KR20140069004A - Glass plate fitted with transparent electroconductive film and glass plate for forming transparent electroconductive film - Google Patents
Glass plate fitted with transparent electroconductive film and glass plate for forming transparent electroconductive film Download PDFInfo
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- KR20140069004A KR20140069004A KR1020147007502A KR20147007502A KR20140069004A KR 20140069004 A KR20140069004 A KR 20140069004A KR 1020147007502 A KR1020147007502 A KR 1020147007502A KR 20147007502 A KR20147007502 A KR 20147007502A KR 20140069004 A KR20140069004 A KR 20140069004A
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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
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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
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
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Abstract
Provided is a glass plate on which a transparent conductive film whose peeling of the transparent conductive film from the alkali barrier film is suppressed and a glass plate for forming the transparent conductive film are provided. A glass plate on which a transparent conductive film is formed is a glass plate 10 on which a transparent conductive film having an alkali barrier film 14 and a transparent conductive film 16 is formed in order from the glass plate 12 side, As a percentage indication, it is preferable that 60 to 75% of SiO 2 , 0 to 3% of Al 2 O 3 , 0 to 15% of CaO, 0 to 12% of MgO, 5 to 20% of Na 2 O, K 2 O + SrO + BaO: 1.1 to 15%, and total iron in terms of Fe 2 O 3 : 0 to 0.06%.
Description
The present invention relates to a glass plate on which a transparent conductive film having a transparent conductive film formed on its surface and a glass plate for forming a transparent conductive film.
A glass plate on which a transparent conductive film is formed 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 on which such a transparent conductive film is formed is usually required to have a high light transmittance.
For example, 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 a solar radiation transmittance (hereinafter referred to as Te). Therefore, a highly transparent glass plate (so-called white plate glass) made of soda lime silica glass in which the content of the colored component (particularly iron) is made very small and the Tv and Te are made high is used for the glass plate serving as the base of the glass substrate for the thin film solar cell Patent Document 1).
On the other hand, in the glass plate on which the transparent conductive film is formed, Na + eluted on the surface of the glass plate over time causes thermal diffusion of Na + when the thin film solar cell element is produced, . Therefore, an alkali barrier film containing SiO 2 as a main component is formed between the glass plate and the transparent conductive film.
However, even if an alkali barrier film is formed, if a current flows for a long time in the transparent conductive film of the glass substrate for a thin film solar cell, Na + contained in the glass plate is electrically attracted to the transparent conductive film and Na + diffuses to the surface of the alkali barrier film As a result, it was found that the phenomenon that the transparent conductive film peeled occurred.
The present invention provides a glass plate on which a transparent conductive film with peeling of a transparent conductive film is formed and a glass plate for forming a transparent conductive film.
The glass plate on which the transparent conductive film of the present invention is formed is a glass plate on which a transparent conductive film having a glass plate and a transparent conductive film is formed,
Wherein said glass plate is a mass percent based on oxide,
68 to 75% of SiO 2 ,
Al 2 O 3 : 0 to 2.5%
CaO: 0 to 15%
MgO: 0 to 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 to 7%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
. ≪ / RTI >
The glass plate is an oxide-based mass percentage indication,
69 to 74% of SiO 2 ,
0.3 to 2.3% of Al 2 O 3 ,
CaO: 3 to 12%
MgO: 1 to 10%
Na 2 O: 7 to 17%
K 2 O: 1.0 to 4.5%,
SrO: 0.1 to 0.8%
0.1 to 0.8% of BaO,
K 2 O + SrO + BaO: 1.5 to 6%
0 to 0.05% of total iron in terms of Fe 2 O 3 ,
.
The volume resistivity log (? (? 占])) of the glass plate at 150 占 폚 is preferably 8.8 to 12.0.
It is preferable that the maximum temperature (T max ) at which film separation does not occur in the DHB test described later is 150 ° C or more.
The glass plate on which the transparent conductive film of the present invention is formed preferably has an alkali barrier film formed between the glass plate and the transparent conductive film.
In the glass plate for forming a transparent conductive film of the present invention,
60 to 75% of SiO 2 ,
Al 2 O 3 : 0 to 3%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5 to 20%
K 2 O + SrO + BaO: 1.1 to 15%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
.
In the glass plate for forming a transparent conductive film of the present invention,
60 to 74% of SiO 2 ,
Al 2 O 3 : 0.3 to 2.5%
CaO: 3 to 12%
MgO: 1 to 10%
Na 2 O: 7 to 17%
K 2 O: 0 to 5%,
SrO: 0 to 5%,
BaO: 0 to 5%,
K 2 O + SrO + BaO: 1.4 to 12%
0 to 0.05% of total iron in terms of Fe 2 O 3 ,
.
