WO2014014116A1 - Passivation film, coating material, solar-cell element, and silicon substrate with passivation film attached thereto - Google Patents
Passivation film, coating material, solar-cell element, and silicon substrate with passivation film attached thereto Download PDFInfo
- Publication number
- WO2014014116A1 WO2014014116A1 PCT/JP2013/069706 JP2013069706W WO2014014116A1 WO 2014014116 A1 WO2014014116 A1 WO 2014014116A1 JP 2013069706 W JP2013069706 W JP 2013069706W WO 2014014116 A1 WO2014014116 A1 WO 2014014116A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- passivation film
- silicon substrate
- vanadium
- passivation
- Prior art date
Links
- 238000002161 passivation Methods 0.000 title claims abstract description 266
- 239000000758 substrate Substances 0.000 title claims abstract description 139
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 137
- 239000010703 silicon Substances 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title claims description 116
- 238000000576 coating method Methods 0.000 title claims description 36
- 239000011248 coating agent Substances 0.000 title claims description 32
- -1 solar-cell element Substances 0.000 title 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 100
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 47
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 45
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 72
- 239000002243 precursor Substances 0.000 claims description 42
- 238000009792 diffusion process Methods 0.000 claims description 35
- 239000012535 impurity Substances 0.000 claims description 21
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 13
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 12
- 229910000312 vanadium group oxide Inorganic materials 0.000 claims description 7
- 239000010408 film Substances 0.000 description 224
- 238000010438 heat treatment Methods 0.000 description 62
- 238000010304 firing Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 37
- 239000000126 substance Substances 0.000 description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 239000010409 thin film Substances 0.000 description 22
- 238000009501 film coating Methods 0.000 description 20
- 125000002524 organometallic group Chemical group 0.000 description 20
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 229910052698 phosphorus Inorganic materials 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- 229910052581 Si3N4 Inorganic materials 0.000 description 13
- 238000011160 research Methods 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000006798 recombination Effects 0.000 description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 9
- 238000005215 recombination Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 230000005669 field effect Effects 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- IDIDIJSLBFQEKY-UHFFFAOYSA-N ethanol;oxovanadium Chemical compound [V]=O.CCO.CCO.CCO IDIDIJSLBFQEKY-UHFFFAOYSA-N 0.000 description 3
- 229910021478 group 5 element Inorganic materials 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QASMZJKUEABJNR-UHFFFAOYSA-N methanolate;tantalum(5+) Chemical compound [Ta+5].[O-]C.[O-]C.[O-]C.[O-]C.[O-]C QASMZJKUEABJNR-UHFFFAOYSA-N 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008571 general function Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- 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
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- 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
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a passivation film, a coating material, a solar cell element, and a silicon substrate with a passivation film.
- the solar cell element is a photoelectric conversion element that converts solar energy into electric energy, and is expected to be further spread in the future as one of pollution-free and infinite renewable energy.
- a solar cell element usually includes a p-type semiconductor and an n-type semiconductor, and generates electron-hole pairs inside the semiconductor by absorbing solar energy.
- the generated electrons are transferred to the n-type semiconductor and the holes (holes) are transferred to the p-type semiconductor, and these are collected by the electrodes, whereby electric energy can be used outside.
- the solar cell element it is important to increase efficiency so that solar energy can be converted into as much electric energy as possible and output.
- Charge loss can occur for various reasons. In particular, the generated electrons and holes are recombined, and the charge is lost.
- a crystalline silicon solar cell element that is currently mainstream uses a p-type silicon substrate 11 having a pyramid structure portion (not shown) for preventing reflection, which is called a texture.
- the n layer 12 is formed on the back surface, and the p + layer 14 is formed on the back surface.
- a silicon nitride (SiN) film 13 is provided as a light-receiving surface passivation film on the light-receiving surface side, and a silver collector electrode called a finger electrode 15 is formed.
- an aluminum electrode 16 that also serves to suppress light transmission on the back surface is formed on the entire surface.
- the silicon n layer 12 is generally formed by diffusing phosphorus into the silicon substrate 11 from a gas phase or a solid phase.
- the p + layer 14 on the back surface is formed by applying heat of 700 ° C. or more at the contact portion between the aluminum and the p-type silicon substrate 11 when forming the aluminum electrode 16 on the back surface. Through this step, aluminum diffuses into the silicon substrate 11 to form an alloy, and the p + layer 14 is formed.
- An electric field derived from a potential difference is formed at the interface between the p-type silicon substrate 11 and the p + layer 14.
- This electric field generated by the p + layer 14 is mainly generated in the p-type silicon substrate 11, and of the holes and electrons diffused on the back surface, the electrons are reflected inside the p-type silicon substrate 11, and holes are formed. Is selectively passed through the p + layer 14. That is, this action brings about an effect of eliminating electrons and reducing recombination of holes and electrons at the back surface interface of the solar cell element.
- a conventional solar cell element having such an aluminum alloy layer on the back surface is widely used as a structure of a solar cell element suitable for mass production because it is relatively easy to manufacture.
- the back surface passivation type solar cell element is inherently present at the interface between the silicon substrate and the passivation film by covering the back surface of the solar cell element with a passivation film. The dangling bond can be terminated. That is, the back surface passivation type solar cell element does not attempt to reduce the carrier recombination rate due to the electric field generated at the p / p + interface, but reduces the density of recombination centers on the back surface itself, and the carrier (hole and hole). To recombine electrons).
- a passivation film that suppresses the carrier recombination rate by lowering the carrier concentration by an electric field generated by a fixed charge in the passivation film is called a field effect passivation film.
- a field effect passivation film that can move carriers away from the recombination centers by an electric field is effective.
- an aluminum oxide film formed by ALD-CVD (Atomic Layer Deposition-Chemical Vapor Deposition) is known.
- ALD-CVD Advanced Chemical Vapor Deposition
- a technique using an aluminum oxide sol-gel coating film as a passivation film is known (for example, International Publication No. 2008/137174 pamphlet, JP 2009-194120 A and B). . Hoex, J. Schmidt, P. Pohl, M. C. M. van de Sanden, W. M. M. Kesseles, “Silicon surface passivation by atomic layer deposited Al2O3”, J Appl. Phys, 104, p.44 (2008)).
- the ALD method has a problem that it is difficult to reduce the cost because the deposition rate is low and high throughput cannot be obtained. Furthermore, after forming the aluminum oxide film, a through hole for making contact with the electrode on the back surface is necessary, and some patterning technique is required.
- the first problem to be solved by the present invention is to realize a passivation film having a long carrier lifetime and a negative fixed charge at a low cost.
- a second problem is to provide a coating type material for realizing the formation of the passivation film.
- a third problem is to realize a low-cost and highly efficient solar cell element using the passivation film at a low cost.
- a fourth problem is to realize a silicon substrate with a passivation film that extends the carrier lifetime of the silicon substrate and has a negative fixed charge at low cost.
- a passivation film for use in a solar cell element having a silicon substrate comprising aluminum oxide and at least one oxide of vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
- the carrier lifetime of the silicon substrate is increased and negative fixed charge is provided. Can do. The reason why the carrier lifetime becomes long is not clear, but one of the reasons may be termination of dangling bonds.
- ⁇ 2> The passivation film according to ⁇ 1>, wherein a mass ratio of the vanadium group element oxide to the aluminum oxide (vanadium group element oxide / aluminum oxide) is 30/70 to 90/10. This can have a large stable negative fixed charge.
- ⁇ 3> The passivation film according to ⁇ 1> or ⁇ 2>, in which a total content of the oxide of the vanadium group element and the aluminum oxide is 90% or more.
- the oxide of the vanadium group element includes any of oxides of two or three kinds of vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide. Any one of ⁇ 1> to ⁇ 3> The passivation film according to claim 1.
- ⁇ 5> Heat treatment of a coating-type material comprising: a precursor of aluminum oxide; and a precursor of an oxide of at least one vanadium group element selected from the group consisting of a precursor of vanadium oxide and a precursor of tantalum oxide.
- the coating type material of the present invention for solving the second problem is as follows. ⁇ 6> an aluminum oxide precursor, and at least one vanadium group element oxide precursor selected from the group consisting of a vanadium oxide precursor and a tantalum oxide precursor, and having a silicon substrate A coating type material used for forming a passivation film of a solar cell element.
- the solar cell element of the present invention for solving the third problem is as follows. ⁇ 7> a p-type silicon substrate; An n-type impurity diffusion layer formed on the first surface side which is the light-receiving surface side of the silicon substrate; A first electrode formed on the impurity diffusion layer; A passivation film formed on the second surface side opposite to the light receiving surface side of the silicon substrate and having an opening; A second electrode formed on the second surface side of the silicon substrate and electrically connected to the second surface side of the silicon substrate through the opening of the passivation film;
- the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
- a p-type impurity diffusion layer formed on part or all of the second surface side of the silicon substrate and doped with an impurity at a higher concentration than the silicon substrate,
- the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
- n-type impurity diffusion layer formed on a part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate, The solar cell element according to ⁇ 9>, wherein the second electrode is electrically connected to the n-type impurity diffusion layer through an opening of the passivation film.
- ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a mass ratio of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 30/70 to 90/10 .
