WO2011081054A1 - 太陽電池セルの製造方法 - Google Patents
太陽電池セルの製造方法 Download PDFInfo
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- WO2011081054A1 WO2011081054A1 PCT/JP2010/072960 JP2010072960W WO2011081054A1 WO 2011081054 A1 WO2011081054 A1 WO 2011081054A1 JP 2010072960 W JP2010072960 W JP 2010072960W WO 2011081054 A1 WO2011081054 A1 WO 2011081054A1
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- antireflection film
- forming solution
- silicon substrate
- film forming
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 118
- 239000012298 atmosphere Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 7
- 230000003667 anti-reflective effect Effects 0.000 claims abstract 4
- 239000002019 doping agent Substances 0.000 claims description 54
- 238000009792 diffusion process Methods 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- -1 titanium alkoxide Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052704 radon Inorganic materials 0.000 claims description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 description 142
- 239000000243 solution Substances 0.000 description 85
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 44
- 229910052710 silicon Inorganic materials 0.000 description 44
- 239000010703 silicon Substances 0.000 description 44
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 28
- 229910052709 silver Inorganic materials 0.000 description 27
- 239000004332 silver Substances 0.000 description 27
- 238000004528 spin coating Methods 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 20
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a method for manufacturing a solar battery cell.
- Solar cells take out current by separating electrons and holes generated in the semiconductor substrate by light incident on the semiconductor substrate at a pn junction.
- an antireflection film can be formed on one main surface of the semiconductor substrate. It is done.
- Patent Document 1 Japanese Patent Laid-Open No. 53-14695
- a coating composition prepared by mixing n-butyl orthotitanate, acetic acid and ethyl alcohol is applied on a silicon substrate and heated in air.
- a technique for forming an antireflection film made of a titanium oxide thin film on a silicon substrate is disclosed.
- Patent Document 2 Japanese Patent Laid-Open No. 54-76629
- a coating composition prepared by mixing ethyl alcohol, phosphorus pentoxide, isopropyl titanate and acetic acid is applied on a silicon substrate and is applied in the atmosphere.
- a titanium oxide thin film containing phosphorus as an impurity is formed on the silicon substrate by heating with, and then phosphorus is diffused from the titanium oxide thin film to the silicon substrate by heating in a nitrogen atmosphere.
- a technique for forming an antireflection film made of a thin film and forming a pn junction inside a silicon substrate is disclosed.
- Patent Document 1 and Patent Document 2 described above when an antireflection film is formed on a silicon substrate by applying a solution on the silicon substrate and heating, it is formed on the silicon substrate. There was a problem that the antireflection film became clouded and the appearance of the solar battery cell was impaired.
- an object of the present invention is to provide a method for manufacturing a solar cell that can stably manufacture a solar cell having an excellent appearance by suppressing the cloudiness of the antireflection film. is there.
- the present invention includes a step of applying an antireflection film forming solution containing at least one of a metal oxide and a metal oxide precursor to one main surface of a semiconductor substrate, and a semiconductor coated with the antireflection film forming solution Heating the substrate, and applying the antireflection film forming solution in an atmosphere in which the water content is 0 g / m 3 or more and 9.4 g / m 3 or less.
- an antireflection film forming solution containing at least one of a metal oxide and a metal oxide precursor to one main surface of a semiconductor substrate, and a semiconductor coated with the antireflection film forming solution Heating the substrate, and applying the antireflection film forming solution in an atmosphere in which the water content is 0 g / m 3 or more and 9.4 g / m 3 or less.
- the antireflection film-forming solution contains a dopant for forming a pn junction in the semiconductor substrate.
- the antireflection film forming solution contains a dopant for forming an n-type dopant diffusion layer in the semiconductor substrate.
- the antireflection film forming solution is applied in an atmosphere containing a dry gas in the step of applying the antireflection film forming solution.
- the antireflection film forming solution is applied while introducing a dry gas into the atmosphere.
