JP4714634B2 - Conductive paste for solar cell electrode - Google Patents
Conductive paste for solar cell electrode Download PDFInfo
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- JP4714634B2 JP4714634B2 JP2006120835A JP2006120835A JP4714634B2 JP 4714634 B2 JP4714634 B2 JP 4714634B2 JP 2006120835 A JP2006120835 A JP 2006120835A JP 2006120835 A JP2006120835 A JP 2006120835A JP 4714634 B2 JP4714634 B2 JP 4714634B2
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- 239000002245 particle Substances 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 26
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- 239000011521 glass Substances 0.000 claims description 16
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- 229910052738 indium Inorganic materials 0.000 claims description 13
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000034 method Methods 0.000 claims description 5
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- LIQDVINWFSWENU-UHFFFAOYSA-K aluminum;prop-2-enoate Chemical compound [Al+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C LIQDVINWFSWENU-UHFFFAOYSA-K 0.000 claims description 2
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 18
- 239000010408 film Substances 0.000 description 12
- -1 B 2 O 3 Inorganic materials 0.000 description 11
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- 238000010304 firing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
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- 239000000020 Nitrocellulose Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Electromagnetism (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photovoltaic Devices (AREA)
Description
本発明は、太陽電池電極用導電性ペースト、特に結晶系シリコン太陽電池のN型半導体上の電極を形成するための導電性ペースト、当該導電性ペーストを焼成してなる太陽電池の電極、当該電極を備えた太陽電池、当該導電性ペーストを用いた太陽電池の製造方法に関する。 The present invention relates to a conductive paste for a solar cell electrode, in particular, a conductive paste for forming an electrode on an N-type semiconductor of a crystalline silicon solar cell, a solar cell electrode formed by firing the conductive paste, and the electrode And a method for producing a solar cell using the conductive paste.
単結晶又は多結晶シリコンを主たる半導体基板材料として用いる従来の太陽電池は、基板表面近傍に設けられたPN接合に発生する電界により、半導体内に入射・吸収された光によって発生する電子・正孔対を分離し、P型半導体及びN型半導体のそれぞれと低接触抵抗になるように形成された電極を介して、電流として外部に取り出す。 Conventional solar cells using single crystal or polycrystalline silicon as the main semiconductor substrate material are electrons / holes generated by light incident / absorbed in the semiconductor due to the electric field generated at the PN junction provided near the substrate surface. The pair is separated and taken out to the outside as an electric current through an electrode formed to have a low contact resistance with each of the P-type semiconductor and the N-type semiconductor.
例えば、一般的な多結晶シリコン太陽電池の場合、B(ボロン原子)等を不純物として添加したP型シリコン基板の片側表面から、P(リン原子)等のN型拡散層を形成可能な元素を拡散させて、PN接合を形成する。この場合、光の閉じ込め効果をもたせるため、P型シリコン基板表面にテクスチャ(凹凸)加工を施してからN型拡散層を形成する。 For example, in the case of a general polycrystalline silicon solar cell, an element capable of forming an N-type diffusion layer such as P (phosphorus atom) from one side surface of a P-type silicon substrate doped with B (boron atom) or the like as an impurity. Diffusion to form a PN junction. In this case, in order to have a light confinement effect, the N-type diffusion layer is formed after texture (unevenness) processing is performed on the surface of the P-type silicon substrate.
N型拡散層側を光入射側とし、窒化ケイ素、酸化チタン等の反射防止膜(膜厚50〜100nm)を介して、バス電極とフィンガー電極からなる光入射側電極を形成する。裏面側のP型シリコン基板側には、光を入射させなくてもよいため、ほぼ全面に裏面側電極を形成する。両電極は、各半導体と低抵抗でオーミック接触する必要がある。 A light incident side electrode composed of a bus electrode and a finger electrode is formed through an antireflection film (film thickness: 50 to 100 nm) such as silicon nitride and titanium oxide with the N-type diffusion layer side as a light incident side. Since light does not need to be incident on the P-type silicon substrate side on the back side, the back side electrode is formed on almost the entire surface. Both electrodes need to be in ohmic contact with each semiconductor with low resistance.
