TWI807034B - Manufacturing method of crystalline solar cell unit - Google Patents
Manufacturing method of crystalline solar cell unit Download PDFInfo
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- TWI807034B TWI807034B TW108118600A TW108118600A TWI807034B TW I807034 B TWI807034 B TW I807034B TW 108118600 A TW108118600 A TW 108118600A TW 108118600 A TW108118600 A TW 108118600A TW I807034 B TWI807034 B TW I807034B
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- passivation film
- aluminum
- solar cell
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- paste composition
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000002161 passivation Methods 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 61
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010304 firing Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 54
- 229910052782 aluminium Inorganic materials 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 98
- 238000007650 screen-printing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000010248 power generation Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 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
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- 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 at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本發明提供一種在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元之製造方法，該製造方法是若為前述單面之情況則在該鈍化膜以接近開口寬度之大小形成一種以上的電極，若為前述兩面之情況則在單方或兩方的鈍化膜以接近開口寬度之大小形成一種以上的電極。 本發明提供一種在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元之製造方法，該製造方法是依序具備下述步驟︰ (1)步驟1，前述單面具有鈍化膜之情況下，該鈍化膜是具有1或2個以上開口之鈍化膜A；前述兩面具有鈍化膜之情況下，則該鈍化膜的單方或兩方是具有1或2個以上開口之鈍化膜A，在覆蓋前述開口之區域形成以電極形成用糊劑組成物構成之塗膜， (2)步驟2，將前述矽基板及前述塗膜進行燒成處理，及 (3)步驟3，至少留下以填埋前述開口之凹部分之態樣所形成之燒成物，並將以除此以外之態樣所形成之燒成物的一部分或全部除去。The present invention provides a method for manufacturing a crystalline solar cell unit with a passivation film on one or both sides of a silicon substrate. In the manufacturing method, if it is the case of one side, one or more electrodes are formed on the passivation film with a size close to the width of the opening; The present invention provides a method for manufacturing a crystalline solar cell unit with a passivation film on one or both sides of a silicon substrate. The manufacturing method includes the following steps in sequence: (1) In step 1, in the case of a passivation film on one side, the passivation film is a passivation film A having one or more openings; in the case of both sides of the passivation film, one or both sides of the passivation film is a passivation film A having one or more openings, and a coating film composed of a paste composition for electrode formation is formed in the area covering the opening, (2) Step 2, firing the aforementioned silicon substrate and the aforementioned coating film, and (3) In step 3, at least the fired product formed to fill the concave portion of the opening is left, and part or all of the fired product formed in other forms is removed.
Description
發明領域field of invention
本發明係有關於一種在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元之製造方法。The invention relates to a manufacturing method of a crystalline solar battery unit with a passivation film on one or both sides of a silicon substrate.
發明背景Background of the invention
近年來，作為高轉換效率的結晶系太陽電池單元，對於矽太陽電池單元之兩面具有絕緣膜(鈍化膜)之結構的電池單元有大規模地研究開發。具體而言，已知有使用了p型矽基板並在兩面形成有鈍化膜與電極之PERC(passivated emitter and rear cell)型結構之電池單元、以及使用了n型矽基板並在兩面形成有鈍化膜與電極之PERT(passivated emitter and rear totally diffused)型結構之電池單元。In recent years, as a crystalline solar cell with high conversion efficiency, there has been extensive research and development of a silicon solar cell with an insulating film (passivation film) on both sides. Specifically, there are known PERC (passivated emitter and rear cell) structure battery cells using a p-type silicon substrate with passivation films and electrodes formed on both sides, and PERT (passivated emitter and rear totally diffused) structure battery cells using an n-type silicon substrate with passivation films and electrodes formed on both surfaces.
又，關於PERC型、PERT型電池單元，已知有在鈍化膜與矽基板之間形成氧化薄膜與矽薄膜使得鈍化效果提高之鈍化接觸型電池單元，以及將該等PERC型、PERT型、鈍化接觸型的電池單元之表面(外表的面)電極集約於電池單元背面的背面接觸型電池單元等。Also, with regard to PERC type and PERT type battery cells, there are known passivation contact type battery cells in which an oxide film and a silicon thin film are formed between a passivation film and a silicon substrate to improve the passivation effect, and a back contact type battery cell in which the surface (outer surface) electrodes of these PERC type, PERT type, and passivation contact type battery cells are concentrated on the back of the battery cell.
此外，在PERC型結構之電池單元當中，將背面鋁電極印刷成直線狀，藉此讓太陽光也能從背面入射，使特性提昇之結構，此種兩面受光型太陽電池單元之開發也正在進行(非專利文獻1，Fig.4、Fig.7等)。In addition, in PERC-type battery cells, the aluminum electrodes on the back are printed in a straight line to allow sunlight to enter from the back and improve the structure. The development of this type of double-sided light-receiving solar cell is also ongoing (Non-Patent Document 1, Fig.4, Fig.7, etc.).
