CN110663119B - Paste composition for solar cell - Google Patents
Paste composition for solar cell Download PDFInfo
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- CN110663119B CN110663119B CN201880033818.XA CN201880033818A CN110663119B CN 110663119 B CN110663119 B CN 110663119B CN 201880033818 A CN201880033818 A CN 201880033818A CN 110663119 B CN110663119 B CN 110663119B
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- glass frit
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- 239000000203 mixture Substances 0.000 title claims abstract description 85
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 48
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000008859 change Effects 0.000 abstract description 15
- 230000008719 thickening Effects 0.000 abstract description 11
- 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 19
- 238000002161 passivation Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010304 firing Methods 0.000 description 13
- -1 for example Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910000676 Si alloy Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 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
- 238000002360 preparation method Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 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
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000006866 deterioration Effects 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 230000005611 electricity Effects 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
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 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
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 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
- 230000003068 static effect Effects 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
- 239000001993 wax Substances 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
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
Abstract
The present application provides a paste composition for solar cells, which can obtain high conversion efficiency in crystalline solar cells, has a stable structure of a glass frit, and can inhibit viscosity change (thickening) with time. Specifically, the present application provides a paste composition for solar cells, which comprises an aluminum powder, an organic carrier and a glass frit, wherein the glass frit contains 50 to 90 mol% of Sb 2 O 3 。
Description
Technical Field
The present application relates to a paste composition for solar cells, and more particularly to a paste composition for forming p on crystalline solar cells having passivation films with openings formed by laser irradiation + Paste composition for solar cell of layer.
Background
In recent years, various researches and developments have been made for the purpose of improving the conversion efficiency (power generation efficiency), reliability, and the like of crystalline solar cells. As one of them, a PERC (passivation emitter and back cell, passivated emitter and rear cell) high conversion efficiency cell having a passivation film formed of silicon nitride, silicon oxide, aluminum oxide, or the like on the cell back side 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, and drying the paste composition as necessary, and then firing the paste composition. Further, it is known that the conversion efficiency of the PERC type high conversion efficiency cell can be improved by appropriately designing the constitution of the electrode layer.
For example, patent document 1 discloses an aluminum paste composition containing 30 to 70mol% of Pb 2+ 、1～40mol％Si 4+ 、10～65mol％B 3+ 、1～25mol％Al 3+ And forming the glass frit. Patent document 2 also relates to a paste composition containing aluminum powder, aluminum-silicon alloy powder, silicon powder, glass powder, and an organic vehicle (organic vehicle), and particularly, as glass powder, "as glass powder, one or two 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) may be contained. In addition, lead-free glass powders such as lead-containing glass powders, bismuth-based glass powders, vanadium-based glass powders, tin-phosphorus-based glass powders, zinc borosilicate-based glass powders, and alkali borosilicate-based glass powders can be used"(patent document 2 [0035 ]]Segments, etc.).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-145865
Patent document 2: japanese patent application laid-open No. 2013-143499
Disclosure of Invention
Technical problem to be solved by the application
However, even according to the techniques disclosed in patent documents 1 and 2, etc., there is still room for improvement in conversion efficiency of the crystalline solar cell. In addition, the conventional paste composition has problems such as unstable structure of the frit, change in viscosity of the paste composition with time (particularly, thickening at 5pa·s or more), and deterioration of coatability (printability) of the paste composition.
The present application 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 obtain high conversion efficiency in a crystalline solar cell, and which has a stable structure of a glass frit and can suppress a change in viscosity (thickening) with time.
Technical means for solving the technical problems
The inventors of the present application have repeatedly studied in order to achieve the above object, and as a result, have found that a paste composition for solar cells containing an aluminum powder, an organic vehicle and a specific glass frit can achieve the above object, and have completed the present application.
That is, the present application relates to the following paste composition for solar cells.
1. A paste composition for solar cells comprising an aluminum powder, an organic carrier and a glass frit, wherein the glass frit comprises 50 to 90 mol% of Sb 2 O 3 。
2. The paste composition for solar cells according to the above 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 the above item 1 or 2, wherein the glass frit further contains SiO 2 And/or B 2 O 3 。
Effects of the application
According to the paste composition for solar cells of the present application, in crystalline solar cells (particularly, PERC-type high conversion efficiency cells), high conversion efficiency can be obtained, and at the same time, the structure of the frit is stable, and the viscosity change (thickening) with time can be suppressed. The paste composition of the present application has good coatability (printability) by suppressing the viscosity change (thickening) with time.
