EP2543077A1 - Photovoltaic cell having a novel tco layer built therein - Google Patents
Photovoltaic cell having a novel tco layer built thereinInfo
- Publication number
- EP2543077A1 EP2543077A1 EP11712934A EP11712934A EP2543077A1 EP 2543077 A1 EP2543077 A1 EP 2543077A1 EP 11712934 A EP11712934 A EP 11712934A EP 11712934 A EP11712934 A EP 11712934A EP 2543077 A1 EP2543077 A1 EP 2543077A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- substrate
- photovoltaic
- zno
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000758 substrate Substances 0.000 claims abstract description 100
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011521 glass Substances 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 31
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 161
- 239000000463 material Substances 0.000 claims description 28
- 238000000137 annealing Methods 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 16
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 13
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 13
- 230000004888 barrier function Effects 0.000 claims description 13
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910021424 microcrystalline silicon Inorganic materials 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 229910021425 protocrystalline silicon Inorganic materials 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 210000004027 cell Anatomy 0.000 description 48
- 235000014692 zinc oxide Nutrition 0.000 description 40
- 239000011787 zinc oxide Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 17
- 238000000151 deposition Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005670 electromagnetic radiation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 210000002381 plasma Anatomy 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910005091 Si3N Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- OANVFVBYPNXRLD-UHFFFAOYSA-M propyromazine bromide Chemical compound [Br-].C12=CC=CC=C2SC2=CC=CC=C2N1C(=O)C(C)[N+]1(C)CCCC1 OANVFVBYPNXRLD-UHFFFAOYSA-M 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical class [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021431 alpha silicon carbide Inorganic materials 0.000 description 1
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 1
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- 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
- H01L31/0352—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 shape or by the shapes, relative sizes or disposition of the semiconductor regions
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the invention relates to a novel photovoltaic cell, comprising in particular a glass substrate coated with a transparent layer of electrically conductive oxide, often called TCO in the field.
- glass substrate refers to a substrate made of mineral glass.
- a photovoltaic module consists of a set of photovoltaic cells often coupled in series with each other. These cells generate a direct current when exposed to light. To provide a suitable power which corresponds to sufficient and expected energy, sufficiently large areas of a multitude of photovoltaic modules are produced. These modules can be integrated on the roofs of houses or commercial premises or placed in fields for centralized energy production.
- a photovoltaic module thus comprises a support substrate and a so-called photovoltaic material which is most often constituted by a stack of N and P doped semiconductors, forming in their electrical contact zone a pn junction.
- Another substrate on the opposite side, protects the photovoltaic material.
- This front face substrate is preferably a transparent mineral glass having a very high light transmittance in the 300 to 1250 nm radiation range.
- the photovoltaic material On each side of the photovoltaic material are electrodes constituted by electrically conductive materials which constitute the positive and negative terminals of the photovoltaic cell.
- the two electrodes (anode and cathode) of the photovoltaic module make it possible to collect the current produced under the effect of light in the photovoltaic material, the transport and the segregation of the charges being due to the difference of potential created between the respectively p-doped and n-doped portions of the semiconductors.
- An example of such a module is for example described in the application WO2006 / 005889, to which reference will be made for the details of the embodiment.
- crystalSin silicon offers as a semiconductor a good energy efficiency, and is the first generation of photovoltaic cells in the form of "Wafers", there is increasing interest in the industry for so-called “thin film” technologies. .
- the material is the seat of the photovoltaic activity, comprising or consisting of amorphous (a-Si) or microcrystalline ( ⁇ - ⁇ ) silicon, or cadmium telluride (CdTe) or chalcopyrite (CIS, CIGS, CiGSe2), is this time directly deposited on the substrate in the form of more or less thick layers.
- a-Si amorphous
- ⁇ - ⁇ microcrystalline
- CdTe cadmium telluride
- CIS, CIGS, CiGSe2 chalcopyrite
- the manufacture of modules on glass substrates, cut at the final size of the modules thus comprises the deposition of a succession of thin layers deposited and formed directly in succession on the substrate, of which at least:
- a thin layer serving as a reflecting rear electrode.
