WO2006025203A1 - 太陽電池およびその製造方法 - Google Patents
太陽電池およびその製造方法 Download PDFInfo
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- WO2006025203A1 WO2006025203A1 PCT/JP2005/014734 JP2005014734W WO2006025203A1 WO 2006025203 A1 WO2006025203 A1 WO 2006025203A1 JP 2005014734 W JP2005014734 W JP 2005014734W WO 2006025203 A1 WO2006025203 A1 WO 2006025203A1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 71
- 238000002161 passivation Methods 0.000 claims abstract description 65
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 130
- 229910052710 silicon Inorganic materials 0.000 claims description 129
- 239000010703 silicon Substances 0.000 claims description 129
- 239000000758 substrate Substances 0.000 claims description 110
- 238000009792 diffusion process Methods 0.000 claims description 34
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 123
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 28
- 238000010586 diagram Methods 0.000 description 21
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- 238000005530 etching Methods 0.000 description 14
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- 229910052581 Si3N4 Inorganic materials 0.000 description 11
- 238000000206 photolithography Methods 0.000 description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
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- 239000002019 doping agent Substances 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
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- 238000010248 power generation Methods 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 238000001259 photo etching Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
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- 239000003929 acidic solution Substances 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
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- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 241000652704 Balta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100520660 Drosophila melanogaster Poc1 gene Proteins 0.000 description 1
- 101100520662 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PBA1 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- RJCRUVXAWQRZKQ-UHFFFAOYSA-N oxosilicon;silicon Chemical compound [Si].[Si]=O RJCRUVXAWQRZKQ-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction 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
- H01L31/18—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 present invention relates to a solar cell and a method for manufacturing a solar cell, and more particularly to a solar cell having a structure in which passivation is applied to the back surface, a back electrode type solar cell in which electrodes are formed only on the back surface, and a method for manufacturing the solar cell.
- Non-Patent Document 1 discloses a PERL (passivated Emitter Rear Roccally diffused) structure.
- FIG. 16 shows a solar cell 61 having the structure described in Non-Patent Document 1.
- a typical conventional solar cell 61 shown in FIG. 16 has an n-type diffusion layer (n + layer) 63 formed on the light receiving surface side of a silicon substrate 62 by, for example, diffusing phosphorus.
- a p-type substrate is used as the silicon substrate 62.
- the n + layer 63 is partially removed to form the contact hole 66, and the n electrode 67 is formed thereon.
- a back surface passivation film 68 is formed, and then partially removed to form a contact hole 69.
- a p + layer 70 is partially formed using the back surface passivation film 68 as a mask.
- Non-Patent Document 1 The solar cell described in Non-Patent Document 1 has the above-described structure, so that a BSF (Back Surface Field) effect is obtained by the locally provided P + layer 70, and at the same time, silicon is formed by the back surface passivation layer 68.
- BSF Back Surface Field
- silicon is formed by the back surface passivation layer 68.
- the dangling bonds of silicon atoms on the back surface layer of the substrate 62 can be terminated, and the surface recombination rate can be reduced.
- the conversion efficiency and the surface recombination velocity at the surface interface are closely linked, and the conversion efficiency can be increased by reducing the surface recombination velocity as described above.
- a solar cell having such a back electrode structure is disclosed as a silicon solar cell for space use in Japanese Patent Laid-Open No. 6-169096 (Patent Document 1).
- a solar cell using a SiN film as a back surface passivation film is described in Japanese Patent Laid-Open No. 9-45945 (Patent Document 2).
- the n-electrode formed on the light-receiving surface is indispensable for taking out the current generated by the incidence of sunlight to the outside. Since no sunlight is incident on this part, no current is generated in that part. Therefore, there is a problem that the conversion efficiency of the solar cell decreases when the area of the n-electrode increases.
- a back electrode type solar cell in which no electrode is formed on the light receiving surface of the solar cell and an n electrode and a p electrode are formed only on the back surface has been proposed (for example, US Pat. No. 4,927,770 (Patent Document)). (See 3)). In this solar cell, since the incidence of sunlight is not hindered by the electrode formed on the light receiving surface, high conversion efficiency can be expected in principle.
- FIG. 17 shows a schematic cross-sectional view of a conventional typical back electrode type solar cell 81 proposed in Patent Document 3.
- n + layers 83 and p + layers 84 are alternately formed on the back surface of the silicon substrate 82.
- a light-receiving surface passivation film 85 and a back-surface passivation film 86 are formed on the light-receiving surface side and the back surface side of the silicon substrate 82, respectively, thereby suppressing carrier recombination.
- the back electrode type solar cell 81 in the example shown in FIG. 17 is manufactured, for example, as follows. First, a silicon oxide film is formed on each of the light receiving surface and the back surface of the silicon substrate 82, and then a silicon nitride film is formed by a plasma CVD method to form a light receiving surface passivation film 85 and a back surface passivation film 86. Next, a part of the back surface passivation film 86 of the silicon substrate 82 is removed by photoetching to form a contact hole 87. Then, a glass layer containing an n-type dopant is deposited on the entire back surface of the silicon substrate 82 by using the CVD method.
