WO2010098167A1 - 太陽電池電極用ペースト組成物 - Google Patents
太陽電池電極用ペースト組成物 Download PDFInfo
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- WO2010098167A1 WO2010098167A1 PCT/JP2010/051174 JP2010051174W WO2010098167A1 WO 2010098167 A1 WO2010098167 A1 WO 2010098167A1 JP 2010051174 W JP2010051174 W JP 2010051174W WO 2010098167 A1 WO2010098167 A1 WO 2010098167A1
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- solar cell
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000011521 glass Substances 0.000 claims abstract description 75
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 239000002003 electrode paste Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 abstract description 44
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 22
- 238000000034 method Methods 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 14
- 239000010703 silicon Substances 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 13
- 239000004332 silver Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 239000004020 conductor Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 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
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000005355 lead glass Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/80—Constructional details
- H10K10/82—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
Definitions
- the present invention relates to a paste composition suitable for a solar cell electrode formed by a fire-through method.
- a general silicon-based solar cell is provided with an antireflection film and a light-receiving surface electrode on an upper surface of a silicon substrate which is a p-type polycrystalline semiconductor via an n + layer, and on the lower surface via a p + layer. It has a structure provided with electrodes (hereinafter simply referred to as “electrodes” when they are not distinguished from each other).
- the antireflection film is for reducing the surface reflectance while maintaining sufficient visible light transmittance, and is made of a thin film of silicon nitride, titanium dioxide, silicon dioxide or the like.
- the light-receiving surface electrode of the solar cell is formed by a method called fire-through, for example.
- this electrode forming method for example, after the antireflection film is provided on the entire surface of the n + layer, a conductive paste is applied on the antireflection film in an appropriate shape by using, for example, a screen printing method, and is fired. Apply.
- the process is simplified as compared with the case where the antireflection film is partially removed and an electrode is formed on the removed portion, and the problem of misalignment between the removed portion and the electrode forming position does not occur. .
- the conductive paste is mainly composed of, for example, silver powder, glass frit (a piece of flaky or powdered glass that is crushed as necessary after melting and quenching the glass raw material), an organic vehicle, and an organic solvent.
- glass frit a piece of flaky or powdered glass that is crushed as necessary after melting and quenching the glass raw material
- organic vehicle for example, an organic solvent.
- the glass component in the conductive paste breaks the antireflection film, so that an ohmic contact is formed by the conductive component in the conductive paste and the n + layer (for example, Patent Documents). See 1).
- a silver-containing paste containing 85 to 99 (wt%) silver and 1 to 15 (wt%) glass the glass is mixed with 15 to 75 (mol%) PbO and 5 to 50 (mol%) SiO. comprises 2, it is a composition that does not contain B 2 O 3 has been proposed (e.g., see Patent Document 4.).
- This silver-containing paste is used for forming an electrode of a solar cell, and the ohmic contact is improved by using the glass having the above composition.
- a thick film conductive composition in which silver powder, a zinc-containing additive, and a glass frit having a softening point in the range of 300 to 600 (° C.) are dispersed in an organic solvent has been proposed (for example, a patent (Ref. 5).
- This thick film conductive composition is for forming a light-receiving surface electrode of a solar cell, and conductivity and solder adhesion are improved by adding zinc.
- the firing temperature greatly affects the solar cell output. If the firing profile deviates from the optimum firing temperature for generating the light-receiving surface electrode from the electrode paste, the action of glass and silver breaking the antireflection film decreases, and as a result ohmic contact between the light-receiving surface electrode and the n + layer As a result, the solar cell output will be reduced.
- the range of the optimum firing temperature is as small as about 10 (° C.) or less, it has been difficult to reliably obtain a high output solar cell. The same applies to various proposals for improving the ohmic contact as described above.
- the optimum firing temperature is the temperature at which the maximum value of the fill factor is obtained.
- each of the silicon substrate there are variations in the thickness of each of the silicon substrate, the antireflection film, and the n layer, etc., so that each optimum firing condition varies. It will be.