- the photovoltaic cells are performed by intermediate laser etching steps between each layer deposition step. These substrates glassmakers, often tempered and integrating photovoltaic cells thus constitute the substrates of the front of the modules.
- a back-face support substrate is generally subsequently laminated against the face provided with the stack of layers of the front-face substrate.
- the electrode arranged against the front glass substrate of the module is of course transparent to let the light energy to the absorber.
- This electrode comprises most often a transparent electrically conductive oxide (often called in the TCO domain for "Transparent Conductive Oxide”).
- TCO thin layers of aluminum doped zinc oxide (AZO), indium doped tin oxide (ITO) , fluorinated doped tin oxide (SnO2: F) or gallium doped zinc oxide (GZO) or boron doped zinc oxide (BZO).
- AZO aluminum doped zinc oxide
- ITO indium doped tin oxide
- SnO2 fluorinated doped tin oxide
- GZO gallium doped zinc oxide
- BZO boron doped zinc oxide
- these layers constituting the electrodes are essential functional components of the thin-film solar cells because they serve to evacuate towards the cathode the electrons or holes formed by the incident electromagnetic radiation in the photovoltaic semiconductor layer.
- their resistivity is as low as possible.
- the TCO-based electrode coating must be deposited at a relatively large physical thickness, of the order of a few hundred nanometers, which is expensive in view of the the price of these materials when they are deposited in thin layers, in particular by the magnetron sputtering technique.
- TCO-based electrode coatings thus lies particularly in the fact that the physical thickness of the material is necessarily a compromise between its final electrical conduction and its final transparency after deposition. In other words, the greater the physical thickness of the material, the higher its conductivity will be, but the lower the transparency and vice versa. In the end, it is not possible with TCO coatings current to independently and satisfactorily optimize the conductivity of the electrode coating and its transparency.
- TCOs Another problem with these TCOs comes from their use in the specific application as an electrode in a photovoltaic module: to give the glass substrate its mechanical strength, the substrates coated with the TCO layer must often undergo a final heat treatment, in particular a quench. Similarly, it is often necessary to heat the TCO layer to increase the crystallinity and hence the conductivity and transparency.
- the deposition of certain photovoltaic layers such as CdTe layers requires an operating temperature of at least 400 ° C and even up to 700 ° C. During successive quenching and / or heating, the stack is thus carried, under ambient or other conditions, at temperatures greater than 500 degrees, or even higher than 600.degree. C., for a few minutes.
- the terms “lower” and “upper” denote the respective positions of the layers relative to one another and with reference to the glass substrate of the front face.
- a layer disposed above the electrode layer (TCO) with reference to the front face glass substrate and as a sub-layer a layer disposed beneath the electrode layer (TCO) is designated as an on-layer. compared to the front face glass substrate.
- the present invention aims at overcoming the drawbacks of the preceding techniques by proposing a solution comprising a stack such that both the optical and electrical conduction properties of the TCO layer are little affected by the heat treatment phases, and are even improved by the latter. .
- the photovoltaic panel incorporating the modules is necessarily subjected, outside, to humid weather conditions. Even though the TCO layers are in principle protected by the front and back substrates, they are necessarily subjected to moisture however over time and their prolonged use outdoors.
- the object of the present invention is also to provide a new transparent substrate, in particular a glass substrate, coated with a transparent TCO electrically conductive oxide layer, making it possible to respond to all the problems previously described, in particular with a view to their use for the manufacture of elements of a photovoltaic module or panel.
- the present invention relates to a photovoltaic cell comprising at least one transparent substrate front face including glass, protecting a stack of layers comprising a layer with photovoltaic properties and two lower and upper electrodes, arranged on either side of said photovoltaic layer, said module being characterized in that at least the lower electrode, that is to say the one closest to the front face substrate, comprises or consists of a transparent coating consisting of a mixed metal oxide of at least the elements Zn, Al and Ga, corresponding to the following composition, in weight percentage on the basis of the corresponding oxides ZnO, Al2O3 and Ga2O3:
- the equivalent weight of AI 2 O 3, as a percentage in the mixed metal oxide, is preferably between 0.5% and 1.8%, especially between 0.6 and 1.5%.
