CN103429544A - 用于光电池的基材 - Google Patents
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- 239000000758 substrate Substances 0.000 title abstract description 3
- 239000011521 glass Substances 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000005329 float glass Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 78
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- 229910004613 CdTe Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-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
- 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 25
- 239000000395 magnesium oxide Substances 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 239000000292 calcium oxide Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 238000007667 floating Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229960001296 zinc oxide Drugs 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- 241000272165 Charadriidae Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- 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
-
- 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
-
- 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
- H01L31/03925—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 AIIBVI compound materials, e.g. CdTe, CdS
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Crystallography & Structural Chemistry (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Photovoltaic Devices (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
本发明涉及包含至少一个浮法玻璃片材的用于光电池的基材，该片材在其面上被提供有至少一个电极，特征在于所述玻璃具有包含以下组分的化学组成，组分的重量含量在下面定义的范围内改变：SiO2 69-75%，Al2O3 0-3%，CaO+MgO 11-16.2%，MgO 0-6.5%，Na2O 9-12.4%，K2O 0-1.5%。
Description
本发明涉及用于光电池的基材的领域。它更准确地涉及包含至少一个浮法玻璃片材的用于光电池的基材，该浮法玻璃片材在其面上被提供有至少一个电极。
薄层状光电材料(其典型地由CdTe或Cu(In,Ga)Se2 (CIGS)制成)的使用允许用包含玻璃片材的基材代替昂贵的硅基材。具有光电性质的材料，通常地和电极，以薄层形式通过蒸发、阴极溅射、化学气相沉积(CVD)或升华(CSS)类型的沉积方法被沉积在玻璃片材上。后者必须通常被加热至高温，或者在沉积期间，或者在沉积之后(退火处理、硒化处理等等)，并且因此经受大约500℃或更高的温度。这些处理使得可以例如改善层的结晶度并因此它们的电子传导或者光电性质。
然而高温具有引起玻璃片材(当它用标准钠-钙-硅玻璃制成时)变形的缺点。
已经提出具有更高耐热性的玻璃，但是它们具有高成本，例如由于使用昂贵的原材料(例如钡或者锶载体)，或者由于特别高的熔点。而且，这些玻璃中一些本身不好通过漂浮方法形成玻璃。
例如从申请US 20100300535和US 20110017297已知对在制备CIS光电池期间使用的高温具有改善耐受性的铝硅酸盐类型玻璃组成。然而，铝硅酸盐(或者硼硅酸盐)玻璃具有较高的划痕性(aptitude à la rayure)，由于高密度而较大的重量，以及较高的折光指数，这迫使光电池生产商在通过激光蚀刻该电极(特别地钼电极)的步骤期间改变该激光的聚焦校准。