兩面受光型之太陽電池藉由減少背面鋁電極之面積，能使入射光量增加。然而，以往使用用於形成背面電極之含鋁糊劑組成物(糊劑組成物)並以網版印刷之方式形成細線是困難的，一般來說用網版印刷所能夠形成之細線是以寬度至200μm左右為其界限。亦即，以往欲形成由寬度未滿200μm之細線構成的直線狀背面電極是困難的。 先行技術文獻 非專利文獻Double-side light-receiving solar cells can increase the amount of incident light by reducing the area of the aluminum electrode on the back. However, conventionally, it has been difficult to form fine lines by screen printing using an aluminum-containing paste composition (paste composition) for forming the back electrode. Generally, the fine lines that can be formed by screen printing are limited to a width of about 200 μm. That is, conventionally, it has been difficult to form a linear back electrode composed of thin lines with a width of less than 200 μm. Prior art literature non-patent literature
[非專利文獻1] 「Understanding the rear-side layout of p-dopede bifacial PERC solar cells with simulation driven experiment」, 7th International Conference on Silicon Photovoltaics, SiliconPV 2017, Energy procedia 124 (2017) 225-234[Non-Patent Document 1] "Understanding the rear-side layout of p-dopede bifacial PERC solar cells with simulation driven experiment", 7th International Conference on Silicon Photovoltaics, SiliconPV 2017, Energy procedia 124 (2017) 225-234
發明概要 發明欲解決之課題Summary of the invention The problem to be solved by the invention
如上述使用用於形成電極之含鋁糊劑組成物(糊劑組成物)形成電極之情況，例如以PERC型結構之電池單元來說，是在矽基板之背面所形成的背面鈍化膜以雷射等形成1或2個以上的開口，並在覆蓋該開口之區域將含鋁糊劑組成物進行印刷、燒成以形成背面鋁電極。又，以填埋了開口之態樣存在的糊劑組成物會在燒成時與矽基板反應而形成電場層(鋁-矽(Al-Si))合金層、p+ 層等)並帶來BSF(back surface field，背電場)效果。For example, in the case of using the aluminum-containing paste composition (paste composition) used to form the electrode to form the electrode, for example, in the case of a battery cell with a PERC structure, one or two or more openings are formed on the back passivation film formed on the back surface of the silicon substrate by laser, and the aluminum-containing paste composition is printed and fired on the area covering the opening to form the back aluminum electrode. In addition, the paste composition existing in the state of filling the opening will react with the silicon substrate during firing to form an electric field layer (aluminum-silicon (Al-Si) alloy layer, p + layer, etc.) and bring about BSF (back surface field, back electric field) effect.
在此，可以採用藉由僅對於覆蓋開口之一部分區域將糊劑組成物進行印刷，使光能從線狀之背面鋁電極彼此之間入射之兩面受光型。此外，因為從背面入射的光量是依據背面鋁電極之面積而定，故希望將背面鋁電極形成為與鈍化膜之開口的寬度相近的尺寸。Here, a double-side light-receiving type in which light can be incident from between the linear back aluminum electrodes by printing the paste composition only on a part of the area covering the opening can be used. In addition, since the amount of light incident from the rear surface depends on the area of the rear aluminum electrode, it is desirable to form the rear aluminum electrode to a size close to the width of the opening of the passivation film.
然而，若使用將糊劑組成物進行網版印刷之方法，會形成相對於開口寬度為數倍寬度之背面鋁電極，因此無法有效率地利用由背面入射的光。However, if the method of screen printing the paste composition is used, a rear aluminum electrode having a width several times larger than the opening width will be formed, so that light incident from the rear cannot be efficiently utilized.
據此，本發明為求改善上述習知技術之問題而完成，是以提供一種在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元之製造方法為目的，該製造方法是在前述單面之情況下會在該鈍化膜；在前述兩面之情況下會在單方或兩方之鈍化膜形成尺寸與開口之寬度相近之一種以上的電極之製造方法。藉由形成尺寸與開口之寬度相近之電極，能獲得更寬廣的受光面積讓入射光更有效利用，能提昇發電特性。 用以解決課題之手段Accordingly, the present invention is completed in order to improve the problems of the above-mentioned prior art, and is aimed at providing a method for manufacturing a crystalline solar cell unit with a passivation film on one or both sides of a silicon substrate. By forming an electrode whose size is similar to the width of the opening, a wider light-receiving area can be obtained to make more effective use of incident light and improve power generation characteristics. means to solve problems
本發明者為達成上述目的，反覆進行深入研究之結果，發現藉由具有特定步驟之結晶系太陽電池單元之製造方法能達成上述目的，以至於完成本發明。In order to achieve the above object, the present inventors conducted intensive research and found that the above object can be achieved by a method of manufacturing a crystalline solar cell unit having specific steps, leading to the completion of the present invention.
亦即，本發明系有關於下述之結晶系太陽電池單元之製造方法。 1.一種結晶系太陽電池單元之製造方法，是製造在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元，該製造方法之特徵在於依序具備下述步驟︰ (1)步驟1，前述單面具有鈍化膜之情況下，該鈍化膜是具有1或2個以上開口之鈍化膜A；前述兩面具有鈍化膜之情況下，則該鈍化膜的單方或兩方是具有1或2個以上開口之鈍化膜A，在覆蓋前述鈍化膜A之前述開口之區域形成以電極形成用糊劑組成物構成之塗膜， (2)步驟2，將前述矽基板及前述塗膜進行燒成處理，及 (3)步驟3，至少留下以填埋前述開口之凹部分之態樣所形成之燒成物，並將以除此以外之態樣所形成之燒成物的一部分或全部除去。 2.如上述項1之結晶系太陽電池單元之製造方法，其中前述開口為平均每1個寬度20~100μm之直線狀。 3.如上述項1或2之結晶系太陽電池單元之製造方法，其中前述電極形成用糊劑組成物是含鋁糊劑組成物，且相對於鋁粉末100質量份，含有玻璃粉末0.1~15質量份。 4.如上述項3之結晶系太陽電池單元之製造方法，其中前述含鋁糊劑組成物含有選自於由下述1)至3)所構成群組中之至少一種：1)玻璃粉末，含有選自於由氧化鉍、氧化鉛、氧化鋅、氧化矽及氧化鋁所構成群組中之至少一種金屬氧化物；2)金屬氧化物；及3)金屬氫氧化物。 發明效果That is, the present invention relates to a method for producing the following crystalline solar cell. 1. A method for manufacturing a crystalline solar cell unit, which is to manufacture a crystalline solar cell unit with a passivation film on one or both sides of a silicon substrate. The manufacturing method is characterized in that the following steps are sequentially included: (1) In step 1, in the case of the passivation film on one side, the passivation film is a passivation film A having one or more openings; in the case of both sides of the passivation film, one or both sides of the passivation film is a passivation film A having one or more openings, and a coating film made of a paste composition for electrode formation is formed in the area covering the opening of the passivation film A, (2) Step 2, firing the aforementioned silicon substrate and the aforementioned coating film, and (3) In step 3, at least the fired product formed to fill the concave portion of the opening is left, and part or all of the fired product formed in other forms is removed. 