CN110663119A - Paste composition for solar cell - Google Patents
Paste composition for solar cell Download PDFInfo
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- CN110663119A CN110663119A CN201880033818.XA CN201880033818A CN110663119A CN 110663119 A CN110663119 A CN 110663119A CN 201880033818 A CN201880033818 A CN 201880033818A CN 110663119 A CN110663119 A CN 110663119A
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- paste composition
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- solar cell
- glass frit
- aluminum
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- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 239000011521 glass Substances 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 51
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000008859 change Effects 0.000 abstract description 13
- 230000008719 thickening Effects 0.000 abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 34
- 229910052710 silicon Inorganic materials 0.000 description 34
- 239000000758 substrate Substances 0.000 description 34
- 239000010703 silicon Substances 0.000 description 33
- 239000004065 semiconductor Substances 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 21
- 238000002161 passivation Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010304 firing Methods 0.000 description 14
- -1 ester compound Chemical class 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
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- 238000000576 coating method Methods 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 2
- 239000004698 Polyethylene Substances 0.000 description 2
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- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 230000008018 melting Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- DJPURDPSZFLWGC-UHFFFAOYSA-N alumanylidyneborane Chemical compound [Al]#B DJPURDPSZFLWGC-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 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
- 239000005011 phenolic resin Substances 0.000 description 1
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical compound [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- 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
-
- 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
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
- Electrodes Of Semiconductors (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a paste composition for a solar cell, which can obtain high conversion efficiency in a crystalline solar cell unit, has a stable structure of a glass frit, and can suppress viscosity change (thickening) with time. Specifically, the present invention provides a paste composition for a solar cell, which contains an aluminum powder, an organic vehicle and a glass frit, wherein the glass frit contains 50 to 90 mol% of Sb2O3。
Description
Technical Field
The present invention relates to a paste composition for a solar cell, and more particularly to a paste composition for forming p-type crystals in a crystalline solar cell having a passivation film provided with an opening by laser irradiation or the like+A paste composition for solar cells of a layer.
Background
In recent years, various studies and developments have been made for the purpose of improving the conversion efficiency (power generation efficiency) and reliability of a crystalline solar cell. As one of them, a PERC (Passivated emitter and rear cell) type high conversion efficiency cell having a passivation film formed of silicon nitride, silicon oxide, aluminum oxide, or the like on the cell rear surface has been attracting attention.
The PERC type high conversion efficiency cell has a structure including an electrode layer containing aluminum as a main component, for example. The electrode layer (particularly the back electrode layer) can be formed, for example, by applying a paste composition mainly composed of aluminum in a pattern shape so as to cover the opening of the passivation film, drying the composition as necessary, and then firing the dried composition. Further, it is known that the conversion efficiency of the PERC type high conversion efficiency cell can be improved by appropriately designing the configuration of the electrode layer.
For example, patent document 1 discloses an aluminum paste composition containing 30 to 70 mol% of Pb2+、1～40mol％Si4+、10～65mol％B3+、1～25mol％Al3+And (3) forming a glass frit. Further, patent document 2 relates to a composition containing an aluminum powder, an aluminum-silicon alloy powder, a silicon powder, a glassThe paste composition of glass powder and organic vehicle (organic vehicle) is described in "the glass powder may contain one or more selected from the group consisting of lead (Pb), bismuth (Bi), vanadium (V), boron (B), silicon (Si), tin (Sn), phosphorus (P) and zinc (Zn). Furthermore, lead-containing glass powder or lead-free glass powder such as bismuth-based, vanadium-based, tin-phosphorus-based, zinc borosilicate-based, alkali borosilicate-based glass powder can be used (patent document 2 [0035 ]]Segments, etc.).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-145865
Patent document 2: japanese patent laid-open publication No. 2013-143499
Disclosure of Invention
Technical problem to be solved by the invention
However, even according to the techniques disclosed in patent documents 1 and 2, there is still room for improvement in conversion efficiency of the crystalline solar cell. Further, the conventional paste composition has problems that the structure of the glass frit is unstable, the viscosity of the paste composition changes with time (particularly, the paste composition thickens at 5Pa · s or more), and the applicability (printability) of the paste composition is lowered.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a paste composition for a solar cell, which can achieve high conversion efficiency in a crystalline solar cell, has a stable glass frit structure, and can suppress a change (thickening) in viscosity with time.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that a paste composition for a solar cell, which contains an aluminum powder, an organic vehicle and a specific glass frit, can achieve the above object, and have completed the present invention.