- the weight equivalent of Ga 2 O 3, as a percentage in the mixed metal oxide, is preferably between 4% and 7%, especially between 4.5 and 6.5%.
- the weight equivalent of ZnO, as a percentage in the mixed metal oxide, is for example between 90% and 95%.
- the transparent coating has a thickness of between 50 and 1500 nm.
- the cell as described above may further comprise a layer or a set of layers of at least one alkaline barrier material originating from the front face substrate of the glass type, in particular when quenching or annealing, between said substrate and the transparent coating layer consisting of a mixed metal oxide of at least the elements Zn, Al and Ga.
- the cell may also comprise a metal blocking layer above and possibly below, with reference to the glass substrate, the transparent coating layer consisting of a mixed metal oxide of at least the elements Zn, Al and Ga.
- the photovoltaic absorber layer generally comprises a thin layer of at least one semiconductor material of the amorphous silicon ( ⁇ -Si), or silicon-carbon ( ⁇ -SiC), preferably hydrogenated, or silicon-germanium ( aSiGe), or microcrystalline silicon (pc-Si), or based on an assembly of thin layers of amorphous silicon on microcrystalline silicon so as to form a tandem cell, or cadmium telluride (CdTe) or CIGS or Tandem CdTe / CIGS.
- ⁇ -Si amorphous silicon
- ⁇ -SiC silicon-carbon
- aSiGe silicon-germanium
- pc-Si microcrystalline silicon
- the invention also relates to a transparent substrate capable of forming the front face of a photovoltaic cell as described above, comprising on one of its faces a transparent coating consisting of a mixed metal oxide of at least the elements Zn, Al and Ga, corresponding to the following composition, in weight percent on the basis of the corresponding oxides ZnO, Al2O3 and Ga2O3:
- Ga 2 O 3 4 to 10%.
- the metal oxide of the Zn oxide type is of course doped with the elements Al and Ga in the proportions described above.
- FIG. 1 a photovoltaic cell 100 according to the present invention.
- This cell comprises on the front face, that is to say on the side exposed to solar radiation, a first transparent glass substrate 10 said front face.
- This substrate may for example be entirely in a glass containing alkalis such as a silico-soda-lime glass.
- the glass-function substrate is preferably made of material (x) having the best possible transparency in the part of the spectrum solar useful for the application as a solar module, that is to say generally the portion of the spectrum ranging from about 300 to about 1300 nm.
- the transparent substrate 10 chosen according to the invention has a high transmission for electromagnetic radiation with a wavelength of 300 to 1250 nm and in particular for sunlight.
- the glass substrate is generally chosen so that its transmission in this range is greater than 75% and in particular greater than 85% or even greater than 95%.
- This substrate is advantageously an extra-clear glass, such as Diamant® glass sold by Saint-Gobain, or a glass having surface roughness, such as Albarino® glass, also sold by Saint-Gobain.
- the substrate 10 may have a total thickness ranging from 0.5 to 10 mm and is used in particular as a protective plate for a photovoltaic cell. It may for this purpose be advantageous to subject it to prior heat treatment such as quenching.
- the front face of the substrate 10 directed towards the light rays (this is the external face) is defined by A, and with B the rear face of the substrate directed towards the rest of the layers of the solar module (it is is the inner face).
- the face B of the substrate 10 is coated with a stack 30 of thin layers according to the methods of the invention. At least one surface portion of the substrate is coated on its side B with at least one layer 1 of a material known for its alkali diffusion barrier properties through the different layers of the stack 30, especially when the The assembly is heated to a high temperature, for example during the various quenching or annealing phases which are indispensable during the manufacturing cycle of the cell.