In the glass plate for forming a transparent conductive film of the present invention,
SiO 2 : 68 to 75%
Al 2 O 3 : 0 to 2.5%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5-20%
K 2 O: 0.8 to 5%
SrO: 0 to 1%
BaO: 0 to 1%
K 2 O + SrO + BaO: 1.1 to 7%
Total iron in terms of Fe 2 O 3 : 0 to 0.06%
.
The glass plate on which the transparent conductive film of the present invention is formed is a glass plate on which a transparent conductive film having a glass plate and a transparent conductive film is formed,
Wherein said glass plate is a mass percent based on oxide,
SiO 2 : 60 to 75%
Al 2 O 3 : 0 to 3%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5-20%
K 2 O + SrO + BaO: 1.1 to 15%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
. ≪ / RTI >
The term " " representing the above numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value, and unless otherwise specified, " in the present specification "
In the glass sheet on which the transparent conductive film of the present invention is formed, peeling of the transparent conductive film is suppressed.
1 is a cross-sectional view showing an example of a glass plate on which a transparent conductive film of the present invention is formed.
2 is a cross-sectional view showing an example of a thin film solar cell.
3 is a cross-sectional view showing an example of a multilayer glass.
<Glass plate on which a transparent conductive film is formed>
The glass plate on which the transparent conductive film of the present invention is formed has a glass plate and a transparent conductive film, preferably an alkali barrier film formed between the glass plate and the transparent conductive film. Another film may be formed between the glass plate and the alkali barrier film, between the alkali barrier film and the transparent conductive film, or on the surface of the glass plate opposite to the transparent conductive film side.
1 is a cross-sectional view showing an example of a glass plate on which a transparent conductive film of the present invention is formed. The
(Glass plate for forming a transparent conductive film)
The glass plate serving as the base of the glass plate on which the transparent conductive film is formed has the following composition (I). The glass plate preferably has the following composition (II), more preferably the following composition (III), particularly preferably the following composition (IV).
Hereinafter, in the present specification, the "transparent conductive film forming glass plate" is also simply referred to as "glass plate". A glass plate on which a transparent conductive film is formed is described as a glass plate on which a transparent conductive film is formed.
(I) As a percentage by mass based on the following oxides,
60 to 75% of SiO 2 ,
Al 2 O 3 : 0 to 3%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5 to 20%
K 2 O + SrO + BaO: 1.1 to 15%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
Lt; / RTI >
(II) As a mass percentage basis on the basis of the following oxides,
68 to 75% of SiO 2 ,
Al 2 O 3 : 0 to 2.5%
CaO: 0 to 15%
MgO: 0 to 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 to 7%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
Lt; / RTI >
(III) a mass percentage based on the following oxides:
69 to 74% of SiO 2 ,
0.3 to 2.3% of Al 2 O 3 ,
CaO: 3 to 12%
MgO: 1 to 10%
Na 2 O: 7 to 17%
K 2 O: 1.0 to 4.5%,
SrO: 0.1 to 0.8%
0.1 to 0.8% of BaO,
K 2 O + SrO + BaO: 1.5 to 6%
0 to 0.05% of total iron in terms of Fe 2 O 3 ,
Lt; / RTI >
(IV) As a mass percentage based on the following oxides,
SiO 2 : 69.3 to 73%,
Al 2 O 3 : 0.5 to 2.1%
CaO: 5 to 10%
MgO: 3 to 8%
Na 2 O: 9 to 15%
K 2 O: 1.3 to 4.0%,
0.2-0.7% SrO,
0.2 to 0.7% of BaO,
K 2 O + SrO + BaO: 2 to 5%
0 to 0.03% of total iron in terms of Fe 2 O 3 ,
Lt; / RTI >
The glass plate in the present invention is a glass plate having a mass percentage based on oxide and a content of K 2 O, SrO, and BaO in the total amount thereof, which is contained in a conventional soda lime silica glass (including a conventional high transmittance glass plate) (For example, 0.4% or less in the case of a high-transmittance glass plate).
When the K / Na ratio is increased, the volume resistivity of the glass plate is increased by the mixed alkali effect (that is, the electrical conductivity is lowered). Also, with respect to the alkaline earth metal / Na ratio, the same tendency as K / Na can be seen. In the case of Sr and Ba having a large atomic radius, this tendency is remarkable. Therefore, the content of K 2 O (or K 2 O, the content of the total amount of SrO and BaO) is, conventional soda lime silica glass surface more than the (conventional includes a high transmission glass plate), becomes higher the volume resistivity of the glass plate (i.e. and the electric conductivity is lowered) due goby long period of time, the current on the glass plate a transparent conductive film formed of a transparent conductive film, a Na + contained in the glass plate and not be pulled electrically good pull by a transparent conductive film, Na + is to the alkali barrier film surface It is not spread well. Therefore, peeling of the transparent conductive film from the alkali barrier film is suppressed.
The content of K 2 O is 0 to 5%, expressed as a mass percentage based on oxide. When the content of K 2 O exceeds 5%, the cost of the raw material remarkably increases, or the viscosity at high temperature rises and the solubility deteriorates. The content of K 2 O is preferably from 1.1 to 4.5%, and more preferably from 1.3 to 4.0%, based on the oxide-based mass percentage.
