WO2014088066A1 - Verre hautement perméable - Google Patents

Verre hautement perméable Download PDF

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Publication number
WO2014088066A1
WO2014088066A1 PCT/JP2013/082698 JP2013082698W WO2014088066A1 WO 2014088066 A1 WO2014088066 A1 WO 2014088066A1 JP 2013082698 W JP2013082698 W JP 2013082698W WO 2014088066 A1 WO2014088066 A1 WO 2014088066A1
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Prior art keywords
glass
transparent conductive
conductive film
highly permeable
present
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PCT/JP2013/082698
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English (en)
Japanese (ja)
Inventor
博之 土屋
淳 笹井
近藤　裕己
志堂寺　栄治
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旭硝子株式会社
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Priority to CN201380063616.7A priority Critical patent/CN104918895A/zh
Priority to JP2014551137A priority patent/JPWO2014088066A1/ja
Publication of WO2014088066A1 publication Critical patent/WO2014088066A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0488—Double glass encapsulation, e.g. photovoltaic cells arranged between front and rear glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a highly permeable glass, and more particularly to a highly permeable glass on which a film such as a transparent conductive film can be formed.
  • Highly transmissive glass having a transparent conductive film on the surface can be used for, for example, solar cell panels and low-reflection glass (Low-E glass).
  • High transmittance glass usually requires high light transmittance. In order to realize this high light transmittance, it is necessary to reduce the coloring components contained in the glass as much as possible. Therefore, a highly permeable glass having a composition with a very small content of iron as a coloring component is used.
  • Patent Document 1 describes a glass plate with a conductive film in which total iron contained in glass is suppressed to less than 0.06% in terms of Fe 2 O 3 .
  • the present invention has been made in view of such a background, and an object of the present invention is to provide a highly permeable glass capable of significantly suppressing peeling of a film placed on the surface.
  • a highly transmissive glass In mass percentage display, Containing more than 0.7% K 2 O, Provided is a highly permeable glass characterized by containing 0.03% or less of total iron converted to Fe 2 O 3 .
  • the logarithm log ( ⁇ ) of the volume resistivity ⁇ ( ⁇ ⁇ cm) at 150 ° C. may be greater than 8.8.
  • the highly transmissive glass according to the present invention is expressed in terms of mass percentage based on oxide, 60-75% SiO 2 , 0-3% Al 2 O 3 , 0-15% CaO, 0-12% MgO, and 5-20% Na 2 O May be included.
  • a transparent conductive film may be formed on the surface.
  • FIG. 1 schematically shows a cross section of a glass product 1 having a high light transmittance.
  • the glass product 1 is formed by forming a transparent conductive film 30 on the surface of a highly transmissive glass 20.
  • reference numeral 25 represents an interface between the highly transmissive glass 20 and the transparent conductive film 30.
  • the transparent conductive film 30 is assumed to contain tin oxide (SnO 2 ) that has been widely used in the past in applications where transparency and conductivity are required.
  • the following can be considered as a peeling mechanism of the transparent conductive film 30 in the glass product 1.
  • sodium ions (Na + ) contained in the highly permeable glass 20 move toward the interface 25 with the transparent conductive film 30.
  • the cause of the movement of sodium ions is not particularly limited.
  • a temperature gradient of the glass product 1 under use conditions, a potential difference due to voltage application, and the like are conceivable.
  • the generated hydrogen reduces tin oxide constituting the transparent conductive film 30 according to the following formula (2) to form metallic tin: 2H 2 + SnO 2 ⁇ Sn + 2H 2 O (2)
  • the inventors of the present application have significant peeling of the transparent conductive film as described above when K 2 O is contained in a predetermined amount or more in the highly permeable glass in which the iron content is suppressed to a certain amount or less. As a result, the present invention has been found.
  • a highly transmissive glass In mass percentage display, Containing more than 0.7% K 2 O, Provided is a highly permeable glass characterized by containing 0.03% or less of total iron converted to Fe 2 O 3 .