That is, the present invention relates to the following paste composition for a solar cell.
1. A paste composition for solar cells, which contains an aluminum powder,An organic vehicle and a glass frit paste composition for a solar cell, wherein the glass frit contains 50 to 90 mol% of Sb2O3。
2. The paste composition for a solar cell according to item 1, wherein the organic vehicle and the glass frit are contained in an amount of 30 to 35 parts by mass and 0.5 to 5.0 parts by mass, respectively, based on 100 parts by mass of the aluminum powder.
3. The paste composition for solar cells according to item 1 or 2 above, wherein the glass frit further comprises SiO2And/or B2O3。
Effects of the invention
According to the paste composition for a solar cell of the present invention, a high conversion efficiency can be obtained in a crystalline solar cell (particularly a PERC type high conversion efficiency cell), and the structure of the glass frit is stable, and the viscosity change (thickening) with time can be suppressed. The paste composition of the present invention has good applicability (printability) by suppressing the change in viscosity (thickening) with time.
Drawings
Fig. 1 is a schematic diagram showing an example of a cross-sectional structure of a PERC type solar cell, wherein (a) is an example of an embodiment thereof, and (b) is another example of an embodiment thereof.
Fig. 2 is a schematic cross-sectional view of electrode structures fabricated in examples and comparative examples.
Detailed Description
Hereinafter, the paste composition for a solar cell of the present invention will be described in detail. In the present specification, the range of "to" means "above and below" unless otherwise specified.
The paste composition for a solar cell of the present invention can be used for forming an electrode of a crystalline solar cell, for example. The crystalline solar cell is not particularly limited, and examples thereof include a PERC (passivantemitter and rear cell) type high conversion efficiency cell (hereinafter, referred to as "PERC type solar cell"). The paste composition for a solar cell of the present invention can be used, for example, for forming a back electrode of a PERC type solar cell. Hereinafter, the paste composition of the present invention is also abbreviated as "paste composition".
First, an example of the structure of the PERC type solar cell will be described.
PERC type solar cell unit
Fig. 1 (a) and (b) are schematic diagrams showing a general cross-sectional structure of the PERC type solar cell. The PERC type solar cell may include a silicon semiconductor substrate 1, an n-type impurity layer 2, an antireflection film (passivation film) 3, a grid electrode (gridelectrode)4, an electrode layer (back electrode layer) 5, an alloy layer 6, and p+The layer 7 serves as a constituent element.
The silicon semiconductor substrate 1 is not particularly limited, and for example, a p-type silicon substrate having a thickness of 180 to 250 μm can be used.
The n-type impurity layer 2 is provided on the light-receiving surface side of the silicon semiconductor substrate 1. The thickness of the n-type impurity layer 2 is, for example, 0.3 to 0.6. mu.m.
The antireflection film 3 and the gate electrode 4 are provided on the surface of the n-type impurity layer 2. The antireflection film 3 is formed of, for example, a silicon nitride film, and is also called a passivation film. The antireflection film 3 functions as a so-called passivation film, and thereby can suppress recombination of electrons on the surface of the silicon semiconductor substrate 1, and as a result, the recombination rate of generated carriers can be reduced. This can improve the conversion efficiency of the PERC type solar cell.
