CN104603076A - Glass substrate for solar cell and solar cell using same - Google Patents
Glass substrate for solar cell and solar cell using same Download PDFInfo
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- CN104603076A CN104603076A CN201380046844.3A CN201380046844A CN104603076A CN 104603076 A CN104603076 A CN 104603076A CN 201380046844 A CN201380046844 A CN 201380046844A CN 104603076 A CN104603076 A CN 104603076A
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- China
- Prior art keywords
- glass substrate
- glass
- solar batteries
- solar cell
- substrate used
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- 239000011521 glass Substances 0.000 title claims abstract description 306
- 239000000758 substrate Substances 0.000 title claims abstract description 218
- 238000004031 devitrification Methods 0.000 claims abstract description 30
- 229910004613 CdTe Inorganic materials 0.000 claims description 47
- 239000006059 cover glass Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000007704 transition Effects 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- 230000009477 glass transition Effects 0.000 abstract description 8
- 238000010248 power generation Methods 0.000 abstract description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 89
- 239000011734 sodium Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 34
- 239000005357 flat glass Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 238000002844 melting Methods 0.000 description 20
- 230000008018 melting Effects 0.000 description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 238000000576 coating method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 230000033228 biological regulation Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011669 selenium Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 6
- 238000006124 Pilkington process Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000007545 Vickers hardness test Methods 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 238000004151 rapid thermal annealing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000002329 Inga feuillei Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- -1 titanic acid ester Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L31/03923—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 including AIBIIICVI compound materials, e.g. CIS, CIGS
-
- 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
-
- 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
- Y02E10/541—CuInSe2 material PV cells
Abstract
Provided are a glass substrate for a solar cell which satisfies high power generation efficiency, high glass transition temperature, predefined average coefficient of thermal expansion, high glass strength, low glass density and properties of high solubility during glass sheet production, excellent mouldability, excellent devitrification inhibiting properties, and the like in a well balanced manner, and a solar cell using the same. The glass substrate for a solar cell comprises, in terms of mass percentage on an oxide basis, 50 to 65% of SiO2, 8 to 15% of Al2O3, 0 to 1% of B2O3, 0 to 10% of MgO, 1 to 12% of CaO, 6 to 12% of SrO, 0 to 3% of BaO, 1 to 7% of ZrO2, 2 to 8% of Na2O, 0 to 8% of K2O, and 15 to 30% of MgO+CaO+SrO+BaO, where SrO/Na2O is 0.8 to 2.5.
Description
Technical field
The present invention relates to the glass substrate of the solar cell for being formed with photoelectric conversion layer between glass substrate and use the solar cell of this glass substrate.In more detail, relate to the glass substrate of the Cu-In-Ga-Se solar cell or CdTe solar cell etc. of the photoelectric conversion layer etc. for the photoelectric conversion layer or CdTe being formed with Cu-In-Ga-Se between glass substrate, and use the solar cell of this substrate.
Background technology
There is the 11-13 race of chalcopyrite crystalline structure, the light of 12-16 compound semiconductor to the wavelength region from visible ray near infrared light of 11-16 compound semiconductor and isometric system or hexagonal system has larger uptake factor.Therefore, its material as high-level efficiency thin-film solar cells and enjoy expectation.Representatively example, can exemplify Cu (In, Ga) Se
2(being denoted as below " CIGS " or " Cu-In-Ga-Se ") and CdTe.
CIGS thin film solar cell is (following, be called " CIGS solar cell ") and CdTe thin film solar cell is (below, be called " CdTe solar cell ") when, consider from cheap and mean thermal expansion coefficients close to the angle of CIGS compound semiconductor, adopt soda-lime glass as substrate, can solar cell be obtained.
In recent years, as CIGS glass substrate used for solar batteries, also proposed can the glass material (for example, referring to patent documentation 1 ~ 5) of thermal treatment temp of withstand high temperatures.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 11-135819 publication
Patent documentation 2: Japanese Patent Laid-Open 2010-118505 publication
Patent documentation 3: Japanese Patent Laid-Open 8-290938 publication
Patent documentation 4: Japanese Patent Laid-Open 2008-280189 publication
Patent documentation 5: Japanese Patent Laid-Open 2010-267965 publication
Summary of the invention
Invent technical problem to be solved
In CIGS solar cell, CIGS photoelectric conversion layer is formed (hereinafter referred to as " cigs layer "), but when making the good solar cell of generating efficiency between glass substrate, preferably heat-treat with at higher temperature, require that glass substrate can tolerate this temperature.But although propose the higher glass composition of annealing point in patent documentation 1 ~ 4, the invention described in patent documentation 1 ~ 4 can not think necessarily have high generation efficiency.
If be described in detail, in the invention that patent documentation 2,4 is recorded, propose the glass used for solar batteries that DEFORMATION POINTS is high, meet the mean thermal expansion coefficients of regulation.But the technical problem of patent documentation 2 guarantees thermotolerance and improves productivity, the technical problem of patent documentation 4 improves surface quality and improves devitrification resistance, all do not solve the technical problem relating to generating efficiency.For this reason, can not assert that the invention described in patent documentation 2,4 has high generation efficiency.
In addition, in patent documentation 3, propose the high DEFORMATION POINTS glass substrate close with patent documentation 2, but be mainly conceived to plasma display purposes due to it, technical problem is different, therefore can not assert that the invention that patent documentation 3 is recorded has high generation efficiency.
And, in patent documentation 4, propose the glass of the mean thermal expansion coefficients containing more boron oxide, high, the satisfied regulation of DEFORMATION POINTS.But, if there is boron in a large number in glass, then as described in patent documentation 5, as boron diffusion in the cigs layer of p-type semiconductor, work as electron donor, likely make decrease in power generation efficiency.And owing to needing the eliminating equipment of boron, there is the problem easily increasing cost.
In patent documentation 5, although the boron in glass reduces, if the concrete glass recorded forms then generating efficiency deficiency, from the viewpoint of the leeway be improved of improving generating efficiency further.
On the other hand, in order to prevent photoelectric conversion layer (cigs layer) stripping in film process or after film forming on glass substrate, require that glass substrate has the mean thermal expansion coefficients of regulation.
From the viewpoint of manufacture and the use of CIGS solar cell, also require that the intensity of glass substrate improves and lightweight, melting when sheet glass is produced, plasticity are good, not devitrification etc.
But the characteristic such as high melting, good plasticity and good anti-increased devitrification resistance making the glass substrate balance used in CIGS solar cell have well when high generation efficiency, high-alkali diffustivity, high glass transition temperature, the mean thermal expansion coefficients of regulation, high strength of glass, low glass density and sheet glass are produced is difficult.
The object of the invention is to, there is provided a kind of balance to have the characteristics such as high melting, good plasticity and good anti-increased devitrification resistance when high generation efficiency, high-alkali diffustivity, high glass transition temperature, the mean thermal expansion coefficients of regulation, high strength of glass, low glass density and sheet glass are produced well, be applicable to the glass substrate of CIGS solar cell and use the solar cell of this substrate.
The technical scheme that technical solution problem adopts
The present inventor in order to solve the problems of the technologies described above the result conscientiously studied is, in glass substrate used for solar batteries, by being set to specific compositing range, can be made into the glass substrate that balance has the characteristic such as high melting, good plasticity and good anti-increased devitrification resistance when high generation efficiency, high-alkali diffustivity, high glass transition temperature, the mean thermal expansion coefficients of regulation, high strength of glass, low glass density and sheet glass are produced well.
That is, the present invention is as described below.
