, and when it is not circular, it means the diameter at the time of converting into a circle with the same bottom area.
  • the height of the crest 12 (the height from the top of the micro-projection 17 on the flat portion 13) is preferably 0.2 to 2.0 ⁇ m, and preferably 0.2 to 0.8 ⁇ m. More preferably, it is 0.3 to 0.6 ⁇ m.
  • the shape of the peak is not limited to a substantially conical shape, a cone having an elliptical shape on the bottom surface, or a pyramid formed from a flat surface.
  • the height of the mountain portion refers to a place where the height difference between the valley portion and the peak portion of the mountain portion formed between other adjacent mountain portions is the largest.
  • the bottom surface diameter of the peak portion is the diameter when the bottom surface is circular, and when it is not circular, it is the diameter when converted into a circular shape with the same bottom area.
  • the distance of the flat portion 13 between the adjacent ridges 12 is preferably 0 to 2.3 ⁇ m as a linear distance, and is 0 to 1.5 ⁇ m. It is more preferable that the thickness is 0.1 to 0.7 ⁇ m.
  • any of the plurality of peaks 12 is discontinuous.
  • the plurality of peaks 12 may be discontinuous and continuous, and the interval between the peaks 12 is 0 to 2.3 ⁇ m, which means that there is no flat portion 13. That is good.
  • the pitch between the peaks 12 is the same value as the pitch between the peaks 15 described above, and is preferably 0.1 to 2.5 ⁇ m, more preferably 0.2 to 1.6 ⁇ m as a linear distance. preferable.
  • Such surface properties in the substrate with the transparent conductive oxide film, the coverage of the small ridges made of the first oxide described later on the transparent substrate, and the nuclei or ridges in the first CVD step and the second CVD step The mass film thickness can be confirmed, for example, by the following method.
  • SEM scanning electron microscope
  • AFM atomic force microscope
  • the coverage of the small oxide portion of the first oxide on the transparent substrate is measured from the SEM photograph, and the area occupied by the small mountain portion on the transparent substrate is determined by the coating surface of the transparent substrate. The value divided by the total area can be evaluated as the surface coverage.
  • the mass film thickness is a detection amount proportional to the metal amount of the metal oxide in a fluorescent X-ray apparatus for a discontinuous metal oxide (first oxide) in a certain area on the transparent substrate. Assuming that the volume of the discontinuous oxide is continuous compared to the detected amount of the fluorescent X-ray apparatus in the same kind of metal oxide with a known film thickness, continuously on a separately prepared substrate The obtained film thickness is shown.
  • the substrate with a transparent conductive oxide film having the double texture structure described above will be described below.
  • the transparent substrate is not necessarily flat and plate-like, and may be curved or irregular.
  • the transparent substrate is required to be a transparent substrate having at least a surface different from that of a first oxide described later and having excellent translucency.
  • Specific examples of the transparent substrate include glass substrates, plastic substrates and the like, and those obtained by applying an alkali barrier layer such as a silicon oxide film, an aluminum oxide film, a zirconium oxide film, and a titanium oxide film on the surface of these substrates.
  • a glass substrate or a glass substrate provided with an alkali barrier layer is preferable from the viewpoint of strength and heat resistance.
  • such a substrate preferably has a high transmittance in the wavelength region of 350 to 800 nm, for example, an average transmittance of 80% or more, is sufficiently insulative, and has high chemical and physical durability. desirable.
  • the glass substrate is made of, for example, colorless and transparent soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and other various glasses.
  • a transparent glass substrate can be used.
  • the substrate with a transparent conductive oxide film produced by the method of the present invention is used for a solar cell substrate, the glass substrate has a thickness of 0.2 to 6.0 mm. It is preferable in terms of rate.
  • a glass substrate made of glass containing sodium such as soda lime silicate glass or a glass substrate made of low alkali content glass an alkaline component from the glass substrate to the transparent conductive oxide film formed on the upper surface thereof
  • a glass substrate provided with the above-described alkali barrier layer it is preferable to use a glass substrate provided with the above-described alkali barrier layer.
  • the first oxide that forms the hill portion is not particularly limited as long as it is a highly transparent oxide in the visible light region. Specific examples thereof include TiO 2 , SnO 2 , In 2 O 3 , ZnO, CdO, CdIn 2 O 4 , CdSnO 3 , MgIn 2 O 4 , CdGa 2 O 4 , GaInO 3 , InGaZnO 4 , Cd 2 Sb 2 O 7 , Cd 2 GeO 4 , CuAlO 2 , CuGaO 2 , SrCu 2 O 2 , Al 2 O 3 etc. are mentioned.
