WO2014014117A1 - パッシベーション膜、塗布型材料、太陽電池素子及びパッシベーション膜付シリコン基板 - Google Patents
パッシベーション膜、塗布型材料、太陽電池素子及びパッシベーション膜付シリコン基板 Download PDFInfo
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- WO2014014117A1 WO2014014117A1 PCT/JP2013/069707 JP2013069707W WO2014014117A1 WO 2014014117 A1 WO2014014117 A1 WO 2014014117A1 JP 2013069707 W JP2013069707 W JP 2013069707W WO 2014014117 A1 WO2014014117 A1 WO 2014014117A1
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- Prior art keywords
- silicon substrate
- passivation film
- aluminum oxide
- cell element
- receiving surface
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- 238000002161 passivation Methods 0.000 title claims abstract description 201
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 140
- 239000010703 silicon Substances 0.000 title claims abstract description 140
- 239000000758 substrate Substances 0.000 title claims abstract description 139
- 239000000463 material Substances 0.000 title claims description 74
- 238000000576 coating method Methods 0.000 title claims description 33
- 239000011248 coating agent Substances 0.000 title claims description 30
- -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 91
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 83
- 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 abstract description 82
- 238000009792 diffusion process Methods 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 12
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 31
- 229910052782 aluminium Inorganic materials 0.000 description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 238000010304 firing Methods 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 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
- 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
- 239000000126 substance Substances 0.000 description 12
- 125000002524 organometallic group Chemical group 0.000 description 11
- 239000004065 semiconductor Substances 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
- 230000008569 process Effects 0.000 description 10
- 230000006798 recombination Effects 0.000 description 10
- 238000005215 recombination Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- 238000004519 manufacturing process 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
- 239000003990 capacitor Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 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
- 125000000217 alkyl group Chemical group 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910021478 group 5 element Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 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
- 238000005245 sintering Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 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
- 239000002019 doping agent Substances 0.000 description 1
- 230000005685 electric field effect 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
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000012528 membrane Substances 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
- 229920003986 novolac Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000000059 patterning Methods 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
- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- 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
-
- 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
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- 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 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.
- the n layer 12 on the light receiving surface 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 has the effect of eliminating electrons and reducing the 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 conventional solar cell element having the p + layer 14 on the back surface as described above there is no deactivation treatment at the interface between the p + layer 14 and the back electrode 16 to reduce the interface recombination rate. Not done.
- the aluminum doped at a high concentration in the p + layer 14 forms recombination centers, the density of recombination centers is high, and the quality as a semiconductor is lower than in other regions.
- 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, International Publication No. 2009/052227, International Publication No. Publication No. 2010/044445 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.44903 (2008)).
- 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 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.
- the coating type material of the present invention for solving the second problem is as follows. ⁇ 6> A coating-type material that includes an aluminum oxide precursor and a niobium oxide precursor and is used to form a passivation film for a solar cell element having a silicon substrate.
- a p-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
- An n-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
- a first electrode formed on the surface of the n-type impurity diffusion layer on the light-receiving surface side of the silicon substrate;
- a p-type impurity diffusion layer formed on a part or all of the back side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate;
- a passivation film comprising aluminum oxide and niobium oxide formed on the back surface of the silicon substrate and having a plurality of openings;
- a second electrode that forms an electrical connection with the surface of the p-type impurity diffusion layer on the back side of the silicon substrate through the plurality of openings;
- a solar cell element comprising:
- An n-type silicon substrate made of single crystal silicon or polycrystalline silicon and having a light receiving surface and a back surface opposite to the light receiving surface;
- a p-type impurity diffusion layer formed on the light-receiving surface side of the silicon substrate;
- a second electrode formed on the back side of the silicon substrate;
- a passivation film formed on the light-receiving surface side surface of the silicon substrate and including a plurality of openings and containing aluminum oxide and niobium oxide;
- a first electrode formed on the surface of the p-type impurity diffusion layer on the light-receiving surface side of the silicon substrate and forming an electrical connection with the surface on the light-receiving surface side of the silicon substrate through the plurality of openings;
- a solar cell element comprising:
- ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a total content of the niobium oxide and the aluminum oxide in the passivation film is 90% by mass or more.
