KR101717508B1 - Glass frit composition for forming solar cell electrode, and paste composition including the same - Google Patents
Glass frit composition for forming solar cell electrode, and paste composition including the same Download PDFInfo
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- KR101717508B1 KR101717508B1 KR1020150170545A KR20150170545A KR101717508B1 KR 101717508 B1 KR101717508 B1 KR 101717508B1 KR 1020150170545 A KR1020150170545 A KR 1020150170545A KR 20150170545 A KR20150170545 A KR 20150170545A KR 101717508 B1 KR101717508 B1 KR 101717508B1
- Authority
- KR
- South Korea
- Prior art keywords
- oxide
- glass frit
- solar cell
- electrode
- weight
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 159
- 239000000203 mixture Substances 0.000 title claims abstract description 116
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 102
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 102
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- LPHBARMWKLYWRA-UHFFFAOYSA-N thallium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tl+3].[Tl+3] LPHBARMWKLYWRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 12
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 12
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 39
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 34
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 27
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 27
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 25
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 20
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 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 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910001947 lithium oxide Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 32
- 239000000758 substrate Substances 0.000 description 30
- 239000010410 layer Substances 0.000 description 20
- 238000010304 firing Methods 0.000 description 13
- 239000012535 impurity Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 acrylic ester Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- 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
-
- 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
-
- 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
-
- 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
Abstract
Description
A glass frit composition for forming a solar cell electrode, and a paste composition containing the same.
The solar cell is a photoelectric conversion device that converts solar energy into electric energy, and has been attracting attention as a next-generation energy resource with no pollution.
In order to increase the efficiency of such a solar cell, it is important to output as much electric energy as possible from solar energy.
However, as the size of the solar cell is reduced, the line resistance and the contact resistance between the semiconductor substrate and the electrode increase, and the efficiency of the battery may be rather reduced.
Embodiments of the present invention provide a glass frit composition for forming a solar cell electrode that can improve the contact between the semiconductor substrate and the electrode to minimize the line resistance and the contact resistance while ensuring thermal stability, And a paste composition containing the same is presented.
Glass for electrode formation of solar cell Frit Composition
In one embodiment of the present invention, there is provided a glass frit composition for forming an electrode of a solar cell, which is a lead (Pb) -thallium (Tl) -bismuth (Bi) -thelrium (Te) glass frit.
Specifically, 27 to 37 wt% of lead oxide (PbO) as the first metal oxide and 27 to 37 wt% of thallium oxide (Tl 2 O 3 ) as the second metal oxide are contained in the total amount of the glass frit (100 wt% (Bi 2 O 3 ) as a third metal oxide, 5 to 18 wt% as a third metal oxide, 20 to 26 wt% as a fourth metal oxide, tellurium (TeO 2 ) The fifth metal oxide includes a glass frit raw material different from the first to fourth metal oxides.
More specifically, the description of the glass frit is as follows.
The glass frit may satisfy the following formula (1).
[Formula 1] 1 <([PbO] + [Bi 2 O 3 ]) / [Tl 2 O 3 ] <10
(PbO), [Bi 2 O 3 ] and [Tl 2 O 3 ] in the above formula (1) are the contents (% by weight) of the lead oxide (PbO) , The content (% by weight) of the bismuth oxide (Bi 2 O 3 ) and the content (% by weight) of the thallium oxide (Tl 2 O 3 ).
The glass frit may satisfy the following formula (2).
[Formula 2] 0.65 < [TeO 2 ] / [Tl 2 O 3 ] < 4.8
(TeO 2 ) and [Tl 2 O 3 ] in the above formula 2 are the contents (wt%) of tellurium oxide (TeO 2 ) relative to the total amount of the glass frit (100 wt% 2 O 3 ) (% by weight).
The fifth metal oxides, silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), boron oxide (B 2 O 3 ), And aluminum oxide (Al 2 O 3 ). The glass frit raw material may be at least one selected from the group consisting of aluminum oxide (Al 2 O 3 ) and aluminum oxide (Al 2 O 3 ).
In this regard, the following description can be applied independently of each other.
The fifth metal oxide is contained and include, with respect to the glass frit total amount (100 wt%), and the silicon oxide (SiO 2) 8 to 11% by weight of the silicon oxide (SiO 2), glass parts of zinc oxide (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), boron oxide (B 2 O 3) oxide, and aluminum oxide from the group comprising (Al 2 O 3) And may include one or more selected metal oxides.
Wherein the fifth metal oxide comprises zinc oxide (ZnO), the zinc oxide (ZnO) is contained in an amount of 0.4 to 3 wt% relative to the total amount of the glass frit (100 wt%), 2 ), tungsten oxide (WO 3 ), lithium oxide (Li 2 O), sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) Based on the total amount of the metal oxide.