両電極は、一般的には、導電性ペーストの印刷、乾燥、焼成によって形成する。導電性ペースト組成と焼成条件は、太陽電池の特性にとって特に重要である。 Both electrodes are generally formed by printing, drying and firing a conductive paste. The conductive paste composition and firing conditions are particularly important for the characteristics of the solar cell.
導電性ペーストは、一般的には、有機バインダ、溶剤、導電性粒子、ガラスフリットを含み、場合により添加物が配合されている。これらの成分は、印刷性や印刷後の形状の制御、電極としての導電性付与、半導体基板との密着性保持、反射防止膜のファイヤースルー、太陽電池の半導体基板及び拡散層との接触抵抗の低減等の役割を担う。 The conductive paste generally contains an organic binder, a solvent, conductive particles, and glass frit, and an additive is optionally blended. These components include control of printability and shape after printing, imparting conductivity as an electrode, maintaining adhesion with a semiconductor substrate, fire-through of an antireflection film, contact resistance with a semiconductor substrate and a diffusion layer of a solar cell. Play a role of reduction.
導電性ペーストを、スクリーン印刷等の方法で半導体基板に直接印刷して、又は拡散層上に形成された反射防止膜上に印刷して、100〜150℃程度の温度で数分間乾燥し、その後、600〜850℃程度で数分間高速焼成して、光入射側電極又は裏面側電極を形成する。焼成条件は、導電性ペースト組成によって良好な太陽電池特性を得るための最適条件が異なるため、ペースト組成に適した条件が選ばれる。 The conductive paste is printed directly on the semiconductor substrate by a method such as screen printing or printed on the antireflection film formed on the diffusion layer, and dried at a temperature of about 100 to 150 ° C. for several minutes, and then Baked at about 600 to 850 ° C. for several minutes to form a light incident side electrode or a back side electrode. As the firing conditions, optimum conditions for obtaining good solar cell characteristics differ depending on the conductive paste composition, and therefore conditions suitable for the paste composition are selected.
結晶系シリコン太陽電池の変換効率と電池特性の安定性に及ぼす電極の影響は大きく、特に光入射側電極の影響は非常に大きい。電極性能の目安として、太陽電池の曲線因子(FF)がある。太陽電池の直列抵抗が高いと、FFは小さくなる傾向にあるが、直列抵抗の構成要素の一つがP型半導体及びN型半導体と電極との接触抵抗である。なお、太陽電池における直列抵抗は、太陽電池の光照射下のI−V(電流−電圧)特性におけるVoc点(開放電圧点)での接線の傾きを指標として評価できる。 The influence of the electrode on the conversion efficiency and the stability of the battery characteristics of the crystalline silicon solar cell is large, and particularly the influence of the light incident side electrode is very large. As a measure of electrode performance, there is a solar cell fill factor (FF). When the series resistance of the solar cell is high, the FF tends to be small, but one of the constituent elements of the series resistance is the contact resistance between the P-type semiconductor and the N-type semiconductor and the electrode. In addition, the series resistance in a solar cell can be evaluated using the slope of the tangent at the Voc point (open voltage point) in the IV (current-voltage) characteristics under light irradiation of the solar cell as an index.
このため、太陽電池の高い変換効率と安定な特性を得ることを目的として、太陽電池電極用導電性ペーストに各種の添加物を配合する以下の方法が、これまでに提案されている。
(i)Bi2O3、B2O3、SiO2を含有するガラスフリットを配合した導電性ペースト(特許文献1)。
(ii)Ti、Zn、Y等の金属やその化合物を0.001〜0.1μmの微細な粒子として添加した導電性ペースト(特許文献2)。
(iii)Ti、Bi、Co、Zr、Fe、Crを含む導電性ペースト(特許文献3)。
(iv)ハロゲン化物を添加した導電性ペースト(特許文献4)。
For this reason, for the purpose of obtaining high conversion efficiency and stable characteristics of solar cells, the following methods have been proposed so far in which various additives are blended into the conductive paste for solar cell electrodes.
