JP2003179239A - Manufacturing method of solar battery and solar battery manufactured thereby - Google Patents
Manufacturing method of solar battery and solar battery manufactured therebyInfo
- Publication number
- JP2003179239A JP2003179239A JP2001375570A JP2001375570A JP2003179239A JP 2003179239 A JP2003179239 A JP 2003179239A JP 2001375570 A JP2001375570 A JP 2001375570A JP 2001375570 A JP2001375570 A JP 2001375570A JP 2003179239 A JP2003179239 A JP 2003179239A
- Authority
- JP
- Japan
- Prior art keywords
- solar cell
- antireflection film
- manufacturing
- silicon
- silicon oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 80
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 77
- 239000010703 silicon Substances 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 72
- 238000000576 coating method Methods 0.000 claims abstract description 63
- 239000011248 coating agent Substances 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 56
- 239000012535 impurity Substances 0.000 claims abstract description 37
- 238000009792 diffusion process Methods 0.000 claims abstract description 27
- 239000002344 surface layer Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 87
- 150000003377 silicon compounds Chemical class 0.000 claims description 56
- 238000010304 firing Methods 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 27
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- -1 silanol compound Chemical class 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910008051 Si-OH Inorganic materials 0.000 claims description 4
- 229910006358 Si—OH Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 21
- 230000003449 preventive effect Effects 0.000 abstract 3
- 239000003973 paint Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 238000000206 photolithography Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000059 patterning Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 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 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 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
- 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
- H01L31/02—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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シリコン太陽電池
の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for manufacturing a silicon solar cell.
【０００２】[0002]
【従来の技術】シリコン太陽電池の製造方法は、まずｐ
型シリコン基板の受光面側にｎ型不純物原子をドーピン
グし、ｎ型不純物領域であるｎ層を形成し、ｐ層とｎ層
との間にｐｎ接合面を形成する。つぎに、ｎ層上にパッ
シベーション膜および反射防止膜を形成する。反射防止
膜は複数層とする場合があり、パッシベーション膜を兼
ねる場合もある。その後、フォトリソグラフィなどによ
りパッシベーション膜および反射防止膜をパターン化
し、ｎ層と接続するように表面電極を形成する。つぎ
に、受光面と反対側の面に、高濃度のｐ型不純物領域で
あるｐ+層を形成し、ｐ+層の上に裏面電極を形成する
と、シリコン太陽電池を製造することができる。シリコ
ン太陽電池が受光すると、ｐｎ接合面に光起電力が生
じ、この起電力により表面電極および裏面電極を介して
負荷に電流が供給される。このシリコン太陽電池の光電
変換効率を高めるためには、受光面側での少数のキャリ
アの再結合を低下させるとともに、太陽光の反射量を抑
える必要がある。したがって、パッシベーション膜と反
射防止膜は、光電変換効率を高める上で重要な機能を発
揮する。2. Description of the Related Art A method for manufacturing a silicon solar cell is first described in p.
An n-type impurity atom is doped on the light-receiving surface side of the type silicon substrate to form an n-layer which is an n-type impurity region, and a pn junction surface is formed between the p-layer and the n-layer. Next, a passivation film and an antireflection film are formed on the n layer. The antireflection film may have a plurality of layers and may also serve as a passivation film. After that, the passivation film and the antireflection film are patterned by photolithography or the like, and a surface electrode is formed so as to be connected to the n layer. Next, a p + layer, which is a high-concentration p-type impurity region, is formed on the surface opposite to the light receiving surface, and a back electrode is formed on the p + layer, whereby a silicon solar cell can be manufactured. When the silicon solar cell receives light, a photoelectromotive force is generated on the pn junction surface, and this electromotive force supplies a current to the load via the front surface electrode and the back surface electrode. In order to increase the photoelectric conversion efficiency of this silicon solar cell, it is necessary to reduce the recombination of a small number of carriers on the light-receiving surface side and suppress the amount of sunlight reflection. Therefore, the passivation film and the antireflection film exert important functions for increasing the photoelectric conversion efficiency.
【０００３】Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｌｅｔ
ｔｅｒｓ、Ｖｏｌ．６２、Ｎｏ．１１、ｐ．１２８０〜
１２８２（１９９３）には、ｐｎ構造を有する太陽電池
の受光面側にＳｉＯ2（二酸化シリコン）からなるパッ
シベーション膜を形成し、パッシベーション膜の上に弗
化マグネシウムおよび硫化亜鉛のような比較的屈折率の
大きい材料からなる反射防止膜を形成し、シリコン太陽
電池の高効率化を図る方法が紹介されている。パッシベ
ーション膜の形成方法としては熱酸化法が採用され、シ
リコン基板を酸素雰囲気中または大気雰囲気中、熱酸化
炉内において、９００℃以上に加熱し、シリコン基板の
表面に酸化膜を形成する。反射防止膜は、弗化マグネシ
ウム、硫化亜鉛、酸化チタンなどを材料として、プラズ
マＣＶＤ法やスパッタ法により形成される。しかし、シ
リコン太陽電池のパッシベーション膜を熱酸化法により
形成しようとすると９００℃〜１２００℃という高温で
処理する必要があり、このような高温の状態に太陽電池
を曝すと、基板の表層へドーピングにより導入した不純
物が再拡散し、太陽電池の光電変換効率が低下する。さ
らに、過熱によりシリコン基板と熱酸化膜との界面に大
きな応力がかかり、太陽電池のライフタイムが短くな
る。一方、プラズマＣＶＤ法やスパッタ法は高真空を必
要とするため、設備が高価となる。また、チャンバ内に
反応生成物に起因してパーティクルが発生するため、パ
ーティクルがシリコン太陽電池に付着して、太陽電池の
機能低下をもたらし、不良品が発生しやすい。さらに、
チャンバ内に堆積したパーティクルを除去するためにチ
ャンバクリーニングが必要となり、生産効率が低下す
る。Applied Physics Let
ters, Vol. 62, No. 11, p. 1280-
1282 (1993), a passivation film made of SiO 2 (silicon dioxide) is formed on the light receiving surface side of a solar cell having a pn structure, and a relatively high refractive index such as magnesium fluoride and zinc sulfide is formed on the passivation film. A method of increasing the efficiency of a silicon solar cell by forming an antireflection film made of a large material has been introduced. A thermal oxidation method is adopted as a method for forming the passivation film, and the silicon substrate is heated to 900 ° C. or higher in a thermal oxidation furnace in an oxygen atmosphere or an air atmosphere to form an oxide film on the surface of the silicon substrate. The antireflection film is formed by a plasma CVD method or a sputtering method using magnesium fluoride, zinc sulfide, titanium oxide or the like as a material. However, in order to form a passivation film of a silicon solar cell by a thermal oxidation method, it is necessary to treat it at a high temperature of 900 ° C. to 1200 ° C. When the solar cell is exposed to such a high temperature state, the surface layer of the substrate is doped with the material. The introduced impurities are re-diffused and the photoelectric conversion efficiency of the solar cell is reduced. Further, overheating places a large stress on the interface between the silicon substrate and the thermal oxide film, which shortens the lifetime of the solar cell. On the other hand, since the plasma CVD method and the sputtering method require high vacuum, the equipment becomes expensive. Further, since particles are generated in the chamber due to the reaction product, the particles adhere to the silicon solar cell, causing a decline in the function of the solar cell, and defective products are likely to occur. further,
Chamber cleaning is required to remove the particles deposited in the chamber, which lowers production efficiency.
【０００４】特開昭５８−２３４８６号公報には、反射
防止膜として酸化タンタル膜、酸化ニオブ膜を、スピン
法、スプレー法、デイップ法により形成する方法が紹介
されている。しかし、この酸化タンタルや酸化ニオブか
らなる膜は、反射防止効果は大きいが、パッシベーショ
ン効果が小さいため、別途パッシベーション膜を設けな
いときは、シリコン基板表面でキャリアの再結合が起こ
り、太陽電池の効率が低下する。また、スピン法、スプ
レー法、ディップ法はプラズマＣＶＤ法やスパッタ法に
比べて安価に成膜できる利点があるが、スピン法により
成膜する場合は、膜材料の利用効率が低く、その多くが
無駄になってしまう。Japanese Patent Laid-Open No. 58-23486 discloses a method of forming a tantalum oxide film or a niobium oxide film as an antireflection film by a spin method, a spray method or a dip method. However, the film made of tantalum oxide or niobium oxide has a large antireflection effect, but has a small passivation effect. Therefore, when a separate passivation film is not provided, carrier recombination occurs on the surface of the silicon substrate, and the efficiency of the solar cell is increased. Is reduced. Further, the spin method, the spray method, and the dip method have an advantage that the film can be formed at a lower cost than the plasma CVD method and the sputtering method. However, when the film is formed by the spin method, the utilization efficiency of the film material is low, and most of them are used. It's wasted.
【０００５】また、上記のいずれの方法においても基板
の表面全体に成膜されるため、受光面側に表面電極を形
成する前に、レジスト塗布、露光、現像、エッチング、
レジスト除去、というフォトリソグラフィが必要とな
り、そのための装置も必要となって、工程が複雑とな
る。In any of the above methods, since the film is formed on the entire surface of the substrate, resist coating, exposure, development, etching, and etching are performed before the surface electrode is formed on the light receiving surface side.
Photolithography such as resist removal is required, and an apparatus for that is also required, which complicates the process.
【０００６】[0006]
【発明が解決しようとする課題】パッシベーション効果
や反射防止効果に優れる太陽電池の製造方法を提供す
る。また、低い温度で、安価に製造することができ、か
つ工程も簡略で生産効率が高く、塗料を有効利用できる
太陽電池の製造方法を提供する。A method of manufacturing a solar cell having excellent passivation effect and antireflection effect is provided. Further, the present invention provides a method for manufacturing a solar cell, which can be manufactured at low temperature at low cost, has a simple process, has high production efficiency, and can effectively use a paint.
【０００７】[0007]
【課題を解決するための手段】本発明の太陽電池の製造
方法は、導電型のシリコン基板の表層にシリコン基板と
異なる導電型の不純物拡散領域を形成し、不純物拡散領
域上にシリコン化合物を含む塗料を塗布した後、乾燥
し、焼成してシリコン酸化物膜を形成する工程とを含む
ことを特徴とする。According to the method of manufacturing a solar cell of the present invention, an impurity diffusion region of a conductivity type different from that of a silicon substrate is formed in a surface layer of a conductivity type silicon substrate, and a silicon compound is contained on the impurity diffusion region. A step of forming a silicon oxide film by applying a coating material, followed by drying and baking.
【０００８】シリコン化合物は、５００℃〜９００℃で
焼成することが好ましく、シリコン酸化物膜の厚さは、
７０ｎｍ〜１５０ｎｍが好ましい。The silicon compound is preferably fired at 500 ° C. to 900 ° C., and the thickness of the silicon oxide film is
70 nm to 150 nm is preferable.