(1) glass substrate used for solar batteries, wherein, represents with the mass percent of following oxide-base standard, contains:
The SiO of 50 ~ 65%
2,
The Al of 8 ~ 15%
2o
3,
The B of 0 ~ 1%
2o
3,
The MgO of 0 ~ 10%,
The CaO of 1 ~ 12%,
The SrO of 6 ~ 12%,
The BaO of 0 ~ 3%,
The ZrO of 1 ~ 7%
2,
The Na of 2 ~ 8%
2o,
The K of 0 ~ 8%
2o,
MgO+CaO+SrO+BaO is 15 ~ 30%,
SrO/Na
2o is 0.8 ~ 2.5.
(2) glass substrate used for solar batteries as described in above-mentioned (1), wherein, second-order transition temperature is more than 640 DEG C.
(3) glass substrate used for solar batteries as described in (1) or (2), wherein, mean thermal expansion coefficients is 70 × 10
-7~ 90 × 10
-7/ DEG C.
(4) glass substrate used for solar batteries according to any one of (1) ~ (3), wherein, viscosity reaches 10
4temperature (T during dPas
4) be less than 1230 DEG C, viscosity reaches 10
2temperature (T during dPas
2) be less than 1650 DEG C, described T
4with devitrification temperature (T
l) pass be T
4-T
l>=-30 DEG C.
(5) glass substrate used for solar batteries according to any one of (1) ~ (4), wherein, density is 2.75g/cm
3below.
(6) glass substrate used for solar batteries according to any one of (1) ~ (5), wherein, Al
2o
3content be 8.5 ~ 14.5%.
(7) glass substrate used for solar batteries according to any one of (1) ~ (6), wherein, the content of CaO is 3 ~ 11%.
(8) glass substrate used for solar batteries according to any one of (1) ~ (6), wherein, the content of CaO is 3 ~ 10%.
(9) glass substrate used for solar batteries according to any one of (1) ~ (8), wherein, Na
2the content of O is 4 ~ 7%.
(10) glass substrate used for solar batteries according to any one of (1) ~ (9), wherein, the content sum of MgO+CaO+SrO+BaO is 17 ~ 23%.
(11) glass substrate used for solar batteries according to any one of (1) ~ (10), wherein, the content of BaO is less than 2%.
(12) glass substrate used for solar batteries according to any one of (1) ~ (11), wherein, SiO
2and Al
2o
3with formula 9SiO
2+ 15Al
2o
3the content value represented is in the scope of 570% ~ 840%.
(13) glass substrate used for solar batteries according to any one of (1) ~ (12), wherein, Na
2o and K
2o with formula 3Na
2o+2K
2the content value that O represents is in the scope of 14% ~ 44%.
(14) a kind of Cu-In-Ga-Se solar cell, wherein, possess glass substrate, cover glass, be configured in the photoelectric conversion layer of the Cu-In-Ga-Se between described glass substrate and described cover glass, the used for solar batteries glass substrate of at least described glass substrate according to any one of above-mentioned (1) ~ (13) in described glass substrate and described cover glass.
(15) a kind of CdTe solar cell, wherein, possess glass substrate, back-panel glass, be configured in the photoelectric conversion layer of the CdTe between described glass substrate and described back-panel glass, the used for solar batteries glass substrate of at least described glass substrate according to any one of above-mentioned (1) ~ (13) in described glass substrate and described back-panel glass.
The effect of invention
Glass substrate balance used for solar batteries of the present invention has the characteristics such as high melting, good plasticity and good anti-increased devitrification resistance when high generation efficiency, high-alkali diffustivity, high glass transition temperature, the mean thermal expansion coefficients of regulation, high strength of glass, low glass density and sheet glass are produced well.In addition, the glass substrate used for solar batteries of the application of the invention, can provide the solar cell that generating efficiency is high.Glass substrate used for solar batteries of the present invention is especially suitable for Cu-In-Ga-Se solar cell and CdTe solar cell.
Accompanying drawing explanation
Fig. 1 is the sectional view of an example of the embodiment schematically representing the solar cell (CIGS solar cell) using glass substrate used for solar batteries of the present invention.
Fig. 2 represents the solar battery cell (a) and sectional view (b) thereof that make on evaluation glass substrate in embodiment.
Fig. 3 represent by the solar battery cell shown in 8 Fig. 2 side by side, evaluation CIGS solar cell on evaluation glass substrate.
Fig. 4 is the sectional view of an example of the embodiment schematically representing the solar cell (CdTe solar cell) using glass substrate used for solar batteries of the present invention.
Embodiment
< glass substrate > used for solar batteries of the present invention
Below, glass substrate used for solar batteries of the present invention is described.
Glass substrate used for solar batteries of the present invention represents to have with the mass percent of following oxide-base standard: contain
The SiO of 50 ~ 65%
2,
The Al of 8 ~ 15%
2o
3,
The B of 0 ~ 1%
2o
3,
The MgO of 0 ~ 10%,
The CaO of 1 ~ 12%,
The SrO of 6 ~ 12%,
The BaO of 0 ~ 3%,
The ZrO of 1 ~ 7%
2,
The Na of 2 ~ 8%
2o,
The K of 0 ~ 8%
2o,
MgO+CaO+SrO+BaO is 15 ~ 30%,
SrO/Na
2o is the composition of 0.8 ~ 2.5.
The second-order transition temperature (Tg) of glass substrate used for solar batteries of the present invention preferably higher than the second-order transition temperature of soda-lime glass, specifically preferably more than 640 DEG C.When glass substrate used for solar batteries of the present invention is used as the glass substrate of CIGS solar cell or CdTe solar cell, in order to ensure the CIGS in high temperature photoelectric conversion layer (following, by " photoelectric conversion layer of CIGS " referred to as " cigs layer ".) or CdTe photoelectric conversion layer (following, by " photoelectric conversion layer of CdTe " referred to as " CdTe layer ".) formation, second-order transition temperature (Tg) more preferably more than 645 DEG C, preferably more than 650 DEG C further, particularly preferably more than 655 DEG C.In order to viscosity when not making melting excessively rises, be more preferably set to less than 750 DEG C.Preferably less than 720 DEG C further, particularly preferably less than 690 DEG C.
Mean thermal expansion coefficients at 50 ~ 350 DEG C of glass substrate used for solar batteries of the present invention preferably 70 × 10
-7~ 90 × 10
-7/ DEG C.When glass substrate used for solar batteries of the present invention is used as the glass substrate of CIGS solar cell, if lower than 70 × 10
-7/ DEG C or more than 90 × 10
-7/ DEG C, then excessive with the thermal expansion difference of cigs layer, the shortcoming such as to be easily peeling.More preferably 85 × 10
-7/ DEG C below.
For glass substrate used for solar batteries of the present invention, viscosity reaches 10
4temperature (T during dPas
4) and devitrification temperature (T
l) the preferred T of relation
4-T
l>=-30 DEG C.If T
4-T
llower than-30 DEG C, then easily devitrification occurs during forming of flat glass, being formed with of sheet glass may become difficulty.T
4-T
lmore preferably more than-20 DEG C, preferred more than-10 DEG C further, particularly preferably more than 0 DEG C, most preferably more than 10 DEG C.Here, devitrification temperature refers to and glass is kept 17 constantly little within specified temperatures, does not generate the maximum temperature of crystal at glass surface and inside.
If consider the plasticity of sheet glass, i.e. flatness and productive raising, then T
4preferably less than 1230 DEG C.T
4more preferably less than 1220 DEG C, preferably less than 1210 DEG C further.
In addition, for glass substrate used for solar batteries of the present invention, consider the melting of glass and homogeneous raising and productive raising, viscosity reaches 10
2temperature (T during dPas
2) preferably less than 1650 DEG C.T
2more preferably less than 1630 DEG C, preferably less than 1620 DEG C further.