- the dry gas contains at least one selected from the group consisting of oxygen, nitrogen, helium, neon, argon, krypton, xenon and radon.
- the antireflection film forming solution is preferably a solution containing titanium alkoxide.
- the present invention it is possible to provide a method for manufacturing a solar cell that can stably manufacture a solar cell having an excellent appearance by suppressing the white turbidity of the antireflection film.
- FIG. 6 is a photograph of the main surface of a p-type polycrystalline silicon substrate immediately after spin coating of an antireflection film forming solution in Example 2.
- FIG. 6 is a photograph of the main surface of a p-type polycrystalline silicon substrate immediately after spin coating of an antireflection film forming solution in Example 3.
- FIG. 6 is a photograph of the main surface of a p-type polycrystalline silicon substrate immediately after spin coating of an antireflection film forming solution in Example 3.
- a p-type silicon substrate 1 made of p-type silicon crystal is prepared as a semiconductor substrate.
- the p-type silicon substrate 1 is obtained by, for example, cutting a silicon ingot obtained by recrystallizing a raw material of p-type silicon crystal in a crucible and then cutting the silicon block with a wire saw. Obtainable.
- the surface of the p-type silicon substrate 1 may be etched with, for example, an alkali solution or an acid solution to remove a damaged layer when the p-type silicon substrate 1 is sliced. Further, fine irregularities (not shown) may be formed on the surface of the p-type silicon substrate 1 by adjusting the etching conditions at this time. When such unevenness is formed on the surface of the p-type silicon substrate 1, the reflection of light incident on the p-type silicon substrate 1 is reduced, and the photoelectric conversion efficiency of the solar battery cell can be increased.
- an antireflection film-forming solution 5 a is formed on one main surface (hereinafter referred to as “first main surface”) which is one surface of the p-type silicon substrate 1.
- first main surface which is one surface of the p-type silicon substrate 1.
- the antireflection film forming solution 5a contains at least one of a metal oxide and a metal oxide precursor in a solvent.
- metal oxide for example, titanium oxide, tin oxide, aluminum oxide, silicon dioxide, silicon oxide, magnesium oxide and the like can be used.
- the metal oxide precursor for example, a material that is a precursor of the above metal oxide such as titanium alkoxide such as titanium tetraisopropoxide (Ti [OCH (CH 3 ) 2 ] 4 ) is used. it can.
- a solvent containing alcohol such as isopropyl alcohol or ethanol can be used.
- the antireflection film forming solution 5a preferably contains a dopant for forming a pn junction in the semiconductor substrate. In this case, it is not necessary to perform a step of diffusing a dopant for forming a pn junction in the semiconductor substrate by applying the antireflection film forming solution 5a, so that the solar cell can be manufactured more efficiently. It tends to be possible.
- diphosphorus pentoxide containing phosphorus which is an n-type dopant can be included in the antireflection film forming solution 5a.
- a compound containing boron which is a p-type dopant, can be included in the antireflection film forming solution 5a.
- FIG. 3 is a schematic diagram illustrating an example of a process of applying the antireflection film forming solution 5a.
- a coating apparatus for the antireflection film forming solution 5a a conventionally known coating apparatus such as a spin coating apparatus, an ink jet coating apparatus, or a screen printing apparatus can be used. A method of spin coating the antireflection film forming solution 5a using a coating apparatus will be described.
- the p-type silicon substrate 1 is installed on the rotating plate 8 installed inside the coating apparatus 11 so that the first main surface of the p-type silicon substrate 1 faces upward.
- the antireflection film forming solution 5a is applied onto the surface of the p type silicon substrate 1 by the application nozzle 9 while rotating the p type silicon substrate 1 by rotating the rotating plate 8.
- Spin coating 5a is performed.
- the content of water is introduced by introducing the dry gas from the dry gas supply device 10 through the dry gas introduction tube 14 into the atmosphere in which the antireflection film forming solution 5a inside the coating device 11 is being spin-coated. Is applied by spin coating of the antireflection film-forming solution 5a in an atmosphere of 0 g / m 3 or more and 9.4 g / m 3 or less.