The content of SrO is 0 to 5%, expressed as a mass percentage based on oxide. If the content of SrO exceeds 5%, the devitrification characteristic (that is, the characteristic that the glass plate is not easily devitrified at the time of molding) deteriorates. The content of SrO is preferably from 0 to 4%, more preferably from 0 to 2%, expressed as a mass percentage based on oxide.
The content of BaO is 0 to 5%, expressed as a mass percentage based on oxide. When the content of BaO exceeds 5%, the devitrification characteristics deteriorate. The content of BaO is preferably from 0 to 4.5%, and more preferably from 0 to 4%, expressed as a mass percentage based on an oxide.
(Hereinafter also referred to as " K 2 O + SrO + BaO " in the present specification) of the total content of K 2 O, SrO and BaO is 1.1 to 15% . When K 2 O + SrO + BaO is less than 1.1%, peeling of the transparent conductive film from the alkali barrier film is not sufficiently suppressed. When K 2 O + SrO + BaO exceeds 15%, there is a high possibility that the liquidus temperature rises and the devitrification characteristic deteriorates. K 2 O + SrO + BaO is preferably 1.4 to 13%, and more preferably 1.4 to 12%, expressed as a mass percentage based on oxide.
Fe 2 O 3 is a coloring component incorporated inevitably in production.
The content of total iron in terms of Fe 2 O 3 is 0 to 0.06%, expressed as a mass percentage based on an oxide. When the content of total iron in terms of Fe 2 O 3 is 0.06% or less, lowering of Tv is suppressed. The content of total iron in terms of Fe 2 O 3 is preferably from 0 to 0.05%, more preferably from 0 to 0.03%, expressed as a mass percentage based on an oxide. In particular, by setting the content of the total iron to 0.01% or less, it becomes easy to make Te of the glass plate (in terms of the thickness of 4 mm in thickness) 90% or more, and the Tv of the glass plate (in terms of the thickness of 4 mm) Or more.
In the present specification, the total iron content is expressed as the amount of Fe 2 O 3 according to a standard method of analysis, but not all iron present in the glass is present as ternary iron. Divalent iron is usually present in the glass. Divalent iron mainly has an absorption peak at a wavelength of about 1000 to 1100 nm, absorption at a wavelength shorter than 800 nm, and a trivalent iron mainly has an absorption peak at a wavelength of about 400 nm. The increase of divalent iron increases the absorption in the near infrared region around 1000 nm, and when expressed by Te, it means that Te is lowered. Therefore, when attention is paid to Tv and Te, the decrease of Tv is suppressed by suppressing the content of total iron in terms of Fe 2 O 3 , and the amount of trivalent iron is made larger than that of bivalent iron, do. Therefore, Tv, in terms of suppressing the Te decrease in, (and described as below, Redox) reduces the overall cheolryang, Fe 2 O 3 in terms of the total iron in the Fe 2 O 3 in mass percentage of divalent iron in terms of the It is preferable to suppress the concentration of the catalyst to a low level.
Redox in the glass plate is preferably 35% or less. When Redox is 35% or less, the decrease of Te is suppressed. Redox is preferably 30% or less.
SiO 2 is the main component of glass.
The content of SiO 2 is 60 to 75%, expressed as a mass percentage based on oxide. If the content of SiO 2 is less than 60%, the stability of the glass is deteriorated. If the content of SiO 2 is more than 75%, the melting temperature of the glass is increased and the glass can not be dissolved. The content of SiO 2 is preferably from 62 to 73%, more preferably from 62 to 72%, expressed as a mass percentage based on oxide. The content of SiO 2 may be from 68 to 75%, preferably from 69 to 75%, and further from 69.3 to 73%.
Al 2 O 3 is a component for improving weather resistance.
The content of Al 2 O 3 is 0 to 3% expressed as a mass percentage based on an oxide. When the content of Al 2 O 3 is more than 3%, the solubility remarkably deteriorates or the volume resistance becomes too low. The content of Al 2 O 3 is preferably from 0 to 2.8%, more preferably from 0 to 2.5%, expressed as a mass percentage based on an oxide. 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 glass raw materials and adjusts viscosity, thermal expansion coefficient and the like.
The content of CaO is 0 to 15%, expressed as a mass percentage based on oxide. If the content of CaO exceeds 15%, the melt temperature increases. The content of CaO is preferably from 3 to 12%, more preferably from 3 to 11% by mass percentage based on oxide. The content of CaO may be 5 to 10%.
MgO is a component that promotes melting of glass raw materials and adjusts viscosity and thermal expansion coefficient.