【０００９】本発明の太陽電池の他の製造方法は、導電
型のシリコン基板の表層にシリコン基板と異なる導電型
の不純物拡散領域を形成し、不純物拡散領域上にシリコ
ン化合物を含む塗料を塗布した後、乾燥し、焼成してシ
リコン酸化物膜を形成する工程と、シリコン酸化物膜上
に反射防止膜材料を含む塗料を塗布した後、乾燥し、焼
成して少なくとも一層の反射防止膜を形成する工程と、
を含むことを特徴とする。In another method of manufacturing a solar cell of the present invention, an impurity diffusion region of a conductivity type different from that of the silicon substrate is formed on the surface layer of a conductivity type silicon substrate, and a coating material containing a silicon compound is applied onto the impurity diffusion region. Then, a step of drying and baking to form a silicon oxide film, and a coating containing an antireflection film material is applied on the silicon oxide film, followed by drying and baking to form at least one antireflection film. And the process of
It is characterized by including.
【００１０】シリコン化合物は、５００℃〜９００℃で
焼成することが好ましく、反射防止膜材料は、２００℃
〜９００℃で焼成することが好ましい。The silicon compound is preferably fired at 500 ° C. to 900 ° C., and the antireflective coating material is 200 ° C.
It is preferable to bake at ˜900 ° C.
【００１１】本発明の太陽電池の他の製造方法は、導電
型のシリコン基板の表層にシリコン基板と異なる導電型
の不純物拡散領域を形成し、不純物拡散領域上にシリコ
ン化合物を含む塗料を塗布した後、乾燥して、シリコン
化合物層を形成する工程と、シリコン化合物層上に反射
防止膜材料を含む塗料を塗布した後、乾燥して、少なく
とも一層の反射防止膜材料層を形成する工程と、シリコ
ン化合物層および反射防止膜材料層を同時に焼成して、
シリコン酸化物膜および反射防止膜を形成する工程と、
を含むことを特徴とする。In another method of manufacturing a solar cell according to the present invention, an impurity diffusion region of a conductivity type different from that of the silicon substrate is formed on the surface layer of a conductivity type silicon substrate, and a coating containing a silicon compound is applied onto the impurity diffusion region. After that, a step of drying to form a silicon compound layer, a step of applying a coating material containing an antireflection film material on the silicon compound layer, and then drying to form at least one antireflection film material layer, Simultaneously firing the silicon compound layer and the antireflection film material layer,
A step of forming a silicon oxide film and an antireflection film,
It is characterized by including.
【００１２】このようにシリコン化合物および反射防止
膜材料を同時焼成するときは、５００℃〜９００℃で焼
成することが好ましい。When the silicon compound and the antireflection film material are simultaneously fired in this way, it is preferable to fire them at 500 ° C. to 900 ° C.
【００１３】シリコン酸化物膜の厚さは、２０ｎｍ以下
が好ましく、反射防止膜の厚さＴｈ（単位ｎｍ）は、反
射防止膜の屈折率をｎとすると、１００／ｎ≦Ｔｈ≦１
７５／ｎであることが好ましい。また、反射防止膜の屈
折率ｎは、１．８〜２．３が好ましい。The thickness of the silicon oxide film is preferably 20 nm or less, and the thickness Th (unit: nm) of the antireflection film is 100 / n≤Th≤1 where n is the refractive index of the antireflection film.
It is preferably 75 / n. The refractive index n of the antireflection film is preferably 1.8 to 2.3.
【００１４】これらの製造方法において、シリコン化合
物は、Ｓｉ−ＯＲ（Ｒは、直鎖状または分枝を有する炭
化水素基を表す。）またはＳｉ−ＯＨで表されるシラノ
ール化合物を含むものを用いる。In these production methods, a silicon compound containing a silanol compound represented by Si-OR (R represents a linear or branched hydrocarbon group) or Si-OH is used. .
【００１５】反射防止膜材料は、少なくとも一種類のＸ
−ＯＲ（Ｘは、Ｌｉ、Ｂｅ、Ｂ、Ｎａ、Ｍｇ、Ａｌ、
Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、
Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｒｂ、Ｓｒ、Ｙ、Ｚ
ｒ、Ｎｂ、Ｍｏ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｃｓ、Ｂ
ａ、Ｌａ、Ｈｆ、Ｔａ、Ｗ、Ｔｌ、Ｐｂ、Ｂｉ、Ｃｅ、
Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈ
ｏ、Ｅｒ、Ｔｍ、Ｙｂ、ＬｕまたはＳｉを表す。）また
はＸ−ＯＨで表される化合物を含むものを用いる。The antireflective coating material is at least one type of X
-OR (X is Li, Be, B, Na, Mg, Al,
K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Z
r, Nb, Mo, Cd, In, Sn, Sb, Cs, B
a, La, Hf, Ta, W, Tl, Pb, Bi, Ce,
Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H
represents o, Er, Tm, Yb, Lu or Si. ) Or a compound containing a compound represented by X—OH is used.
【００１６】シリコン化合物を含む塗料は、インクジェ
ット法により塗布することが好ましい。The coating material containing a silicon compound is preferably applied by an inkjet method.
【００１７】反射防止膜材料を含む塗料は、インクジェ
ット法により塗布することが好ましい。The coating material containing the antireflection film material is preferably applied by an inkjet method.
【００１８】本発明の太陽電池は、上述の方法により製
造されることを特徴とする。The solar cell of the present invention is characterized by being manufactured by the method described above.
【００１９】[0019]
【発明の実施の形態】（実施の形態１）本発明の太陽電
池の製造方法は、導電型のシリコン基板の表層にシリコ
ン基板と異なる導電型の不純物拡散領域を形成する太陽
電池の製造方法であって、不純物拡散領域上にシリコン
化合物を含む塗料を塗布した後、乾燥し、焼成してシリ
コン酸化物膜を形成する工程を含むことを特徴とする。(Embodiment 1) A method of manufacturing a solar cell according to the present invention is a method of manufacturing a solar cell in which an impurity diffusion region having a conductivity type different from that of a silicon substrate is formed on a surface layer of a conductivity type silicon substrate. It is characterized by including a step of forming a silicon oxide film by applying a coating material containing a silicon compound on the impurity diffusion region, then drying and baking the coating material.
【００２０】かかる方法により、導電型のシリコン基板
の表層にシリコン基板と異なる導電型の不純物拡散領域
を形成し、不純物拡散領域上にシリコン酸化物膜が形成
されていることを特徴とする太陽電池が製造される。By such a method, the impurity diffusion region of the conductivity type different from that of the silicon substrate is formed on the surface layer of the conductivity type silicon substrate, and the silicon oxide film is formed on the impurity diffusion region. Is manufactured.
【００２１】実施の形態１の製造工程を図１に示す。ｐ
型のシリコン基板の受光面側の表層に、ｐ型のシリコン
基板と異なる導電型の不純物であるリンなどのＶ族原子
を拡散させて厚さ０．３μｍ〜１μｍのｎ層１１３を形
成し、ｐ層１１２との間にｐｎ接合面が形成されている
シリコン基板１１１を製造する（図１（ａ））。この場
合、ｎ型のシリコン基板を用い、ホウ素などのＩＩＩ族
原子を拡散させてｐ層を形成することによりｐｎ接合面
を形成してもよい。また、シリコン基板は単結晶シリコ
ン基板、多結晶シリコン基板のいずれを用いてもよい。The manufacturing process of the first embodiment is shown in FIG. p
In the surface layer on the light-receiving surface side of the p-type silicon substrate, an n-layer 113 having a thickness of 0.3 μm to 1 μm is formed by diffusing a group V atom such as phosphorus, which is an impurity of a conductivity type different from that of the p-type silicon substrate. A silicon substrate 111 having a pn junction surface formed with the p layer 112 is manufactured (FIG. 1A). In this case, a pn junction surface may be formed by using a n-type silicon substrate and diffusing Group III atoms such as boron to form a p layer. As the silicon substrate, either a single crystal silicon substrate or a polycrystalline silicon substrate may be used.
【００２２】ｐｎ接合の形成後、シリコン化合物を含む
塗料１１４を受光面側に塗布する（図１（ｂ））。塗布
は、スピン法、スプレー法、デイップ法などを使用す
る。After the pn junction is formed, a coating 114 containing a silicon compound is applied to the light receiving surface side (FIG. 1 (b)). For coating, a spin method, a spray method, a dip method or the like is used.
【００２３】シリコン化合物を含む塗料１１４は、基板
上に塗布された後、乾燥し、焼成すると、シリコン酸化
物膜１１５ａを形成する（図１（ｃ））。シリコン化合
物は、パッシベーション効果の大きいシリコン酸化物膜
を形成する点で、Ｓｉ−ＯＨまたはＳｉ−ＯＲで表され
るシラノール結合を有する化合物、すなわちシラノール
化合物を含むものが好ましい。ここに、Ｒは、直鎖状ま
たは分枝を有する炭化水素基である。シラノール化合物
としては、たとえば、Ｓｉ（ＯＣ2Ｈ5）4（テトラエト
キシシラン）、Ｓｉ（ＯＣＨ（ＣＨ3）2）4（テトライ
ソプロポキシシラン）、（ＣＨ3）2Ｓｉ（ＯＣＨ3）
2（ジメトキシジメチルシラン）などの有機物やテトラ
エトキシシランを加水分解することによって得られるＳ
ｉ（ＯＨ）4などの無機物を使用することができる。シ
ラノール化合物は、焼成後、シリコン酸化物となる。The coating 114 containing a silicon compound is applied onto the substrate, then dried and baked to form a silicon oxide film 115a (FIG. 1C). The silicon compound is preferably a compound having a silanol bond represented by Si—OH or Si—OR, that is, a compound containing a silanol compound in terms of forming a silicon oxide film having a large passivation effect. Here, R is a linear or branched hydrocarbon group. Examples of silanol compounds include Si (OC 2 H 5 ) 4 (tetraethoxysilane), Si (OCH (CH 3 ) 2 ) 4 (tetraisopropoxysilane), and (CH 3 ) 2 Si (OCH 3 ).
S obtained by hydrolyzing organic substances such as 2 (dimethoxydimethylsilane) and tetraethoxysilane
Inorganic substances such as i (OH) 4 can be used. The silanol compound becomes silicon oxide after firing.
【００２４】シリコン化合物は、エタノールなどの有機
溶剤に配合し、必要に応じて酢酸エチルを加え、混合し
て、塗料とする。The silicon compound is mixed with an organic solvent such as ethanol, and ethyl acetate is added if necessary, and mixed to prepare a coating material.
【００２５】塗料の乾燥は、塗料中の液体成分、主に有
機溶剤を除去するために行なう。乾燥は、８０℃〜２０
０℃で行なうことが好ましい。乾燥は、１００℃、１５
０℃、２００℃のように多段階に設定して行なうことも
できる。The coating material is dried to remove the liquid component in the coating material, mainly the organic solvent. Drying is from 80 ° C to 20
It is preferable to carry out at 0 ° C. Drying is 100 ℃, 15
It is also possible to set the temperature in multiple stages such as 0 ° C and 200 ° C.