- ⁇ 12> The solar cell element according to any one of ⁇ 7> to ⁇ 11>, wherein the total content of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 90% or more.
- the oxide of the vanadium group element includes an oxide of two or three vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide, ⁇ 7> to ⁇ 12>
- the solar cell element according to any one of the above.
- the silicon substrate with a passivation film of the present invention for solving the fourth problem is as follows. ⁇ 14> a silicon substrate; The passivation film for a solar cell element according to any one of ⁇ 1> to ⁇ 5> provided on the entire surface or a part of the silicon substrate, A silicon substrate with a passivation film.
- a passivation film having a long silicon carrier lifetime and a negative fixed charge can be realized at low cost.
- a coating type material for realizing the formation of the passivation film can be provided.
- a low-cost and highly efficient solar cell element using the passivation film can be realized.
- a silicon substrate with a passivation film having a long carrier lifetime and a negative fixed charge can be realized at low cost.
- the term “process” is not only an independent process, but is included in this term if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
- a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
- the term “layer” includes a configuration of a shape formed in part in addition to a configuration of a shape formed on the entire surface when observed as a plan view.
- the passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide. It is what was included.
- the passivation film includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, thereby extending the carrier lifetime of the silicon substrate and negative fixed charge. Can have. Therefore, the passivation film of the present invention can improve the photoelectric conversion efficiency of the silicon solar cell element. Furthermore, since the passivation film of the present invention can be formed using a coating method or a printing method, the film formation process is simple and the film formation throughput is high. As a result, pattern formation is easy and cost reduction can be achieved.
- the amount of fixed charges possessed by the passivation film can be controlled by changing the composition of the passivation film.
- the vanadium group element is a Group 5 element in the periodic table, and is an element selected from vanadium, niobium, and tantalum.
- the passivation film having the function of band bending by the fixed charge in the film [2] is called a field effect passivation film, and it works to prevent recombination by chasing either holes or electrons with the charge.
- a field effect passivation film In a solar cell element using a normal p-type silicon substrate, electrons are extracted from the light-receiving surface side and holes are extracted from the back surface side among the generated carriers.
- a field effect passivation film having a negative fixed charge is required in order to drive electrons back to the light receiving surface (for example, JP 2012-33759 A). Publication).
- the fixed charge of the passivation film can be made negative by using the oxide of the vanadium group element and aluminum oxide in combination, and further, the oxide of the vanadium group element and the aluminum oxide
- the mass ratio [oxide of vanadium group element / aluminum oxide] is set to 30/70 to 90/10, whereby a large stabilized negative fixed charge is obtained. Tend to be achieved.
- the passivation film of the present invention can be formed using a coating method or a printing method, the film formation process is simple and the film formation throughput is high. As a result, in the present embodiment, pattern formation is easy and cost reduction can be achieved.
- the mass ratio of the oxide of vanadium group element to aluminum oxide is preferably 35/65 to 90/10, from the viewpoint that the negative fixed charge can be stabilized, and is preferably 50/50 to 90/10. More preferably.
- the mass ratio of vanadium group element oxide and aluminum oxide in the passivation film is determined by energy dispersive X-ray spectroscopy (EDX), secondary ion mass spectrometry (SIMS), and high frequency inductively coupled plasma mass spectrometry (ICP-MS). ) Can be measured. Specific measurement conditions are as follows in the case of ICP-MS, for example. Dissolving the passivation film in acid or alkaline aqueous solution, atomizing this solution and introducing it into Ar plasma, measuring the wavelength and intensity by spectroscopically analyzing the light emitted when the excited element returns to the ground state, Element qualification is performed from the obtained wavelength, and quantification is performed from the obtained intensity.
- EDX energy dispersive X-ray spectroscopy
- SIMS secondary ion mass spectrometry
- ICP-MS high frequency inductively coupled plasma mass spectrometry
- the total content of the vanadium group element oxide and aluminum oxide in the passivation film is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of maintaining good characteristics.
- the components other than the oxide of vanadium group elements and aluminum oxide in the passivation film increase, the effect of negative fixed charges increases.
- components other than vanadium group oxide and aluminum oxide may be contained as organic components from the viewpoint of improving the film quality and adjusting the elastic modulus.
- the presence of the organic component in the passivation film can be confirmed by elemental analysis and measurement of the FT-IR of the film.
- vanadium oxide As the oxide of the vanadium group element, it is preferable to select vanadium oxide (V 2 O 5 ) from the viewpoint of obtaining a larger negative fixed charge. Since vanadium oxide has a negative fixed charge larger than that of tantalum oxide, carrier recombination can be more effectively prevented.
- the passivation film may include two or three vanadium group oxides selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide as the vanadium group element oxide.
- the passivation film is preferably obtained by heat-treating a coating-type material, and can be obtained by forming a coating-type material using a coating method or a printing method, and then removing organic components by heat treatment. More preferred. That is, the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a vanadium group element oxide precursor. Details of the coating type material will be described later.
- the coating type material of the present embodiment is a coating type material used for a passivation film for a solar cell element having a silicon substrate, and includes a precursor of aluminum oxide, a precursor of vanadium oxide, and a precursor of tantalum oxide. And a precursor of an oxide of at least one vanadium group element selected from the group.
- a precursor of the oxide of the vanadium group element contained in the coating material a precursor of vanadium oxide (V 2 O 5 ) is selected from the viewpoint of the negative fixed charge of the passivation film formed from the coating material. It is preferable.
- the coating type material is composed of two or three vanadium group elements selected from the group consisting of vanadium oxide precursors, niobium oxide precursors and tantalum oxide precursors as vanadium group oxide precursors. An oxide precursor may also be included.
- the aluminum oxide precursor can be used without particular limitation as long as it produces aluminum oxide.
- As the aluminum oxide precursor it is preferable to use an organic aluminum oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and a chemically stable viewpoint.
- Examples of the organic aluminum oxide precursor include aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , Kojundo Chemical Laboratory Co., Ltd., SYM-AL04.
- the precursor of the oxide of the vanadium group element can be used without particular limitation as long as it generates an oxide of the vanadium group element.
- the vanadium group element oxide precursor is preferably an organic vanadium group oxide oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and chemically stable. .
- organic vanadium oxide precursors examples include vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13), High Purity Chemical Laboratory, V-02 can be mentioned.
- organic tantalum oxide precursors include tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12), Kojundo Chemical Laboratory, Ta-10-P Can be mentioned.
- organic niobium oxide precursors examples include niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), High Purity Chemical Laboratory, Nb-05. Can be mentioned.
- a passivation film By forming a coating type material containing an organic vanadium group oxide precursor and an organic aluminum oxide precursor using a coating method or a printing method, and then removing the organic components by a heat treatment, A passivation film can be obtained. Therefore, as a result, a passivation film containing an organic component may be used.
- the content of the organic component in the passivation film is more preferably less than 10% by mass, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
- the solar cell element (photoelectric conversion device) of the present embodiment has a passivation film (insulating film, protective insulating film) described in the first embodiment in the vicinity of the photoelectric conversion interface of the silicon substrate, that is, aluminum oxide and oxidized It has a film containing at least one oxide of a vanadium group element selected from the group consisting of vanadium and tantalum oxide.
- a vanadium group element selected from the group consisting of vanadium and tantalum oxide.
- FIGS. 2 to 5 are sectional views showing first to fourth configuration examples of the solar cell element using a passivation film on the back surface of the present embodiment.
- silicon substrate crystalline silicon substrate, semiconductor substrate
- silicon substrate either single crystal silicon or polycrystalline silicon
- a p-type crystalline silicon substrate or an n-type crystalline silicon substrate may be used.
- silicon substrate 1 either p-type crystalline silicon or n-type crystalline silicon may be used. From the viewpoint of further exerting the effects of the present invention, p-type crystalline silicon is more suitable.
- the single crystal silicon or polycrystalline silicon used for the silicon substrate 1 may be any material, but single crystal silicon or polycrystalline silicon having a resistivity of 0.5 ⁇ ⁇ cm to 10 ⁇ ⁇ cm is preferable.
- n is obtained by doping (adding) a group V element such as phosphorus on the light-receiving surface side (upper side, first surface, surface in the figure) of the p-type silicon substrate 1.
- a mold diffusion layer 2 is formed.
- a pn junction is formed between the silicon substrate 1 and the diffusion layer 2.
- a light receiving surface antireflection film 3 such as a silicon nitride (SiN) film, and a first electrode 5 (light receiving surface side electrode, first surface electrode, upper surface electrode) using silver (Ag) or the like. , Surface electrode) is formed.
- the light receiving surface antireflection film 3 may also have a function as a light receiving surface passivation film. By using the SiN film, both functions of the light receiving surface antireflection film and the light receiving surface passivation film can be provided.
- the solar cell element of the present invention may or may not have the light-receiving surface antireflection film 3.
- the light receiving surface of the solar cell element is preferably formed with a concavo-convex structure (texture structure) in order to reduce the reflectance on the surface, but the solar cell element of the present invention has a texture structure. Even if it does not have.
- a BSF (Back Surface Field) layer 4 which is a layer doped with a group III element such as aluminum or boron is formed on the back side of the silicon substrate 1 (the lower side, the second side, and the back side in the figure).