本发明的目的是通过提出具有改善耐热性的玻璃组成克服这些缺点，该改善的耐热性使得它与在制备基于薄层光电材料(特别由CdTe或者Cu(In,Ga)Se2 (CIGS)制成)的电池期间使用的方法相容，另外允许通过漂浮方法和在非常有利的经济条件下制备玻璃。
为此目的，本发明一个主题是包含至少一个浮法玻璃片材的用于光电池的基材，该片材在面上被提供有至少一个电极，特征在于所述玻璃具有包含以下组分的化学组成，组分的重量含量在下面定义的范围内改变:
SiO2 69-75%
Al2O3 0-3%
CaO+MgO 11-16.2%
MgO 0-6.5%
Na2O 9-12.4%，尤其9-12%
K2O 0-1.5%。
虽然为钠-钙-硅类型，如同标准玻璃，这些组成令人惊讶地允许为玻璃基材提供高耐热性，其特征特别为比标准玻璃高至少30℃的下限退火温度(températures inférieures de recuit)。
SiO2、Al2O3、CaO、MgO、Na2O、K2O的重量含量的总和优选地为至少95%，特别地98%。SrO、BaO和/或ZrO2的含量有利地为零以便不损害玻璃片材的成本。氧化锑和三氧化二砷的含量还有利地为零，这是由于这些氧化物与漂浮方法不相容。该组成的其它组分可以是来源于原材料的杂质(特别地氧化铁)或者由于熔化炉或者精制剂(尤其SO3)的耐火材料的退化产生。
二氧化硅(SiO2)是该玻璃的主要构成要素。在过低的含量时，该玻璃的耐水解性，特别地在碱性介质中的耐水解性将过于降低。另一方面，高于75%的含量将引起该玻璃的粘度的高度不利的提高。二氧化硅含量优选地为至少70%，特别地71%和/或最多74%，特别地73%。
氧化铝(Al2O3)允许提高玻璃的耐水解性并且降低它的折光指数，当该基材用来构成该光电池的正面基材时，后者优点为特别显著的。氧化铝含量优选地为至少0.5%，特别地1%、1.5%或者2%和/或最多2.5%。
加入石灰(CaO)具有降低该玻璃的在高温时的粘度，并因此促进其熔化和精制，同时提高下限退火温度并因此提高热稳定性的优点。可以归结于这种氧化物的液相线温度和折光指数的提高然而引起限制其含量。氧化镁(MgO)用于改善该玻璃的化学稳定性和降低它的粘度。高含量然而导致增大反玻璃化的风险。CaO含量优选地为至少8%，甚至9%，甚至10%和/或最多13%，特别地12%。
钠碱(Na2O)用于降低在高温时的粘度和液相线温度。过高的含量然而导致玻璃的耐水解性和它的热稳定性退化，同时提高成本。钾碱(K2O)具有相同的优点和缺点。Na2O含量优选地为至少9.5%，甚至10%或者11%，甚至11.5%和/或最多12%。K2O的含量优选地为最多1%，特别地0.5%，甚至0.3%或者0.1%。实际上，看起来钾碱显著地降低该玻璃的下限退火温度。
根据第一种优选实施方案，MgO的重量含量为最多1%，特别地0.5%，甚至0.1%。CaO含量有利地为至少11.5%，甚至12%。Na2O含量优选地为至少10%，甚至11%。有利地它为最多12%。特别优选的组成包含以下组分，组分的重量含量为在下面定义的范围内：
SiO2 71-74.2%
Al2O3 0-3%
CaO 11.5-13%
MgO 0-1%
Na2O 11-12.4%，尤其11-12%
K2O 0-1.5%。
根据第二种优选的实施方案，MgO的重量含量为至少4%，甚至4.5%或者5%和/或至少6%。CaO含量优选地为9至11%，特别地为9至10.5%。Na2O含量有利地为至少9.5%，甚至10%和/或最多12%或者11%。特别优选的组成包含以下组分，组分的重量含量为在下面定义的范围内：
SiO2 70-74%
Al2O3 0-2%
CaO 9-10.5%
MgO 4-6.5%，尤其4-6%
Na2O 10-11%
K2O 0-1%。
根据第三种实施方案，CaO的重量含量为至少9%，特别地10%和/或最多12%，特别地11%。MgO的重量含量优选地为至少4%和/或最多5%。Na2O含量优选地为至少11%。
特别优选的组成包含以下组分，组分的重量含量为在下面定义的范围内：
SiO2 69-72%，尤其69-71%
Al2O3 1-3%，尤其1.7-3%
CaO 10-12%，尤其10.1-11%
MgO 4-5%
Na2O 11-12.4%，尤其11.5-12%
K2O 0-1%，尤其0-0.3%。
该玻璃可以在借助于电极和/或借助于架空和/或浸没和/或设置在炉顶中的燃烧器(使得火焰能接触原料或者玻璃浴)加热的连续炉中进行熔化。原料通常为粉状的并且包含天然材料(沙、长石、石灰石、白云石、霞石正长岩等等)或者人工材料(碳酸钠或者碳酸钾、硫酸钠等等)。将原料进料到炉中然后经历在该术语的物理意义上的熔化反应和各种化学反应，其引起获得玻璃浴。然后将熔化玻璃输送至成型步骤，在此期间玻璃片将形成它的形状。成型以已知方式通过漂浮方法进行实施，即通过将熔化玻璃(具有大约3000泊的粘度)倾倒在熔化锡浴上。然后使获得的玻璃带小心地退火以在被切成希望的尺寸之前消除在它内部的全部热应力。该玻璃片材的厚度典型地为2至6 mm，特别地2.5至4 mm。