Drawings
Fig. 1 is a schematic diagram showing an example of a cross-sectional structure of a PERC type solar cell, (a) being an example of an embodiment thereof, and (b) being another example of an embodiment thereof.
Fig. 2 is a schematic cross-sectional view of the electrode structures fabricated in the examples and comparative examples.
Detailed Description
The paste composition for solar cells of the present application will be described in detail below. In the present specification, unless otherwise specified, the range indicated by "to" means "above and below".
The paste composition for solar cells of the present application 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 PERC (Passivated emitter and rear cell) type high conversion efficiency cells (hereinafter referred to as "PERC type solar cell"). The paste composition for solar cells of the present application can be used, for example, to form a back electrode of a PERC solar cell. Hereinafter, the paste composition of the present application is also abbreviated as "paste composition".
First, an example of the structure of a 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 a PERC type solar cell. The PERC type solar cell can include a silicon semiconductor substrate 1, an n-type impurity layer 2, an antireflection film 3, a gate electrode 4, an electrode layer (back electrode layer) 5, an alloy layer 6, and a p + 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 μm.
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 thus 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 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. Further, a contact hole (opening) formed so as to penetrate the anti-reflective coating (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 method using so-called LCO (laser contact opening ) having an opening portion 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 application, and is formed in a predetermined pattern shape. The electrode layer 5 may be formed so as to cover the entire rear surface of the PERC solar cell as shown in the embodiment of fig. 1 (a), or may be formed so as to cover the contact hole and the vicinity thereof as shown in the embodiment of fig. 1 (b). Since the main component of the electrode layer 5 is aluminum, the electrode layer 5 is an aluminum electrode layer.
The electrode layer 5 can be formed, for example, by 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 needed, the electrode layer 5 can be formed by, for example, firing at a temperature exceeding the melting point of aluminum (about 660 ℃) for a short period of time.
In the present application, the firing temperature is not particularly limited as long as it exceeds the melting point of aluminum (about 660 ℃), but 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 where 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 bring about 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 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 applying the paste composition so as to cover the contact hole 9 (opening) of the antireflection film (passivation film) 3 provided on the back surface side, drying the paste composition as necessary, and then firing the paste composition. Here, by forming the back electrode 8 using the paste composition of the present application, high conversion efficiency can be obtained in the solar cell unit. Further, since the paste composition of the present application can suppress the viscosity change (thickening) with time, it has good coatability (printability) even when a certain time has elapsed from the start of preparation.
2. Paste composition
The paste composition of the application is a paste composition for solar cells containing aluminum powder, an organic carrier and a glass fritThe glass frit comprises 50 to 90 mol% of Sb 2 O 3 。
As described above, by using the paste composition, the back electrode of a solar cell such as a PERC solar cell can be formed. That is, the paste composition of the present application 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 application, in a crystalline solar cell (particularly, a PERC solar cell), high conversion efficiency can be obtained, and at the same time, the structure of the frit is stable, and the viscosity change (thickening) with time can be suppressed.
The paste composition contains aluminum powder, an organic vehicle and a glass frit as constituent components. Further, by including aluminum powder (conductive material) in the paste composition, the sintered body formed by firing the coating film of the paste composition can exhibit conductivity for electrical connection with the silicon substrate.
(aluminum powder)
The aluminum powder contained in the paste composition exhibits conductivity in the aluminum electrode layer formed by firing the paste composition. Further, the aluminum powder is formed by forming the aluminum-silicon alloy layer 6 and p between the aluminum-silicon alloy layer and the silicon semiconductor substrate 1 at the time of firing the paste composition + Layer 7 achieves 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 an increased filling property of the aluminum powder, and the electric resistance can be effectively reduced.
Further, when the shape of the aluminum powder is spherical, in the electrode layer 5 formed of the paste composition, the contact point of the silicon semiconductor substrate 1 and the aluminum powder increases, and thus a good BSF layer is easily formed. When the aluminum powder is spherical in shape, the average particle diameter 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. For example, aluminum alloys include aluminum-silicon alloys, aluminum-boron alloys, and the like.
