CN115093128A - Glass substrate with film and method for producing same - Google Patents
Glass substrate with film and method for producing same Download PDFInfo
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- CN115093128A CN115093128A CN202210718437.3A CN202210718437A CN115093128A CN 115093128 A CN115093128 A CN 115093128A CN 202210718437 A CN202210718437 A CN 202210718437A CN 115093128 A CN115093128 A CN 115093128A
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- 239000011521 glass Substances 0.000 title claims abstract description 167
- 239000000758 substrate Substances 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 17
- 239000006060 molten glass Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010583 slow cooling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000006124 Pilkington process Methods 0.000 claims description 4
- 239000005344 low-emissivity glass Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 106
- 238000002834 transmittance Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910004613 CdTe Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 239000005357 flat glass Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000572 ellipsometry Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002202 sandwich sublimation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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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
- C03C17/3429—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 at least one of the coatings being a non-oxide coating
- C03C17/3441—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 at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
-
- 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
-
- 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
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- Engineering & Computer Science (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Surface Treatment Of Glass (AREA)
- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to a glass substrate with a film and a method for manufacturing the same. A film-provided glass substrate comprising a glass substrate, an undercoat layer and a functional transparent film in this order, wherein the undercoat layer comprises, in this order from the glass substrate side, an SiOxCy layer and SiO 2 The layers are formed.
Description
The application is a divisional application of Chinese patent application with an application number of 202010655792.1, namely 7/9/2020.
Technical Field
The present invention relates to a film-coated glass substrate and a method for manufacturing the same, and more particularly to a film-coated glass substrate which is a transparent electrode substrate or Low-emissivity (Low-E) glass used for a solar cell.
Background
Glass substrates with films have properties such as transparency, chemical stability, high hardness, heat resistance, insulation properties, and excellent optical properties, and therefore are used in various fields such as optical components, electrical components, and electronic components, in addition to window glass materials as building members.
For example, in a solar cell, a glass substrate with a film is used as a transparent electrode substrate in which a transparent conductive film is formed on a surface of a glass substrate. In the field of construction, Low emissivity glass (Low-E glass) having heat insulating properties and heat insulating properties imparted thereto by forming an oxide film or a metal film on the surface of a glass substrate is used.
However, due to high-temperature heat treatment and long-term use in manufacturing a solar cell, alkali ions diffuse from the glass substrate. This may cause deterioration in performance such as a decrease in transparency, a decrease in conductivity (increase in resistivity), and a decrease in chemical and physical durability of the transparent conductive film or the metal oxide film (hereinafter referred to as a functional transparent film).
In view of the above, patent document 1 discloses a conductive glass in which an alkali barrier film for suppressing alkali diffusion from an alkali-containing glass and a conductive film are sequentially stacked on a surface of the glass, wherein the alkali barrier film is an oxide film containing tin and silicon as main components.
In addition, patent document 2 also discloses, as a base film, a base film containing silicon, oxygen, and carbon as a film having barrier properties in order to prevent diffusion of an alkali component from a glass plate to a transparent conductive film.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. H06-191894
Patent document 2: japanese patent laid-open publication No. 2005-029463
Disclosure of Invention
Problems to be solved by the invention
However, SiO is used 2 When the functional transparent film is used as an undercoat layer for preventing diffusion of alkali, not only reflection of light due to a difference in refractive index from the functional transparent film causes a decrease in transmittance, but also color development of glass due to the reflection may be observed.
Further, when SiOxCy containing silicon, oxygen, and carbon is used as an undercoat layer, it decomposes to release carbon when left in a high-temperature environment such as a film formation process temperature in manufacturing a solar cell, a heat strengthening treatment of Low-E glass, or the like, because of Low heat resistance. Since the elements of the functional transparent film are extracted by the desorbed carbon, the composition of the functional transparent film changes, and the properties such as electrical conductivity and heat radiation property are degraded. Further, when exposed to a severe environment such as a higher temperature and a longer time, the undercoat layer itself is broken and peeled off.
Accordingly, an object of the present invention is to provide a film-coated glass substrate which has high transmittance, i.e., Low reflectance, can freely control color tone, and has excellent heat resistance, and which can be used as a transparent electrode substrate for a solar cell or Low-E glass.
Means for solving the problems
The present invention relates to the following [1] to [6 ].