The antireflection film (passivation film) 3 may be provided on the back surface side of the silicon semiconductor substrate 1, that is, on the surface opposite to the light-receiving surface. In addition, a contact hole (opening) formed so as to penetrate the antireflection film (passivation film) 3 on the back surface side and cut a part of the back surface of the silicon semiconductor substrate 1 is formed on the back surface side of the silicon semiconductor substrate 1. The method of forming the contact hole is not limited, and a so-called LCO (laser contact opening) method in which an opening is formed by laser irradiation or the like is generally used.
The electrode layer 5 is formed so as to be in contact with the silicon semiconductor substrate 1 through the contact hole. The electrode layer 5 is a member formed of the paste composition of the present invention, and is formed in a predetermined pattern shape. As shown in the embodiment (a) of fig. 1, the electrode layer 5 may be formed so as to cover the entire back surface of the PERC type solar cell, or may be formed so as to cover the contact hole and the vicinity thereof, as shown in the embodiment (b) of fig. 1. Since the electrode layer 5 is mainly composed of aluminum, the electrode layer 5 is an aluminum electrode layer.
The electrode layer 5 can be formed by, for example, applying a paste composition in a predetermined pattern shape and firing the paste composition. The coating method is not particularly limited, and examples thereof include known methods such as screen printing. After the paste composition is applied and dried as necessary, for example, firing is performed at a temperature exceeding the melting point of aluminum (about 660 ℃) for a short time to form the electrode layer 5.
In the present invention, the firing temperature is not limited as long as it exceeds the melting point of aluminum (about 660 ℃ C.), and is preferably about 750 to 950 ℃ and more preferably about 780 to 900 ℃. The firing time can be appropriately set in accordance with the firing temperature within a range in which the desired electrode layer 5 can be formed.
When firing is performed in this manner, aluminum contained in the paste composition diffuses into the silicon semiconductor substrate 1. Thereby, an aluminum-silicon (Al-Si) alloy layer (alloy layer 6) is formed between the electrode layer 5 and the silicon semiconductor substrate 1, and at the same time, p as an impurity layer is formed by diffusion of aluminum atoms+Layer 7.
P+The layer 7 can provide an effect of preventing recombination of electrons and improving collection efficiency of generated carriers, that is, a so-called BSF (Back Surface Field) effect.
The electrode formed by the electrode layer 5 and the alloy layer 6 is a back surface electrode 8 shown in fig. 1. Therefore, the back electrode 8 is formed using a paste composition, and for example, the back electrode 8 can be formed by coating the back electrode so as to cover the contact hole 9 (opening) of the antireflection film (passivation film) 3 provided on the back surface, drying the coating if necessary, and then firing the dried coating. Here, by forming the back electrode 8 using the paste composition of the present invention, high conversion efficiency can be obtained in the solar cell. Further, since the paste composition of the present invention can suppress the change in viscosity (thickening) with time, it has good applicability (printability) even when a certain time has elapsed from the preparation.
2. Paste composition
The paste composition for a solar cell comprises aluminum powder, an organic vehicle and a glass frit, and is characterized in that the glass frit comprises 50 to 90 mol% of Sb2O3。
As described above, by using the paste composition, a back electrode of a solar cell such as a PERC type solar cell can be formed. That is, the paste composition of the present invention can be used for forming a back electrode for a solar cell, which is electrically contacted with a silicon substrate through an opening (contact hole) provided in a passivation film formed on the silicon substrate. Further, according to the paste composition of the present invention, in a crystalline solar cell (in particular, a PERC type solar cell), high conversion efficiency can be obtained, and the structure of the glass frit is stable, and the viscosity change (thickening) with time can be suppressed.
The paste composition comprises aluminum powder, an organic vehicle and a glass frit as constituent components. Further, by including aluminum powder (conductive material) in the paste composition, a sintered body formed by firing a coating film of the paste composition can exhibit conductivity to be electrically connected to the silicon substrate.