- the solar cell element of the present invention may or may not have the BSF layer 4.
- Electrodes 6 back surface side electrode, second surface electrode, back surface electrode are formed.
- the contact region (the surface on the back surface side of the silicon substrate 1 when the BSF layer 4 is not provided) and the second electrode 6 are electrically connected.
- a passivation film 7 (passivation layer) containing aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide is provided in a portion excluding the opening OA). Is formed.
- the passivation film 7 of the present invention can have a negative fixed charge. Due to this fixed charge, electrons which are minority carriers among the carriers generated in the silicon substrate 1 by light rebound to the surface side. For this reason, a short circuit current increases and it is anticipated that photoelectric conversion efficiency will improve.
- the second electrode 6 is formed on the entire surface of the contact region (opening OA) and the passivation film 7.
- the second electrode 6 is formed only in the region (opening OA).
- the second electrode 6 may be formed only on the contact region (opening OA) and part of the passivation film 7. Even with the solar cell element having the configuration shown in FIG. 3, the same effect as that of FIG. 2 (first configuration example) can be obtained.
- the BSF layer 4 is formed only on a part of the back side including the contact region (opening OA portion) with the second electrode 6, and FIG. 2 (first configuration example). Thus, it is not formed on the entire back surface side. Even with the solar cell element having such a configuration (FIG. 4), the same effect as that of FIG. 2 (first configuration example) can be obtained. Further, according to the solar cell element of the third configuration example of FIG. 4, the BSF layer 4, that is, the impurity is doped at a higher concentration than the silicon substrate 1 by doping a group III element such as aluminum or boron. Since the area is small, it is possible to obtain higher photoelectric conversion efficiency than that in FIG. 2 (first configuration example).
- FIG. 5 a fourth configuration example shown in FIG. 5 will be described.
- the second electrode 6 is formed on the entire surface of the contact region (opening OA) and the passivation film 7, but in FIG. 5 (fourth configuration example), the contact The second electrode 6 is formed only in the region (opening OA).
- the second electrode 6 may be formed only on the contact region (opening OA) and part of the passivation film 7. Even with the solar cell element having the configuration shown in FIG. 5, the same effect as that of FIG. 4 (third configuration example) can be obtained.
- the second electrode 6 when the second electrode 6 is applied by a printing method and baked at a high temperature to form the entire surface on the back side, a convex warpage tends to occur in the temperature lowering process. Such warpage may cause damage to the solar cell element, which may reduce the yield. Further, the problem of warpage increases as the silicon substrate becomes thinner. The cause of this warp is that stress is generated because the second electrode 6 made of metal (for example, aluminum) has a larger thermal expansion coefficient than the silicon substrate, and the shrinkage in the temperature lowering process is correspondingly large.
- metal for example, aluminum
- the electrode structure tends to be symmetrical vertically. This is preferable because stress due to the difference in thermal expansion coefficient is not easily generated. However, in that case, it is preferable to provide a separate reflective layer.
- a texture structure is formed on the surface of the silicon substrate 1 shown in FIG.
- the texture structure may be formed on both sides of the silicon substrate 1 or only on one side (light receiving side).
- the damaged layer of the silicon substrate 1 is removed by immersing the silicon substrate 1 in a heated potassium hydroxide or sodium hydroxide solution.
- a texture structure is formed on both surfaces or one surface (light receiving surface side) of the silicon substrate 1 by immersing in a solution containing potassium hydroxide and isopropyl alcohol as main components.
- this step may be omitted.
- a phosphorus diffusion layer (n + layer) is formed as the diffusion layer 2 on the silicon substrate 1 by thermal diffusion of phosphorus oxychloride (POCl 3 ) or the like.
- the phosphorus diffusion layer can be formed, for example, by applying a coating-type doping material solution containing phosphorus to the silicon substrate 1 and performing heat treatment. After the heat treatment, the phosphorus glass layer formed on the surface is removed with an acid such as hydrofluoric acid, whereby a phosphorus diffusion layer (n + layer) is formed as the diffusion layer 2.
- the method for forming the phosphorus diffusion layer is not particularly limited.
- the phosphorus diffusion layer may be formed so that the depth from the surface of the silicon substrate 1 is in the range of 0.2 ⁇ m to 0.5 ⁇ m, and the sheet resistance is in the range of 40 ⁇ / ⁇ (ohm / square) to 100 ⁇ / ⁇ . preferable.
- a BSF layer 4 on the back surface side is formed by applying a coating-type doping material solution containing boron, aluminum or the like to the back surface side of the silicon substrate 1 and performing heat treatment.
- a coating-type doping material solution containing boron, aluminum or the like for the application, methods such as screen printing, ink jet, dispensing, spin coating and the like can be used.
- the BSF layer 4 is formed by removing the layer of boron glass, aluminum or the like formed on the back surface with hydrofluoric acid, hydrochloric acid or the like.
- the method for forming the BSF layer 4 is not particularly limited.
- the BSF layer 4 is preferably formed so that the concentration range of boron, aluminum, etc.
- the solar cell element of the present invention may or may not have the BSF layer 4, this step may be omitted.
- both the diffusion layer 2 on the light receiving surface and the BSF layer 4 on the back surface are formed using a coating-type doping material solution
- the above-described doping material solution is applied to both surfaces of the silicon substrate 1 and diffused.
- the phosphorus diffusion layer (n + layer) and the BSF layer 4 as the layer 2 may be formed in a lump, and then the phosphorus glass, boron glass, etc. formed on the surface may be removed in a lump.
- a silicon nitride film as the light-receiving surface antireflection film 3 is formed on the diffusion layer 2.
- the method for forming the light receiving surface antireflection film 3 is not particularly limited.
- the light-receiving surface antireflection film 3 is preferably formed to have a thickness in the range of 50 to 100 nm and a refractive index in the range of 1.9 to 2.2.
- the light-receiving surface antireflection film 3 is not limited to a silicon nitride film, and may be a silicon oxide film, an aluminum oxide film, a titanium oxide film, or the like.
- the surface antireflection film 3 such as a silicon nitride film can be produced by a method such as plasma CVD or thermal CVD, and is preferably produced by plasma CVD that can be formed in a temperature range of 350 ° C. to 500 ° C.
- the passivation film 7 includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
- an organometallic decomposable coating material from which aluminum oxide can be obtained after firing and a precursor represented by a commercially available organometallic decomposition coating material from which an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide is obtained after firing.
- a material including a body (passivation material) is applied and heat-treated (fired) (see Embodiment 1).
- the formation of the passivation film 7 can be performed as follows, for example.
- the thickness of the passivation film 7 formed by the above method is usually about several tens of nanometers as measured by an ellipsometer.
- the coating type material is applied to a predetermined pattern including the contact area (opening OA) by a method such as screen printing, offset printing, inkjet printing, or dispenser printing.
- the above coating type material is pre-baked in the range of 80 ° C. to 180 ° C. after evaporation to evaporate the solvent, and then in a nitrogen atmosphere or in air at 600 ° C. to 1000 ° C. for 30 minutes to 3 hours. It is desirable to perform a degree of heat treatment (annealing) to form a passivation film 7 (oxide film).
- the opening (contact hole) OA is formed on the BSF layer 4 in a dot shape or a line shape.
- the passivation film 7 used in the solar cell element has a mass ratio of oxide of vanadium group element to aluminum oxide (oxide of vanadium group element / aluminum oxide) of 30. It is preferably within the range of / 70 to 90/10, more preferably within the range of 35/65 to 90/10, and even more preferably within the range of 50/50 to 90/10. Thereby, the negative fixed charge can be stabilized.
- the total content of vanadium group element oxide and aluminum oxide is 90% or more.
- the 1st electrode 5 is formed by forming the paste which has silver (Ag) as a main component on the light-receiving surface antireflection film 3 by screen printing, and performing heat processing (fire through).
- the shape of the 1st electrode 5 may be arbitrary shapes, for example, may be a well-known shape which consists of a finger electrode and a bus-bar electrode.
- the 2nd electrode 6 which is an electrode of the back side is formed.
- the 2nd electrode 6 can be formed by apply
- the shape of the second electrode 6 is desirably the same shape as the shape of the BSF layer 4, a shape covering the entire back surface, a comb shape, a lattice shape, or the like.
- the first electrode 5 and the second electrode 6 are printed by first printing pastes for forming the first electrode 5 and the second electrode 6 that are electrodes on the light receiving surface side, and then performing heat treatment (fire-through). The electrodes 6 may be formed together.
- the BSF layer 4 is formed in a contact portion between the second electrode 6 and the silicon substrate 1 in a self-alignment manner. Is formed.
- the BSF layer 4 may be separately formed by applying a coating-type doping material solution containing boron, aluminum or the like to the back side of the silicon substrate 1 and then heat-treating it. .
- the diffusion layer 2 is formed by a layer doped with a group III element such as boron
- the BSF layer 4 is formed by doping a group V element such as phosphorus.
- a leakage current flows through a portion where the inversion layer formed at the interface due to the negative fixed charge and the metal on the back surface are in contact with each other, and the conversion efficiency may be difficult to increase.
- FIG. 6 is a cross-sectional view illustrating a configuration example of a solar cell element using the light-receiving surface passivation film of the present embodiment.