【００２６】塗料の焼成は、シリコン化合物をシリコン
酸化物にするために行なう。焼成は、５００℃〜９００
℃で行なうことが好ましく、６００℃〜８００℃がより
好ましい。図５に、シリコン化合物の焼成温度とキャリ
ア寿命（ライフタイム）との関係についての測定結果を
示す。図５から明らかなとおり、焼成温度が５００℃未
満では、キャリア寿命が短く、すなわちパッシベーショ
ン効果が低くなり、太陽電池の性能が低下する。一方、
９００℃より高いと、膜が緻密化し、屈折率が大きくな
り、パッシベーション性も向上するが、このような過熱
にシリコン基板を曝すと、シリコン基板の不純物拡散領
域において不純物の再拡散が起こり、太陽電池の性能が
低下する。また、過熱によりシリコン酸化物膜と基板間
の応力が大きくなり、保護膜の剥離によるパッシベーシ
ョン性の低下という問題が発生し得る。焼成は、大気中
または窒素雰囲気中で行なう。The baking of the paint is carried out in order to convert the silicon compound into silicon oxide. Firing is 500 ° C to 900
It is preferable to carry out at a temperature of 600C, more preferably 600C to 800C. FIG. 5 shows the measurement results of the relationship between the firing temperature of silicon compounds and the carrier lifetime (lifetime). As is clear from FIG. 5, when the firing temperature is lower than 500 ° C., the carrier life is short, that is, the passivation effect is low and the performance of the solar cell is low. on the other hand,
When the temperature is higher than 900 ° C., the film becomes dense, the refractive index becomes large, and the passivation property is improved. However, when the silicon substrate is exposed to such overheating, impurities are re-diffused in the impurity diffusion region of the silicon substrate, and Battery performance is reduced. Further, the stress between the silicon oxide film and the substrate increases due to overheating, which may cause a problem of deterioration of passivation property due to peeling of the protective film. The firing is performed in the air or a nitrogen atmosphere.
【００２７】シリコン基板の上に形成される反射防止膜
の厚さをＴｈ、入射する光線の波長をλ、反射防止膜の
屈折率をｎとすると、入射する光線の反射を極小にする
には
Ｔｈ＝λ／４ｎ
の関係にあることが好ましい。また、太陽光線のうちエ
ネルギー強度が大きい波長域は４００ｎｍ〜７００ｎｍ
であるため、太陽光線の反射防止効果を高めるうえで
は、波長４００ｎｍ〜７００ｎｍの光線に対する反射率
を小さくするのが好ましく、エネルギーが最大である波
長５００ｎｍの光線に対する反射率を小さくするのがよ
り好ましい。本実施の形態では、シリコン酸化物膜が反
射防止膜を兼ね，シリコン酸化物の屈折率ｎは１．４０
〜１．４５であることから、シリコン酸化物膜の厚さ
は、反射防止効果を高める点で、７０ｎｍ〜１５０ｎｍ
が好ましく、１００ｎｍ程度がより好ましい。When the thickness of the antireflection film formed on the silicon substrate is Th, the wavelength of the incident light beam is λ, and the refractive index of the antireflection film is n, the reflection of the incident light beam can be minimized. It is preferable that Th = λ / 4n. In addition, the wavelength range of sunlight having a large energy intensity is 400 nm to 700 nm.
Therefore, in order to enhance the effect of preventing reflection of sunlight, it is preferable to reduce the reflectance with respect to light rays having a wavelength of 400 nm to 700 nm, and it is more preferable to reduce the reflectance with respect to light rays having a maximum wavelength of 500 nm. . In this embodiment, the silicon oxide film also serves as the antireflection film, and the refractive index n of the silicon oxide is 1.40.
The thickness of the silicon oxide film is 70 nm to 150 nm in order to enhance the antireflection effect.
Is preferable, and about 100 nm is more preferable.
【００２８】シリコン酸化物膜１１５ａの形成後、レジ
スト塗布、露光、現像、エッチング、レジスト除去の各
工程からなるフォトリソグラフィなどにより、シリコン
酸化物膜１１５ａをパターン化してシリコン酸化物膜１
１５ｂを形成する（図１（ｄ））。その後、表面電極１
１６を形成する（図１（ｅ））。After the silicon oxide film 115a is formed, the silicon oxide film 115a is patterned by photolithography, which includes resist coating, exposure, development, etching, and resist removal steps.
15b is formed (FIG. 1 (d)). Then, the surface electrode 1
16 is formed (FIG. 1E).
【００２９】表面電極の形成後、受光面と反対側の面に
ｐ+層を形成した後、裏面電極を形成すると（いずれも
図示していない。）、本願発明の太陽電池を製造するこ
とができる。After forming the front surface electrode and then forming the p + layer on the surface opposite to the light receiving surface, and forming the back surface electrode (neither is shown), the solar cell of the present invention can be manufactured. it can.
【００３０】本実施の形態では、シリコン酸化物膜を形
成した後に裏面電極を形成するが、裏面電極を形成した
後にシリコン酸化物膜を形成してもよい。In the present embodiment, the back electrode is formed after forming the silicon oxide film, but the silicon oxide film may be formed after forming the back electrode.
【００３１】本実施の形態によれば、従来の熱酸化法に
比べて焼成温度が低く、製造コストが安く、また簡略化
した工程により製造することができる。本発明により製
造する太陽電池は、パッシベーション効果および反射防
止効果が優れる。According to this embodiment, the firing temperature is lower than that of the conventional thermal oxidation method, the manufacturing cost is low, and the manufacturing process can be simplified. The solar cell manufactured by the present invention has excellent passivation effect and antireflection effect.
【００３２】（実施の形態２）本発明の太陽電池の他の
製造方法は、導電型のシリコン基板の表層にシリコン基
板と異なる導電型の不純物拡散領域を形成する太陽電池
の製造方法であって、不純物拡散領域上にシリコン化合
物を含む塗料を塗布した後、乾燥し、焼成してシリコン
酸化物膜を形成する工程と、シリコン酸化物膜上に反射
防止膜材料を含む塗料を塗布した後、乾燥し、焼成して
少なくとも一層の反射防止膜を形成する工程と、を含む
ことを特徴とする。(Second Embodiment) Another method for manufacturing a solar cell according to the present invention is a method for manufacturing a solar cell in which an impurity diffusion region having a conductivity type different from that of a silicon substrate is formed on a surface layer of a conductivity type silicon substrate. After applying a coating containing a silicon compound on the impurity diffusion region, drying and baking to form a silicon oxide film, and applying a coating containing an antireflection film material on the silicon oxide film, Drying and firing to form at least one antireflection film.
【００３３】かかる方法により、導電型のシリコン基板
の表層にシリコン基板と異なる導電型の不純物拡散領域
を形成し、不純物拡散領域上にシリコン酸化物膜が形成
され、シリコン酸化物膜上に少なくとも一層の反射防止
膜が形成されていることを特徴とする太陽電池が製造さ
れる。By this method, an impurity diffusion region of a conductivity type different from that of the silicon substrate is formed on the surface layer of the conductivity type silicon substrate, a silicon oxide film is formed on the impurity diffusion region, and at least one layer is formed on the silicon oxide film. The solar cell is manufactured by forming the antireflection film.
【００３４】実施の形態１では、シリコン酸化物膜がパ
ッシベーション膜および反射防止膜兼ねており、一種類
の成膜で済むため非常に簡便な方法である。しかし、シ
リコン酸化物の屈折率は１．４０〜１．４５であり、シ
リコン太陽電池の反射防止膜に最も適している屈折率が
１．８〜２．３であることから見ると、少し小さい点で
改良の余地がある。実施の形態２では、シリコン太陽電
池の反射防止膜として適している窒化ケイ素や酸化チタ
ンなどを使用する。In the first embodiment, the silicon oxide film serves as both the passivation film and the antireflection film, and only one kind of film formation is required, which is a very simple method. However, the refractive index of silicon oxide is 1.40 to 1.45, and the refractive index most suitable for the antireflection film of silicon solar cells is 1.8 to 2.3. There is room for improvement in this respect. In the second embodiment, silicon nitride or titanium oxide, which is suitable as an antireflection film for a silicon solar cell, is used.
【００３５】実施の形態２の製造工程を図２に示す。ｐ
型のシリコン基板の受光面側の表層に、ｐ型のシリコン
基板と異なる導電型の不純物であるリンなどのＶ族原子
を拡散させて厚さ０．３μｍ〜１μｍのｎ層１２３を形
成し、ｐ層１２２との間にｐｎ接合面が形成されている
シリコン基板１２１を製造する（図２（ａ））。この場
合、ｎ型のシリコン基板を用い、ホウ素などのＩＩＩ族
原子を拡散させてｐ層を形成することによりｐｎ接合面
を形成してもよい。また、シリコン基板は単結晶シリコ
ン基板、多結晶シリコン基板のいずれを用いてもよい。FIG. 2 shows the manufacturing process of the second embodiment. p
In the surface layer on the light-receiving surface side of the p-type silicon substrate, an n-layer 123 having a thickness of 0.3 μm to 1 μm is formed by diffusing V group atoms such as phosphorus, which is an impurity of a conductivity type different from that of the p-type silicon substrate, A silicon substrate 121 having a pn junction surface formed with the p layer 122 is manufactured (FIG. 2A). In this case, a pn junction surface may be formed by using a n-type silicon substrate and diffusing Group III atoms such as boron to form a p layer. As the silicon substrate, either a single crystal silicon substrate or a polycrystalline silicon substrate may be used.
【００３６】つぎに、受光面側にシリコン化合物１２４
を塗布し（図２（ｂ））、乾燥し、焼成を行ない、シリ
コン酸化物膜１２５ａを形成する（図２（ｃ））。塗
布、シリコン化合物、乾燥および焼成の条件は、実施の
形態１と同様である。Next, the silicon compound 124 is formed on the light-receiving surface side.
Is applied (FIG. 2 (b)), dried and baked to form a silicon oxide film 125a (FIG. 2 (c)). The conditions of coating, silicon compound, drying and baking are the same as those in the first embodiment.
【００３７】シリコン酸化物膜１２５ａの厚さは、１ｎ
ｍ〜２０ｎｍが好ましく、１ｎｍ〜１５ｎｍがより好ま
しい。１ｎｍより薄いとパッシベーション効果が不十分
となり、２０ｎｍより厚いと、シリコン酸化物膜と反射
防止膜との界面における太陽光線の反射量が大きくなっ
てしまう。The thickness of the silicon oxide film 125a is 1n.
m-20 nm is preferable, and 1 nm-15 nm is more preferable. If it is thinner than 1 nm, the passivation effect becomes insufficient, and if it is thicker than 20 nm, the amount of reflection of sunlight at the interface between the silicon oxide film and the antireflection film becomes large.