  • At least one selected from the group consisting of TiO 2 and SnO 2 is preferably used, and an oxide containing SnO 2 as a main component is particularly preferable.
  • an oxide having a main component indicates that 50 mol% or more of the component is the oxide.
  • the first oxide that forms the ridges preferably has a refractive index of 1.8 to 2.2 at a wavelength of 400 to 800 nm, and more preferably 1.9 to 2.1.
  • the first oxide is made of the first oxide. It is preferable because the reflection of light at the interface between the small mountain portion and the continuous layer made of the second oxide is controlled and the transmittance does not decrease.
  • the small hill portions made of the first oxide are discontinuous between adjacent small ridge portions, and the state where the small ridge portions are formed on the substrate is a group of discontinuous oxides. It is not an oxide film, that is, a continuous oxide film.
  • substrate part which is not covered with a small mountain part naturally has the absorption loss of the incident light by a small mountain part, it can increase the incident light quantity to a photoelectric converting layer. For this reason, it is essential that it is not a continuous film.
  • These ridges are portions that increase the haze ratio (that is, increase the degree of light scattering), and are not electrically conductive or highly conductive in order to suppress absorption by free electrons and make them highly transparent.
  • the dopant generating carriers such as fluorine has a content of less than 0.01 mol% with respect to SnO 2 .
  • the dopant generating carriers such as fluorine has a content of less than 0.01 mol% with respect to SnO 2 .
  • the second oxide forming the continuous layer is required to be a transparent conductive oxide that is transparent in the visible light region and has conductivity, and specific examples thereof include SnO 2 , ZnO, In 2 O 3 and the like may be mentioned, and two or more of them may be used in combination, and it is preferable that these oxides are the main components and a dopant for developing conductivity is contained.
  • SnO 2 preferably contains 0.01 to 4 mol% of fluorine or antimony as a dopant with respect to SnO 2 .
  • ZnO preferably contains 0.02 to 5 mol% of ZnO as a dopant with respect to at least one selected from the group consisting of boron, Al and Ga.
  • In 2 O 3 preferably contains 0.02 to 4 mol% of Sn as a dopant with respect to In 2 O 3 .
  • doping using these dopants may be based on hydrogen halide. Specific examples of such a hydrogen halide include HF and HBr.
  • the conductive electron density of the substrate with a transparent conductive oxide film is improved.
  • the conductive electron density is preferably 5 ⁇ 10 19 to 4 ⁇ 10 20 cm ⁇ 3 , and more preferably 1 ⁇ 10 20 to 2 ⁇ 10 20 cm ⁇ 3 . If the conductive electron density is within this range, the light absorption amount of the continuous layer made of the second oxide is small, highly transparent, and highly durable against active hydrogen species. Transparency is not impaired even by hydrogen plasma irradiation generally used for forming, which is preferable.
  • the second oxide forming the continuous layer preferably has a refractive index of 1.8 to 2.2 at a wavelength of 400 to 800 nm, and more preferably 1.9 to 2.1. .
  • the first oxide and the second oxide are provided between the small hill portion made of the first oxide and the continuous layer made of the second oxide. It is preferable to form oxide layers composed of oxides having different compositions (hereinafter also simply referred to as “different oxide layers”). By forming such different oxide layers, it becomes easy to form a large number of micro-convex portions on the surface of the continuous layer made of the second oxide, and has a double texture structure having the above-described peak portions and flat portions. Can be easily formed.
  • the flow of the raw material gas on the transparent substrate 11 is changed to be transparent as indicated by the arrow G as shown by the arrow g in the injector 200 having the double flow structure shown in FIG. It is used as a double-flow injector that is in the same direction as the conveying direction of the substrate 11 and in the opposite direction.
  • the dual-flow injector 200 as a dual-flow injector, the transport direction of the transparent substrate 11 can be reduced. This is because even if stagnation occurs in the flow of the raw material gas in the opposite direction, there is no problem in forming different oxide layers.
  • the transparent conductive oxide film having a multilayer structure having such different oxide layers it is required to reduce reflection at the interface between the layers.
  • the refractive index of the first oxide, the different oxide and the second oxide be as close as possible, or that the different oxide layers be as thin as possible when the refractive indices are separated.
  • the refractive index at the wavelength of 400 to 800 nm of the first oxide that forms the ridges and the second oxide that forms the continuous layer is 1. 8 to 2. 2. Further, it is preferably 1. 9 to 2. 1.