- the maximum value of the fill factor is obtained in a sufficiently wide temperature range for each substrate, but the optimum firing temperature range for each lot that is determined by the overlapping range of the optimum firing temperature range of each substrate in the production lot is It was narrow due to the above variation.
- the takt time of the solar cell manufacturing process is as short as about 3 seconds per sheet, it is impossible to optimize the firing conditions in consideration of the variation of each sheet.
- the present invention has been made in the background of the above circumstances, and an object thereof is to provide a solar cell electrode paste composition having a wide optimum firing temperature range in a firing step of solar cell production.
- the gist of the present invention is a paste composition for a solar cell electrode comprising conductive powder, glass frit, and a vehicle, wherein (a) the glass frit is an oxide. It is made of glass containing PbO 46 to 57 (mol%), B 2 O 3 1 to 7 (mol%), and SiO 2 38 to 53 (mol%) in terms of conversion.
- the solar cell electrode paste composition has a glass frit constituting PbO 46 to 57 (mol%), B 2 O 3 1 to 7 (mol%), SiO 2 38 to 53 (mol). %),
- the optimum firing temperature range of the solar cell that uses this to form the light-receiving surface electrode is widened.
- the optimum firing temperature range for each production lot extends to about 30-40 (° C). Therefore, the fire-through property is improved and the ohmic contact is improved, so that the average output per production lot is improved.
- PbO is a component that lowers the softening point of glass and is essential for enabling low-temperature firing.
- PbO in order to obtain good fire-through properties, it is necessary that PbO is 46 (mol%) or more and 57 (mol%) or less.
- the amount of PbO is more preferably 49 (mol%) or more, and further preferably 54 (mol%) or less. That is, the range of 49 to 54 (mol%) is more preferable.
- B 2 O 3 is a glass-forming oxide (that is, a component that forms a glass skeleton), and is an essential component for lowering the softening point of glass.
- B 2 O 3 in order to obtain good fire-through properties, B 2 O 3 needs to be 1 (mol%) or more and 7 (mol%) or less.
- the amount of B 2 O 3 is more preferably 3 (mol%) or more, and further preferably 5 (mol%) or less. That is, the range of 3 to 5 (mol%) is more preferable.
- SiO 2 is a glass forming oxide and is an essential component for increasing the chemical resistance of glass.
- SiO 2 in order to obtain good fire-through properties, SiO 2 needs to be 38 (mol%) or more and 53 (mol%) or less.
- the amount of SiO 2 is more preferably 43 (mol%) or more, and more preferably 48 (mol%) or less. That is, the range of 43 to 48 (mol%) is more preferable.
- the glass constituting the electrode paste of the present invention may contain other various glass components and additives as long as the properties are not impaired.
- Al, Zr, Na, Li, Ca, Zn, Mg, K, Ti, Ba, Sr, etc. may be contained. These may be included in a total range of 10 (mol%) or less, for example.
- Patent Document 3 is composed of glass containing glass frit in the range of Bi 2 O 3 20 (mol%) or more, B 2 O 3 50 (mol%) or less, SiO 2 60 (mol%) or less.
- a conductive paste is described.
- the purpose of this conductive paste is to improve that lead-based glass has poor wettability and connection reliability cannot be obtained when lead terminals or the like are attached using lead-free solder.
- proposals focusing on the composition of the glass frit constituting the conductive paste have been made in the past.
- the conductive paste is completely different in purpose and composition from the electrode paste of the present invention. Is different.
- the glass frit has an average particle diameter in the range of 0.5 to 3 ( ⁇ m).
- the average particle size is 0.5 ( ⁇ m) or more, the dispersibility at the time of preparing the paste is further improved, and thus good printability is obtained.
- the larger the average particle size of the glass frit the more difficult it is to melt the glass and the FF value tends to decrease, so to obtain a sufficiently high FF value, the average particle size should be 3 ( ⁇ m) or less. Is preferred.
- the solar cell electrode paste composition includes the glass frit in a ratio within a range of 7 to 35 (vol%) with respect to the entire paste.