- 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 becomes easy, and cost reduction can be achieved.
- components other than niobium oxide and aluminum oxide may be included 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.
- the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a niobium oxide precursor. Details of the coating type material will be described next.
- the coating material of the present embodiment includes an aluminum oxide precursor and a niobium oxide precursor, and is used for forming a passivation film for a solar cell element having a silicon substrate.
- 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.
- Electrodes 6 back surface side electrode, second surface electrode, back surface electrode are formed.
- the carrier lifetime is also increased after heat treatment (firing). Since it showed a certain value, 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 4 2.35 g (0.0075 mol) of commercially available niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21) and commercially available aluminum triisopropoxide (structural formula: Al ( 1.02 g (0.005 mol) of OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25) and 10 g of novolac resin were dissolved in 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to obtain a passivation material (c -2) was prepared.
- V niobium
- Nb OC 2 H 5
- aluminum triisopropoxide structural formula: Al ( 1.02 g (0.005 mol) of OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25)
- 10 g of novolac resin were dissolved in 10 g of diethylene glycol monobutyl
- the mass ratio of niobium oxide and aluminum oxide [niobium oxide / Aluminum oxide (mass%)] is preferably 30/70 to 90/10 (30/70 to 90/10), and the mass ratio of niobium oxide to aluminum oxide is 30/70 to 80/20. It is more preferable. Further, the mass ratio of niobium oxide and aluminum oxide is preferably 50/50 to 90/10 from the viewpoint that both improvement of carrier lifetime and negative fixed charge can be achieved.
- the elemental analysis and the FT-IR measurement results of the passivation film show that the film contains components other than niobium oxide and aluminum oxide as organic components, but it contains niobium oxide and aluminum oxide. If the ratio, that is, the content (mass) of niobium oxide and aluminum oxide in the passivation film is preferably 80% or more, more preferably 90% or more, better characteristics can be maintained.
- a SiN film produced by plasma CVD was formed as the light-receiving surface antireflection film 3 on the light-receiving surface side.
- the passivation material (a-1) prepared in Example 1 was applied to the area excluding the contact area (opening OA) on the back side of the silicon substrate 1 by the ink jet method. Thereafter, 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 3 was separately prepared as the passivation film 7.
- the fire-through process in which the SiN film is not perforated is described, but 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 shown in 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 4.
- the solar cell element having the passivation film 7 including the niobium oxide and aluminum oxide layers has both increased short-circuit current and open-circuit voltage compared to the solar cell element not having the passivation film 7, and the conversion efficiency ( It was found that the photoelectric conversion efficiency was improved by 1% at the maximum, and the effect of the present invention was obtained.
