WO2011013469A1 - ペースト組成物およびそれを用いた太陽電池素子 - Google Patents
ペースト組成物およびそれを用いた太陽電池素子 Download PDFInfo
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- WO2011013469A1 WO2011013469A1 PCT/JP2010/060944 JP2010060944W WO2011013469A1 WO 2011013469 A1 WO2011013469 A1 WO 2011013469A1 JP 2010060944 W JP2010060944 W JP 2010060944W WO 2011013469 A1 WO2011013469 A1 WO 2011013469A1
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- Prior art keywords
- oxide
- paste composition
- aluminum
- glass frit
- electrode layer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000011521 glass Substances 0.000 claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 239000010703 silicon Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000004065 semiconductor Substances 0.000 claims abstract description 42
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 26
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 96
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000010304 firing Methods 0.000 abstract description 17
- 239000000843 powder Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 3
- 238000007792 addition Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- -1 glycol ethers Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
Classifications
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- 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
- 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
- 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 generally relates to a paste composition and a solar cell element using the same, and more specifically, aluminum used for forming an electrode on a silicon semiconductor substrate constituting a crystalline silicon solar cell.
- the present invention relates to a paste composition containing powder and a solar cell element formed using the paste composition.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2000-90734
- Patent Document 2 Japanese Patent Application Laid-Open No. 2004-134775
- FIG. 1 is a diagram schematically showing a general cross-sectional structure of a solar cell element.
- the solar cell element is formed using a p-type silicon semiconductor substrate 1 having a thickness of 180 to 250 ⁇ m.
- a p-type silicon semiconductor substrate 1 having a thickness of 180 to 250 ⁇ m.
- an n-type impurity layer 2 having a thickness of 0.3 to 0.6 ⁇ m, and an antireflection film 3 and a grid electrode 4 are formed thereon.
- An aluminum electrode layer 5 is formed on the back side of the p-type silicon semiconductor substrate 1.
- the aluminum electrode layer 5 is formed by applying an aluminum paste composition made of aluminum powder, glass frit, and organic vehicle by screen printing or the like, drying it, and firing it at a temperature of 660 ° C. (melting point of aluminum) or higher for a short time. Is formed. During the firing, aluminum diffuses into the p-type silicon semiconductor substrate 1, thereby forming an Al—Si alloy layer 6 between the aluminum electrode layer 5 and the p-type silicon semiconductor substrate 1.
- a p + layer 7 is formed as an impurity layer by atomic diffusion. Due to the presence of the p + layer 7, a BSF (Back Surface Field) effect that prevents recombination of electrons and improves the collection efficiency of generated carriers can be obtained.
- BSF Back Surface Field
- the p-type silicon semiconductor substrate 1 is not warped, and no blisters or aluminum balls are generated on the aluminum electrode layer 5.
- appearance characteristics are also required for the p-type semiconductor substrate 1 and the aluminum electrode layer 5. That is, there is a demand for an aluminum paste composition that can satisfy such appearance characteristics.
- Patent Document 3 discloses an Al—Mg alloy powder and a compound containing Mg as a main component in an aluminum powder as a conductive paste capable of forming a back electrode with high adhesion strength. Additions are disclosed.
- Patent Document 4 discloses a composite in which a fine low-melting glass powder is fixed to a fine Al powder surface as a conductive paste capable of forming a back electrode having high adhesion strength. The use of Al powder is disclosed.
- Patent Document 5 discloses that an Al—Si eutectic structure layer can be uniformly formed at the interface between a back electrode and a p-type Si semiconductor substrate without any gap.
- a conductive paste capable of improving the conversion efficiency of the battery Al powder, glass frit, and vehicle are contained, and the glass frit is Bi 2 O 3 : 30 to 70 mol%, B 2 O 3 : Those containing 20 to 60 mol% and SiO 2 : 10 to 50 mol% are disclosed.
- the glass frit included in the aluminum paste for forming the back electrode of the solar cell is mainly composed of PbO—B 2 O 3 —SiO 2 , PbO—B 2 O 3 —Al 2 O 3 , PbO—B 2.
- Those containing oxides such as O 3 —ZnO, Bi 2 O 3 —B 2 O 3 —SiO 2 and Bi 2 O 3 —B 2 O 3 —ZnO are known.