  • the highly permeable glass according to the present invention is characterized by containing 0.03% or less of total iron converted to Fe 2 O 3 in terms of mass percentage.
  • the highly permeable glass in the present invention can exhibit high permeability.
  • the solar radiation transmittance at a thickness of 3.2 mm of the highly transmissive glass in one embodiment of the present invention is 90% or more.
  • the light transmittance of the highly transmissive glass is, for example, 90.5% or more, and preferably 90.8% or more.
  • the highly transmissive glass according to the present invention is characterized by containing K 2 O in excess of 0.7% in terms of mass percentage.
  • the volume resistance ⁇ of the highly permeable glass can be increased.
  • volume resistance ( ⁇ ) is an index correlated with the reciprocal of electrical conductivity.
  • the mobility of sodium ions in the glass decreases as the volume resistance ( ⁇ ) of the glass increases.
  • the volume resistance ⁇ increases as the content of potassium contained in the glass increases.
  • the highly permeable glass in the present invention contains a relatively “high concentration” of potassium, which can increase the volume resistance ⁇ of the highly permeable glass. Moreover, the mobility of sodium ions is suppressed by increasing the volume resistance ⁇ of the highly permeable glass. Therefore, when the transparent conductive film is formed on the surface of the highly permeable glass in the present invention, the reaction of the above-described formula (1) is suppressed at the interface between the highly permeable glass and the transparent conductive film, and the transparent conductive film It is possible to significantly suppress peeling of the film.
  • the iron content is preferably 0.02% or less, and 0.01% or less as the total iron amount converted to Fe 2 O 3. It is more preferable that The smaller the iron content, the higher the light transmittance of the highly transmissive glass.
  • 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 exists as trivalent iron. Absent. Usually, 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, and also absorbs at a wavelength shorter than a wavelength of 800 nm. 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 around 1000 nm, which means that Te decreases when expressed in terms of energy transmittance (Te).
  • Te energy transmittance
  • the amount of potassium may be, for example, 1.0% or more, preferably 1.2% or more in terms of K 2 O.
  • the amount of potassium in K 2 O in terms is preferably 5% or less. If the amount of potassium exceeds 5%, the raw material cost will increase significantly. On the other hand, if the amount of potassium exceeds 5%, the viscosity of the glass at a high temperature increases and the solubility deteriorates.
  • the highly transmissive glass according to one embodiment of the present invention may have a logarithm of volume resistivity ⁇ ( ⁇ ⁇ cm) at 150 ° C., that is, log ( ⁇ ) exceeding 8.8.
  • the value of log ( ⁇ ) at 150 ° C. is preferably 8.9 or more, and more preferably 8.95 or more.
  • the volume resistivity ⁇ of the glass is a value measured by a method based on ASTM C657-78.
  • the highly permeable glass according to one embodiment of the present invention may be, for example, soda lime silicate glass.
  • the highly transmissive glass according to an embodiment of the present invention is, for example, expressed in mass percentage on an oxide basis, 60-75% SiO 2 , 0-3% Al 2 O 3 , 0-15% CaO, 0-12% MgO, and 5-20% Na 2 O May be included.
  • SiO 2 is a main component of soda lime silicate glass.
  • the content of SiO 2 is preferably 62 to 73% and more preferably 62 to 72% in terms of mass percentage based on oxide.
  • Al 2 O 3 is a component that improves the weather resistance of the glass.
  • 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.
  • CaO is a component that promotes the melting of the glass raw material and adjusts the viscosity and the coefficient of thermal expansion.
  • the content of CaO is preferably 3 to 12%, more preferably 3 to 11% in terms of mass percentage based on oxide.
  • MgO is a component that promotes the melting of the glass raw material and adjusts the viscosity, thermal expansion coefficient, and the like.