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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。
<1> 酸化アルミニウムと酸化ニオブとを含み、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ニオブを含むことにより、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える。
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。
<6> 酸化アルミニウム前駆体及び酸化ニオブ前駆体を含み、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。
<7> 単結晶シリコン又は多結晶シリコンからなり、受光面及び前記受光面とは反対側の裏面を有するp型のシリコン基板と、
前記シリコン基板の受光面側に形成されたn型の不純物拡散層と、
前記シリコン基板の受光面側の前記n型の不純物拡散層の表面に形成された第1電極と、
前記シリコン基板の裏面側の表面に形成され、複数の開口部を有する酸化アルミニウムと酸化ニオブを含むパッシベーション膜と、
前記複数の開口部を通して、前記シリコン基板の裏面側の表面と電気的な接続を形成している第2電極と、
を備える太陽電池素子。
前記シリコン基板の受光面側に形成されたn型の不純物拡散層と、
前記シリコン基板の受光面側の前記n型の不純物拡散層の表面に形成された第1電極と、
前記シリコン基板の裏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型の不純物拡散層と、
前記シリコン基板の裏面側の表面に形成され、複数の開口部を有する酸化アルミニウムと酸化ニオブを含むパッシベーション膜と、
前記複数の開口部を通して、前記シリコン基板の裏面側の前記p型の不純物拡散層の表面と電気的な接続を形成している第2電極と、
を備える太陽電池素子。
前記シリコン基板の受光面側に形成されたp型の不純物拡散層と、
前記シリコン基板の裏面側に形成された第2電極と、
前記シリコン基板の受光面側の表面に形成され、複数の開口部を有する酸化アルミニウムと酸化ニオブを含むパッシベーション膜と、
前記シリコン基板の受光面側の前記p型の不純物拡散層の表面に形成され、前記複数の開口部を通して前記シリコン基板の受光面側の表面と電気的な接続を形成している第1電極と、
を備える太陽電池素子。
<12> 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。
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ニオブとを含むようにしたものである。
本実施の形態の塗布型材料は、酸化アルミニウム前駆体及び酸化ニオブ前駆体を含み、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の形成に用いられる。
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ニオブを含む膜を有するものである。酸化アルミニウムと酸化ニオブを含むことにより、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。
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。
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。
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ニオブを含む膜を有するものである。酸化アルミニウムと酸化ニオブを含むことにより、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。
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分解塗布型材料[(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)により酸化ニオブ(Nb2O5)が得られる市販の有機金属分解塗布型材料[(株)高純度化学研究所Nb-05、濃度5質量%]を3.0g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。
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分解塗布型材料[株式会社高純度化学研究所、SYM-AL04、濃度2.3質量%]と、熱処理(焼成)により酸化ニオブ(Nb2O5)が得られる市販の有機金属分解塗布型材料[株式会社高純度化学研究所、Nb-05、濃度5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。
市販のニオブ(V)エトキシド(構造式:Nb(OC2H5)5、分子量:318.21)を3.18g(0.010mol)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)とをシクロヘキサン80gに溶解して、濃度5質量%のパッシベーション材料(c-1)を調製した。
市販のニオブ(V)エトキシド(構造式:Nb(OC2H5)5、分子量:318.21)を2.35g(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(c-2)を調製した。
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分解塗布型材料[(株)高純度化学研究所SYM-AL04、濃度2.3質量%]と、熱処理(焼成)により酸化ニオブ(Nb2O5)が得られる市販の有機金属分解塗布型材料[(株)高純度化学研究所Nb-05、濃度5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(b-1)~(b-7)を調製した。
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(b-7)では、負の固定電荷密度を得ることができなかった。