- a part of the passivation film 86 at that portion is removed by photoetching to form a contact hole 88.
- a glass layer containing a P-type dopant is deposited on the back side of the silicon substrate 82 by using the CVD method.
- an n + layer 83 and a p + layer 84 are formed on the back surface of the silicon substrate 82.
- all the glass layer deposited on the back surface passivation film 86 is removed, and the silicon substrate 82 is heat-treated at a high temperature of 900 ° C. or higher in a hydrogen atmosphere.
- the interface between the silicon substrate 82 and the backside passivation film 86 between the silicon oxide film and the silicon oxide film is hydrogenated.
- an aluminum film is deposited on the back surface side of the silicon substrate 82 by sputtering.
- an n-electrode 89 and a p-electrode 90 are formed.
- the oxide film and the nitride film formed on the oxide film formed as the passivation film on the back surface first remain until the end.
- Patent Document 1 JP-A-6-169096
- Patent Document 2 JP-A-9-45945
- Patent Document 3 US Patent No. 4927770
- Non-Patent Literature l Appl. Phys. Lett. Vol. 57, No. 6 (1990) p602—604 Disclosure of the Invention
- Non-Patent Document 1 and Patent Document 1 ! solar cells use thermal oxidation as a method for forming a back surface passivation film.
- high-temperature treatment higher than 1000 ° C has high energy costs, and in addition to impurity re-diffusion, the efficiency of solar cells is reduced, and a large stress is applied to the interface between the silicon substrate and the silicon oxide film.
- a passivation film is formed before the diffusion process, and this passivation film can be used as a diffusion mask.
- the passivation property is reduced by high-temperature treatment during diffusion. There are concerns.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a highly efficient solar cell and a method for manufacturing the same without causing the conventional problems. It is to be.
- the solar cell of the present invention is characterized in that it has a passivation film composed of two layers of an oxide silicon film on at least a part of the substrate surface.
- the solar cell does not have an electrode on the light receiving surface side but has an electrode on the side opposite to the light receiving surface.
- the n-type diffusion layer and the p-type diffusion layer are formed on the substrate surface, and the passivation film covers the at least one of the n-type diffusion layer and the p-type diffusion layer. It is preferred that it is formed.
- the solar cell of the present invention preferably has a first oxide silicon film thickness of 40 to 400 A and a second silicon oxide film thickness of 400 A or more.
- At least a part of the substrate surface is formed of a passivated silicon oxide film.
- a method for manufacturing a battery is provided.
- the second oxide silicon film is formed by atmospheric pressure CVD or SOG.
- FIG. 1 is a diagram schematically showing a solar cell 1 according to a first embodiment of the present invention.
- FIG. 2 is a graph showing the results of comparative experiments for performance evaluation between the solar cell of the present invention and a conventional solar cell.
- FIG. 3 is a diagram for explaining a method of manufacturing the solar cell 1 shown in FIG. 1.
- FIG. 4 is a diagram for explaining a method of manufacturing the solar cell 1 shown in FIG. 1.
- FIG. 5 is a diagram for explaining a method of manufacturing the solar cell 1 shown in FIG. 1.
- FIG. 6 is a diagram schematically showing a solar cell 21 according to a second embodiment of the present invention.
- FIG. 7 is a diagram for explaining a method of manufacturing the solar cell 21 shown in FIG. 6.
- FIG. 8 is a diagram for explaining a method of manufacturing solar cell 21 shown in FIG. 6.
- FIG. 9 is a diagram for explaining a method of manufacturing solar cell 21 shown in FIG. 6.
- FIG. 10 is a diagram for explaining a method of manufacturing the solar cell 21 shown in FIG. 6.
- FIG. 11 is a diagram for explaining a method of manufacturing solar cell 21 shown in FIG. 6.
- FIG. 12 is a diagram schematically showing a solar cell 21 ′ according to a third embodiment of the present invention.
- FIG. 13 is a diagram for explaining a method of manufacturing the solar cell 21 ′ shown in FIG.
- FIG. 14 is a diagram schematically showing a solar cell 1 ′ according to a fourth embodiment of the present invention.
- FIG. 15 is a diagram schematically showing a solar cell 21 ′′ according to a fifth embodiment of the present invention.
- FIG. 16 is a diagram schematically showing a typical conventional solar cell 61.
- FIG. 17 is a diagram schematically showing a conventional typical back electrode type solar cell 81.
- FIG. 1 is a diagram schematically showing a solar cell 1 as a preferred example of the present invention.
- the solar cell 1 of the present invention is characterized in that a nosedation film made of two layers of an oxide silicon film is provided on at least a part of the substrate surface.
- a nosedation film made of two layers of an oxide silicon film is provided on at least a part of the substrate surface.
- the side on which light is intended to be incident when formed as a solar cell is referred to as a “light receiving surface side”, and the light receiving surface of the substrate 2 in the thickness direction.
