WO2013047806A1 - 透明導電膜付きガラス板および透明導電膜形成用ガラス板 - Google Patents
透明導電膜付きガラス板および透明導電膜形成用ガラス板 Download PDFInfo
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- WO2013047806A1 WO2013047806A1 PCT/JP2012/075192 JP2012075192W WO2013047806A1 WO 2013047806 A1 WO2013047806 A1 WO 2013047806A1 JP 2012075192 W JP2012075192 W JP 2012075192W WO 2013047806 A1 WO2013047806 A1 WO 2013047806A1
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- glass plate
- transparent conductive
- conductive film
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- bao
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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
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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
- 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
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
Definitions
- the present invention relates to a glass plate with a transparent conductive film having a transparent conductive film formed on the surface and a glass plate for forming a transparent conductive film.
- the glass plate with a transparent conductive film is used as a glass substrate for a thin film solar cell, a low emission glass plate (Low-E glass plate) and the like.
- a glass plate with a transparent conductive film usually requires high light transmittance.
- a glass substrate for a thin film solar cell is required to have a sufficiently high visible light transmittance (hereinafter referred to as Tv) and solar radiation transmittance (hereinafter referred to as Te).
- Tv visible light transmittance
- Te solar radiation transmittance
- the glass plate serving as the base of the glass substrate for a thin-film solar cell has a highly transmissive glass plate (so-called white plate) made of soda-lime silica glass in which the content of coloring components (particularly iron) is extremely reduced and Tv and Te are increased. Glass) is used (see Patent Document 1).
- an alkali barrier film containing SiO 2 as a main component is provided between the glass plate and the transparent conductive film.
- the present invention provides a glass plate with a transparent conductive film and a glass plate for forming a transparent conductive film in which peeling of the transparent conductive film is suppressed.
- the glass plate with a transparent conductive film of the present invention is a glass plate with a transparent conductive film having a glass plate and a transparent conductive film,
- the glass plate is an oxide-based mass percentage display, SiO 2 : 68 to 75%, Al 2 O 3 : 0 to 2.5%, CaO: 0 to 15%, MgO: 0-12%, Na 2 O: 5 to 20%, K 2 O: 0.8-5% SrO: 0 to 1%, BaO: 0 to 1%, K 2 O + SrO + BaO: 1.1-7% Total iron converted to Fe 2 O 3 : 0 to 0.06%, It is characterized by including.
- the glass plate is an oxide-based mass percentage display, SiO 2 : 69 to 74%, Al 2 O 3 : 0.3 to 2.3%, CaO: 3-12%, MgO: 1-10%, Na 2 O: 7 to 17%, K 2 O: 1.0 to 4.5%, SrO: 0.1 to 0.8%, BaO: 0.1 to 0.8%, K 2 O + SrO + BaO: 1.5-6%, Total iron converted to Fe 2 O 3 : 0 to 0.05%, It is preferable to contain.
- the volume resistivity (log ( ⁇ [ ⁇ ⁇ cm])) at 150 ° C. of the glass plate is preferably 8.8 to 12.0.
- the maximum temperature (T max ) at which film peeling does not occur in the DHB test described later is preferably 150 ° C. or higher.
- the glass plate with a transparent conductive film of the present invention preferably has an alkali barrier film provided between the glass plate and the transparent conductive film.
- the glass plate for transparent conductive film formation of the present invention is a mass percentage display based on the following oxide, SiO 2 : 60 to 75%, Al 2 O 3 : 0 to 3%, CaO: 0 to 15%, MgO: 0-12% Na 2 O: 5 to 20%, K 2 O + SrO + BaO: 1.1-15% Total iron converted to Fe 2 O 3 : 0 to 0.06%, It is preferable to contain.
- the glass plate for transparent conductive film formation of the present invention is a mass percentage display based on the following oxide, SiO 2 : 60 to 74%, Al 2 O 3 : 0.3 to 2.5%, CaO: 3-12%, MgO: 1-10%, Na 2 O: 7 to 17%, K 2 O: 0 to 5%, SrO: 0-5% BaO: 0 to 5%, K 2 O + SrO + BaO: 1.4-12%, Total iron converted to Fe 2 O 3 : 0 to 0.05%, It is preferable to contain.
- the glass plate for transparent conductive film formation of the present invention is a mass percentage display based on the following oxide, SiO 2 : 68 to 75% Al 2 O 3 : 0 to 2.5% CaO: 0 to 15% MgO: 0-12% Na 2 O: 5 to 20% K 2 O: 0.8 to 5% SrO: 0 to 1% BaO: 0 to 1% K 2 O + SrO + BaO: 1.1-7% Total iron converted to Fe 2 O 3 : 0 to 0.06%, It is preferable to contain.
- the glass plate with a transparent conductive film of the present invention is a glass plate with a transparent conductive film having a glass plate and a transparent conductive film
- the glass plate is an oxide-based mass percentage display, SiO 2 : 60 to 75% Al 2 O 3 : 0 to 3% CaO: 0 to 15% MgO: 0-12% Na 2 O: 5 to 20% K 2 O + SrO + BaO: 1.1 to 15% Total iron converted to Fe 2 O 3 : 0 to 0.06%, It is characterized by including.
- the term “to” indicating the above numerical range is used in the sense that the numerical values described before and after it are used as the lower limit value and the upper limit value. Unless otherwise specified, “to” is the same in the following specification. Used with meaning.
- the glass plate with a transparent conductive film of the present invention is one in which peeling of the transparent conductive film is suppressed.
- the glass plate with a transparent conductive film of the present invention has a glass plate and a transparent conductive film, and preferably has an alkali barrier film provided between the glass plate and the transparent conductive film. Another film may be provided between the glass plate and the alkali barrier film, between the alkali barrier film and the transparent conductive film, and / or on the surface of the glass plate opposite to the transparent conductive film side.
- FIG. 1 is a cross-sectional view showing an example of a glass plate with a transparent conductive film of the present invention.
- the glass plate 10 with a transparent conductive film includes a glass plate 12, an alkali barrier film 14 formed on one surface of the glass plate 12, and a transparent conductive film 16 formed on the surface of the alkali barrier film 14.
- the glass plate used as the base of a glass plate with a transparent conductive film has the following composition (I).
- the glass plate preferably has the following composition (II), more preferably has the following composition (III), and particularly preferably has the following composition (IV).
- the “glass plate for forming a transparent conductive film” is also simply referred to as “glass plate”.
- the glass plate with a transparent conductive film is referred to as a glass plate with a transparent conductive film.