- the present inventor has formed a solar cell using a titanium alkoxide (for example, Ti [OCH (CH 3 ) 2 ] 4 ) solution as the antireflection film forming solution. It has been found that the antireflection film becomes cloudy and the appearance of the solar battery cell may be impaired. Further, it has been found that such clouding of the antireflection film occurs relatively remarkably when diphosphorus pentoxide is mixed and used as the n-type dopant material in the antireflection film forming solution.
- a titanium alkoxide for example, Ti [OCH (CH 3 ) 2 ] 4
- the cause of white turbidity of the antireflection film is the hygroscopicity of the metal oxide and / or metal oxide precursor. That is, general metal oxides and metal oxide precursors used in the antireflection film forming solution have high hygroscopicity, and when applied in a high humidity atmosphere, the moisture in the atmosphere Reacts with and causes white turbidity of the antireflection film.
- diphosphorus pentoxide is also highly hygroscopic and is considered to promote this cloudiness.
- the antireflection film-forming solution 5a in an atmosphere having a water content of 0 g / m 3 or more and 9.4 g / m 3 or less, It has been found that the anti-reflection film formed from the anti-reflection film forming solution 5a can suppress white turbidity and can stably produce solar cells having an excellent appearance, thereby completing the present invention. It was.
- FIG. 4 is a schematic diagram illustrating another example of the step of applying the antireflection film forming solution 5a.
- the coating apparatus 11 is installed in the drying chamber 12, and an antireflection film is formed in the coating apparatus 11 while introducing the drying gas 7 from the drying gas introduction unit 13 into the atmosphere inside the drying chamber 12. It is characterized in that an application step of the solution 5a is performed.
- the antireflection film is formed in an atmosphere having a water content of 0 g / m 3 or more and 9.4 g / m 3 or less by the dry gas 7 introduced from the dry gas introduction unit 13 into the atmosphere inside the drying chamber 12.
- the solution 5a can be applied.
- FIG. 5 is a schematic diagram illustrating another example of the step of applying the antireflection film forming solution 5a.
- the example shown in FIG. 5 is characterized in that the dry gas supply device 10 shown in FIG. 3 and the dry gas introduction unit 13 shown in FIG. 4 are used in combination.
- water is supplied by the dry gas introduced from the dry gas supply device 10 through the dry gas introduction pipe 14 into the coating device 11 and the dry gas 7 introduced from the dry gas introduction unit 13 into the atmosphere inside the drying chamber 12.
- the antireflection film-forming solution 5a can be applied as an atmosphere having a content of 0 g / m 3 to 9.4 g / m 3 .
- the dry gas for example, a gas having a water content of 0 g or more and 9.4 g or less per 1 m 3 of the dry gas can be used. Further, as the dry gas, it is preferable to use a gas containing at least one selected from the group consisting of oxygen, nitrogen, helium, neon, argon, krypton, xenon and radon. In this case, since the reaction between the antireflection film forming solution 5a and the dry gas can be suppressed, the white turbidity of the antireflection film can be further effectively suppressed and a solar cell having an excellent appearance can be stably obtained. There is a tendency to be able to manufacture.
- the p-type silicon substrate 1 coated with the antireflection film forming solution 5a is heated.
- the antireflection film forming solution 5a contains an n-type dopant, for example, as shown in the schematic cross-sectional view of FIG. 6, the antireflection film forming solution is formed on the first main surface of the p-type silicon substrate 1.
- the solution 5 a is heated to form the antireflection film 5, and n-type dopant diffuses from the antireflection film forming solution 5 a to the surface of the p-type silicon substrate 1 on the first main surface of the p-type silicon substrate 1.
- the n-type dopant diffusion layer 4 is formed.
- the p-type silicon substrate 1 coated with the antireflection film forming solution 5a is heated, for example, at a temperature of 800 ° C. to 950 ° C. for 5 to 30 minutes, for example.