- the side opposite to the side is called the “back side”.
- FIG. 1 shows an example in which two layers of passivation films 3 and 4 made of an oxide silicon film are provided on the surface opposite to the light receiving surface side (back side) of the substrate 2.
- the substrate 2 in the solar cell 1 of the present invention is not particularly limited as long as it is a semiconductor substrate that has been widely used in the production of solar cells. Crystals such as a single crystal silicon substrate and a polycrystalline silicon substrate It may be an amorphous silicon substrate, which is an amorphous silicon substrate that is not only a silicon substrate. The substrate 2 may be a ⁇ type silicon substrate or a ⁇ type silicon substrate. The substrate 2 used in the present invention preferably has a plane index of (100) when a fine non-reflective structure (texture structure) is formed on the substrate surface.
- the size of the substrate 2 is not particularly limited, and examples thereof include a 125 mm square cross-sectional shape.
- the thickness of the substrate 2 is not particularly limited, but it is preferably 100 to 500 / z m, and it is preferably 150 to 300 111. This is because when the thickness of the substrate 2 is less than 100 ⁇ m, light on the long wavelength side of sunlight tends to be not effectively used. When the thickness of the substrate 2 exceeds 500 m, bonding near the light-receiving surface occurs. This is because the distance that the carrier travels until the generated carrier takes out the electrode force on the back surface becomes longer, and the efficiency tends to decrease.
- the substrate 2 preferably has a specific resistance of 0.5 to 50 ⁇ cm, more preferably 0.5 to 10 ⁇ cm. This is because using a substrate 2 with a specific resistance of less than 0.5 ⁇ cm tends to reduce the lifetime of the substrate, and using a substrate 2 with a specific resistance exceeding 50 ⁇ cm, The resistance when the carrier moves increases and the solar cell effect This is because the rate tends to decrease.
- the specific resistance indicates a value measured by a specific resistance measuring device, for example.
- the solar cell of the present invention is characterized by having two layers of silicon oxide films 3 and 4 as a passivation film.
- first silicon oxide film 3 the first layer (substrate side) of the silicon oxide film 3
- second silicon oxide film 4 the second layer of silicon oxide film 4
- the thickness of the first and second oxide silicon films 3 and 4 in the present invention is not particularly limited, but the thickness of the first silicon oxide film 3 is preferably 40 to 400 A. 80 More preferably, it is ⁇ 200A. This is because the passivation effect tends to decrease when the thickness of the first oxide silicon film 3 is less than 40 A, and 1000 ° when the thickness of the first oxide silicon film 3 exceeds 400 A.
- the silicon oxide film must be formed at a high temperature of C or higher. At this time, the power generation efficiency of the solar cell is reduced due to re-diffusion of impurities, and a large stress is applied to the interface between the silicon substrate and the silicon oxide film. This is because there is a possibility that it may occur.
- the second oxide silicon film 4 has a thickness of preferably 400A or more, more preferably 1000 to 6000A, and more preferably 2000 to 5000. I. This is because, when the thickness of the second oxide silicon film 4 is less than 400 A, the novation effect tends to be low.
- FIG. 2 is a graph showing the results of comparison experiments for performance evaluation between the solar cell of the present invention and the conventional solar cell.
- samples with the passivation films (a) to (d) below were formed on both sides of an n-type substrate with a specific resistance of 4 to 6 ⁇ 'cm, and the effective lifetime was measured by the reflection microwave photoconductive decay method. This was done by measuring ⁇ .
- the surface state density on the substrate surface is small, s increases. As a result, the effective lifetime is increased.
- the defects such as DB (Dangling Bond) inside the substrate are reduced, the effective lifetime increases as the normal lifetime b increases.
- the interface characteristics of the passivation film Z substrate and the internal characteristics of the semiconductor such as DB can be evaluated by measuring the effective lifetime. As shown in Fig. 2, when two layers of silicon oxide film are used as a passivation film, the highest effective lifetime is obtained, and a powerful two-layer silicon oxide film is used. High efficiency can also be expected in the manufactured solar cell of the present invention.
- the solar cell of the present invention has been widely adopted in the art, as long as it includes a two-layered silicon oxide film as a passivation film, and other constituent elements are not particularly limited. It has appropriate components and structures.
- the solar cell 1 of the example shown in FIG. 1 includes an n-type diffusion layer (n + layer) 6 and a light-receiving surface passivation film 9 in which contact holes 10 are formed at a predetermined interval on the light-receiving surface side of the substrate 2. And an n-electrode 11 formed so as to fill the contact hole 10. Further, the solar cell 1 is formed by forming contact holes 7 at a predetermined interval in the two layers of the silicon oxide films 3 and 4 formed on the back side, and forming the contact holes 7 on the substrate 2.
- a P-type diffusion layer (p + layer) 8 formed in a portion not covered with the silicon film 3 and 4 and a p-electrode 12 filled with the contact hole 7 and formed on the entire back surface side. .