  • Such different oxides include oxides of one or more elements selected from the group consisting of Si, Sn, Al, Zr, and Ti. It is preferable to have an article as a main component. Moreover, since the different oxide needs to have high translucency, it is more preferably SiO 2 that is non-crystalline. In addition to these reasons, (1) a small mountain portion made of the first oxide and a good covering property to the transparent substrate, (2) easy production, (3) an amorphous film, For reasons such as being likely to become an amorphous film, it is preferable to use an oxide mainly composed of SiO 2 as a different oxide. Note that the oxide composed mainly of SiO 2, show that more than 50% of the component is SiO 2.
  • the oxide containing SiO 2 contains the same tin component as the first and second oxides. It is preferable in that the layer tends to be less likely to cause a defect that deteriorates conductivity when the layer is formed.
  • the molar ratio of tin to silicon is 0.2: 0.8 to 0 when the composition ratio of the metal element of the oxide to be formed is expressed as a molar ratio. Preferably between 5: 0.5.
  • the molar ratio of tin is smaller than 0.2, the effect of making it difficult to produce defects that deteriorate the conductivity in the continuous layer made of the second oxide is reduced. More preferably, the molar ratio of tin to silicon is between 0.3: 0.7 and 0.5: 0.5.
  • the thickness of the different oxide layers is preferably 2 to 40 nm, and more preferably 5 to 30 nm.
  • a substrate with a transparent conductive oxide film having the following characteristics can be obtained.
  • the substrate with a transparent conductive oxide film produced by the method of the present invention has a spectral haze ratio of 10 to 95% over the entire wavelength range of 400 to 800 nm, and when the C light source haze ratio is measured with a haze meter over the entire transparent substrate.
  • the C light source haze ratio is 30 to 90%, preferably 30 to 80%, more preferably 30 to 70%, and variation in the C light source haze ratio is small.
  • the spectral haze ratio is preferably 25% or more in the wavelength region of 400 to 600 nm, and particularly preferably 10 to 80% in the wavelength region of 600 to 800 nm.
  • the variation in the C light source haze ratio of the substrate with the transparent conductive oxide film is smaller, the light scattering property in the solar cell using the substrate with the transparent conductive oxide film is uniform, and the power generation unevenness in the plane of the solar cell Can be eliminated.
  • the C light source haze ratio variation is small, it is possible to prevent the appearance of the entire solar cell panel from deteriorating due to unevenness of the haze when the solar cell is formed, and to improve the design.
  • the “spectral haze ratio” indicates the ratio of the scattering component in the transmitted light.
  • the haze rate depends on the wavelength, the haze rate is Hz ( ⁇ ), the total transmittance is T total ( ⁇ ), the straight component of transmitted light is T direct ( ⁇ ), and the scattered component of transmitted light is T diffuse ( ⁇ ). Then, the haze ratio of each wavelength is obtained from the following Hz ( ⁇ ).
  • C light source haze ratio indicates a haze ratio measured with a C light source.
  • “variation in C light source haze ratio” is a value obtained by dividing (difference between the maximum value and the minimum value of C light source haze ratio) by an average value.
  • the C light source haze ratio was measured at intervals of 10 mm for a length of 300 mm (excluding within 15 mm from the end of the substrate) in the transport direction. It is a value obtained by dividing the difference (the difference between the maximum value and the minimum value of the C light source haze ratio) by the average value.
  • C light source haze ratio indicates a haze ratio measured with a C light source.
  • “variation in C light source haze ratio” is a value obtained by dividing (difference between the maximum value and the minimum value of C light source haze ratio) by an average value.
  • the C light source haze ratio was measured at intervals of 10 mm for a length of 300 mm (excluding within 15 mm from the end of the substrate) in the transport direction. It is a value obtained by dividing the difference (the difference between the maximum value and the minimum value of the C light source haze ratio) by the average value.
  • the transport-type atmospheric pressure CVD apparatus refers to an apparatus that performs surface treatment of a substrate by performing CVD (Chemical Vapor Deposition) on the substrate to be transported in a state of normal pressure (also referred to as atmospheric pressure).
  • the carrier-type atmospheric pressure CVD apparatus is used for forming the small ridges by performing the first CVD process and the second CVD process according to the procedure described later, so that the discontinuous ridges are uniformly formed on the transparent substrate. It is because it can form. Moreover, the reason why the transfer type atmospheric pressure CVD apparatus is used is that it is suitable for mass-producing a substrate with a transparent conductive oxide film.
  • the nuclei having a peak height of 100 to 400 nm are formed on the transparent substrate in the first CVD process, and then the nuclei formed are used as the starting point and 0.2 mil in the second CVD process.
  • a ridge with a height of ⁇ 2.0 ⁇ m is formed on the transparent substrate.
  • FIG. 2 is a view schematically showing an example of a single-flow injector used in the first CVD process of the present invention.