【００３８】シリコン酸化物膜１２５ａの形成後、反射
防止膜１２６ａを形成する（図２（ｄ））。反射防止膜
１２６ａは、Ｌｉ、Ｂｅ、Ｂ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、
Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎ
ｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｒｂ、Ｓｒ、Ｙ、Ｚｒ、
Ｎｂ、Ｍｏ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｃｓ、Ｂａ、Ｌ
ａ、Ｈｆ、Ｔａ、Ｗ、Ｔｌ、Ｐｂ、Ｂｉ、Ｃｅ、Ｐｒ、
Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅ
ｒ、Ｔｍ、Ｙｂ、ＬｕまたはＳｉの酸化物、窒化物、硫
化物、弗化物などで形成することができる。これらの成
膜はＣＶＤ法、スパッタ法、蒸着などにより行なうこと
ができる。一方、反射防止膜は、反射防止膜材料をスピ
ン法、スプレー法、ディップ法などにより塗布し、乾燥
した後、焼成して形成することもできる。ＣＶＤ法、ス
パッタ法、蒸着などにより成膜した場合には塗膜の表面
性が良好である。一方、塗布、乾燥、焼成の手順による
ときは、安価に成膜できる。After forming the silicon oxide film 125a, an antireflection film 126a is formed (FIG. 2D). The antireflection film 126a includes Li, Be, B, Na, Mg, Al, K,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr,
Nb, Mo, Cd, In, Sn, Sb, Cs, Ba, L
a, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr,
Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, E
It can be formed of an oxide, nitride, sulfide, or fluoride of r, Tm, Yb, Lu, or Si. These films can be formed by a CVD method, a sputtering method, vapor deposition or the like. On the other hand, the antireflection film can also be formed by applying an antireflection film material by a spin method, a spray method, a dip method, etc., drying and then firing. When the film is formed by the CVD method, the sputtering method, the vapor deposition, etc., the surface property of the coating film is good. On the other hand, when the procedure of coating, drying and baking is used, the film can be formed at low cost.
【００３９】反射防止膜材料としては、屈折率が比較的
高く、太陽光線の反射防止効果に優れた酸化物となる点
で、少なくとも一種類のＸ−ＯＲまたはＸ−ＯＨで表さ
れる化合物を含むものが好ましい。Ｘは、Ｌｉ、Ｂｅ、
Ｂ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃ
ｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇ
ｅ、Ｒｂ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｃｄ、Ｉｎ、
Ｓｎ、Ｓｂ、Ｃｓ、Ｂａ、Ｌａ、Ｈｆ、Ｔａ、Ｗ、Ｔ
ｌ、Ｐｂ、Ｂｉ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅ
ｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ
またはＳｉを表す。また、Ｒは、直鎖状または分枝を有
する炭化水素基を表す。Ｘは、焼成後、金属酸化物とな
ったときの屈折率の高さ、有機溶媒への易溶性、取扱い
の簡便性、また安価である点で、Ｔｉが好ましい。金属
化合物としては、２種類以上のＸを含むのものを混合し
て使用してもよい。混合して使用すると、屈折率を変化
させることが容易になるが、取扱いが複雑になり、膜成
分のバラツキが生じやすい。Ｘ−ＯＲまたはＸ−ＯＨで
表される化合物は焼成後、ＸｍＯｎ（ｍ、ｎは、正の整
数を表す。）で表される金属酸化物となる。As the antireflection film material, at least one kind of compound represented by X-OR or X-OH is used because it is an oxide having a relatively high refractive index and an excellent antireflection effect against sunlight. Those containing are preferable. X is Li, Be,
B, Na, Mg, Al, K, Ca, Sc, Ti, V, C
r, Mn, Fe, Co, Ni, Cu, Zn, Ga, G
e, Rb, Sr, Y, Zr, Nb, Mo, Cd, In,
Sn, Sb, Cs, Ba, La, Hf, Ta, W, T
l, Pb, Bi, Ce, Pr, Nd, Pm, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Or represents Si. R represents a linear or branched hydrocarbon group. X is preferably Ti because it has a high refractive index when it becomes a metal oxide after firing, is easily soluble in an organic solvent, is easy to handle, and is inexpensive. As the metal compound, those containing two or more kinds of X may be mixed and used. When mixed and used, it is easy to change the refractive index, but the handling becomes complicated and variations in the film components are likely to occur. The compound represented by X-OR or X-OH becomes a metal oxide represented by XmOn (m and n are positive integers) after firing.
【００４０】反射防止膜の屈折率ｎは、１．８〜２．３
が好ましく、２．０〜２．２がより好ましい。屈折率ｎ
が１．８より小さくても、２．３より大きくても反射損
が大きくなる。The refractive index n of the antireflection film is 1.8 to 2.3.
Is preferable, and 2.0-2.2 is more preferable. Refractive index n
Is smaller than 1.8 or larger than 2.3, the reflection loss becomes large.
【００４１】反射防止膜の屈折率ｎは、Ｘ−ＯＲやＸ−
ＯＨで表される化合物の配合量により調整することがで
きる。２種類の元素Ｘ１、Ｘ２のＸ−ＯＲやＸ−ＯＨを
配合する場合、焼成後の反射防止膜の屈折率ｎは、反射
防止膜材料中に含有している元素Ｘ１、Ｘ２の酸化物の
屈折率とその濃度にほぼ比例して、おおむねつぎの式が
成り立つ。The refractive index n of the antireflection film is X-OR or X-.
It can be adjusted by the compounding amount of the compound represented by OH. When mixing X-OR and X-OH of two kinds of elements X1 and X2, the refractive index n of the antireflection film after firing is determined by comparing the oxides of the elements X1 and X2 contained in the antireflection film material. The following equation holds approximately in proportion to the refractive index and its concentration.
【００４２】ｎ＝｛（元素Ｘ１の酸化物の屈折率）×
（Ｘ１−ＯＲ＋Ｘ１−ＯＨの重量）＋（元素Ｘ２の酸化
物の屈折率）×（Ｘ２−ＯＲ＋Ｘ２−ＯＨの重量）｝÷
｛（Ｘ１−ＯＲ＋Ｘ１−ＯＨの重量）＋（Ｘ２−ＯＲ＋
Ｘ２−ＯＨの重量）｝
したがって、Ｘ−ＯＲやＸ−ＯＨで表される化合物の配
合量を調整することにより、反射防止膜の屈折率ｎを適
正値である１．８〜２．３に合せるように設計できる。
たとえば、反射防止膜材料として、Ｓｉ（ＯＣ2Ｈ5）4
（テトラエトキシシラン）とＴｉ（ＯＣＨ（ＣＨ3）2）
4（チタン酸イソプロピル）を３：７の重量比で配合し
たものを用いると、５００℃で焼成した揚合の屈折率ｎ
はＳｉＯ 2が１．４５であり、ＴｉＯ2が２．２であるか
ら、反射防止膜の屈折率ｎはつぎのようになる。N = {(refractive index of oxide of element X1) ×
(Weight of X1-OR + X1-OH) + (oxidation of element X2
Refractive index of material) × (weight of X2-OR + X2-OH)} ÷
{(X1-OR + X1-OH weight) + (X2-OR +
X2-OH weight)}
Therefore, the compound represented by X-OR or X-OH
By adjusting the total amount, the refractive index n of the antireflection film can be adjusted appropriately.
It can be designed to match a positive value of 1.8 to 2.3.
For example, as an antireflection film material, Si (OC2HFive)Four
(Tetraethoxysilane) and Ti (OCH (CH3)2)
Four(Isopropyl titanate) in a weight ratio of 3: 7
If you use a
Is SiO 2Is 1.45, and TiO2Is 2.2
The refractive index n of the antireflection film is as follows.
【００４３】
ｎ＝｛（ＳｉＯ2の屈折率）×（Ｓｉ−ＯＲ＋Ｓｉ−Ｏ
Ｈの重量）＋（ＴｉＯ2の屈折率）×（Ｔｉ−ＯＲ＋Ｔ
ｉ−ＯＨの重量）｝÷｛（Ｓｉ−ＯＲ＋Ｓｉ−ＯＨの重
量）＋（Ｔｉ−ＯＲ＋Ｔｉ−ＯＨの重量）｝
＝（ｌ．４５×３＋２．２×７）÷（３＋７）
＝１．９８
反射防止膜材料として配合させる元素は３種類以上でも
よいが、取り扱いが複雑になるため、２種類までが好ま
しい。また、ＳｉＯ2の屈折率は１．４５であるのに対
して、他の酸化物の屈折率は２．０〜２．４程度である
ため、屈折率を大きく変化させるにはＸの１つはシリコ
ンであることが好ましい。N = {(refractive index of SiO 2 ) × (Si-OR + Si-O
(Weight of H) + (refractive index of TiO 2 ) × (Ti-OR + T
i-OH weight)} / {(Si-OR + Si-OH weight) + (Ti-OR + Ti-OH weight)} = (1.45 * 3 + 2.2 * 7) / (3 + 7) = 1.98 reflection There may be three or more kinds of elements to be blended as the material for the prevention film, but two or more kinds are preferable because handling becomes complicated. Further, SiO 2 has a refractive index of 1.45, whereas other oxides have a refractive index of about 2.0 to 2.4. Is preferably silicon.
【００４４】反射防止膜材料は、エタノールなどの有機
溶剤に配合し、必要に応じて酢酸エチルを加えて、混合
し、塗料とする。The antireflection film material is mixed with an organic solvent such as ethanol, and ethyl acetate is added if necessary, and mixed to prepare a coating material.
【００４５】反射防止膜材料の乾操は、液体成分、主に
有機溶剤を除去するために行い、８０℃〜２００℃で行
なうことが好ましい。Drying of the antireflection film material is carried out to remove liquid components, mainly organic solvent, and it is preferable to carry out at 80 ° C. to 200 ° C.
【００４６】反射防止膜材料の焼成は、反射防止膜材料
を結晶化して反射防止膜を形成するために行なう。焼成
は、２００℃〜９００℃で行なうことが好ましい。２０
０℃未満では、大気中または窒素雰囲気中において十分
に結晶化しない。一方、９００℃より高温にすると、基
板内で不純物が再拡散し、また、シリコン基板、シリコ
ン酸化物膜および反射防止膜間における応力が大きくな
って、膜の剥離や基板の破損が生じやすい。一方、低い
温度で焼成すると焼成後の屈折率が低くなり、高い温度
で焼成すると焼成後の屈折率が高くなる。このため、前
述したＸ−ＯＲやＸ−ＯＨの配合量により屈折率を調整
できるほか、焼成温度によっても屈折率を調整すること
ができる。たとえば、Ｔｉの場合、２００℃で焼成する
と屈折率は１．８となり、５００℃で焼成すると屈折率
は２．０となる。The firing of the antireflection film material is performed to crystallize the antireflection film material to form an antireflection film. The firing is preferably performed at 200 ° C to 900 ° C. 20
If the temperature is lower than 0 ° C, crystallization is not sufficiently performed in the air or the nitrogen atmosphere. On the other hand, when the temperature is higher than 900 ° C., the impurities are re-diffused in the substrate, and the stress between the silicon substrate, the silicon oxide film and the antireflection film is increased, and the film is likely to be peeled off or the substrate is damaged. On the other hand, baking at a low temperature lowers the refractive index after baking, and baking at a higher temperature increases the refractive index after baking. Therefore, the refractive index can be adjusted by the compounding amount of X-OR or X-OH described above, and the refractive index can also be adjusted by the firing temperature. For example, Ti has a refractive index of 1.8 when fired at 200 ° C. and a refractive index of 2.0 when fired at 500 ° C.