- the thickness of the n + layer 6 in the solar cell 1 of the present invention is not particularly limited, but is 0.2 to 0.
- It is preferably 6 / z m, more preferably 0.3 to 0.5 / z m. This is because when the thickness of the n layer 6 is less than 0.6, the impurity doping amount tends not to be high, and when the thickness of the n + layer 6 exceeds 0.6 m, it is short of sunlight. This is because light on the wavelength side cannot be effectively used.
- the light-receiving surface passivation film 9 is formed of, for example, a silicon nitride film, an oxide silicon film, or the like. Of these, the silicon nitride film is preferably used from the viewpoint of obtaining an antireflection effect.
- the thickness of the light-receiving surface passivation film 9 is not particularly limited, but the light-receiving surface passivation film 9 is not limited.
- the optimum film thickness can be calculated by calculating the refractive index power of each of the sibesion film 9, air, and the silicon substrate. Even if the thickness of the light-receiving surface passivation film 9 is larger or smaller than the optimum value, sunlight tends not to be used effectively.
- the film thickness is 700 A with respect to the refractive index 2.0 of the light-receiving surface passivation film 9.
- the n electrode 11 formed on the light receiving surface side is formed by, for example, a method of printing and baking a conductive paste containing copper powder by a screen printing method, or a vapor deposition method.
- the method of vapor-depositing TiZPdZAg is mentioned.
- a method of depositing TiZPdZAg by a deposition method is preferable.
- a method of forming the p-electrode 12 formed on the back surface side of the solar cell for example, a method of printing and baking a conductive paste containing aluminum powder by a screen printing method, or AlZTiZPdZAg by a vapor deposition method. Or the method of vapor-depositing TiZPdZAg is mentioned. Among them, the method of depositing AlZTiZPdZAg or Ti ZPdZAg by vapor deposition is preferred because of the high power generation efficiency of solar cells.
- the present invention also provides a method for manufacturing a solar cell of the present invention having the above-described structure.
- the present invention is a method of manufacturing a solar cell having a passivation film made of two layers of an oxide silicon film on at least a part of a substrate surface, the first layer being a first layer of an oxide silicon film.
- the silicon oxide film is formed by heat treatment at 750 to 1000 ° C. for 20 minutes to 1 hour in an oxygen atmosphere. By forming the first oxide silicon film under such conditions, a solar cell including the first oxide silicon film having a suitable thickness described above can be manufactured.
- the first oxide silicon film is formed in a temperature range of 750 to 1000 ° C., preferably in a temperature range of 800 to 950 ° C. This is because if the temperature during the formation of the first oxide silicon film is less than 750 ° C., a very long time tends to be required for the formation of the oxide silicon film, and the first acid silicon film is formed. If the temperature during the formation of the silicon film exceeds 1 000 ° C, the power generation efficiency of the solar cell decreases due to the re-diffusion of impurities, and a large stress is applied to the interface between the silicon substrate and the silicon oxide film.
- the second oxide silicon film which is the second oxide silicon film
- the second oxide silicon film is formed by atmospheric pressure CVD or SOG (Spin On Glass).
- Forming the second oxide silicon film by atmospheric pressure CVD has the advantage that the oxide silicon film can be formed at a low temperature, and the second oxide silicon film is formed by SOG. This is because the formation of a film has the advantage that a dangerous gas such as silane used in the atmospheric pressure CVD method is not used.
- FIGS. 3 to 5 are views for explaining a method of manufacturing the solar cell 1 of the present invention of the example shown in FIG.
- a preferred example of the method for producing a solar cell of the present invention will be specifically described.
- a single crystal or polycrystal silicon ingot (not shown) for preparing a silicon wafer is prepared, and the silicon ingot is sliced to obtain a substrate 2.
- a silicon ingot can be suitably sliced by using a disk-shaped blade or a wire saw, as is usually done in the art.
- the substrate 2 is etched with an acidic or alkaline solution since a damaged layer generated when slicing from the ingot is present in the vicinity of the surface.
- alkaline etching solution is a sodium hydroxide solution (concentration: about 50%).
- etching conditions include about 1 to 5 minutes when the mixed acid of hydrofluoric acid and nitric acid is used, and about 4 to 8 minutes when the sodium hydroxide solution is used.
- a silicon oxide film is formed on the back surface of the substrate 2 by an atmospheric pressure CVD method.
- the silicon oxide film formed here has a thickness of about 8000 A that can withstand the texture treatment.
- Substrate 2 after the formation of the silicon oxide film is immersed in an aqueous solution containing sodium hydroxide or potassium hydroxide and isopropyl alcohol (with a liquid temperature of about 75 to 85 ° C).
- anisotropic etching along the silicon crystal orientation proceeds on the light-receiving surface side, and a fine pyramid-shaped texture surface by the (111) plane can be formed.
- the back side remains flat because it is protected by the silicon oxide film.
- Figs. 1 and 3 to 5 the technology of the light receiving surface is used. The structure of the steel is omitted.