The preferred 2.75g/cm of density of glass substrate used for solar batteries of the present invention
3below.If density is more than 2.75g/cm
3, then the heavier mass of glass substrate and not preferred.Density is 2.73g/cm more preferably
3below, further preferably 2.71g/cm
3below.In addition, when the method using float glass process or scorification etc. conventional manufactures glass substrate, if consider to be located in the glass compositing range that can easily carry out manufacturing, then 2.4g/cm is generally
3above.
The brittleness desired value of glass substrate used for solar batteries of the present invention is preferably lower than 7000m
-1/2.If brittleness desired value is 7000m
-1/2above, then in the manufacturing process of solar cell, glass substrate becomes and easily breaks, thus not preferred.More preferably 6900m
-1/2below, further preferably 6800m
-1/2below, particularly preferably 6700m
-1/2below, 6600m is more preferably
-1/2below.In addition, when the method using float glass process or scorification etc. conventional manufactures glass substrate, if consider to be located in the glass compositing range that can easily carry out manufacturing, then 5000m is generally
-1/2above.
In the present invention, the value (people such as J.Sehgal, J.Mat.Sci.Lett., 14,167 (1995)) that the brittleness desired value of glass substrate used for solar batteries obtains as defining " B " by following formula (1).
C/a=0.0056B
2/3p
1/6formula (1)
Here, P is the press-in load of Vickers indenter, and a, c are the length (comprising the overall length of 2 Cracks of the symmetry of pressure head) of the catercorner length of Vickers indentation and the crackle from corner generation respectively.Adopt size and the formula (1) of the Vickers indentation produced after squeezing into the surface of various glass, calculate brittleness desired value B.
In glass substrate used for solar batteries of the present invention, the reason being defined as above-mentioned composition is as described below.
SiO
2：
SiO
2the composition of the skeleton forming glass, lower than 50 quality % (below, by " quality % " referred to as " % ".Identical below.) time, the thermotolerance of glass substrate and chemical durability may be made to decline, and mean thermal expansion coefficients increases.Preferably more than 52%, more preferably more than 53%, particularly preferably more than 53.5%, further preferably more than 54%.
But, during more than 65%, the problem that high temperature viscosity rises, melting is deteriorated of glass may be produced.Preferably less than 63%, more preferably less than 62%, further preferably less than 61%, particularly preferably less than 59%, be more preferably less than 57.5%.
Al
2O
3：
Al
2o
3improve second-order transition temperature, improve weathering resistance (tanning by the sun property), thermotolerance and chemical durability, improve Young's modulus.If its content is lower than 8%, then second-order transition temperature may be made to reduce.And mean thermal expansion coefficients likely increases.Preferably more than 8.5%, more preferably more than 9%, further preferably more than 10%, particularly preferably more than 11%, be more preferably more than 12%.
But if more than 15%, then the high temperature viscosity of glass likely can be made to increase, melting is deteriorated.In addition, devitrification temperature may be made to increase, plasticity is deteriorated.Preferably less than 14.5%, more preferably less than 14%.
SiO
2and Al
2o
3:
SiO
2and Al
2o
3the composition of the thermotolerance increasing glass substrate, therefore preferred with formula 9SiO
2+ 15Al
2o
3(that is, (SiO
2containing % × 9) and (Al
2o
3containing % × 15) total) in the content value that the represents scope more than 570%.More preferably more than 600%, further preferably more than 630%, particularly preferably more than 660%.But, due to SiO
2and Al
2o
3make the high temperature viscosity of glass increase, have the effect that melting is deteriorated, therefore preferred with formula 9SiO
2+ 15Al
2o
3in the scope of the content value represented below 840%.More preferably less than 800%, further preferably less than 760%, particularly preferably less than 720%.
B
2O
3：
In order to improve melting etc., the B of 1% can be contained at the most
2o
3.If content is more than 1%, then second-order transition temperature likely declines, or mean thermal expansion coefficients likely diminishes, and is not preferred for the technique forming photoelectric conversion layer.In addition, devitrification temperature rises, and easy devitrification, is difficult to carry out forming of flat glass.Preferred content is below 0.5%.More preferably in fact not containing B
2o
3.
In addition, " not containing in fact " refers to and does not contain except the inevitable impurity except being mixed into from raw material etc., does not namely intentionally make it contain.Identical below.
MgO：
MgO is owing to having viscosity when reducing the fusing of glass, promote the effect of fusing and can contain.Preferably more than 1.5%, more preferably more than 1%.If below 10%, then can obtain desired mean thermal expansion coefficients.In addition preferably devitrification temperature does not rise.Preferably less than 7%, more preferably 5%, further preferably less than 3%, particularly preferably less than 2.5%.
CaO：
CaO owing to having viscosity when reducing the fusing of glass, promote the effect of fusing and can containing 1 ~ 12%.Preferably more than 2%, more preferably more than 3%, further preferably more than 4%, particularly preferably more than 5%.But if more than 12%, the mean thermal expansion coefficients of glass substrate likely increases.In addition, sodium (Na) becomes and is difficult to move in glass substrate, may make decrease of power generation.Preferably less than 11%, more preferably less than 10%, further preferably less than 9%, particularly preferably less than 8.5%.
SrO：
SrO owing to having viscosity when reducing the fusing of glass, promote the effect of fusing and can containing 6 ~ 12%.In addition, by containing SrO in glass substrate, when glass substrate used for solar batteries of the present invention is used as the glass substrate of CIGS solar cell, promotion sodium (Na) is had to the effect of the cigs layer diffusion on glass substrate.Preferably more than 6.3%, more preferably more than 6.5%, further preferably more than 7%.But if containing more than 12%, the density of glass substrate increases, and brittleness desired value likely increases.Preferably less than 11%, more preferably less than 10%, further preferably less than 9%, particularly preferably less than 8.5%.
BaO：
BaO is owing to having viscosity when reducing the fusing of glass, promote the effect of fusing and can contain.But if containing more than 3%, the mean thermal expansion coefficients of glass substrate increases, and density increases, and brittleness desired value likely increases.In addition, Young's modulus may be made to reduce.Preferably less than 2.5%, more preferably less than 2%.
ZrO
2：
ZrO
2owing to having viscosity when reducing the fusing of glass, promote the effect of fusing and can containing more than 1%.If below 7%, generating efficiency is good, and the not devitrification even if devitrification temperature rises also, sheet glass is easily shaped.Preferably less than 6%, more preferably less than 5%, further preferably less than 4.5%.In addition, preferably more than 2%, more preferably more than 2.5%, further preferably more than 3%, particularly preferably more than 3.5%.
TiO
2：
If owing to containing TiO
2then devitrification temperature rises, therefore preferably not containing TiO
2.But glass substrate used for solar batteries of the present invention, compared with common soda-lime glass, easily generates alveolar layer dissolving on glass surface when glass substrate manufactures.If generation alveolar layer, then the temperature of melten glass does not rise, and is difficult to become clarification, and productivity has the tendency of variation.In order to make the alveolar layer thinning that generates on molten glass surface or disappearance, the alveolar layer that sometimes can generate on molten glass surface supply is as the titanium compound of defoamer.Titanium compound enters in melten glass, as TiO
2exist.This titanium compound can be inorganic titanium compound (such as, titanium tetrachloride, titanium oxide etc.), also can be organic titanic compound.As organic titanic compound, titanic acid ester or derivatives thereof, titanium chelate or derivatives thereof, acidylate titanium or derivatives thereof, titanous oxalate acid esters etc. can be exemplified.Due to above-mentioned reason, TiO
2allow in glass substrate, to contain 0.2% below as impurity.