  • the content of MgO is preferably 2 to 12% and more preferably 2 to 6% in terms of mass percentage based on oxide.
  • Na 2 O is a component that promotes melting of the glass raw material.
  • 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.
  • the highly transmissive glass according to an embodiment of the present invention may further include TiO 2 , ZrO 2 , and Li 2 O.
  • the content of TiO 2 is preferably 0 to 2% in terms of oxide-based mass percentage. If the content of TiO 2 exceeds 2%, the glass plate may be colored.
  • the ZrO 2 content is preferably 0 to 3% in terms of mass percentage based on oxide. When the content of Zr exceeds 3%, the melting characteristics deteriorate.
  • Li 2 O may promote melting of glass raw material, to lower the melting temperature.
  • the content of Li 2 O is 0 to 3% in terms of mass percentage based on oxide. When the content of Li 2 O exceeds 3%, the stability of the glass deteriorates. Moreover, raw material cost will rise remarkably.
  • the highly transmissive glass according to an embodiment of the present invention may include SO 3 , SnO 2 , Sb 2 O 3 , and the like used as a fining agent.
  • the highly transmissive glass is: (I) mixing a glass matrix composition raw material weighed to a target composition with other additives to prepare a glass raw material; (Ii) melting the glass raw material to produce molten glass; (Iii) after refining the molten glass, forming a glass plate having a predetermined thickness by a float method or a downdraw method (fusion method); (Iv) cooling the glass plate, and (V) cutting the glass plate to a predetermined size, It is manufactured through.
  • dolomite having a low iron content as a glass matrix composition raw material (mainly including a mixture of magnesium carbonate (MgCO 3 ) and calcium carbonate (CaCO 3 ))
  • a glass matrix composition raw material mainly including a mixture of magnesium carbonate (MgCO 3 ) and calcium carbonate (CaCO 3 )
  • raw materials containing sodium carbonate (Na 2 CO 3 ) and alumina (Al 2 O 3 ) or aluminum hydroxide (Al (OH) 3 have been used.
  • step (i) the glass matrix composition raw material is adjusted so that the high-permeability glass after production contains K 2 O exceeding 0.7%.
  • the highly permeable glass after production has a significantly high volume resistivity ⁇ , and even if a transparent conductive film is formed on the surface of the highly permeable glass, the peeling of the transparent conductive film is significantly suppressed. Can do.
  • an additive may be added to the glass raw material.
  • the additive may be, for example, cullet and clarifier.
  • the fining agent may be, for example, SO 3 , SnO 2 , or Sb 2 O 3 .
  • the glass raw material is melted by, for example, continuously supplying the glass raw material to a glass melting furnace (melting kiln), and by using heavy oil, gas, electricity, etc. It may be performed by heating to ° C.
  • a highly transmissive glass according to an embodiment of the present invention can be manufactured.
  • a transparent conductive film may be provided on the surface of the highly transmissive glass according to an embodiment of the present invention.
  • Examples of such a transparent conductive film include a film containing SnO 2 as a main component, a film containing ZnO as a main component, and a film containing tin-doped indium oxide (ITO) as a main component.
  • the “main component” means that the component is contained in 90% or more in terms of oxide based mass percentage.
  • film made of SnO 2 film made of fluorine-doped tin oxide (FTO), and film or the like made of antimony-doped tin oxide.
  • FTO fluorine-doped tin oxide
  • Such a transparent conductive film may be formed on the highly transmissive glass according to the present invention by, for example, a thermal decomposition method, a CVD method, a sputtering method, a vapor deposition method, an ion plating method, or a spray method.
  • the thickness of the transparent conductive film may be, for example, in the range of 200 nm to 1200 nm.
  • the highly transmissive glass according to an embodiment of the present invention is characterized by containing K 2 O in excess of 0.7% in terms of mass percentage. Therefore, it is possible to obtain a transparent conductive film that hardly peels off from the highly permeable glass.