2. The method of manufacturing a crystalline solar cell according to item 1 above, wherein the openings are straight lines with an average width of 20 to 100 μm. 3. The method for producing a crystalline solar cell according to item 1 or 2 above, wherein the paste composition for electrode formation is an aluminum-containing paste composition and contains 0.1 to 15 parts by mass of glass powder relative to 100 parts by mass of aluminum powder. 4. The method for manufacturing a crystalline solar cell unit according to item 3 above, wherein the aforementioned aluminum-containing paste composition contains at least one selected from the group consisting of the following 1) to 3): 1) glass powder containing at least one metal oxide selected from the group consisting of bismuth oxide, lead oxide, zinc oxide, silicon oxide, and aluminum oxide; 2) metal oxide; and 3) metal hydroxide. Invention effect
依據本發明之結晶系太陽電池單元之製造方法，在鈍化膜中具有1或2個以上開口之鈍化膜A在覆蓋前述開口之區域塗布電極形成用糊劑組成物，針對該電極形成用糊劑組成物之塗膜之燒成物中至少留下以填埋前述開口之凹部分之態樣所形成之燒成物，並將以除此以外之態樣所形成之燒成物的一部分或全部除去，藉此，能以與開口寬度相近之尺寸大小形成一種以上的電極。藉由形成尺寸與開口寬度相近之電極，能確保更寬廣的受光面積而更有效利用入射光，使發電特性提升。According to the manufacturing method of the solar battery unit of the invention, the passivation film A with more than 1 or more opening in the passivation film A. The coating electrode of the aforementioned opening area is used to form a paste composition. At least the burning material formed by the coating of the coating film formed by the electrode formed by the coating film of the paste. In addition, a part or or all of the burning objects formed by the state of the state can form a electrode of more than or more with the size of the opening width similar to the opening width. By forming electrodes whose size is similar to the width of the opening, a wider light-receiving area can be ensured to make more effective use of incident light and improve power generation characteristics.
用以實施發明之形態form for carrying out the invention
以下對於本發明之結晶系太陽電池單元之製造方法(亦稱「本發明之製造方法」)進行更詳細之說明。The manufacturing method of the crystalline solar cell unit of the present invention (also referred to as "the manufacturing method of the present invention") will be described in more detail below.
本發明之製造方法是製造在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元之方法，其特徵在於依序具備︰ (1)步驟1，前述單面具有鈍化膜之情況下，該鈍化膜是具有1或2個以上開口之鈍化膜A；前述兩面具有鈍化膜之情況下，則該鈍化膜的單方或兩方是具有1或2個以上開口之鈍化膜A，在覆蓋前述鈍化膜A之前述開口之區域形成以電極形成用糊劑組成物構成之塗膜， (2)步驟2，將前述矽基板及前述塗膜進行燒成處理，及 (3)步驟3，至少留下以填埋前述開口之凹部分之態樣所形成之燒成物，並將以除此以外之態樣所形成之燒成物的一部分或全部除去。The manufacturing method of the present invention is a method of manufacturing a crystalline solar cell unit having a passivation film on one or both sides of a silicon substrate, and is characterized in that: (1) In step 1, in the case of the passivation film on one side, the passivation film is a passivation film A having one or more openings; in the case of both sides of the passivation film, one or both sides of the passivation film is a passivation film A having one or more openings, and a coating film made of a paste composition for electrode formation is formed in the area covering the opening of the passivation film A, (2) Step 2, firing the aforementioned silicon substrate and the aforementioned coating film, and (3) In step 3, at least the fired product formed to fill the concave portion of the opening is left, and part or all of the fired product formed in other forms is removed.
依據上述本發明之製造方法，將電極形成用糊劑組成物塗布在鈍化膜中具有1或2個以上開口之鈍化膜A之可覆蓋前述開口之區域，且該電極形成用糊劑組成物之塗膜之燒成物中至少留下以填埋前述開口之凹部分之態樣所形成之燒成物，並將以除此以外之態樣所形成之燒成物的一部分或全部除去，藉由具備此步驟，能以與開口寬度相近之尺寸形成一種以上的電極。藉由形成尺寸與開口寬度相近之電極，能確保更寬廣的受光面積，更有效利用入射光，使發電特性提升。According to the above-mentioned production method of the present invention, the paste composition for electrode formation is applied to the region of the passivation film A having one or more openings in the passivation film that can cover the openings, and the fired product of the coating film of the electrode-forming paste composition leaves at least the fired product that fills the concave portion of the opening, and part or all of the fired product that is formed in other forms is removed. By forming electrodes whose size is similar to the opening width, a wider light-receiving area can be ensured, the incident light can be used more effectively, and the power generation characteristics can be improved.
以下，將參照圖式並對於本發明之製造方法進行每個步驟的說明。Hereinafter, each step of the manufacturing method of the present invention will be described with reference to the drawings.
本發明之結晶系太陽電池單元之製造方法是在矽基板之單面或兩面具有鈍化膜之結晶系太陽電池單元之製造方法，前述單面具有鈍化膜之情況下，該鈍化膜是具有1或2個以上開口之鈍化膜A；前述兩面具有鈍化膜之情況下，則該鈍化膜的單方或兩方是具有1或2個以上開口之鈍化膜A。在此，不屬於鈍化膜A之鈍化膜就是指不具備開口的鈍化膜。The method for manufacturing a crystalline solar cell unit of the present invention is a method for manufacturing a crystalline solar cell unit with a passivation film on one or both sides of a silicon substrate. In the case of a passivation film on one side, the passivation film is a passivation film A having one or more openings; Here, the passivation film that does not belong to the passivation film A refers to a passivation film that does not have an opening.