MgO, CaO, SrO and BaO:
For MgO, CaO, SrO and BaO, decline from the viscosity during fusing of glass, promote that the aspect of fusing is considered, containing CaO and SrO and can containing being selected from least a kind of MgO and BaO, (that is, the total amount of these alkaline-earth metals oxides (RO) is also referred to as (MgO+CaO+SrO+BaO) for their total amount.) be set to more than 15%.But if total amount is more than 30%, devitrification temperature likely rises, plasticity is deteriorated.Preferably more than 16%, more preferably more than 17%.In addition, preferably less than 26%, more preferably less than 23%, further preferably less than 20%, particularly preferably less than 18%.
Na
2O：
Na
2o improves contributive composition when glass substrate used for solar batteries of the present invention is used as the glass substrate of CIGS solar cell to the generating efficiency of CIGS solar cell, is required composition.In addition, because have the viscosity reduced under glass melting temperature, make glass be easy to the effect melted, it is made to contain 2 ~ 8%.Spread in the cigs layer that sodium (Na) is formed on the glass substrate, can generating efficiency be improved, if but content may be insufficient to the diffusion in the cigs layer on glass substrate lower than 2%, Na, and generating efficiency also may be not enough.Preferred content is more than 3%, and more preferably content is more than 4%.
If Na
2o content more than 8%, then mean thermal expansion coefficients increase, the tendency that has second-order transition temperature to reduce.In addition, the tendency also having chemical durability to be deteriorated.In addition, Young's modulus may be made to reduce.Content preferably less than 7.5%, more preferably less than 7%, further preferably less than 6.5%.
K
2O：
K
2o is owing to having and Na
2the effect that O is identical, makes it contain 0 ~ 8%.But if more than 8%, second-order transition temperature declines, mean thermal expansion coefficients becomes large, and proportion likely becomes large.When containing preferably more than 0.5%, more preferably more than 1%, further preferably more than 3.5%.In addition, preferably less than 7%, more preferably less than 6%, further preferably less than 5%, particularly preferably less than 4.5%.
Na
2o and K
2o:
Na
2o and K
2o improves contributive composition to the generating efficiency of CIGS solar cell.In addition, owing to there being the viscosity reduced under glass melting temperature, the effect that it easily melts is made, preferably with formula 3Na
2o+2K
2o (that is, (Na
2o's contains % × 3) and (K
2o containing % × 2) total) in the content value that the represents scope more than 14%.More preferably more than 16%, further preferably more than 18%, particularly preferably more than 20%.Due to Na
2o and K
2o makes mean thermal expansion coefficients increase, and makes the tendency that second-order transition temperature declines, preferably with formula 3Na
2o+2K
2in the scope of the content value that O represents below 44%.More preferably less than 40%, further preferably less than 36%, particularly preferably less than 32%.
SrO and Na
2the ratio of O:
SrO and Na
2ratio (the SrO/Na of O
2o) more than 0.8 is set to.If relative to Na
2the amount SrO of O is less, then promote when making CIGS solar cell that Na has to the effect of the cigs layer diffusion on glass substrate the tendency weakened.Preferably more than 0.9, more preferably more than 1.0, further preferably more than 1.1.If but more than 2.5, then the proportion of glass substrate is likely excessive.Preferably less than 2.1, more preferably less than 1.8, further preferably less than 1.6, particularly preferably less than 1.4.
Glass substrate used for solar batteries of the present invention is mainly made up of (containing SiO in above-mentioned scope above-mentioned in essence
2, Al
2o
3, B
2o
3, MgO, CaO, SrO, BaO, ZrO
2, Na
2o and K
2the glass of O mainly forms) form, but in the scope not damaging object of the present invention, to count the ratio (Japanese: inside cut り) that above-mentioned glass mainly forms, can according to respectively containing less than 1% and with above-mentioned TiO
2amount to the condition containing less than 5%, containing other compositions following.Such as, in order to improve the object of weathering resistance, melting, increased devitrification resistance, UV-preventing, specific refractory power etc., sometimes ZnO, Li can be contained
2o, WO
3, Nb
2o
5, V
2o
5, Bi
2o
3, MoO
3, P
2o
5deng.
In addition, in order to improve the melting, clarification of glass, can not count the ratio (Japanese: cut り outward) that above-mentioned glass mainly forms, according in glass respectively containing less than 1% and total amount is the SO of less than 2%
3, F, Cl, SnO
2condition, these raw materials are added in main constitutive material.
In addition, in order to improve the chemical durability of glass substrate, in glass to count the ratio that above-mentioned glass mainly forms, can containing the Y counting less than 2% with total amount
2o
3, La
2o
3.
In addition, in glass substrate used for solar batteries of the present invention, in order to ensure transmissivity, improve generating efficiency, relative to above-mentioned main composition (containing SiO in above-mentioned scope
2, Al
2o
3, B
2o
3, MgO, CaO, SrO, BaO, ZrO
2, Na
2o and K
2the glass of O mainly forms) 100 mass parts, preferably according to Fe
2o
3the condition of counting the content of below 0.06 mass parts of converting is to containing ferriferous oxide.More preferably below 0.055 mass parts, further preferably below 0.05 mass parts, particularly preferably below 0.045 mass parts.But, when not limitting transmissivity (situation about such as using as the substrate of CIGS solar cell is inferior), the easness of heating when the raw material few from the viewpoint of use iron level and fusing, relative to above-mentioned main composition 100 mass parts, with Fe
2o
3convert meter, and the content of ferriferous oxide is preferably below 0.2 mass parts, more preferably below 0.15 mass parts, further preferably below 0.12 mass parts.
In addition, if the content of ferriferous oxide is more than 0.01 mass parts, then owing to can use the industrial raw material being inevitably mixed into ferriferous oxide composition, industrial production becomes easy and preferred.In addition, if the content of ferriferous oxide is more than 0.01 mass parts, then because the absorption of radiation during fusing enlarges markedly, the temperature of melten glass becomes easy rising, can not cause the obstacle in manufacture.More preferably more than 0.015 mass parts, further preferably more than 0.02 mass parts.
In addition, in the present invention, as ferriferous oxide, red iron oxide (Japanese: man's cap used in ancient times handle), brown iron oxide etc. can be exemplified.
In addition, if consider environmental pressure, glass substrate used for solar batteries of the present invention is not preferably in fact containing As
2o
3, Sb
2o
3.In addition, stably float forming is carried out if considered, preferably in fact not containing ZnO.But glass substrate used for solar batteries of the present invention is not limited to the shaping adopting float glass process, also can manufacture by adopting the shaping of scorification.
The manufacture method > of < glass substrate used for solar batteries of the present invention
The manufacture method of glass substrate used for solar batteries of the present invention is described.
When manufacturing glass substrate used for solar batteries of the present invention, implement to melt, clarify operation and forming process in the same manner as in time manufacturing glass substrate used for solar batteries in the past.In addition, glass substrate used for solar batteries of the present invention is containing alkalimetal oxide (Na
2o, K
2o) alkali-containing glass substrate, therefore can use SO effectively
3as finings, be applicable to adopting float glass process and scorification (glass tube down-drawing) as manufacturing process.
In the manufacturing process of glass substrate used for solar batteries, as being the method for tabular by forming of glass, along with the maximization of solar cell, preferably using can easily and stably to the float glass process that large-area glass substrate forms.
The preferred configuration of the manufacture method of glass substrate used for solar batteries of the present invention is described.