电极优选地呈沉积在基材上的薄层形式(通常在该基材的一个整面上)，直接地与基材接触或者与至少一个下层接触。它可以是透明导电薄层，例如基于(氟掺杂或者锑掺杂的)氧化锡，(铝掺杂或者镓掺杂的)氧化锌，或者基于氧化铟锡(ITO)。它还可以是薄的金属层，例如由钼制成。当该基材用来形成光电池的正面基材时通常使用透明层，如在下文中更详细地解释的那样。措辞“正面”理解为表示日光辐射首先穿过的面。
为薄层形式的电极可以是通过不同的沉积方法，如化学气相沉积(CVD)或者阴极溅射沉积，特别地磁场增强阴极溅射(磁控管溅射方法)被沉积在该基材上。在CVD方法中，使卤素或者有机金属前体蒸发并且通过载气输送至热玻璃的表面，在那里它们在热量的作用下分解以形成薄层。CVD方法的优点是可以在用于经漂浮方法的玻璃片材的成型方法内使用它。因此在玻璃片材在锡浴上，在锡浴的出口或在玻璃退火炉中时(即在玻璃片材进行退火以消除机械应力时)，可以沉积该层。CVD方法是特别适合于沉积氟掺杂或者锑掺杂的氧化锡层。阴极溅射方法本身将优选地用于沉积钼层、掺杂氧化锌层或ITO层。
本发明的另一主题是半导体器件，其包含至少一个根据本发明的基材和至少一个沉积在所述至少一个基材上的具有光电性质的材料薄层。
该具有光电性质的材料优选地选自CdTe和Cu(In,Ga)Se2 (CIGS)类型的化合物。术语“(In,Ga)”理解为表示该材料可以以任何可能的含量组合包含In和/或Ga：In1-xGax，x可以取0至1的任何值。特别地，x可以是零(CIS类型材料)。具有光电性质的材料还可以用非晶硅或者多晶硅制成。
该光电材料被沉积在半导体器件上，在电极上方，通常与电极接触。不同的沉积技术是可能的，作为实例，尤其可以提到蒸发、阴极溅射、化学气相沉积(CVD)、电解沉积或升华(CSS)。举例来说，在CIGS类型层的情况下，可以提到阴极溅射或者电解沉积方法(后面是硒化处理步骤)或者共-蒸发。
附加电极可以被沉积在光电材料层上(并且特别地与其接触)。它可以是透明导电薄层，例如基于(氟掺杂或者锑掺杂的)氧化锡，(铝掺杂或者镓掺杂的)氧化锌，或者基于氧化铟锡(ITO)。它还可以是金属层，例如由金制成或者由镍和铝的合金制成。当该基材用来形成光电池的背面基材时通常使用透明层，如在下文中更详细地解释的那样。还可以将缓冲层插在光电材料层和附加电极之间。在CIGS类型材料的情况下，它可以是例如CdS层。
本发明的另一主题是包含根据本发明的半导体器件的光电池。本发明的主题最后是包含多个根据本发明的光电池的光电组件。
取决于使用的技术，根据本发明的基材可以是该光电池的正面或者背面基材。举例来说，在基于CIGS的光电材料的情况下，CIGS层通常被沉积在背面基材(提供有它的电极，电极典型地由钼制成)上。因此，正是该背面基材这时具有玻璃片材，该玻璃片材具有先前描述的有利化学组成。另一方面，在CdTe技术的情况下，该光电材料通常被沉积在正面基材上，使得上述的化学组成用于正面基材的玻璃片材。
该光电池通过使正面基材和背面基材接合形成，例如借助于由热固性塑料，例如PVB、PU或者EVA制成的层压中间层来进行。
根据第一种实施方案，根据本发明的光电池包含，作为正面基材，根据本发明的基材，所述基材的玻璃片材的化学组成另外以最多0.02%，特别地0.015%的重量含量包含氧化铁。在这种情况下，实际上重要的是，该玻璃的光学透射是尽可能高的。该玻璃片材优选地不包含任何不同于氧化铁(其存在是不可避免的)的吸收可见辐射或者红外辐射的试剂(特别地对于380至1000 nm的波长)。特别地，该玻璃的组成优选地不包含选自以下试剂的试剂，或者不包含任何以下试剂：过渡元素氧化物，如CoO、CuO、Cr2O3、MnO2，稀土氧化物，如CeO2、La2O3、Nd2O3，或为元素状态的着色剂，如Se、Ag、Cu、Au。这些试剂经常具有非常强的不希望的染色效果，其在非常低的含量(有时约数ppm或者更少)时显示(1 ppm=0.0001%)。仍然为了使该玻璃的光学透射最大化，氧化还原值(定义为在用FeO形式表示的亚铁离子含量和用Fe2O3形式表示的铁总含量之间的比率)优选地最多0.2，特别地0.1。该玻璃片材优选地使得它的根据标准ISO 9050:2003计算的能量传递(TE)大于或等于90%，特别地90.5%，甚至91%，甚至91.5%，对于3.2 mm的厚度而言。该正面基材在携带电极的面相对的面上可以被提供有抗反射涂层，其例如由多孔二氧化硅制成或者包含高和低折光指数层交替变化的薄层堆叠体。在这种实施方案的范围中，典型地使用根据本发明的基材，其提供有由ITO制成和/或由掺杂SnO2制成的电极，由CdTe制成的光电材料，由金制成的或者由镍和铝合金制成的附加电极。背面基材优选地由标准钠-钙-硅玻璃制成。