  • the single-flow injector 100 includes a source gas supply nozzle 110, an exhaust nozzle 120, and a seal gas supply nozzle 130.
  • the transparent substrate 11 is conveyed by the conveyor belt 300. Further, with respect to the transport direction, the transport direction side is referred to as “transport direction downstream”, and the reverse direction of transport is referred to as “transport direction upstream”.
  • the source gas supply nozzle 110 supplies source gas onto the transparent substrate 11.
  • the exhaust nozzle 120 is provided on the downstream side in the transport direction of the transparent substrate 11 with respect to the source gas supply nozzle 110, and sucks and removes the gas generated by the reaction in the first CVD process and the excess source gas.
  • the seal gas supply nozzle 130 is provided on the upstream side in the transport direction of the transparent substrate 11 with respect to the source gas supply nozzle 110, blocks the transparent substrate on which the first CVD step is performed from the external atmosphere, and the source gas is transparent substrate 11
  • a seal gas (usually nitrogen (N 2 )) is supplied for the purpose of preventing a reverse flow upstream in the transport direction.
  • a source gas supply nozzle 110 shown in FIG. 2 is a case where SnO 2 is used as the first oxide, and a nozzle 111 for supplying tin tetrachloride (SnCl 4 ) as a main material as a source gas, And a nozzle 112 for supplying water (H 2 O), which is an auxiliary material, and hydrogen chloride (HCl) for the purpose of controlling the reaction for generating SnO 2 (the reaction for generating nuclei). ing.
  • the combination of the feedstock and nozzle shown here is an example, and is not limited to this. That is, water and hydrogen chloride may be supplied from the nozzle 111, tin tetrachloride may be supplied from the nozzle 112, tin tetrachloride and hydrogen chloride may be supplied from the nozzle 111, and water may be supplied from 112. It is also preferable to mix water, hydrogen chloride and tin tetrachloride and supply them from the nozzle 111. In this case, an inert gas such as nitrogen is supplied from the nozzle 112.
  • tin tetrachloride as the main raw material from the nozzle 111 and supply water and hydrogen chloride from the nozzle 112 because the flow orthogonal to the transparent substrate 11 tends to be the most stable airflow.
  • tin tetrachloride as a main raw material, water as an auxiliary raw material, and hydrogen chloride supplied for the purpose of controlling a reaction for generating SnO 2 (a reaction for generating a nucleus) are usually nitrogen, argon, etc. Supplied with the carrier gas.
  • the source gas supplied onto the transparent substrate 11 flows in the same direction as the direction of conveyance of the transparent substrate indicated by the arrow G, as indicated by the arrow g.
  • Such a stagnation in the flow of the source gas means that the nuclei formed on the transparent substrate when the dual-flow injector 200 is used as the double-flow injector in the first CVD process for forming nuclei on the transparent substrate.
  • This is considered to be a cause of non-uniformity in the transport direction of the transparent substrate.
  • the distribution of the nuclei formed on the transparent substrate is non-uniform in the transport direction of the transparent substrate. It is estimated that this is the cause of the variation in the C light source haze rate along the direction.
  • the flow of the source gas on the transparent substrate is the same as the transport direction of the transparent substrate. No stagnation occurs, the distribution of nuclei formed on the transparent substrate does not become non-uniform in the transport direction of the transparent substrate, and the distribution of nuclei formed on the transparent substrate becomes uniform.
  • the manufactured substrate with a transparent conductive oxide film variation in the C light source haze ratio is suppressed along the transport direction of the transparent substrate, and the variation in C light source haze ratio is sufficiently small.
  • the C light source haze ratio is measured for the substrate with a conductive oxide film, specifically, the entire transparent substrate, a substrate with a transparent conductive oxide film having a small variation in the C light source haze ratio can be obtained.
  • the injector 200 having the double flow structure shown in FIG. 3 is used as a single flow injector, the flow of the raw material gas on the transparent substrate is the same as the transport direction of the transparent substrate.
  • the flow of slag does not cause stagnation, the distribution of nuclei formed on the transparent substrate does not become uneven in the transport direction of the transparent substrate, and the distribution of nuclei formed on the transparent substrate becomes uniform.
  • the C light source haze ratio may vary along the transport direction of the transparent substrate.
  • a transparent conductive oxide film substrate that is suppressed and has a sufficiently small variation in the C light source haze ratio. Specifically, when the C light source haze ratio is measured over the entire transparent substrate, the C light source haze ratio variation is small.
  • a substrate with a conductive oxide film can be obtained.
  • the molar ratio of hydrogen chloride to tin tetrachloride (hereinafter simply referred to as “HCl / SnCl 4 ”) in the source gas is 1 to 12 in the first CVD step.