First, the melten glass obtained by the frit of fusing regulation is configured as tabular.Such as, be the condition preparation raw material of above-mentioned composition according to the glass substrate of gained, above-mentioned raw materials dropped in smelting furnace continuously, is heated to 1550 ~ 1700 DEG C, obtain melten glass.Then, adopt such as float glass process, this melten glass is configured as banded sheet glass.
Then, by the sheet glass of band shape after the pull-out of float forming stove, be cooled to room temperature state by cooling way, after cutting, obtain glass substrate used for solar batteries.
The purposes > of < glass substrate used for solar batteries of the present invention
Glass substrate used for solar batteries of the present invention is owing to having the mean thermal expansion coefficients of regulation, high strength of glass, low glass density, and high melting, good plasticity and good devitrification preventive during sheet glass production, and second-order transition temperature is high, alkali diffustivity is also high, therefore when generating efficiency being contributed to for when CIGS solar cell, CIGS glass substrate used for solar batteries is thus suitable as.
When glass substrate used for solar batteries of the present invention is used for the glass substrate of CIGS solar cell, preferably the thickness of glass substrate is made as below 3mm, more preferably below 2mm, further preferred below 1.5mm.
In addition, the method forming cigs layer is on the glass substrate not particularly limited, but it is high from the viewpoint of second-order transition temperature, Heating temperature when forming cigs layer can be set to 500 ~ 700 DEG C, preferably 550 ~ 700 DEG C, more preferably 580 ~ 700 DEG C, preferably 600 ~ 700 DEG C further, particularly preferably 620 ~ 700 DEG C.
When only glass substrate used for solar batteries of the present invention being used for the glass substrate of CIGS solar cell, cover glass etc. is not particularly limited.As other examples of the composition of cover glass, soda-lime glass etc. can be exemplified.
When glass substrate used for solar batteries of the present invention is used as the cover glass of CIGS solar cell, preferably the thickness of cover glass is set to below 3mm, more preferably below 2mm, further preferred below 1.5mm.
In addition, in the manufacture of CIGS solar cell, be not particularly limited the method for assembling cover glass on the glass substrate with cigs layer, when carrying out heating assembling, its Heating temperature can be set to 500 ~ 700 DEG C, preferably 600 ~ 700 DEG C.
If glass substrate used for solar batteries of the present invention to be used for glass substrate and the cover glass of CIGS solar cell simultaneously, then because mean thermal expansion coefficients is identical, so the thermal distortion etc. when there is not solar cell assembling, preferably.
In addition, glass substrate used for solar batteries of the present invention is owing to having the mean thermal expansion coefficients of regulation, high strength of glass, low glass density, and high melting, good plasticity and good devitrification preventive during sheet glass production, be therefore suitable as CdTe glass substrate used for solar batteries.
Due to the covering (ス ー パ ー ス ト レ ー ト adopted at CdTe solar cell, superstrate) in type structure, glass substrate is exposed to outside, and the glass substrate of the present invention used for solar batteries therefore with high strength of glass is also suitable as CdTe glass substrate used for solar batteries.
In addition, when CdTe layer is formed with high temperature film forming, the generating efficiency of CdTe solar cell can therefore can be conducive to owing to having high glass transition temperature.
When glass substrate used for solar batteries of the present invention is used for the glass substrate of CdTe solar cell, preferably the thickness of glass substrate is set to below 3mm, more preferably below 2mm, further preferred below 1.5mm.In addition, the method forming CdTe layer is on the glass substrate not particularly limited, but it is high from the viewpoint of second-order transition temperature, Heating temperature when forming CdTe layer can be set to 500 ~ 700 DEG C, preferably 550 ~ 700 DEG C, more preferably 580 ~ 700 DEG C, preferably 600 ~ 700 DEG C further, particularly preferably 620 ~ 700 DEG C.
When only glass substrate used for solar batteries of the present invention being used for the glass substrate of CdTe solar cell, back-panel glass etc. is not particularly limited.As other examples of the composition of back-panel glass, soda-lime glass etc. can be exemplified.
When glass substrate used for solar batteries of the present invention is used as the back-panel glass of CdTe solar cell, preferably the thickness of back-panel glass is set to below 3mm, more preferably below 2mm, further preferred below 1.5mm.
In addition, in the manufacture of CdTe solar cell, be not particularly limited the method for assembling back-panel glass on the glass substrate with CdTe layer, when carrying out heating assembling, its Heating temperature can be set to 500 ~ 700 DEG C, preferably 600 ~ 700 DEG C.
If glass substrate used for solar batteries of the present invention to be used for glass substrate and the back-panel glass of CdTe solar cell simultaneously, then because mean thermal expansion coefficients is identical, so the thermal distortion etc. when there is not solar cell assembling, preferably.
< CIGS solar cell of the present invention >
Then, CIGS solar cell of the present invention is described.
CIGS solar cell of the present invention possesses glass substrate, cover glass, is configured in the photoelectric conversion layer of the Cu-In-Ga-Se between above-mentioned glass substrate and above-mentioned cover glass, and in above-mentioned glass substrate and above-mentioned cover glass, at least above-mentioned glass substrate is glass substrate used for solar batteries of the present invention.
Use the following drawings, CIGS solar cell of the present invention is described in detail.In addition, the present invention is not limited to accompanying drawing.
Fig. 1 is the sectional view of an example of the embodiment schematically representing CIGS solar cell of the present invention.In Fig. 1, CIGS solar cell 1 of the present invention comprises glass substrate 5, cover glass 19 and the cigs layer between glass substrate 5 and cover glass 19 9.The preferred above-mentioned illustrated glass substrate of the present invention used for solar batteries of glass substrate 5.Solar cell 1 has the back electrode layer of the Mo film as positive electrode 7 on a glass substrate 5, has cigs layer 9 thereon.The composition of cigs layer can illustrate Cu (In
1-xga
x) Se
2.X represents the ratio of components of In and Ga, 0 < x < 1.
On cigs layer 9, as buffer layer 11, there is CdS (Cadmium Sulfide), ZnS (zinc sulphide) layer, ZnO (zinc oxide) layer, Zn (OH)
2(zinc hydroxide) layer or their mixed crystal layer.Across buffer layer 9, have ZnO or ITO or be doped with the nesa coating 13 of ZnO (AZO) etc. of Al, the Al electrode (aluminium electrode) etc. also had in the above as negative potential 15 takes out electrode.At the needed position of these interlayers, can antireflection film be set.In Fig. 1, between nesa coating 13 and negative potential 15, be provided with antireflection film 17.
In addition, negative potential 15 can arrange cover glass 19, when necessary, resin seal can be carried out by between negative potential and cover glass, or bond with the transparent resin of bonding.Cover glass can use glass substrate used for solar batteries of the present invention.
In the present invention, can by the end part seal of the end of cigs layer or solar cell.As the material for sealing, such as, can exemplify the material identical with glass substrate used for solar batteries of the present invention, other glass, resins etc.
In addition, the thickness of each layer of solar cell shown in the drawings is not by the restriction of accompanying drawing.
CIGS solar cell of the present invention uses glass substrate used for solar batteries of the present invention as glass substrate, in the subordinate phase of the film formation process of cigs layer, by carrying out film forming by under the heating condition of cigs layer more than 500 DEG C, higher generating efficiency can be obtained.The Heating temperature of subordinate phase preferably more than 550 DEG C, more preferably more than 580 DEG C, preferably more than 600 DEG C further, particularly preferably more than 620 DEG C.
Other operations beyond the film formation process of the cigs layer in the manufacture method of CIGS solar cell, such as, the film forming etc. of buffer layer or transparent conductive film layer can be carried out in the mode that the operation of the manufacture method with common CIGS solar cell is identical.