- the diffusion layer 2 on the light receiving surface side is p-type doped with boron and collects holes on the light receiving surface side and electrons on the back surface side of the generated carriers. Therefore, it is preferable that the passivation film 7 having a negative fixed charge is on the light receiving surface side.
- An antireflection film made of SiN or the like may be further formed on the passivation film 7 by CVD or the like.
- the silicon substrate with a passivation film of the present embodiment is composed of a silicon substrate and the passivation film described in the first embodiment provided on the entire surface or part of the silicon substrate, that is, aluminum oxide, vanadium oxide, and tantalum oxide. And a film containing at least one oxide of a vanadium group element selected from the group consisting of:
- the passivation film includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, thereby extending the carrier lifetime of the silicon substrate and negative fixed charge.
- the characteristics (photoelectric conversion efficiency) of the solar cell element can be improved.
- Example 1 ⁇ When vanadium oxide is used as the oxide of vanadium group element> [Example 1] 3.0 g of a commercially available organometallic thin film coating type material (Co., Ltd., High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass%) from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing) 6.0 g of a commercially available organometallic thin film coating type material [Vitamin Purity Laboratory, V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) is obtained by heat treatment (firing) By mixing, a passivation material (a-1) as a coating type material was prepared.
- passivation of passivation material (a-1) on one side of a 725 ⁇ m thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) from which a natural oxide film was previously removed with hydrofluoric acid having a concentration of 0.49% by mass It was applied and placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing vanadium oxide and vanadium oxide [vanadium oxide / aluminum oxide 63/37 (mass%)]. It was 51 nm when the film thickness was measured with the ellipsometer. When the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
- the passivation material (a-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to a heat treatment (firing) at 650 ° C. for 1 hour in a nitrogen atmosphere.
- a sample in which both surfaces of the substrate were covered with a passivation film was produced.
- the carrier lifetime of this sample was measured with a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
- the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
- the carrier lifetime was 380 ⁇ s.
- the decrease in carrier lifetime (from 400 ⁇ s to 380 ⁇ s) was within ⁇ 10%, and the decrease in carrier lifetime was small.
- the passivation film obtained by heat-treating (firing) the passivation material (a-1) showed a certain degree of passivation performance and a negative fixed charge.
- Example 2 In the same manner as in Example 1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass] %] And a commercially available organic metal thin film coating type material [Vitamin Purity Laboratory, V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) can be obtained by heat treatment is changed in ratio. Then, the passivation materials (a-2) to (a-7) shown in Table 1 were prepared.
- each of the passivation materials (a-2) to (a-7) was applied to one side of a p-type silicon substrate and heat-treated (fired) to produce a passivation film.
- the voltage dependence of the capacitance of the obtained passivation film was measured, and the fixed charge density was calculated therefrom.
- the carrier lifetime was measured using a sample obtained by applying a passivation material on both sides of a p-type silicon substrate and performing heat treatment (firing).
- the passivation materials (a-2) to (a-7) are all negative after the heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film. It was found that all the passivation films obtained from the passivation materials (a-2) to (a-7) stably show negative fixed charges and can be suitably used as a passivation for a p-type silicon substrate. .
- Example 3 As a compound for obtaining vanadium oxide (V 2 O 5 ) by heat treatment (firing), commercially available vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13) is 1 0.02 g (0.010 mol) and a compound obtained from aluminum oxide (Al 2 O 3 ) by heat treatment (calcination), commercially available aluminum triisopropoxide (structure: Al (OCH (CH 3 ) 2 ) 3 , A passivation material (b-1) having a concentration of 5% by mass was prepared by dissolving 2.04 g (0.010 mol) of molecular weight: 204.25) in 60 g of cyclohexane.
- the passivation material (b-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (firing) at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain silicon.
- a sample in which both surfaces of the substrate were covered with a passivation film was produced.
- the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
- the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
- the passivation film obtained by heat-treating (sintering) the passivation material (b-1) exhibited a certain degree of passivation performance and a negative fixed charge.
- Example 4 1.52 g (0.0075 mol) of commercially available vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13) and commercially available aluminum triisopropoxide (structural formula : Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25), 1.02 g (0.005 mol) and 10 g of novolak resin were dissolved in 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to passivate. Material (b-2) was prepared.
- the passivation material (b-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere.
- a sample in which both surfaces of the substrate were covered with a passivation film was produced.
- the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 170 ⁇ s.
- the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
- the passivation film obtained by curing the passivation material (b-2) exhibited a certain degree of passivation performance and a negative fixed charge.
- tantalum oxide is used as the oxide of vanadium group element>
- Commercially available organometallic thin film coating type material [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing) and oxidation by heat treatment
- a commercially available organometallic thin film coating type material [Tapuro Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10 mass%] from which tantalum (Ta 2 O 5 ) can be obtained is mixed at a different ratio, and Passivation materials (c-1) to (c-6) shown in Fig. 2 were prepared.
- Each of the passivation materials (c-1) to (c-6) is a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ) from which the natural oxide film has been removed in advance with hydrofluoric acid having a concentration of 0.49% by mass.
- (Cm) was spin-coated on one side, placed on a hot plate, and pre-baked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and tantalum oxide. Using this passivation film, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
- each of the passivation materials (c-1) to (c-6) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
- the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
- the passivation materials (c-1) to (c-6) are all negative after heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film.
- Example 6 As a compound from which tantalum oxide (Ta 2 O 5 ) can be obtained by heat treatment (firing), 1.18 g (0.002) of commercially available tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12) is obtained. As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d-1) having a concentration of 5% by mass.
- a passivation material d-1 having a concentration of 5% by mass.
- passivation of passivation material (d-1) to one side of a 725 ⁇ m thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) with natural oxide film removed beforehand with hydrofluoric acid at a concentration of 0.49% by mass It was applied and placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, heating was performed at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and tantalum oxide. When the film thickness was measured with an ellipsometer, it was 40 nm. As a result of elemental analysis, it was found that Ta / Al / C 75/22/3 (wt%). When the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
- the passivation material (d-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere.
- a sample in which both surfaces of the substrate were covered with a passivation film was produced.
- the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 610 ⁇ s.
- the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
- the passivation film obtained by heat-treating the passivation material (d-1) showed a certain degree of passivation performance and a negative fixed charge.
- Example 7 As a compound for obtaining tantalum oxide (Ta 2 O 5 ) by heat treatment (firing), 1.18 g (0.005 mol) of commercially available tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12) ) And aluminum oxide (Al 2 O 3 ) obtained by heat treatment (firing), a commercially available aluminum triisopropoxide (structure: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25) 1.02 g (0.005 mol) and 10 g of novolak resin were dissolved in a mixture of 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to prepare a passivation material (d-2).
- the passivation material (d-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain silicon.
- a sample in which both surfaces of the substrate were covered with a passivation film was produced.
- the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 250 ⁇ s.
- the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
- the passivation film obtained by heat-treating (sintering) the passivation material (d-2) exhibited a certain degree of passivation performance and a negative fixed charge.
- the passivation film containing aluminum oxide and vanadium oxide and the passivation film containing aluminum oxide and tantalum oxide exhibit negative fixed charges and have an effect of improving the carrier lifetime due to the passivation. It has been found.
- a passivation film containing aluminum oxide and two or three vanadium group oxides selected from the group consisting of vanadium oxide, niobium oxide and tantalum oxide as oxides of vanadium group elements is examined as follows. did.
- Example 8 Commercially available organometallic thin film coating material that can be obtained by heat treatment (firing) aluminum oxide (Al 2 O 3 ) [High Purity Chemical Laboratory Co., Ltd., SYM-AL04, concentration 2.3 mass%], heat treatment (firing) Commercially available organic metal thin film coating material (VCO, Ltd., V-02, concentration 2 mass%) from which vanadium oxide (V 2 O 5 ) can be obtained by heat treatment, and tantalum oxide (Ta 2 O 5 ), a commercially available organometallic thin film coating type material [High Purity Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10% by mass] is mixed to form a passivation material (e -1) was prepared (see Table 3).
- organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
- aluminum oxide Al 2 O 3
- heat treatment firing
- Niobium oxide Nb 2 O
- VCO high purity chemical research laboratory V-02, concentration 2 mass%
- vanadium oxide V 2 O 5
- heat treatment firing
- e-2 passivation material
- organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), heat treatment (firing) Niobium oxide (Nb) by commercially available organometallic thin film coating material [Tapurio Chemical Lab. Ta-10-P, concentration 10% by mass] from which tantalum oxide (Ta 2 O 5 ) can be obtained, and heat treatment (firing) 2 O 5 ), a commercially available organometallic thin film coating material [High Purity Chemical Laboratory Nb-05, concentration 5 mass%] is mixed to form a passivation material (e-3) which is a coating material Was prepared (see Table 3).
- organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
- aluminum oxide Al 2 O 3
- heat treatment firing
- Tantalum oxide Ti 2 O 5
- heat treatment Niobium oxide
- a commercially available organometallic thin film coating type material [Co., Ltd., High Purity Chemical Laboratory Ta-10-P, concentration 10% by mass] and heat treatment (firing).