- the conventional glass frit containing PbO and B 2 O 3 as main components has an action of promoting the reaction between the aluminum powder in the aluminum paste and the silicon of the substrate during the baking of the aluminum paste.
- Patent Document 6 Japanese Patent Publication No. 2008-543080 proposes a paste composition that does not contain harmful substances such as Pb and Cd.
- the conventional glass frit containing PbO and B 2 O 3 as main components causes a rapid reaction between aluminum and silicon, resulting in an increase in the amount of Al—Si alloy produced, and blisters and aluminum balls are formed on the aluminum electrode layer. May be more likely to occur.
- a paste composition containing as little PbO as possible is required.
- the aluminum electrode layer 5 is not peeled off during or after the production of the solar cell module, and the aluminum electrode layer 5 is peeled off from the p-type silicon semiconductor substrate 1 after the produced solar cell module is installed outdoors.
- the water that has penetrated into the solar cell module does not react with the aluminum electrode layer 5.
- the hydrogen gas generated by the reaction between the aluminum electrode layer 5 and moisture does not generate bubbles in the solar cell module and that the back surface protection sheet does not turn yellow.
- Patent Document 3 discloses a paste composition that does not contain harmful substances such as Pb and Cd. However, no consideration is given to the property of suppressing the reaction between the aluminum electrode layer obtained after firing and moisture. It has not been.
- the glass frit component contained in the paste composition further improves the adhesion between the aluminum electrode layer obtained after firing and the silicon semiconductor substrate, and the relationship between the aluminum electrode layer and moisture. There is no disclosure of inhibiting the reaction.
- an object of the present invention is to solve the above-mentioned problems, and has the appearance characteristics that the silicon semiconductor substrate is not warped and blisters and aluminum balls are not generated in the aluminum electrode layer obtained after firing.
- a paste composition capable of satisfying the characteristics of not only satisfying but also improving the adhesion between the aluminum electrode layer and the silicon semiconductor substrate and suppressing the reaction between the aluminum electrode layer and moisture; It is providing the solar cell element provided with the electrode formed using the composition.
- the paste composition according to the present invention has the following characteristics.
- a paste composition according to the present invention is a paste composition for forming an electrode on a silicon semiconductor substrate, and includes an aluminum powder, an organic vehicle, and a glass frit, and the glass frit includes titanium oxide, At least one transition metal oxide selected from the group consisting of vanadium oxide, iron oxide, molybdenum oxide, neodymium oxide, and tungsten oxide is included.
- the glass frit preferably contains no lead, or preferably contains 0.1% by mass or less of lead.
- the glass frit further comprises boron oxide, bismuth oxide, silicon oxide, aluminum oxide, tin oxide, phosphorus oxide, manganese oxide, barium oxide, antimony oxide, lithium oxide, sodium oxide, And it is preferable that at least 1 sort (s) chosen from the group which consists of potassium oxide is included.
- the transition metal oxide is preferably contained in an amount of 10% by mass to 95% by mass in the glass frit.
- the paste composition of this invention it is preferable to contain 0.03 mass% or more and 10 mass% or less of glass frit in the said paste composition.
- the solar cell element according to the present invention includes an electrode formed by applying a paste composition having any of the above-described characteristics on a silicon semiconductor substrate and then baking the paste composition.
- the silicon semiconductor substrate is not warped and obtained after firing.
- the aluminum electrode layer does not generate blisters or balls of aluminum, it improves the adhesion between the aluminum electrode layer and the silicon semiconductor substrate, and the reaction between the aluminum electrode layer and moisture. Since the characteristic of suppressing can be satisfy
- the paste composition of the present invention includes a glass frit in addition to the aluminum powder and the organic vehicle, and includes a transition metal oxide of a type in which the glass frit is limited.
- the glass frit is said to have an effect of assisting the reaction between aluminum and silicon and sintering of the aluminum powder itself.
- a glass frit having a conventional composition when used, the adhesion between the aluminum electrode layer obtained after firing and the silicon semiconductor substrate is improved, and the reaction between the aluminum electrode layer and moisture is suppressed. A solar cell element having the characteristics could not be obtained.