- This barrier layer 1 in face B of the substrate makes it possible in particular to avoid, or even to block, the diffusion of Na from the glass to the upper layers.
- this alkali barrier layer may be based on a dielectric material chosen from nitrides, oxides or oxynitrides of silicon, or nitrides, oxides or oxynitrides of zirconium. It may especially be Si3N 4 , Sn x Zn y O z , SiO 2, SiO x N y , ⁇ 2, optionally doped. Among all these, the Si3N silicon nitride makes it possible in particular to obtain an excellent barrier effect to alkalis.
- This alkali barrier layer, especially when based on silicon nitride may not be stoichiometric. It can be sub-stoichiometric in nature, or even super-stoichiometric.
- the layer 1 is not necessarily unique and it is envisaged in the context of the present invention to replace it with a set of layers having this same function to constitute an effective barrier to alkalis.
- the thickness of the barrier layer 1 (or of all the barrier layers) is between 5 and 200 nm, preferably between 10 and 100 nm and for example substantially close to 20 to 25 nm.
- an electroconductive layer 3 according to the invention of the type "Transparent Conductive Oxide” TCO.
- This layer constitutes the lower electrode of the photovoltaic cell.
- this layer consists of a material chosen from zinc oxides doped jointly by Al, Ga, in the proportions described above.
- another additional doping element chosen in particular from In, B, Ti, V, Y, Zr.
- This conductive layer is as transparent as possible, and has a high transmission of light in all wavelengths corresponding to the absorption spectrum of the material constituting the functional layer, so as not to reduce the efficiency of the solar module unnecessarily. .
- the thickness of this electroconductive layer is between 50 and 1500 nm, preferably between 200 and 800 nm, and substantially close to 600-700 nm.
- the TCO layer of the substrates according to the invention has a high electrical conductivity, a high transparency to electromagnetic radiation and in particular to sunlight as will be described in the examples which follow.
- the electro-conductive layer 3 of mixed zinc oxide doped with gallium and aluminum according to the invention must have a resistance per square of at most 30 ohms / square, in particular at most 20 ohms / square, or even not more than 10 ohms / square in the PV module.
- the transparent electrically conductive oxide layer according to the invention has a transmission of at least 65% and preferably of at least 70% and particularly preferably of more than 75% or even more than 80% for the waves. electromagnetic waves with a wavelength of 300 nm to 1250 nm in the photovoltaic module.
- At least the transparent layer of electrically conductive oxide TCO, and preferably also all its protective layers are successively deposited in the same device by the known techniques for deposition of thin layers under vacuum, in particular by the techniques conventional sputtering in the field of deposition of thin films, especially magnetron sputtering techniques, as will be described in more detail below.
- the surface of the transparent layer of electrically conductive oxide may be provided with a texturing whose roughness (RMS) is between 1 nm to 250 nm, more particularly when the photovoltaic layer is of the silicon type.
- the roughness is preferably from 20 nm to 180 nm and particularly preferably from 40 nm to 140 nm.
- the Texture size can be determined for example by scanning electron microscopy (SEM) or atomic force microscopy (AFM).
- the roughness (root-mean-squared roughness or RMS) is for example determined according to the ISO 25178 standard using an atomic force microscope.
- the electroconductive layer serving as the lower electrode may then be covered with a layer 4 of protection against oxidation.
- the invention may also be provided to incorporate in the stack forming the electrode at least one metal blocking layer 2, alone or in combination with the protective layer 4 against oxidation.
- This metal layer 2 by oxidizing, creates an oxide layer of the metal in question during the heat treatment of the lower electrode, more precisely for example a quenching or annealing substrate coated with said electrode.
- the metal blocking layer may be based on titanium, nickel, chromium or niobium, used alone or as a mixture.
- the primary stack 40 of thin layers thus formed is covered with a functional layer 5 comprising the materials enabling the energy conversion between the light rays and the electrical energy, as previously described.