- the glass plate in the present invention is expressed in mass percentage on the basis of oxide, and the total content of K 2 O, SrO and BaO is contained in ordinary soda lime silica glass (including ordinary high transmission glass plate).
- the total content is higher than the total content (for example, 0.4% or less in the case of a highly transmissive glass plate).
- the volume resistivity of the glass plate increases due to the mixed alkali effect (that is, the electrical conductivity decreases). Also, the alkaline earth metal / Na ratio shows the same tendency as K / Na, and this tendency is particularly remarkable in the case of Sr and Ba having a large atomic radius.
- the content of K 2 O (or K 2 O, the total content of SrO and BaO) is, the larger than normal soda-lime-silica glass (including normal high transmittance glass sheet.),
- a glass plate Since the volume resistivity is high (that is, the electric conductivity is low), even if a current flows through the transparent conductive film of the glass plate with a transparent conductive film for a long time, Na + contained in the glass plate is electrically transparent. It becomes difficult for the film to be attracted to the film, and it becomes difficult for Na + to diffuse to the surface of the alkali barrier film. Therefore, peeling of the transparent conductive film from the alkali barrier film can be suppressed.
- the content of K 2 O is 0 to 5% in terms of mass percentage based on oxide. When the content of K 2 O exceeds 5%, the raw material cost is remarkably increased, or the viscosity at high temperature is increased and the solubility is deteriorated.
- the content of K 2 O is preferably 1.1 to 4.5%, more preferably 1.3 to 4.0% in terms of mass percentage based on oxide.
- the content of SrO is 0 to 5% in terms of mass percentage based on oxide.
- the content of SrO is preferably 0 to 4%, more preferably 0 to 2% in terms of mass percentage based on oxide.
- the content of BaO is 0 to 5% in terms of mass percentage based on oxide. When the content of BaO exceeds 5%, the devitrification characteristics deteriorate.
- the content of BaO is preferably 0 to 4.5%, more preferably 0 to 4% in terms of mass percentage based on oxide.
- K 2 O + SrO + BaO The total content of K 2 O, SrO and BaO (hereinafter, this total amount is also referred to as “K 2 O + SrO + BaO”) is 1.1 to 15% in terms of oxide based mass percentage. It is. When K 2 O + SrO + BaO is less than 1.1%, peeling of the transparent conductive film from the alkali barrier film cannot be sufficiently suppressed. If K 2 O + SrO + BaO exceeds 15%, the liquidus temperature rises and the possibility that the devitrification characteristics deteriorate is increased. K 2 O + SrO + BaO is preferably 1.4 to 13%, more preferably 1.4 to 12%, in terms of mass percentage based on oxide.
- Fe 2 O 3 is a coloring component inevitably mixed in production.
- the total iron content converted to Fe 2 O 3 is 0 to 0.06% in terms of mass percentage based on oxide. If the total iron content converted to Fe 2 O 3 is 0.06% or less, a decrease in Tv can be suppressed.
- the total iron content converted to Fe 2 O 3 is preferably 0 to 0.05%, more preferably 0 to 0.03% in terms of mass percentage based on oxide. In particular, by making the total iron content 0.01% or less, it becomes easy to make the Te (plate thickness 4 mm equivalent) of the glass plate 90% or more, and the Tv (plate thickness) of the glass plate. 4 mm thickness conversion) is preferably 90% or more, which is preferable.
- the total iron content is expressed as the amount of Fe 2 O 3 according to the standard analysis method, but not all iron present in the glass is present as trivalent iron.
- divalent iron is present in the glass.
- Divalent iron has an absorption peak mainly in the vicinity of a wavelength of 1000 to 1100 nm, absorption also at a wavelength shorter than a wavelength of 800 nm, and trivalent iron has an absorption peak mainly in the vicinity of a wavelength of 400 nm.
- An increase in divalent iron results in an increase in absorption in the near-infrared region of around 1000 nm, and when this is expressed in Te, it means that Te decreases.
- Tv in terms of suppressing the decrease of Te, reduce Zentetsuryou, mass percentage of divalent iron in terms of Fe 2 O 3 in the total iron in terms of Fe 2 O 3 (hereinafter referred to as Redox. ) Is preferably kept low.
- the redox in the glass plate is preferably 35% or less. If Redox is 35% or less, a decrease in Te can be suppressed. Redox is more preferably 30% or less.
- SiO 2 is a main component of glass.
- the content of SiO 2 is 60 to 75% in terms of mass percentage based on oxide. When the content of SiO 2 is less than 60%, the stability of the glass is lowered. If the content of SiO 2 exceeds 75%, the melting temperature of the glass rises and there is a possibility that it cannot be melted.
- the content of SiO 2 is preferably 62 to 73% and more preferably 62 to 72% in terms of mass percentage based on oxide. Further, the content of SiO 2 may be 68 to 75%, preferably 69 to 75%, and more preferably 69.3 to 73%.
- Al 2 O 3 is a component that improves weather resistance.
- the content of Al 2 O 3 is 0 to 3% in terms of mass percentage based on oxide. When the content of Al 2 O 3 exceeds 3%, the solubility is remarkably deteriorated or the volume resistance is too low.
- the content of Al 2 O 3 is preferably 0 to 2.8%, more preferably 0 to 2.5% in terms of mass percentage based on oxide. Further, the content of Al 2 O 3 may be 0.3 to 2.3%, preferably 0.5 to 2.1%.
- CaO is a component that promotes melting of the glass raw material and adjusts viscosity, thermal expansion coefficient, and the like.
- the content of CaO is 0 to 15% in terms of mass percentage based on oxide. When the content of CaO exceeds 15%, the devitrification temperature increases.
- the content of CaO is preferably 3 to 12%, more preferably 3 to 11% in terms of mass percentage based on oxide.
- the CaO content may be 5 to 10%.
- MgO is a component that promotes melting of the glass raw material and adjusts viscosity, thermal expansion coefficient, and the like.
- the content of MgO is 0 to 12% in terms of mass percentage based on oxide. When the content of MgO exceeds 12%, the devitrification temperature increases.
- the content of MgO is preferably 2 to 12% and more preferably 2 to 6% in terms of mass percentage based on oxide. Further, the content of MgO may be 1 to 10%, preferably 3 to 8%.
- Na 2 O is an essential component that promotes melting of the glass raw material.
- the content of Na 2 O is 5 to 20% in terms of mass percentage based on oxide. When the content of Na 2 O is less than 5%, it becomes difficult to dissolve the glass raw material. When the content of Na 2 O exceeds 20%, weather resistance and stability of the glass plate may be deteriorated.