The fifth metal oxides and includes the tungsten oxide (WO 3), with respect to the glass frit total amount (100 wt%), containing the tungsten oxide (WO 3) is 2 to 3% by weight, the remainder portion is a silicon oxide (SiO 2 ), zinc oxide (ZnO), lithium oxide (Li 2 O), sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) And may include one or more selected metal oxides.
Wherein the fifth metal oxide comprises the lithium oxide (Li 2 O), the lithium oxide (Li 2 O) is contained in an amount of 0.7 to 2 wt% based on the total amount of the glass frit (100 wt%), A group containing silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) May be contained in the metal oxide.
Wherein the fifth metal oxide comprises the sodium oxide (Na 2 O), the sodium oxide (Na 2 O) is contained in an amount of 0.05 to 2 wt% with respect to the total amount of the glass frit (100 wt%), A group including silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), lithium oxide (Li 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) May be included in the metal oxide.
Wherein the fifth metal oxide comprises the boron oxide (B 2 O 3 ), the boron oxide (B 2 O 3 ) is contained in an amount of 0.5 to 2% by weight based on the total amount of the glass frit (100% portion comprises a silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), and aluminum oxide (Al 2 O 3) oxide And at least one metal oxide selected from the group consisting of metal oxides.
Wherein the fifth metal oxide comprises the aluminum oxide (Al 2 O 3 ), the aluminum oxide (Al 2 O 3 ) is contained in an amount of 0.7 to 2% by weight based on the total amount of the glass frit (100% portion comprises a silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), and boron oxide (B 2 O 3) oxide And at least one metal oxide selected from the group consisting of metal oxides.
On the other hand, the glass frit can independently satisfy the following physical properties.
The softening point (Tdsp) of the glass frit may satisfy a temperature range of more than 230 deg. C and less than 350 deg.
The crystallization temperature (Tc) of the glass frit may satisfy a temperature range exceeding 260 ° C but lower than 370 ° C.
The line resistance of the glass frit may be less than 3.1 u? 占 (m (excluding 0 占 ㆍ 占 ㎝ m).
The contact resistivity of the glass frit may be less than 2 m? 占 ㎠ m but excluding 0 m? 占 ㎠ m.
Adhesion of the glass frit may be more than 3 N.
Solar cell For electrode formation of solar cell Paste paste composition
In another embodiment of the present invention, a conductive powder; Glass frit; And an organic vehicle, wherein the glass frit is a paste composition for forming an electrode of a solar cell, wherein the glass frit is a lead (Pb) -thallium (Tl) -bismuth (Bi) .
Specifically, 27 to 37 wt% of lead oxide (PbO) as the first metal oxide and 27 to 37 wt% of thallium oxide (Tl 2 O 3 ) as the second metal oxide are contained in the total amount of the glass frit (100 wt% (Bi 2 O 3 ) as a third metal oxide, 5 to 18 wt% as a third metal oxide, 20 to 26 wt% as a fourth metal oxide, tellurium (TeO 2 ) The fifth metal oxide includes a glass frit raw material different from the first to fourth metal oxides.
More specifically, the glass frit may be the same as described above, and a redundant description thereof will be omitted.
The conductive powder may be at least one selected from the group consisting of Ag powder, Ag powder, Al powder, Al powder, Cu powder, Ni powder, Ni powder, Containing alloy powder, and at least one kind of conductive powder selected from the group consisting of copper-containing alloy powders.
The organic vehicle may include an organic binder and an organic solvent.
The electrically conductive powder may be contained in an amount of 86 to 90 wt%, the glass frit may be contained in an amount of 1.5 to 3.0 wt%, and the organic vehicle may be contained in an amount of 7 to 12.5 wt% based on the total amount of the paste composition (100 wt% .
The paste composition may further comprise an additive.
The additive may be contained in an amount of 0.1 to 5% by weight based on the total amount of the paste composition (100% by weight).
Electrode of solar cell
In another embodiment of the present invention, there is provided an electrode for a solar cell manufactured using the glass frit composition described above.
Independently, another embodiment of the present invention provides an electrode for a solar cell solar cell manufactured using the above-described paste composition.
Solar cell
In another embodiment of the present invention, there is provided a semiconductor device comprising: a semiconductor substrate; And an electrode disposed on at least one side of the semiconductor substrate and formed using the glass frit composition described above.
Independently, in another embodiment of the present invention, there is provided a solar cell comprising at least one electrode formed on at least one surface of the semiconductor substrate and formed using the paste composition described above.