- Examples of semiconductor materials with photovoltaic properties which are suitable for use in the thin layer 5 in the solar cells according to the invention are, for example, amorphous silicon (a-Si), microcrystalline silicon (pc-Si), polycrystalline silicon (pc-Si), gallium arsenide (in monolayer), gallium arsenide (in two layers), gallium arsenide (in three layers), gallium and indium nitride, cadmium telluride and copper-indium (gallium) sulfur-selenium compounds.
- a-Si amorphous silicon
- pc-Si microcrystalline silicon
- pc-Si polycrystalline silicon
- gallium arsenide in monolayer
- gallium arsenide in two layers
- gallium arsenide in three layers
- gallium and indium nitride gallium and indium nitride
- cadmium telluride copper-indium (gallium) sulfur-selenium compounds.
- the photovoltaic semiconductor layer of the thin-film solar cells according to the invention can use a single semiconductor transition (single junction) or several semiconductor transitions (multi-phase). junction).
- Semiconductor layers that have the same interband transition can only use part of the sunlight; on the other hand, different semiconductor layers having different interband transitions are sensitive to an extended range of wavelengths of sunlight.
- the functional layer 5 is covered with a conductive layer 6, possibly transparent, TCO type as previously described or non-transparent type, such as molybdenum or other metallic material.
- this electrode layer may be based on ITO (indium and tin oxide) or on metal (silver, copper, aluminum, molybdenum), on fluorine-doped tin oxide or on doped zinc oxide. al.
- thermoplastic interlayer 7 of a known type, for example PU, PVB or EVA, to form the final solar cell 100.
- the photovoltaic cell according to the invention as just described can be obtained using a method comprising the following steps:
- Step a) comprising vacuum deposition by spraying, is a usual and known method for producing thin layers of materials that vaporize with difficulty.
- the surface of a solid body of suitable composition, called a target is sprayed by firing energy-rich ions from low-pressure plasmas, for example oxygen ions (O + ) and / or ions of Argon (Ar + ) or neutral particles, after which the pulverized materials are deposited in thin layers on the substrates (see Rômpp Online, 2008, "Sputtering").
- Magnetic field supported spraying often referred to as magnetron sputtering, is preferably used.
- the partial pressure of oxygen or argon can vary widely and thus be easily adapted to the needs of each particular case.
- the partial pressure levels of the gases in the plasma and the electric power required for the spraying can be defined according to the dimensions of the transparent substrates and the thickness of the layers (in particular TCO) to be deposited.
- the drawback of such techniques is however that the layers obtained have a low degree of crystallinity of the constituent materials, in particular TCOs, and therefore requires an annealing step to recrystallize said materials.
- the layers are sputtered successively in continuous installations and already dimensioned accordingly by means of suitable sputtering targets.
- the unheated transparent substrate is coated on its surface with a transparent layer of electrically conductive oxide comprising zinc, aluminum and gallium.
- a target is preferably used which has a composition corresponding substantially or exactly to that of the TCO layer finally obtained on the substrate.
- the spraying technique supported by the action of a magnetic field often called magnetron sputtering.
- two targets in the same magnetron chamber and to spray simultaneously on top of the substrate.
- One of these targets consists of aluminum doped ZnO and the other of gallium doped ZnO, in order to obtain the TCO layer of the desired formulation.
- the invention it is also possible according to the invention to use three different targets respectively ZnO, Ga2O3 and Al2O3 which are simultaneously sprayed in a single chamber using three radio frequency generators, according to the rules of the art.
- the partial pressure levels in the plasma at low pressure and the electric power necessary for the adequate spraying of the different targets and the attainment of the desired content of Zn, Al and Ga are defined according to the rules of the art, as well as the thickness of the TCO layer to be deposited.
- the skilled person can easily adjust the setting of different treatment parameters using his professional knowledge, possibly with some guidance tests.
- the TCO layer according to the invention by a reactive deposit, especially by spraying, in an atmosphere containing oxygen, at least one target.