In the present application, the aluminum powder contains an aluminum-silicon alloy, and the silicon content in the aluminum powder is preferably 10 to 25 at%. The silicon content is more preferably 15 to 22 atomic%. By using such aluminum powder, adhesion to the silicon semiconductor substrate 1 is further improved.
In addition, when the aluminum powder is composed of only high-purity aluminum and is an aluminum alloy, the presence of unavoidable impurities and trace amounts of additive elements derived from the raw materials is not excluded.
(organic Carrier)
As the organic vehicle, a material in which various additives and resins are dissolved in a solvent as needed can be used. Alternatively, the resin may be used as the organic vehicle without containing a solvent.
The solvent may be any known solvent, and specific examples thereof include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and the like.
As the various additives, for example, antioxidants, anticorrosive agents, antifoaming agents, thickening agents, adhesion promoters (tackifiers), coupling agents, static electricity imparting agents, polymerization inhibitors, thixotropic agents, anti-settling agents, and the like can be used. Specifically, for example, polyethylene glycol ester compounds, polyethylene glycol ether compounds, polyoxyethylene sorbitan ester compounds, sorbitan alkyl ester compounds, aliphatic polycarboxylic acid compounds, phosphoric acid ester compounds, amide amine (amid) salts of polyester acids, oxidized polyethylene compounds, fatty acid amide waxes, and the like can be used.
As the resin, a known resin may be used, and two or more of ethylcellulose, nitrocellulose, polyvinyl butyral, a phenol resin, a melamine resin, a urea resin, a xylene resin, an alkyd resin, an unsaturated polyester resin, an acrylic resin, a polyimide resin, a furan resin, a polyurethane resin, a thermosetting resin such as an isocyanate compound and a cyanate ester compound, polyethylene, polypropylene, polystyrene, an ABS resin, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, polysulfone, polyimide, polyether sulfone, polyarylate, polyether ether ketone, polytetrafluoroethylene, a silicone resin, and the like may 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 proportions of the components can be the same as those of the known organic vehicle.
The content of the organic carrier is not particularly limited, and is preferably 20 to 45 parts by mass, particularly preferably 30 to 35 parts by mass, relative to 100 parts by mass of the aluminum powder, for example, from the viewpoint of having good printability.
(glass frit)
The glass frit is considered to have an effect of contributing to the reaction of aluminum powder with silicon and the sintering of aluminum powder itself.
In the paste composition of the present application, the glass frit (100 mol%) contains 50 to 90 mol% of Sb 2 O 3 . By using this frit, the viscosity change (thickening) of the paste composition with time can be suppressed, and thus the paste composition has good coatability (printability) even when a certain period of time has elapsed from the start of production. Sb in glass frit 2 O 3 The content is preferably 50 to 90 mol%, and, among them, 52 to 70mol%, the structure of the frit is particularly stable, and the viscosity change (thickening) with time can be suppressed. In addition, when Sb 2 O 3 When the content is less than 50 mol%, the conversion efficiency (Eff) of the solar cell unit may be lowered, and the paste composition may be thickened to 5pa·s or more with time. In addition, when Sb 2 O 3 If the content is more than 90 mol%, vitrification is difficult, and the electrode material may not be used. In addition, when Sb 2 O 3 When the content is more than 70mol% and not more than 90 mol%, the composition of the frit may be lowered within a permissible range of practical use due to a difference in temperature or pressure or manufacturing conditions of the frit, although the composition can be used as an electrode material.
The glass frit preferably further contains SiO 2 And/or B 2 O 3 As a means for removing Sb 2 O 3 The remainder of the process. As the glass frit, it is expected to be made of Sb 2 O 3 -B 2 O 3 2 components of (2), or Sb 2 O 3 -B 2 O 3 -SiO 2 Any one of the 3 components of (a) is constituted, but other components may be further contained within a range not affecting the effect of the present application. Removing Sb 2 O 3 The content of the components other than B is not limited 2 O 3 The content of (2) is preferably 30 to 40 mol%, more preferably 30 to 36 mol%. SiO (SiO) 2 The content of (2) is preferably 0 to 14 mol%, more preferably 0 to 5 mol%. As additive of SiO 2 The 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 per 100 parts by mass of the aluminum powder, for example. At this time, the adhesion to the silicon semiconductor substrate 1 and the antireflection film 3 (passivation film) is good, and the electric resistance is not easily increased.