< CdTe solar cell of the present invention >
Then, CdTe solar cell of the present invention is described.
Solar cell of the present invention possesses glass substrate, back-panel glass, is configured in the photoelectric conversion layer (CdTe layer) of the CdTe between above-mentioned glass substrate and above-mentioned back-panel glass, and in above-mentioned glass substrate and above-mentioned back-panel glass, at least above-mentioned glass substrate is glass substrate used for solar batteries of the present invention.Or, also can be the solar cell that use has water tolerance, the notacoria (Japanese: バ ッ Network Off ィ Le system) of oxytolerant perviousness replaces back-panel glass in the formation of above-mentioned solar cell.
Use the following drawings, solar cell of the present invention is described in detail.In addition, the present invention is not limited to accompanying drawing.
Fig. 4 is the sectional view of an example of the embodiment schematically representing CdTe solar cell of the present invention.
In Fig. 4, solar cell of the present invention (CdTe solar cell) 21 possesses the CdTe layer 25 of the glass substrate 22 of thickness 1 ~ 3mm, the back-panel glass 27 of thickness 1 ~ 3mm and the thickness between glass substrate 22 and back-panel glass 27 3 ~ 15 μm.Heating temperature when forming CdTe layer or nesa coating is more than 500 DEG C, preferably more than 550 DEG C, more preferably more than 580 DEG C, preferably more than 600 DEG C further, particularly preferably more than 620 DEG C.Glass substrate 22 is preferably made up of above-mentioned illustrated glass substrate of the present invention used for solar batteries.
CdTe solar cell 21 possesses the nesa coating 23 of thickness 100 ~ 1000nm on glass substrate 22.Heating temperature when forming CdTe layer or nesa coating is more than 500 DEG C, preferably more than 550 DEG C, more preferably more than 580 DEG C, preferably more than 600 DEG C further, particularly preferably more than 620 DEG C.
As nesa coating 23, such as, can exemplify the In being doped with Sn
2o
3or be doped with the In of F
2o
3deng.Nesa coating 23 possesses the buffer layer 24 (such as, CdS layer) of thickness 50 ~ 300nm, this buffer layer 24 possesses CdTe layer 25.And there is the backplate 26 (being such as doped with the carbon dioxide process carbon electrode or Mo electrode etc. of Cu) of 100 ~ 1000nm in CdTe layer 25, overleaf electrode 26 possesses back-panel glass 27.Resin seal or the resin bond with bonding is preferably carried out between backplate 26 and back-panel glass 27.Back-panel glass 27 can use glass substrate used for solar batteries of the present invention.
In the present invention, can by the end part seal of the end of CdTe layer or solar cell.As the material for sealing, such as, can exemplify the material identical with CdTe of the present invention glass substrate used for solar batteries, other glass material, resins etc.
In addition, the thickness of each layer of solar cell shown in the drawings is not by the restriction of accompanying drawing.
Embodiment
Below, by embodiment and Production Example, the present invention will be described in more detail, but the present invention is not limited to these embodiments and Production Example.
Embodiment (example 1 ~ 13,17 ~ 31) and the comparative example (example 14 ~ 16) of glass substrate used for solar batteries of the present invention are shown.
According to the raw material of each composition of glass composition preparation represented in table 1 ~ 4, relative to the raw material of this glass substrate composition of 100 mass parts, add with SO in above-mentioned raw materials
3convert and count the vitriol of 0.1 mass parts, use platinum crucible to heat at the temperature of 1650 DEG C and melt for 3 hours.In addition, in table 1 ~ 4, Fe
2o
3blended amount be expressed as relative to main composition (containing SiO in above-mentioned scope
2, Al
2o
3, B
2o
3, MgO, CaO, SrO, BaO, ZrO
2, Na
2o and K
2the glass of O mainly forms) mass parts of 100 mass parts.
During fusing, insert platinum stirring rod and stir 1 hour, carry out homogenizing of glass.Then, pour out melten glass, cool after being configured as tabular, obtain sheet glass.
Measure the mean thermal expansion coefficients (unit: × 10 of the sheet glass of gained thus
-7/ DEG C), second-order transition temperature T
g(unit: DEG C), density (unit: g/cm
3), brittleness desired value (unit: m
-1/2), viscosity reaches 10
4temperature (T during dPas
4) (unit: DEG C), viscosity reaches 10
2temperature (T during dPas
2) (unit: DEG C), devitrification temperature (T
l) (unit: DEG C), Na diffusing capacity, generating efficiency, be shown in table 1 ~ 4.The measuring method of each physical property is as follows.
In addition, in embodiment, measure sheet glass, each physical property is identical value in sheet glass with glass substrate.By implementing processing, grinding to the sheet glass of gained, glass substrate can be made.
The mean thermal expansion coefficients of (1) 50 ~ 350 DEG C:
This mean thermal expansion coefficients uses differential dilatometer (TMA) to measure, and obtains according to the standard of JIS R3102 (nineteen ninety-five degree).
(2)Tg：
Tg is the value recorded with TMA, obtains according to the standard of JIS R3103-3 (calendar year 2001 degree).
(3) density:
Density by Archimedes method to cut out from sheet glass, do not measure containing the glass block of about 20g of bubble.
(4) brittleness desired value:
Brittleness desired value is size and the above formula (1) of the Vickers indentation utilizing the surface squeezing into aforesaid various sheet glass to produce afterwards, calculates brittleness desired value.
(5) viscosity:
Viscosity uses rotational viscosimeter to measure, and reaches 10 to viscosities il
2temperature T during dPas
2(reference temperature of melting) and viscosities il reach 10
4temperature T during dPas
4(reference temperature of plasticity) measures.
(6) devitrification temperature (T
l):
Devitrification temperature is placed in platinum ware by the glass block 5g cut out from sheet glass, keeps 17 hours in electric furnace.Using the glass block after maintenance, the Schwellenwert of the surperficial and inner not temperature of crystallize out is as devitrification temperature.
(7) generating efficiency:
Generating efficiency is that the sheet glass of gained is used for solar cell substrate, as described belowly manufactures evaluation solar cell, uses this evaluation solar cell to carry out the evaluation of generating efficiency.Result is shown in table 1 ~ 4.
For the manufacture of evaluation solar cell, use below Fig. 2,3 and symbol be described.
In addition, the Rotating fields of evaluation solar cell is except the cover glass 19 without the solar cell of Fig. 1 and antireflection film 17, almost identical with the Rotating fields of the solar cell shown in Fig. 1.
The sheet glass of gained is processed into size is 3cm × 3cm, thickness is the glass substrate of 1.1mm.On glass substrate 5a, Mo (molybdenum) film as positive electrode 7a is formed with sputter equipment.Film forming is at room temperature implemented, and obtains the Mo film that thickness is 500nm.
On positive electrode 7a (Mo film), with sputter equipment with CuGa alloys target film forming for CuGa alloy layer, then use In target film forming to be In layer, form the precursor film of In-CuGa by this.Film forming is at room temperature implemented.With make the composition of the precursor film recorded by fluorescent X-ray become Cu/ (Ga+In) than be 0.8, Ga/ (Ga+In) adjusts the thickness of each layer than the condition being 0.25, obtaining thickness is the precursor film of 650nm.
RTA (Rapid Thermal Annealing: rapid thermal annealing) device is used to carry out heat treated under argon and Selenium hydride mixed atmosphere (relative to argon, Selenium hydride is 5 volume %) to precursor film.First, as the first stage, keep 10 minutes in 500 DEG C, make Cu, In and Ga and Se reaction, then, as subordinate phase, then keep 30 minutes in 580 DEG C, make CIGS crystal growth, thus obtain cigs layer 9a.The thickness of the cigs layer 9a of gained is 2 μm.