- silver containing silver powder, glass frit, resin, and organic solvent is formed on the surface of the antireflection film 5 on the first main surface of the p-type silicon substrate 1.
- the paste 2a is printed by screen printing or the like, and aluminum containing, for example, aluminum powder, glass frit, resin and organic solvent on the second main surface which is the surface opposite to the first main surface of the p-type silicon substrate 1
- a silver paste (not shown) is printed on the aluminum paste 3a.
- FIG. 9 shows a photograph of the appearance of the main surface of the p-type polycrystalline silicon substrate immediately after the above spin coating. As shown in FIG. 9, when the antireflection film forming solution was spin-coated in an atmosphere having a water content of 9.4 g / m 3 , no cloudiness was generated in the antireflection film forming solution.
- a commercially available silver paste is printed on the surface of the antireflection film on the main surface of the p-type polycrystalline silicon substrate, and the side opposite to the side on which the antireflection film is formed on the p-type polycrystalline silicon substrate.
- a commercially available aluminum paste was printed on almost the entire main surface, and a silver paste was printed on a part of the surface of the aluminum paste, and the silver paste and the aluminum paste were each dried in a temperature atmosphere of about 150 ° C.
- FIG. 10 shows a photograph of the appearance of the main surface of the p-type polycrystalline silicon substrate immediately after the spin coating. As shown in FIG. 10, even when the antireflection film forming solution is spin-coated in an atmosphere of 25 ° C. with a water content of 6.7 g / m 3 , the antireflection film forming solution is clouded. There wasn't.
- the p-type polycrystalline silicon substrate after the application of the anti-reflection film forming solution is heated to reflect the titanium oxide film on the main surface of the p-type polycrystalline silicon substrate.
- a protective film was formed, and an n-type dopant diffusion layer was formed on the main surface of the p-type polycrystalline silicon substrate.
- no cloudiness was generated in the antireflection film.
- Example 2 Thereafter, in the same manner as in Example 1, a solar battery cell of Example 2 was produced. Also in the solar cell of Example 2, the antireflection film was not clouded, and a solar cell excellent in appearance could be produced. Therefore, in the production method of Example 2, the antireflection film was also clouded. It is possible to stably produce a solar battery cell that has an excellent appearance by being suppressed.
- FIG. 11 shows a photograph of the appearance of the main surface of the p-type polycrystalline silicon substrate immediately after the spin coating. As shown in FIG. 11, even when the antireflection film forming solution is spin-coated in an atmosphere of 25 ° C. with a water content of 6.4 g / m 3 , white turbidity is generated in the antireflection film forming solution. There wasn't.
- Example 4 Instead of the p-type polycrystalline silicon substrate used in Examples 1 to 3, an n-type single crystal silicon substrate having two substantially square main surfaces each having a side of 156 mm and a thickness of 120 ⁇ m was produced.
- the n-type single crystal silicon substrate was prepared by slicing an n-type single crystal silicon ingot with a wire saw and then etching with an alkaline solution to remove the damaged layer on the surface.
- n is formed on the main surface of the n-type single crystal silicon substrate that is not covered with the diffusion mask. A type dopant diffusion layer was formed, and then the diffusion mask was removed.
- n-type single crystal silicon not covered with the diffusion mask A p-type dopant diffusion layer was formed on the main surface of the substrate, and then the diffusion mask was removed.
- a solution for forming an antireflection film was applied by spin coating.
- the atmosphere inside the spin coating apparatus during spin coating of the antireflection film forming solution was an atmosphere of 25 ° C. with a water content of 9.4 g / m 3 .
- an antireflection film made of a titanium oxide film is formed on the main surface of the n-type single crystal silicon substrate.
- an n-type dopant diffusion layer was formed by diffusing phosphorus into the main surface of the n-type single crystal silicon substrate.