(I) A conductive paste containing glass frit containing Bi 2 O 3 , B 2 O 3 , and SiO 2 (Patent Document 1).
(Ii) A conductive paste in which a metal such as Ti, Zn, or Y or a compound thereof is added as fine particles of 0.001 to 0.1 μm (Patent Document 2).
(Iii) A conductive paste containing Ti, Bi, Co, Zr, Fe, and Cr (Patent Document 3).
(Iv) A conductive paste to which a halide is added (Patent Document 4).
しかしながら、いずれの導電性ペーストにおいても、それを用いて形成した電極を備えた太陽電池において、十分高いFF(曲線因子)が得られず、また電極を形成するための焼成温度の変動によるFFの変化が大きい、といった問題があった。 However, in any of the conductive pastes, a sufficiently high FF (curve factor) cannot be obtained in a solar cell including an electrode formed using the conductive paste, and the FF of the FF due to fluctuations in the firing temperature for forming the electrode is not obtained. There was a problem that the change was large.
本発明は、上記の問題を解決して、とりわけ結晶系シリコン太陽電池のN型半導体にオーミック接触させる電極において、高いFFを安定して得ることができる太陽電池電極用導電性ペースト、並びに当該導電性ペーストを焼成してなる太陽電池の電極(特にN型半導体上の電極)、当該電極を備えた太陽電池及び当該導電性ペーストを用いた太陽電池の製造方法を提供することを目的とする。 The present invention solves the above-mentioned problems, and in particular, an electrode for making ohmic contact with an N-type semiconductor of a crystalline silicon solar cell, and a conductive paste for a solar cell electrode capable of stably obtaining a high FF, and the conductive material It aims at providing the manufacturing method of the solar cell using the electrode (especially electrode on an N type semiconductor) of the solar cell formed by baking a conductive paste, the solar cell provided with the said electrode, and the said conductive paste.
一般に、電極中にIII族元素が存在するとアクセプターレベルが形成されるため、このような電極をN型半導体と接合させると、N型半導体に形成されているドナーレベルと補償することとなり、接触抵抗が高くなることが予想される。本発明者らは、太陽電池電極用導電性ペーストにIII族元素であるAl、Ga、In又はTlを化合物として配合した場合、かかるペーストを用いて形成したN型半導体上の電極は、予想に反して、N型半導体との間の接触抵抗が低く、太陽電池に優れたFFをもたらすことを見出し、本発明を完成するに至った。 In general, when a group III element is present in an electrode, an acceptor level is formed. Therefore, when such an electrode is joined to an N-type semiconductor, it compensates for the donor level formed in the N-type semiconductor. Resistance is expected to increase. When the present inventors blended a group III element Al, Ga, In or Tl as a compound in a conductive paste for solar cell electrodes, an electrode on an N-type semiconductor formed using such a paste is expected. On the other hand, the present inventors have found that the contact resistance with the N-type semiconductor is low and brings an excellent FF to the solar cell, and the present invention has been completed.
すなわち、本発明は、有機バインダと、溶剤と、導電性粒子と、ガラスフリットと、Al、Ga、In又はTlを含む化合物とを含有する、ことを特徴とする太陽電池電極用導電性ペーストである。また、本発明は、上記の導電性ペーストを焼成してなる太陽電池の電極に関する。さらに、本発明は、上記の電極を備えた太陽電池に関する。加えて本発明は、上記の導電性ペーストを用いた太陽電池の製造方法に関する。 That is, the present invention is a conductive paste for a solar cell electrode comprising an organic binder, a solvent, conductive particles, glass frit, and a compound containing Al, Ga, In, or Tl. is there. Moreover, this invention relates to the electrode of the solar cell formed by baking said electrically conductive paste. Furthermore, this invention relates to the solar cell provided with said electrode. In addition, this invention relates to the manufacturing method of the solar cell using said electrically conductive paste.
本発明の導電性ペーストによれば、高いFFの太陽電池を得ることができ、太陽電池の性能を向上させることができる。 According to the conductive paste of the present invention, a high FF solar cell can be obtained, and the performance of the solar cell can be improved.