- the content of Na 2 O is preferably 7 to 19% and more preferably 9 to 17% in terms of mass percentage based on oxide. Further, the content of Na 2 O may be 9 to 15%.
- the glass plate of the present invention is not essential, but may further contain TiO 2 , ZrO 2 , Li 2 O, and B 2 O 3 .
- TiO 2 is contained, the content of TiO 2 is preferably 0 to 2% in terms of oxide-based mass percentage.
- the glass plate is colored, Tv and Te decreases.
- ZrO 2 is a component that improves the chemical durability of glass and improves physical strength such as elastic modulus and hardness.
- the content of ZrO 2 is preferably 0 to 3% in terms of mass percentage based on oxide.
- the content of ZrO 2 exceeds 3%, the melting characteristics deteriorate, and the devitrification temperature increases.
- Li 2 O is a component that promotes melting of the glass raw material and lowers the melting temperature. If Li 2 O is contained, the content of Li 2 O, by mass percentage based on oxides, 0-3%. When the content of Li 2 O exceeds 3%, the stability of the glass deteriorates. Moreover, raw material cost will rise remarkably.
- B 2 O 3 is a component that promotes melting of the glass raw material, but when added to soda lime silica glass, there are many disadvantages such as generation of striae due to volatilization and furnace wall erosion, which is not suitable for production. .
- the content of B 2 O 3 is preferably 1% or less, more preferably substantially not contained, in terms of a mass percentage based on the oxide.
- substantially not contained means that an amount of impurities may be mixed.
- the glass plate preferably contains SO 3 used as a fining agent.
- the total sulfur content converted to SO 3 is preferably 0.01 to 0.5% in terms of mass percentage based on oxide. If the total sulfur content converted to SO 3 exceeds 0.5%, reboyl is generated in the process of cooling the molten glass, and the foam quality may be deteriorated. If the total sulfur content converted to SO 3 is less than 0.01%, a sufficient clarification effect cannot be obtained.
- the total sulfur content converted to SO 3 is more preferably 0.05 to 0.5%, and further preferably 0.2 to 0.4%, expressed in terms of mass percentage on an oxide basis.
- the glass plate may contain SnO 2 used as a fining agent.
- the total tin content converted to SnO 2 is preferably 0 to 1% in terms of oxide-based mass percentage.
- the surface layer of the glass substrate cullet with a transparent conductive film glass SnO 2 film is laminated may be used as the glass raw material of SnO 2 component as a transparent electrode material.
- the glass plate may contain Sb 2 O 3 used as a fining agent.
- the total antimony content converted to Sb 2 O 3 is preferably 0 to 0.5%. If the content of all antimony converted to Sb 2 O 3 exceeds 0.5%, the glass plate after forming becomes cloudy in the float method.
- the total antimony content converted to Sb 2 O 3 is preferably 0 to 0.1% in terms of mass percentage based on oxide.
- Glass plate is colored components, S, NiO, MoO 3, CoO, preferably contains no Cr 2 O 3, V 2 O 5, or MnO substantially.
- Substantially free of S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , or MnO means that S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , or It means that MnO is not contained at all or S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , and MnO may be included as impurities inevitably mixed in production. If S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , or MnO is not substantially contained, a decrease in Tv and Te can be suppressed.
- Te of the glass plate (4 mm thickness conversion, that is, the glass plate thickness is converted to 4 mm) is preferably 80% or more, and more preferably 82.7% or more.
- Te is the solar radiation transmittance calculated by measuring the transmittance with a spectrophotometer according to JIS R 3106 (1998) (hereinafter simply referred to as JIS R 3106).
- JIS R 3106 spectrophotometer according to JIS R 3106 (1998) (hereinafter simply referred to as JIS R 3106).
- Te (4 mm thickness conversion) is preferably 90% or more, 91% or more, more preferably 91.5%. The above is more preferable.
- Tv (4 mm thickness conversion) of the glass plate is preferably 80% or more, and more preferably 82% or more.
- Tv is the visible light transmittance calculated by measuring the transmittance with a spectrophotometer in accordance with JIS R 3106. As the coefficient, the standard light A and the value of the 2-degree visual field are used. Further, when the content of Fe 2 O 3 which is a coloring component in the composition is 0.01% or less, Tv (4 mm thickness conversion) is preferably 90% or more, and more preferably 91% or more.
- the volume resistivity (log ( ⁇ [ ⁇ ⁇ cm])) at 150 ° C. of the glass plate is preferably from 9.0 to 12, and more preferably from 9.1 to 12. If the volume resistivity at 150 ° C. of the glass plate is 9.0 or more, peeling of the transparent conductive film from the alkali barrier film can be more reliably suppressed.
- the volume resistivity (log ( ⁇ [ ⁇ ⁇ cm])) at 200 ° C. of the glass plate is preferably 7.8 to 12, and more preferably 7.9 to 11. If the volume resistivity at 200 ° C. of the glass plate is 7.8 or more, peeling of the transparent conductive film from the alkali barrier film can be more reliably suppressed.
- the volume resistivity of the glass plate is measured by a method based on ASTM C657-78.
- the glass plate is produced, for example, through the following steps (i) to (V) in order.
- Various glass matrix composition raw materials, cullet, fining agent, etc. are mixed so as to obtain a target composition to prepare glass raw materials.
- a glass raw material is melted to obtain molten glass.
- IIv Cool the glass plate.
- V A glass plate is cut into a predetermined size.
- a step (iii-1) of forming an alkali barrier film on the glass plate surface is added, and a step of forming a transparent conductive film on the alkali barrier film surface of the glass plate (iii- 2) may be added.
- steps (iii-1) and (iii-2) a glass plate with a transparent conductive film can be produced on-line using the glass plate production process.
- glass matrix composition raw material examples include those used as raw materials for ordinary soda lime silica glass, such as silica sand, dolomite, and soda ash.
- clarifying agent examples include SO 3 , SnO 2 , and Sb 2 O 3 .
- the melting of the glass raw material is performed, for example, by continuously supplying the glass raw material to a glass melting furnace (melting kiln) and heating to about 1300 to 1600 ° C. with heavy oil, gas, electricity or the like.
- the glass plate with a transparent conductive film is formed by forming a transparent conductive film on the surface of the glass plate manufactured as described above, or by forming an alkali barrier film on the surface of the glass plate manufactured as described above. It is manufactured by forming a transparent conductive film on the surface. Further, the alkali barrier film surface of the glass plate with the alkali barrier film produced by adding the alkali barrier film forming step (iii-1) in the glass plate production steps (i) to (V). A transparent conductive film may be formed on the substrate.