- first oxide silicon films 3 and 5 are formed on both surfaces of the substrate 2 by thermal oxidation.
- the temperature at this time is preferably about 750 ° C to 1000 ° C, more preferably 800 ° C to 950 ° C. By treating at this temperature for about 20 to 60 minutes, the temperature is about 40 to 400A.
- First oxide silicon films 3, 5 can be formed (Fig. 3).
- a second oxide silicon film 4 is formed on the back surface side by atmospheric pressure CVD or SOG.
- the temperature and the gas flow rate ratio are not particularly limited.
- the temperature is 450 ° C.
- a material for forming the SOG film is applied on the first oxide silicon film 3 by the spin coat method and dried in an oven. Drying can be performed in two stages, for example, 80 ° C and 200 ° C. After that, it is fired in a nitrogen atmosphere in a tube furnace at 700 ° C to 800 ° C to form an SOG film.
- the film thickness at this time is not particularly specified, but it is desirable that the thickness be 3000 A or more in consideration of the fact that the film is etched when PSG and BSG are etched.
- the annealing effect is obtained by heat treatment in a hydrogen atmosphere diluted to 3% with nitrogen at a temperature of about 400 to 500 ° C for about 15 to 60 minutes. Is obtained.
- the first oxide silicon film 5 on the light receiving surface side is etched by immersing the substrate 2 in about 2.5% dilute hydrofluoric acid.
- the second oxide silicon film 4 on the back side is also etched to some extent, but the second silicon oxide film 4 is almost left because it has a sufficient thickness with respect to the first silicon oxide film 5. become.
- n + layer 6 is formed on the light receiving surface side after the first oxide silicon film 5 is removed.
- the n + layer 6 can be formed by a conventionally known appropriate method, and the method is not particularly limited. For example, at a temperature of 700 ° C to 1000 ° C in a tube furnace using POC1,
- the n + layer 6 can be formed by diffusing phosphorus (P) on the light receiving surface side by heat treatment for 15 to 60 minutes. Further, the n + layer 6 may be formed by performing a heat treatment by spinning on a dopant solution containing phosphorus on the light receiving surface. As a result of any of these treatments, an n + layer 6 is formed on the light receiving surface, but on the back surface side, the first oxide silicon film 3 The n + layer is not formed because the second oxide silicon film 4 functions as a diffusion preventing layer (FIG. 4). Then, the attached PSG is removed with dilute hydrofluoric acid.
- P phosphorus
- a silicon oxide film is formed on the light receiving surface side by an atmospheric pressure CVD method.
- the thickness of the silicon oxide film formed here is not particularly limited as long as it has a sufficient thickness that works as a diffusion preventing film, but is preferably 2000 to 4000A.
- the first oxide silicon film 3 and the second oxide silicon film 4 on the back side are partially etched by photolithography to form contact holes 7.
- a p + layer 8 is formed in a portion exposed from the contact hole 7 on the back surface side.
- the formation of the p + layer 8 can be performed by a conventionally known appropriate method, and the method is not particularly limited. For example, using BBr in a tube furnace at a temperature of 700-1000 ° C,
- the p + layer 8 can be formed by heat treating for 100 minutes and partially diffusing boron (B) on the back surface.
- the P + layer 8 can also be formed by spin-on a dopant solution containing boron to the light receiving surface and performing heat treatment. As a result, the p + layer 8 is partially formed on the back side.
- BSG adhering to the above diffusion can be removed by using hydrofluoric acid or the like after heat treatment for 15 to 60 minutes at a temperature of about 500 to 600 ° C in an oxygen atmosphere. it can. After that, the back side is protected using UV tape that is cured by ultraviolet rays, and only the silicon oxide film on the light receiving side is etched. Then, a light-receiving surface passivation film 9 is formed on the light-receiving surface side (FIG. 5).
- the light-receiving surface passivation film 9 is a force that can be formed by an appropriate method using a material conventionally used in this field.
- the surface passivation film 9 can be formed, which is preferable.
- FIG. 6 is a diagram schematically showing another preferred example of the solar cell 21 of the present invention.
- an n + layer and a p + layer are formed on the substrate surface, and a passivation film is formed so as to cover at least one of the n + layer and the p + layer.
- a solar cell in which an n + layer and a p + layer are formed on one surface of the substrate and a passivation film is formed so as to cover the n + layer and the P + layer is particularly preferable.
- the force is such that the n + layer 6 and the n electrode 11 are provided on the light receiving surface side, and the p + layer 8 and the p electrode 12 are provided on the back surface side. Therefore, as shown in FIG.
- the electrode is not provided on the light-receiving surface side, and an electrode is provided on the opposite side to the light-receiving surface side.
- a solar cell having the following structure is referred to as a “back electrode type solar cell.”)
- the solar cell of the present invention is realized as a back electrode type as shown in FIG. For this reason, the light receiving surface does not hinder the incidence of sunlight.
- the solar cell 21 in the example shown in FIG. 6 includes only the light-receiving surface passivation film 33 on the light-receiving surface side.