【００４７】反射防止膜の厚さをＴｈ、入射する光線の
波長をλ、反射防止膜の屈折率をｎとすると、前述のと
おり、入射する光線の反射を極小にするには、
Ｔｈ＝λ／４ｎ
の関係にあることが必要である。また、太陽光線のうち
エネルギー強度が大きい波長域である４００ｎｍ〜７０
０ｎｍにおいて反射率を小さくするのが好ましく、エネ
ルギーが最大である波長５００ｎｍの光線に対する反射
率を小さくするのがより好ましい。したがって、反射防
止膜の厚さＴｈ（単位ｎｍ）は、
４００／４ｎ≦Ｔｈ≦７００／４ｎ
１００／ｎ≦Ｔｈ≦１７５／ｎ
が好ましく、
Ｔｈ＝５００／４ｎ
＝１２５／ｎ
がより好ましい。Assuming that the thickness of the antireflection film is Th, the wavelength of the incident light beam is λ, and the refractive index of the antireflection film is n, as described above, to minimize the reflection of the incident light beam, Th = λ It is necessary to have a relationship of / 4n. In addition, 400 nm to 70, which is a wavelength range in which the energy intensity of sunlight is large,
It is preferable to reduce the reflectance at 0 nm, and it is more preferable to reduce the reflectance for a light beam having a wavelength of 500 nm at which the energy is maximum. Therefore, the thickness Th (unit: nm) of the antireflection film is preferably 400 / 4n ≦ Th ≦ 700 / 4n 100 / n ≦ Th ≦ 175 / n, and more preferably Th = 500 / 4n = 125 / n.
【００４８】反射防止膜の厚さＴｈは、反射防止膜の屈
折率ｎにより異なるが、屈折率ｎの適正値は１．８〜
２．３であることから、通常は４０ｎｍ〜１００ｎｍが
好ましく、５０ｎｍ〜８０ｎｍがより好ましい。The thickness Th of the antireflection film varies depending on the refractive index n of the antireflection film, but an appropriate value of the refractive index n is 1.8 to.
Since it is 2.3, 40 nm to 100 nm is usually preferable, and 50 nm to 80 nm is more preferable.
【００４９】反射防止膜１２６ａの形成後、フォトリソ
グラフィなどによりパターン化を行ない、シリコン酸化
物膜１２５ｂと反射防止膜１２６ｂとし（図２
（ｅ））、つづいて表面電極１２７を形成する（図２
（ｆ））。After forming the antireflection film 126a, patterning is performed by photolithography or the like to form a silicon oxide film 125b and an antireflection film 126b (see FIG. 2).
(E)), and then the surface electrode 127 is formed (FIG. 2).
(F)).
【００５０】つぎに、受光面と反対側の面にｐ+層を形
成した後、裏面電極を形成し（いずれも図示していな
い。）、太陽電池を製造することができる。Next, a p + layer is formed on the surface opposite to the light receiving surface, and then a back surface electrode is formed (neither is shown) to manufacture a solar cell.
【００５１】反射防止膜は、１層目の反射防止膜よりも
屈折率の小さい材料、たとえば弗化マグネシウム、弗化
セリウム、酸化アルミニウム、酸化シリコンなどを用い
て、一層目の反射防止膜上に積層すると、反射防止効果
を高めることができる点で好ましい。The antireflection film is formed on the first antireflection film by using a material having a refractive index smaller than that of the first antireflection film, such as magnesium fluoride, cerium fluoride, aluminum oxide or silicon oxide. Lamination is preferable in that the antireflection effect can be enhanced.
【００５２】パッシべ−ション膜および反射防止膜を形
成した後に、裏面電極を形成するが、裏面電極を形成し
てからパッシべ−ション膜および反射防止膜を形成して
もよい。Although the back electrode is formed after forming the passivation film and the antireflection film, the passivation film and the antireflection film may be formed after forming the back electrode.
【００５３】本実施の形態によれば、従来より焼成温度
が低く、安価であり、簡略化された工程により製造する
ことができる。この太陽電池は、優れたパッシべ−ショ
ン効果および反射防止効果を奏し、高い光電変換効率を
有する。According to the present embodiment, the firing temperature is lower than before, the cost is low, and the manufacturing process can be simplified. This solar cell has an excellent passivation effect and an antireflection effect, and has high photoelectric conversion efficiency.
【００５４】（実施の形態３）本発明の太陽電池の他の
製造方法は、導電型のシリコン基板の表層にシリコン基
板と異なる導電型の不純物拡散領域を形成する太陽電池
の製造方法において、不純物拡散領域上にシリコン化合
物を含む塗料を塗布した後、乾燥して、シリコン化合物
層を形成する工程と、シリコン化合物層上に反射防止膜
材料を含む塗料を塗布した後、乾燥して、少なくとも一
層の反射防止膜材料層を形成する工程と、シリコン化合
物層および反射防止膜材料層を同時に焼成して、シリコ
ン酸化物膜および反射防止膜を形成する工程と、を含む
ことを特徴とする。(Embodiment 3) Another method for manufacturing a solar cell according to the present invention is the method for manufacturing a solar cell in which an impurity diffusion region of a conductivity type different from that of the silicon substrate is formed in the surface layer of a conductivity type silicon substrate. Applying a coating containing a silicon compound on the diffusion region and then drying it to form a silicon compound layer, and applying a coating containing an antireflection film material on the silicon compound layer, then drying it to form at least one layer. And a step of simultaneously firing the silicon compound layer and the antireflection film material layer to form the silicon oxide film and the antireflection film.
【００５５】かかる方法により、導電型のシリコン基板
の表層にシリコン基板と異なる導電型の不純物拡散領域
を形成し、不純物拡散領域上にシリコン酸化物膜が形成
され、シリコン酸化物膜上に少なくとも一層の反射防止
膜が形成されていることを特徴とする太陽電池が製造さ
れる。By this method, an impurity diffusion region of a conductivity type different from that of the silicon substrate is formed on the surface layer of the conductivity type silicon substrate, a silicon oxide film is formed on the impurity diffusion region, and at least one layer is formed on the silicon oxide film. The solar cell is manufactured by forming the antireflection film.
【００５６】実施の形態２においては、シリコン酸化物
膜や反射防止膜の形成方法として、シリコン化合物や反
射防止膜材料を塗布し、乾操し、焼成する方法を用い
た。この方法は、ＣＶＤ法などに比べて真空装置を必要
としないため、安価に製造することができる利点があ
る。しかし、実施の形態２の方法では、シリコン化合物
および反射防止膜材料は別々に焼成するため、焼成が二
工程となり、焼成装置も二台以上必要となり、それだけ
製造時間も長くなる。実施の形態３では、この点を改善
するため、シリコン化合物および反射防止膜材料を一工
程で焼成する。In the second embodiment, as a method of forming the silicon oxide film or the antireflection film, a method of applying a silicon compound or an antireflection film material, drying and firing is used. Since this method does not require a vacuum device as compared with the CVD method and the like, it has an advantage that it can be manufactured at low cost. However, in the method of the second embodiment, since the silicon compound and the antireflection film material are separately fired, the firing has two steps, two or more firing devices are required, and the manufacturing time becomes longer accordingly. In the third embodiment, in order to improve this point, the silicon compound and the antireflection film material are fired in one step.
【００５７】実施の形態３の製造工程を図３に示す。ｐ
型のシリコン基板の受光面側の表層に、ｐ型のシリコン
基板と異なる導電型の不純物であるリンなどのＶ族原子
を拡散させて厚さ０．３μｍ〜１μｍのｎ層１３３を形
成し、ｐ層１３２との間にｐｎ接合面が形成されている
シリコン基板１３１を製造する（図３（ａ））。この場
合、ｎ型のシリコン基板を用い、ホウ素などのＩＩＩ族
原子を拡散させてｐ層を形成することによりｐｎ接合面
を形成してもよい。また、シリコン基板は単結晶シリコ
ン基板、多結晶シリコン基板のいずれを用いてもよい。The manufacturing process of the third embodiment is shown in FIG. p
In the surface layer on the light-receiving surface side of the p-type silicon substrate, an n-layer 133 having a thickness of 0.3 μm to 1 μm is formed by diffusing a group V atom such as phosphorus which is an impurity of a conductivity type different from that of the p-type silicon substrate. A silicon substrate 131 having a pn junction surface formed with the p layer 132 is manufactured (FIG. 3A). In this case, a pn junction surface may be formed by using a n-type silicon substrate and diffusing Group III atoms such as boron to form a p layer. As the silicon substrate, either a single crystal silicon substrate or a polycrystalline silicon substrate may be used.
【００５８】ｐｎ接合の形成後、受光面側にシリコン化
合物を塗布し、乾操して、シリコン化合物層１３４を形
成する（図３（ｂ））。塗布、シリコン化合物および乾
燥の条件などは実施の形態１と同様である。After forming the pn junction, a silicon compound is applied to the light-receiving surface side and dried to form a silicon compound layer 134 (FIG. 3B). The conditions of coating, silicon compound and drying are the same as those in the first embodiment.
【００５９】つぎに、シリコン化合物層上に、反射防止
膜材料を塗布し、乾操して、反射防止膜材料層１３６を
形成する（図３（ｃ））。塗布、反射防止膜材料および
乾燥の条件などは実施例２と同様である。Next, an antireflection film material is applied on the silicon compound layer and dried to form an antireflection film material layer 136 (FIG. 3C). The conditions of coating, antireflection film material and drying are the same as in Example 2.
【００６０】その後、シリコン化合物層１３４および反
射防止膜材料層１３６を同時に焼成して、シリコン酸化
物膜１３５ａおよび反射防止膜１３７ａを形成する（図
３（ｄ））。焼成は、５００℃〜９００℃で行なうこと
が好ましく、６００℃〜８００℃がより好ましい。焼成
温度が５００℃未満では、パッシべ−ション効果を奏す
るシリコン酸化物膜が得られない。一方、９００℃より
高いと基板内の不純物が再拡散し、太陽電池の性能が低
下する。Then, the silicon compound layer 134 and the antireflection film material layer 136 are simultaneously fired to form a silicon oxide film 135a and an antireflection film 137a (FIG. 3 (d)). The firing is preferably performed at 500 ° C to 900 ° C, more preferably 600 ° C to 800 ° C. If the firing temperature is lower than 500 ° C., a silicon oxide film having a passivation effect cannot be obtained. On the other hand, when the temperature is higher than 900 ° C., the impurities in the substrate are re-diffused and the performance of the solar cell is degraded.