- a glass plate with a transparent conductive film is produced by adding a step (iii-2) of forming a transparent conductive film on the surface of the alkali barrier film after the step (iii-1) of forming the alkali barrier film. Also good.
- the transparent conductive film include a film mainly composed of SnO 2 , a film mainly composed of ZnO, and a film mainly composed of tin-doped indium oxide (ITO).
- a film containing SnO 2 as a main component is preferable from the viewpoint of a material having little influence on the power generation layer when components are mixed into the power generation layer.
- the “main component” means that the component is contained in 90% or more in terms of oxide based mass percentage.
- Examples of the film containing SnO 2 as a main component include a film made of SnO 2 , a film made of fluorine-doped tin oxide (FTO), and a film made of antimony-doped tin oxide.
- Examples of the method for forming the transparent conductive film include a thermal decomposition method, a CVD method, a sputtering method, a vapor deposition method, an ion plating method, and a spray method.
- the thickness of the transparent conductive film is preferably 200 to 1200 nm.
- Alkali barrier film As the alkali barrier film, a film containing SiO 2 as a main component, a film containing a mixed oxide of SiO 2 and SnO 2 as a main component, a multilayer film of SiO 2 and SnO 2 , Al 2 O 3 , ZrO 2 , or SiOC And the like.
- the “main component” means that the component is contained in 90% or more in terms of oxide based mass percentage.
- Examples of the method for forming the alkali barrier film include a thermal decomposition method, a CVD method, a sputtering method, a vapor deposition method, an ion plating method, and a spray method.
- the thickness of the alkali barrier film is preferably 10 nm or more from the viewpoint of alkali barrier performance, and is preferably 500 nm or less from the viewpoint of cost.
- Examples of other films that may be provided between the glass plate and the alkali barrier film include a TiO 2 film and a SnO 2 film.
- Examples of other films that may be provided between the alkali barrier film and the transparent conductive film include mixed oxides of SiO 2 and SnO 2 and multilayer films.
- Examples of other films that may be provided on the surface of the glass plate opposite to the transparent conductive film include an antireflection film.
- Other films themselves themselves may have alkali barrier performance.
- the content of K 2 O is 0.8% or more in terms of oxide based mass percentage, and K 2 O, SrO and BaO. Since the total content of is 1.1% or more in terms of mass percentage based on oxide, the volume resistivity of the glass plate is increased (that is, the electrical conductivity is decreased). As a result, even if a current flows through the transparent conductive film of the glass plate with the transparent conductive film for a long time, Na + contained in the glass plate is not easily attracted to the transparent conductive film, and Na + is the surface of the alkali barrier film. Difficult to diffuse. Therefore, peeling of the transparent conductive film can be suppressed. Further, since the total iron content converted to Fe 2 O 3 is 0 to 0.06% in terms of mass percentage based on oxide, Tv is sufficiently high.
- FIG. 2 is a cross-sectional view showing an example of a thin film solar cell.
- a thin film solar cell element 22 is formed on one surface of a glass plate 12 via an alkali barrier film 14.
- An antireflection film (not shown) or the like may be provided on the other surface of the glass plate 12 (that is, the surface opposite to the surface on which the thin film solar cell element 22 is formed).
- the glass plate with a transparent conductive film of the present invention can be suitably used for all thin film solar cells in which a transparent conductive film is provided on a glass plate such as a thin film silicon solar cell and a CdTe thin film solar cell.
- the thin film solar cell element 22 includes a transparent electrode layer 24, a photoelectric conversion layer 26 (that is, a power generation layer), and a back electrode layer 28 in order from the glass plate 12 side.
- the transparent electrode layer 24 is a layer made of the transparent conductive film 16 described above.
- the photoelectric conversion layer 26 is a layer made of a thin film semiconductor.
- the thin film semiconductor include an amorphous silicon semiconductor, a microcrystalline silicon semiconductor, a compound semiconductor (for example, chalcopyrite semiconductor, CdTe semiconductor, etc.), an organic semiconductor, and the like.
- Examples of the material for the back electrode layer 28 include materials that do not transmit light (for example, silver and aluminum) and materials that transmit light (for example, ITO, SnO 2 , and ZnO).
- FIG. 3 is a cross-sectional view showing an example of a multi-layer glass using a Low-E glass plate.
- the multilayer glass 30 includes two glass plates 12, a frame-like spacer 34 that is disposed at the periphery of the glass plate 12 so that a gap 32 is formed between the glass plates 12, the spacer 34, and the glass plate 12 and a sealing material (not shown) provided between the glass plate 12 and the glass plate 12 on the gap 32 side of the multilayer glass in order from the glass plate 12 side.
- a glass plate with a transparent conductive film provided with a film 16 is used.
- a low reflection film (not shown) or the like may be provided on the surface of the glass plate 12 on the side opposite to the gap 32 side.
- Example 1 is a comparative example.
- Each performance of the glass plate for transparent conductive film formation and the glass plate with a transparent conductive film was measured and determined as follows.
- the amount of divalent iron in the glass plate required for the calculation of Redox was obtained by converting from the transmittance at a wavelength of 1000 nm obtained by transmittance measurement. Here, after subtracting the influence of reflection at a wavelength of 1000 nm as 8%, it was converted into an absorption coefficient, and the amount of divalent iron was quantified based on a calibration curve prepared in advance by a wet analysis method.
- Tv The obtained glass plate was polished to a thickness of 4 mm, and the visible light transmittance (Tv) defined by JIS R 3106 (by the A light source) was measured.
- the obtained glass plate was polished to a thickness of 4 mm, and the solar transmittance (Te) defined by JIS R 3106 was measured.
- volume resistivity The volume resistivity of the glass plate was measured by a method based on ASTM C657-78.
- As the glass plate a glass plate having a size of about 50 mm ⁇ 50 mm and optically polished on both sides to a thickness of about 4 mm was used.
- the ease of peeling of the transparent conductive film can be estimated by a Dump Heat Bias (DHB) type durability test (hereinafter referred to as a DHB test).
- the DHB test is a test for simultaneously evaluating electrical and thermal attack on a test piece coated with a thin film. As shown in the following (1) to (4), a glass plate with a transparent conductive film (sample) is heated for a sufficient time until it becomes stable at a set temperature, and at the same time, an electric field is applied to the glass plate with a transparent conductive film. Is called.
- the sample was placed between two electrodes.
- the side where the transparent conductive film was not formed was brought into contact with the graphite electrode (anode), and the transparent conductive film side was brought into contact with the copper electrode (cathode) covered with aluminum.