[1]A film-coated glass substrate comprising a glass substrate, an undercoat layer and a functional transparent film in this order, wherein the undercoat layer comprises, in this order from the glass substrate side, an SiOxCy layer and an SiO 2 The layers are formed.
[2]As described above [1]The glass substrate with the film is characterized in that the thickness of the SiOxCy layer is 10-90 nm, and the Si layer is made of SiO 2 The thickness of the layer is 10nm to 90 nm.
[3]As described above [1]Or [ 2]]The glass substrate with a film, wherein the functional transparent film comprises SnO as a main component 2 。
[4] A solar cell comprising the film-provided glass substrate according to any one of [1] to [3] as a transparent electrode substrate.
[5] A Low-emissivity (Low-E) glass, wherein the Low-emissivity glass comprises the film-attached glass substrate according to any one of [1] to [3] above.
[6]A method for manufacturing a glass substrate with a film by using a float process, the method comprising: the method for manufacturing the glass ribbon comprises a melting step of heating glass raw materials to obtain molten glass, a fining step of removing bubbles from the molten glass, a forming step of forming the molten glass from which the bubbles have been removed into a plate shape to obtain a glass ribbon, and a slow cooling step of slowly cooling the glass ribbon to room temperature, wherein a film forming step is included between the forming step and the slow cooling step, and in the film forming step, a SiOxCy layer and a SiO are continuously formed on the surface of the glass ribbon in this order by an in-line CVD method 2 A layer and a functional transparent film.
Effects of the invention
According to the film-coated glass substrate of the present invention, when used as a transparent electrode substrate for a solar cell or Low-E glass, the undercoat layer does not peel off even when exposed to a high-temperature environment, and properties such as high conductivity, Low emissivity, and high light transmittance can be maintained. Further, since the refractive index can be adjusted by changing the composition of the SiOxCy layer constituting the undercoat layer, the color tone of the film-coated glass substrate can be freely controlled.
Drawings
Fig. 1 is a schematic cross-sectional view showing the structure of a glass substrate with a film.
Fig. 2 is a schematic cross-sectional view showing the structure of a CdTe solar cell.
Description of the reference symbols
1 glass substrate with film
10 glass substrate
20 base coat
21 SiOxCy layer
22 SiO 2 Layer(s)
30 functional transparent film
40 n type layer
50 p type layer
60 back electrode
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented within a range not departing from the gist of the present invention. "to" indicating a numerical range is used to include numerical values described before and after the range as a lower limit value and an upper limit value.
< glass substrate with film >
As shown in FIG. 1, the film-equipped glass substrate 1 of the present invention is characterized by comprising a glass substrate 10, an undercoat layer 20 and a functional transparent film 30 in this order, the undercoat layer 20 comprising a SiOxCy layer 21 and a SiO in this order from the glass substrate 10 side 2 Layer 22.
(undercoat layer)
By using a SiOxCy layer and SiO in this order from the glass substrate side 2 The layer structure is used as a primer layer, and the primer layer does not peel off even under a high-temperature environment, and can prevent diffusion of alkali from a glass substrate, and further, can prevent reflection of light and can control the color tone of a glass substrate with a film.
The refractive index of the glass substrate is about 1.4 to about 1.5, whereas the refractive index of the functional transparent film differs depending on the composition thereof, but in the case where the functional transparent film is a film containing a metal oxide as a main component, the refractive index of the functional transparent film is about 2. In contrast, in the SiOxCy layer, the refractive index can be easily controlled by changing the slight difference in the content ratio (y) of carbon C. Therefore, reflection of light can be suppressed, and a glass substrate with a film having high transmittance can be obtained. In addition, when the glass substrate with the film is desired to be colored, the color tone can be controlled.
On the other hand, the SiOxCy layer is easily decomposed by heat, and C is easily diffused and moved under high temperature conditions. In particular, it was found that C diffuses into the functional transparent film in an environment of 600 ℃ or higher, and reduces the conductive substance and the low-emissivity substance as impurities, thereby having an effect of increasing the sheet resistance.
The increase in sheet resistance in a high-temperature environment is a factor of, for example, a significant decrease in solar cell characteristics, because the resistance of the functional transparent film increases when high-temperature treatment such as a process of manufacturing a solar cell is performed. In addition, when the Low-E glass is produced, the Low emissivity substance is reduced, which causes deterioration of Low emissivity.