- the antireflective film is suitably dissolved by the glass frit in the paste, so that a better ohmic contact can be obtained and the FF value can be further increased.
- the glass frit is contained in an amount of 7 (vol%) or more, the solubility of the antireflection film becomes extremely high, so that the optimum firing temperature range is further widened.
- it is 35 (vol%) or less, since an insulating layer is difficult to form, the high electroconductivity between an electrode and a board
- the conductive powder is a silver powder.
- the conductive powder copper powder, nickel powder or the like can be used, but silver powder is most preferable because high conductivity can be obtained.
- the solar cell electrode paste composition contains 64 to 90 parts by weight of the silver powder and 5 to 20 parts by weight of the vehicle. By doing so, it is possible to obtain a conductive composition that can produce an electrode having good printability, high conductivity, and good solder wettability. If the silver powder is too small, high conductivity cannot be obtained, and if it is excessive, the fluidity is lowered and the printability is deteriorated. If the glass frit is too small, the adhesion to the substrate is insufficient. If the glass frit is excessive, the glass floats on the electrode surface after firing, resulting in poor solder wettability.
- the silver powder is not particularly limited, and the basic effect of the present invention that the optimum firing temperature range can be expanded regardless of the shape of the powder, such as a spherical shape or a scale shape, can be enjoyed.
- the printability is excellent and the filling rate of the silver powder in the coating film is increased. Therefore, in combination with the use of highly conductive silver, Compared with the case where silver powder of another shape such as a shape is used, the conductivity of the electrode generated from the coating film is increased. Therefore, the line width can be further reduced while ensuring the necessary conductivity. Therefore, if the conductive composition is applied to the light-receiving surface electrode to reduce the line width, the light-receiving area capable of absorbing solar energy can be further increased, and thus a solar cell with higher conversion efficiency can be obtained.
- the conductive composition of the present invention can be suitably used for the light-receiving surface electrode because it can suitably control the diffusion of silver during the electrode formation by fire-through as described above.
- it is not limited to the light receiving surface electrode, and can be used as a back surface electrode.
- the back electrode is composed of an aluminum film covering the entire surface and a strip-like electrode overlapping therewith, but is also suitable as a constituent material of the strip-like electrode.
- the glass frit can be synthesized from various raw materials that can be vitrified within the composition range, and examples thereof include oxides, carbonates, nitrates, etc.
- the Si source include silicon dioxide SiO 2.
- B source boron oxide B 2 O 3 can be used, and as the Pb source, red lead Pb 3 O 4 can be used.
- composition includes other components such as Al and Zr in addition to the main components Si, B and Pb, for example, their oxides, hydroxides, carbonates, nitrates and the like may be used.
- FIG. 3 It is a schematic diagram which shows the cross-sectional structure of the solar cell with which the paste composition for electrodes of one Example of this invention was applied for formation of a light-receiving surface electrode. It is a figure which shows an example of the light-receiving surface electrode pattern of the solar cell of FIG. It is the figure which represented the main component composition of the glass frit used by the Example and the comparative example to the triangular diagram. In the triangular diagram of FIG. 3, it is a figure which expands and shows the area
- FIG. 1 is a diagram schematically showing a cross-sectional structure of a silicon-based solar cell 10 to which a conductive composition according to an embodiment of the present invention is applied.
- a solar cell 10 is formed on a silicon substrate 12 which is, for example, a p-type polycrystalline semiconductor, an n + layer 14 and a p + layer 16 respectively formed on the upper and lower surfaces thereof, and the n + layer 14.
- the antireflection film 18 and the light receiving surface electrode 20, and the back electrode 22 formed on the p + layer 16 are provided.
- the n + layer 14 and the p + layer 16 are provided by forming layers having a high impurity concentration on the upper and lower surfaces of the silicon substrate 12, and the thickness dimension of the high concentration layer, that is, the layers 14 and 16 are formed.
- the thickness dimension is, for example, about 0.5 ( ⁇ m).
- the impurity contained in the n + layer 14 is, for example, phosphorus (P) that is an n-type dopant
- the impurity contained in the p + layer 16 is, for example, boron (B) that is a p-type dopant.