根据第二种实施方案，根据本发明的光电池包含，作为背面基材，根据本发明的基材，所述基材的玻璃片材的化学组成另外以至少0.05%，特别地在0.08至2%，特别地0.08至0.2%的重量含量包含氧化铁。在这种实施方案的范围中，典型地使用根据本发明的基材，其被提供有由钼制成的电极、由CIGS制成的光电材料、由掺杂ZnO制成的附加电极。高含量的氧化铁(0.5%至2%)在这种情况下可以校正美学外观(由于存在钼)。正面基材优选地由具有标准钠-钙-硅组成的极明亮玻璃制成。
本发明在阅读在下面的非限制性示例实施方案的详细说明将得到很好理解。
在下面表1和2举例说明根据本发明的某些组成(实施例1至10)以及标准组成(对比实施例C1)。
除了按重量计的化学组成，所述表指示以下物理性质：
- 下限退火温度，称为S并且用℃表示；
- 玻璃具有100泊的粘度时的温度，称为T2并且用℃表示，
- 玻璃具有3162泊的粘度时的温度，称为T3.5并且用℃表示，
- 成型余量，称为ΔT并且用℃表示，对应于在温度T3.5和液相线温度之间的差值。
表1
| C1 | 1 | 2 | 3 | 4 | |
| SiO2 | 71.8 | 71.8 | 72.0 | 72.8 | 70.9 |
| Al2O3 | 0.6 | 1.35 | 1.3 | 0.9 | 1.8 |
| CaO | 9.5 | 9.9 | 10.0 | 9.8 | 10.0 |
| MgO | 4.0 | 5.5 | 5.6 | 5.7 | 6.2 |
| Na2O | 13.7 | 10.5 | 10.9 | 10.7 | 10.8 |
| K2O | 0 | 0.75 | 0 | 0 | 0.1 |
| SO3 | 0.28 | 0.22 | 0.23 | 0.23 | 0.3 |
| S(℃) | 510 | 537 | 542 | 538 | 547 |
| T2(℃) | 1421 | 1474 | 1475 | 1463 | 1467 |
| T3.5(℃) | 1093 | 1154 | 1155 | 1147 | 1145 |
| ΔT(℃) | 78 | 14 | 5 | 17 | 45 |
表2
| 5 | 6 | 7 | 8 | 9 | 10 | |
| SiO2 | 73.3 | 72.2 | 73.1 | 73.4 | 71.3 | 70.1 |
| Al2O3 | 1.6 | 1.7 | 1.95 | 1.8 | 2.0 | 2.1 |
| CaO | 9.6 | 12.8 | 12.6 | 11.9 | 12.8 | 10.6 |
| MgO | 4.8 | 0.1 | 0.3 | 0.9 | 0.1 | 4.3 |
| Na2O | 10.1 | 11.8 | 11.8 | 11.6 | 11.4 | 11.8 |
| K2O | 0.38 | 1.3 | 0.06 | 0.08 | 0.4 | 0.7 |
| SO3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| S(℃) | 542 | 536 | 541 | 539 | 539 | 535 |
| T2(℃) | 1513 | 1469 | 1470 | 1482 | 1451 | 1464 |
| T3.5(℃) | 1166 | 1132 | 1146 | 1144 | 1133 | 1125 |
| ΔT(℃) | 22 | 14 | 35 |
所述组成允许获得具有比标准玻璃高约30℃的下限退火温度的玻璃。其由此获得更好的机械性能，和在制备太阳能电池的步骤期间更少可能变形的玻璃片材。
这些玻璃组成在优良的条件下是可以漂浮的，如通过其正的成型余量得到证实。它们还具低的划痕性，低密度和特别好地适合于用于蚀刻该钼电极层的方法的折光指数。
Claims (15)
1.包含至少一个浮法玻璃片材的用于光电池的基材，该玻璃片材在面上被提供有至少一个电极，特征在于所述玻璃具有包含以下组分的化学组成，组分的重量含量在下面定义的范围内改变:
SiO2 69-75%
Al2O3 0-3%
CaO+MgO 11-16.2%
MgO 0-6.5%
Na2O 9-12.4%
K2O 0-1.5%。
2.根据前述权利要求的基材，其中SiO2、Al2O3、CaO、MgO、Na2O、K2O的重量含量的总和为至少95%，特别地98%。
3.根据前述权利要求之一的基材，其中MgO的重量含量为最多1%，特别地0.5%。
4.根据前一权利要求的基材，其中该玻璃具有包含以下组分的化学组成，组分的重量含量为在下面定义的范围内：
SiO2 71-74.2%
Al2O3 0-3%
CaO 11.5-13%
MgO 0-1%
Na2O 11-12.4%，尤其11-12%
K2O 0-1.5%。
5.根据权利要求1或2的基材，其中MgO的重量含量为至少4%。
6.根据前一权利要求的基材，其中该玻璃具有包含以下组分的化学组成，组分的重量含量为在下面定义的范围内：
SiO2 70-74%
Al2O3 0-2%
CaO 9-10.5%
MgO 4-6%
Na2O 10-11%
K2O 0-1%。
7.根据权利要求5的基材，其中该玻璃具有包含以下组分的化学组成，组分的重量含量为在下面定义的范围内：
SiO2 69-72%，尤其69-71%