In contrast, in the present invention, SiO is further formed between the SiOxCy layer and the functional transparent film 2 The layer can suppress diffusion of C and realize high heat resistance without impairing the effects of high transmittance, color tone controllability, and the like obtained from the SiOxCy layer.
In contrast to SiOxCy layers, SiO 2 Since the layer has a dense film quality and high coverage, the diffusion and migration of C can be sufficiently suppressed even in a very thin layer of about 10 nm.
Furthermore, SiO 2 The layer is a flat film having a refractive index of about 1.44 to about 1.50. On the other hand, the SiOxCy layer and SiO are formed so that the SiOxCy layer has irregularities on the surface thereof depending on the film formation conditions and the refractive index thereof also greatly changes from 1.54 to 1.75 2 The degree of freedom in changing the refractive index and flatness of the entire structure as needed can be increased by stacking the layers.
The SiOxCy layer can easily change its refractive index by changing a slight difference in the content ratio of carbon C represented by y, and thus can control transmittance and color tone. In SiOxCy, the value of x may be in the range of 1.00 to 1.95, the value of y may be in the range of 0.05 to 1.00, the value of x is preferably 1.85 or less, and further preferably 1.20 or more, and the value of y is preferably 0.15 or more, and further preferably 0.80 or less. In addition, by reducing the ratio represented by y/x, the refractive index can be lowered. Conversely, by increasing the ratio represented by y/x, the refractive index can be increased.
From the viewpoint of sufficient coverage, the thickness of the SiOxCy layer is preferably 10nm or more, and more preferably 20nm or more. The thickness of the SiOxCy layer is preferably 90nm or less from the viewpoint of suppressing the absorption of light. The thickness of the SiOxCy layer can be determined by X-ray photoelectron spectroscopy (XPS) or ellipsometry (spectroscopic measurement method エリプソメトリー).
From the viewpoint of sufficient coverage, SiO 2 The thickness of the layer is preferably 7nm or more, more preferably 10nm or more. In addition, from the viewpoint of optimization of optical design, SiO 2 The thickness of the layer is preferably 90nm or less, more preferably 50nm or less. In addition, SiO 2 The thickness of the layer can be determined by X-ray photoelectron spectroscopy (XPS) or ellipsometry (spectroscopic エリプソメトリー).
(functional transparent film)
The functional transparent film may have at least one of conductivity and low emissivity, and the functional transparent film having low emissivity may be a metal film such as silver, SnO 2 Or ZnO 2 And the like, and therefore also has conductivity.
When the film-coated glass substrate is used as a transparent electrode for a solar cell, the resistivity of the functional transparent film is preferably 0.001 Ω · cm or less, more preferably 0.0008 Ω · cm or less, and still more preferably 0.0006 Ω · cm or less. The lower the resistivity of the functional transparent film, the more preferable, but in practice, the lower the resistivity is 0.0001 Ω · cm or more. In the present specification, the resistivity (R) of the functional transparent film t ) The measurement can be performed on the glass substrate with the film by using a hall effect measurement device.
In the case of using a film-coated glass substrate as the Low-E glass, the emissivity value of the functional transparent film is preferably 0.25 or less, and more preferably 0.20 or less. The lower the emissivity of the functional transparent film, the more preferable, but in practice, the lower the emissivity is 0.05 or more. The emissivity can be measured according to the method defined in JIS R3106: 2019.
The thickness of the functional transparent film is preferably 800nm or less, and more preferably 600nm or less, from the viewpoint of ensuring high transmittance. In addition, the thickness of the functional transparent film is preferably 300nm or more, more preferably 400nm or more, from the viewpoint of not excessively increasing the resistance. The thickness of the functional transparent film can be measured using a stylus type step meter or a fluorescent X-ray analyzer.
In addition, when a film-coated glass substrate is used as a transparent electrode substrate for a solar cell, sheet resistance is important as electrical characteristics of a functional transparent film. This is the resistance of the electrode film substantially defined by the resistivity/film thickness. By adjusting the resistivity and the film thickness, the sheet resistance can be set to a preferable value. The sheet resistance in this case is preferably 20 Ω/□ or less, and more preferably 12 Ω/□ or less, from the viewpoint of reducing voltage loss in the wiring.