- the voltage was maintained at 500 V and the voltage application time was maintained for 15 minutes.
- the transparent conductive film side of the sample was exposed to an atmosphere having a relative humidity of 100% for 1 hour to cause aggregation on the transparent conductive film side.
- the aggregation humidity and water temperature were 55 ° C.
- the vaporization temperature was 50 ° C. ⁇ 2 ° C.
- the glass plates of Examples 1 to 31 were produced as follows.
- a glass raw material was prepared by mixing silica sand, other various glass matrix composition raw materials and a fining agent (SO 3 ) so as to have the compositions shown in Tables 1-1 to 1-5.
- the glass raw material was put in a crucible and heated in an electric furnace at 1500 ° C. for 3 hours to obtain molten glass.
- Molten glass was poured onto a carbon plate and cooled. Both surfaces were polished to obtain a glass plate having a thickness of 4 mm.
- the transmittance of the glass plate was measured every 1 nm using a spectrophotometer (manufactured by Hitachi, Ltd., U-4100) to determine Tv, Te, and volume resistivity. The results are shown in Tables 1-1 to 1-5.
- T max is shown in Table 1.
- the temperature at which the volume resistivity (log ( ⁇ [ ⁇ ⁇ cm])) at 150 ° C. is 8.8 is defined as the predicted T max when the glass thickness is 4 mm, and is estimated using the above prediction formula. Indicates temperature.
- a [K] and B indicate the slope A and the intercept B (dimensionless) in obtaining the volume resistance value.
- Example 1 (corresponding to Example 5 of Patent Document 1) where the total content of K 2 O + SrO + BaO is small, the temperature T max at which peeling of the transparent conductive film occurs in the DHB test was low.
- the temperature T at which the transparent conductive film is peeled off by the DHB test It was found that max was increased to 160 ° C. or higher, and peeling of the transparent conductive film from the alkali barrier film was suppressed over a long period of time.
- the glass plate with a transparent conductive film of the present invention is useful as a glass substrate for a thin film solar cell, a low emission glass plate (Low-E glass plate) and the like. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-212265 filed on September 28, 2011 are incorporated herein as the disclosure of the present invention. .
- Glass plate with transparent conductive film 10 Glass plate with transparent conductive film 12 Glass plate (Glass plate for forming transparent conductive film) DESCRIPTION OF SYMBOLS 14 Alkali barrier film 16 Transparent electrically conductive film 20 Thin film solar cell 22 Thin film solar cell element 24 Transparent electrode layer 26 Photoelectric conversion layer 28 Back surface electrode layer 30 Multi-layer glass 32 Space
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Abstract
Description
前記ガラス板が、酸化物基準の質量百分率表示で、
SiO2 :68~75%、
Al2O3 :0~2.5%、
CaO :0~15%、
MgO :0~12%、
Na2O :5~20%、
K2O :0.8~5%、
SrO :0~1%、
BaO :0~1%、
K2O+SrO+BaO :1.1~7%、
Fe2O3に換算した全鉄:0~0.06%、
を含むことを特徴とする。
前記ガラス板は、酸化物基準の質量百分率表示で、
SiO2 :69~74%、
Al2O3 :0.3~2.3%、
CaO :3~12%、
MgO :1~10%、
Na2O :7~17%、
K2O :1.0~4.5%、
SrO :0.1~0.8%、
BaO :0.1~0.8%、
K2O+SrO+BaO :1.5~6%、
Fe2O3に換算した全鉄:0~0.05%、
を含むことが好ましい。
後述するDHB試験における膜はがれが起きない最高温度(Tmax)は、150℃以上であることが好ましい。
本発明の透明導電膜付きガラス板は、前記ガラス板と前記透明導電膜との間に設けられたアルカリバリア膜を有することが好ましい。
また、本発明の透明導電膜形成用ガラス板は、下記酸化物基準の質量百分率表示で、
SiO2 :60~75%、
Al2O3 :0~3%、
CaO :0~15%、
MgO :0~12%