- the two layers of silicon oxide films 23 and 24 formed on the back surface side have contact holes 27 and 30 formed at predetermined intervals, respectively.
- the silicon oxide film 23 on the back surface side of the substrate 22 is formed.
- P + layer 28 is formed in a portion not covered with 24, and
- n + layer 31 is formed in a portion not covered with silicon oxide films 23, 24 on the back side of substrate 22 by forming contact hole 30.
- Protective oxide silicon films 29 and 32 are formed so as to fill the contact holes 27 and 30, and the protective oxide silicon films 29 and 32 have contact holes smaller in diameter than the contact holes 27 and 30, respectively.
- a p-electrode 36 formed so as to fill the contact holes 27, 34 adjacent to the p + layer 28, and an n-electrode 37 formed so as to fill the contact holes 30, 35 adjacent to the n layer 31. And further comprising.
- the preferred thickness and forming material of the light-receiving surface passivation film 33 and the preferred forming material of the ⁇ electrode 36 and the n electrode 37 are the solar cell of the example shown in FIG. This is the same as described above for the light-receiving surface passivation film 9, p-electrode 12, and n-electrode 11 in FIG.
- the protective oxide silicon film 29 in the solar cell 21 is not particularly limited as long as it has a sufficient thickness to act as a diffusion preventing film, but is preferably about 2000 to 4000 A. Protection The thickness of the protective oxide silicon film 32 is not particularly limited, but is 1000 to 4000 A in order to avoid contact between the n + layer 31 and the n electrode 37 at portions other than the contact hole 34. Is preferred.
- FIGS. 7 to 11 are diagrams for explaining a method of manufacturing the solar cell 21 in the example shown in FIG.
- the solar cell 21 shown in FIG. 6 can be manufactured, for example, by the following procedure.
- the substrate 22 obtained by slicing the silicon ingot is subjected to surface etching with an acidic or alkaline solution.
- the first oxide silicon films 23 and 25 and the second oxide film are formed on both surfaces of the substrate 22 by thermal oxidation and atmospheric pressure CVD or SOG. Silicon films 24 and 26 are formed (FIG. 7).
- the first oxide silicon film 23 and the second oxide silicon film 24 on the back side are partially etched using photolithography to form contact holes 27.
- a P + layer 28 is partially formed by diffusion of boron or the like in a portion exposed by the contact hole 27 on the back side of the substrate 22.
- the P + layer 28 is not formed except for the portion exposed from the contact hole 27 on the back side of the substrate 22 (FIG. 8).
- the formation method and conditions of the p + layer 28 and the removal of BSG can be performed in the same manner as described above.
- a protective oxide silicon film 29 is formed on the back side of the substrate 22 by atmospheric pressure CVD so as to fill the contact hole 27.
- the thickness of the protective silicon oxide film 29 is not particularly limited as long as it has a sufficient thickness that works as a diffusion preventing layer, but is preferably 2000 to 4000 A force. Note that the protective silicon oxide film formed on the second silicon oxide film 24 is omitted in FIGS.
- a contact hole 30 is further formed on the back side of the substrate 22 by photolithography. Then, an n + layer 31 is formed in a portion exposed from the contact hole 30 on the back side of the substrate 22. Also in this case, the n + layer is not formed in portions other than the contact hole 30 (FIG. 9).
- the formation method and conditions of the n + layer 31 and the removal of PSG can be performed in the same manner as described above.
- a protective silicon oxide film 32 is formed on the back side of the substrate 22 by atmospheric pressure CVD so as to fill the contact hole 30.
- the thickness of the protective oxide silicon film 32 depends on the light-receiving surface. In order to work as a back surface protective film when a texture structure is applied to the film, it is preferable to set the thickness to about 8000 A. It should be noted that the protective oxide silicon film formed on the second silicon oxide film 24 and the protective oxide silicon film 29 is not shown in FIGS.
- the light-receiving surface passivation film 33 is formed on the light-receiving surface side described above.
- the antireflection effect can also be obtained by similarly forming the light-receiving surface passivation film 33 with a silicon nitride film (FIG. 11).
- contact holes 34 and 35 having diameters smaller than the contact holes 27 and 30 are formed in the protective oxide silicon films 29 and 32, respectively.
- a p electrode 36 is formed on the portion where the p + layer 28 is exposed, and an n electrode 37 is formed on the portion where the n + layer 31 is exposed. In this way, the back electrode type solar cell 21 shown in FIG. 6 can be manufactured.
- FIG. 12 is a diagram schematically showing a solar cell 21 'of still another preferred example of the present invention.
- the solar cell of the present invention is a back electrode type solar cell
- the structure shown in FIG. 12 may be used in addition to the structure shown in FIG.
- the solar cell 21 ′ of the example shown in FIG. 12 parts having the same configuration as the solar cell 21 of the example shown in FIG.
- two layers of silicon oxide films 23 and 24 have contact holes 41 and 42, respectively.