- the antireflection film 18 is a thin film made of, for example, silicon nitride Si 3 N 4 , and is provided with an optical thickness of, for example, about 1 ⁇ 4 of the visible light wavelength. It has a very low reflectivity of about 2%.
- the light-receiving surface electrode 20 is made of, for example, a thick film conductor having a uniform thickness. As shown in FIG. 2, the light-receiving surface electrode 20 is a comb having a large number of thin line portions substantially on the entire surface of the light-receiving surface 24. Are provided in a planar shape.
- the above thick film conductor is composed of thick film silver containing about 67 to 98 (wt%) Ag and about 2 to 33 (wt%) glass. The glass is an oxide equivalent value, and PbO This lead glass contains 46 to 57 (mol%), B 2 O 3 in a range of 1 to 7 (mol%), and SiO 2 in a ratio of 38 to 53 (mol%).
- the thickness dimension of the conductor layer is, for example, in the range of 15 to 20 ( ⁇ m), for example, about 17 ( ⁇ m), and the width dimension of each thin wire portion is in the range of, for example, 80 to 130 ( ⁇ m). It is about 100 ( ⁇ m) and has sufficiently high conductivity.
- the back electrode 22 is formed by applying a full-surface electrode 26 formed by applying a thick film material containing aluminum as a conductor component on the p + layer 16 over almost the entire surface, and a strip-like application on the full-surface electrode 26.
- the band-shaped electrode 28 made of thick film silver is formed.
- the belt-like electrode 28 is provided in order to make it possible to solder a conducting wire or the like to the back electrode 22.
- the light-receiving surface electrode 20 is composed of thick film silver containing lead glass having the above-described composition in the range of 2 to 33 (wt%) as described above.
- the firing margin is large as compared with a solar cell using various kinds of glass conventionally used.
- the light-receiving surface electrode 20 as described above is formed by a well-known fire-through method using an electrode paste made of, for example, conductor powder, glass frit, vehicle, and solvent.
- An example of the manufacturing method of the solar cell 10 including the formation of the light receiving surface electrode will be described below together with the manufacturing method of the conductive composition of the comparative example.
- the glass frit is produced. Silicon dioxide SiO2 as Si source, boron oxide B 2 O 3 as B source, lead oxide Pb 3 O 4 as Pb source, aluminum oxide Al 2 O 3 as Al source, zirconium oxide ZrO 2 as Zr source, Table 1 shows sodium oxide Na 2 O as the Na source, lithium oxide Li 2 O as the Li source, calcium oxide CaO as the Ca source, zinc oxide ZnO as the Zn source, and magnesium oxide MgO as the Mg source. It was weighed and prepared so as to have the composition shown. This was put into a crucible and melted for about 30 minutes to 1 hour at a temperature in the range of 900 to 1100 (° C.) depending on the composition to be vitrified. The obtained glass is pulverized using an appropriate pulverizer such as a pot mill to obtain powder having an average particle size of 0.4 ( ⁇ m), 0.6 ( ⁇ m), 1.5 ( ⁇ m), 3.0 ( ⁇ m), 4.0 ( ⁇ m). It was.
- the conductor powder for example, a commercially available spherical silver powder having an average particle diameter in the range of 1 to 3 ( ⁇ m), for example, about 2 ( ⁇ m) was prepared.
- the vehicle is prepared by dissolving an organic binder in an organic solvent.
- butyl carbitol acetate is used as the organic solvent
- ethyl cellulose is used as the organic binder.
- the ratio of ethyl cellulose in the vehicle is, for example, about 15 (wt%).
- a solvent added separately from the vehicle is, for example, butyl carbitol acetate. That is, although not limited to this, the same solvent as that used for the vehicle may be used. This solvent is added for the purpose of adjusting the viscosity of the paste.
- the paste materials above for example, the ratio of conductor powder 64 to 82 (wt%), glass frit 2 to 20 (wt%), vehicle 13 (wt%), solvent 3 (wt%) Then, after mixing using a stirrer or the like, for example, a dispersion treatment is performed using a three-roll mill. Thereby, the electrode paste is obtained.