Na2O :5~20%、
K2O+SrO+BaO :1.1~15%、
Fe2O3に換算した全鉄:0~0.06%、
を含むことが好ましい。
また、本発明の透明導電膜形成用ガラス板は、下記酸化物基準の質量百分率表示で、
SiO2 :60~74%、
Al2O3 :0.3~2.5%、
CaO :3~12%、
MgO :1~10%、
Na2O :7~17%、
K2O :0~5%、
SrO :0~5%、
BaO :0~5%、
K2O+SrO+BaO :1.4~12%、
Fe2O3に換算した全鉄:0~0.05%、
を含むことが好ましい。
また、本発明の透明導電膜形成用ガラス板は、下記酸化物基準の質量百分率表示で、
SiO2 :68~75%
Al2O3 :0~2.5%
CaO :0~15%
MgO :0~12%
Na2O :5~20%
K2O :0.8~5%
SrO :0~1%
BaO :0~1%
K2O+SrO+BaO :1.1~7%
Fe2O3に換算した全鉄:0~0.06%、
を含むことが好ましい。
また、本発明の透明導電膜付きガラス板は、ガラス板と、透明導電膜とを有する透明導電膜付きガラス板であって、
前記ガラス板が、酸化物基準の質量百分率表示で、
SiO2 :60~75%
Al2O3 :0~3%
CaO :0~15%
MgO :0~12%
Na2O :5~20%
K2O+SrO+BaO :1.1~15%
Fe2O3に換算した全鉄:0~0.06%、
を含むことを特徴とする。
上記した数値範囲を示す「~」とは、その前後に記載された数値を下限値および上限値として含む意味で使用され、特段の定めがない限り、以下本明細書において「~」は、同様の意味をもって使用される。
本発明の透明導電膜付きガラス板は、ガラス板と、透明導電膜とを有し、好ましくはガラス板と透明導電膜との間に設けられたアルカリバリア膜とを有する。ガラス板とアルカリバリア膜との間、アルカリバリア膜と透明導電膜との間、およびまたは透明導電膜側とは反対側のガラス板の表面に、他の膜が設けられていても構わない。
透明導電膜付きガラス板のベースとなるガラス板は、下記の組成(I)を有する。ガラス板は、下記の組成(II)を有することが好ましく、下記の組成(III)を有することがより好ましく、特に下記の組成(IV)を有することが好ましい。
以下、本明細書において、「透明導電膜形成用ガラス板」は、単に「ガラス板」とも記す。透明導電膜付きガラス板は、透明導電膜付きガラス板と記す。
SiO2 :60~75%、
Al2O3 :0~3%、
CaO :0~15%、
MgO :0~12%
Na2O :5~20%、
K2O+SrO+BaO :1.1~15%、
Fe2O3に換算した全鉄:0~0.06%、
を含む。
(II)下記酸化物基準の質量百分率表示で、
SiO2 :68~75%、
Al2O3 :0~2.5%、
CaO :0~15%、
MgO :0~12%、
Na2O :5~20%、
K2O :0.8~5%、
SrO :0~1%、
BaO :0~1%、
K2O+SrO+BaO :1.1~7%、
Fe2O3に換算した全鉄:0~0.06%、
を含む。
SiO2 :69~74%、
Al2O3 :0.3~2.3%、
CaO :3~12%、
MgO :1~10%、
Na2O :7~17%、
K2O :1.0~4.5%、
SrO :0.1~0.8%、
BaO :0.1~0.8%、
K2O+SrO+BaO :1.5~6%、
Fe2O3に換算した全鉄:0~0.05%、
を含む。
SiO2 :69.3~73%、
Al2O3 :0.5~2.1%、
CaO :5~10%、
MgO :3~8%、
Na2O :9~15%、
K2O :1.3~4.0%、
SrO :0.2~0.7%、
BaO :0.2~0.7%、
K2O+SrO+BaO :2~5%、
Fe2O3に換算した全鉄:0~0.03%、
を含む。
Fe2O3に換算した全鉄の含有量は、酸化物基準の質量百分率表示で、0~0.06%である。Fe2O3に換算した全鉄の含有量が0.06%以下であれば、Tvの低下が抑えられる。Fe2O3に換算した全鉄の含有量は、酸化物基準の質量百分率表示で、0~0.05%が好ましく、0~0.03%がより好ましい。特に、この全鉄の含有量を0.01%以下とすることにより、ガラス板のTe(板厚4mm厚さ換算)を90%以上とすることが容易となり、またガラス板のTv(板厚4mm厚さ換算)を90%以上とすることが容易となり、好ましい。
SiO2の含有量は、酸化物基準の質量百分率表示で、60~75%である。SiO2の含有量が60%未満では、ガラスの安定性が低下する。SiO2の含有量が75%を超えると、ガラスの溶解温度が上昇し、溶解できなくなるおそれがある。SiO2の含有量は、酸化物基準の質量百分率表示で、62~73%が好ましく、62~72%がより好ましい。また、SiO2の含有量は、68~75%、好ましくは69~75%、さらには69.3~73%であってもよい。
Al2O3の含有量は、酸化物基準の質量百分率表示で、0~3%である。Al2O3の含有量が3%を超えると、溶解性が著しく悪化する、もしくは体積抵抗が低くなりすぎる。Al2O3の含有量は、酸化物基準の質量百分率表示で、0~2.8%が好ましく、0~2.5%がより好ましい。また、Al2O3の含有量は、0.3~2.3%、好ましくは0.5~2.1%であってもよい。
CaOの含有量は、酸化物基準の質量百分率表示で、0~15%である。CaOの含有量が15%を超えると、失透温度が上昇する。CaOの含有量は、酸化物基準の質量百分率表示で、3~12%が好ましく、3~11%がより好ましい。また、CaOの含有量は、5~10%であってもよい。
MgOの含有量は、酸化物基準の質量百分率表示で、0~12%である。MgOの含有量が12%を超えると、失透温度が上昇する。MgOの含有量は、酸化物基準の質量百分率表示で、2~12%が好ましく、2~6%がより好ましい。また、MgOの含有量は、1~10%、好ましくは3~8%であってもよい。
Na2Oの含有量は、酸化物基準の質量百分率表示で、5~20%である。Na2Oの含有量が5%未満では、ガラス原料の溶解が困難になる。Na2Oの含有量が20%を超えると、ガラス板の耐候性および安定性が悪化する。Na2Oの含有量は、酸化物基準の質量百分率表示で、7~19%が好ましく、9~17%がより好ましい。さらにNa2Oの含有量は、9~15%であってもよい。
TiO2が含有される場合、TiO2の含有量は、酸化物基準の質量百分率表示で、0~2%が好ましい。TiO2の含有量が2%を超えると、ガラス板が着色し、TvおよびTeが低下する。
ZrO2が含有される場合、ZrO2の含有量は、酸化物基準の質量百分率表示で0~3%が好ましい。ZrO2の含有量が3%を超えると、溶融特性が悪化する、また、失透温度が上昇する。
Li2Oが含有される場合、Li2Oの含有量は、酸化物基準の質量百分率表示で、0~3%である。Li2Oの含有量が3%を超えると、ガラスの安定性が悪化する。また、原料コストが著しく上昇してしまう。
B2O3が含有される場合、B2O3の含有量は、酸化物基準の質量百分率表示で、1%以下が好ましく、実質的に含有しないことがより好ましい。ここで、実質的に含有しないとは不純物程度の量が混入してもよいことを意味する。
また、組成中の着色成分であるFe2O3含有量が0.01%以下の場合は、Te(4mm厚さ換算)は90%以上が好ましく、91%以上、より好ましくは91.5%以上がより好ましい。
また、組成中の着色成分であるFe2O3含有量が0.01%以下の場合は、Tv(4mm厚さ換算)は90%以上が好ましく、91%以上がより好ましい。
ここで、ガラス板の体積抵抗率は、ASTM C657-78に準拠した方法で測定される。
(i)目標とする組成になるように、各種のガラス母組成原料、カレット、清澄剤等を混合し、ガラス原料を調製する。
(ii)ガラス原料を溶融させて溶融ガラスとする。
(iii)溶融ガラスを清澄した後、フロート法またはダウンドロー法(フュージョン法)により所定の厚さのガラス板に成形する。