  • nuclei are likely to be formed on the transparent substrate, and thereafter, it is preferable for controlling the surface coverage of the transparent substrate by the small ridges formed by performing the second CVD step.
  • HCl / SnCl 4 is preferably 5 to 10.
  • the source gas can be accompanied by a carrier gas made of nitrogen or the like that is not involved in the reaction.
  • the distance between the tip of the source gas supply nozzle 110 (nozzle 111, nozzle 112) and the transparent substrate 11 is preferably 2 to 20 mm. If the distance between the two is less than 2 mm, the tip of the source gas supply nozzle 110 (nozzle 111, nozzle 112) may be in contact with the transparent substrate 11. On the other hand, if the distance between the two is 20 mm or more, the source gas does not reach the transparent substrate 11, and there is a possibility that a nucleus having a height of 100 to 400 nm cannot be formed on the transparent substrate 11.
  • the distance between the two is more preferably 2 to 12 mm, and further preferably 5 to 12 mm. The distance between the two means the narrowest distance between the surface of the nozzle on the transparent substrate side and the surface of the transparent substrate when there is a step on the surface of the nozzle on the transparent substrate side.
  • the double-flow injector 200 shown in FIG. 3 is passed through the transparent substrate 11 indicated by the arrow G as indicated by the arrow g. 11 using a double-flow injector that is in the same direction as the transport direction of 11 and in the opposite direction.
  • a small peak having a height of 0.2 to 2.0 ⁇ m is formed on the transparent substrate starting from the nucleus formed so that the distribution on the transparent substrate is uniform in the first CVD process.
  • the double-flow injector 200 as a double-flow injector, even if stagnation occurs in the flow of the raw material gas in the direction opposite to the transport direction of the transparent substrate 11, the small peaks formed on the transparent substrate 11 The distribution is not adversely affected, and the distribution of the hills formed on the transparent substrate 11 is uniform.
  • the oxide is deposited, the distribution is less affected even if the stagnation occurs in the second CVD process because of the property that the oxide is deposited more easily than the deposition on the transparent substrate.
  • the film formation with the double-flow injector is faster than the film formation with the single-flow injector, so that the reaction of the raw material between the injector and the transparent substrate is sufficiently accelerated. It is necessary to use in the process.
  • the distance between the tip of the source gas supply nozzle 210 and the transparent substrate 11 is preferably 2 to 20 mm. If the distance between the two is less than 2 mm, the tip of the source gas supply nozzle 210 and the transparent substrate 11 may come into contact with each other. On the other hand, if the distance between the two is 20 mm or more, the source gas does not reach the transparent substrate 11, and there is a possibility that a small ridge having a height of 0.2 to 2.0 ⁇ m cannot be formed on the transparent substrate 11.
  • the distance between the two is more preferably 2 to 12 mm, and further preferably 5 to 12 mm. The distance between the two means the narrowest distance between the surface of the nozzle on the transparent substrate side and the surface of the transparent substrate when there is a step on the surface of the nozzle on the transparent substrate side.
  • the surface coverage on the transparent base of the small ridge formed by performing the first CVD step and the second CVD step is 10 to 70%. More preferably, the surface coverage is 10 to 50%.
  • the flow of the raw material gas on the transparent substrate 11 is changed between the direction of conveyance of the transparent substrate 11 indicated by the arrow G as shown by the arrow g in the injector 200 having the double flow structure shown in FIG. Used as a double-flow injector with the same direction and reverse direction.
  • the dual-flow injector 200 as a dual-flow injector, the transport direction of the transparent substrate 11 can be reduced. This is because even if stagnation occurs in the flow of the raw material gas in the reverse direction, there is no problem in forming the continuous layer.
  • using the double-flow injector 200 as a double-flow injector is preferable in terms of preventing the influence of disturbance during the formation of the continuous layer and having a high film formation speed.
  • the raw material gas can be mixed with nitrogen gas so that the total of tin tetrachloride and trichlorosilane is 0.1% by volume, and sprayed together with water vapor.
  • the double-flow injector 200 it is preferable to use the double-flow injector 200 as a double-flow injector in terms of preventing the influence of a disturbance during the formation of different oxide layers and having a high deposition rate.
  • a glass substrate provided with an alkali barrier layer as a transparent substrate and a layer for reducing the difference in refractive index between the surface of the glass substrate and the layer provided thereon are provided on the glass surface.
  • a transfer type atmospheric pressure CVD apparatus it is preferable to form these layers using a transfer type atmospheric pressure CVD apparatus because it is suitable for mass production of a substrate with a transparent conductive oxide film.