The content of MgO is 0 to 12% as expressed as a mass percentage based on an oxide. If the content of MgO exceeds 12%, the melt temperature increases. The content of MgO is preferably from 2 to 12%, more preferably from 2 to 6%, expressed as a mass percentage based on the oxide. The content of MgO may be 1 to 10%, preferably 3 to 8%.
Na 2 O is an essential component for promoting the melting of the glass raw material.
The content of Na 2 O is 5 to 20% in terms of mass percentage based on oxide. If the content of Na 2 O is less than 5%, it becomes difficult to dissolve the glass raw material. If the content of Na 2 O exceeds 20%, the weather resistance and stability of the glass plate deteriorate. The content of Na 2 O is preferably from 7 to 19%, more preferably from 9 to 17% by mass percentage based on the oxide. The content of Na 2 O may be 9 to 15%.
In the glass plate of the present invention, although not essential, it may contain TiO 2 , ZrO 2 , Li 2 O, and B 2 O 3 .
In the case where TiO 2 is contained, the content of TiO 2 is preferably 0 to 2% by mass percentage based on oxide. When the content of TiO 2 exceeds 2%, the glass plate is colored, and Tv and Te decrease.
ZrO 2 is a component that improves the chemical durability of glass and improves physical strength such as elastic modulus and hardness.
When ZrO 2 is contained, the content of ZrO 2 is preferably from 0 to 3% by mass percentage based on oxide. If the content of ZrO 2 exceeds 3%, the melting characteristics deteriorate and the melt temperature increases.
Li 2 O is a component that promotes melting of the glass raw material and lowers the melting temperature.
In the case where Li 2 O is contained, the content of Li 2 O is 0 to 3% expressed as a mass percentage based on oxide. When the content of Li 2 O exceeds 3%, the stability of the glass deteriorates. In addition, the raw material cost remarkably increases.
B 2 O 3 is a component for promoting melting of glass raw materials, but when added to soda lime silica glass, there are many problems such as generation of ream due to volatilization and erosion of furnace walls, which is not suitable for production.
In the case where B 2 O 3 is contained, the content of B 2 O 3 is preferably not more than 1%, more preferably not substantially, in mass percentage based on oxide. Here, substantially not containing means that the amount of the impurity may be mixed.
The glass plate preferably contains SO 3 used as a refining agent. The content of the total sulfur in terms of SO 3 is preferably from 0.01 to 0.5% by mass percentage based on oxide. If the content of the total sulfur in terms of SO 3 exceeds 0.5%, there is a fear that the quality of the foam may deteriorate due to the generation of reboil in the process of cooling the molten glass. When the content of total sulfur in terms of SO 3 is less than 0.01%, sufficient purifying effect can not be obtained. The content of the total sulfur in terms of SO 3 is 0.05 to 0.5%, more preferably 0.2 to 0.4%, in terms of mass percentage based on oxide.
The glass plate may contain SnO 2 used as a refining agent. The content of total tin in terms of SnO 2 is preferably 0 to 1% as expressed as a mass percentage based on an oxide. It is also possible to use a glass cullet in which a transparent conductive film in which a SnO 2 film is laminated on a surface layer of a glass substrate as a transparent electrode material is used as a glass raw material for a SnO 2 component.
The glass plate may contain Sb 2 O 3 used as a refining agent. The content of the total antimony in terms of Sb 2 O 3 is preferably 0 to 0.5%. If the content of the total antimony in terms of Sb 2 O 3 exceeds 0.5%, the glass plate after the molding becomes cloudy in the case of the float method. The content of total antimony in terms of Sb 2 O 3 is preferably 0 to 0.1%, expressed as a mass percentage based on oxide.
Glass plate, it is preferred that the colored component of S, NiO, MoO 3, CoO, Cr 2 O 3, V 2 O 5, or that is substantially free of MnO. S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , or MnO is substantially free from S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , Or may contain S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 and MnO as impurities inevitably incorporated in the production. S, NiO, MoO 3 , CoO, Cr 2 O 3 , V 2 O 5 , or MnO, the lowering of Tv and Te is suppressed.
The Te of the glass plate (in terms of 4 mm thickness, that is, the plate thickness of the glass plate is 4 mm) is preferably 80% or more, more preferably 82.7% or more. Te is a solar radiation transmittance calculated by measuring the transmittance by a spectrophotometer according to JIS R 3106 (1998) (hereinafter simply referred to as JIS R 3106).
When the Fe 2 O 3 content in the composition is 0.01% or less, Te (in terms of 4 mm thickness) is preferably 90% or more, more preferably 91% or more, and still more preferably 91.5% or more.
The Tv (in terms of 4 mm thickness) of the glass plate is preferably 80% or more, and more preferably 82% or more. Tv is a visible light transmittance calculated by measuring the transmittance by a spectrophotometer according to JIS R 3106. [ The coefficient uses the standard value of light A, 2 degree field of view.
When the Fe 2 O 3 content in the composition is 0.01% or less, the Tv (in terms of 4 mm thickness) is preferably 90% or more, and more preferably 91% or more.