- the total amount of the conductor powder and the glass frit was 84 (wt%), and the total amount of the vehicle and the solvent was 16 (wt%).
- Table 1 shows the composition of the glass frit in each of the examples and the comparative examples, the particle size, the added amount, and the characteristics of the solar cell 10 when the light-receiving surface electrode 20 is formed using each glass frit. This is a summary of the evaluation results.
- the glass frit amount is expressed as a volume with respect to the entire paste.
- the n + layer 14 and the p + are diffused or implanted into an appropriate silicon substrate by a well-known method such as a thermal diffusion method or ion plantation.
- a silicon substrate 12 is produced.
- a silicon nitride thin film is formed thereon by an appropriate method such as spin coating, and the antireflection film 18 is provided.
- the electrode paste is screen-printed on the antireflection film 18 with the pattern shown in FIG. This is dried at, for example, 150 (° C.), and further baked at a temperature in the range of 760 to 900 (° C.) in a near infrared furnace.
- the glass component in the electrode paste dissolves the antireflection film 18 in the firing process, and the electrode paste breaks the antireflection film 18, so that the conductor component in the electrode paste, that is, silver and the n + layer 14
- ohmic contact between the silicon substrate 12 and the light receiving surface electrode 20 is obtained.
- the light receiving surface electrode 20 is formed in this way.
- the said back surface electrode 22 may be formed after the said process, it can also be formed by baking simultaneously with the light-receiving surface electrode 20.
- FIG. When the back electrode 22 is formed, the entire surface electrode 26 made of a thick aluminum film is formed by applying, for example, an aluminum paste to the entire back surface of the silicon substrate 12 by screen printing or the like and performing a baking process. Further, the strip electrode 28 is formed by applying the electrode paste on the surface of the entire surface electrode 26 in a strip shape using a screen printing method or the like and performing a baking treatment. Thereby, the back electrode 22 which consists of the full surface electrode 26 which covers the whole back surface, and the strip
- the characteristics shown in the rightmost column 2 of Table 1 described above are the firing temperature for each of the Examples and Comparative Examples in which the glass composition, particle size, and addition amount were variously changed.
- the light-receiving surface electrode 20 is changed within the above range, the output of the obtained solar cell 10 is measured, the maximum value of the fill factor FF, and the FF value equal to or higher than 1% lower than the maximum value. This is the result of evaluating the temperature range in which the above is obtained, that is, the firing margin.
- the output of the solar cell 10 was measured using a commercially available solar simulator.
- the solar cell can be used if an FF value of 70 or more is obtained, but it is of course preferable that the FF value is higher.
- FF values of 74 to 75 are obtained, and a sufficiently high output can be obtained.
- a sufficiently wide firing margin of 30 to 40 (° C.) is obtained.
- PbO is 46 to 57 (mol%)
- B 2 O 3 is 1 to 7 (mol%)
- SiO 2 is 38 to 53 (mol%).
- the FF value is sufficiently high and the firing margin is sufficiently wide.
- Al 2 O 3 is 3 (mol%) or less
- ZrO 2 is 5 (mol%) or less
- Na 2 O is 3 (mol%).
- Li 2 O is 7 (mol%) or less
- CaO is 2 (mol%) or less
- ZnO is 1 (mol%) or less
- MgO is contained in the range of 5 (mol%) or less. Special characteristics can be obtained.
- the firing margin is a value that takes into account the influence of variations in substrate thickness within the production lot on the optimum firing temperature. That is, even when the thickness variation is taken into consideration, the temperature range in which “FF maximum value ⁇ 1%” is obtained is sufficiently wide as 30 to 40 (° C.).