(aluminum powder)
The aluminum powder contained in the paste composition exerts conductivity in the aluminum electrode layer formed by firing the paste composition. Further, the aluminum powder is formed by forming an aluminum-silicon alloy layer 6 and p between the aluminum-silicon alloy layer and the silicon semiconductor substrate 1 when the aluminum powder is fired into a paste composition+Layer 7 to obtain the BSF effect.
The shape of the aluminum powder is not particularly limited, and may be any of spherical, elliptical, amorphous, scaly, fibrous, and the like. If the aluminum powder is spherical in shape, the electrode layer 5 formed of the paste composition has a high filling property with aluminum powder, and the resistance can be effectively reduced.
In addition, when the aluminum powder is spherical in shape, contact points between the silicon semiconductor substrate 1 and the aluminum powder increase in the electrode layer 5 formed of the paste composition, and thus a good BSF layer is easily formed. When the aluminum powder is spherical, the average particle diameter as measured by a laser diffraction method is preferably in the range of 1 to 10 μm.
The aluminum powder may be composed of only high-purity aluminum or may contain an aluminum alloy. Examples of the aluminum alloy include an aluminum-silicon alloy and an aluminum-boron alloy.
In the present invention, the aluminum powder contains an aluminum-silicon alloy, and the silicon content in the aluminum powder is preferably 10 to 25 atomic%. The silicon content is more preferably 15 to 22 atomic%. By using such an aluminum powder, the adhesion to the silicon semiconductor substrate 1 is further improved.
In any case where the aluminum powder is composed of only high-purity aluminum or an aluminum alloy, the presence of unavoidable impurities and trace amounts of additional elements derived from the raw materials are not excluded.
(organic vehicle)
As the organic vehicle, a material in which various additives and resins are dissolved in a solvent as necessary can be used. Alternatively, the resin may be used as an organic vehicle without including a solvent.
The solvent may be a known solvent, and specific examples thereof include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and the like.
Examples of the various additives include an antioxidant, an anticorrosive agent, an antifoaming agent, a thickener, a tackifier (tagfider), a coupling agent, an electrostatic charge imparting agent, a polymerization inhibitor, a thixotropic agent, and an anti-settling agent. Specifically, for example, a polyethylene glycol ester compound, a polyethylene glycol ether compound, a polyoxyethylene sorbitan ester compound, a sorbitan alkyl ester compound, an aliphatic polycarboxylic acid compound, a phosphate ester compound, an amidoamine (amidoamine) salt of a polyester acid, an oxidized polyethylene compound, a fatty acid amide wax, or the like can be used.
As the resin, known types can be used, and two or more of thermosetting resins such as ethyl cellulose, cellulose nitrate, polyvinyl butyral, phenol resin, melamine resin, urea resin, xylene resin, alkyd resin, unsaturated polyester resin, acrylic resin, polyimide resin, furan resin, polyurethane resin, isocyanate compound, cyanate ester compound, polyethylene, polypropylene, polystyrene, ABS resin, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polysulfone, polyimide, polyethersulfone, polyarylate, polyether ether ketone, polytetrafluoroethylene, silicone resin, and the like can be used in combination.
The proportions of the resin, the solvent and the various additives contained in the organic vehicle can be arbitrarily adjusted, and for example, the same component ratio as that of a known organic vehicle can be set.
The content of the organic vehicle is not particularly limited, and is, for example, preferably 20 to 45 parts by mass, and particularly preferably 30 to 35 parts by mass, based on 100 parts by mass of the aluminum powder, from the viewpoint of good printability.
(glass frit)
The glass frit is considered to have an action of contributing to the reaction between the aluminum powder and silicon and the sintering of the aluminum powder itself.