The functional transparent film may be constituted by only one layer exhibiting at least one of conductivity and low emissivity and a light-transmitting property (light-transmitting property), and may have another layer having another function, and is not particularly limited.
When a film-coated glass substrate is used as a transparent electrode substrate for a solar cell, a conventionally known functional transparent film can be used as a functional transparent film exhibiting electrical conductivity and light transmittance, and for example, it is preferable that the main component is SnO 2 、ZnO、In 2 O 3 More preferably SnO 2 Or ZnO, more preferably SnO 2 . The main component of the functional transparent film is a content of 50 wt% or more, preferably 70 wt% or more, and more preferably 85 wt% or more, based on the total components constituting the film. The upper limit is not particularly limited, and when the main component is doped with a dopant, the upper limit is preferably 99.9 wt% or less.
As the dopant, F, Sb, Al, Ga, B are preferableSn, etc., preferably in an amount of 0.1 to 5.0 wt%. Examples of the doped film include: fluorine-doped SnO 2 In doped with Sn 2 O 3 In doped with fluorine 2 O 3 Antimony doped SnO 2 Al-doped ZnO, Ga-doped ZnO, and the like. Doping with a dopant generates conductive carriers and makes the resistance low, and is therefore preferable.
When a glass substrate with a film is used as the Low-E glass, a conventionally known functional transparent film can be used as the functional transparent film exhibiting Low emissivity and light transmittance. For example, it is preferable to be composed of a metal film and a protective film or a metal oxide film for protecting the metal film. As the metal film, for example, a film of Ag or the like is preferable. In this case, the protective film is preferably ZnO or SnO 2 And so on. As the metal oxide film, for example, SnO as a main component is preferable 2 、ZnO、In 2 O 3 More preferably SnO 2 Or ZnO, more preferably SnO 2 And may be doped with a dopant. The main component of the film is the same as that of the functional transparent film in the case where the film-attached glass substrate is used as a transparent electrode substrate for a solar cell.
In addition, the same dopant as that used for the functional transparent film in the case of using the film-attached glass substrate as the transparent electrode substrate for a solar cell can be used as the dopant in doping the dopant, and for example, SnO doped with fluorine at a high concentration can be listed 2 Antimony doped SnO 2 And the like.
The composition of the functional transparent film can be identified by X-ray photoelectron spectroscopy (XPS) or Secondary Ion Mass Spectrometry (SIMS).
(glass substrate)
The glass substrate used may be the same glass substrate as that used for conventional transparent electrode substrates for solar cells and Low-E glass. For example, SiO-containing 2 、Al 2 O 3 、B 2 O 3 、MgO、CaO、SrO、BaO、ZrO 2 、Na 2 O and K 2 O as a basic composition. More specifically, it may contain 60 to 75% of SiO in terms of mole percentage based on oxide 2 1 to 7.5 percent of Al 2 O 3 0 to 1% of B 2 O 3 8.5 to 12.5 percent of MgO, 1 to 6.5 percent of CaO, 0 to 3 percent of SrO, 0 to 3 percent of BaO and 0 to 3 percent of ZrO 2 1 to 8 percent of Na 2 O and 2 to 12% of K 2 O glass substrate. However, the glass substrate of the present application is not limited to these compositions.
In consideration of the power generation efficiency of the solar cell and the light transmittance of the Low-E glass, the average transmittance of the glass substrate with respect to light having a wavelength of 500nm to 800nm is preferably 90.3% or more, more preferably 90.4% or more, and still more preferably 90.5% or more in terms of 2mm thickness. The average transmittance can be measured according to the method defined in JIS R3106: 2019.
In addition, the glass substrate preferably has good heat resistance because it may be exposed to a high-temperature environment or subjected to heat treatment when manufacturing a solar cell or when manufacturing Low-E glass.
Specifically, the glass transition temperature (Tg) is preferably 640 ℃ or higher, more preferably 645 ℃ or higher, and still more preferably 655 ℃ or higher. On the other hand, in order not to excessively increase the viscosity at the time of melting, the glass transition temperature is preferably 750 ℃ or less, more preferably 720 ℃ or less, and further preferably 690 ℃ or less. The glass transition temperature can be measured according to the method defined in JIS K7121-1987.