  • a double-flow injector 200 is indicated by an arrow G, as indicated by an arrow g, where the flow of the source gas on the transparent substrate 11 is indicated by an arrow g. It is used as a double-flow injector that is in the same direction as the transport direction of the transparent substrate 11 and in the opposite direction.
  • the production method of the present invention is not limited to this.
  • nitrogen gas 210 L / containing 100% monosilane gas 1 L / min using a transfer type atmospheric pressure CVD apparatus.
  • nitrogen gas 210 L / min containing oxygen gas 200 L / min are sprayed from the source gas supply nozzle 210 of the double-flow nozzle 200 (used as a double-flow nozzle) shown in FIG. 3 to form a silica film as an alkali barrier layer.
  • a silica film as an alkali barrier layer.
  • a first oxide is formed using nitrogen gas as a carrier gas at a location where the glass substrate with an alkali barrier layer reaches 590 ° C. using a carrier-type atmospheric pressure CVD apparatus.
  • nitrogen gas as a carrier gas
  • tin tetrachloride water and hydrogen chloride as source gases
  • tin tetrachloride is supplied from nozzle 111 of single-flow injector 100 shown in FIG. 2
  • water and hydrogen chloride are supplied from nozzle 112
  • the raw material on the glass substrate is supplied.
  • HCl / SnCl 4 in the source gas is set to 2.6 in terms of mol ratio, and the distance between the tip of the source gas supply nozzle 110 (nozzle 111, nozzle 112) and the alkali barrier layer (silica film) is set to 6 mm. be able to.
  • a feed gas of the double-flow nozzle 200 (used as a double-flow nozzle) shown in FIG.
  • a source gas is sprayed from the supply nozzle 210 to form a 350 nm high hill portion made of SnO 2 .
  • HCl / SnCl 4 in the source gas is set to 2.7
  • the distance between the tip of the source gas supply nozzle 210 and the alkali barrier layer (silica film) is set to 11 mm.
  • an F-doped SnO 2 layer is formed as a continuous layer made of the second oxide
  • the transparent substrate temperature is adjusted to 570 ° C.
  • tin tetrachloride, water, and HF gas are sprayed to form a transparent layer.
  • An F-doped SnO 2 layer is formed while moving the substrate.
  • Tin tetrachloride can be heated in advance to 80 ° C.
  • nitrogen gas can be transferred at 6 L / min, and sprayed onto the transparent substrate.
  • a SnO 2 film containing fluorine as a dopant as a continuous layer made of the second oxide is sprayed onto the transparent substrate so that water heated to 100 ° C. is 65 g / min and HF gas is 1.3 L / min. Can be formed.
  • Example 1 In the present embodiment, the discontinuous ridges 15 made of the first oxide are formed on the transparent substrate 11 of the substrate 10 with the transparent conductive oxide film having the double texture structure shown in FIG. The procedure up to the formation was carried out to evaluate the shape of the small ridges 15 formed on the transparent substrate 11, the C light source haze ratio, and the variation thereof.
  • tin tetrachloride was heated in advance to 90 ° C., nitrogen gas was bubbled and transferred at 2.9 L / min, and water was vaporized at 37.3 cc / min with a flash evaporator. Hydrogen chloride gas was introduced at 5.4 L / min simultaneously with the transfer of tin tetrachloride and water. Further, HCl / SnCl 4 in the source gas was set to 2.6 in terms of a molar ratio, and the distance between the tip of the source gas supply nozzle 110 (nozzle 111, nozzle 112) and the alkali barrier layer (silica film) was set to 6 mm.
  • tin tetrachloride and water are flowed together with nitrogen gas at 198.8 L / min.
  • No. 1 nozzle (used as a double-flow nozzle) was sprayed from a raw material gas supply nozzle to form a 350 nm high hill portion made of SnO 2 .
  • tin tetrachloride was sprayed onto the alkali barrier layer (silica film) by heating the container to 90 ° C. in advance and bubbling and transferring nitrogen gas at 4.42 L / min. Water was sprayed by vaporizing 14.7 cc / min with a flash evaporator. The distance between the nozzle tip and the substrate was 11 mm.
  • the SnO 2 film was not a continuous film but formed a small portion.
  • the coverage of the glass substrate surface (silica film surface) with SnO 2 forming the hill portion was 40%, and the height of the hill portion made of SnO 2 Is 0.35 ⁇ m, the bottom diameter of SnO 2 is 0.4 to 1.0 ⁇ m, the distance between adjacent small peaks is 0.1 to 0.8 ⁇ m, and the pitch between adjacent small peaks is 0.5 to It was 1.2 ⁇ m.