The volume resistivity log (? (? 占])) of the glass plate at 150 占 폚 is preferably 9.0 to 12, more preferably 9.1 to 12. When the volume resistivity of the glass sheet at 150 캜 is 9.0 or more, the peeling of the transparent conductive film from the alkali barrier film is more reliably suppressed. Similarly, the volume resistivity log (? (? 占])) of the glass plate at 200 占 폚 is preferably 7.8 to 12, more preferably 7.9 to 11. When the volume resistivity of the glass plate at 200 캜 is 7.8 or more, the peeling of the transparent conductive film from the alkali barrier film is more reliably suppressed.
Here, the volume resistivity of the glass plate is measured by a method in accordance with ASTM C657-78.
The glass plate is manufactured by, for example, the following steps (i) to (V).
(I) A glass raw material is prepared by mixing various kinds of glass mother material, cullet, refining agent and the like so as to achieve a target composition.
(Ii) The glass raw material is melted to be melted glass.
(Iii) After refining the molten glass, it is formed into a glass plate having a predetermined thickness by a float method or a down-draw method (fusion method).
(Iv) Cool the glass plate.
(V) The glass plate is cut into a predetermined size.
After the step (iii), a step (iii-1) of forming an alkali barrier film on the surface of the glass plate and a step (iii-2) of forming a transparent conductive film on the alkali barrier film surface of the glass plate may be added . By adding these processes (iii-1) and (iii-2), a glass plate on which a transparent conductive film is formed can be manufactured on-line using a glass plate manufacturing process.
Examples of raw glass parent materials include those used as raw materials for conventional soda lime silica glass such as silica sand, dolomite, and soda ash.
Examples of the cleaning agent include SO 3 , SnO 2 , Sb 2 O 3 , and the like.
The melting of the glass raw material is carried out, for example, by continuously supplying the glass raw material to a glass melting furnace (melting furnace) and heating the glass raw material to about 1300 to 1600 캜 by heavy oil, gas, electricity or the like.
The glass plate on which the transparent conductive film is formed is produced by forming a transparent conductive film on the glass sheet surface prepared as described above or by forming an alkali barrier film on the glass sheet surface prepared as described above and forming a transparent conductive film on the alkali barrier film surface . The above-described step (iii-1) of forming an alkali barrier film is added to the above-described steps (i) to (V) of producing the glass sheet, and a transparent conductive film is formed on the surface of the alkali- . Further, a glass sheet on which a transparent conductive film is formed may be produced by adding the step (iii-2) of forming a transparent conductive film on the alkali-barrier film surface next to the above-described step (iii-1) for forming an alkali-barrier film.
(Transparent conductive film)
As the transparent conductive film, a film containing SnO 2 as a main component, a film containing ZnO as a main component, a film containing tin-doped indium oxide (ITO) as a main component and the like can be mentioned. A film mainly composed of SnO 2 is preferable because it is a material having little influence on the power generation layer when it is incorporated into the power generation layer. Here, the " main component " means that the component is contained in an amount of 90% or more based on the 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 fluoro-doped tin oxide (FTO), a film made of antimony doped tin oxide, and the like.
Examples of the method of 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)
Alkali barrier film include, as a main component film, SiO 2 and the multilayer film, Al 2 O in the film and the SiO 2 and SnO 2 as a main component a mixed oxide of the SnO 2 3, ZrO 2, or SiOC composed mainly of SiO 2 Film and the like. Here, the " main component " means that the component is contained in an amount of 90% or more based on the oxide-based mass percentage.
Examples of the method of 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 in terms of alkali barrier performance, and is preferably 500 nm or less in terms of cost.
(Other membrane)
Other films that may be formed between the glass plate and the alkali barrier film include a TiO 2 film, a SnO 2 film, and the like.
Other films that may be formed between the alkali barrier film and the transparent conductive film include mixed oxides of SiO 2 and SnO 2 , multilayer films, and the like.
Other films that may be formed on the surface of the glass plate opposite to the transparent conductive film side include an antireflection film and the like.
Further, the other film itself may have an alkali barrier performance.
In the glass plate on which the transparent conductive film of the present invention described above is formed, it is preferable that the content of K 2 O is 0.8% or more as expressed as a mass percentage based on the oxide, and the total content of K 2 O, SrO, Since it is 1.1% or more as a percentage indication, the volume resistivity of the glass plate is increased (that is, the electrical conductivity is lowered). As a result, even if a current flows for a long time in the transparent conductive film of the glass plate on which the transparent conductive film is formed, Na + contained in the glass plate is not attracted to the electrically transparent conductive film well and Na + is not diffused well to the surface of the alkali- do. Therefore, peeling of the transparent conductive film is suppressed.
Further, the content of total iron in terms of Fe 2 O 3 is 0 to 0.06% in terms of percentage of mass based on oxide, so that Tv is sufficiently high.