In addition, from the viewpoint of suppressing warpage of the module during assembly, the average thermal expansion coefficient of the glass substrate at 50 ℃ to 350 ℃ is preferably 70 × 10 -7 /. degree.C.or higher, more preferably 80X 10 -7 Above/° c. On the other hand, from the viewpoint of suppressing peeling or the like, the average thermal expansion coefficient of the glass substrate at 50 ℃ to 350 ℃ is preferably 90 × 10 -7 /. degree.C.or less, more preferably 85X 10 -7 Below/° c. It is to be noted that the average thermal expansion coefficient may be in accordance with JIS R3102-1995.
The thickness of the glass substrate is not particularly limited, but is preferably 0.7mm or more, more preferably 1.1mm or more, and further preferably 6.0mm or less, more preferably 4.0mm or less, from the viewpoint of strength and transmittance.
< method for producing glass substrate with film >
The film-attached glass substrate 1 can be obtained by laminating a SiOxCy layer 21 and SiO as the undercoat layer 20 in this order on the glass substrate 10 2 Layer 22, and functional transparent film 30.
Specifically, the glass substrate can be obtained by a melting step of heating a glass raw material to obtain molten glass, a fining step of removing bubbles from the molten glass, a forming step of forming the molten glass into a plate shape to obtain a glass ribbon, and a slow cooling step of slowly cooling the glass ribbon to a room temperature state. Alternatively, the glass substrate may be produced by forming molten glass into a block, slowly cooling the block, and then cutting and polishing the block.
The above-mentioned steps may be performed by various conventionally known methods. The manufacturing method is not limited to the embodiment, and modifications, improvements, and the like may be appropriately performed within a range in which the object of the present invention can be achieved.
Forming an SiOxCy layer and SiO as an undercoat layer in this order on a glass substrate 2 Layer, and then forming a functional transparent film.
The undercoat layer and the functional transparent film can be formed by a CVD (Chemical Vapor Deposition) method, a sputtering method, an electroless plating method, a wet coating method, or the like. The sputtering method is a method for forming a film on a glass substrate to be manufactured, and the chemical plating method is a method for manufacturing a mirror.
Among them, the CVD method is preferable, and the on-line CVD method described later is more preferable.
Specifically, the in-line CVD method is a method for manufacturing a glass substrate with a film using a float process, and includes: a melting step of heating a glass raw material to obtain molten glass, a fining step of removing bubbles from the molten glass, and a step of forming the molten glass from which the bubbles have been removed into a sheet shapeA forming step of obtaining a glass ribbon and a slow cooling step of slowly cooling the glass ribbon to room temperature, and further preferably a film forming step of continuously forming a SiOxCy layer and SiO layer in this order on the surface of the glass ribbon by an in-line CVD method is included between the forming step and the slow cooling step 2 A layer and a functional transparent film.
The in-line CVD method is a kind of CVD method, and is a method of directly forming a film on a surface of glass in a process of manufacturing a glass substrate on a float line. That is, the undercoat layer and the functional transparent film are not formed after the glass substrate is obtained, but formed in the middle of the step of obtaining the glass substrate.
Specifically, in the production of a glass substrate, a glass ribbon is moved over a molten tin bath and then slowly cooled, thereby continuously producing a glass substrate, and a film forming step of an undercoat layer and a functional transparent film is continuously performed on the upper surface of the glass ribbon while the glass ribbon is being moved.
More specifically, in the above-described method for producing a glass substrate, a film-coated glass substrate is obtained by forming an undercoat layer and a functional transparent film while blowing a gas material onto the surface of glass and reacting the gas material while the glass is still hot between the float line and the slow cooling step in the forming step.
The inline CVD method is preferable because it can form an undercoat layer and a functional transparent film in a series of steps for producing a glass substrate, and thus can reduce the production cost. In this case, since the film is formed on-line, the composition of the layer to be formed is limited. For example, when a film-coated glass substrate is used as a transparent electrode substrate of a solar cell, a preferable embodiment includes an undercoat layer comprising a SiOxCy layer and SiO in this order 2 The layer and the functional transparent film are SnO doped with fluorine 2 A film as a main component. In the case of using a film-coated glass substrate as the Low-E glass, a preferable embodiment includes an undercoat layer comprising an SiOxCy layer and SiO layer in this order 2 The layer and the functional transparent film are doped with high concentrationFluorine-doped SnO 2 SnO doped with antimony 2 A film as a main component.