矽基板之單面具有鈍化膜A之情況中，可舉例如鈍化膜A是背面鈍化膜，且是以尺寸與開口之寬度相近之方式形成背面電極(例如背面鋁電極)之態樣。又，矽基板之兩面具有鈍化膜A之情況中，可舉例如在背面鈍化膜以尺寸與開口之寬度相近之方式形成背面電極(例如背面鋁電極)，並且在表面(外表之面；以下同)鈍化膜以尺寸與開口之寬度相近之方式形成表面電極(例如銀電極、銅電極或鋁電極)之態樣。In the case where the passivation film A is provided on one side of the silicon substrate, for example, the passivation film A is a rear passivation film, and a rear electrode (such as a rear aluminum electrode) is formed in a size similar to the width of the opening. In addition, in the case where the passivation film A is provided on both sides of the silicon substrate, for example, a back electrode (such as a back aluminum electrode) is formed on the back passivation film in a size similar to the width of the opening, and a surface electrode (such as a silver electrode, a copper electrode, or an aluminum electrode) is formed on the surface (outer surface; the same below) in a passivation film with a size close to the width of the opening.
如此這般，本發明之製造方法所能適用的態樣可因應電極種類與設置電極之面而有多種多樣，即使是要在矽基板之表面及/或背面之任一者設置電極之情況，亦能在可覆蓋具有1或2個以上開口之鈍化膜A之前述開口之區域形成由電極形成用糊劑組成物(因應電極之種類，含鋁糊劑組成物、含銀糊劑組成物、含銅糊劑組成物等)構成之塗膜(後述步驟1)，再經過後述步驟2、3將燒成物進行加工而以與開口寬度相近之尺寸形成一種以上的電極。此外，若是矽基板的兩面(表面及背面)具有鈍化膜A之情況，對於表面鈍化膜A之後述步驟1(還有後述步驟2、3)以及對於背面鈍化膜A之後述步驟1(還有後述步驟2、3)可以兩面同時進行，亦可不同時而是表面背面分別進行。以下特別對於PERC型結構之電池單元，於表面背面的鈍化膜當中在背面鈍化膜A之開口部分，以尺寸與開口之寬度相近之方式形成背面鋁電極之態樣(亦稱「本態樣」)作為例示並說明本發明。In this way, the applicable aspect of the manufacturing method of the present invention can be varied depending on the type of electrode and the surface on which the electrode is provided. Even if the electrode is to be provided on either the surface and/or the back surface of the silicon substrate, a coating film composed of a paste composition for electrode formation (aluminum-containing paste composition, silver-containing paste composition, copper-containing paste composition, etc.) The fired product is processed through steps 2 and 3 described later to form more than one electrode with a size close to the width of the opening. In addition, if there are passivation films A on both sides (surface and back) of the silicon substrate, step 1 (also steps 2 and 3 described later) after the passivation film A on the surface and step 1 (steps 2 and 3 described later) after the passivation film A on the back surface can be performed on both sides at the same time, or not at the same time, but the front and back sides can be performed separately. In the following, especially for battery cells with PERC type structure, in the passivation film on the front and back of the opening part of the back passivation film A, the form of forming the back aluminum electrode in a manner similar to the width of the opening (also referred to as "this form") is used as an example and description of the present invention.
步驟1(糊劑組成物塗布於覆蓋開口之區域) 步驟1是對於覆蓋前述鈍化膜A之前述開口之區域形成由電極形成用糊劑組成物構成之塗膜。Step 1 (paste composition is applied to the area covering the opening) Step 1 is to form a coating film made of a paste composition for electrode formation on a region covering the opening of the passivation film A.
作為矽基板，可使用例如p型矽基板、n型矽基板、該等組合而成之矽基板等。以下對於本態樣將參照使用了p型矽基板(p-type Si)1之圖3~5並進行說明。As the silicon substrate, for example, a p-type silicon substrate, an n-type silicon substrate, or a combination thereof can be used. Hereinafter, this aspect will be described with reference to FIGS. 3 to 5 using a p-type silicon substrate (p-type Si) 1 .
矽基板1(p型矽基板)之厚度並無限定，以180~250μm為合適。The thickness of the silicon substrate 1 (p-type silicon substrate) is not limited, and is preferably 180-250 μm.
矽基板1之一方的面(外表之面)可以使用例如具備有厚度0.3~0.6μm之n型矽層3、由氮化矽膜構成並作為防反射膜之表面鈍化膜2、以及作為柵電極之銀(Ag)電極4之物。One surface (outer surface) of the silicon substrate 1 can be used, for example, having an n-type silicon layer 3 with a thickness of 0.3 to 0.6 μm, a surface passivation film 2 as an antireflection film composed of a silicon nitride film, and a silver (Ag) electrode 4 as a gate electrode.
在與具備有銀電極4之面呈相反之側(背面)，可使用例如具備有作為氧化鋁膜及氮化矽膜之積層膜之背面鈍化膜5者。On the side (rear surface) opposite to the surface provided with the silver electrode 4, for example, a rear passivation film 5 provided with a laminated film of an aluminum oxide film and a silicon nitride film can be used.
背面鈍化膜5設置有1或2個以上的開口6。亦即，本態樣中背面鈍化膜5就是鈍化膜A。開口6是用於與矽基板1接觸之開口，可藉由雷射照射、蝕刻等而形成。開口6的型態不受限定，可適宜地採用直線狀、曲線狀、虛線狀、點狀等。又，形成複數個開口6時不限定其搭配排列，可以採用規則性的搭配排列或隨機性的搭配排列。The rear passivation film 5 is provided with one or more than two openings 6 . That is, the rear passivation film 5 is the passivation film A in this embodiment. The opening 6 is an opening for contacting the silicon substrate 1 and can be formed by laser irradiation, etching, and the like. The shape of the opening 6 is not limited, and can be suitably used in a straight line, a curved line, a dotted line, or a dot. Also, when forming a plurality of openings 6 , the matching arrangement is not limited, and a regular matching arrangement or a random matching arrangement can be adopted.
本發明中，開口6是以每1個都是寬度20~100μm之直線狀為佳，從控制電極圖案之觀點來看，開口6是以矽基板1之俯視視角下呈現直橫且規則性地形成為佳。In the present invention, the openings 6 are preferably straight lines with a width of 20-100 μm each. From the viewpoint of the control electrode pattern, the openings 6 are preferably formed vertically, horizontally and regularly from the top view of the silicon substrate 1 .