As described above, the paste composition of the present application is particularly preferably composed of: the glass frit comprises 30 to 35 parts by mass of an organic vehicle and 0.5 to 5.0 parts by mass of glass frit per 100 parts by mass of aluminum powder. By setting the range to this, high conversion efficiency can be obtained, and the structure of the frit is stable, and the viscosity change (thickening) with time can be suppressed.
The paste composition of the present application is suitable for forming an electrode layer of a solar cell (particularly, a rear electrode 8 of a PERC solar cell as shown in fig. 1), for example. Thus, the paste composition of the present application can also be used as a solar cell back electrode forming agent.
Examples
Hereinafter, the present application will be specifically described with reference to examples and comparative examples. However, the present application is not limited to the examples.
Example 1
(preparation of paste composition)
Using dispersing apparatus (dispersing machine) to let inD generated by gas atomization method 50 100 parts by mass of 4.0 mu m aluminum powder and Sb 2 O 3 -B 2 O 3 1.5 parts by mass of a glass frit (70 mol% to 30 mol%) was creamed into 35 parts by mass of a resin liquid obtained by dissolving ethyl cellulose in diethylene glycol butyl ether. Thus, a paste composition was obtained.
(production of fired substrate as solar cell)
A baked substrate of 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 first prepared. Then, as shown in fig. 2 (B), a YAG laser having a wavelength of 532nm was used as a laser oscillator, and a contact hole 9 having a width D of 50 μm and a depth of 1 μm was formed in the back surface of the silicon semiconductor substrate 1. The silicon semiconductor substrate 1 has a resistance value of 3Ω·cm and is a back surface passivation type single crystal.
Although not shown in fig. 2, the passivation film is regarded as a member included in the silicon semiconductor substrate 1, and 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. 2 (C), 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 which the contact hole 9 was formed) using a screen printer so as to be 1.0 to 1.1 g/pc. Next, although not shown, ag paste prepared by a known technique is printed on the light receiving surface.
Then, the mixture was baked using an infrared oven set at 800 ℃. By this firing, as shown in fig. 2 (D), the electrode layer 5 is formed, and at the time of this firing, aluminum diffuses into the silicon semiconductor substrate 1, whereby the al—si alloy layer 6 is formed between the electrode layer 5 and the silicon semiconductor substrate 1, and at the same time, p is formed as an impurity layer formed by diffusion of aluminum atoms + Layer (BSF layer) 7. Thus, a baked substrate for evaluation was produced.
(evaluation of solar cell)
In the evaluation of the obtained solar cell, a solar simulator (solar simulator) of WACOM electroric co., ltd. was used: WXS-156S-10, I-V measuring apparatus: IV 15040-10I-V assays were performed. The fired substrate with Eff of 19.0% or more was set as acceptable.
(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 viscosity change before and after the test was measured using a viscometer. The measurement was performed using a CONE & PLATE viscometer DV2T manufactured by AMETEK. Inc. according to the 2.3CONE & PLATE viscometer method of JIS K5600. The fired substrate having a viscosity change of less than 5 Pa.s before and after the test was set to be acceptable.
(evaluation of adhesion of electrode layer 5 (aluminum electrode))
The adhesion of the electrode layer 5 (aluminum electrode) was evaluated in the following manner: after a contact tape (12 mm 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 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 contact tape attached was calculated using analysis software capable of performing binarization processing. The evaluation of the adhesion was performed by the same person in the same posture, angle, force path and at a constant speed. The case where no aluminum was attached to the invisible tape at all was evaluated as "o", and the case where even a small amount was attached was evaluated as "x".
Example 2
Except for using Sb 2 O 3 -B 2 O 3 A paste composition was prepared and evaluated in the same manner as in example 1 except that 1.5 parts by mass of the frit was used (65 mol% to 35 mol%).
Example 3
Except for using Sb 2 O 3 -B 2 O 3 1.5 parts by mass of glass frit (60 mol% to 40 mol%) and the likeA paste composition was prepared in the same manner as in example 1 and evaluated.