【００６１】シリコン酸化物膜の厚さは、実施の形態２
と同様に、１ｎｍ〜２０ｎｍが好ましく、１ｎｍ〜１５
ｎｍがより好ましい。The thickness of the silicon oxide film is the same as in the second embodiment.
Similarly, 1 nm to 20 nm is preferable, and 1 nm to 15 nm
nm is more preferred.
【００６２】反射防止膜の屈折率ｎは、実施の形態２と
同様に、１．８〜２．３が好ましく、２．０〜２．２が
より好ましい。The refractive index n of the antireflection film is preferably 1.8 to 2.3, more preferably 2.0 to 2.2, as in the second embodiment.
【００６３】反射防止膜の厚さＴｈは、実施の形態２と
同様に、
１００／ｎ≦Ｔｈ≦１７５／ｎ
が好ましく、
Ｔｈ＝１２５／ｎ
がより好ましい。したがって、Ｔｈは、通常は４０ｎｍ
〜１００ｎｍが好ましく、５０ｎｍ〜８０ｎｍがより好
ましい。The thickness Th of the antireflection film is preferably 100 / n ≦ Th ≦ 175 / n, more preferably Th = 125 / n, as in the second embodiment. Therefore, Th is usually 40 nm
-100 nm is preferable, and 50 nm-80 nm is more preferable.
【００６４】焼成後、フォトリソグラフィなどによりパ
ターン化を行ない、シリコン酸化物膜１３５ｂと反射防
止膜１３７ｂを形成し（図３（ｅ））、つづいて表面電
極１３８を形成する（図３（ｆ））。After baking, patterning is performed by photolithography or the like to form a silicon oxide film 135b and an antireflection film 137b (FIG. 3 (e)), and then a surface electrode 138 (FIG. 3 (f)). ).
【００６５】つぎに、受光面側と反対側の面にｐ+層を
形成した後、裏面電極を形成し（いずれも図示していな
い。）、太陽電池が得られる。Next, a p + layer is formed on the surface opposite to the light-receiving surface side, and then a back surface electrode is formed (neither is shown) to obtain a solar cell.
【００６６】パッシべ−ション膜および反射防止膜を形
成してから裏面電極を形成しているが、裏面電極を形成
してからパッシべ−ション膜および反射防止膜を形成し
てもよい。Although the back electrode is formed after forming the passivation film and the antireflection film, the passivation film and the antireflection film may be formed after forming the back electrode.
【００６７】本実施の形態３においては、実施の形態２
と比較して、シリコン化合物および反射防止膜材料の焼
成を同時に行なうため、焼成装置の簡略化、焼成時間の
短縮を図ることができる。The third embodiment is different from the second embodiment.
As compared with the above, since the silicon compound and the antireflection film material are fired at the same time, the firing apparatus can be simplified and the firing time can be shortened.
【００６８】（実施の形態４）シリコン化合物を含む塗
料や反射防止膜材料を含む塗料は、インクジェット法に
より塗布することが好ましい。(Embodiment 4) A coating material containing a silicon compound or a coating material containing an antireflection film material is preferably applied by an inkjet method.
【００６９】実施の形態１〜３では、シリコン化合物お
よび反射防止膜材料の塗布方法としてスピン法、スプレ
ー法、デイップ法などを使用した。しかし、これらのい
ずれの方法においても、塗布材料が基板全面に塗布され
るため、塗布材料の利用効率が低く、その多くが無駄に
なる。また、同様の理由により、表面電極を形成する前
にフォトリソグラフィなどによるパターン化工程が必要
となる。本実施の形態４では、シリコン化合物および反
射防止膜材料の塗布方法として、インクジェット法を使
用することにより、塗布しようとする領域にのみ塗布す
るため、塗布材料の無駄を減らし、塗布材料の有効利用
を図ることができる。また、塗布工程においてパターン
化されるため、フォトリソグラフィなどによるパターン
化が不要となる。In the first to third embodiments, the spin method, spray method, dip method and the like are used as the coating method of the silicon compound and the antireflection film material. However, in any of these methods, since the coating material is coated on the entire surface of the substrate, the utilization efficiency of the coating material is low, and most of it is wasted. For the same reason, a patterning process such as photolithography is required before forming the surface electrode. In the fourth embodiment, the inkjet method is used as the method for applying the silicon compound and the antireflection film material, so that only the area to be applied is applied, so that the waste of the application material is reduced and the effective use of the application material is achieved. Can be achieved. Moreover, since patterning is performed in the coating process, patterning by photolithography or the like is unnecessary.
【００７０】実施の形態４の製造工程を図４に示す。ｐ
型のシリコン基板の受光面側の表層に、ｐ型のシリコン
基板と異なる導電型の不純物であるリンなどのＶ族原子
を拡散させてｎ層１４３を形成し、ｐ層１４２との間で
ｐｎ接合が形成されているシリコン基板１４１を製造す
る（図４（ａ））。この場合、ｎ型のシリコン基板を用
い、ホウ素などのＩＩＩ族原子を拡散させてｐ層を形成
し、ｎ層との間でｐｎ接合を形成してもよい。また、シ
リコン基板は、単結晶シリコン基板、多結晶シリコン基
板のいずれを用いてもよい。The manufacturing process of the fourth embodiment is shown in FIG. p
In the surface layer on the light-receiving surface side of the p-type silicon substrate, an n-layer 143 is formed by diffusing a Group V atom such as phosphorus, which is an impurity of a conductivity type different from that of the p-type silicon substrate, and is formed between the p-layer 142 and the A silicon substrate 141 in which a bond is formed is manufactured (FIG. 4A). In this case, an n-type silicon substrate may be used, a group III atom such as boron may be diffused to form a p-layer, and a pn junction may be formed between the n-layer and the n-layer. As the silicon substrate, either a single crystal silicon substrate or a polycrystalline silicon substrate may be used.
【００７１】つぎに、シリコン化合物を含む塗料１４４
を受光面側にインクジェット法により塗布する。塗布
は、インクヘッド１４９を用いて行ない、表面電極１４
８を形成する部分には塗料１４４を塗布しないように
し、パターン化を行なう（図４（ｂ））。塗料１４４
は、シリコン化合物を有機溶剤に混合し、調製する。イ
ンクジェット法に使用する塗布装置は、塗料１４４をシ
リコン基板１４１上に塗布するインクヘッド１４９のほ
か、シリコン基板１４１を保持して、シリコン基板１４
１を進行させる基板チャック（いずれも図示していな
い。）およびシリコン基板１４１の外形寸法を測定して
インクヘッド１４９にその情報を伝達する基板形状測定
装置（図示していない。）を具備していることが好まし
い。Next, a coating 144 containing a silicon compound
Is applied to the light receiving surface side by an inkjet method. The application is performed using the ink head 149, and the surface electrode 14
Patterning is performed without applying the paint 144 to the portion forming 8 (FIG. 4B). Paint 144
Is prepared by mixing a silicon compound with an organic solvent. The coating device used in the inkjet method includes an ink head 149 that coats the coating material 144 on the silicon substrate 141, as well as a silicon substrate 141 that holds the silicon substrate 141.
1 and a substrate shape measuring device (not shown) for measuring the outer dimensions of the silicon substrate 141 and transmitting the information to the ink head 149. Is preferred.
【００７２】塗料１４４の塗布後、乾操し、焼成を行な
うことにより、所定のパターン化が既に形成されたシリ
コン酸化物膜１４５を形成する（図４（ｃ））。シリコ
ン酸化物膜１４５の厚さは、シリコン酸化物膜が反射防
止膜を兼ねるときは、実施の形態１と同様であり、７０
ｎｍ〜１５０ｎｍが好ましい。一方、シリコン酸化物膜
をパッシベーション膜として用い、シリコン酸化物膜の
上に別に反射防止膜を形成するときは、シリコン酸化物
膜の厚さは、１ｎｍ〜２０ｎｍが好ましい。シリコン化
合物、乾燥および焼成などの条件は、実施の形態１と同
様である。After the coating material 144 is applied, it is dried and baked to form a silicon oxide film 145 on which a predetermined pattern is formed (FIG. 4C). The thickness of the silicon oxide film 145 is the same as that in the first embodiment when the silicon oxide film also serves as the antireflection film.
nm-150 nm is preferable. On the other hand, when a silicon oxide film is used as a passivation film and an antireflection film is separately formed on the silicon oxide film, the thickness of the silicon oxide film is preferably 1 nm to 20 nm. Conditions such as the silicon compound, drying and firing are the same as those in the first embodiment.
【００７３】つぎに、シリコン酸化物膜１４５の上に、
反射防止膜材料を含む塗料１４６をインクジェット法に
より塗布する。塗布は、インクヘッド１５０を用いて行
ない、表面電極１４８を形成する部分には塗料１４６を
塗布しないようにし、パターン化を行なう（図４
（ｃ））。塗料１４６は、反射防止膜材料を有機溶剤に
混合し、調製する。インクジェット法に使用する塗布装
置の仕様は、シリコン化合物を塗布する塗布装置の仕様
と同様である。Next, on the silicon oxide film 145,
A coating material 146 containing an antireflection film material is applied by an inkjet method. The application is performed using the ink head 150, and the portion where the surface electrode 148 is formed is not applied with the coating material 146, and patterning is performed (FIG. 4).
(C)). The coating material 146 is prepared by mixing an antireflection film material with an organic solvent. The specifications of the coating device used for the inkjet method are the same as the specifications of the coating device for coating the silicon compound.
【００７４】塗料１４６の塗布後、乾操し、焼成を行な
うことにより、所定のパターン化が既になされている反
射防止膜１４７を形成する（図４（ｄ））。反射防止膜
材料、乾燥、焼成の条件および反射防止膜１４７の厚さ
は、実施の形態２と同様である。反射防止膜１４７は、
複数層としてもよい。また、実施の形態３におけるよう
に、シリコン化合物および反射防止膜材料の焼成を同時
に行なってもよい。シリコン酸化物膜が反射防止膜を兼
ねるときは、図４（ｃ）および（ｄ）に示す工程は省略
される。After the coating material 146 is applied, it is dried and baked to form an antireflection film 147 which has been patterned in a predetermined manner (FIG. 4 (d)). The antireflection film material, the conditions of drying and firing, and the thickness of the antireflection film 147 are the same as those in the second embodiment. The antireflection film 147 is
It may have a plurality of layers. Further, as in the third embodiment, the silicon compound and the antireflection film material may be fired at the same time. When the silicon oxide film also serves as the antireflection film, the steps shown in FIGS. 4C and 4D are omitted.
【００７５】つぎに、表面電極１４８を形成し（図４
（ｅ））、受光面と反対側の面にｐ+層を形成した後、
裏面電極を形成し（いずれも図示していない。）、太陽
電池を製造することができる。Next, the surface electrode 148 is formed (see FIG.
(E)), after forming the p + layer on the surface opposite to the light receiving surface,
A solar cell can be manufactured by forming a back electrode (neither is shown).
【００７６】パッシべ−ション膜を形成してから裏面電
極を形成しているが、裏面電極を形成してからパッシべ
−ション膜を形成してもよい。Although the back electrode is formed after forming the passivation film, the passivation film may be formed after forming the back electrode.