<Thin film solar cell>
The glass plate on which the transparent conductive film of the present invention is formed is preferable as a glass substrate for a thin film solar cell.
2 is a cross-sectional view showing an example of a thin film solar cell. The thin film
The glass plate on which the transparent conductive film of the present invention is formed can be suitably used in thin film solar cells which form a transparent conductive film on a glass plate such as a thin film silicon solar cell or a CdTe thin film solar cell.
The thin film
The
The
Examples of the material of the back electrode layer 28 include a material having no light transmitting property (for example, silver or aluminum) and a material having light permeability (for example, ITO, SnO 2 , ZnO and the like).
<Double Layer Glass>
Since the glass plate on which the transparent conductive film of the present invention is formed has low-E (low emissivity) properties, it can be used as a low-E glass plate.
3 is a cross-sectional view showing an example of a multilayer glass using a Low-E glass plate. The
Example
Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples.
[Examples 1 to 31]
Examples 2 to 31 are examples, and Example 1 is a comparative example.
The respective performances of the glass plate for forming the transparent conductive film and the glass plate having the transparent conductive film were determined and measured as follows.
(Redox)
The amount of Fe 2 O 3 in the obtained glass sheet is the content (% = mass percentage) of total iron in terms of Fe 2 O 3 , as determined by fluorescent X-ray measurement.
The amount of bivalent iron in the glass plate necessary for the calculation of Redox was calculated on the basis of the transmittance at a wavelength of 1000 nm obtained by measuring the transmittance. In this case, the influence of reflection at a wavelength of 1000 nm was subtracted to 8%, and then converted into an absorption coefficient, and the amount of bivalent iron was quantified based on the calibration curve previously prepared by a wet analysis method.
(TV)
The obtained glass plate was polished to a thickness of 4 mm, and the visible light transmittance (Tv) according to JIS R 3106 (by the A light source) was measured.
(Te)
The obtained glass plate was polished to a thickness of 4 mm, and the solar radiation transmittance (Te) according to JIS R 3106 was measured.
(Volume resistivity)
The volume resistivity of the glass plate was measured by a method in accordance with ASTM C657-78. As the glass plate, a glass plate having a size of about 50 mm x 50 mm and having a thickness of about 4 mm was optically polished on both sides. A metal Al film was formed on both sides of the glass plate by a vapor deposition method to form an electrode, and the volume resistivity at 100 ° C, 150 ° C, and 200 ° C was measured. Also, the volume resistance value of an arbitrary point is obtained by using the slope A and the slice B obtained from the relationship between the volume resistivity at each temperature (log (? (? 占))) and the reciprocal of the absolute temperature (1 / T) , And was obtained from the following prediction formula.
log (? [? · cm]) = A / T + B
(DHB test)
The durability test of the Dump Heat Bias (DHB) type (hereinafter referred to as the DHB test) makes it possible to estimate the ease of peeling of the transparent conductive film.
The DHB test is a test that simultaneously evaluates the electrical and thermal attack of a thin film coated specimen. As shown in the following (1) to (4), by heating the glass plate (sample) on which the transparent conductive film is formed for a sufficient time until the glass plate is stabilized at the set temperature, and simultaneously applying an electric field to the glass plate on which the transparent conductive film is formed.
(1) A sample was arranged between two electrodes. The side where the transparent conductive film was not formed was brought into contact with the graphite electrode (anode), and the side of the transparent conductive film was brought into contact with the copper electrode (cathode) covered with aluminum. After heating to the set temperature, the voltage was maintained at 500 V and the voltage application time was 15 minutes.
(2) After cooling to room temperature, the side of the transparent conductive film of the sample was exposed in an atmosphere of 100% relative humidity for 1 hour to cause aggregation on the side of the transparent conductive film. The coagulation humidity and water temperature were set to 55 ° C and the gasification temperature was set to 50 ° C ± 2 ° C.
(3) Whether or not the peeling of the transparent conductive film occurred was confirmed on the surface of the sample on the side of the transparent conductive film. The presence or absence of peeling was defined as the occurrence of peeling if there is at least one peeling portion that can be visually confirmed in the sample.
(4) A plurality of other samples prepared under the same conditions were prepared, and the tests were carried out three times for each set temperature. The temperature at which the transparent conductive film of the sample was peeled off was defined as T max (占 폚). It was determined that the higher the T max , the more the transparent conductive film did not peel off for a long time (that is, the durability was high).
The mechanism of the occurrence of peeling at the interface between the alkali barrier film (SiO 2 ) and the transparent conductive film (SnO 2 ) is as follows: Na + contained in the glass plate acts as a positive And the following reaction takes place at the interface, so that peeling occurs at the interface adhered by the Sn-O bond.
1. Na + + e - > Na
2. H 2 O + Na → NaOH + 1 / 2H 2
3. 2H 2 + SnO 2 → Sn + 2H 2 O
The glass plates of Examples 1 to 31 were produced as follows.