Example 4
Except for using Sb 2 O 3 -B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 1.5 parts by mass of the frit was used (55 mol% to 35 mol% to 10 mol%).
Example 5
Except for using Sb 2 O 3 -B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 1.5 parts by mass of the frit was used (52 mol% to 34 mol% to 14 mol%).
Example 6
Except for using Sb 2 O 3 -B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 0.5 parts by mass of the glass frit was used (52 mol% to 34 mol% to 14 mol%).
Example 7
Except for using Sb 2 O 3 -B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 5.0 parts by mass of the frit was used (52 mol% to 34 mol% to 14 mol%).
Comparative example 1
Except for using B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 1.5 parts by mass of a glass frit of BaO-CaO-ZnO (35 mol% to 10 mol%).
Comparative example 2
Sb 2 O 3 (100 mol%) cannot be vitrified. That is, except for using Sb which is not vitrified 2 O 3 1.5 parts by mass of a frit (fraction) in addition to (100 mol%),a paste composition was prepared in the same manner as in example 1 and evaluated.
Comparative example 3
Sb 2 O 3 -B 2 O 3 The glass frit (46 to 54 mol%) absorbs moisture and deliquesces, and if added, water is mixed into the paste, and thus cannot be used as an electrode material.
Comparative example 4
Except for using B 2 O 3 A paste composition was prepared and evaluated in the same manner as in example 1 except that 1.5 parts by mass of a glass frit of BaO-CaO-ZnO (27 mol% to 45 mol% to 10 mol% to 18 mol%).
Comparative example 5
In addition to using SiO 2 -Al 2 O 3 -B 2 O 3 A paste composition was prepared and evaluated in the same manner as in example 1, except that 1.5 parts by mass of a frit of PbO (1 mol% to 4 mol% to 30 mol% to 65 mol% to 10 mol%).
Comparative example 6
Except for using Sb 2 O 3 -B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 0.4 parts by mass of the glass frit was used (52 mol% to 34 mol% to 14 mol%).
Comparative example 7
Except for using Sb 2 O 3 -B 2 O 3 -SiO 2 A paste composition was prepared and evaluated in the same manner as in example 1 except that 6.0 parts by mass of the frit was used (52 mol% to 34 mol% to 14 mol%).
The conditions and the evaluation results of each example and comparative example are shown in table 1 below.
From the results shown in Table 1, it was found that the paste compositions of examples 1 to 7 using the glass frits specified in the present application were used, and that the glass frits were stable in structure and suppressed in viscosity change (thickening) with time, while achieving high conversion efficiency. On the other hand, it was found that the paste compositions of comparative examples 1 to 7, in which the glass frit defined in the present application was not used, were inferior in conversion efficiency and/or paste viscosity change to the paste compositions of examples 1 to 7. In particular at Sb 2 O 3 In comparative example 2 having a content of more than 90 mol%, sb 2 O 3 The glass is not vitrified and cannot be used as an electrode material. In comparative example 6 in which the glass frit addition amount was 0.4 parts by mass, the conversion efficiency was less than 19.0%, and in comparative example 7 in which the glass frit addition amount 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: antireflection films (passivation films); 4: a gate; 5: an electrode layer; 6: an alloy layer; 7: p is p + A layer; 8: a back electrode; 9: a contact hole (opening); 10: paste composition.
Claims (1)
1. A paste composition for solar cells, which comprises an aluminum powder, an organic carrier and a glass frit, and is characterized by comprising 30-35 parts by mass of the organic carrier and 0.5-5.0 parts by mass of the glass frit per 100 parts by mass of the aluminum powder, wherein the glass frit contains 52-70 mol% of Sb 2 O 3 And contains SiO 2 And/or B 2 O 3 ，B 2 O 3 The content of (C) is 30-40 mol%, siO 2 The content of (C) is 0 to 14 mol%.
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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 |
| CN112542530B (en) * | 2020-12-01 | 2024-03-08 | 浙江晶科能源有限公司 | Photovoltaic cell and preparation method thereof |
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| JPWO2018221578A1 (en) | 2020-04-02 |
| JP7013458B2 (en) | 2022-01-31 |
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