【００７７】本実施の形態４においては、インクジェッ
ト法により塗布するため、塗料の有効利用を図ることが
でき、またフォトリソグラフィ工程が不要であり、製造
工程を簡略化できる。In the fourth embodiment, since coating is carried out by the ink jet method, the paint can be effectively used, and the photolithography process is not required, so that the manufacturing process can be simplified.
【００７８】（実施例１）厚さ０．３ｍｍのｐ型シリコ
ン基板の受光面側にリンを拡散させて厚さ０．５μｍの
ｎ層を形成した。５ｇのＳｉ（ＯＣ2Ｈ5）4（テトラエ
トキシシラン）を９５ｇのエタノールを主成分とする有
機溶剤に混合し、塗料とした。この塗料をスピン法によ
り受光面側に塗布した後、８０℃、２００℃で１分間ず
つ乾燥した。つぎに７００℃で１０分間焼成を行ない、
シリコン酸化物膜を形成した。この膜には、ＳｉＯ2が
含まれており、厚さ１３０ｎｍ、屈折率１．４２であっ
た。シリコン酸化物膜の形成後、レジスト塗布、露光、
現像、エッチング、レジスト除去の各工程からなるフォ
トリソグラフィにより、シリコン酸化物膜をパターン化
し、表面電極を形成した。表面電極の形成後、受光面と
反対側の表面に裏面電極を形成し、太陽電池を製造し
た。Example 1 Phosphorus was diffused on the light receiving surface side of a p-type silicon substrate having a thickness of 0.3 mm to form an n layer having a thickness of 0.5 μm. 5 g of Si (OC 2 H 5 ) 4 (tetraethoxysilane) was mixed with 95 g of an organic solvent containing ethanol as a main component to prepare a coating material. This coating material was applied to the light-receiving surface side by the spin method, and then dried at 80 ° C. and 200 ° C. for 1 minute each. Next, perform firing at 700 ° C for 10 minutes,
A silicon oxide film was formed. This film contained SiO 2 , and had a thickness of 130 nm and a refractive index of 1.42. After forming the silicon oxide film, resist coating, exposure,
The silicon oxide film was patterned by photolithography including the steps of development, etching, and resist removal to form a surface electrode. After forming the front surface electrode, a back surface electrode was formed on the surface opposite to the light receiving surface to manufacture a solar cell.
【００７９】従来の熱酸化法により、９００℃〜１２０
０℃という高温で焼成する方法に比べて、本実施例にお
ける焼成温度は７００℃と低温であり、製造コストも安
価であった。この太陽電池は、パッシベーション効果お
よび反射防止効果はともに十分に優れていた。By the conventional thermal oxidation method, 900 ° C. to 120 ° C.
Compared with the method of firing at a high temperature of 0 ° C., the firing temperature in this example was as low as 700 ° C., and the manufacturing cost was low. This solar cell was sufficiently excellent in both the passivation effect and the antireflection effect.
【００８０】（実施例２）実施例１と同様に、厚さ０．
３ｍｍのｐ型シリコン基板の受光面側にリンを拡散させ
て厚さ０．５μｍのｎ層を形成した。０．４ｇのＳｉ
（ＯＣ2Ｈ5）4（テトラエトキシシラン）を９９．６ｇ
のエタノールを主成分とする有機溶剤に混合し、塗料と
した。この塗料をスピン法により基板の受光面側に塗布
した後、８０℃、２００℃で１分間ずつ乾燥を行なっ
た。つぎに、７００℃で１０分間焼成を行ない、シリコ
ン酸化物膜を形成した。このシリコン酸化物膜には、Ｓ
ｉＯ2が含まれており、厚さは１０ｎｍであった。シリ
コン酸化物膜の形成後、３ｇのＴｉ（ＯＣＨ（Ｃ
Ｈ3）2）4（チタン酸イソプロピル）を９７ｇの２−プ
ロパノールを主成分とする有機溶剤に混合し、塗料とし
た。この塗料をスピン法により受光面側に塗布した後、
８０℃、２００℃で１分間ずつ乾燥を行なった。つぎ
に、５００℃で１０分間焼成を行ない、反射防止膜を形
成した。この反射防止膜には、ＴｉＯ2が含まれてお
り、厚さは７０μｍであった。つぎに、フォトリソグラ
フィによりシリコン酸化物膜および反射防止膜をパター
ン化し、表面電極を形成した。最後に、裏面電極を形成
し、太陽電池を製造した。(Embodiment 2) As in Embodiment 1, the thickness is 0.
Phosphorus was diffused on the light-receiving surface side of a 3 mm p-type silicon substrate to form an n layer having a thickness of 0.5 μm. 0.4g Si
99.6 g of (OC 2 H 5 ) 4 (tetraethoxysilane)
It was mixed with an organic solvent containing ethanol as a main component to prepare a paint. This coating material was applied to the light-receiving surface side of the substrate by a spin method, and then dried at 80 ° C. and 200 ° C. for 1 minute each. Next, firing was performed at 700 ° C. for 10 minutes to form a silicon oxide film. This silicon oxide film contains S
It contained iO 2 and had a thickness of 10 nm. After forming the silicon oxide film, 3 g of Ti (OCH (C
H 3) 2) 4 (mixed isopropyl titanate) in an organic solvent mainly composed of 2-propanol 97 g, and the coating material. After applying this paint to the light-receiving surface side by the spin method,
It was dried at 80 ° C. and 200 ° C. for 1 minute each. Next, baking was performed at 500 ° C. for 10 minutes to form an antireflection film. This antireflection film contained TiO 2 and had a thickness of 70 μm. Next, the silicon oxide film and the antireflection film were patterned by photolithography to form a surface electrode. Finally, the back electrode was formed and the solar cell was manufactured.
【００８１】実施例１と同様に、従来の熱酸化法より低
温で焼成でき、工程も簡略であった。また、シリコン酸
化物よりも高い屈折率を有する反射防止膜を設けたこと
により、光電変換効率の高い太陽電池が得られた。Similar to the first embodiment, the firing can be performed at a lower temperature than the conventional thermal oxidation method, and the process is simple. Further, by providing an antireflection film having a higher refractive index than silicon oxide, a solar cell having high photoelectric conversion efficiency was obtained.
【００８２】（実施例３）実施例１と同様に、厚さ０．
３ｍｍのｐ型シリコン基板の受光面側にリンを拡散させ
て厚さ０．５μｍのｎ層を形成した。０．４ｇのＳｉ
（ＯＣ2Ｈ5）4（テトラエトキシシラン）を９９．６ｇ
のエタノールを主成分とする有機溶剤に混合し、塗料と
した。この塗料をスピン法により基板の受光面側に塗布
した後、８０℃、２００℃で１分間ずつ乾燥を行なっ
た。つづいて、３ｇのＴｉ（ＯＣＨ（ＣＨ3）2）4（チ
タン酸イソプロピル）を９７ｇの２−プロパノールを主
成分とする有機溶剤に混合し、塗料とした。この塗料を
スピン法によりシリコン化合物層上に塗布した後、８０
℃、２００℃で１分間ずつ乾燥を行なった。つぎに、７
００℃で１０分間焼成を行ない、シリコン酸化物膜およ
び反射防止膜を形成した。シリコン酸化物膜には、Ｓｉ
Ｏ2が含まれ、厚さは１０ｎｍであった。一方、反射防
止膜には、ＴｉＯ2が含まれ、厚さは７０ｎｍであっ
た。つぎに、フォトリソグラフィによりシリコン酸化物
膜および反射防止膜をパターン化し、表面電極を形成し
た。最後に、裏面電極を形成し、太陽電池を製造した。(Third Embodiment) As in the first embodiment, the thickness is 0.
Phosphorus was diffused on the light-receiving surface side of a 3 mm p-type silicon substrate to form an n layer having a thickness of 0.5 μm. 0.4g Si
99.6 g of (OC 2 H 5 ) 4 (tetraethoxysilane)
It was mixed with an organic solvent containing ethanol as a main component to prepare a paint. This coating material was applied to the light-receiving surface side of the substrate by a spin method, and then dried at 80 ° C. and 200 ° C. for 1 minute each. Subsequently, 3 g of Ti (OCH (CH 3 ) 2 ) 4 (isopropyl titanate) was mixed with 97 g of an organic solvent containing 2-propanol as a main component to obtain a paint. After applying this paint on the silicon compound layer by the spin method,
Drying was carried out at 1 ° C and 200 ° C for 1 minute each. Next, 7
Firing was carried out at 00 ° C. for 10 minutes to form a silicon oxide film and an antireflection film. The silicon oxide film contains Si
It contained O 2 and had a thickness of 10 nm. On the other hand, the antireflection film contained TiO 2 and had a thickness of 70 nm. Next, the silicon oxide film and the antireflection film were patterned by photolithography to form a surface electrode. Finally, the back electrode was formed and the solar cell was manufactured.
【００８３】製造された太陽電池は、実施例２と同様
に、シリコン基板上にシリコン酸化物膜が形成され、シ
リコン酸化物膜上に反射防止膜が形成されていたが、本
実施例では、実施例２と異なり、シリコン化合物および
反射防止膜材料は同時に焼成したため、焼成時間を短縮
することができるとともに、製造工程を簡略化できた。In the manufactured solar cell, the silicon oxide film was formed on the silicon substrate and the antireflection film was formed on the silicon oxide film as in the second embodiment. Unlike Example 2, since the silicon compound and the antireflection film material were fired at the same time, the firing time could be shortened and the manufacturing process could be simplified.
【００８４】（実施例４）シリコン化合物を含む塗料お
よび反射防止膜材料を含む塗料をインクジェット法によ
り塗布した以外は、実施例２と同様にして太陽電池を製
造した。塗布は、表面電極を形成する部分には塗料を塗
布しないようにパターン化しながら行なった。製造した
太陽電池におけるシリコン酸化物膜の厚さは１０ｎｍで
あり、反射防止膜の厚さは７０ｎｍであった。Example 4 A solar cell was manufactured in the same manner as in Example 2 except that the coating material containing the silicon compound and the coating material containing the antireflection film material were applied by the ink jet method. The application was performed while patterning so that the paint was not applied to the area where the surface electrode was formed. In the manufactured solar cell, the silicon oxide film had a thickness of 10 nm, and the antireflection film had a thickness of 70 nm.
【００８５】製造した太陽電池自体は、実施例２と同様
の構成を有するものであったが、本実施例では、実施例
２と異なり、インクジェット法により塗布したため、塗
料の無駄がなく、またフォトリソグラフィによるパター
ン化が不要であり、工程が簡略化できた。The manufactured solar cell itself had the same structure as in Example 2. However, unlike Example 2, in this example, the coating was carried out by the ink jet method, and there was no waste of paint, The patterning by lithography is not necessary and the process can be simplified.