- an etching mask is formed on a part of the silicon oxide film formed on one main surface of the n-type single crystal silicon substrate by an inkjet printing method, and the silicon oxide film part not covered with the etching mask is formed.
- the n-type dopant diffusion layer and the p-type dopant diffusion layer were respectively exposed by etching. Thereafter, the etching mask was removed.
- region by the etching of a silicon oxide film was made smaller than the area of each area
- a silver paste was printed on each exposed region of the n-type dopant diffusion layer and the p-type dopant diffusion layer by a screen printing method, and dried in an atmosphere at about 150 ° C.
- the area where the silver paste was printed was larger than the area of the silicon oxide film removal area and smaller than the area of each of the n-type dopant diffusion layer and the p-type dopant diffusion layer. That is, the silver paste was printed on each region of the n-type dopant diffusion layer and the p-type dopant diffusion layer so as to cover a part of the silicon oxide film.
- a silver paste printed on one main surface of the n-type single crystal silicon substrate was baked in air at a temperature of 860 ° C. to form a silver electrode.
- the solar battery cell of Example 4 was produced.
- An antireflection film was formed on one main surface of the n-type single crystal silicon substrate of the solar battery cell of Example 4, and an n-type dopant diffusion layer was formed immediately below the antireflection film.
- a silicon oxide film and a silver electrode are formed on the other main surface of the n-type single crystal silicon substrate of the solar battery cell of Example 4, and an n-type dopant diffusion is directly below each of the silicon oxide film and the silver electrode.
- a layer and a p-type dopant diffusion layer were formed.
- a solar battery cell was produced in the same manner as in Example 4 except that the content of water in the atmosphere inside the spin coating apparatus during spin coating of the antireflection film forming solution was 6.7 g / m 3. In this case, the cloudiness of the antireflection film did not occur.
- a solar battery cell was produced in the same manner as in Example 4 except that the content of water in the atmosphere inside the spin coater during spin coating of the antireflection film forming solution was 6.4 g / m 3. In this case, the cloudiness of the antireflection film did not occur.
- FIG. 12 shows a photograph of the appearance of the main surface of the p-type polycrystalline silicon substrate immediately after the spin coating.
- the antireflection film forming solution is spin-coated in an atmosphere of 25 ° C. with a water content of 11.2 g / m 3 , white turbidity is generated in the antireflection film forming solution. It was.
- the p-type polycrystalline silicon substrate after the application of the anti-reflection film forming solution is heated to reflect the titanium oxide film on the main surface of the p-type polycrystalline silicon substrate.
- a protective film was formed, and an n-type dopant diffusion layer was formed on the main surface of the p-type polycrystalline silicon substrate.
- white turbidity still occurred in the antireflection film.
- Example 1 Thereafter, in the same manner as in Example 1, a solar battery cell of Comparative Example 1 was produced.
- the antireflection film has white turbidity, and a solar battery cell having a deteriorated appearance is manufactured. Therefore, in the manufacturing method of Comparative Example 1, the white turbidity of the antireflection film is suppressed. A solar battery cell having an excellent appearance cannot be stably produced.
- Example 2 Thereafter, in the same manner as in Example 1, a solar battery cell of Comparative Example 2 was produced.
- a white turbidity was generated in the antireflection film, and a solar cell having a deteriorated appearance was manufactured. Therefore, in the manufacturing method of Comparative Example 2, the white turbidity of the antireflection film was suppressed. A solar battery cell having an excellent appearance cannot be stably produced.