- the glass frit containing a limited kind of transition metal oxide is included in the paste, whereby the reaction between aluminum and silicon can be controlled so as not to proceed excessively. Thereby, it is thought that generation
- the mechanism is not clear, but not only can the reaction between aluminum and silicon be controlled, but also aluminum and Reaction with moisture can be suppressed.
- the mechanical strength of the aluminum electrode layer can be improved, and the adhesion between the aluminum electrode layer and the silicon of the substrate can be improved. Can also be improved.
- transition metal oxide As the limited type of transition metal oxide, at least one selected from the group consisting of titanium oxide, vanadium oxide, iron oxide, molybdenum oxide, neodymium oxide, and tungsten oxide can be used.
- the glass frit of the present invention contains at least one of the limited transition metal oxides as an essential component, but boron oxide, bismuth oxide, silicon oxide can be used as an oxide for constituting a glass having predetermined characteristics. Further, at least one selected from the group consisting of aluminum oxide, tin oxide, phosphorus oxide, manganese oxide, barium oxide, antimony oxide, lithium oxide, sodium oxide and potassium oxide can be used.
- the content of the limited type of transition metal oxide in the glass frit of the present invention is not particularly limited, but preferably the content of the transition metal oxide is 10% by mass or more and 95% by mass in the glass frit. % Or less. If the content of the transition metal oxide is less than 10% by mass, the effect of addition of the transition metal oxide is insufficient, improving the adhesion between the aluminum electrode layer and the silicon semiconductor substrate, and the aluminum electrode layer and moisture. It is impossible to combine the characteristics of suppressing the reaction with the.
- the content of the transition metal oxide is 25% by mass or more, more preferably 30% by mass or more.
- the upper limit of the content of the transition metal oxide is not particularly limited. However, when the content of the transition metal oxide exceeds 95% by mass, vitrification becomes difficult, which is not preferable.
- the glass frit of the present invention can be used by further containing other oxides and compounds as subcomponents, if necessary.
- the method for producing the glass frit of the present invention is not particularly limited, and various raw materials are prepared, melted, vitrified, pulverized and dried so as to have a predetermined glass frit composition by a known glass production method. And classification to obtain a predetermined glass frit.
- the glass frit content is preferably 0.03% by mass or more and 10% by mass or less in the paste composition. If the glass frit content is less than 0.03% by mass, it has the characteristics of improving the adhesion between the aluminum electrode layer and the silicon semiconductor substrate and suppressing the reaction between the aluminum electrode layer and moisture. However, since it is not sufficient to suppress the generation of blisters or aluminum balls in the aluminum electrode layer, the surface resistance of the aluminum electrode layer and the surface resistance of the p + layer are increased, which is not preferable. When the glass frit content exceeds 10% by mass, it has the characteristics of improving the adhesion between the aluminum electrode layer and the silicon semiconductor substrate and suppressing the reaction between the aluminum electrode layer and moisture.
- the glass frit content is 0.05% by mass or more and 8% by mass or less.
- the average particle size of the glass frit particles included in the paste composition of the present invention is not particularly limited, but is preferably 10 ⁇ m or less.
- the content of the aluminum powder included in the paste composition of the present invention is preferably 60% by mass or more and 85% by mass or less. If the content of the aluminum powder is less than 60% by mass, the resistance of the aluminum electrode layer obtained after firing becomes high, which may cause a decrease in energy conversion efficiency of the solar cell. When the content of the aluminum powder exceeds 85% by mass, the applicability of the paste in screen printing or the like is lowered.
- a wide range of aluminum powder having an average particle size of 1 to 20 ⁇ m can be used, and when blended in a paste composition, it is preferably 2 to 15 ⁇ m, more preferably 3 to 10 ⁇ m. Good.
- the average particle diameter of the aluminum powder is less than 1 ⁇ m, the specific surface area of the aluminum powder increases, which is not preferable.
- the average particle diameter of the aluminum powder exceeds 20 ⁇ m, an appropriate viscosity cannot be obtained when the paste composition is formed by including the aluminum powder, which is not preferable.
- the aluminum powder included in the paste composition of the present invention is not particularly limited to the shape of the powder and the method for producing the powder.