Glass raw materials were prepared by mixing silica sand, various other glassy starting materials and a refining agent (SO 3 ) so as to have the compositions shown in Tables 1-1 to 1-5. The glass raw material was placed in a crucible and heated in an electric furnace at 1500 DEG C for 3 hours to obtain a molten glass. The molten glass was flown out onto a carbon plate and cooled. The both surfaces were polished to obtain a glass plate having a thickness of 4 mm. The glass plate was measured for transmittance per 1 nm using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), and Tv, Te, and volume resistivity were determined. The results are shown in Tables 1-1 to 1-5.
A TiO 2 film having a thickness of 8 nm, an alkali barrier film made of SiO 2 having a thickness of 25 nm, and a transparent conductive film made of SnO 2 having a thickness of 550 nm were formed on the surface of the glass plate heated to 580 ° C by the CVD method. The glass plate on which the transparent conductive film was formed was subjected to the DHB test. Table 1 shows T max . Here, the temperature at which the volume resistivity (log (p [OMEGA .cm]) at 150 DEG C reaches 8.8 is defined as the expected Tmax when the glass thickness is 4 mm, and the estimated Lt; / RTI >
In Tables 1-1 to 1-5, A [K] and B represent the slope A and the slice B (dimensionless) when calculating the volume resistivity value.
[Table 1-1]
[Table 1-2]
[Table 1-3]
[Table 1-4]
[Table 1-5]
In Example 1 (corresponding to Example 5 of Patent Document 1) in which the total content of K 2 O + SrO + BaO was small, the temperature T max at which peeling of the transparent conductive film occurred by the DHB test was low. On the other hand, in Examples 2 to 31 in which the total content of K 2 O, SrO, and BaO is 1.1% or more in terms of mass percentage based on oxide, the temperature T max at which peeling of the transparent conductive film occurs by the DHB test is 160 ° C or more And the peeling of the transparent conductive film from the alkali barrier film was suppressed over a long period of time.
Industrial availability
The glass plate on which the transparent conductive film of the present invention is formed is useful as a glass substrate for a thin film solar cell, a low-emission glass plate (Low-E glass plate), and the like.
The entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2011-212265 filed on September 28, 2011 are hereby incorporated herein by reference.
10: Glass plate on which a transparent conductive film is formed
12: Glass plate (glass plate for forming a transparent conductive film)
14: Alkali barrier film
16: transparent conductive film
20: Thin film solar cell
22: Thin film solar cell element
24: transparent electrode layer
26: Photoelectric conversion layer
28: back electrode layer
30: Double layer glass
32: Pore
34: Spacer
Claims (9)
Wherein the glass plate is a mass percent based on the following oxides:
SiO 2 : 68 to 75%
Al 2 O 3 : 0 to 2.5%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5-20%
K 2 O: 0.8 to 5%
SrO: 0 to 1%
BaO: 0 to 1%
K 2 O + SrO + BaO: 1.1 to 7%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
And a transparent conductive film formed on the transparent conductive film.
Wherein the glass plate is a mass percent based on the following oxides:
69 to 74% of SiO 2 ,
0.3 to 2.3% of Al 2 O 3 ,
CaO: 3 to 12%
MgO: 1 to 10%
Na 2 O: 7 to 17%
K 2 O: 1.0 to 4.5%,
SrO: 0.1 to 0.8%
0.1 to 0.8% of BaO,
K 2 O + SrO + BaO: 1.5 to 6%
0 to 0.05% of total iron in terms of Fe 2 O 3 ,
And a transparent conductive film containing the transparent conductive film.
Wherein the glass plate has a transparent conductive film having a volume resistivity log (? (? 占])) of from 8.8 to 12.0 at 150 占 폚.
A glass plate on which a transparent conductive film having a maximum temperature (T max ) at which film separation does not occur in the DHB test is 150 ° C or higher.
And a transparent conductive film having an alkali barrier film formed between the glass plate and the transparent conductive film.
60 to 75% of SiO 2 ,
Al 2 O 3 : 0 to 3%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5 to 20%
K 2 O + SrO + BaO: 1.1 to 15%
0 to 0.06% of total iron in terms of Fe 2 O 3 ,
Wherein the transparent conductive film is a glass substrate.
As a percent mass indication based on the following oxides,
60 to 74% of SiO 2 ,
Al 2 O 3 : 0.3 to 2.5%
CaO: 3 to 12%
MgO: 1 to 10%
Na 2 O: 7 to 17%
K 2 O: 0 to 5%,
SrO: 0 to 5%,
BaO: 0 to 5%,
K 2 O + SrO + BaO: 1.4 to 12%
0 to 0.05% of total iron in terms of Fe 2 O 3 ,
Wherein the transparent conductive film is a glass substrate.