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Abstract
Description
まず、1辺が156mmの正方形状の2つの主面を有し、かつ厚さ200μmのp型多結晶シリコン基板を作製した。ここで、p型多結晶シリコン基板は、p型多結晶シリコンインゴットをワイヤソーでスライスした後にアルカリ溶液でエッチングして表面のダメージ層を除去することによって作製した。
雰囲気中の水の含有量を6.7g/m3としたこと以外は実施例1と同様にして、p型多結晶シリコン基板の一方の主面上に反射防止膜形成用溶液をスピン塗布した。
雰囲気中の水の含有量を6.4g/m3としたこと以外は実施例1と同様にして、p型多結晶シリコン基板の一方の主面上に反射防止膜形成用溶液をスピン塗布した。
実施例1~3で用いたp型多結晶シリコン基板の代わりに、1辺が156mmの略正方形状の2つの主面を有し、かつ厚さ120μmのn型単結晶シリコン基板を作製した。ここで、n型単結晶シリコン基板は、n型単結晶シリコンインゴットをワイヤソーでスライスした後にアルカリ溶液でエッチングして表面のダメージ層を除去することによって作製した。
雰囲気中の水の含有量を11.2g/m3としたこと以外は実施例1と同様にして、p型多結晶シリコン基板の一方の主面上に反射防止膜形成用溶液をスピン塗布した。
雰囲気中の水の含有量を9.7g/m3としたこと以外は実施例1と同様にして、p型多結晶シリコン基板の一方の主面上に反射防止膜形成用溶液をスピン塗布した。
以上の実施例1~3および比較例1~2の結果を検討すると、水の含有量が9.4g/m3以下の雰囲気でp型多結晶シリコン基板の一方の主面上に反射防止膜形成用溶液を塗布した場合には、反射防止膜の白濁を抑制して優れた外観を有する太陽電池セルを安定して製造することができ、水の含有量が低下してもその傾向は変わらなかったことから、水の含有量が0g/m3以上9.4g/m3以下の雰囲気で反射防止膜形成用溶液を塗布すれば、反射防止膜の白濁を抑制して優れた外観を有する太陽電池セルを安定して製造することができると考えられる。
Claims (7)
- 半導体基板(1)の一方の主面に金属酸化物および金属酸化物前駆体の少なくとも一方を含有する反射防止膜形成用溶液(5a)を塗布する工程と、
前記反射防止膜形成用溶液(5a)が塗布された前記半導体基板(1)を加熱する工程と、を含み、
前記反射防止膜形成用溶液(5a)を塗布する工程において、前記反射防止膜形成用溶液(5a)は、水の含有量が0g/m3以上9.4g/m3以下の雰囲気で塗布される、太陽電池セルの製造方法。 - 前記反射防止膜形成用溶液(5a)が、前記半導体基板(1)にpn接合を形成するためのドーパントを含む、請求項1に記載の太陽電池セルの製造方法。
- 前記反射防止膜形成用溶液(5a)が、前記半導体基板(1)にn型ドーパント拡散層(4)を形成するためのドーパントを含む、請求項1または2に記載の太陽電池セルの製造方法。
- 前記反射防止膜形成用溶液(5a)を塗布する工程において、前記反射防止膜形成用溶液(5a)は、前記雰囲気が乾燥気体(7)を含む雰囲気で塗布される、請求項1から3のいずれかに記載の太陽電池セルの製造方法。
- 前記反射防止膜形成用溶液(5a)を塗布する工程において、前記反射防止膜形成用溶液(5a)は、前記雰囲気中に乾燥気体(7)を導入しながら塗布される、請求項1から4のいずれかに記載の太陽電池セルの製造方法。
- 前記乾燥気体(7)は、酸素、窒素、ヘリウム、ネオン、アルゴン、クリプトン、キセノンおよびラドンからなる群から選択された少なくとも1種を含む、請求項4または5に記載の太陽電池セルの製造方法。
- 前記反射防止膜形成用溶液(5a)は、チタンアルコキシドを含む溶液である、請求項1から6のいずれかに記載の太陽電池セルの製造方法。
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EP10840911A EP2521186A1 (en) | 2009-12-28 | 2010-12-21 | Method for manufacturing a solar cell |
CN2010800596151A CN102687284A (zh) | 2009-12-28 | 2010-12-21 | 太阳能电池单元的制造方法 |
JP2011547552A JPWO2011081054A1 (ja) | 2009-12-28 | 2010-12-21 | 太陽電池セルの製造方法 |
US13/515,045 US20120301998A1 (en) | 2009-12-28 | 2010-12-21 | Method for manufacturing solar cell |
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JP2009-297479 | 2009-12-28 | ||
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US (1) | US20120301998A1 (ja) |
EP (1) | EP2521186A1 (ja) |
JP (1) | JPWO2011081054A1 (ja) |
KR (1) | KR20120085333A (ja) |
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JP2015026693A (ja) * | 2013-07-25 | 2015-02-05 | 株式会社ユーテック | 膜の製造方法及びマルチチャンバー装置 |