- a commercially available organometallic thin film coating type material [High purity chemical research laboratory Nb-05, concentration 5 mass%] was mixed to prepare a passivation material (e-4) as a coating type material (see Table 3). ).
- each of the passivation materials (e-1) to (e-4) is a 725 ⁇ m thick 8-inch p-type film in which the natural oxide film is previously removed with a hydrofluoric acid having a concentration of 0.49% by mass.
- a silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) was spin-coated on one side, placed on a hot plate, and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 650 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and two or more vanadium group element oxides.
- each of the passivation materials (e-1) to (e-4) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
- the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
- Example 9 In the same manner as in Example 1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass] %] And a commercially available organic metal thin film coating type material [Vitamin Purity Chemical Laboratory Co., Ltd., V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) is obtained by heat treatment (firing), or heat treatment Commercially available organic metal thin film coating type material [Tapuro Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10 mass%] from which tantalum oxide (Ta 2 O 5 ) can be obtained by (firing) is applied by coating. Passivation materials (f-1) to (f-8) as mold materials were prepared (see Table 4).
- each of the passivation materials (f-1) to (f-9) was applied to one side of a p-type silicon substrate, and then heat treatment (firing) was performed to produce a passivation film, Using this, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
- each of the passivation materials (f-1) to (f-9) was applied to both surfaces of a p-type silicon substrate, and a sample obtained by heat treatment (firing) was used. career lifetime was measured. The results obtained are summarized in Table 4.
- a passivation film containing aluminum oxide and vanadium oxide and a passivation film containing aluminum oxide and tantalum oxide exhibit a negative fixed charge, and have an effect of improving the carrier lifetime by the passivation.
- the mass ratio of vanadium oxide to aluminum oxide is 30/70 to 90/10, more preferably 35/65 to 90/10, which improves carrier lifetime and provides a stable negative fixed charge. It is more preferable from the viewpoint of achieving both.
- the mass ratio of tantalum oxide to aluminum oxide is 30/70 to 90/10, more preferably 35/65 to 90/10, which improves carrier lifetime and provides stable negative fixed charge. It is more preferable from the viewpoint of achieving both.
- the passivation film elements other than oxides of vanadium group elements in the film (here, vanadium oxide or tantalum oxide) and aluminum oxide are included as organic components from elemental analysis and FT-IR measurement results of the film. It can be seen that the content (mass) of the vanadium group element oxide (here vanadium oxide or tantalum oxide) and aluminum oxide in the passivation film is 90% or more, more preferably 95% or more. Therefore, it tends to maintain better characteristics as a passivation film.
- a passivation film containing aluminum oxide and an oxide of two or more vanadium group elements exhibits a negative fixed charge and has an effect of improving the carrier lifetime due to passivation.
- Example 10 Using a single crystal silicon substrate with boron as a dopant as the silicon substrate 1, a solar cell element having the structure shown in FIG. 4 was produced. After the surface of the silicon substrate 1 was textured, a coating type phosphorous diffusion material was applied only to the light receiving surface side, and a diffusion layer 2 (phosphorus diffusion layer) was formed by heat treatment. Thereafter, the coating type phosphorus diffusing material was removed with dilute hydrofluoric acid.
- a SiN film was formed by plasma CVD on the light receiving surface side as the light receiving surface antireflection film 3.
- the passivation material (a-1) prepared in Example 1 was applied to the region excluding the contact region (opening OA) on the back surface side of the silicon substrate 1 by an inkjet method.
- heat treatment was performed to form a passivation film 7 having an opening OA.
- a sample using the passivation material (c-1) prepared in Example 5 was separately prepared as the passivation film 7.
- a paste mainly composed of silver was screen-printed on the light-receiving surface antireflection film 3 (SiN film) formed on the light-receiving surface side of the silicon substrate 1 in the shape of predetermined finger electrodes and bus bar electrodes.
- a paste mainly composed of aluminum was screen-printed on the entire surface.
- heat treatment fire-through
- electrodes first electrode 5 and second electrode 6
- aluminum is diffused into the opening OA on the back surface to form the BSF layer 4.
- the fire-through process in which the SiN film is not perforated is described.
- the opening OA is first formed in the SiN film by etching or the like, and then the silver electrode is formed. You can also
- the passivation film 7 is not formed in the above manufacturing process, an aluminum paste is printed on the entire back surface, the p + layer 14 corresponding to the BSF layer 4 and the electrode 16 corresponding to the second electrode.
- a solar cell element having the structure of FIG.
- characteristic evaluation a short circuit current, an open circuit voltage, a fill factor, and conversion efficiency
- the characteristic evaluation was performed according to JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005). The results are shown in Table 5.
- the solar cell element having the passivation film of the present invention has both the short-circuit current and the open-circuit voltage increased, and the conversion efficiency (photoelectric conversion efficiency) is maximum as compared with the solar electronic element not having the passivation film. It has been found that the effect of the present invention can be obtained with an improvement of 0.6%.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Photovoltaic Devices (AREA)
- Paints Or Removers (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
以上の問題点に鑑み、本発明が解決しようとする第1の課題は、シリコン基板のキャリアライフタイムを長くし且つ負の固定電荷を有するパッシベーション膜を低コストで実現することである。第2の課題は、そのパッシベーション膜の形成を実現するための塗布型材料を提供することである。第3の課題は、そのパッシベーション膜を用いた低コストで効率の高い太陽電池素子を低コストで実現することである。第4の課題は、シリコン基板のキャリアライフタイムを長くし且つ負の固定電荷を有するパッシベーション膜付シリコン基板を低コストで実現することである。 However, since the negative fixed charge is unstable in the aluminum oxide coating film, it tends to be difficult to obtain the negative fixed charge by the CV (Capacitance Voltage) method.
In view of the above problems, the first problem to be solved by the present invention is to realize a passivation film having a long carrier lifetime and a negative fixed charge at a low cost. A second problem is to provide a coating type material for realizing the formation of the passivation film. A third problem is to realize a low-cost and highly efficient solar cell element using the passivation film at a low cost. A fourth problem is to realize a silicon substrate with a passivation film that extends the carrier lifetime of the silicon substrate and has a negative fixed charge at low cost.
<1>酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含み、シリコン基板を有する太陽電池素子に用いられるパッシベーション膜。
酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含むことにより、シリコン基板のキャリアライフタイムを長くし且つ負の固定電荷を有することができる。キャリアライフタイムが長くなる理由は明らかではないが、その理由の一つとして、ダングリングボンドの終端が考えられる。 Means for solving the above problems include the following aspects.
<1> A passivation film for use in a solar cell element having a silicon substrate, comprising aluminum oxide and at least one oxide of vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
By including aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, the carrier lifetime of the silicon substrate is increased and negative fixed charge is provided. Can do. The reason why the carrier lifetime becomes long is not clear, but one of the reasons may be termination of dangling bonds.
これにより大きな安定した負の固定電荷をもつことができる。 <2> The passivation film according to <1>, wherein a mass ratio of the vanadium group element oxide to the aluminum oxide (vanadium group element oxide / aluminum oxide) is 30/70 to 90/10.
This can have a large stable negative fixed charge.
<6>酸化アルミニウムの前駆体と、酸化バナジウムの前駆体及び酸化タンタルの前駆体からなる群より選択される少なくとも1種のバナジウム族元素の酸化物の前駆体と、を含み、シリコン基板を有する太陽電池素子のパッシベーション膜の形成に用いられる塗布型材料。 The coating type material of the present invention for solving the second problem is as follows.
<6> an aluminum oxide precursor, and at least one vanadium group element oxide precursor selected from the group consisting of a vanadium oxide precursor and a tantalum oxide precursor, and having a silicon substrate A coating type material used for forming a passivation film of a solar cell element.
<7>p型のシリコン基板と、
前記シリコン基板の受光面側である第1面側に形成されたn型の不純物拡散層と、
前記不純物拡散層上に形成された第1電極と、
前記シリコン基板の受光面側とは逆の第2面側に形成され、開口部を有するパッシベーション膜と、
前記シリコン基板の第2面側に形成され、前記シリコン基板の第2面側と前記パッシベーション膜の開口部を通して電気的に接続されている第2電極と、を備え、
前記パッシベーション膜は、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含む太陽電池素子。 The solar cell element of the present invention for solving the third problem is as follows.
<7> a p-type silicon substrate;
An n-type impurity diffusion layer formed on the first surface side which is the light-receiving surface side of the silicon substrate;
A first electrode formed on the impurity diffusion layer;
A passivation film formed on the second surface side opposite to the light receiving surface side of the silicon substrate and having an opening;
A second electrode formed on the second surface side of the silicon substrate and electrically connected to the second surface side of the silicon substrate through the opening of the passivation film;
The said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
前記第2電極は、前記p型の不純物拡散層と前記パッシベーション膜の開口部を通して電気的に接続されている、<7>に記載の太陽電池素子。 <8> A p-type impurity diffusion layer formed on part or all of the second surface side of the silicon substrate and doped with an impurity at a higher concentration than the silicon substrate,
The solar cell element according to <7>, wherein the second electrode is electrically connected to the p-type impurity diffusion layer through an opening of the passivation film.