On the other hand, the off-line CVD method is also a kind of CVD method, and is a method of forming an undercoat layer and a functional transparent film by reaction of a gas material while feeding a glass substrate which is manufactured in advance through a glass manufacturing process and cut into an appropriate size into an electric furnace again, similarly to the on-line CVD method. While there is an advantage that the transport speed and the substrate temperature can be set according to the film formation, the manufacturing cost is increased as compared with the in-line CVD method
In the case of using the sputtering method, a very small amount of a special gas is injected into a vacuum chamber, and a voltage is applied to an appropriate sputtering target, whereby an undercoat layer and a functional transparent film are formed on a glass substrate, and a film-coated glass substrate is obtained.
Since the sputtering method forms a layer on a glass substrate on which a plate is previously formed, it is possible to form layers of desired various compositions, although it costs manufacturing.
In the case of the CVD method, the thickness of the undercoat layer and the functional transparent film can be controlled by the kind of the raw material, the concentration of the raw material gas, the blowing flow rate of the raw material gas to the glass ribbon or the glass substrate, the substrate temperature, the residence time of the reaction gas from the structure of the coating beam (コーティングビーム), and the like. In the case of the sputtering method, the thickness can be controlled by sputtering time, voltage, or the like.
< solar cell >
The present invention relates to a solar cell having the above film-attached glass substrate as a transparent electrode substrate. The configuration of the transparent electrode substrate is preferably the same as that described in < glass substrate with film >.
The solar cell of the present invention is preferably a solar cell subjected to a heat treatment at a high temperature such as an annealing treatment in the production process thereof, and examples thereof include CdTe solar cells. However, the application to other solar cells is not excluded.
As shown in fig. 2, the CdTe solar cell has a structure in which an n-type layer 40, a p-type layer 50, and a back surface electrode (anode) 60 are sequentially stacked on the surface of a functional transparent film 30 of a glass substrate with a film as a transparent electrode substrate.
In the case of CdTe solar cells, an n-type layer is formed on the surface of the transparent electrode substrate on the surface layer side, and conventionally known n-type layers can be used as the n-type layer.
The thickness of the n-type layer is preferably 30nm or more, and preferably 100nm or less.
The n-type layer can be formed by a close space sublimation method, and the thickness and the film quality of the n-type layer can be adjusted by changing the sublimation speed or the temperature of the substrate.
The p-type layer is typically CdTe. The thickness of the p-type layer is preferably 3 μm or more, and preferably 15 μm or less.
The p-type layer can be formed by a close space sublimation method, and the thickness and the film quality of the p-type layer can be adjusted by changing the sublimation speed or the temperature of the substrate.
The back electrode functions as an anode, and a conventionally known back electrode can be used. Examples of the electrode include an electrode having a structure in which metal material films of silver (Ag), molybdenum (Mo), or the like are stacked, and a carbon electrode doped with Cu. In addition, a back plate glass may be further provided on the back electrode. The back sheet glass may have water resistance and oxygen permeation resistance, and a back film containing a resin may be used instead of the back sheet glass.
The back electrode and the back plate glass or the back film are bonded together by resin encapsulation (resin encapsulation) or a resin for bonding.
The thickness of the back electrode is preferably 100nm or more, and preferably 1000nm or less. The thickness of the back sheet glass or the back film is preferably 1mm or more, and preferably 3mm or less.
The end of the p-type layer containing CdTe or the end of the CdTe solar cell can be sealed. Examples of the material for sealing include glass having the same composition as the glass substrate in the transparent electrode substrate, glass having another composition, and resin.
< Low-E glass >
The present invention relates to a Low-E glass comprising the above glass substrate with a film. The preferred embodiment of the Low-E glass is the same as that described in < glass substrate with film >.
Namely, the Low-E glass is formed by sequentially forming an SiOxCy layer and SiO on the surface of a glass substrate 2 The glass obtained by laminating the functional transparent film and the functional transparent film may be a conventionally known film, and may be composed of, for example, a metal film and a protective film for protecting the metal film, or may be composed of a metal oxide film.