パッシベーション材料(d-1)として、熱処理(焼成)により酸化チタン(TiO2)が得られる市販の有機金属分解塗布型材料[(株)高純度化学研究所Ti-03-P、濃度3質量%]、パッシベーション材料(d-2)として、熱処理(焼成)によりチタン酸バリウム(BaTiO3)が得られる市販の有機金属分解塗布型材料[(株)高純度化学研究所BT-06、濃度6質量%]、パッシベーション材料(d-3)として、熱処理(焼成)により酸化ハフニウム(HfO2)が得られる市販の有機金属分解塗布型材料[(株)高純度化学研究所Hf-05、濃度5質量%]を準備した。
すなわち、酸化ニオブと酸化アルミニウムとを併用することにより負の固定電荷を有するパッシベーション膜を得ることができ、負の固定電荷を安定化できるという観点から、酸化ニオブと酸化アルミニウムの質量比[酸化ニオブ/酸化アルミニウム(質量%)]が30/70~90/10(30/70以上90/10以下)であることが好ましく、酸化ニオブと酸化アルミニウムの質量比が30/70~80/20であることがより好ましい。また、酸化ニオブと酸化アルミニウムの質量比が50/50~90/10であることが、キャリアライフタイムの向上と負の固定電荷を両立できるという観点から好ましい。
シリコン基板1として、ボロンをドーパント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。
また、パッシベーション膜7として、実施例3で調製したパッシベーション材料(c-1)を用いたサンプルも別途作製した。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (12)
- 酸化アルミニウムと酸化ニオブとを含み、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。
- 前記酸化ニオブと前記酸化アルミニウムとの質量比(酸化ニオブ/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。
- 前記酸化ニオブ及び前記酸化アルミニウムの総含有率が90質量%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。
- 更に有機成分を含む請求項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。
- 酸化アルミニウム前駆体及び酸化ニオブ前駆体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。
- 酸化アルミニウム前駆体及び酸化ニオブ前駆体を含み、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。
- 単結晶シリコン又は多結晶シリコンからなり、受光面及び前記受光面とは反対側の裏面を有するp型のシリコン基板と、
前記シリコン基板の受光面側に形成されたn型の不純物拡散層と、
前記シリコン基板の受光面側の前記n型の不純物拡散層の表面に形成された第1電極と、
前記シリコン基板の裏面側の表面に形成され、複数の開口部を有する酸化アルミニウムと酸化ニオブとを含むパッシベーション膜と、
前記複数の開口部を通して、前記シリコン基板の裏面側の表面と電気的な接続を形成している第2電極と、
を備える太陽電池素子。 - 単結晶シリコン又は多結晶シリコンからなり、受光面及び前記受光面とは反対側の裏面を有するp型のシリコン基板と、
前記シリコン基板の受光面側に形成されたn型の不純物拡散層と、
前記シリコン基板の受光面側の前記n型の不純物拡散層の表面に形成された第1電極と、
前記シリコン基板の裏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型の不純物拡散層と、
前記シリコン基板の裏面側の表面に形成され、複数の開口部を有する酸化アルミニウムと酸化ニオブを含むパッシベーション膜と、
前記複数の開口部を通して、前記シリコン基板の裏面側の前記p型の不純物拡散層の表面と電気的な接続を形成している第2電極と、
を備える太陽電池素子。 - 単結晶シリコン又は多結晶シリコンからなり、受光面及び前記受光面とは反対側の裏面を有するn型のシリコン基板と、
前記シリコン基板の受光面側に形成されたp型の不純物拡散層と、
前記シリコン基板の裏面側に形成された第2電極と、
前記シリコン基板の受光面側の表面に形成され、複数の開口部を有する酸化アルミニウムと酸化ニオブを含むパッシベーション膜と、を備え、
前記シリコン基板の受光面側の前記p型の不純物拡散層の表面に形成され、前記複数の開口部を通して前記シリコン基板の受光面側の表面と電気的な接続を形成している第1電極と、
を備える太陽電池素子。 - 前記パッシベーション膜における前記酸化ニオブと前記酸化アルミニウムの質量比(酸化ニオブ/酸化アルミニウム)が30/70~90/10である請求項7~請求項9のいずれか1項に記載の太陽電池素子。
- 前記パッシベーション膜における前記酸化ニオブ及び前記酸化アルミニウムの総含有率が90質量%以上である請求項7~請求項10のいずれか1項に記載の太陽電池素子。
- 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。
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Also Published As
Publication number | Publication date |
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CN104471716A (zh) | 2015-03-25 |
CN104471716B (zh) | 2017-08-29 |
EP2876690A1 (en) | 2015-05-27 |
US20150214391A1 (en) | 2015-07-30 |
TWI587528B (zh) | 2017-06-11 |
KR20150038114A (ko) | 2015-04-08 |
TW201411858A (zh) | 2014-03-16 |
EP2876690A4 (en) | 2016-03-02 |
JPWO2014014117A1 (ja) | 2016-07-07 |
JP6350279B2 (ja) | 2018-07-04 |
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