前記シリコン基板の受光面側である第1面側に形成されたp型の不純物拡散層と、
前記不純物拡散層上に形成された第1電極と、
前記シリコン基板の受光面側とは逆の第2面側に形成され、開口部を有するパッシベーション膜と、
前記シリコン基板の第2面側に形成され、前記シリコン基板の第2面側と前記パッシベーション膜の開口部を通して電気的に接続されている第2電極と、を備え、
前記パッシベーション膜は、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含む太陽電池素子。 <9> an n-type silicon substrate;
A p-type impurity diffusion layer formed on the first surface which is the light-receiving surface side of the silicon substrate;
A first electrode formed on the impurity diffusion layer;
A passivation film formed on the second surface side opposite to the light receiving surface side of the silicon substrate and having an opening;
A second electrode formed on the second surface side of the silicon substrate and electrically connected to the second surface side of the silicon substrate through the opening of the passivation film;
The said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
前記第2電極は、前記n型の不純物拡散層と前記パッシベーション膜の開口部を通して電気的に接続されている、<9>に記載の太陽電池素子。 <10> An n-type impurity diffusion layer formed on a part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate,
The solar cell element according to <9>, wherein the second electrode is electrically connected to the n-type impurity diffusion layer through an opening of the passivation film.
<14>シリコン基板と、
前記シリコン基板上の全面又は一部に設けられる<1>~<5>のいずれか1項に記載の太陽電池素子用パッシベーション膜と、
を有するパッシベーション膜付シリコン基板。 The silicon substrate with a passivation film of the present invention for solving the fourth problem is as follows.
<14> a silicon substrate;
The passivation film for a solar cell element according to any one of <1> to <5> provided on the entire surface or a part of the silicon substrate,
A silicon substrate with a passivation film.
本実施の形態のパッシベーション膜は、シリコン太陽電池素子に用いられるパッシベーション膜であり、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含むようにしたものである。 (Embodiment 1)
The passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide. It is what was included.
本実施の形態の塗布型材料は、シリコン基板を有する太陽電池素子用のパッシベーション膜に用いる塗布型材料であって、酸化アルミニウムの前駆体と、酸化バナジウムの前駆体及び酸化タンタルの前駆体からなる群より選択される少なくとも1種のバナジウム族元素の酸化物の前駆体と、を含む。塗布型材料が含有するバナジウム族元素の酸化物の前駆体としては、塗布材料より形成されるパッシベーション膜の負の固定電荷の観点からは、酸化バナジウム(V2O5)の前駆体を選択することが好ましい。塗布型材料は、バナジウム族元素の酸化物の前駆体として、酸化バナジウムの前駆体、酸化ニオブの前駆体及び酸化タンタルの前駆体からなる群より選択される2種又は3種のバナジウム族元素の酸化物の前駆体を含んでもよい。 (Embodiment 2)
The coating type material of the present embodiment is a coating type material used for a passivation film for a solar cell element having a silicon substrate, and includes a precursor of aluminum oxide, a precursor of vanadium oxide, and a precursor of tantalum oxide. And a precursor of an oxide of at least one vanadium group element selected from the group. As a precursor of the oxide of the vanadium group element contained in the coating material, a precursor of vanadium oxide (V 2 O 5 ) is selected from the viewpoint of the negative fixed charge of the passivation film formed from the coating material. It is preferable. The coating type material is composed of two or three vanadium group elements selected from the group consisting of vanadium oxide precursors, niobium oxide precursors and tantalum oxide precursors as vanadium group oxide precursors. An oxide precursor may also be included.
本実施の形態の太陽電池素子(光電変換装置)は、シリコン基板の光電変換界面の近傍に上記実施の形態1で説明したパッシベーション膜(絶縁膜、保護絶縁膜)、すなわち、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物とを含む膜を有するものである。酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物とを含むことにより、シリコン基板のキャリアライフタイムを長くし且つ負の固定電荷を有することができ、太陽電池素子の特性(光電変換効率)を向上させることができる。 (Embodiment 3)
The solar cell element (photoelectric conversion device) of the present embodiment has a passivation film (insulating film, protective insulating film) described in the first embodiment in the vicinity of the photoelectric conversion interface of the silicon substrate, that is, aluminum oxide and oxidized It has a film containing at least one oxide of a vanadium group element selected from the group consisting of vanadium and tantalum oxide. By containing aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, the carrier lifetime of the silicon substrate can be extended and negative fixed charges can be obtained. And the characteristics (photoelectric conversion efficiency) of the solar cell element can be improved.
まず、本実施の形態の太陽電池素子の構造について図2~図5を参照しながら説明する。図2~図5は、本実施の形態の裏面にパッシベーション膜を用いた太陽電池素子の第1~第4構成例を示す断面図である。 <Description of structure>
First, the structure of the solar cell element of the present embodiment will be described with reference to FIGS. 2 to 5 are sectional views showing first to fourth configuration examples of the solar cell element using a passivation film on the back surface of the present embodiment.
次に、上記構成をもつ本実施の形態の太陽電池素子(図2~図5)の製造方法の一例について説明する。ただし、本発明は、以下に述べる方法で作製した太陽電池素子に限るものではない。 <Product description>
Next, an example of a method for manufacturing the solar cell element (FIGS. 2 to 5) of the present embodiment having the above configuration will be described. However, the present invention is not limited to the solar cell element produced by the method described below.
本実施の形態のパッシベーション膜付シリコン基板は、シリコン基板と、シリコン基板上の全面又は一部に設けられる上記実施の形態1で説明したパッシベーション膜、すなわち、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含む膜を有するものである。パッシベーション膜が酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含むことにより、シリコン基板のキャリアライフタイムを長くし且つ負の固定電荷を有することができ、太陽電池素子の特性(光電変換効率)を向上させることができる。 (Embodiment 4)
The silicon substrate with a passivation film of the present embodiment is composed of a silicon substrate and the passivation film described in the first embodiment provided on the entire surface or part of the silicon substrate, that is, aluminum oxide, vanadium oxide, and tantalum oxide. And a film containing at least one oxide of a vanadium group element selected from the group consisting of: The passivation film includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, thereby extending the carrier lifetime of the silicon substrate and negative fixed charge. The characteristics (photoelectric conversion efficiency) of the solar cell element can be improved.
[実施例1]
熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、SYM-AL04、濃度2.3質量%]を3.0gと、熱処理(焼成)により酸化バナジウム(V2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、V-02、濃度2質量%]を6.0gとを混合して、塗布型材料であるパッシベーション材料(a-1)を調製した。 <When vanadium oxide is used as the oxide of vanadium group element>
[Example 1]
3.0 g of a commercially available organometallic thin film coating type material (Co., Ltd., High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass%) from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing) 6.0 g of a commercially available organometallic thin film coating type material [Vitamin Purity Laboratory, V-02,
実施例1と同様に、熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、SYM-AL04、濃度2.3質量%]と、熱処理により酸化バナジウム(V2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、V-02、濃度2質量%]とを、比率を変えて混合して、表1に示すパッシベーション材料(a-2)~(a-7)を調製した。 [Example 2]
In the same manner as in Example 1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass] %] And a commercially available organic metal thin film coating type material [Vitamin Purity Laboratory, V-02,
熱処理(焼成)により酸化バナジウム(V2O5)が得られる化合物として、市販のバナジウム(V)オキシトリエトキシド(構造式:VO(OC2H5)3、分子量:202.13)を1.02g(0.010mol)と、熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる化合物として、市販のアルミニウムトリイソプロポキシド(構造式:Al(OCH(CH3)2)3、分子量:204.25)を2.04g(0.010mol)とをシクロヘキサン60gに溶解して、濃度5質量%のパッシベーション材料(b-1)を調製した。 [Example 3]
As a compound for obtaining vanadium oxide (V 2 O 5 ) by heat treatment (firing), commercially available vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13) is 1 0.02 g (0.010 mol) and a compound obtained from aluminum oxide (Al 2 O 3 ) by heat treatment (calcination), commercially available aluminum triisopropoxide (structure: Al (OCH (CH 3 ) 2 ) 3 , A passivation material (b-1) having a concentration of 5% by mass was prepared by dissolving 2.04 g (0.010 mol) of molecular weight: 204.25) in 60 g of cyclohexane.
市販のバナジウム(V)オキシトリエトキシド(構造式:VO(OC2H5)3、分子量:202.13)を1.52g(0.0075mol)と、市販のアルミニウムトリイソプロポキシド(構造式:Al(OCH(CH3)2)3、分子量:204.25)を1.02g(0.005mol)と、ノボラック樹脂10gとを、ジエチレングリコールモノブチルエーテルアセタート10gとシクロヘキサン10gに溶解して、パッシベーション材料(b-2)を調製した。 [Example 4]
1.52 g (0.0075 mol) of commercially available vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13) and commercially available aluminum triisopropoxide (structural formula : Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25), 1.02 g (0.005 mol) and 10 g of novolak resin were dissolved in 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to passivate. Material (b-2) was prepared.