本発明の太陽電池電極用導電性ペーストは、有機バインダと、溶剤と、導電性粒子と、ガラスフリットと、Al、Ga、In又はTlを含む化合物とを含有する。 The conductive paste for solar cell electrodes of the present invention contains an organic binder, a solvent, conductive particles, glass frit, and a compound containing Al, Ga, In, or Tl.
(1)有機バインダと溶剤
有機バインダと溶剤は、導電性ペーストの粘度調整等の役割を担うものであり、いずれも特に限定されない。有機バインダを溶剤に溶解させて使用することもできる。
(1) Organic Binder and Solvent The organic binder and the solvent play a role of adjusting the viscosity of the conductive paste and are not particularly limited. It is also possible to use an organic binder dissolved in a solvent.
有機バインダとしては、セルロース系樹脂、例えばエチルセルロース、ニトロセルロース等;(メタ)アクリル系樹脂、例えばポリメチルアクリレート、ポリメチルメタクリレート等が挙げられ、有機溶媒としては、アルコール類、例えばターピネオール(α−ターピネオール、β−ターピネオール等);エステル類、例えばヒドロキシ基含有エステル類(2,2,4―トリメチル−1,3−ペンタンジオールモノイソブチラート、ブチルカルビトールアセテート等)を使用することが出来る。 Examples of the organic binder include cellulose resins such as ethyl cellulose and nitrocellulose; (meth) acrylic resins such as polymethyl acrylate and polymethyl methacrylate. Organic solvents include alcohols such as terpineol (α-terpineol). And β-terpineol); esters such as hydroxy group-containing esters (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, butyl carbitol acetate, etc.) can be used.
(2)導電性粒子
導電性粒子は、特に限定されず、例えば、Ag、Cu、Ni等が挙げられる。空気中でも焼成できるため、Agが好ましい。導電性粒子の形状・平均粒子寸法は、特に限定されず、当該分野で公知のものを使用することができる。導電性粒子の形状としては、球状、リン片状、等が挙げられる。導電性粒子の平均粒子寸法は、作業性の点等から、0.05〜10μmが好ましく、好ましくは0.1〜5μmである。なお、平均粒子寸法とは、球状の場合は粒子径、りん片状の場合は粒子薄片の長径、針状の場合は長さのそれぞれ平均をいう。
(2) Conductive particles The conductive particles are not particularly limited, and examples thereof include Ag, Cu, and Ni. Ag is preferable because it can be fired in air. The shape and average particle size of the conductive particles are not particularly limited, and those known in the art can be used. Examples of the shape of the conductive particles include a spherical shape and a flake shape. The average particle size of the conductive particles is preferably 0.05 to 10 μm, preferably 0.1 to 5 μm, from the viewpoint of workability. The average particle size means the average of the particle diameter in the case of a spherical shape, the long diameter of the particle flake in the case of a flake shape, and the length in the case of a needle shape.
(3)ガラスフリット
ガラスフリットは、特に限定されず、Pb系ガラスフリット、例えばPbO−B2O3-SiO2系等;Pbフリー系ガラスフリット、例えばBi2O3−B2O3−SiO2−CeO2−LiO2−NaO2系等が挙げられる。ガラスフリットの形状・大きさは、特に限定されず、当該分野で公知のものを使用することができる。ガラスフリットの形状としては、球状、不定形等が挙げられる。ガラスフリットの平均粒子寸法は、作業性の点等から、0.01〜10μmが挙げられ、好ましくは0.05〜1μmである。平均粒子寸法は、上記のとおりであるが、不定形の場合は、最長の径のそれぞれ平均をいう。
(3) Glass frit The glass frit is not particularly limited, and is a Pb glass frit such as PbO—B 2 O 3 —SiO 2 ; Pb free glass frit such as Bi 2 O 3 —B 2 O 3 —SiO Examples include 2- CeO 2 —LiO 2 —NaO 2 system. The shape and size of the glass frit are not particularly limited, and those known in the art can be used. Examples of the shape of the glass frit include a spherical shape and an indefinite shape. The average particle size of the glass frit is 0.01 to 10 μm, preferably 0.05 to 1 μm, from the viewpoint of workability. The average particle size is as described above, but in the case of an irregular shape, it means the average of the longest diameters.