糊劑組成物只要是用於電極形成之糊劑組成物即可，本態樣中是用於形成背面鋁電極之含鋁糊劑組成物，更詳細地說，是將鋁粉末分散於有機溶劑之糊。The paste composition may be any paste composition as long as it is used for electrode formation. In this embodiment, it is an aluminum-containing paste composition for forming a rear aluminum electrode, and more specifically, it is a paste in which aluminum powder is dispersed in an organic solvent.
鋁粉末之組成並無特別限制，可使用純度99wt%以上之純鋁，亦可使用合適的鋁合金粉末。The composition of the aluminum powder is not particularly limited, and pure aluminum with a purity above 99 wt % can be used, and suitable aluminum alloy powder can also be used.
鋁粉末的型態可為球狀、橢圓體等但並無特別限制。其中，球狀者的印刷性良好，且與矽有良好的反應，故屬較佳。鋁粉末之尺寸為平均粒子徑1μm以上20μm以下時，從印刷性、反應性等之觀點來看，係屬較佳。而1μm以上6μm以下更是適合。The shape of the aluminum powder can be spherical, ellipsoid, etc. but not particularly limited. Among them, the spherical one has good printability and good reaction with silicon, so it is better. When the size of the aluminum powder is an average particle diameter of 1 μm or more and 20 μm or less, it is preferable from the viewpoints of printability and reactivity. More than 1 μm and less than 6 μm are more suitable.
糊劑組成物相對於鋁粉末100重量份，是以含有玻璃粉末0.1~15重量份為佳。The paste composition preferably contains 0.1 to 15 parts by weight of glass powder relative to 100 parts by weight of aluminum powder.
玻璃粉末之組成並無特別限定，可使用含有選自於由B2 O3 、Bi2 O3 、ZnO、SiO2 、Al2 O3 、BaO、CaO、SrO、V2 O5 、Sb2 O3 、WO3 、P2 O5 及TeO2 所構成之群中一種以上成分之玻璃粉末。該等之中，使用含有B2 O3 成分之玻璃粉末(鉍系玻璃粉末)時，因能提昇矽與鋁之反應性，故屬較佳。 The composition of the glass powder is not particularly limited, and glass powder containing one or more components selected from the group consisting of B2O3 , Bi2O3 , ZnO, SiO2, Al2O3 , BaO, CaO , SrO , V2O5 , Sb2O3 , WO3 , P2O5 , and TeO2 can be used. Among them, the use of glass powder (bismuth-based glass powder) containing B 2 O 3 is preferable because the reactivity between silicon and aluminum can be increased.
本發明中，因為要在後述步驟3當中去除糊劑組成物的燒成物之一部分，為了提高除去性，糊劑組成物較佳為含有能抑制燒結之玻璃粉末、氧化物、氫氧化物等。In the present invention, since part of the burnt product of the paste composition is to be removed in step 3 described later, the paste composition preferably contains glass powder, oxide, hydroxide, etc. that can suppress sintering in order to improve removability.
關於上述抑制燒結之玻璃粉末，可使用含有60重量%的氧化鉍、氧化鉛、氧化鋅、氧化矽及氧化鋁當中任一氧化金屬之玻璃粉末。關於上述抑制燒結之氧化物，可舉出氧化矽、氧化鋁、氧化鈣、氧化鉍、氧化鉛、氧化鋅、氧化鍺等。上述抑制燒結之氫氧化物可舉出氫氧化鋁、氫氧化鋅等。As the glass powder for suppressing sintering, a glass powder containing 60% by weight of any metal oxide among bismuth oxide, lead oxide, zinc oxide, silicon oxide, and aluminum oxide can be used. Examples of the above-mentioned oxides for inhibiting sintering include silicon oxide, aluminum oxide, calcium oxide, bismuth oxide, lead oxide, zinc oxide, and germanium oxide. Aluminum hydroxide, zinc hydroxide, etc. are mentioned as the said hydroxide which suppresses sintering.
糊劑組成物中，一般而言除了鋁粉末以外，還含有有機溶劑、樹脂、玻璃粉末等。該組成並不受限定，在糊劑組成物100質量%當中，可以設定為鋁粉末佔60重量%以上90重量%以下、有機溶劑佔2重量%以上20重量%以下、殘餘部分佔2重量%以上20重量%以下。Generally, the paste composition contains an organic solvent, resin, glass powder, etc. in addition to aluminum powder. The composition is not limited, and in 100% by mass of the paste composition, the aluminum powder accounts for 60% by weight to 90% by weight, the organic solvent accounts for 2% by weight to 20% by weight, and the remainder accounts for 2% by weight to 20% by weight.
有機溶劑並無特別限定，可使用例如二乙二醇單丁醚、松油醇等。The organic solvent is not particularly limited, and for example, diethylene glycol monobutyl ether, terpineol, or the like can be used.
步驟1當中，在覆蓋鈍化膜A之1或2個以上的開口之區域形成以糊劑組成物構成之塗膜，而塗布方法並不受限定，例如可使用網版印刷或點膠(dispensing)之方法。此時，糊劑組成物會以填埋(充填)開口之凹部分的態樣進行塗布，同時以從開口之端部起算1μm以上1000μm以下之範圍對於覆蓋鈍化膜A之區域進行塗布。此外，糊劑組成物之塗布膜厚(鈍化膜A上的塗布膜厚)是以10μm以上40μm以下為佳。塗布後會在常溫或加溫下進行乾燥。In step 1, a coating film made of a paste composition is formed on the area covering one or more openings of the passivation film A, and the coating method is not limited, for example, screen printing or dispensing can be used. At this time, the paste composition is applied so as to fill (fill) the concave portion of the opening, and at the same time, apply the paste composition to the region covering the passivation film A in the range of 1 μm to 1000 μm from the end of the opening. In addition, the coating film thickness (coating film thickness on the passivation film A) of the paste composition is preferably not less than 10 μm and not more than 40 μm. After coating, it will be dried at room temperature or under heating.