[実施例5]
熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、SYM-AL04、濃度2.3質量%]と、熱処理により酸化タンタル(Ta2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、Ta-10-P、濃度10質量%]とを比率を変えて混合して、表2に示すパッシベーション材料(c-1)~(c-6)を調製した。 <When tantalum oxide is used as the oxide of vanadium group element>
[Example 5]
Commercially available organometallic thin film coating type material [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing) and oxidation by heat treatment A commercially available organometallic thin film coating type material [Tapuro Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10 mass%] from which tantalum (Ta 2 O 5 ) can be obtained is mixed at a different ratio, and Passivation materials (c-1) to (c-6) shown in Fig. 2 were prepared.
熱処理(焼成)により酸化タンタル(Ta2O5)が得られる化合物として、市販のタンタル(V)メトキシド(構造式:Ta(OCH3)5、分子量:336.12)を1.18g(0.0025mol)と、熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる化合物として、市販のアルミニウムトリイソプロポキシド(構造式:Al(OCH(CH3)2)3、分子量:204.25)を2.04g(0.010mol)とをシクロヘキサン60gに溶解して、濃度5質量%のパッシベーション材料(d-1)を調製した。 [Example 6]
As a compound from which tantalum oxide (Ta 2 O 5 ) can be obtained by heat treatment (firing), 1.18 g (0.002) of commercially available tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12) is obtained. As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d-1) having a concentration of 5% by mass.
熱処理(焼成)により酸化タンタル(Ta2O5)が得られる化合物として、市販のタンタル(V)メトキシド(構造式:Ta(OCH3)5、分子量:336.12)1.18g(0.005mol)と、熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる化合物として、市販のアルミニウムトリイソプロポキシド(構造式:Al(OCH(CH3)2)3、分子量:204.25)を1.02g(0.005mol)と、ノボラック樹脂10gとを、ジエチレングリコールモノブチルエーテルアセタート10gとシクロヘキサン10gの混合物に溶解して、パッシベーション材料(d-2)を調製した。 [Example 7]
As a compound for obtaining tantalum oxide (Ta 2 O 5 ) by heat treatment (firing), 1.18 g (0.005 mol) of commercially available tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12) ) And aluminum oxide (Al 2 O 3 ) obtained by heat treatment (firing), a commercially available aluminum triisopropoxide (structure: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25) 1.02 g (0.005 mol) and 10 g of novolak resin were dissolved in a mixture of 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to prepare a passivation material (d-2).
上記実施例1~7に示されるとおり、酸化アルミニウムと酸化バナジウムを含むパッシベーション膜、及び酸化アルミニウムと酸化タンタルを含むパッシベーション膜において、負の固定電荷を示し、パッシベーションによるキャリアライフタイム向上の効果があることが判明した。 <When two or more vanadium group element oxides are used>
As shown in the first to seventh embodiments, the passivation film containing aluminum oxide and vanadium oxide and the passivation film containing aluminum oxide and tantalum oxide exhibit negative fixed charges and have an effect of improving the carrier lifetime due to the passivation. It has been found.
熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、SYM-AL04、濃度2.3質量%]、熱処理(焼成)により酸化バナジウム(V2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、V-02、濃度2質量%]、及び熱処理(焼成)により酸化タンタル(Ta2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、Ta-10-P、濃度10質量%]を混合して、塗布型材料であるパッシベーション材料(e-1)を調製した(表3参照)。 [Example 8]
Commercially available organometallic thin film coating material that can be obtained by heat treatment (firing) aluminum oxide (Al 2 O 3 ) [High Purity Chemical Laboratory Co., Ltd., SYM-AL04, concentration 2.3 mass%], heat treatment (firing) Commercially available organic metal thin film coating material (VCO, Ltd., V-02,
実施例1と同様に、熱処理(焼成)により酸化アルミニウム(Al2O3)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、SYM-AL04、濃度2.3質量%]と、熱処理(焼成)により酸化バナジウム(V2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、V-02、濃度2質量%]、又は熱処理(焼成)により酸化タンタル(Ta2O5)が得られる市販の有機金属薄膜塗布型材料[(株)高純度化学研究所、Ta-10-P、濃度10質量%]を混合して、塗布型材料であるパッシベーション材料(f-1)~(f-8)を調製した(表4参照)。 [Example 9]
In the same manner as in Example 1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass] %] And a commercially available organic metal thin film coating type material [Vitamin Purity Chemical Laboratory Co., Ltd., V-02,
一方、酸化アルミニウムが100質量%となるパッシベーション材料(f-9)では、負の固定電荷密度を得ることができなかった。 As shown in Table 4, when the aluminum oxide / vanadium oxide or tantalum oxide in the passivation material is 90/10 and 80/20, the fixed charge density varies greatly, and the negative fixed charge density is stable. However, it was confirmed that a negative fixed charge density can be realized by using aluminum oxide and niobium oxide. When measured by the CV method using a passivation material in which aluminum oxide / vanadium oxide or tantalum oxide is 90/10 and 80/20, a passivation film showing a positive fixed charge is obtained in some cases. It turns out that it has not reached to show stably. Note that a passivation film exhibiting a positive fixed charge can be used as a passivation film for an n-type silicon substrate.
On the other hand, a negative fixed charge density could not be obtained with the passivation material (f-9) containing 100% by mass of aluminum oxide.
以上の結果から、次のことが考察できる。 <Summary>
From the above results, the following can be considered.
シリコン基板1として、ボロンをドーパントとした単結晶シリコン基板を用いて、図4に示す構造の太陽電池素子を作製した。シリコン基板1の表面をテクスチャー処理した後、塗布型のリン拡散材を受光面側のみに塗布し、熱処理により拡散層2(リン拡散層)を形成した。その後、塗布型のリン拡散材を希フッ酸で除去した。 [Example 10]
Using a single crystal silicon substrate with boron as a dopant as the
Claims (14)
- 酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含み、シリコン基板を有する太陽電池素子に用いられるパッシベーション膜。 A passivation film for use in a solar cell element having a silicon substrate, comprising aluminum oxide and at least one oxide of vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
- 前記バナジウム族元素の酸化物と前記酸化アルミニウムの質量比(バナジウム族元素の酸化物/酸化アルミニウム)が30/70~90/10である請求項1に記載のパッシベーション膜。 The passivation film according to claim 1, wherein the mass ratio of the vanadium group element oxide to the aluminum oxide (vanadium group oxide / aluminum oxide) is 30/70 to 90/10.
- 前記バナジウム族元素の酸化物及び前記酸化アルミニウムの総含有率が90%以上である請求項1又は請求項2に記載のパッシベーション膜。 The passivation film according to claim 1, wherein the total content of the oxide of the vanadium group element and the aluminum oxide is 90% or more.
- 前記バナジウム族元素の酸化物として、酸化バナジウム、酸化ニオブ及び酸化タンタルよりなる群から選択される2種又は3種のバナジウム族元素の酸化物を含む請求項1~請求項3のいずれか1項に記載のパッシベーション膜。 The oxide of the vanadium group element includes an oxide of two or three vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide. The passivation film described in 1.
- 酸化アルミニウムの前駆体と、酸化バナジウムの前駆体及び酸化タンタルの前駆体からなる群より選択される少なくとも1種のバナジウム族元素の酸化物の前駆体と、を含む塗布型材料の熱処理物である請求項1~請求項4のいずれか1項に記載のパッシベーション膜。 A heat-treated product of a coating-type material comprising: a precursor of aluminum oxide; and a precursor of an oxide of at least one vanadium group element selected from the group consisting of a precursor of vanadium oxide and a precursor of tantalum oxide. The passivation film according to any one of claims 1 to 4.
- 酸化アルミニウムの前駆体と、酸化バナジウムの前駆体及び酸化タンタルの前駆体からなる群より選択される少なくとも1種のバナジウム族元素の酸化物の前駆体と、を含み、シリコン基板を有する太陽電池素子のパッシベーション膜の形成に用いられる塗布型材料。 A solar cell element having a silicon substrate, comprising: a precursor of aluminum oxide; and a precursor of an oxide of at least one vanadium group element selected from the group consisting of a precursor of vanadium oxide and a precursor of tantalum oxide Coating type material used to form a passivation film.