In the paste composition of the present invention, the glass frit (100 mol%) contains 50 to 90 mol% of Sb2O3. By using such a glass frit, the paste composition can be inhibited from changing in viscosity (thickening) with time, and therefore has good coatability (printability) even when a certain time has elapsed from the start of preparation. Sb in glass frit2O3The content of the glass frit is preferably 50 to 90 mol%, and particularly 52 to 70 mol%, since the structure of the glass frit is particularly stable and the change in viscosity (thickening) with time can be suppressed. In addition, when Sb is present2O3When the content is less than 50 mol%, the conversion efficiency (Eff) of the solar cell may decrease, and the paste composition may thicken to 5Pa · s or more with time. In addition, when Sb is present2O3If the content is more than 90 mol%, vitrification is difficult,may not be used as an electrode material. In addition, when Sb is present2O3When the content is more than 70 mol% and 90 mol% or less, the glass frit can be used as an electrode material, but the structure of the glass frit may be reduced within an allowable range for practical use due to a difference in temperature, pressure, or manufacturing conditions of the glass frit.
The glass frit preferably further contains SiO2And/or B2O3As for removing Sb2O3The remainder of the process. As the glass frit, it is desired that it is made of Sb2O3-B2O32 component(s) of (1), or Sb2O3-B2O3-SiO2Any of the 3 components in (1) above may be contained, but other components may be contained within a range not affecting the effect of the present invention. Except for Sb2O3The content of other components is not limited, B2O3The content of (b) is preferably 30 to 40 mol%, more preferably 30 to 36 mol%. SiO 22The content of (b) is preferably 0 to 14 mol%, more preferably 0 to 5 mol%. As addition of SiO2The lower limit of the content is preferably 1 mol%.
The content of the glass frit is not particularly limited, and is preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the aluminum powder, for example. In this case, the silicon semiconductor substrate 1 and the antireflection film 3 (passivation film) have good adhesion and the resistance is not easily increased.
As described above, the paste composition of the present invention is particularly preferably composed of: the aluminum powder contains 30 to 35 parts by mass of an organic vehicle and 0.5 to 5.0 parts by mass of a glass frit per 100 parts by mass of aluminum powder. By setting the range, high conversion efficiency can be obtained, and the structure of the glass frit is stable, and the change in viscosity (thickening) with time can be suppressed.
The paste composition of the present invention is suitable for forming an electrode layer of a solar cell (particularly, the back electrode 8 of a PERC type solar cell shown in fig. 1), for example. Therefore, the paste composition of the present invention can also be used as a solar cell back electrode forming agent.
Examples
The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.
Example 1
(preparation of paste composition)
Using a dispersing apparatus (disperser), D produced by gas atomization50100 parts by mass of 4.0 μm aluminum powder and Sb2O3-B2O31.5 parts by mass of a glass frit (70 to 30 mol%) was pasted in 35 parts by mass of a resin solution obtained by dissolving ethyl cellulose in diethylene glycol butyl ether. Thus, a paste composition was obtained.
(production of fired substrate for solar cell)
A fired substrate as a solar cell for evaluation was produced as follows.
First, as shown in fig. 2 a, a silicon semiconductor substrate 1 (including a passivation film on the back surface side) having a thickness of 180 μm is prepared. Then, as shown in FIG. 2B, a YAG laser having a wavelength of 532nm was used as a laser oscillator to form a contact hole 9 having a width D of 50 μm and a depth of 1 μm in the rear surface of the silicon semiconductor substrate 1. The silicon semiconductor substrate 1 had a resistance value of 3 Ω · cm and was a back surface passivation type single crystal.
In fig. 2, although not shown, the passivation film is regarded as a member included in the silicon semiconductor substrate 1, and the passivation film is included on the back surface side of the silicon semiconductor substrate 1 as a laminate of a 30nm aluminum oxide layer and a 100nm silicon nitride layer.
Next, as shown in fig. 2C, the paste composition 10 obtained above was printed on the surface of the silicon semiconductor substrate 1 so as to cover the entire rear surface (the surface on the side where the contact holes 9 were formed) at a density of 1.0 to 1.1g/pc using a screen printer. Next, although not shown, an Ag paste prepared by a known technique is printed on the light-receiving surface.