- the components of the organic vehicle included in the paste composition of the present invention are not particularly limited, but resins such as ethyl cellulose and alkyd, and solvents such as glycol ethers and terpineols can be used.
- the content of the organic vehicle in the paste is preferably 15% by mass or more and 40% by mass or less. When the content of the organic vehicle is less than 15% by mass, the printability of the paste is lowered and a good aluminum electrode layer cannot be formed. Moreover, when the content of the organic vehicle exceeds 40% by mass, not only the viscosity of the paste increases, but also there arises a problem that the firing of aluminum is hindered due to the presence of the excessive organic vehicle.
- the resin compounding ratio in an organic vehicle is not specifically limited, It is preferable that they are 5 mass% or more and 20 mass% or less.
- the paste composition of the present invention can be used by containing various additives such as a dispersant, a plasticizer, an anti-settling agent, and a thixotropic agent that adjust the properties of the aluminum paste as necessary.
- the composition of the additive is not particularly limited, but the additive content is preferably 10% by mass or less.
- an organic vehicle in which 65 to 80% by mass of aluminum powder and 10% by mass of ethyl cellulose are dissolved in 90% by mass of a glycol ether organic solvent is contained within a range of 20 to 35% by mass.
- a paste composition to which a glass frit containing a limited transition metal oxide was added was prepared.
- Paste compositions (Examples 1 to 12) were prepared by mixing with a mixer. Further, a paste composition containing a glass frit containing a transition metal oxide other than the limited type of the present invention or a conventional glass frit containing no transition metal oxide in the same manner as described above (Comparative Example 1) To 5) were produced.
- the aluminum powder is composed of particles having an average particle diameter of 3 to 10 ⁇ m or a shape close to a sphere in terms of ensuring reactivity with the silicon semiconductor substrate, coating properties, and uniformity of the coating film. Powder was used. Glass frit having an average particle diameter of 1 to 5 ⁇ m was used.
- the various paste compositions described above were applied onto a p-type silicon semiconductor substrate having a thickness of 180 ⁇ m and a size of 155 mm ⁇ 155 mm using a 165 mesh screen printing plate, printed, and dried.
- the coating amount was set to 1.5 ⁇ 0.1 g / sheet before drying.
- the paste After drying the p-type silicon semiconductor substrate on which the paste was printed, the paste was baked in an air atmosphere in an infrared continuous baking furnace.
- the temperature of the firing zone of the firing furnace was set to 780 to 800 ° C., and the residence time (firing time) of the substrate was set to 6 to 10 seconds. After firing, cooling was performed to obtain a structure in which an aluminum electrode layer 5 and an Al—Si alloy layer 6 were formed on a p-type silicon semiconductor substrate 1 as shown in FIG.
- the amount of blisters and aluminum balls generated per measured surface area 150 ⁇ 150 mm 2 of the aluminum electrode layer 5 was visually counted, and the total value is shown in Table 1.
- the target value of the generation amount of blisters and aluminum balls is set to 5.
- the surface resistance of the back electrode 8 composed of the aluminum electrode layer 5 and the Al—Si alloy layer 6 that affects the ohmic resistance between the electrodes was measured with a 4-probe surface resistance measuring instrument.
- the p-type silicon semiconductor substrate 1 on which the back electrode 8 is formed is immersed in an aqueous hydrochloric acid solution, whereby the aluminum electrode layer 5 and the Al—Si alloy layer 6 are dissolved and removed, and the p-type silicon on which the p + layer 7 is formed.
- the surface resistance of the semiconductor substrate 1 was measured with the above surface resistance measuring instrument.
- the target surface resistance value is 18 m ⁇ / ⁇ or less for the aluminum electrode layer 5 and 16 ⁇ / ⁇ or less for the p + layer 7.
- the reactivity of the aluminum electrode layer 5 with moisture is determined by immersing the p-type silicon semiconductor substrate 1 on which the back electrode 8 is formed in warm water having a temperature of 70 ° C. ⁇ 2 ° C. for 3 minutes, from the surface of the aluminum electrode layer 5 being immersed.