- p型のシリコン基板と、
前記シリコン基板の受光面側である第1面側に形成されたn型の不純物拡散層と、
前記不純物拡散層上に形成された第1電極と、
前記シリコン基板の受光面側とは逆の第2面側に形成され、開口部を有するパッシベーション膜と、
前記シリコン基板の第2面側に形成され、前記シリコン基板の第2面側と前記パッシベーション膜の開口部を通して電気的に接続されている第2電極と、を備え、
前記パッシベーション膜は、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含む太陽電池素子。 a p-type silicon substrate;
An n-type impurity diffusion layer formed on the first surface side which is the light-receiving surface side of the silicon substrate;
A first electrode formed on the impurity diffusion layer;
A passivation film formed on the second surface side opposite to the light receiving surface side of the silicon substrate and having an opening;
A second electrode formed on the second surface side of the silicon substrate and electrically connected to the second surface side of the silicon substrate through the opening of the passivation film;
The said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide. - 前記シリコン基板の第2面側の一部又は全部に形成され、前記シリコン基板より高濃度に不純物が添加されたp型の不純物拡散層を有し、
前記第2電極は、前記p型の不純物拡散層と前記パッシベーション膜の開口部を通して電気的に接続されている、請求項7に記載の太陽電池素子。 A p-type impurity diffusion layer formed on a part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate;
The solar cell element according to claim 7, wherein the second electrode is electrically connected to the p-type impurity diffusion layer through an opening of the passivation film. - n型のシリコン基板と、
前記シリコン基板の受光面側である第1面側に形成されたp型の不純物拡散層と、
前記不純物拡散層上に形成された第1電極と、
前記シリコン基板の受光面側とは逆の第2面側に形成され、開口部を有するパッシベーション膜と、
前記シリコン基板の第2面側に形成され、前記シリコン基板の第2面側と前記パッシベーション膜の開口部を通して電気的に接続されている第2電極と、を備え、
前記パッシベーション膜は、酸化アルミニウムと、酸化バナジウム及び酸化タンタルからなる群より選択される少なくとも1種のバナジウム族元素の酸化物と、を含む太陽電池素子。 an n-type silicon substrate;
A p-type impurity diffusion layer formed on the first surface which is the light-receiving surface side of the silicon substrate;
A first electrode formed on the impurity diffusion layer;
A passivation film formed on the second surface side opposite to the light receiving surface side of the silicon substrate and having an opening;
A second electrode formed on the second surface side of the silicon substrate and electrically connected to the second surface side of the silicon substrate through the opening of the passivation film;
The said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide. - 前記シリコン基板の第2面側の一部又は全部に形成され、前記シリコン基板より高濃度に不純物が添加されたn型の不純物拡散層を有し、
前記第2電極は、前記n型の不純物拡散層と前記パッシベーション膜の開口部を通して電気的に接続されている、請求項9に記載の太陽電池素子。 An n-type impurity diffusion layer formed on part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate;
10. The solar cell element according to claim 9, wherein the second electrode is electrically connected to the n-type impurity diffusion layer through an opening of the passivation film. - 前記パッシベーション膜の前記バナジウム族元素の酸化物と前記酸化アルミニウムの質量比が30/70~90/10である、請求項7~請求項10のいずれか1項に記載の太陽電池素子。 The solar cell element according to any one of claims 7 to 10, wherein a mass ratio of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 30/70 to 90/10.
- 前記パッシベーション膜の前記バナジウム族元素の酸化物及び前記酸化アルミニウムの総含有率が90%以上である、請求項7~請求項11のいずれか1項に記載の太陽電池素子。 The solar cell element according to any one of claims 7 to 11, wherein a total content of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 90% or more.
- 前記バナジウム族元素の酸化物として、酸化バナジウム、酸化ニオブ、及び酸化タンタルよりなる群から選択される2種又は3種のバナジウム族元素の酸化物を含む、請求項7~請求項12のいずれか1項に記載の太陽電池素子。 The oxide of the vanadium group element includes an oxide of two or three vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide. The solar cell element according to item 1.
- シリコン基板と、
前記シリコン基板上の全面又は一部に設けられる請求項1~請求項5のいずれか1項に記載の太陽電池素子用パッシベーション膜と、
を有するパッシベーション膜付シリコン基板。 A silicon substrate;
The passivation film for a solar cell element according to any one of claims 1 to 5, which is provided on the entire surface or a part of the silicon substrate,
A silicon substrate with a passivation film.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380037776.4A CN104488087B (en) | 2012-07-19 | 2013-07-19 | Passivating film, application type material, solar cell device and the silicon substrate with passivating film |
JP2014525900A JP6434310B2 (en) | 2012-07-19 | 2013-07-19 | Passivation film, coating type material, solar cell element, and silicon substrate with passivation film |
KR20157003336A KR20150038021A (en) | 2012-07-19 | 2013-07-19 | Passivation film, coating material, solar-cell element, and silicon substrate with passivation film attached thereto |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-160336 | 2012-07-19 | ||
JP2012160336 | 2012-07-19 | ||
JP2012218389 | 2012-09-28 | ||
JP2012-218389 | 2012-09-28 | ||
JP2013011934 | 2013-01-25 | ||
JP2013-011934 | 2013-01-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014014116A1 true WO2014014116A1 (en) | 2014-01-23 |
Family
ID=49948936
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/069706 WO2014014116A1 (en) | 2012-07-19 | 2013-07-19 | Passivation film, coating material, solar-cell element, and silicon substrate with passivation film attached thereto |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6434310B2 (en) |
KR (1) | KR20150038021A (en) |
CN (1) | CN104488087B (en) |
TW (1) | TWI599064B (en) |
WO (1) | WO2014014116A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107425083A (en) * | 2017-07-26 | 2017-12-01 | 顺德中山大学太阳能研究院 | A kind of lamination back of the body passivation solar cell and preparation method thereof |
CN108389928B (en) * | 2018-03-30 | 2020-08-25 | 顺德中山大学太阳能研究院 | Solar cell and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003533892A (en) * | 2000-05-15 | 2003-11-11 | バッテル・メモリアル・インスティチュート | Enclosed microelectronic device |
WO2009145140A1 (en) * | 2008-05-27 | 2009-12-03 | コニカミノルタホールディングス株式会社 | Dye-sensitized solar cell |
JP2012069592A (en) * | 2010-09-21 | 2012-04-05 | Pi R & D Co Ltd | Polyimide resin composition for forming rear reflective layer of fuel cell and method for forming rear reflective layer of fuel cell using the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5464775B2 (en) * | 2004-11-19 | 2014-04-09 | エイエスエム インターナショナル エヌ.ヴェー. | Method for producing metal oxide film at low temperature |
-
2013
- 2013-07-19 CN CN201380037776.4A patent/CN104488087B/en not_active Expired - Fee Related
- 2013-07-19 KR KR20157003336A patent/KR20150038021A/en active IP Right Grant
- 2013-07-19 JP JP2014525900A patent/JP6434310B2/en not_active Expired - Fee Related
- 2013-07-19 WO PCT/JP2013/069706 patent/WO2014014116A1/en active Application Filing
- 2013-07-19 TW TW102125997A patent/TWI599064B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003533892A (en) * | 2000-05-15 | 2003-11-11 | バッテル・メモリアル・インスティチュート | Enclosed microelectronic device |
WO2009145140A1 (en) * | 2008-05-27 | 2009-12-03 | コニカミノルタホールディングス株式会社 | Dye-sensitized solar cell |
JP2012069592A (en) * | 2010-09-21 | 2012-04-05 | Pi R & D Co Ltd | Polyimide resin composition for forming rear reflective layer of fuel cell and method for forming rear reflective layer of fuel cell using the same |
Also Published As
Publication number | Publication date |
---|---|
JP6434310B2 (en) | 2018-12-05 |
TWI599064B (en) | 2017-09-11 |
KR20150038021A (en) | 2015-04-08 |
JPWO2014014116A1 (en) | 2016-07-07 |
CN104488087A (en) | 2015-04-01 |
TW201409730A (en) | 2014-03-01 |
CN104488087B (en) | 2017-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6350279B2 (en) | Coating type material, solar cell element, and silicon substrate with field effect passivation film | |
EP2650923B1 (en) | Solar cell, solar cell module and method of making a solar cell | |
EP2650926B1 (en) | Solar cell and method of making a solar cell | |
JP5440433B2 (en) | Solar cell manufacturing method and film forming apparatus | |
WO2006117980A1 (en) | Solar cell manufacturing method, solar cell, and semiconductor device manufacturing method | |
WO2014014109A9 (en) | Passivation-layer-forming composition, semiconductor substrate having passivation layer, method for manufacturing semiconductor substrate having passivation layer, solar-cell element, method for manufacturing solar-cell element, and solar cell | |
JP2013165160A (en) | Method for manufacturing solar cell, and solar cell | |
WO2014014110A9 (en) | Composition for forming passivation layer, semiconductor substrate having passivation layer, production method for semiconductor substrate having passivation layer, solar cell element, production method for solar cell element, and solar cell | |
KR102083249B1 (en) | Passivation-layer-forming composition, semiconductor substrate having passivation layer, method for manufacturing semiconductor substrate having passivation layer, solar-cell element, method for manufacturing solar-cell element, and solar cell | |
JP2015050277A (en) | Solar cell and process of manufacturing the same | |
JP2012038852A (en) | Solar cell and method for manufacturing the same | |
JP6434310B2 (en) | Passivation film, coating type material, solar cell element, and silicon substrate with passivation film | |
WO2014014107A9 (en) | Composition for forming passivation layer, semiconductor substrate with passivation layer, method for producing said semiconductor substrate, solar cell element, and method for producing same | |
WO2012012167A1 (en) | Methods of forming a floating junction on a solar cell with a particle masking layer | |
JP4903531B2 (en) | Solar cell element | |
JP2009295913A (en) | Solar cell and method of manufacturing the same | |
WO2014014115A9 (en) | Semiconductor substrate with passivation layer and method of manufacturing same | |
JP2004327675A (en) | Semiconductor device and method for manufacturing the same | |
WO2016125803A1 (en) | Solar cell element and method for manufacturing same | |
JP2004128438A (en) | Semiconductor device and method of manufacturing the same | |
JP5994895B2 (en) | Manufacturing method of solar cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13820515 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014525900 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20157003336 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13820515 Country of ref document: EP Kind code of ref document: A1 |