[ examples ]
The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
[ example 1]
As shown below, the undercoat layer and the functional transparent film were formed by an in-line atmospheric pressure CVD (chemical vapor deposition) method while the glass substrate was produced by the float method, thereby obtaining a film-attached glass substrate.
Molten glass comprising soda-lime-silica glass is poured into a float furnace at 1500 to 1600 ℃ and a sheet glass is formed while continuously flowing a glass ribbon.
Monosilane (SiH) was supplied from the first coating beam located on the most upstream side of the glass ribbon at a temperature of 700 ℃ 4 )0.538 kg/hr, 1.07 kg/hr of ethylene, CO 2 A SiOxCy layer having a film thickness of 55nm was formed on the glass ribbon by using 10.9 kg/hr of gas and 4.90 kg/hr of nitrogen gas.
Next, 0.12 kg/hr of monosilane, 0.36 kg/hr of ethylene, and CO were supplied from a second coating beam located on the downstream side of the glass ribbon at 620 ℃ 2 Gas 30.0 kg/hr and nitrogen 1.0 kg/hr to form SiO with a film thickness of 10nm 2 And (3) a layer.
Further, a mixed gas containing monobutyl tin trichloride, oxygen, water, nitrogen and trifluoroacetic acid was supplied from a third coating beam located immediately downstream thereof to form SnO having a film thickness of 400nm 2 : f (fluorine-doped tin film) as a component. The mixed gas is a gas supplied in a liquid or gaseous stateAnd a mixed gas obtained by mixing the raw materials with a mixer while heating and vaporizing the raw materials. The amounts of the respective raw materials supplied from the third coating beam were 20.5L/hr (liquid phase) of monobutyltin trichloride and 35.7Nm of oxygen gas 3 Hour, 88.6 kg/hour of water, 4.9L/hour of trifluoroacetic acid (liquid phase). The thickness of the glass substrate with film was 3.2 mm.
[ example 2]
The amount of each raw material supplied from the first coating beam was changed to: 0.553 kg/h monosilane, 1.90 kg/h ethylene, CO 2 A SiOxCy layer having a film thickness of 45nm was formed on the glass ribbon with 5.69 kg/hr of gas and 10.8 kg/hr of nitrogen gas, and the amounts of the respective raw materials supplied from the second coating beam were changed: monosilane 0.23 kg/hr, ethylene 0.73 kg/hr, CO 2 Gas (30.0 kg/hr) and nitrogen (0.588 kg/hr) were added to form SiO with a film thickness of 20nm 2 A film-coated glass substrate was obtained in the same manner as in example 1 except for the layer.
Comparative example 1
Without film formation from the first coating beam, 0.12 kg/hr of monosilane, 0.36 kg/hr of ethylene, and CO were supplied from the second coating beam 2 Gas 30.0 kg/hr and nitrogen 1.0 kg/hr to form SiO with a film thickness of 10nm 2 A film-coated glass substrate was obtained in the same manner as in example 1 except for the layer.
Comparative example 2
The amount of each raw material supplied from the second coating beam was changed without performing film formation from the first coating beam: monosilane 0.23 kg/hr, ethylene 0.73 kg/hr, CO 2 Gas (30.0 kg/hr) and nitrogen (0.588 kg/hr) were added to form SiO film having a thickness of 20nm 2 A film-coated glass substrate was obtained in the same manner as in example 1 except for the layer.
Comparative example 3
Supplying monosilane (SiH) from the first coating beam 4 )0.538 kg/hr, 1.07 kg/hr of ethylene, CO 2 A belting film was obtained in the same manner as in example 1, except that a SiOxCy layer having a film thickness of 55nm was formed on the glass ribbon with 10.9 kg/hr of gas and 4.90 kg/hr of nitrogen gas, and no film was formed from the second coating beamA glass substrate of the film.
Comparative example 4
The amount of each raw material supplied from the first coating beam was changed to: 0.553 kg/h monosilane, 1.90 kg/h ethylene, CO 2 A film-coated glass substrate was obtained in the same manner as in example 1, except that a SiOxCy layer having a film thickness of 45nm was formed on the glass ribbon with 5.69 kg/hr of gas and 10.8 kg/hr of nitrogen gas, and the film was not formed on the second coating beam.