- a p-electrode 43 filling the contact hole 41 so as to be adjacent to the p + layer 28 and an n-electrode 44 filling the contact hole 42 so as to be adjacent to the n + layer 31 are provided.
- a p + layer 28 and an n + layer 31 are respectively formed on the back surface side of the substrate 22 at intervals in the same manner as described in the method for manufacturing the solar cell 21 described above. Form a texture structure.
- Each of the n electrodes 44 is formed so as to fill the contact hole 42 adjacent to the n + layer 31.
- Such a solar cell 21 ′ having the structure shown in FIG. 12 includes the solar cell 21 having the structure shown in FIG. 6 in which the p + layer and the n layer are formed after the formation of the two silicon oxide films as described above. In comparison, it has the advantage that higher characteristics can be obtained.
- FIGS. 14 and 15 are diagrams schematically showing another preferred example of the solar cell 21 ′ ′ of the present invention.
- the solar cells 1 ′ and 21 ′′ shown in FIGS. 14 and 15 are shown in FIGS. 1 and 6 except that the first oxide silicon film and the second silicon oxide film are also formed on the light receiving surface side.
- the parts having the same configuration are denoted by the same reference numerals, and the description thereof is omitted.
- a first silicon oxide film 51 and a second silicon oxide film 52 are laminated in order of the substrate 2 side force, respectively, as shown in FIG.
- each of the silicon films 57 is formed in this manner, and in the present invention, two layers of silicon oxide silicon are formed on both sides of the substrate. In this way, two layers of silicon oxide film are formed on both sides of the substrate, so that two layers of silicon oxide film are formed only on one side of the substrate.
- solar cells 1 'and 21' 'having a higher open circuit voltage can be realized.
- the thicknesses of the first oxide silicon films 51 and 56 and the second oxide silicon films 52 and 57 on the light-receiving surface side in the batteries 1 ′ and 21 ′ ′ are determined from the respective refractive indexes and the refractive indexes of the substrates 2 and 22. There is no particular limitation as long as it is selected by a combination that calculates and reduces reflection of light.
- the solar cell 1 of the present invention having the structure shown in FIG. 1 was manufactured by the procedure described above with reference to FIGS.
- a p-type silicon substrate (size: 125 mm square, thickness: 250 m, electrical resistivity: 3 ⁇ cm) is sliced from the ingot as the substrate 2, and a damage layer near the surface generated during slicing Was removed by etching with sodium hydroxide.
- a damage layer near the surface generated during slicing was removed by etching with sodium hydroxide.
- about 8000 A of silicon oxide film 5 is formed on the back surface of substrate 2 by atmospheric pressure CVD, and this is an aqueous solution containing potassium hydroxide and isopropyl alcohol (liquid temperature: 75 to 85 ° C).
- anisotropic etching along the silicon crystal orientation was advanced to form a fine pyramid-shaped textured surface with the (111) plane.
- the back side of the substrate was protected by the silicon oxide film 5, it remained flat 3;
- the silicon oxide film 5 remaining on the back surface was completely etched away using hydrofluoric acid, and then the first silicon oxide films 3 and 5 were formed on both surfaces of the substrate 2 by thermal oxidation. .
- the first silicon oxide films 3 and 5 were formed under conditions of 850 ° C. and 25 minutes, and a thickness of about 60A was formed.
- a second oxide silicon film 4 having a thickness of 4000 A was formed on the back side of the substrate 2 by atmospheric pressure CVD.
- heat treatment was performed at 450 ° C. for 20 minutes in a hydrogen atmosphere diluted to 3% with nitrogen.
- the first oxide silicon film 5 on the light receiving surface side was etched by penetrating the substrate 2 into 2.5% dilute hydrofluoric acid.
- the light receiving surface was heat-treated in a tube furnace at 900 ° C for 25 minutes.
- Phosphorus (P) was diffused on the side to form an n + layer 6.
- the first silicon oxide film 3 and the second silicon oxide film 4 function as a diffusion preventing layer, so that no n + layer is formed. Thereafter, the attached PSG was removed with dilute hydrofluoric acid.
- oxide silicon film is formed on the light-receiving surface side by atmospheric pressure CVD method, and the first oxide silicon film 3 and the second oxide silicon film 4 on the back side are partially formed by photolithography. Etching was performed to form contact hole 7. Then use BBr in a tube furnace for 1000
- Heat treatment was carried out at 40 ° C. for 40 minutes, and boron (B) was diffused into a portion exposed from the contact hole 7 on the back side of the substrate 2 to form a p + layer 8.
- BSG adhering to the diffusion in an oxygen atmosphere After heat treatment at 550 ° C. for 30 minutes, it was removed using hydrofluoric acid. Thereafter, the back surface side was protected using UV tape, and only the silicon oxide film on the light receiving surface side was removed by etching, and then a silicon nitride film was formed as the light receiving surface passivation film 9 on the light receiving surface side.