Al2O3 1-3%，尤其1.7-3%
CaO 10-12%，尤其10.1-11%
MgO 4-5%
Na2O 11-12.4%，尤其11.5-12%
K2O 0-1%。
8.根据前述权利要求之一的基材，其中所述电极是钼薄层，或者基于氟掺杂或者锑掺杂的氧化锡的，基于铝掺杂或者镓掺杂的氧化锌的，或者基于氧化铟锡的透明导电薄层。
9.半导体器件，其包含至少一个根据前述权利要求之一的基材和至少一个沉积在所述至少一个基材上的具有光电性质的材料的薄层。
10.根据前一权利要求的半导体器件，其中该具有光电性质的材料选自CdTe和Cu(In,Ga)Se2类型的化合物。
11.光电池，其包含根据前述器件权利要求之一的半导体器件。
12.根据前一权利要求的光电池，其包含根据权利要求1-8之一的基材作为正面基材，所述基材的玻璃片材的化学组成另外以最多0.02%，特别地0.015%的重量含量包含氧化铁。
13.根据权利要求11的光电池，其包含根据权利要求1-8之一的基材作为背面基材，所述基材的玻璃片材的化学组成另外以至少0.05%，特别地为在0.08至2%范围内的重量含量包含氧化铁。
14.根据前一权利要求的光电池，其中具有光电性质的材料是Cu(In,Ga)Se2类型的化合物，电极是钼薄层。
15.光电组件，其包含多个根据前述电池权利要求之一的光电池。
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| US9717648B2 (en) | 2013-04-24 | 2017-08-01 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
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| US9707153B2 (en) | 2013-04-24 | 2017-07-18 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
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| US9849066B2 (en) | 2013-04-24 | 2017-12-26 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
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- 2012-03-08 JP JP2013557162A patent/JP6050261B2/ja not_active Expired - Fee Related
- 2012-03-08 EA EA201391295A patent/EA024896B1/ru not_active IP Right Cessation
- 2012-03-08 KR KR1020137023645A patent/KR20140064713A/ko active IP Right Grant
- 2012-03-08 EP EP12713214.0A patent/EP2683665B1/fr not_active Not-in-force
- 2012-03-08 MX MX2013010220A patent/MX2013010220A/es active IP Right Grant
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- 2012-03-08 WO PCT/FR2012/050485 patent/WO2012146844A1/fr active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6050261B2 (ja) | 2016-12-21 |
| EP2683665B1 (fr) | 2018-05-30 |
| US8940996B2 (en) | 2015-01-27 |
| EA024896B1 (ru) | 2016-10-31 |
| FR2972446B1 (fr) | 2017-11-24 |
| EP2683665A1 (fr) | 2014-01-15 |
| JP2014508708A (ja) | 2014-04-10 |
| CA2826465A1 (fr) | 2012-11-01 |
| FR2972446A1 (fr) | 2012-09-14 |
| MX2013010220A (es) | 2013-10-25 |
| US20120234368A1 (en) | 2012-09-20 |
| KR20140064713A (ko) | 2014-05-28 |
| WO2012146844A1 (fr) | 2012-11-01 |
| EA201391295A1 (ru) | 2014-01-30 |
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