步驟2(燒成處理) 步驟2是對前述矽基板及前述塗膜進行燒成處理。Step 2 (firing treatment) Step 2 is to perform firing treatment on the aforementioned silicon substrate and the aforementioned coating film.
燒成處理可在大氣氣體環境或氮氣氣體環境下進行。燒成溫度是以500℃以上1000℃以下為佳，更以650℃以上850℃以下為佳。燒成時間可依據燒成溫度進行調整，可設為3秒以上300秒以下。The firing treatment can be performed in an atmospheric gas environment or a nitrogen gas environment. The firing temperature is preferably above 500°C and below 1000°C, more preferably above 650°C and below 850°C. The firing time can be adjusted according to the firing temperature, and can be set to not less than 3 seconds and not more than 300 seconds.
藉由燒成處理，在本態樣中開口之凹部分的糊劑組成物所含的鋁與矽基板接觸之部分會發生鋁與矽之反應，進而形成電場層(Al-Si合金層8、p+ 層9)，在開口的凹部分之外側會形成糊劑組成物之燒成物7(參照圖4)。接著，因為上述p+ 層9存在，能防止電子再結合，且提昇生成載體之收集效率，亦即能獲得BSF效果。In this embodiment, the aluminum contained in the paste composition in the concave portion of the opening is in contact with the silicon substrate through the firing process, and the aluminum and silicon react to form an electric field layer (Al-Si alloy layer 8, p + layer 9), and a fired product 7 of the paste composition is formed outside the concave portion of the opening (see FIG. 4 ). Then, because of the presence of the above-mentioned p + layer 9, electron recombination can be prevented, and the collection efficiency of generated carriers can be improved, that is, the BSF effect can be obtained.
步驟3(除去燒成物之一部分的處理) 步驟3是至少留下以填埋前述開口之凹部分之態樣所形成之燒成物，並將以除此以外之態樣所形成之燒成物的一部分或全部除去。Step 3 (treatment to remove a part of the burnt product) Step 3 is to leave at least the fired product formed to fill the concave portion of the opening, and remove part or all of the fired product formed in other aspects.
步驟3中，至少留下以填埋前述開口之凹部分之態樣所形成之燒成物(圖4之合金層8及p+ 層9)，並將以除此以外之態樣所形成之燒成物(在開口外部形成之糊劑組成物之燒成物︰圖4之燒成物7)的一部分或全部除去。In step 3, at least the fired product formed to fill the concave portion of the opening (alloy layer 8 and p + layer 9 in FIG. 4 ) is left, and part or all of the fired product formed in other forms (fired product of the paste composition formed outside the opening: fired product 7 in FIG. 4 ) is removed.
在除去燒成物7的一部分或全部之際，可利用酸蝕刻、研磨等。又，當糊劑組成物含有會抑制燒結之玻璃粉末、氧化物、氫氧化物等之情況下，不須研磨等而能使燒成物7之一部分或全部自然地剝離。本態樣中，為了最有效地利用從背面入射的光，將形成於開口外部之燒成物7全部除去即可，但即使除去至少一部分就能比習知更提高光的利用率，因此可適宜地設定除去之比例。When removing part or all of the fired product 7, acid etching, grinding, or the like can be used. Also, when the paste composition contains glass powder, oxides, hydroxides, etc. that inhibit sintering, part or all of the fired product 7 can be naturally peeled off without grinding or the like. In this aspect, in order to utilize the light incident from the back most effectively, it is sufficient to remove all the burnt objects 7 formed outside the opening, but even if at least a part of them is removed, the utilization efficiency of light can be improved more than conventional ones, so the ratio of removal can be appropriately set.
本態樣中，藉由經過上述步驟1~3(特別是步驟3)，能夠形成尺寸與鈍化膜之開口寬度實質上相同或近似的背面鋁電極，故能更有效利用從背面入射的光。In this aspect, by going through the above steps 1-3 (especially step 3), the rear aluminum electrode whose size is substantially the same or similar to the opening width of the passivation film can be formed, so that the light incident from the rear can be more effectively used.
又，本態樣中在所形成的背面鋁電極之上，藉由以周知之技術形成銀、銅、鎳等金屬鍍膜，能維持電極面積同時降低電極之電阻值。In addition, in this aspect, metal plating films such as silver, copper, and nickel are formed on the back aluminum electrode formed by known techniques, so that the electrode area can be maintained and the resistance value of the electrode can be reduced.
此外，本發明不限定於上述本態樣，於PERC型、PERT型、鈍化接觸型、背面接觸型之各種電池單元當中，在矽基板之表面及/或背面之鈍化膜A形成尺寸與開口之寬度相近之一種以上的電極時，能夠廣泛地適用。關於背面鋁電極係如同上述說明，然而關於其他種類的電極，在本發明領域內周知之電極、周知之電極形成用糊劑組成物都能適用本發明之製造方法並進行製作。 實施例In addition, the present invention is not limited to the above-mentioned present aspect, and can be widely applied in PERC type, PERT type, passivation contact type, and back contact type battery cells, when forming more than one type of electrode with a size similar to the width of the opening on the passivation film A on the surface and/or back surface of the silicon substrate. The rear aluminum electrode is as described above, but for other types of electrodes, well-known electrodes and well-known paste compositions for electrode formation in the field of the present invention can be applied to the production method of the present invention and produced. Example
以下例示實施例及比較例並具體說明本發明。然而，本發明並不受實施例所限定。Examples and comparative examples are shown below to specifically describe the present invention. However, this invention is not limited to an Example.
實施例1 相對於鋁粉末100質量份，加入鉍系玻璃粉末3質量份、及有機載體29質量份，於周知之混合機進行混合並製作出糊劑組成物。Example 1 3 parts by mass of bismuth-based glass powder and 29 parts by mass of organic vehicle were added to 100 parts by mass of aluminum powder, and mixed with a known mixer to prepare a paste composition.