By CBD (Chemical Bath Deposition: chemical bath deposition) method, on cigs layer 9a, film forming is the CdS layer as buffer layer 11a.Specifically, first, in beaker, the thiocarbamide of the Cadmium Sulphate of concentration 0.01M, concentration 1.0M, the ammonia of concentration 15M and pure water are mixed.Then, be dipped in by cigs layer in above-mentioned mixed solution, each beaker put into the thermostatic bath in advance water temperature being adjusted to 70 DEG C, film forming is the CdS layer of 50 ~ 80nm.
Then, with sputter equipment on CdS layer more by the following method film forming be nesa coating 13a.First, use ZnO target film forming to be ZnO layer, then, use AZO target (containing the Al of 1.5 % by weight
2o
3znO target) film forming is AZO layer.The film forming of each layer is at room temperature implemented, and obtains the double-deck nesa coating 13a that thickness is 480nm.
By the aluminium film (here, U-shaped electrode length is vertical 8mm, horizontal 4mm, electrode width 0.5mm) that the EB vapour deposition method thickness formed on the AZO layer of nesa coating 13a as the negative potential 15a of U-shaped is 1 μm.
Finally, from nesa coating 13a side scraping to cigs layer 9a, blocking is as shown in Figure 2 carried out with mechanical scribe (Japanese: メ カ ニ カ Le ス Network ラ イ Block).Fig. 2 (a) A-A ' sectional view that to be the figure observing 1 solar battery cell from above, Fig. 2 (b) be in Fig. 2 (a).The width of a unit is 0.6cm, length is 1cm, and the area outside removing negative potential 15a is 0.5cm
2, as shown in Figure 3, one piece of glass substrate 5a can obtain 8 unit altogether.
At solar simulator, (under mountain, DENSO Corporation (Shan Xiaelectricityzhuan Co., Ltd.) is made, evaluation CIGS solar cell (namely, being manufactured with the evaluation glass substrate 5a of above-mentioned 8 unit) is set YSS-T80A), positive terminal (not shown) is connected on voltage generator by the positive electrode 7a being coated with InGa solvent in advance, in the lower end of the U-shaped of negative potential 15a, negative terminal 16a is connected on voltage generator.With temperature adjuster, the homo(io)thermism in solar simulator is controlled at 25 DEG C.Irradiate simulated solar irradiation, after 60 seconds, change voltage from-1V to+1V with the interval of 0.015V, measure 8 unit current value separately.
Following formula (2) is utilized to calculate generating efficiency according to electric current during this irradiation and voltage characteristic.Using the value of unit most effective in 8 unit as the value of the generating efficiency of each glass substrate, be shown in table 1 ~ 4.The illumination of the light source used in test is 0.1W/cm
2.
Generating efficiency [%]=V
oc[V] × J
sc[A/cm
2illumination [the W/cm of the light source used in] × FF [zero dimension] × 100/ test
2] ... formula (2)
Generating efficiency is by open circuit voltage (V
oc) and short-circuit current density (J
sc) and the multiplying of Fill factor (FF) calculate.
In addition, open circuit voltage (V
oc) be by output rating during terminal opening, short-circuit current (I
sc) electric current when being short circuit.Short-circuit current density (J
sc) be I
scthe value obtained divided by the area of the unit beyond removing negative potential.
In addition, by providing the point of peak power output to be called peak power output point, the voltage of this point is called maximum voltage value (V
max), electric current is called maximum current value (I
max).By maximum voltage value (V
max) and maximum current value (I
max) product value divided by open circuit voltage (V
oc) and short-circuit current (I
sc) product value and the value obtained obtain as Fill factor (FF).Use above-mentioned value, calculate generating efficiency.
(8) Na diffusing capacity:
Na diffusing capacity is to check the diffusible effect of the alkali of glass substrate, and the RTA device when evaluation solar cell in using above-mentioned generating efficiency to evaluate makes, measures Na diffusing capacity after the 2nd stage of heat treated just terminates.Measuring method is as follows.
After the 2nd stage of carrying out heat treated with above-mentioned RTA device terminates, secondary ion mass spectrometry with halogen labeling (SIMS) is utilized to measure in cigs layer to sample
23the integrated intensity of Na.The value recorded in table 1 ~ 4 be glass substrate that example 12 is used as 100 time relative quantity.
In addition, the calculated value of the Na diffusing capacity in the present embodiment is the Na diffusing capacity obtained regression coefficient with each moiety by multiple regression analysis to the Na diffusing capacity of practical measurement in the present embodiment and calculate.
SO in glass
3remaining quantity is 100 ~ 500ppm.
[table 1]
[table 2]
[table 3]
[table 4]
From table 1 ~ 4, the second-order transition temperature Tg of the glass substrate of embodiment (example 1 ~ 13, example 17 ~ 31) is high, and Na diffusing capacity is many.For this reason, think and can carry out film forming with high temperature to cigs layer, make the growth of CIGS crystallization good by this, generating efficiency uprises.And the glass substrate of embodiment (example 1 ~ 9, example 11 ~ 13) is due to T
4-T
ldevitrification characteristic good more than-30 DEG C, because mean thermal expansion coefficients is 70 × 10
-7~ 90 × 10
-7/ DEG C, density is 2.75g/cm
3light weight below, because brittleness desired value is lower than 7000m
-1/2and intensity is high, balance has the characteristic of glass substrate used for solar batteries well.
Known glass substrate used for solar batteries of the present invention can meet high generation efficiency, high glass transition temperature, the mean thermal expansion coefficients of regulation, high strength of glass, low glass density, good anti-devitrification characteristic whole when sheet glass is produced.For this reason, cigs layer is not peeled off from the glass substrate of band Mo film, and when assembling solar battery (specifically, when adding thermal-adhering to the glass substrate and cover glass with cigs layer), glass substrate is difficult to distortion.In addition, due to T
2be less than 1650 DEG C, T
4be less than 1230 DEG C, thus sheet glass produce time melting, have excellent formability.
On the other hand, the glass substrate of comparative example (example 14,15) is few due to Na diffusing capacity when making CIGS solar cell, therefore can not obtain high generation efficiency.
In addition, the glass substrate of comparative example (example 16) is low due to second-order transition temperature, and thermotolerance has problems.For this reason, be difficult to carry out film forming with high temperature to cigs layer.In addition due to than great, brittleness desired value at 7000m
-1/2have problems in intensity above.
Glass substrate used for solar batteries of the present invention is applicable to CIGS glass substrate used for solar batteries.In addition, CdTe glass substrate used for solar batteries is also applicable to.
Glass substrate used for solar batteries of the present invention not only can be used for CIGS solar cell or CdTe glass substrate used for solar batteries, also can be used for cover glass or back-panel glass, and can be used for other substrate used for solar batteries or cover glass.
The possibility that industry utilizes
Glass substrate used for solar batteries of the present invention balance can have the characteristics such as high melting, good plasticity and good anti-increased devitrification resistance when high generation efficiency, high glass transition temperature, the mean thermal expansion coefficients of regulation, high strength of glass, low glass density and sheet glass are produced well, and the glass substrate used for solar batteries of the application of the invention can provide the solar cell that generating efficiency is high.Glass substrate used for solar batteries of the present invention is especially suitable for Cu-In-Ga-Se solar cell and CdTe solar cell.
In addition, the announcement of full content as specification sheets of the present invention of the specification sheets of No. 2012-198334, the Japanese patent application that on September 10th, 2012 files an application, claims, accompanying drawing and summary is quoted here.