(iv)ガラス板を冷却する。
(V)ガラス板を所定の大きさに切断する。
なお、上記工程(iii)の後に、ガラス板表面にアルカリバリア膜を形成する工程(iii-1)を付加し、またこのガラス板のアルカリバリア膜面に透明導電膜を形成する工程(iii-2)を付加してもよい。これら工程(iii-1)および(iii-2)を付加することによって透明導電膜付きガラス板をガラス板製造工程を利用してオンラインで製造することができる。
清澄剤としては、SO3、SnO2、またはSb2O3等が挙げられる。
(透明導電膜)
透明導電膜としては、SnO2を主成分とする膜、ZnOを主成分とする膜、スズドープ酸化インジウム(ITO)を主成分とする膜等が挙げられ、原料コスト、量産性、透明導電膜の成分が発電層へ混入した際に発電層への影響の少ない材料の点から、SnO2を主成分とする膜が好ましい。ここで、「主成分」とは、該成分が酸化物基準の質量百分率表示で、90%以上含まれていることを意味する。
透明導電膜の形成方法としては、熱分解法、CVD法、スパッタリング法、蒸着法、イオンプレーティング法、またはスプレー法等が挙げられる。
透明導電膜の厚さは、200~1200nmが好ましい。
アルカリバリア膜としては、SiO2を主成分とする膜、SiO2とSnO2の混合酸化物を主成分とする膜やSiO2とSnO2の多層膜、Al2O3、ZrO2、またはSiOCを主成分とする膜等が挙げられる。ここで、「主成分」とは、該成分が酸化物基準の質量百分率表示で、90%以上含まれていることを意味する。
アルカリバリア膜の厚さは、アルカリバリア性能の点から、10nm以上が好ましく、コストの点から、500nm以下が好ましい。
ガラス板とアルカリバリア膜との間に設けてもよい他の膜としては、TiO2膜、SnO2膜等が挙げられる。
アルカリバリア膜と透明導電膜との間に設けてもよい他の膜としては、SiO2とSnO2の混合酸化物や多層膜等が挙げられる。
透明導電膜側とは反対側のガラス板の表面に設けてもよい他の膜としては、反射防止膜等が挙げられる。
なお、他の膜自身にアルカリバリア性能があってもよい。
また、Fe2O3に換算した全鉄の含有量が、酸化物基準の質量百分率表示で、0~0.06%であるため、Tvが充分に高くなる。
本発明の透明導電膜付きガラス板は、薄膜太陽電池用ガラス基板として好適である。
図2は、薄膜太陽電池の一例を示す断面図である。薄膜太陽電池20は、ガラス板12の一方の表面に、アルカリバリア膜14を介して、薄膜太陽電池素子22を形成したものである。ガラス板12の他方の表面(すなわち、薄膜太陽電池素子22の形成面と反対側の面)に反射防止膜(図示略)等を設けてもよい。
本発明の透明導電膜付きガラス板は、薄膜シリコン系太陽電池、CdTe系薄膜太陽電池等のガラス板上に透明導電膜を設ける薄膜太陽電池全般に好適に用いることができる。
透明電極層24は、上述した透明導電膜16からなる層である。
光電変換層26は、薄膜半導体からなる層である。薄膜半導体としては、アモルファスシリコン系半導体、微結晶シリコン系半導体、化合物半導体(例えば、カルコパイライト系半導体、CdTe系半導体等)、有機系半導体等が挙げられる。
裏面電極層28の材料としては、光透過性を有さない材料(例えば、銀、アルミニウム等)、光透過性を有する材料(例えば、ITO、SnO2、ZnO等)が挙げられる。
本発明の透明導電膜付きガラス板は、Low-E(Low Emissivity、低輻射)性能を有するので、Low-Eガラス板として用いることもできる。
図3は、Low-Eガラス板を用いた複層ガラスの一例を示す断面図である。複層ガラス30は、2枚のガラス板12と、ガラス板12間に空隙32が形成されるようにガラス板12の周縁部に介在配置される枠状のスペーサ34と、スペーサ34とガラス板12との間に設けられたシール材(図示略)とを有し、一方のガラス板12として、複層ガラスの空隙32側には、ガラス板12側から順に、アルカリバリア膜14、透明導電膜16が設けられた透明導電膜付きガラス板が使用されている。空隙32側とは反対側のガラス板12の表面に低反射膜(図示略)等を設けてもよい。
〔例1~31〕
例2~31は実施例であり、例1は比較例である。
透明導電膜形成用ガラス板および透明導電膜付きガラス板の各性能は、下記のようにして測定して求めた。
得られたガラス板のFe2O3量は、蛍光X線測定によって求めた、Fe2O3に換算した全鉄の含有量(%=質量百分率)である。
Redoxの算出に必要なガラス板中の2価の鉄の量は、透過率測定によって得られた、波長1000nmの透過率から換算して求めた。ここでは、波長1000nmでの反射による影響を8%として差し引いた後に吸収係数に変換し、湿式分析法により事前に作成した検量線を元に2価の鉄の量を定量した。
得られたガラス板を4mm厚さに研磨し、JIS R 3106規定の可視光透過率(Tv)(A光源によるもの)を測定した。
得られたガラス板を4mm厚さに研磨し、JIS R 3106規定の日射透過率(Te)を測定した。
ガラス板の体積抵抗率は、ASTM C657-78に準拠した方法で測定した。ガラス板としては、約50mm×50mmの大きさを有し、両面を光学研磨して厚さ約4mmにしたものを用いた。該ガラス板の両面に、蒸着法で金属Al膜を形成して電極とし、100℃、150℃、200℃における体積抵抗率を測定した。また任意の点の体積抵抗値は、各温度における体積抵抗率(log(ρ[Ω・cm]))と絶対温度の逆数(1/T)の関係から求められる傾きAと切片Bを用いて、以下の予測式から求めた。
log(ρ[Ω・cm])=A/T+B
Dump Heat Bias(DHB)タイプの耐久性試験(以下、DHB試験と記す。)によって、透明導電膜の剥離のしやすさを見積もることができる。
DHB試験は、薄膜をコートした試験片への電気的、熱的攻撃を同時に評価する試験である。下記(1)~(4)に示すように、透明導電膜付きガラス板(サンプル)を、設定温度で安定するまで充分な時間加熱し、同時に透明導電膜付きガラス板に電界をかけることによって行われる。
(2)室温まで冷却した後、サンプルの透明導電膜側を、相対湿度100%の雰囲気に1時間暴露し、透明導電膜側に凝集を起こさせた。凝集湿度、水温は、55℃とし、気化温度は、50℃±2℃とした。
(3)サンプルの透明導電膜側の表面に、透明導電膜の剥離が発生しているか否かを確認した。なお、剥離の有無は、サンプル内に目視で確認できる剥離部分が1か所でもあれ、剥離が発生したと定義した。
(4)同一条件で作製した別のサンプルを複数用意し、試験は、各設定温度について3回ずつ行った。サンプルの透明導電膜が剥がれてしまった温度をTmax(℃)とした。Tmaxが高いほど、透明導電膜が長期間剥離しにくい(すなわち、耐久性が高い)と判断した。
1. Na+ + e- → Na
2. H2O + Na → NaOH + 1/2H2
3. 2H2 + SnO2 → Sn + 2H2O
表1-1~1-5に示す組成となるように、珪砂、その他の各種のガラス母組成原料および清澄剤(SO3)を混合し、ガラス原料を調製した。ガラス原料をるつぼに入れ、電気炉中にて1500℃で3時間加熱し、溶融ガラスとした。溶融ガラスをカーボン板上に流し出し、冷却した。両面を研磨し、厚さ4mmのガラス板を得た。ガラス板について、分光光度計(日立製作所社製、U-4100)を用いて1nmごとに透過率を測定し、Tv、Te、体積抵抗率を求めた。結果を表1-1~1-5に示す。
なお、表1-1~1-5において、A[K]とBは、体積抵抗値を求めるに当たっての傾きAと切片B(無次元)を示す。
なお、2011年9月28日に出願された日本特許出願2011-212265号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
12 ガラス板(透明導電膜形成用ガラス板)
14 アルカリバリア膜