(4)Al、Ga、In又はTlを含む化合物
本発明の導電性ペーストは、Al、Ga、In又はTlを含む化合物を含有する。これらの化合物は、単独でも、2種以上併用してもよい。
(4) Compound containing Al, Ga, In or Tl The conductive paste of the present invention contains a compound containing Al, Ga, In or Tl. These compounds may be used alone or in combination of two or more.
化合物としては、酸化物、水酸化物、有機金属化合物が挙げられる。本明細書では、有機金属化合物は各種の金属を含む有機化合物を指すこととし、ジケトン錯体やカルボン酸塩が利用できる。ジケトン錯体としては、アセチルアセトン金属錯体、アセト酢酸金属錯体、ジエチルマロン酸エステル金属錯体、シクロペンタジエン錯体等が挙げられる。カルボン酸塩としては、(メタ)アクリル酸金属化合物、ナフテン酸金属化合物、オクチル酸金属化合物、ステアリン酸金属化合物、パルミチン酸金属化合物等が挙げられ、好ましくはアセチルアセトン金属錯体又はオクチル酸金属化合物である。 Examples of the compound include oxides, hydroxides, and organometallic compounds. In this specification, an organometallic compound refers to an organic compound containing various metals, and diketone complexes and carboxylates can be used. Examples of the diketone complex include acetylacetone metal complex, acetoacetate metal complex, diethylmalonate metal complex, cyclopentadiene complex, and the like. Examples of the carboxylate include a (meth) acrylic acid metal compound, a naphthenic acid metal compound, an octylic acid metal compound, a stearic acid metal compound, and a palmitic acid metal compound, preferably an acetylacetone metal complex or an octylic acid metal compound. .
Al化合物としては、Al2O3、Al(OH)3、Al(C5H7O2)3、アクリル酸アルミニウム等;Ga化合物としては、Ga2O3、Ga(OH)3、Ga(C5H7O2)3等;In化合物としては、In2O3、In(OH)3、In(C5H7O2)3等;Tl化合物としては、Tl2O3、Tl(OH)3、Tl(C5H7O2)3等が挙げられる。 Examples of the Al compound include Al 2 O 3 , Al (OH) 3 , Al (C 5 H 7 O 2 ) 3 , aluminum acrylate, etc .; Examples of the Ga compound include Ga 2 O 3 , Ga (OH) 3 , Ga ( C 5 H 7 O 2 ) 3 etc .; In compounds such as In 2 O 3 , In (OH) 3 , In (C 5 H 7 O 2 ) 3 etc .; Tl compounds include Tl 2 O 3 , Tl ( OH) 3 , Tl (C 5 H 7 O 2 ) 3 and the like.
Al、Ga、In又はTlを含む化合物は、通常、固体又は液体であり、このまま導電性ペーストに配合することができる。固体の場合は、形状やサイズの影響は少ないが、作業性の点等から平均粒子寸法が0.05〜10μmであることが好ましく、例えば0.15〜5μmのものを使用することができ、また、トルエン、エタノール、アセチルアセトン、塩化メチレン等を溶媒として、これらに溶解又は分散させて使用することもできる。 The compound containing Al, Ga, In, or Tl is usually a solid or a liquid, and can be blended into the conductive paste as it is. In the case of a solid, although the influence of the shape and size is small, the average particle size is preferably 0.05 to 10 μm from the viewpoint of workability and the like, for example, 0.15 to 5 μm can be used, Further, toluene, ethanol, acetylacetone, methylene chloride or the like can be used as a solvent by being dissolved or dispersed in them.