Then, firing was performed using an infrared band furnace (red outer ベ ル ト furnace) set at 800 ℃. By this firing, as shown in fig. 2 (D), the electrode layer 5 is formed, and this firing is performedDuring firing, aluminum diffuses into the silicon semiconductor substrate 1, whereby an Al — Si alloy layer 6 is formed between the electrode layer 5 and the silicon semiconductor substrate 1, and p is formed as an impurity layer formed by diffusion of aluminum atoms+Layer (BSF layer) 7. Thus, a fired substrate for evaluation was produced.
(evaluation of solar cell)
In the evaluation of the resulting solar cell unit, a solar simulator (solar simulator) of WACOM electrical co, ltd: WXS-156S-10, I-V assay apparatus: IV 15040-10I-V measurements were performed. The fired substrate having an Eff of 19.0% or more was set as a pass.
(evaluation of viscosity Change with time of paste composition)
The prepared paste composition was left in an oven at 50 ℃ for 1 week, and the change in viscosity before and after the test was measured using a viscometer. As the viscometer, a CONE & PLATE type viscometer DV2T manufactured by ametek.inc. was used, and measurement was performed in accordance with 2.3CONE & PLATE viscometer method of JIS K5600. The fired substrate having a viscosity change of less than 5 pas before and after the test was set as a pass.
(evaluation of adhesion of electrode layer 5 (aluminum electrode))
The evaluation of the adhesion of the electrode layer 5 (aluminum electrode) was carried out in the following manner: after a stealth tape (12mm wide, manufactured by 3M Company) having a length of about 3cm was attached to the surface of the electrode layer 5 (aluminum electrode) formed on the back surface of the silicon semiconductor substrate 1, the tape was strongly peeled off at an angle of 45 degrees with respect to the silicon semiconductor substrate 1, and the ratio of the total area of the portion to which aluminum was attached to the area of the original stealth tape attached was calculated using analysis software capable of performing binarization. The evaluation of the adhesion was performed by the same person at the same posture, angle, force and constant speed. The invisible tape was evaluated as "good" when no aluminum was adhered to the tape, and as "good" when only a small amount of aluminum was adhered to the tape.
Example 2
Except for using Sb2O3-B2O3(65 mol% -35 mol%) of glass frit, and a reaction product of a metal oxide and a metal oxideA paste composition was prepared and evaluated in the same manner as in example 1.
Example 3
Except for using Sb2O3-B2O3A paste composition was prepared and evaluated in the same manner as in example 1, except that 1.5 parts by mass of glass frit (60 mol% to 40 mol%).
Example 4
Except for using Sb2O3-B2O3-SiO2A paste composition was prepared and evaluated in the same manner as in example 1, except that 1.5 parts by mass of glass frit (55 mol% to 35 mol% to 10 mol%).
Example 5
Except for using Sb2O3-B2O3-SiO2A paste composition was prepared and evaluated in the same manner as in example 1, except that 1.5 parts by mass of glass frit (52 mol% to 34 mol% to 14 mol%).
Example 6
Except for using Sb2O3-B2O3-SiO2A paste composition was prepared and evaluated in the same manner as in example 1, except that 0.5 part by mass of glass frit (52 mol% to 34 mol% to 14 mol%).
Example 7
Except for using Sb2O3-B2O3-SiO2A paste composition was prepared and evaluated in the same manner as in example 1, except that 5.0 parts by mass of glass frit (52 mol% to 34 mol% to 14 mol%).
Comparative example 1
Except using B2O3-SiO2A paste composition was prepared in the same manner as in example 1 except for 1.5 parts by mass of a glass frit of-BaO-CaO-ZnO (35 mol% to 10 mol% to 35 mol% to 10 mol%), and evaluation was performed.