  • FIG. 2 shows a thin film solar cell provided with a highly transmissive glass according to an embodiment of the present invention.
  • the thin film solar cell 100 is configured by disposing an alkali barrier film 130 and a thin film solar cell element 140 on one surface of a glass plate 120.
  • an antireflection film or the like may be provided on the other surface of the glass plate 120 (that is, the surface opposite to the surface on which the thin film solar cell element 140 is formed).
  • the thin film solar cell 100 may be a thin film silicon solar cell or a CdTe thin film solar cell.
  • the alkali barrier film 130 is installed to prevent the sodium ions in the glass plate 120 from diffusing toward the thin film solar cell element 140 during use of the thin film solar cell 100. However, the alkali barrier film 130 may be omitted.
  • the thin film solar cell element 140 is configured by laminating a transparent electrode layer 150, a photoelectric conversion layer (that is, a power generation layer) 160, and a back electrode layer 170 in this order from the side close to the glass plate 120.
  • the transparent electrode layer 150 is made of a transparent conductive film such as tin oxide (SnO 2 ) or ITO.
  • the photoelectric conversion layer 160 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 (eg, chalcopyrite semiconductor, CdTe semiconductor, etc.), an organic semiconductor, and the like.
  • the back electrode layer 170 may be made of, for example, a material that does not transmit light (for example, silver, aluminum, or the like) or a material that transmits light (for example, ITO, SnO 2 , or ZnO).
  • the glass plate 120 is comprised with the highly permeable glass by one Example of this invention which has the above characteristics. That is, the glass plate 120 is characterized by containing K 2 O in excess of 0.7% in terms of mass percentage. For this reason, the glass plate 120 has a significantly high volume resistivity ⁇ and can significantly suppress the movement of sodium ions.
  • FIG. 3 shows a multilayer glass provided with a highly transmissive glass according to an embodiment of the present invention.
  • the multilayer glass 200 is configured by laminating a first glass plate 212A and a second glass plate 212B so that a gap 260 is formed therebetween.
  • a frame-shaped sealing material 265 is disposed around the gap 260, so that the gap 260 can be blocked from the external environment.
  • the first glass plate 212A is configured by laminating an alkali barrier film 240 and a transparent conductive film 250 in this order on a Low-E glass substrate 230 having Low-E (Low Emissivity) performance.
  • the alkali barrier film 240 may be omitted.
  • a low reflection film or the like may be provided on the surface of the second glass plate 212B far from the gap 260.
  • the glass substrate 230 is made of a highly transmissive glass according to an embodiment of the present invention having the above-described characteristics. That is, the glass substrate 230 is characterized by containing K 2 O in excess of 0.7% in terms of mass percentage. For this reason, the glass substrate 230 has a significantly high volume resistivity ⁇ , and can significantly suppress the movement of sodium ions.
  • the multilayer glass 200 provided with such a glass substrate 230 even if the alkali barrier film 240 is not present, peeling of the transparent conductive film 250 from the glass substrate 230 can be significantly suppressed. .
  • Examples 1 to 8 were produced by the method described below, and their characteristics were evaluated.
  • Examples 1 to 6 are examples, and examples 7 to 8 are comparative examples.
  • Example 1 Each raw material was mixed so as to have the composition shown in the column of Example 1 in Table 1 below to prepare a glass raw material.
  • the obtained glass raw material was put in a crucible and heated in an electric furnace at 1500 ° C. for 3 hours to obtain molten glass.
  • the glass plate was manufactured by pouring molten glass on a carbon plate and cooling it. Thereafter, both surfaces of the glass plate were polished to obtain a glass plate having a thickness of 3.2 mm (the glass plate according to Example 1).
  • Example 2 Each raw material was mixed so as to have a composition shown in the column of Example 2 in Table 1 described above to prepare a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 2) was obtained in the same manner as in Example 1.