導電性ペーストから電極を形成する際のAl、Ga、In又はTlを含む化合物の作用は不明であるが、以下のように考えられる。電極の形成においては、導電性ペーストを基板上に塗布・乾燥させた後、一般に、600〜800℃の焼成温度でイン−アウトが数分間という短時間の焼成を行う。このような温度と時間では、N型半導体基板のシリコンとIII族元素の置換が生ずるとは考え難い。その一方で、これらの化合物が還元された金属は、比較的低い融点を有するため、焼成工程で、還元された金属が融解した状態で分散して、導体/電極界面に存在し良好な接触の形成に寄与すると考えられる。 The action of the compound containing Al, Ga, In, or Tl when forming an electrode from the conductive paste is unknown, but is considered as follows. In forming the electrode, after applying and drying the conductive paste on the substrate, generally, baking is performed for a short time of several minutes at a baking temperature of 600 to 800 ° C. At such temperature and time, it is unlikely that substitution of silicon and group III elements in the N-type semiconductor substrate occurs. On the other hand, since the reduced metal of these compounds has a relatively low melting point, the reduced metal is dispersed in a molten state in the firing step, and is present at the conductor / electrode interface and has good contact. It is thought that it contributes to formation.
(5)金属酸化物
本発明の導電性ペーストには、酸化亜鉛、酸化チタン、酸化スズ、酸化銅又は酸化ニッケルを併用すると、高いFFを得る上で効果的である。これら特定の金属酸化物は、単独でも、2種以上を併用してもよい。
(5) Metal oxide When the conductive paste of the present invention is used in combination with zinc oxide, titanium oxide, tin oxide, copper oxide or nickel oxide, it is effective in obtaining a high FF. These specific metal oxides may be used alone or in combination of two or more.
これら特定の金属酸化物は、導電性ペーストの焼成過程で導電性粒子の過度な焼結を防ぐと同時に、ガラスフリットに由来する液化したガラスの広がりを抑制し、導電性粒子が半導体表面と接触する場を作ることに寄与し、さらには有機バインダ由来のCO等による還元性雰囲気で還元されて半導体化しうることも良好な接触を得るのに役立っていると考えられる。これら特定の金属酸化物のうち、酸化亜鉛、酸化チタン、酸化スズが好ましく、具体的には、ZnO、TiO2、SnO2である。 These specific metal oxides prevent excessive sintering of the conductive particles during the firing process of the conductive paste and at the same time suppress the spread of the liquefied glass derived from the glass frit, so that the conductive particles are in contact with the semiconductor surface. It is considered that it is useful for obtaining good contact because it contributes to the creation of a field to be formed and can be reduced to a semiconductor by reducing in a reducing atmosphere such as CO derived from an organic binder. Of these specific metal oxides, zinc oxide, titanium oxide, and tin oxide are preferable, and specifically ZnO, TiO 2 , and SnO 2 .
特定の金属酸化物は、通常、常温で固体であり、形状・平均粒子寸法は特に限定されない。形状としては、球形、不定形等が挙げられる。平均粒子寸法としては、分散性等の点から0.05〜1μmのものが好ましい。 The specific metal oxide is usually solid at room temperature, and the shape and average particle size are not particularly limited. Examples of the shape include a spherical shape and an indefinite shape. The average particle size is preferably 0.05 to 1 μm from the viewpoint of dispersibility.
本発明の導電性ペーストには、本発明の効果を損なわない範囲で、分散剤、可塑剤等の任意成分を配合してもよい。 You may mix | blend arbitrary components, such as a dispersing agent and a plasticizer, with the electrically conductive paste of this invention in the range which does not impair the effect of this invention.
本発明の導電性ペーストにおいては、十分な接着強度を確保し、かつ接触抵抗の増加を抑制する点から、ガラスフリットは、導電性粒子100重量部に対して、0.5〜10重量部であることが好ましく、より好ましくは1〜5重量部である。この範囲であれば、良好な接着強度と低接触抵抗値を得ることができる。 In the conductive paste of the present invention, the glass frit is 0.5 to 10 parts by weight with respect to 100 parts by weight of the conductive particles from the viewpoint of securing sufficient adhesive strength and suppressing increase in contact resistance. It is preferable that it is 1 to 5 parts by weight. Within this range, good adhesive strength and low contact resistance can be obtained.