- a metal used in the composition of said layer Al, Zn, Ga
- the elements Zn and Al can be sprayed in an atmosphere containing oxygen or oxygen, from a first target made of an alloy of these two metals, in the required proportions, and Element Ga can be simultaneously introduced by the sputtering of another target constituted by Ga 2 O 3 oxide.
- the heat treatment according to step b) is therefore a crucial step for the final performance of the photovoltaic cell and determines in particular its final yield.
- the substrate coated with the stack 40 is typically heated between 300 ° C and 750 ° C, preferably between 500 ° C and 700 ° C and in particular between 600 ° C and 700 ° C, under different atmospheres, for example in an atmosphere containing oxygen.
- the treatment step can be carried out by means of usual and known devices, for example ovens traditionally used in the glass industry (quenching furnace), continuously traversed by the glass ribbon and suitably dimensioned. These continuously traversed furnaces usually use air or an inert gas as a heat transfer fluid. Thanks to this heat treatment b) of the coated and heated substrate, the oxide layer is thus made crystalline and its resistivity then decreases sharply. This gives the TCO layer according to the invention described above.
- the transparent substrates covered with the TCO layer are cooled, preferably before carrying out the following treatment step c), for example by cold air or cold inert gas flows, but they can also be allowed to cool. passively.
- the coated substrate preferably has a temperature of 20 ° C to 30 ° C. In this way, the risk of damaging the substrates by thermal stresses and / or the risk of uncontrolled evaporation or decomposition of liquids which are brought into contact with the coated substrates during or possibly before the processing step c) which follows.
- the transparent layer of electrically conductive oxide may be etched by means of an etching agent and the etching agent is then rinsed.
- Etching agents may be gaseous or liquid; they are preferably liquid.
- the liquid etching agents may contain liquid organic compounds, liquid inorganic compounds, solutions of organic or inorganic solid, liquid or gaseous compounds in organic solvents, as well as aqueous solutions of organic or inorganic, solid and liquid compounds. or gaseous.
- Aqueous solutions of acids or bases of organic or inorganic origin are preferably used.
- Volatile organic or inorganic acids, and in particular inorganic acids are preferably used.
- the substrate carrying the transparent electrode TCO may also be manufactured and possibly etched independently of the other constituent elements of the module in order to be delivered to an assembler having the semiconductor deposition technology, responsible for the photocatalytic activity itself.
- the lower electrode 6, that is to say facing the interior of the cell relative to the incident radiation, is preferably reflective of said radiation. Its deposition (step e)) is carried out in a known manner by a vacuum deposition technique.
- the rear-face substrate 20 is laminated to the assembly by means of a plastic film 7 of the polyvinyl butyral (PBV) or ethylene-vinyl-acetate (EVA) type. according to well known techniques for obtaining a laminated glazing.
- PBV polyvinyl butyral
- EVA ethylene-vinyl-acetate
- a TCO layer a few hundred nanometers thick
- the deposition of a TCO layer is carried out according to two methods: by sputtering a ZnO ceramic target previously co-doped in gallium and aluminum on a diamond® glass in an Argon carrier gas (Example 1 to 3) or by co-spraying on a diamond® glass using three targets of ZnO, Ga2O3 and Al2O3 in an Argon carrier gas (Examples 4 to 10) .
- the Al and Ga levels are given by reference to the weight percentages of the corresponding oxides Al.sub.2O.sub.3 or Ga.sub.2O.sub.3 in the mixed oxide of zinc, aluminum and gallium constituting the TCO.
- Target-substrate distance 5 cm
- a first stack obtained from target 1, according to the invention (example 1) comprising a TCO layer consisting of a mixed oxide of ZnO doped with 1.5% by weight of Al 2 O 3 and 5.5% Ga2O3 weight,
- a second stack obtained from target 2, according to the prior art (example 2), comprising a TCO layer consisting of a ZnO oxide doped with 1.5% by weight of Al 2 O 3
- a third stack obtained from the target 3, according to the prior art (example 3), comprising a TCO layer consisting of a ZnO oxide doped with 3% by weight of Ga 2 O 3.