  • Example 3 Each raw material was mixed so as to have a composition shown in the column of Example 3 in Table 1 described above to prepare a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 3) was obtained in the same manner as in Example 1.
  • Example 4 Each raw material was mixed so that the composition shown in the column of Example 4 in Table 1 was prepared, thereby preparing a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 4) was obtained in the same manner as in Example 1.
  • Example 5 Each raw material was mixed so as to have the composition shown in the column of Example 5 in Table 1 described above to prepare a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 5) was obtained in the same manner as in Example 1.
  • Example 6 Each raw material was mixed so as to have the composition shown in the column of Example 6 in Table 1 described above to prepare a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 6) was obtained in the same manner as in Example 1.
  • Example 7 Each raw material was mixed so as to have a composition shown in the column of Example 7 in Table 1 described above to prepare a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 7) was obtained in the same manner as in Example 1.
  • Example 8 Each raw material was mixed so as to have a composition shown in the column of Example 8 in Table 1 described above to prepare a glass raw material. Thereafter, a glass plate having a thickness of 3.2 mm (a glass plate according to Example 8) was obtained in the same manner as in Example 1.
  • the energy transmittance was measured using the glass samples according to Examples 1 to 8.
  • the energy transmittance was measured by LAMBDA950 manufactured by PerkinElmer.
  • the “energy transmittance” is the total solar energy transmittance defined in ISO 9050: 2003 (E).
  • the amount of divalent iron in the glass plate necessary for the calculation of Redox was determined by conversion from the transmittance at a wavelength of 1000 nm obtained by measuring the transmittance.
  • volume resistivity measurement The volume resistivity ⁇ of the glass plates according to Examples 1 to 8 was measured. The volume resistivity ⁇ was measured by a method based on ASTM C657-78.
  • a metal Al film was formed by vapor deposition on both surfaces of each glass plate having a size of about 50 mm ⁇ about 50 mm, and these were used as electrodes for measurement. Moreover, the measurement was implemented in the state which hold
  • Example 1 The measurement results are summarized in Table 1 above. Examples 1 to 7 are predicted values, and Example 8 is an actually measured value.
  • DHB test A DHB test was performed using the glass plates according to Examples 1 to 8.
  • the DHB test is an abbreviation of the Dump Heat Bias test, and in this test, it is possible to grasp the peel resistance of the transparent conductive film installed on the surface of the glass plate.
  • DHB test is conducted as follows.
  • a glass plate (sample) with a transparent conductive film is prepared.
  • the voltage application device has two electrodes (anode / cathode) and the sample is placed between the two electrodes.
  • the anode is made of a graphite plate
  • the cathode is made of a copper plate coated with aluminum.
  • the sample is placed so that the transparent conductive film side is in contact with the anode and the exposed surface side of the glass plate is in contact with the cathode.
  • a voltage is applied between both electrodes, that is, the sample.
  • the applied voltage is 500 V
  • the application time is 15 minutes.
  • the sample is exposed to the transparent conductive film side of the sample in a high temperature / high humidity environment for 1 hour.
  • the water temperature is 55 ° C.
  • the environmental temperature is 50 ⁇ 2 ° C.
  • the relative humidity of the environment is 100%.
  • This operation was performed in a sealed container, and water was kept at the above water temperature at the bottom of the container, and the conductive thin film portion of the sample placed at the top of the container was kept at the above aggregation temperature.
  • the vaporization temperature represents the temperature of the vapor in the container.
  • Such a test is performed by changing the sample temperature at the time of voltage application, and the maximum temperature at which the transparent conductive film of the sample does not peel is defined as the maximum endurance temperature Tmax (° C.).
  • the maximum durable temperature Tmax (° C.) measured by such a DHB test is an index of the peel resistance of the transparent conductive film formed on the sample, that is, the higher the maximum durable temperature Tmax (° C.), the more the glass plate It can be considered that good adhesion is made between the transparent conductive film and the transparent conductive film.