【００８６】今回開示された実施の形態はすべての点で
例示であって制限的なものではないと考えられるべきで
ある。本発明の範囲は上記した説明ではなくて特許請求
の範囲によって示され、特許請求の範囲と均等の意味お
よび範囲内でのすべての変更が含まれることが意図され
る。The embodiments disclosed this time are to be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.
【００８７】[0087]
【発明の効果】本発明の太陽電池は、パッシベーション
効果や反射防止効果に優れる。本発明の太陽電池の製造
方法によれば、低い温度で安価に製造することができ、
工程も簡略で生産効率が高く、塗料を有効利用できる。The solar cell of the present invention is excellent in the passivation effect and the antireflection effect. According to the method for manufacturing a solar cell of the present invention, it can be manufactured at low temperature at low cost,
The process is simple, the production efficiency is high, and the paint can be effectively used.
【図１】 本発明の実施の形態１に係る太陽電池の製造
工程を表した模式図である。FIG. 1 is a schematic diagram showing a manufacturing process of a solar cell according to a first embodiment of the present invention.
【図２】 本発明の実施の形態２に係る太陽電池の製造
工程を表した模式図である。FIG. 2 is a schematic diagram showing a manufacturing process of a solar cell according to a second embodiment of the present invention.
【図３】 本発明の実施の形態３に係る太陽電池の製造
工程を表した模式図である。FIG. 3 is a schematic diagram showing a manufacturing process of a solar cell according to a third embodiment of the present invention.
【図４】 本発明の実施の形態４に係る太陽電池の製造
工程を表した模式図である。FIG. 4 is a schematic diagram showing a manufacturing process of a solar cell according to a fourth embodiment of the present invention.
【図５】 シリコン化合物の焼成温度とキャリア寿命と
の関係を表すグラフである。FIG. 5 is a graph showing the relationship between the firing temperature of silicon compounds and the carrier lifetime.
１１１ シリコン基板、１１２ ｐ層、１１３ ｎ層、
１１５ａ，１１５ｂシリコン酸化物膜、１１６ 表面電
極、１２６ａ，１２６ｂ 反射防止膜、１４９，１５０
インクヘッド。111 silicon substrate, 112 p layer, 113 n layer,
115a, 115b silicon oxide film, 116 surface electrode, 126a, 126b antireflection film, 149, 150
Ink head.
Claims (15)
ン基板と異なる導電型の不純物拡散領域を形成する太陽
電池の製造方法において、 前記不純物拡散領域上にシリコン化合物を含む塗料を塗
布した後、乾燥し、焼成してシリコン酸化物膜を形成す
る工程を含むことを特徴とする太陽電池の製造方法。1. A method of manufacturing a solar cell in which a conductivity type impurity diffusion region different from that of the silicon substrate is formed in a surface layer of a conductivity type silicon substrate, wherein after coating a coating containing a silicon compound on the impurity diffusion region, A method of manufacturing a solar cell, comprising the steps of drying and firing to form a silicon oxide film.
ｍ〜１５０ｎｍである請求項１記載の太陽電池の製造方
法。2. The thickness of the silicon oxide film is 70 n
The method for producing a solar cell according to claim 1, wherein the thickness is m to 150 nm.
ン基板と異なる導電型の不純物拡散領域を形成する太陽
電池の製造方法において、 前記不純物拡散領域上にシリコン化合物を含む塗料を塗
布した後、乾燥し、焼成してシリコン酸化物膜を形成す
る工程と、 前記シリコン酸化物膜上に反射防止膜材料を含む塗料を
塗布した後、乾燥し、焼成して少なくとも一層の反射防
止膜を形成する工程と、を含むことを特徴とする太陽電
池の製造方法。3. A method of manufacturing a solar cell, comprising: forming an impurity diffusion region of a conductivity type different from that of the silicon substrate on a surface layer of a conductivity type silicon substrate; and applying a coating material containing a silicon compound on the impurity diffusion region, Drying and baking to form a silicon oxide film; and applying a coating material containing an antireflection film material on the silicon oxide film, and then drying and baking to form at least one antireflection film. The manufacturing method of the solar cell characterized by including the process.
ン基板と異なる導電型の不純物拡散領域を形成する太陽
電池の製造方法において、 前記不純物拡散領域上にシリコン化合物を含む塗料を塗
布した後、乾燥して、シリコン化合物層を形成する工程
と、 前記シリコン化合物層上に反射防止膜材料を含む塗料を
塗布した後、乾燥して、少なくとも一層の反射防止膜材
料層を形成する工程と、 前記シリコン化合物層および前記反射防止膜材料層を同
時に焼成して、シリコン酸化物膜および反射防止膜を形
成する工程と、を含むことを特徴とする太陽電池の製造
方法。4. A method of manufacturing a solar cell, comprising: forming an impurity diffusion region of a conductivity type different from that of the silicon substrate on a surface layer of a conductivity type silicon substrate; and applying a coating material containing a silicon compound on the impurity diffusion region, A step of drying to form a silicon compound layer, a step of applying a coating material containing an antireflection film material on the silicon compound layer, and a step of drying to form at least one antireflection film material layer; And a step of simultaneously firing the silicon compound layer and the antireflection film material layer to form a silicon oxide film and an antireflection film.
ｍ以下である請求項３または４記載の太陽電池の製造方
法。5. The silicon oxide film has a thickness of 20 n.
The method for producing a solar cell according to claim 3, wherein the solar cell has a thickness of m or less.
は、前記反射防止膜の屈折率をｎとすると、 １００／ｎ≦Ｔｈ≦１７５／ｎ であることを特徴とする請求項３または４記載の太陽電
池の製造方法。6. The thickness Th (unit: nm) of the antireflection film.
Is 100 / n ≦ Th ≦ 175 / n, where n is the refractive index of the antireflection film. 6. The method for manufacturing a solar cell according to claim 3, wherein
２．３である請求項３または４記載の太陽電池の製造方
法。7. The refractive index n of the antireflection film is 1.8 to
It is 2.3, The manufacturing method of the solar cell of Claim 3 or 4.
は、直鎖状または分枝を有する炭化水素基を表す。）ま
たはＳｉ−ＯＨで表されるシラノール化合物を含むこと
を特徴とする請求項１、３または４のいずれかに記載の
太陽電池の製造方法。8. The silicon compound is Si—OR (R
Represents a straight-chain or branched hydrocarbon group. ) Or a silanol compound represented by Si-OH is included, The manufacturing method of the solar cell in any one of Claim 1, 3 or 4 characterized by the above-mentioned.
類のＸ−ＯＲ（Ｘは、Ｌｉ、Ｂｅ、Ｂ、Ｎａ、Ｍｇ、Ａ
ｌ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｒｂ、Ｓｒ、Ｙ、
Ｚｒ、Ｎｂ、Ｍｏ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｃｓ、Ｂ
ａ、Ｌａ、Ｈｆ、Ｔａ、Ｗ、Ｔｌ、Ｐｂ、Ｂｉ、Ｃｅ、
Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈ
ｏ、Ｅｒ、Ｔｍ、Ｙｂ、ＬｕまたはＳｉを表す。）また
はＸ−ＯＨで表される化合物を含むことを特徴とする請
求項３または４記載の太陽電池の製造方法。9. The antireflection film material is at least one kind of X-OR (X is Li, Be, B, Na, Mg, A).
l, K, Ca, Sc, Ti, V, Cr, Mn, Fe, C
o, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y,
Zr, Nb, Mo, Cd, In, Sn, Sb, Cs, B
a, La, Hf, Ta, W, Tl, Pb, Bi, Ce,
Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H
represents o, Er, Tm, Yb, Lu or Si. ) Or a compound represented by X-OH is contained, The manufacturing method of the solar cell of Claim 3 or 4 characterized by the above-mentioned.
００℃で焼成することを特徴とする請求項１または３記
載の太陽電池の製造方法。10. The silicon compound has a temperature of 500 ° C. to 9 ° C.
The method for manufacturing a solar cell according to claim 1 or 3, wherein firing is performed at 00 ° C.
００℃で焼成することを特徴とする請求項３記載の太陽
電池の製造方法。11. The antireflection film material is 200 ° C. to 9 ° C.
The method for manufacturing a solar cell according to claim 3, wherein firing is performed at 00 ° C.
止膜材料は、５００℃〜９００℃で焼成することを特徴
とする請求項４記載の太陽電池の製造方法。12. The method for manufacturing a solar cell according to claim 4, wherein the silicon compound and the antireflection film material are fired at 500 ° C. to 900 ° C.
ンクジェット法により塗布することを特徴とする請求項
１、３または４のいずれかに記載の太陽電池の製造方
法。13. The method for manufacturing a solar cell according to claim 1, wherein the coating material containing the silicon compound is applied by an inkjet method.
ンクジェット法により塗布することを特徴とする請求項
３または４記載の太陽電池の製造方法。14. The method of manufacturing a solar cell according to claim 3, wherein the coating material containing the antireflection film material is applied by an inkjet method.
法により製造されることを特徴とする太陽電池。15. A solar cell manufactured by the method according to any one of claims 1 to 14.
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| JP2009283549A (en) * | 2008-05-20 | 2009-12-03 | Mitsubishi Electric Corp | Method for manufacturing solar cell, and method for manufacturing solar cell module |
| JP2010065174A (en) * | 2008-09-12 | 2010-03-25 | Mitsubishi Chemicals Corp | Composition, antireflection film substrate, and solar cell system |
| JP2012038852A (en) * | 2010-08-05 | 2012-02-23 | Shin Etsu Chem Co Ltd | Solar cell and method for manufacturing the same |
| KR20130121089A (en) | 2010-09-30 | 2013-11-05 | 미쓰비시 마테리알 가부시키가이샤 | Composition for antireflective film for solar cell, antireflective film for solar cell, method for manufacturing antireflective film for solar cell, and solar cell |
| WO2024021895A1 (en) * | 2022-07-26 | 2024-02-01 | 隆基绿能科技股份有限公司 | Solar cell and preparation method, and photovoltaic module |
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| JP2009283549A (en) * | 2008-05-20 | 2009-12-03 | Mitsubishi Electric Corp | Method for manufacturing solar cell, and method for manufacturing solar cell module |
| JP4703687B2 (en) * | 2008-05-20 | 2011-06-15 | 三菱電機株式会社 | Method for manufacturing solar cell and method for manufacturing solar cell module |
| JP2010065174A (en) * | 2008-09-12 | 2010-03-25 | Mitsubishi Chemicals Corp | Composition, antireflection film substrate, and solar cell system |
| JP2012038852A (en) * | 2010-08-05 | 2012-02-23 | Shin Etsu Chem Co Ltd | Solar cell and method for manufacturing the same |
| KR20130121089A (en) | 2010-09-30 | 2013-11-05 | 미쓰비시 마테리알 가부시키가이샤 | Composition for antireflective film for solar cell, antireflective film for solar cell, method for manufacturing antireflective film for solar cell, and solar cell |
| WO2024021895A1 (en) * | 2022-07-26 | 2024-02-01 | 隆基绿能科技股份有限公司 | Solar cell and preparation method, and photovoltaic module |
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