- TCO layers of Examples 2 and 3 are those currently used commercially for this type of TCO.
- Table 1 The evolution of the resistivity and the resistance per square was measured on the substrates according to Examples 1 to 3 during annealing at 550 ° C. in air. The annealing has been extended for each of the substrates until, on the one hand, the minimum value of the electrical conductivity of the TCO layer is determined as well as the duration of the heat treatment leading to the said minimum value of the electrical conductivity of the TCO layer, before the sudden increase of the latter due to the degradation of said layer. The results obtained are visible in FIG. 2. The values obtained from the resistivities and resistances per square measured on the TCO layers of Examples 1 to 3, after various annealing times at 550 ° C., are reported in Table 2 below. . Annealing Annealing Annealing Annealing after depot
- Such a difference is particularly decisive for the use of such layers in the photovoltaic application because it allows greater flexibility in the overall manufacturing process of photovoltaic cells, especially if certain components must be deposited hot, such as CdTe active layers or if various successive annealing and tempering steps must be performed successively during the manufacture of the cell, as is most often necessary.
- the optical properties of the substrates provided with the various TCO layers according to Examples 1 to 3 were also measured for the same target value of the resistance per square of 10 ohms / square representative of an acceptable conductivity of the layers.
- TCO for photovoltaic application.
- annealing was performed at 550 ° C in air for each of the substrates.
- the heat treatment has been prolonged, according to the data shown in FIG. 2, until a resistance / square equal to or as close as possible to 10 ohms / square is obtained.
- the light transmission T L of these 3 samples at 10 ohms / D was measured.
- the ASQE parameter was also determined by carrying out the product of integrating the absorption spectrum of the substrate comprising the TCO layer, over the entire considered domain (300-2500 microns), with the quantum efficiency spectrum QE of the material considered (that is to say a-Si, ⁇ - ⁇ , CdTE or tandem between a-Si / ⁇ - ⁇ ⁇ ) for this same domain.
- the quantum efficiency QE is in a known manner the expression of the probability (between 0 and 1) that an incident photon with a wavelength according to the abscissa is transformed into an electron-hole pair for the photovoltaic material considered.
- the quantum efficiency curve QE of said materials is presented in FIG.
- the performance of photovoltaic cells obtained from the substrates according to Examples 1 to 3 were also measured in the case of a CdTe type photovoltaic layer. More precisely, in accordance with the cell described according to FIG. 1, on the substrates according to examples 1 to 3, whose resistance of the TCO layer in the cell is adjusted to 10 ohms / square, a layer was deposited according to conventional techniques. photovoltaic type CdTe, and a rear electrode type Gold. The characteristics of the cell (according to the model of an equivalent electrical circuit for a solar cell or "solar cell equivalent" circuit according to the English term) are measured classically according to usual settings:
- this is the solar efficiency of the cell, defined as the percentage of power converted (and collected) from the light absorbed for a solar cell connected to the electrical circuit. This term is calculated by making the ratio of the maximum power point Pm by the product of the irradiance of the incident light (E in W / m 2 ) under standard conditions and the surface of the solar cell (in m 2 ). Standard conditions mean a temperature of 25 ° C and an irradiance of 1000 W / m 2 according to the AM1.5 spectrum.
- the target ZnO is disposed in the spraying chamber in the central position and the other two targets are inclined towards the target ZnO so as to create a composition gradient.
- the conditions in the spray chamber are as follows:
- Ga 2 O 3 16 to 120W
- Target-substrate distance 150 mm
- the powers applied to the targets are modified so as to vary the respective proportions of the constituents ZnO, Al 2 O 3 and Ga 2 O 3 in the TCO films.
- the substrate according to Example 4 is in accordance with the invention.
- the substrates according to Examples 5 to 10 are given for comparison. More specifically, the front-face substrates according to Comparative Examples 5 and 6 comprise a TCO layer of ZnO type co-doped Al and Ga, starting from FIG. co-sputtering of the three previous targets, but under conditions resulting in doping Al and Ga not in accordance with the invention.