  • a sample having a TiO 2 film, a SiO 2 film, and a tin oxide (SnO 2 ) film formed on one surface of the glass plates according to Examples 1 to 8 was used as a sample for the DHB test.
  • the tin oxide film was prepared by heating the glass plates according to Examples 1 to 8 to 580 ° C., and then by CVD, an 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 thickness of 550 nm.
  • a transparent conductive film made of SnO 2 was formed.
  • Example 8 having a low K 2 O content has a low temperature T max at which peeling of the transparent conductive film occurs in the DHB test.
  • the temperature T max at which peeling of the transparent conductive film occurs is increased in the DHB test, It was found that peeling of the transparent conductive film from the alkali barrier film can be suppressed over a long period of time.
  • the present invention can be used, for example, for solar cell panels and low reflection glass (Low-E glass).

Abstract

L'invention concerne un verre hautement perméable qui est caractéristique en ce qu'il contient, en pourcentage en masse, plus de 0.7% de K2O, et au maximum 0,03% de fer total en termes de Fe2O3.
PCT/JP2013/082698 2012-12-07 2013-12-05 Verre hautement perméable WO2014088066A1 (fr)

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CN201380063616.7A CN104918895A (zh) 2012-12-07 2013-12-05 高透射性玻璃
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016115880A (ja) * 2014-12-17 2016-06-23 積水化学工業株式会社 有機無機ハイブリッド太陽電池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0585768A (ja) * 1991-03-22 1993-04-06 Pilkington Plc 硼珪酸ガラス組成
WO2000014021A1 (fr) * 1998-09-04 2000-03-16 Nippon Sheet Glass Co., Ltd. Verre clair a facteur de transmission eleve et son procede de production, plaque de verre a couche electro-conductrice et son procede de production, et article de verre
JP2000226228A (ja) * 1999-02-05 2000-08-15 Corning Inc 太陽電池のカバ―ガラス
WO2001066477A1 (fr) * 2000-03-06 2001-09-13 Nippon Sheet Glass Co., Ltd. Verre plat a coefficient de transmission eleve
WO2009060871A1 (fr) * 2007-11-06 2009-05-14 Asahi Glass Company, Limited Plaque de verre pour substrat
JP2011256102A (ja) * 2010-06-09 2011-12-22 Schott Ag 特殊清澄法による透明ガラスまたは透明引上げガラスの製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7087307B2 (en) * 2001-12-28 2006-08-08 Nippon Sheet Glass Company, Limited Glass sheet and glass sheet photoelectric converter device
FR2937798B1 (fr) * 2008-10-24 2010-12-24 Saint Gobain Substrat verrier avec electrode notamment destine a un dispositif a diode electroluminescente organique
FR2972446B1 (fr) * 2011-03-09 2017-11-24 Saint Gobain Substrat pour cellule photovoltaique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0585768A (ja) * 1991-03-22 1993-04-06 Pilkington Plc 硼珪酸ガラス組成
WO2000014021A1 (fr) * 1998-09-04 2000-03-16 Nippon Sheet Glass Co., Ltd. Verre clair a facteur de transmission eleve et son procede de production, plaque de verre a couche electro-conductrice et son procede de production, et article de verre
JP2000226228A (ja) * 1999-02-05 2000-08-15 Corning Inc 太陽電池のカバ―ガラス
WO2001066477A1 (fr) * 2000-03-06 2001-09-13 Nippon Sheet Glass Co., Ltd. Verre plat a coefficient de transmission eleve
WO2009060871A1 (fr) * 2007-11-06 2009-05-14 Asahi Glass Company, Limited Plaque de verre pour substrat
JP2011256102A (ja) * 2010-06-09 2011-12-22 Schott Ag 特殊清澄法による透明ガラスまたは透明引上げガラスの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016115880A (ja) * 2014-12-17 2016-06-23 積水化学工業株式会社 有機無機ハイブリッド太陽電池

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