- the n-electrode 11 is formed so as to fill the contact hole 10 on the light-receiving surface side by vacuum deposition. Formed. On the back side, a p-electrode 12 covering the entire surface was formed so as to fill the contact hole 7 by vacuum deposition. In this way, the solar cell 1 having the structure shown in FIG. 1 was manufactured.
- the solar cell 21 of the present invention having the structure shown in FIG. 6 was manufactured by the procedure described above with reference to FIGS.
- Example 1 the damaged layer of the n-type silicon substrate (size: 125 mm square, thickness: 250 m, electrical resistivity: 3 ⁇ cm) was removed by etching.
- the first oxide silicon films 23 and 25 and the second oxide silicon films 24 and 26 are attached to the back side of the substrate 22 by thermal oxidation and atmospheric pressure CVD. And formed on the light receiving surface side.
- Example 1 the first oxide silicon film 23 and the second oxide silicon film 24 on the back surface side were partially etched by photolithography to form contact holes 27. Boron was diffused under the same conditions as in Example 1 to form a P + layer 28 in a portion exposed from the contact hole 27 on the back surface of the substrate 22. Thereafter, BSG was removed in the same manner as in Example 1.
- a protective oxide silicon film 29 having a thickness of about 4000 A was formed on the back side of the substrate 22 by atmospheric pressure CVD, and contact holes 30 were formed again by photolithography. Then, phosphorous was diffused this time using the same diffusion method and conditions as in Example 1, and an n + layer 31 was formed in a portion exposed from the contact hole 30 on the back surface side of the substrate 22.
- a protective oxide silicon film 32 having a thickness of 8000 A was formed on the back side of the substrate 22 by atmospheric pressure CVD so as to fill the contact hole 30. Thereafter, the back side was protected using UV tape or the like which is cured by ultraviolet rays, and only the first oxide silicon film 25 and the second silicon oxide film 26 on the light receiving surface side were etched. After peeling off the UV tape, a texture structure was formed on the side of the course using the acid etching solution described above. Next, implement In the same manner as in Example 1, a silicon nitride film was formed as the light-receiving surface passivation film 33 on the light-receiving surface side of the substrate 22.
- contact holes 34 and 35 having a diameter smaller than that of the contact holes 27 and 30 are formed in the protective oxide silicon films 29 and 32, respectively.
- the p electrode 36 was formed on the portion where the p + layer 28 was exposed, and the n electrode 37 was formed on the portion where the n + layer 31 was exposed. In this way, the back electrode type solar cell 21 shown in FIG. 6 was manufactured.
- Example 1 except that the first oxide silicon film 51 (thickness: 6 nm) and the second oxide silicon film 52 (thickness: 400 nm) are formed on the light receiving surface side of the substrate 2 instead of the light receiving surface passivation film 9
- the solar cell 1 ′ having the structure shown in FIG.
- Example 1 except that the first oxide silicon film 56 (thickness: 6 nm) and the second oxide silicon film 57 (thickness: 400 nm) are formed on the light receiving surface side of the substrate 2 instead of the light receiving surface passivation film 33
- the solar cell 21 ′ ′ having the structure shown in FIG.
- Example 2 After the texture structure was formed in the same manner as in Example 2, all of the silicon oxide film on the substrate 22 was removed by etching with hydrofluoric acid. Thereafter, the first silicon oxide film 23 was formed on both surfaces of the substrate 22 by thermal oxidation. Next, after forming the second oxide silicon film 24 only on the back surface by the atmospheric pressure CVD method, it was infiltrated with dilute hydrofluoric acid, and only the first oxide silicon film on the light receiving surface side was removed. Next, dilute hydrofluoric acid was permeated, and the silicon oxide film on the light receiving surface was etched to form a light receiving surface passivation film 33.
- contact holes 41 and 42 were formed in the first oxide silicon film 23 and the second oxide silicon film 24 by photolithography, respectively, and then the p electrode 43 and the n electrode.
- a solar cell 21 ′ having the structure shown in FIG. 12 was manufactured.
- Example 5 in which the first oxide silicon film and the second oxide silicon film were formed after the formation of the p + layer and the n + layer was higher than Example 2. Sex was obtained.
- a solar cell 1 having the structure shown in FIG. 1 was manufactured in the same manner as in Example 1 except that the second oxide silicon film 4 was formed by the SOG method.
- the formation of the second oxide silicon film 4 by the SOG method was performed by first applying a material for forming the SOG film on the first oxide silicon film 3 by the spin coating method and drying in the oven. Drying was performed in two stages, 80 ° C and 200 ° C. After that, it was fired in a nitrogen atmosphere in an 800 ° C tube furnace to form an SOG film.
- a solar cell was obtained in the same manner as in Example 5 except that instead of the first oxide silicon film 23 and the second oxide silicon film 24, a single layer silicon nitride film was formed by the atmospheric pressure CVD method. Was made.
- Example 5 The characteristics of the solar cells obtained in Example 5 and Comparative Examples 1 and 2 were evaluated using a solar simulator and an output measuring device. The results are shown in Table 2.
- Example 5 1 .00 1 .00 1 .00 1 .00 1 .00
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