- Comparative Examples 12 to 15 the glass composition is included in the scope of the present invention, and the characteristics are slightly lower than those in Examples 1 to 22, but the glass compositions can be used for solar cells. Therefore, these can be added to the examples, but here they are classified as comparative examples. Comparative Examples 12 and 13 have the same composition as Example 10, but the amount of glass frit added is too small (5 (vol%)) or excessive (47 (vol%)), so the FF value is slightly lower. It stays at 70-71. However, this value satisfies the minimum requirements for solar cell applications, and the firing margin is sufficiently wide at 30 (° C.), and thus the present invention includes such a configuration.
- Comparative Examples 14 and 15 the composition is the same as that of Example 4, but the particle size of the glass frit is too small (0.4 ( ⁇ m)) or too large (4.0 ( ⁇ m)).
- the firing margin is limited to a narrow range of 15 to 20 ° C.
- this FF value satisfies the minimum requirements for solar cell applications and can be said to be improved as compared with Comparative Examples 1 to 11 in which the firing margin is 10 (° C.) or less. Such a configuration is also included.
- the glass composition constituting the glass frit is 46 to 57 (mol%) PbO and 1 to 7 (mol%) B 2 O 3 (preferably 3 (mol%) or more. ) If SiO 2 is in the range of 38 to 53 (mol%), an electrode paste having an FF value of 70 or more and a firing margin of 15 (° C.) or more can be obtained. Further, when the addition amount of the glass frit is in the range of 7 to 35 (vol%), a higher FF value can be obtained than in the case outside the range. If the particle size of the glass frit is in the range of 0.5 to 3.0 ( ⁇ m) (preferably 0.6 to 3.0 ( ⁇ m)), the firing margin can be expanded to 30 (° C.) or more.
- FIG. 3 is a triangular diagram showing the composition ratios of the main components Pb, B, and Si of the glass frit used in Examples 1 to 10 and Comparative Examples 1 to 10 shown in Table 1, respectively.
- FIG. 5 shows an enlarged region in which the compositions of other examples and comparative examples except comparative example 11 are distributed.
- the other examples and comparative examples described above are compositions that are significantly different from those of Comparative Example 11, and the others are listed because they contain other components or have the same composition but different particle sizes or addition amounts. Was omitted.
- the range surrounded by the alternate long and short dash line and shaded is the composition range of the main component of the present invention.
- the compositions of Comparative Examples 1 to 15 are selected so as to be distributed around the periphery.
- Comparative Examples 1 and 5 to 8 which are relatively close to the composition range of the examples, the maximum FF value is sufficiently high, but the firing margin becomes narrow to 5 to 10 (° C.).
- FIG. 5 shows an enlarged view of the region in the vicinity of the embodiment shown in FIG.
- Table 1 an FF value of 74 (%) or more and a firing margin of 30 (° C.) or more can be obtained within the range of the present embodiment, regardless of the glass frit having any composition.
- a glass frit having a composition within the range surrounded by the two-dot chain line in FIG. 5 is used, a more preferable result is obtained with an FF value of 75 (%) and a firing margin of 40 (° C.).
- PbO is in the range of 49 to 54 (mol%)
- B 2 O 3 is in the range of 3 to 5 (mol%)
- SiO 2 is in the range of 43 to 48 (mol%).
- glass frit is used.
- the electrode paste of the solar cell 10 has a glass frit constituting 46 to 57 (mol%) of PbO, 1 to 7 (mol%) of B 2 O 3 , SiO 2 Is made of glass in the range of 38 to 53 (mol%), the optimum firing temperature range of the solar cell 10 for forming the light-receiving surface electrode 20 by using this is widened.
- the optimum firing temperature range for each production lot extends to about 30-40 (° C). Therefore, the fire-through property is improved and the ohmic contact is improved, so that the average output per production lot is improved.
- the antireflection film 18 is made of a silicon nitride film.
- the constituent material is not particularly limited, and various other materials such as titanium dioxide TiO 2 generally used for solar cells. Those consisting of can be used as well.
- the present invention is applicable to any solar cell that can form a light-receiving surface electrode by a fire-through method.
- the substrate material is not particularly limited.