- the presence or absence of gas generation and the presence or absence of discoloration of the aluminum electrode layer 5 after immersion were visually confirmed.
- the case where gas generation from the surface of the aluminum electrode layer 5 during the immersion was hardly recognized was evaluated as A, the case where it was somewhat recognized as B, and the case where it was considerably recognized as C.
- the case where the discoloration of the aluminum electrode layer 5 after the immersion was hardly recognized was evaluated as A, the case where it was somewhat recognized as B, and the case where it was recognized as C as C.
- Table 1 shows the results of the blister and aluminum ball generation, the surface resistance of the back electrode 8, the surface resistance of the p + layer 7, the peel test, and the water immersion test measured as described above.
- the limited types of the present invention were compared with the paste compositions (Comparative Examples 1 to 5) to which the conventional glass frit containing no transition metal oxide of the limited type of the present invention was added.
- a paste composition (Examples 1 to 12) using glass frit containing any transition metal oxide, the electrode function of the aluminum electrode layer and the BSF effect are not lowered, and the adhesion of the aluminum electrode layer is improved. It can be seen that the reaction between the aluminum electrode layer and moisture can be suppressed, and the generation of blisters and aluminum balls can be further suppressed.
- 1 p-type silicon semiconductor substrate, 2: n-type impurity layer, 3: antireflection film, 4: grid electrode, 5: aluminum electrode layer, 6: Al—Si alloy layer, 7: p + layer, 8: back electrode .
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Abstract
Description
ガラスフリットは、アルミニウムとシリコンとの反応やアルミニウム粉末自身の焼結を助ける作用があるとされている。しかしながら、従来の組成のガラスフリットを使用した場合には、焼成後に得られるアルミニウム電極層とシリコン半導体基板との密着性を向上させることと、アルミニウム電極層と水分との反応を抑制すること、という特性を兼ね備えた太陽電池素子を得ることができなかった。本発明では、限定された種類の遷移金属酸化物を含むガラスフリットを、ペースト中に含ませることにより、アルミニウムとシリコンとの反応を、過度に進行しないように制御することができる。これにより、焼成後に得られるアルミニウム電極層に、ブリスターやアルミニウムの玉が発生するのを抑えることができると考えられる。
本発明のペースト組成物に含められるアルミニウム粉末の含有量は、60質量%以上85質量%以下であることが好ましい。アルミニウム粉末の含有量が60質量%未満では、焼成後に得られるアルミニウム電極層の抵抗が高くなり、太陽電池のエネルギー変換効率の低下を招く恐れがある。アルミニウム粉末の含有量が85質量%を超えると、スクリーン印刷等におけるペーストの塗布性が低下する。
本発明のペースト組成物に含められる有機質ビヒクルの成分は、特に限定されないが、エチルセルロースやアルキッド等の樹脂と、グリコールエーテル系やターピネオール系などの溶剤を使用することができる。有機質ビヒクルのペースト中の含有量は、15質量%以上40質量%以下であることが好ましい。有機質ビヒクルの含有量が15質量%未満になると、ペーストの印刷性が低下し、良好なアルミニウム電極層を形成することができない。また、有機質ビヒクルの含有量が40質量%を超えると、ペーストの粘度が増大するだけでなく、過剰な有機質ビヒクルの存在によりアルミニウムの焼成が阻害されるという問題が生じる。有機質ビヒクル中の樹脂配合比率は、特に限定されないが、5質量%以上20質量%以下であることが好ましい。
本発明のペースト組成物は、必要に応じてアルミニウムペーストの特性を調整する分散剤、可塑剤、沈降防止剤、チクソ剤、など各種添加剤を含ませて使用することができる。添加剤の組成は特に制限されないが、添加剤の含有量を10質量%以下にするのが好ましい。
Claims (7)