16 透明導電膜
20 薄膜太陽電池
22 薄膜太陽電池素子
24 透明電極層
26 光電変換層
28 裏面電極層
30 複層ガラス
32 空隙
34 スペーサ
Claims (9)
- ガラス板と、透明導電膜とを有する透明導電膜付きガラス板であって、
前記ガラス板が、下記酸化物基準の質量百分率表示で、
SiO2 :68~75%
Al2O3 :0~2.5%
CaO :0~15%
MgO :0~12%
Na2O :5~20%
K2O :0.8~5%
SrO :0~1%
BaO :0~1%
K2O+SrO+BaO :1.1~7%
Fe2O3に換算した全鉄:0~0.06%、
を含むことを特徴とする透明導電膜付きガラス板。 - 前記ガラス板が、下記酸化物基準の質量百分表示で、
SiO2 :69~74%、
Al2O3 :0.3~2.3%、
CaO :3~12%、
MgO :1~10%、
Na2O :7~17%、
K2O :1.0~4.5%、
SrO :0.1~0.8%、
BaO :0.1~0.8%、
K2O+SrO+BaO :1.5~6%、
Fe2O3に換算した全鉄:0~0.05%、
を含む、請求項1に記載の透明導電膜付きガラス板。 - 前記ガラス板の150℃における体積抵抗率(log(ρ[Ω・cm]))が、8.8~12.0である、請求項1または2に記載の透明導電膜付きガラス板。
- DHB試験における膜はがれが起きない最高温度(Tmax)が、150℃以上である、請求項1~3のいずれか一項に記載の透明導電膜付きガラス板。
- 前記ガラス板と前記透明導電膜との間に設けられたアルカリバリア膜を有する、請求項1~4のいずれか一項に記載の透明導電膜付きガラス板。
- 下記酸化物基準の質量百分率表示で、
SiO2 :60~75%、
Al2O3 :0~3%、
CaO :0~15%、
MgO :0~12%
Na2O :5~20%、
K2O+SrO+BaO :1.1~15%、
Fe2O3に換算した全鉄:0~0.06%、
を含むことを特徴とする透明導電膜形成用ガラス板。 - 下記酸化物基準の質量百分表示で、
SiO2 :60~74%、
Al2O3 :0.3~2.5%、
CaO :3~12%、
MgO :1~10%、
Na2O :7~17%、
K2O :0~5%、
SrO :0~5%、
BaO :0~5%、
K2O+SrO+BaO :1.4~12%、
Fe2O3に換算した全鉄:0~0.05%、
を含む、請求項6に記載の透明導電膜形成用ガラス板。 - 下記酸化物基準の質量百分表示で、
SiO2 :68~75%
Al2O3 :0~2.5%
CaO :0~15%
MgO :0~12%
Na2O :5~20%
K2O :0.8~5%
SrO :0~1%
BaO :0~1%
K2O+SrO+BaO :1.1~7%
Fe2O3に換算した全鉄:0~0.06%、
を含む、請求項6に記載の透明導電膜形成用ガラス板。 - ガラス板と、透明導電膜とを有する透明導電膜付きガラス板であって、
前記ガラス板が、下記酸化物基準の質量百分率表示で、
SiO2 :60~75%
Al2O3 :0~3%
CaO :0~15%
MgO :0~12%
Na2O :5~20%
K2O+SrO+BaO :1.1~15%
Fe2O3に換算した全鉄:0~0.06%、
を含むことを特徴とする透明導電膜付きガラス板。
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KR1020147007502A KR20140069004A (ko) | 2011-09-28 | 2012-09-28 | 투명 도전막이 형성된 유리판 및 투명 도전막 형성용 유리판 |
JP2013536454A JP5962663B2 (ja) | 2011-09-28 | 2012-09-28 | 透明導電膜付きガラス板 |
CN201280047009.7A CN103842307A (zh) | 2011-09-28 | 2012-09-28 | 带透明导电膜的玻璃板及透明导电膜形成用玻璃板 |
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KR (1) | KR20140069004A (ja) |
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WO2016091673A1 (en) * | 2014-12-09 | 2016-06-16 | Agc Glass Europe | Chemically temperable glass sheet |
EP3103776A1 (en) * | 2015-06-08 | 2016-12-14 | AGC Glass Europe | Chemically temperable glass sheet |
WO2016198249A1 (en) * | 2015-06-08 | 2016-12-15 | Agc Glass Europe | Glass sheet capable of having controlled warping through chemical strengthening |
EP3230222A1 (en) * | 2014-12-09 | 2017-10-18 | AGC Glass Europe | Chemically temperable glass sheet |
US10370288B2 (en) * | 2015-05-05 | 2019-08-06 | Agc Glass Europe | Glass sheet capable of having controlled warping through chemical strengthening |
JP2021011403A (ja) * | 2019-07-05 | 2021-02-04 | Agc株式会社 | Cspミラー用ガラス基板、その製造方法、及びcspミラー |
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CN106129132A (zh) * | 2016-08-23 | 2016-11-16 | 江苏亚太新能源科技有限公司 | 一种太阳能钢化玻璃 |
CN108196387B (zh) * | 2018-01-02 | 2021-03-30 | 重庆京东方光电科技有限公司 | 衬底基板及其制造装置、制备方法和显示装置 |
FR3128707A1 (fr) * | 2021-11-04 | 2023-05-05 | Arc France | Composition de verre sodo-calcique incolore |
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- 2012-09-28 KR KR1020147007502A patent/KR20140069004A/ko not_active Application Discontinuation
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WO2016198249A1 (en) * | 2015-06-08 | 2016-12-15 | Agc Glass Europe | Glass sheet capable of having controlled warping through chemical strengthening |
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JP2021011403A (ja) * | 2019-07-05 | 2021-02-04 | Agc株式会社 | Cspミラー用ガラス基板、その製造方法、及びcspミラー |
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