- the front face substrates according to Comparative Examples 7 to 9 comprise a TCO layer of the AZO type with different Al doping levels.
- the front face substrate according to Comparative Example 10 comprises a TCO layer of the GZO type.
- Table 5 shows in more detail the composition of the different stacks prepared and their physical thicknesses (real).
- the resistivities of the different TCO layers on the substrates of Examples 4 to 10 were measured according to standard techniques before and after annealing in an oven under ambient atmosphere at 550 ° C. for 1 to 3 minutes, the duration of the treatment being adjusted to finally obtain the minimum resistivity for each TCO layer. The results are reported in Table 6. In the table, for ease of comparison, the resistivities are relative to the resistivity initially measured on the TCO layer of Example 4 according to the invention, prior to annealing. Type Percent Relative Resistivity
- Example 4 ZnO: Al, GaAl: 0.5; Ga: 10 1 0.37
- Example 6 ZnO: Al, Ga Al: 1.6; Ga: 3.5 1, 6 3.9
- Example 7 ZnO: Al Al: 0.5 45 150
- Example 10 ZnO: Ga Ga: 8.5 5.5 1, 7
- the substrate provided with the TCO layer according to the invention exhibits, before and especially after annealing, the lowest resistivity values, which justifies its use as an electrode layer in photovoltaic cells of the following type. of those previously described. It has also been sought to measure the moisture resistance properties of the various substrates according to the preceding examples.
- the test consisted of subjecting substrates with TCO layers to severe humidity and temperature conditions, that is to say to an atmosphere with 85% moisture content. relative, at a temperature of 85 ° C and for 14 days.
- Table 7 The results reported in Table 7 show a much higher behavior and moisture resistance of the layer of Example 4 according to the invention compared to that of the AZO-type layer (Example 8). Similarly, the layer of Example 4 has a much better resistance over time compared to the GZO layer (Example 10), the resistivity of the TCO layer according to Example 4 even seeming almost stabilized at very low levels at the end of the moisture resistance test.
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Abstract
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FR1051454A FR2956924B1 (en) | 2010-03-01 | 2010-03-01 | PHOTOVOLTAIC CELL INCORPORATING A NEW TCO LAYER |
PCT/FR2011/050406 WO2011107701A1 (en) | 2010-03-01 | 2011-02-28 | Photovoltaic cell having a novel tco layer built therein |
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KR20140140187A (en) * | 2013-05-28 | 2014-12-09 | 삼성코닝어드밴스드글라스 유한회사 | ZnO BASED SPUTTERING TARGET AND PHOTOVOLTAIC CELL HAVING PASSIVATION LAYER DEPOSITED BY THE SAME |
KR102030915B1 (en) * | 2015-04-10 | 2019-10-10 | 세키스이가가쿠 고교가부시키가이샤 | Interlayer for laminated glass, laminated glass, and production method for interlayer for laminated glass |
CN105274486A (en) * | 2015-11-18 | 2016-01-27 | 南京迪纳科光电材料有限公司 | Preparing method for amorphous AlGaZnO transparent electrode material |
CN110165001B (en) * | 2019-06-03 | 2020-11-24 | 南阳理工学院 | Rare earth doped photovoltaic thin film material and preparation method thereof |
CN114093969B (en) * | 2020-07-31 | 2024-04-12 | 苏州阿特斯阳光电力科技有限公司 | Battery piece, photovoltaic module with battery piece and manufacturing method of photovoltaic module |
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US20070029186A1 (en) * | 2005-08-02 | 2007-02-08 | Alexey Krasnov | Method of thermally tempering coated article with transparent conductive oxide (TCO) coating using inorganic protective layer during tempering and product made using same |
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US20080178932A1 (en) * | 2006-11-02 | 2008-07-31 | Guardian Industries Corp. | Front electrode including transparent conductive coating on patterned glass substrate for use in photovoltaic device and method of making same |
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