With respect to each of the obtained film-attached glass substrates, evaluations were made with respect to transmittance, 650 ℃ heat resistance, and refractive index of the SiOxCy layer under the following conditions. The results are shown in Table 1.
(transmittance)
The measured light was made incident on the film-attached glass substrate from the glass substrate side by using a spectrophotometer Lambda950 (manufactured by perkin elmer), the transmittance was measured every 2nm in the wavelength range of 300nm to 1280nm, and the average value of the transmittances in the wavelength range of 400nm to 800nm was taken as the representative value of the transmittances.
(650 ℃ C. Heat resistance (resistance change ratio))
The glass substrate with the film was cut into a size of 1cm square, and a sheet resistance value before heating was measured using a hall effect measuring apparatus (HL 5500PC, produced by incident Optical Technologies). Subsequently, the belt conveyor furnace (manufactured by DENKO) was set to 650 ℃ and heated for 116 minutes while being conveyed at a speed of 11.2 mm/minute. Nitrogen gas is continuously supplied into the furnace, and an atmosphere having an oxygen concentration of 10ppm or less is maintained. After heating, the sheet resistance value (sheet resistance value after heating) was measured again by the same method as described above, and from these results, a value represented by (sheet resistance value after heating)/(sheet resistance value before heating) was obtained as the 650 ℃ heat resistance (resistance change ratio). The value of the 650 ℃ heat resistance (resistance change ratio) is 1 or more, and the closer the value is to 1, the higher the heat resistance is.
(refractive index of SiOxCy layer)
The obtained glass substrate with film was treated with 10 wt% hydrochloric acid aqueous solution and zinc powderLine etching treatment to remove SnO 2 : f (fluorine-doped tin film) as a component. Then, the film was washed with water and dried by an ultrasonic cleaner, and the refractive index of the SiOxCy layer constituting the glass substrate with the film was measured by an ellipsometer (spectroscopic エリプソメトリー) M-2000I (manufactured by j.a. woollam corporation).
TABLE 1
As shown in Table 1, it was found that the film had an SiOxCy layer and SiO layer in this order by formation 2 The glass substrate with a film, which has a layer as a primer layer, has excellent heat resistance while maintaining a high transmittance of 82% or more.
Industrial applicability
The film-coated glass substrate of the present invention has high transmittance, can control the refractive index, that is, the color tone, and is excellent in heat resistance, and therefore is very useful as a transparent electrode substrate for a solar cell or Low-E glass.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. The present application is based on japanese laid-open application No. 2019-130304, filed on 12/7/2019, the contents of which are incorporated herein by reference.
Claims (4)
1. A film-coated glass substrate comprising a glass substrate, an undercoat layer and a functional transparent film in this order, wherein the undercoat layer comprises, in this order from the glass substrate side, an SiOxCy layer and an SiO 2 A layer, and the main component of the functional transparent film is SnO 2 。
2. A solar cell, wherein the solar cell has the film-equipped glass substrate according to claim 1 as a transparent electrode substrate.
3. A Low emissivity (Low-E) glass, wherein the Low emissivity glass comprises the film bearing glass substrate of claim 1.
4. A method for producing a glass substrate with a film by a float process, wherein,
the method for manufacturing a glass substrate with a film includes: a melting step of heating a glass raw material to obtain molten glass, a fining step of removing bubbles from the molten glass, a forming step of forming the molten glass from which the bubbles have been removed into a sheet to obtain a glass ribbon, and a slow cooling step of slowly cooling the glass ribbon to room temperature, wherein the steps of melting, fining and cooling are performed in such a manner that the glass ribbon is gradually cooled to room temperature
A film forming step of successively forming an SiOxCy layer and an SiO layer on the surface of the glass ribbon by an in-line CVD method, wherein a film forming step of successively forming the SiOxCy layer and the SiO layer on the surface of the glass ribbon is included between the forming step and the slow cooling step 2 A layer and a functional transparent film.
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| JP2019130304A JP7020458B2 (en) | 2019-07-12 | 2019-07-12 | Glass substrate with film and its manufacturing method |
| CN202010655792.1A CN112209627A (en) | 2019-07-12 | 2020-07-09 | Glass substrate with film and method for producing same |
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| JP2929779B2 (en) * | 1991-02-15 | 1999-08-03 | トヨタ自動車株式会社 | Water-repellent glass with carbon coating |
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