晶片尺寸為邊長156mm正方形之PERC型太陽電池之背面鈍化膜(鈍化膜A)具有寬45μm之線狀的膜開口，於該太陽電池單元背面將糊劑組成物使用開口寬60μm寬之網版罩在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布，並在100℃下乾燥10分鐘，以及在700℃以上4秒以下進行燒成。燒成後藉由對太陽電池單元進行酸蝕刻而除去掉除了填埋開口部之態樣以外的糊劑組成物之燒成物，製作出太陽電池單元樣本。The back passivation film (passivation film A) of a PERC type solar cell with a wafer size of 156 mm in side length has a linear film opening with a width of 45 μm. On the back of the solar cell unit, the paste composition is applied by screen printing on the area covering the opening width of the back passivation film using a screen mask with an opening width of 60 μm, dried at 100° C. for 10 minutes, and fired at 700° C. for 4 seconds. After firing, the solar battery cell was acid-etched to remove the fired product except for the form filling the opening, and a solar battery cell sample was produced.
圖1(b)顯示實施例1製作之太陽電池單元樣本當中的背面鋁電極透過雷射顯微鏡之上方觀察像。又，圖2(b)顯示實施例1製作之太陽電池單元樣本當中的背面鋁電極透過SEM之剖面觀察像。FIG. 1( b ) shows the top observation image of the aluminum electrode on the back of the solar cell unit sample produced in Example 1 through a laser microscope. In addition, FIG. 2( b ) shows a cross-sectional observation image of the rear aluminum electrode of the solar cell unit sample produced in Example 1 through SEM.
實施例2 除了使用開口寬100μm寬之網版罩將糊劑組成物在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布以外，與實施例1同樣地進行並獲得太陽電池單元樣本。Example 2 A solar cell sample was obtained in the same manner as in Example 1, except that the paste composition was applied by screen printing to the area covering the opening width of the rear passivation film using a screen mask with an opening width of 100 μm.
實施例3 除了使用開口寬150μm寬之網版罩將糊劑組成物在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布以外，與實施例1同樣地進行並獲得太陽電池單元樣本。Example 3 A solar cell sample was obtained in the same manner as in Example 1, except that the paste composition was applied by screen printing on the area covering the opening width of the rear passivation film using a screen mask with an opening width of 150 μm.
比較例1 相對於鋁粉末100質量份，加入鉍系玻璃粉末3質量份、及有機載體29質量份，於周知之混合機進行混合並製作出糊劑組成物。Comparative example 1 3 parts by mass of bismuth-based glass powder and 29 parts by mass of organic vehicle were added to 100 parts by mass of aluminum powder, and mixed with a known mixer to prepare a paste composition.
晶片尺寸為邊長156mm正方形之PERC型太陽電池之背面鈍化膜(鈍化膜A)具有寬45μm之線狀的膜開口，於該太陽電池單元背面將糊劑組成物使用開口寬50μm寬之網版罩在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布，並在100℃下乾燥10分鐘，以及在700℃以上4秒以下進行燒成，製作出太陽電池單元樣本。The rear passivation film (passivation film A) of a PERC type solar cell with a wafer size of 156 mm side length has a linear film opening with a width of 45 μm. On the back of the solar cell unit, the paste composition is applied by screen printing on the area covering the opening width of the rear passivation film using a screen mask with an opening width of 50 μm, dried at 100°C for 10 minutes, and fired at 700°C for 4 seconds to produce a solar cell sample.
比較例2 除了使用開口寬60μm之網版罩將糊劑組成物在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布以外，與比較例1同樣地進行並獲得太陽電池單元樣本。Comparative example 2 A solar cell sample was obtained in the same manner as in Comparative Example 1, except that the paste composition was applied by screen printing on the area covering the opening width of the rear passivation film using a screen mask with an opening width of 60 μm.
圖1(a)顯示比較例2製作之太陽電池單元樣本當中的背面鋁電極透過雷射顯微鏡之上方觀察像。又，圖2(a)顯示比較例2製作之太陽電池單元樣本當中的背面鋁電極透過SEM(掃描型電子顯微鏡)之剖面觀察像。FIG. 1( a ) shows the top observation image of the aluminum electrode on the back of the solar cell unit sample produced in Comparative Example 2 through a laser microscope. In addition, FIG. 2( a ) shows a cross-sectional observation image of the back aluminum electrode of the solar cell sample produced in Comparative Example 2 through SEM (scanning electron microscope).
比較例3 除了使用開口寬100μm寬之網版罩將糊劑組成物在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布以外，與比較例1同樣地進行並獲得太陽電池單元樣本。Comparative example 3 A solar cell sample was obtained in the same manner as in Comparative Example 1, except that the paste composition was applied by screen printing on the area covering the opening width of the rear passivation film using a screen mask with an opening width of 100 μm.
比較例4 除了使用開口寬150μm寬之網版罩將糊劑組成物在覆蓋背面鈍化膜開口寬度之區域以網版印刷進行塗布以外，與比較例1同樣地進行並獲得太陽電池單元樣本。Comparative example 4 A solar cell sample was obtained in the same manner as in Comparative Example 1, except that the paste composition was applied by screen printing on the area covering the opening width of the rear passivation film using a screen mask with an opening width of 150 μm.
試驗例1 對於所獲得之太陽電池單元樣本之背面鋁電極使用雷射顯微鏡(KEYENCE社製)進行觀察，測定出線寬。又，於太陽光模擬器((股)WACOM電創社)製)光下，測定背面側之發電特性Isc。Test example 1 The back aluminum electrode of the obtained solar battery cell sample was observed using a laser microscope (manufactured by KEYENCE Corporation), and the line width was measured. Also, the power generation characteristic Isc on the back side was measured under light of a solar simulator (manufactured by Wacom Denso Co., Ltd.).
將已測定之電極寬與Isc特性之結果顯示於表1。The results of the measured electrode width and Isc characteristics are shown in Table 1.