According to embodiments of the present invention, the efficiency and thermal stability of the solar cell can be improved.
1 is a schematic diagram of a solar cell according to an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.
In general, the electrode of a solar cell is prepared by mixing a conductive powder, glass frit, and an organic vehicle, and further adding an additive as needed to prepare a paste composition, Or on both sides, and patterning the paste composition, and then firing and drying the applied paste composition.
Considering such an electrode forming process, it is understood that lowering the line resistance and the contact resistance by improving the contact property between the semiconductor substrate and the electrode formed thereon is an important factor for increasing the efficiency of the solar cell.
Specifically, the glass frit is formed by etching an antireflection film during a firing process, melting the conductive powder to produce metal crystal grains in the emitter region, Not only serves to lower the line resistance and the contact resistance by improving the adhesion, but also induces an effect of softening and lowering the firing temperature.
In this regard, in the embodiments of the present invention, it is aimed to improve the efficiency and thermal stability of the solar cell by commonly applying the glass frit ensuring the thermal stability while reducing the contact resistance between the electrode and the semiconductor substrate.
Glass for electrode formation of solar cell Frit Composition
In one embodiment of the present invention, there is provided a glass frit composition for forming an electrode of a solar cell, which is a lead (Pb) -thallium (Tl) -bismuth (Bi) -thelrium (Te) glass frit.
Specifically, 27 to 37 wt% of lead oxide (PbO) as the first metal oxide and 27 to 37 wt% of thallium oxide (Tl 2 O 3 ) as the second metal oxide are contained in the total amount of the glass frit (100 wt% (Bi 2 O 3 ) as a third metal oxide, 5 to 18 wt% as a third metal oxide, 20 to 26 wt% as a fourth metal oxide, tellurium (TeO 2 ) The fifth metal oxide includes a glass frit raw material different from the first to fourth metal oxides.
In other words, the glass frit composition contains lead oxide (PbO), thallium oxide (Tl 2 O 3 ), bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO 2 ) as main components, (Pb) -thallium (Tl) -bismuth (Bi) -tellurium (Te) -based glass frit, which contains glass frit raw materials different from the main components.
A lead (Pb) -thallium (Tl) -bismuth (Bi) -Terruri (Te) glass frit satisfying the respective ranges of the respective contents described above has a low line resistance and contact resistance between the electrode and the semiconductor substrate , And the thermal stability is ensured. This fact is supported by the embodiments described below and evaluation examples thereof. More specifically, the description of the glass frit is as follows.
The organic frit has a composition expressed by the following formula 1 with respect to each content of lead oxide (PbO), thallium oxide (Tl 2 O 3 ), bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO 2 ) And < RTI ID = 0.0 > 2, < / RTI >
[Formula 1] 1 <([PbO] + [Bi 2 O 3 ]) / [Tl 2 O 3 ] <10
(PbO), [Bi 2 O 3 ] and [Tl 2 O 3 ] in the above formula (1) are the contents (% by weight) of the lead oxide (PbO) , The content (% by weight) of the bismuth oxide (Bi 2 O 3 ) and the content (% by weight) of the thallium oxide (Tl 2 O 3 ).
When the value of [PbO] + [Bi 2 O 3 ]) / [Tl 2 O 3 ] is 10% by weight or more, the contact resistance is increased. (For example, a silicon wafer) and a conductive powder (for example, silver powder) is lowered, and the cell efficiency is lowered. On the other hand, if the range of the formula (1) is satisfied, both the line resistance and the contact resistance can be appropriately controlled, so that an improved efficiency can be expected.
[Formula 2] 0.65 < [TeO 2 ] / [Tl 2 O 3 ] < 4.8
(TeO 2 ) and [Tl 2 O 3 ] in the above formula 2 are the contents (wt%) of tellurium oxide (TeO 2 ) relative to the total amount of the glass frit (100 wt% 2 O 3 ) (% by weight).
In the above formula 2, when the value of [TeO 2 ] / [Tl 2 O 3 ] is 4.8 or more, the contact resistance increases, and when it is 0.65 or less, the line resistivity and the contact resistance increase, . On the other hand, if the range of the formula 2 is satisfied, both the contact resistance resistance and the adhesive force are appropriately controlled, and thus the improved battery efficiency can be expected.
In other words, in the case where the main component is lead oxide (PbO), thallium oxide (Tl 2 O 3 ), bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO 2 ) And 2, the line resistance and the contact resistance are lowered as compared with the case of not satisfying at least one of the expressions (1), (2) and (3), and the softening point is softened at a proper softening point Can contribute to lowering.