また、Al、Ga、In又はTlを含む化合物は、導電性粒子100重量部に対して、0.001〜10重量部であることが好ましく、より好ましくは0.02〜5重量部である。この範囲であると、配合の効果が十分得られやすい。 Moreover, it is preferable that the compound containing Al, Ga, In, or Tl is 0.001-10 weight part with respect to 100 weight part of electroconductive particles, More preferably, it is 0.02-5 weight part. If it is within this range, the effect of blending can be easily obtained.
さらに、特定の金属酸化物を配合する場合、特定の金属酸化物は、導電性粒子100重量部に対して、0.5〜15重量部であることが好ましく、より好ましくは2〜10重量部である。この範囲であると、配合の効果が十分得られやすい。なお、特定の金属酸化物を使用する場合、Al、Ga、In又はTlの化合物は、上記配合範囲の下限の近くでも(例えば、導電性粒子100重量部に対して0.1重量部未満、例えば0.001〜0.08重量部)、十分な効果を発揮しうる。 Furthermore, when mix | blending a specific metal oxide, it is preferable that a specific metal oxide is 0.5-15 weight part with respect to 100 weight part of electroconductive particles, More preferably, 2-10 weight part It is. If it is within this range, the effect of blending can be easily obtained. In addition, when using a specific metal oxide, the compound of Al, Ga, In, or Tl is near the lower limit of the above blending range (for example, less than 0.1 parts by weight with respect to 100 parts by weight of conductive particles, For example, 0.001 to 0.08 parts by weight) can exhibit a sufficient effect.
なお、有機バインダ及び溶剤は、導電性ペーストの塗布・印刷法に応じて、適切な粘度となるよう、適宜、量を選択することができる。 The amount of the organic binder and the solvent can be appropriately selected so as to have an appropriate viscosity according to the method for applying and printing the conductive paste.
本発明の導電性ペーストの製造方法は、特に限定されず、有機バインダ、溶剤、導電性粒子、ガラスフリット、Al、Ga、In又はTlを含む化合物、場合により金属酸化物、その他の任意成分を、まず、プラネタリーミキサー等で混練りし、次に3本ロール(金属又はセラミック製)等で分散を行うことにより調製することができる。 The method for producing the conductive paste of the present invention is not particularly limited, and an organic binder, a solvent, conductive particles, a glass frit, a compound containing Al, Ga, In, or Tl, optionally a metal oxide, and other optional components. First, it can be prepared by kneading with a planetary mixer or the like and then dispersing with a three roll (made of metal or ceramic).
本発明の導電性ペーストは、太陽電池用電極の製造に使用することができ、N型半導体に対し良好な接触を得ることができるため、N型半導体(例えば、N型拡散層)上の電極を形成するために有用である。 Since the conductive paste of the present invention can be used for manufacturing an electrode for a solar cell and can obtain good contact with an N-type semiconductor, the electrode on the N-type semiconductor (for example, an N-type diffusion layer). Is useful for forming.
太陽電池用電極の製造及び太陽電池の製造方法は、特に限定されない。図1を用いて、一例を説明する。 The production of the solar cell electrode and the production method of the solar cell are not particularly limited. An example will be described with reference to FIG.
P型多結晶シリコン基板4の表面に、場合によりテクスチャを形成し、その後、P(リン)等を900℃で熱拡散させて、N型拡散層3を形成する。次いで、窒化ケイ素薄膜、酸化チタン等の反射防止膜2をプラズマCVD法等によって50〜100nmの膜厚で形成する。光入射側電極として、本発明の導電性ペーストを反射防止膜2上にスクリーン印刷し、150℃程度で溶剤を蒸発させ乾燥させる。次に裏面側電極として、場合により、アルミニウム電極用ペーストを、スクリーン印刷で、P型多結晶シリコン基板4の裏面に、印刷し、乾燥させる。次いで焼成して、光入射側電極1及び裏面電極5を備えた太陽電池セルを得る。 A texture is optionally formed on the surface of the P-type polycrystalline silicon substrate 4, and then P (phosphorus) or the like is thermally diffused at 900 ° C. to form the N-type diffusion layer 3. Next, an antireflection film 2 such as a silicon nitride thin film or titanium oxide is formed to a thickness of 50 to 100 nm by a plasma CVD method or the like. As the light incident side electrode, the conductive paste of the present invention is screen-printed on the antireflection film 2, and the solvent is evaporated at about 150 ° C. and dried. Next, as the back surface side electrode, an aluminum electrode paste is optionally printed on the back surface of the P-type polycrystalline silicon substrate 4 by screen printing and dried. Next, baking is performed to obtain a solar battery cell including the light incident side electrode 1 and the back surface electrode 5.