As a percent mass indication based on the following oxides,
SiO 2 : 68 to 75%
Al 2 O 3 : 0 to 2.5%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5-20%
K 2 O: 0.8 to 5%
SrO: 0 to 1%
BaO: 0 to 1%
K 2 O + SrO + BaO: 1.1 to 7%
Total iron in terms of Fe 2 O 3 : 0 to 0.06%
And a transparent conductive film formed on the glass substrate.
Wherein the glass plate is a mass percent based on the following oxides:
SiO 2 : 60 to 75%
Al 2 O 3 : 0 to 3%
CaO: 0 to 15%
MgO: 0 to 12%
Na 2 O: 5-20%
K 2 O + SrO + BaO: 1.1 to 15%
Total iron in terms of Fe 2 O 3 : 0 to 0.06%
And a transparent conductive film formed on the transparent conductive film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011212265 | 2011-09-28 | ||
| JPJP-P-2011-212265 | 2011-09-28 | ||
| PCT/JP2012/075192 WO2013047806A1 (en) | 2011-09-28 | 2012-09-28 | Glass plate fitted with transparent electroconductive film and glass plate for forming transparent electroconductive film |
Publications (1)
| Publication Number | Publication Date |
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| KR20140069004A true KR20140069004A (en) | 2014-06-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020147007502A KR20140069004A (en) | 2011-09-28 | 2012-09-28 | Glass plate fitted with transparent electroconductive film and glass plate for forming transparent electroconductive film |
Country Status (5)
| Country | Link |
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| JP (1) | JP5962663B2 (en) |
| KR (1) | KR20140069004A (en) |
| CN (1) | CN103842307A (en) |
| TW (1) | TW201318997A (en) |
| WO (1) | WO2013047806A1 (en) |
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| EP3031783A1 (en) * | 2014-12-09 | 2016-06-15 | AGC Glass Europe | Chemically temperable glass sheet |
| EP3103776A1 (en) * | 2015-06-08 | 2016-12-14 | AGC Glass Europe | Chemically temperable glass sheet |
| JP2018505117A (en) * | 2014-12-09 | 2018-02-22 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Chemically temperable glass plate |
| JP2018514494A (en) * | 2015-05-05 | 2018-06-07 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Glass plate that can have controlled warpage due to chemical strengthening |
| CN107683268A (en) * | 2015-06-08 | 2018-02-09 | 旭硝子欧洲玻璃公司 | Can be by chemical enhanced and the glass plate with controlled warpage |
| CN106129132A (en) * | 2016-08-23 | 2016-11-16 | 江苏亚太新能源科技有限公司 | A kind of solar energy safety glass |
| CN108196387B (en) * | 2018-01-02 | 2021-03-30 | 重庆京东方光电科技有限公司 | Substrate base plate, manufacturing device and preparation method thereof and display device |
| JP2021011403A (en) * | 2019-07-05 | 2021-02-04 | Ａｇｃ株式会社 | Glass substrate for csp mirror, method for manufacturing the same, and csp mirror |
| FR3128707A1 (en) * | 2021-11-04 | 2023-05-05 | Arc France | Composition of colorless soda-lime glass |
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| JP3731281B2 (en) * | 1996-03-14 | 2006-01-05 | 旭硝子株式会社 | Substrate glass composition |
| EP0795522B1 (en) * | 1996-03-14 | 1999-08-18 | Asahi Glass Company Ltd. | Glass composition for a substrate |
| JPH11240733A (en) * | 1998-02-27 | 1999-09-07 | Asahi Glass Co Ltd | Glass composition for substrate |
| EP1116699B1 (en) * | 1998-09-04 | 2006-02-15 | NIPPON SHEET GLASS CO., Ltd. | Light-colored glass of high transmittance and method for production thereof, glass plate with electrically conductive film and method for production thereof, and glass article |
| JP3465642B2 (en) * | 1998-09-04 | 2003-11-10 | 日本板硝子株式会社 | Light-colored high-transmission glass and method for producing the same |
| WO2001066477A1 (en) * | 2000-03-06 | 2001-09-13 | Nippon Sheet Glass Co., Ltd. | Flat glass having high transmittance |
| WO2003057638A1 (en) * | 2001-12-28 | 2003-07-17 | Nippon Sheet Glass Company, Limited | Sheet glass and photoelectric converter-use sheet glass |
| CN101842328B (en) * | 2007-11-06 | 2013-06-26 | 旭硝子株式会社 | Glass plate for substrate |
| FR2937798B1 (en) * | 2008-10-24 | 2010-12-24 | Saint Gobain | GLASS SUBSTRATE WITH ELECTRODE PARTICULARLY FOR ORGANIC ELECTROLUMINESCENT DIODE DEVICE |
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- 2012-09-28 KR KR1020147007502A patent/KR20140069004A/en not_active Application Discontinuation
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| JPWO2013047806A1 (en) | 2015-03-30 |
| JP5962663B2 (en) | 2016-08-03 |
| TW201318997A (en) | 2013-05-16 |
| WO2013047806A1 (en) | 2013-04-04 |
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