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Abstract
Description
12:シリコン基板
14:n+層
16:p+層
18:反射防止膜
20:受光面電極
22:裏面電極
24:受光面
26:全面電極
28:帯状電極
Claims (4)
- 導電性粉末と、ガラスフリットと、ベヒクルとを含む太陽電池電極用ペースト組成物であって、
前記ガラスフリットが酸化物換算でPbO 46~57(mol%)、B2O3 1~7(mol%)、SiO2 38~53(mol%)の範囲内の割合で含むガラスから成ることを特徴とする太陽電池電極用ペースト組成物。 - 前記ガラスフリットは平均粒径が0.5~3(μm)の範囲内である請求項1の太陽電池電極用ペースト組成物。
- 前記ガラスフリットをペースト全体に対して7~35(vol%)の範囲内の割合で含むものである請求項1または請求項2の太陽電池電極用ペースト組成物。
- 前記導電性粉末は銀粉末である請求項1乃至請求項3の何れか1項に記載の太陽電池電極用ペースト組成物。
Priority Applications (4)
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KR1020117022303A KR101674233B1 (ko) | 2009-02-25 | 2010-01-28 | 태양 전지 전극용 페이스트 조성물 |
DE112010000891T DE112010000891T5 (de) | 2009-02-25 | 2010-01-28 | Pastenzusammensetzung für Solarzellenelektrode |
CN201080017522.2A CN102405530B (zh) | 2009-02-25 | 2010-01-28 | 太阳能电池电极用膏组合物 |
US13/203,359 US8512601B2 (en) | 2009-02-25 | 2010-01-28 | Paste composition for solar cell electrode |
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JP2009-043154 | 2009-02-25 | ||
JP2009043154A JP5059042B2 (ja) | 2009-02-25 | 2009-02-25 | 太陽電池電極用ペースト組成物 |
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JP (1) | JP5059042B2 (ja) |
KR (1) | KR101674233B1 (ja) |
CN (1) | CN102405530B (ja) |
DE (1) | DE112010000891T5 (ja) |
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WO2013018462A1 (ja) * | 2011-07-29 | 2013-02-07 | 株式会社ノリタケカンパニーリミテド | 太陽電池用導電性ペースト組成物 |
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JP2012142422A (ja) * | 2010-12-28 | 2012-07-26 | Noritake Co Ltd | 太陽電池用導電性ペースト用ガラス |
JP5820278B2 (ja) * | 2012-01-10 | 2015-11-24 | シャープ株式会社 | 太陽電池及び太陽電池の製造方法 |
JP2013243279A (ja) * | 2012-05-22 | 2013-12-05 | Namics Corp | 太陽電池の電極形成用導電性ペースト |
KR101600652B1 (ko) | 2012-11-12 | 2016-03-07 | 제일모직주식회사 | 태양전지 전극용 페이스트 및 이로부터 제조된 전극 |
CN103021567A (zh) * | 2012-12-04 | 2013-04-03 | 彩虹集团公司 | 一种硅基太阳能用正面电极银浆的制备方法 |
US20170291846A1 (en) * | 2016-04-07 | 2017-10-12 | Heraeus Precious Metals North America Conshohocken Llc | Halogenide containing glasses in metallization pastes for silicon solar cells |
JP6266079B2 (ja) * | 2016-11-22 | 2018-01-24 | ナミックス株式会社 | 太陽電池の電極形成用導電性ペースト及び太陽電池の製造方法 |
WO2019183931A1 (zh) * | 2018-03-30 | 2019-10-03 | 深圳市首骋新材料科技有限公司 | 晶硅太阳能电池正面导电浆料及其制备方法和太阳能电池 |
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KR20110115620A (ko) | 2011-10-21 |
KR101674233B1 (ko) | 2016-11-08 |
JP5059042B2 (ja) | 2012-10-24 |
CN102405530A (zh) | 2012-04-04 |
US20110309312A1 (en) | 2011-12-22 |
TW201035993A (en) | 2010-10-01 |
DE112010000891T5 (de) | 2012-06-14 |
TWI492245B (zh) | 2015-07-11 |
US8512601B2 (en) | 2013-08-20 |
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JP2010199334A (ja) | 2010-09-09 |
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