実施例における太陽電池は以下のようにして製造した。B(ボロン)をドープしたP型多結晶シリコン基板(基板厚み200μm)の表面に、ウエットエッチングによってテクスチャを形成した。その後、P(リン)を熱拡散させて、N型拡散層(厚み0.3μm)を形成した。次いで、プラズマCVD法によって、シランガスとアンモニアガスから窒化ケイ素薄膜(厚み約60nm)からなる反射防止膜を形成した。得られた反射防止膜付き基板を、15mmx15mmに切断して使用した。 The solar cell in the examples was manufactured as follows. A texture was formed by wet etching on the surface of a P-type polycrystalline silicon substrate (substrate thickness 200 μm) doped with B (boron). Thereafter, P (phosphorus) was thermally diffused to form an N-type diffusion layer (thickness 0.3 μm). Next, an antireflection film comprising a silicon nitride thin film (thickness: about 60 nm) was formed from silane gas and ammonia gas by plasma CVD. The obtained substrate with antireflection film was cut into 15 mm × 15 mm for use.
下記表記載の成分(重量部表示)を、プラネタリーミキサーと3本ロールで混合することにより調製したペーストを、スクリーン印刷で、反射防止膜上に、膜厚が約20μmになるように、バス電極とフィンガー電極からなるパターンで印刷し、150℃で約1分間乾燥した。 A paste prepared by mixing the components shown in the table below (parts by weight) with a planetary mixer and three rolls is screen-printed on the antireflection film so that the film thickness is about 20 μm. It printed with the pattern which consists of an electrode and a finger electrode, and dried at 150 degreeC for about 1 minute.
次に、アルミニウム電極用ペーストを、スクリーン印刷で、P型多結晶シリコン基板1の裏面に、膜厚が約20μmになるように印刷し、150℃で約1分間乾燥した。 Next, the aluminum electrode paste was printed on the back surface of the P-type polycrystalline silicon substrate 1 by screen printing so that the film thickness was about 20 μm, and dried at 150 ° C. for about 1 minute.
その後、両面のペーストを印刷・乾燥させた基板を、ピーク温度725℃、イン−アウト2分間で焼成して、光入射側電極及び裏面電極を備えた太陽電池セルを得た。 Thereafter, the substrate on which the paste on both sides was printed and dried was baked at a peak temperature of 725 ° C. for 2 minutes in-out to obtain a solar battery cell provided with a light incident side electrode and a back electrode.
太陽電池セルの電流−電圧特性を、ソーラーシミュレータ光(AM1.5、エネルギー密度100mW/cm2)のもとで測定し、測定結果から、FFを算出した。 The current-voltage characteristics of the solar battery cells were measured under solar simulator light (AM1.5, energy density 100 mW / cm 2 ), and FF was calculated from the measurement results.
各導電性ペーストの組成は、下記表1〜3のとおりである。FFの値をあわせて示す。実施例は、いずれも、Al、Ga、In又はTlを含む化合物を含有しない比較例に比べて、良好なFFを示した。 The composition of each conductive paste is as shown in Tables 1 to 3 below. The FF value is also shown. The examples all showed better FF than the comparative examples not containing a compound containing Al, Ga, In or Tl.
1 光入射側電極
2 反射防止膜
3 N型拡散層
4 P型シリコン基板
5 裏面電極
DESCRIPTION OF SYMBOLS 1 Light incident side electrode 2 Antireflection film 3 N type diffused layer 4 P type silicon substrate 5 Back surface electrode
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