Comparative example 2
Sb2O3(100 mol%) was not vitrified. I.e. except for using Sb which has not been vitrified2O3A paste composition was prepared and evaluated in the same manner as in example 1, except that 1.5 parts by mass of frit (frit) (100 mol%).
Comparative example 3
Sb2O3-B2O3(46 mol% to 54 mol%) of the glass frit absorbs moisture and deliquesces, and when added, water is mixed into the paste, and thus the glass frit cannot be used as an electrode material.
Comparative example 4
Except using B2O3A paste composition was prepared in the same manner as in example 1 except for 1.5 parts by mass of a glass frit of-BaO-CaO-ZnO (27 mol% to 45 mol% to 10 mol% to 18 mol%), and evaluation was performed.
Comparative example 5
Except for using SiO2-Al2O3-B2O3A paste composition was prepared in the same manner as in example 1 except for 1.5 parts by mass of a glass frit of-PbO (1 mol% to 4 mol% to 30 mol% to 65 mol% to 10 mol%) and evaluated.
Comparative example 6
Except for using Sb2O3-B2O3-SiO2A paste composition was prepared and evaluated in the same manner as in example 1, except that 0.4 part by mass of glass frit (52 mol% to 34 mol% to 14 mol%).
Comparative example 7
Except for using Sb2O3-B2O3-SiO2A paste composition was prepared and evaluated in the same manner as in example 1, except that 6.0 parts by mass of the glass frit was used (52 mol% to 34 mol% to 14 mol%).
The conditions and the evaluation results of the examples and comparative examples are shown in table 1 below.
From the results in table 1, it is understood that when the paste compositions of examples 1 to 7 using the glass frit specified in the present invention were used, high conversion efficiency was obtained, the structure of the glass frit was stable, and the change in viscosity (thickening) with time was suppressed. On the other hand, it is found that the paste compositions of comparative examples 1 to 7, in which the glass frit specified in the present invention was not used, were inferior in conversion efficiency and/or change in paste viscosity to those of the paste compositions of examples 1 to 7. Especially in Sb2O3In comparative example 2 having a content of more than 90 mol%, Sb2O3It was not vitrified and could not be used as an electrode material. In comparative example 6 in which the amount of the glass frit added was 0.4 parts by mass, the conversion efficiency was less than 19.0%, and in comparative example 7 in which the amount of the glass frit added was 6.0% by mass, the adhesion of the electrode layer 5 (aluminum electrode) was poor.
Description of the reference numerals
1: a silicon semiconductor substrate; 2: an n-type impurity layer; 3: an antireflection film (passivation film); 4: a gate electrode; 5: an electrode layer; 6: an alloy layer; 7: p is a radical of+A layer; 8: a back electrode; 9: a contact hole (opening portion); 10: a paste composition.
Claims (3)
1. A paste composition for a solar cell, which contains an aluminum powder, an organic vehicle and a glass frit, wherein the glass frit contains 50 to 90 mol% of Sb2O3。
2. The paste composition for solar cells according to claim 1, wherein the organic vehicle is contained in an amount of 30 to 35 parts by mass and the glass frit is contained in an amount of 0.5 to 5.0 parts by mass, based on 100 parts by mass of the aluminum powder.
3. The paste composition for solar cells according to claim 1 or 2, wherein the glass frit further contains SiO2And/or B2O3。
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| PCT/JP2018/020749 WO2018221578A1 (en) | 2017-05-31 | 2018-05-30 | Paste composition for solar battery |
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| CN109493991B (en) * | 2018-12-28 | 2020-03-27 | 广州市儒兴科技开发有限公司 | Boron slurry for PERC battery |
| CN110600555A (en) * | 2019-08-29 | 2019-12-20 | 苏州腾晖光伏技术有限公司 | Antireflection film structure and PERC battery |
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| CN110663119B (en) | 2023-08-29 |
| JP7013458B2 (en) | 2022-01-31 |
| WO2018221578A1 (en) | 2018-12-06 |
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