  • the C light source haze ratio was measured with a C light source haze ratio meter (TC-H III, manufactured by Tokyo Denshoku Co., Ltd.) at intervals of 10 mm for each of the 300 mm substrates in the direction perpendicular to the conveying direction of the soda lime glass substrate.
  • the variation of the C light source haze ratio was determined by dividing the average value from the difference between the maximum value and the minimum value of the measured value of the C light source haze ratio.
  • the C light source haze ratio was a minimum of 48.5%, a maximum of 50.3%, an average of 49.8%, and a standard deviation of 0.4, and the variation of the C light source haze ratio was determined to be 3.5%.
  • Example 2 In this example, the same procedure as in Example 1 was performed except that the following points in the first CVD process were different. That is, the same procedure as in Example 1 was performed except that the supply of hydrogen chloride gas was 5.5 L / min and HCl / SnCl 4 in the source gas was 2.6. After performing the second CVD step, when the uneven shape of the film surface was observed by SEM, it was found that the SnO 2 film was not a continuous film but formed a small ridge portion composed of macro unevenness.
  • the coverage of the glass substrate surface (silica film surface) with SnO 2 forming the hill portion was 40%, and the height of the hill portion made of SnO 2 Is 0.4 ⁇ m, the bottom diameter of SnO 2 ridges is 0.4 to 1.0 ⁇ m, the interval between adjacent ridges is 0.1 to 0.8 ⁇ m, and the pitch between adjacent ridges is 0.5 to It was 1.2 ⁇ m.
  • the C light source haze rate and its variation were measured. As a result, the minimum was 49.8%, the maximum was 52.1%, the average was 50.6%, and the standard deviation was 1.3. It was calculated to be 4.5%.
  • This comparative example uses a double-flow injector 200 shown in FIG. 3 as a double-flow injector in the first CVD process, and is made of SnO 2 having a height of 200 nm by spraying a source gas onto a glass substrate under the following conditions.
  • the same procedure as in Example 1 was performed except that the nucleus was formed on the alkali barrier layer (silica film). That is, a gas obtained by mixing all of tin tetrachloride, water, hydrogen chloride gas, and nitrogen gas at 67 L / min was simultaneously blown from the raw material gas supply nozzle 210 of the double-flow nozzle 200 shown in FIG.
  • tin tetrachloride was sprayed on the alkali barrier layer (silica film) by heating to 85 ° C. in advance and bubbling and transferring nitrogen gas at 5.52 L / min. Water was sprayed by vaporizing 62.8 cc / min with a flash evaporator. Further, hydrogen chloride gas was sprayed onto the alkali barrier layer (silica film) at a rate of 2.0 L / min simultaneously with the transfer of tin tetrachloride and water.
  • the SnO 2 film was not a continuous film but formed a small ridge portion composed of macro unevenness.
  • the coverage of the glass substrate surface (silica film surface) with SnO 2 forming the hill portion was 40%, and the height of the hill portion made of SnO 2 Is 0.4 ⁇ m, the bottom diameter of SnO 2 ridges is 0.8 to 1.0 ⁇ m, the interval between adjacent ridges is 0.1 to 1.0 ⁇ m, and the pitch between adjacent ridges is 0.9 to It was 2.0 ⁇ m.
  • the C light source haze ratio and its variation were measured. As a result, the minimum was 19.1%, the maximum was 34.9%, the average was 28.6%, and the standard deviation was 4.6. It was calculated to be 55.2%.
  • the reason why the C light source haze ratio of the comparative example is lower than that of Examples 1 and 2 is that HCl / SnCl 4 in the source gas in the first CVD process is high.
  • the distribution of nuclei on the transparent substrate is more dense.
  • the distribution of the small ridges formed through the second CVD process on the transparent substrate becomes more dense, and the C light source haze ratio increases.
  • the distribution on the transparent substrate (soda lime glass substrate) in the small hills becomes denser, the formation of nuclei on the transparent substrate tends to be uneven. That is, in some cases, two or more nuclei are united, and the nuclei have irregular sizes.
  • Examples 1 and 2 are absolute values of C light source haze as compared with the comparative example. In spite of being large, the variation of the C light source haze is much smaller in the example than in the comparative example both in absolute value and ratio. Therefore, by making the gas flow direction on the transparent substrate the same as the transport direction of the transparent substrate during the first CVD step, Examples 1 and 2 are transparent with higher uniformity of nuclei formed than the comparative example. A substrate is obtained.
  • Example 1 and 2 and the comparative example the C light source haze ratio and the C light source haze ratio variation were obtained after the small mountain portion was created.