Nomenclature
1CIGS solar cell
5,5a glass substrate
7,7a positive electrode
9,9a cigs layer
11,11a buffer layer
13,13a nesa coating
15,15a negative potential
17 antireflection films
19 cover glass
21 CdTe solar cells
22 glass substrates
23 nesa coatings
24 buffer layers
25 CdTe layer
26 backplates
27 back-panel glass
Claims (15)
1. a glass substrate used for solar batteries, is characterized in that,
Represent with the mass percent of following oxide-base standard, contain:
The SiO of 50 ~ 65%
2,
The Al of 8 ~ 15%
2o
3,
The B of 0 ~ 1%
2o
3,
The MgO of 0 ~ 10%,
The CaO of 1 ~ 12%,
The SrO of 6 ~ 12%,
The BaO of 0 ~ 3%,
The ZrO of 1 ~ 7%
2,
The Na of 2 ~ 8%
2o,
The K of 0 ~ 8%
2o,
MgO+CaO+SrO+BaO is 15 ~ 30%,
SrO/Na
2o is 0.8 ~ 2.5.
2. glass substrate used for solar batteries as claimed in claim 1, is characterized in that, second-order transition temperature is more than 640 DEG C.
3. glass substrate used for solar batteries as claimed in claim 1 or 2, is characterized in that, mean thermal expansion coefficients is 70 × 10
-7~ 90 × 10
-7/ DEG C.
4. the glass substrate used for solar batteries according to any one of claims 1 to 3, it is characterized in that, viscosity reaches 10
4temperature T during dPas
4be less than 1230 DEG C, viscosity reaches 10
2temperature T during dPas
2be less than 1650 DEG C, described T
4with devitrification temperature T
lpass be T
4-T
l>=-30 DEG C.
5. the glass substrate used for solar batteries according to any one of Claims 1 to 4, is characterized in that, density is 2.75g/cm
3below.
6. the glass substrate used for solar batteries according to any one of Claims 1 to 5, is characterized in that, Al
2o
3content be 8.5 ~ 14.5%.
7. the glass substrate used for solar batteries according to any one of claim 1 ~ 6, is characterized in that, the content of CaO is 3 ~ 11%.
8. the glass substrate used for solar batteries according to any one of claim 1 ~ 6, is characterized in that, the content of CaO is 3 ~ 10%.
9. the glass substrate used for solar batteries according to any one of claim 1 ~ 8, is characterized in that, Na
2the content of O is 4 ~ 7%.
10. the glass substrate used for solar batteries according to any one of claim 1 ~ 9, is characterized in that, the content sum of MgO+CaO+SrO+BaO is 17 ~ 23%.
11. glass substrates used for solar batteries according to any one of claim 1 ~ 10, it is characterized in that, the content of BaO is less than 2%.
12. glass substrates used for solar batteries according to any one of claim 1 ~ 11, is characterized in that, SiO
2and Al
2o
3with formula 9SiO
2+ 15Al
2o
3the content value represented is in the scope of 570% ~ 840%.
13. glass substrates used for solar batteries according to any one of claim 1 ~ 12, is characterized in that, Na
2o and K
2o with formula 3Na
2o+2K
2the content value that O represents is in the scope of 14% ~ 44%.
14. 1 kinds of Cu-In-Ga-Se solar cells, it is characterized in that, possess glass substrate, cover glass, be configured in the photoelectric conversion layer of the Cu-In-Ga-Se between described glass substrate and described cover glass, the used for solar batteries glass substrate of at least described glass substrate according to any one of claim 1 ~ 13 in described glass substrate and described cover glass.
15. 1 kinds of CdTe solar cells, it is characterized in that, possess glass substrate, back-panel glass, be configured in the photoelectric conversion layer of the CdTe between described glass substrate and described back-panel glass, the used for solar batteries glass substrate of at least described glass substrate according to any one of claim 1 ~ 13 in described glass substrate and described back-panel glass.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-198334 | 2012-09-10 | ||
| JP2012198334 | 2012-09-10 | ||
| PCT/JP2013/072595 WO2014038409A1 (en) | 2012-09-10 | 2013-08-23 | Glass substrate for solar cell and solar cell using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104603076A true CN104603076A (en) | 2015-05-06 |
Family
ID=50237022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380046844.3A Pending CN104603076A (en) | 2012-09-10 | 2013-08-23 | Glass substrate for solar cell and solar cell using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6128128B2 (en) |
| KR (1) | KR20150054793A (en) |
| CN (1) | CN104603076A (en) |
| TW (1) | TW201416335A (en) |
| WO (1) | WO2014038409A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3125308A4 (en) * | 2014-03-25 | 2017-11-22 | Kaneka Corporation | Method for manufacturing compound semiconductor solar cell |
| GB201505091D0 (en) | 2015-03-26 | 2015-05-06 | Pilkington Group Ltd | Glass |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011037683A (en) * | 2009-08-14 | 2011-02-24 | Nippon Sheet Glass Co Ltd | Glass substrate |
| WO2011049146A1 (en) * | 2009-10-20 | 2011-04-28 | 旭硝子株式会社 | Glass sheet for cu-in-ga-se solar cells, and solar cells using same |
| WO2012090695A1 (en) * | 2010-12-27 | 2012-07-05 | 旭硝子株式会社 | Electronic device and method for manufacturing same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19942259C1 (en) * | 1999-09-04 | 2001-05-17 | Schott Glas | Alkaline earth aluminum borosilicate glass and its uses |
| JP2008280189A (en) * | 2007-05-08 | 2008-11-20 | Nippon Electric Glass Co Ltd | Glass substrate for solar cell, and method of manufacturing the same |
| JP5733811B2 (en) * | 2008-12-19 | 2015-06-10 | 日本電気硝子株式会社 | Manufacturing method of glass substrate for solar cell |
| JP2012030287A (en) * | 2010-06-28 | 2012-02-16 | Shin Nippon Koki Co Ltd | Apparatus for manufacturing cylindrical can |
| JP5915892B2 (en) * | 2011-05-10 | 2016-05-11 | 日本電気硝子株式会社 | Glass plate for thin film solar cell |
| JP2013003063A (en) * | 2011-06-20 | 2013-01-07 | Toshiba Corp | Sensor for power apparatus and power apparatus having the same |
| WO2013105625A1 (en) * | 2012-01-12 | 2013-07-18 | 日本電気硝子株式会社 | Glass |
-
2013
- 2013-08-23 KR KR1020157005775A patent/KR20150054793A/en unknown
- 2013-08-23 JP JP2014534286A patent/JP6128128B2/en active Active
- 2013-08-23 CN CN201380046844.3A patent/CN104603076A/en active Pending
- 2013-08-23 WO PCT/JP2013/072595 patent/WO2014038409A1/en active Application Filing
- 2013-09-02 TW TW102131522A patent/TW201416335A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011037683A (en) * | 2009-08-14 | 2011-02-24 | Nippon Sheet Glass Co Ltd | Glass substrate |
| WO2011049146A1 (en) * | 2009-10-20 | 2011-04-28 | 旭硝子株式会社 | Glass sheet for cu-in-ga-se solar cells, and solar cells using same |
| WO2012090695A1 (en) * | 2010-12-27 | 2012-07-05 | 旭硝子株式会社 | Electronic device and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6128128B2 (en) | 2017-05-17 |
| TW201416335A (en) | 2014-05-01 |
| WO2014038409A1 (en) | 2014-03-13 |
| KR20150054793A (en) | 2015-05-20 |
| JPWO2014038409A1 (en) | 2016-08-08 |
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