- シリコン半導体基板(1)の上に電極(8)を形成するためのペーストであって、アルミニウム粉末と、有機質ビヒクルと、ガラスフリットとを含み、ガラスフリットが、酸化チタン、酸化バナジウム、酸化鉄、酸化モリブデン、酸化ネオジウム、および、酸化タングステンからなる群より選ばれた遷移金属酸化物を少なくとも1種含む、ペースト組成物。
- 前記ガラスフリットが、鉛を含まない、請求項1に記載のペースト組成物。
- 前記ガラスフリットが、鉛を0.1質量%以下含む、請求項1に記載のペースト組成物。
- 前記ガラスフリットは、さらに、酸化ホウ素、酸化ビスマス、酸化シリコン、酸化アルミニウム、酸化錫、酸化リン、酸化マンガン、酸化バリウム、酸化アンチモン、酸化リチウム、酸化ナトリウム、および、酸化カリウムからなる群より選ばれた少なくとも1種を含む、請求項1に記載のペースト組成物。
- 前記遷移金属酸化物を、前記ガラスフリット中において、10質量%以上95質量%以下含む、請求項1に記載のペースト組成物。
- 前記ガラスフリットを、当該ペースト組成物中において、0.03質量%以上10質量%以下含む、請求項1に記載のペースト組成物。
- 請求項1に記載のペースト組成物をシリコン半導体基板(1)の上に塗布した後、焼成することにより形成した電極(8)を備えた、太陽電池素子。
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US13/381,028 US20120103414A1 (en) | 2009-07-30 | 2010-06-28 | Paste composition and solar cell element using the same |
EP10804216.9A EP2461366A4 (en) | 2009-07-30 | 2010-06-28 | PULP COMPOSITION AND SOLAR CELL ELEMENT USING THE SAME |
CN2010800339275A CN102473756A (zh) | 2009-07-30 | 2010-06-28 | 糊组合物及使用其的太阳能电池元件 |
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JP2009177413A JP2011035024A (ja) | 2009-07-30 | 2009-07-30 | ペースト組成物およびそれを用いた太陽電池素子 |
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US20150357488A1 (en) * | 2012-12-28 | 2015-12-10 | Heraeus Deutschland GmbH & Co., KG | Electro-conductive paste comprising a vanadium containing compound in the preparation of electrodes in mwt solar cells |
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KR101719885B1 (ko) * | 2011-07-25 | 2017-03-24 | 히타치가세이가부시끼가이샤 | 반도체 기판 및 그 제조 방법, 태양 전지 소자, 그리고 태양 전지 |
US20150155401A1 (en) * | 2012-06-12 | 2015-06-04 | Heraeus Precious Metals North America Conshohocken Llc | Electroconductive paste with adhesion enhancer |
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WO2014156964A1 (ja) * | 2013-03-29 | 2014-10-02 | 昭栄化学工業株式会社 | 太陽電池素子表面電極用導電性ペースト及び太陽電池素子の製造方法 |
DE102013106272B4 (de) | 2013-06-17 | 2018-09-20 | Hanwha Q Cells Gmbh | Wafersolarzelle und Solarzellenherstellungsverfahren |
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JP6490012B2 (ja) * | 2013-11-28 | 2019-03-27 | 東洋アルミニウム株式会社 | 回路基板の製造方法 |
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JP2016213284A (ja) * | 2015-05-01 | 2016-12-15 | 東洋アルミニウム株式会社 | Perc型太陽電池用アルミニウムペースト組成物 |
CN108028187B (zh) * | 2015-09-24 | 2022-06-07 | 东洋铝株式会社 | 膏状组合物及硅锗层的形成方法 |
WO2018221578A1 (ja) * | 2017-05-31 | 2018-12-06 | 東洋アルミニウム株式会社 | 太陽電池用ペースト組成物 |
KR102406747B1 (ko) * | 2018-12-21 | 2022-06-08 | 창저우 퓨전 뉴 머티리얼 씨오. 엘티디. | 태양전지 전극 형성 방법 및 태양전지 |
CN110021672A (zh) * | 2019-04-17 | 2019-07-16 | 北京大学深圳研究生院 | 用于制备光伏电池背面导体的组合物、铝浆和光伏电池 |
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JP2011035024A (ja) | 2011-02-17 |
CN102473756A (zh) | 2012-05-23 |
EP2461366A1 (en) | 2012-06-06 |
TW201109392A (en) | 2011-03-16 |
US20120103414A1 (en) | 2012-05-03 |
KR20120032568A (ko) | 2012-04-05 |
EP2461366A4 (en) | 2013-05-29 |
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