  • the distribution of the haze ratio of the transparent conductive oxide film using these small ridges is considered to have the same tendency. Therefore, in the transparent conductive oxide film having the small ridges of Examples 1 and 2, when the solar cell is formed, the appearance of the entire solar cell panel due to the haze unevenness is prevented from being deteriorated, and the design property is improved. It is considered possible.
  • the present invention has low resistance and high transparency, has good light scattering performance in the entire wavelength range of sunlight (300 nm to 3 ⁇ m), is excellent in mass productivity, and has a sufficiently small variation in C light source haze ratio.
  • a substrate with a conductive oxide film can be obtained.
  • it is useful for the manufacturing method of the base

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Abstract

L'invention concerne un procédé de fabrication d'un substrat ayant un film d'oxyde conducteur transparent de faible résistance et de haute transparence, et ayant d'excellentes caractéristiques de production de masse, ayant d'excellentes performances de dispersion optique dans toute la région de longueur d'onde de la lumière du soleil (300 nm à 3 µm), et avec lequel un substrat ayant un film d'oxyde conducteur transparent d'une variabilité suffisamment petite du facteur de trouble de source de lumière C peut être obtenu. De manière spécifique, un substrat ayant un film d'oxyde conducteur transparent peut être obtenu, dans lequel la variabilité du facteur de trouble de source de lumière C est inférieure à 15 % lorsque le facteur de trouble de source de lumière C est mesuré sur toute la surface du substrat. Le procédé est un procédé de fabrication d'un substrat ayant un film d'oxyde conducteur transparent, dans lequel, sur le substrat transparent, est disposé un film d'oxyde conducteur transparent dans lequel une pluralité de sections collines sont disposées de manière séparée sur le substrat transparent et une face du substrat transparent comprend une pluralité de sections collines et une pluralité de sections plates. Ces sections collines et les surfaces de ces sections plates sont munies de manière continue d'une pluralité de saillies microscopiques, le diamètre de face inférieure de ces saillies étant de 0,1 à 0,3 µm, et le rapport hauteur de ces saillies/diamètre de face inférieure de ces saillies étant de 0,7 à 1,2. Le procédé de fabrication d'un substrat ayant un film d'oxyde conducteur transparent est caractérisé en ce qu'il comprend une procédure consistant à former sur le substrat transparent des sections monticules discontinues faites d'un premier oxyde à l'aide d'un dispositif de dépôt chimique en phase vapeur à pression normale du type à transport, et une procédure consistant à former une couche continue faite d'un second oxyde, à l'aide d'un dispositif de dépôt chimique en phase vapeur à pression normale du type à transport, sur les sections monticules et, sur ce substrat transparent, là où les sections monticules ne sont pas formées. Cette procédure de formation de sections monticules comprend : une première étape de dépôt chimique en phase vapeur pour former des noyaux ayant des hauteurs de 100 à 400 nm ; et une seconde étape de dépôt chimique en phase vapeur pour former des sections monticules ayant des hauteurs de 0,2 à 2,0 µm, comme points de départ. Dans la première étape de dépôt chimique en phase vapeur, la direction d'écoulement du gaz de matière première qui est injecté à partir d'un injecteur est identique à la direction d'avance du substrat transparent. Dans la seconde étape de dépôt chimique en phase vapeur et dans la procédure de formation de la couche continue, les directions d'écoulement du gaz de matière première qui est injecté à partir de l'injecteur sont deux directions, à savoir la même direction que la direction d'avance du substrat transparent et la direction opposée à celles-ci.
PCT/JP2012/066056 2011-06-23 2012-06-22 Procédé de fabrication de substrat ayant un film d'oxyde conducteur transparent Ceased WO2012176899A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005027229A1 (fr) * 2003-08-29 2005-03-24 Asahi Glass Company, Limited Base dotee d'un film conducteur transparent et son procede de production
JP2005347490A (ja) * 2004-06-02 2005-12-15 Asahi Glass Co Ltd 透明導電性酸化物膜付き基体およびその製造方法ならびに光電変換素子
WO2011044325A2 (fr) * 2009-10-08 2011-04-14 Stewart Engineers, Inc. Procédés d'ajustement de la nucléation lors du dépôt de couches

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005027229A1 (fr) * 2003-08-29 2005-03-24 Asahi Glass Company, Limited Base dotee d'un film conducteur transparent et son procede de production
JP2005347490A (ja) * 2004-06-02 2005-12-15 Asahi Glass Co Ltd 透明導電性酸化物膜付き基体およびその製造方法ならびに光電変換素子
WO2011044325A2 (fr) * 2009-10-08 2011-04-14 Stewart Engineers, Inc. Procédés d'ajustement de la nucléation lors du dépôt de couches

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