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CN104810252B (zh) * | 2014-01-24 | 2018-07-06 | 中芯国际集成电路制造(上海)有限公司 | 底部抗反射涂层的涂布方法 |
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JPS53146995A (en) | 1977-05-27 | 1978-12-21 | Sharp Corp | Production of titanium oxide film |
JPS5476629A (en) | 1977-11-30 | 1979-06-19 | Sharp Corp | Coating composition |
JP2005033063A (ja) * | 2003-07-08 | 2005-02-03 | Sharp Corp | 太陽電池用反射防止膜およびその作製方法 |
JP2010065174A (ja) * | 2008-09-12 | 2010-03-25 | Mitsubishi Chemicals Corp | 組成物、反射防止膜基板、並びに、太陽電池システム |
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US4251285A (en) * | 1979-08-14 | 1981-02-17 | Westinghouse Electric Corp. | Diffusion of dopant from optical coating and single step formation of PN junction in silicon solar cell and coating thereon |
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US7193237B2 (en) * | 2002-03-27 | 2007-03-20 | Mitsubishi Chemical Corporation | Organic semiconductor material and organic electronic device |
AU2003281895A1 (en) * | 2002-12-05 | 2004-06-23 | Unaxis Balzers Ag | Method and apparatus for control of layer thicknesses |
JP4424307B2 (ja) * | 2003-04-18 | 2010-03-03 | 日立化成工業株式会社 | 枝分れ構造を有するポリキノリン共重合体およびこれを用いた有機エレクトロルミネセンス素子 |
KR101256301B1 (ko) * | 2006-07-19 | 2013-04-18 | 히타치가세이가부시끼가이샤 | 유기 일렉트로닉스용 재료, 유기 일렉트로닉스 소자 및 유기 일렉트로루미네센스 소자 |
CN101490864A (zh) * | 2006-07-19 | 2009-07-22 | 日立化成工业株式会社 | 有机电子材料、有机电子元件和有机电致发光元件 |
-
2010
- 2010-12-21 WO PCT/JP2010/072960 patent/WO2011081054A1/ja active Application Filing
- 2010-12-21 US US13/515,045 patent/US20120301998A1/en not_active Abandoned
- 2010-12-21 EP EP10840911A patent/EP2521186A1/en not_active Withdrawn
- 2010-12-21 CN CN2010800596151A patent/CN102687284A/zh active Pending
- 2010-12-21 KR KR1020127016284A patent/KR20120085333A/ko not_active Application Discontinuation
- 2010-12-21 JP JP2011547552A patent/JPWO2011081054A1/ja active Pending
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JPS53146995A (en) | 1977-05-27 | 1978-12-21 | Sharp Corp | Production of titanium oxide film |
JPS5476629A (en) | 1977-11-30 | 1979-06-19 | Sharp Corp | Coating composition |
JP2005033063A (ja) * | 2003-07-08 | 2005-02-03 | Sharp Corp | 太陽電池用反射防止膜およびその作製方法 |
JP2010065174A (ja) * | 2008-09-12 | 2010-03-25 | Mitsubishi Chemicals Corp | 組成物、反射防止膜基板、並びに、太陽電池システム |
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JP2015026693A (ja) * | 2013-07-25 | 2015-02-05 | 株式会社ユーテック | 膜の製造方法及びマルチチャンバー装置 |
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KR20120085333A (ko) | 2012-07-31 |
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