[表1]
由表1結果可知，依據本發明之方法製造出的太陽電池單元樣本，可確認到電極寬變狹窄，且背面側之發電特性Isc提昇。From the results in Table 1, it can be seen that the electrode width of the solar cell sample manufactured according to the method of the present invention is narrowed, and the power generation characteristic Isc on the back side is improved.
以網版印刷塗布糊劑組成物時，若使用50μm寬的網版時會在印刷後之塗膜確認到有斷線，故以使用60μm以上寬度之網版為佳。若以習知方法進行電極形成，即使使用60μm寬的網版，所形成的電極仍然會變寬至130μm左右，故用習知方法難以形成60μm以下的電極。When applying the paste composition by screen printing, if a screen with a width of 50 μm is used, breaks will be confirmed in the coated film after printing, so it is better to use a screen with a width of 60 μm or more. If electrodes are formed by conventional methods, even if a 60 μm wide screen is used, the formed electrodes will still be widened to about 130 μm, so it is difficult to form electrodes below 60 μm by conventional methods.
關於包含有將除了填埋鈍化膜A之開口部的態樣以外之糊劑組成物的燒成物除去之步驟的樣本(實施例1~3)，不論網版印刷的線寬，結果最終的電極寬是60μm以下，故可使用60μm至數100μm之任意寬的網版寬度。Regarding the samples (Examples 1 to 3) including the step of removing the baked product of the paste composition except for the aspect of filling the opening of the passivation film A, the final electrode width was 60 μm or less regardless of the line width of the screen printing, so a screen width of any width from 60 μm to several 100 μm can be used.
1‧‧‧矽基板 2‧‧‧表面鈍化膜 3‧‧‧n型矽層(n+發射層) 4‧‧‧銀電極 5‧‧‧背面鈍化膜(鈍化膜A) 6‧‧‧雷射開口 7‧‧‧糊劑組成物之燒成物 8‧‧‧Al-Si合金層 9‧‧‧p+層1‧‧‧Silicon substrate 2‧‧‧Surface passivation film 3‧‧‧n-type silicon layer (n + emitter layer) 4‧‧‧Silver electrode 5‧‧‧Rear passivation film (passivation film A) 6‧‧‧Laser opening 7‧‧‧Fired product of paste composition 8‧‧‧Al-Si alloy layer 9‧‧‧p + layer
圖1(a)是比較例2所製作的太陽電池單元樣本當中，以雷射顯微鏡觀察背面鋁電極之上方觀察像。圖1(b)是實施例1所製作的太陽電池單元樣本當中，以雷射顯微鏡觀察背面鋁電極之上方觀察像。 圖2(a)是比較例2所製作的太陽電池單元樣本當中，以SEM(掃描式電子顯微鏡)觀察背面鋁電極之剖面觀察像。圖2(b)是實施例1所製作的太陽電池單元樣本當中，以SEM觀察背面鋁電極之剖面觀察像。 圖3是顯示背面鈍化膜5具有2個開口6之矽基板1的示意圖。 圖4是顯示將含鋁糊劑組成物塗布於覆蓋了背面鈍化膜5之2個開口6的區域，並進行乾燥及燒成後的剖面之示意圖。在此，符號7是含鋁糊劑組成物之燒成物，符號8是Al-Si合金層，符號9是p+ 層。 圖5是圖4中將存在於開口的外側(不屬於填埋凹部分之態樣的部分)之含鋁糊劑組成物之燒成物7除去之後的示意圖。該示意圖中，Al-Si層8作為背面鋁電極而發揮作用。FIG. 1( a ) is an observation image of the solar cell unit sample produced in Comparative Example 2, observed with a laser microscope above the aluminum electrode on the back surface. FIG. 1( b ) is an observation image of the solar cell unit sample produced in Example 1, observed with a laser microscope above the rear aluminum electrode. 2( a ) is a cross-sectional observation image of the rear aluminum electrode observed by SEM (scanning electron microscope) among the solar battery cell samples produced in Comparative Example 2. FIG. 2( b ) is a cross-sectional image of the rear aluminum electrode observed by SEM among the solar battery cell samples produced in Example 1. FIG. FIG. 3 is a schematic diagram showing a silicon substrate 1 with two openings 6 in the rear passivation film 5 . FIG. 4 is a schematic diagram showing a cross-section after coating the aluminum-containing paste composition on the area covering the two openings 6 of the rear passivation film 5 , drying and firing. Here, symbol 7 is a fired product of the aluminum-containing paste composition, symbol 8 is an Al-Si alloy layer, and symbol 9 is a p + layer. FIG. 5 is a schematic view after removing the burned product 7 of the aluminum-containing paste composition existing outside the opening (the portion not belonging to the aspect of filling the concave portion) in FIG. 4 . In this schematic diagram, the Al—Si layer 8 functions as a rear aluminum electrode.
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| JP2011165668A (en) * | 2010-02-12 | 2011-08-25 | Giga Solar Materials Corp | Conductive aluminum paste and its manufacturing method, solar cell, and its module |
| JP2013512546A (en) * | 2009-11-25 | 2013-04-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Aluminum paste and its use in the manufacture of passivating emitters and back contact silicon solar cells. |
| JP2013219355A (en) * | 2012-04-04 | 2013-10-24 | Samsung Sdi Co Ltd | Method for manufacturing photoelectric element |
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| TWI518932B (en) * | 2014-07-24 | 2016-01-21 | 茂迪股份有限公司 | Solar cell and module comprising the same |
| KR20160122467A (en) * | 2015-04-14 | 2016-10-24 | 엘지전자 주식회사 | Method for manufacturing solar cell |
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| JP2011165668A (en) * | 2010-02-12 | 2011-08-25 | Giga Solar Materials Corp | Conductive aluminum paste and its manufacturing method, solar cell, and its module |
| JP2013219355A (en) * | 2012-04-04 | 2013-10-24 | Samsung Sdi Co Ltd | Method for manufacturing photoelectric element |
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| JPWO2019230728A1 (en) | 2021-07-15 |
| WO2019230728A1 (en) | 2019-12-05 |
| CN112424952A (en) | 2021-02-26 |
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