On the other hand, the fifth metal oxide is not particularly limited as long as it is generally different from the first to fourth metal oxides among the metal oxides used in the glass frit composition.
Examples of the fifth metal oxide include silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), lithium oxide (Li 2 O), sodium oxide (Na 2 O) (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ), or a mixture of two or more metal oxides may be used.
Specifically, with respect to the latter case, the following descriptions can be applied independently to each other.
The fifth metal oxide is contained and include, with respect to the glass frit total amount (100 wt%), and the silicon oxide (SiO 2) 8 to 11% by weight of the silicon oxide (SiO 2), glass parts of zinc oxide (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), boron oxide (B 2 O 3) oxide, and aluminum oxide from the group comprising (Al 2 O 3) And may include one or more selected metal oxides.
Wherein the fifth metal oxide comprises zinc oxide (ZnO), the zinc oxide (ZnO) is contained in an amount of 0.4 to 3 wt% relative to the total amount of the glass frit (100 wt%), 2 ), tungsten oxide (WO 3 ), lithium oxide (Li 2 O), sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) Based on the total amount of the metal oxide.
The fifth metal oxides and includes the tungsten oxide (WO 3), with respect to the glass frit total amount (100 wt%), containing the tungsten oxide (WO 3) is 2 to 3% by weight, the remainder portion is a silicon oxide (SiO 2 ), zinc oxide (ZnO), lithium oxide (Li 2 O), sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) And may include one or more selected metal oxides.
Wherein the fifth metal oxide comprises the lithium oxide (Li 2 O), the lithium oxide (Li 2 O) is contained in an amount of 0.7 to 2 wt% based on the total amount of the glass frit (100 wt%), A group containing silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) May be contained in the metal oxide.
Wherein the fifth metal oxide comprises the sodium oxide (Na 2 O), the sodium oxide (Na 2 O) is contained in an amount of 0.05 to 2 wt% with respect to the total amount of the glass frit (100 wt%), A group including silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), lithium oxide (Li 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 ) May be included in the metal oxide.
Wherein the fifth metal oxide comprises the boron oxide (B 2 O 3 ), the boron oxide (B 2 O 3 ) is contained in an amount of 0.5 to 2% by weight based on the total amount of the glass frit (100% portion comprises a silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), and aluminum oxide (Al 2 O 3) oxide And at least one metal oxide selected from the group consisting of metal oxides.
Wherein the fifth metal oxide comprises the aluminum oxide (Al 2 O 3 ), the aluminum oxide (Al 2 O 3 ) is contained in an amount of 0.7 to 2% by weight based on the total amount of the glass frit (100% portion comprises a silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), and boron oxide (B 2 O 3) oxide And at least one metal oxide selected from the group consisting of metal oxides.
Of course, a mixture of all the metal oxides exemplified above can be used as the fifth metal oxide. In this case, the silicon oxide (SiO 2 ) is contained in an amount of 8 to 11% by weight, the zinc oxide (ZnO) is contained in an amount of 0.4 to 3% by weight based on the total amount of the glass frit (100% WO 3 ) is contained in an amount of 2 to 3 wt%, lithium oxide (Li 2 O) is contained in an amount of 0.7 to 2 wt%, sodium oxide (Na 2 O) is contained in an amount of 0.05 to 2 wt% B 2 O 3 ) in an amount of 0.5 to 2% by weight and aluminum oxide (Al 2 O 3 ) in an amount of 0.7 to 2% by weight.
As described above, the glass frit mainly contains lead oxide (PbO), thallium oxide (Tl 2 O 3 ), bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO 2 ) And a metal oxide which is a glass frit composition different from the main component, and each component satisfies a specific content range, excellent physical properties can be exhibited.
More specifically, the glass frit can lower the line resistance and the contact resistance by improving the adhesiveness between the electrode and the semiconductor substrate, and can satisfy the ranges of adhesion, line resistance, and contact resistance described below .
Adhesion of the glass frit may be more than 3 N.
The line resistance of the glass frit may be less than 3.1 u? 占 (m (excluding 0 占 ㆍ 占 ㎝ m).
The contact resistivity of the glass frit may be less than 2 m? 占 ㎠ m but excluding 0 m? 占 ㎠ m.
Further, the glass frit can contribute to lowering the firing temperature by softening at the optimum softening point, and can satisfy the ranges of the softening point and the crystallization temperature described below.
The softening point (Tdsp) of the glass frit may satisfy a temperature range of more than 230 deg. C and less than 350 deg.
The crystallization temperature (Tc) of the glass frit may satisfy a temperature range exceeding 260 ° C but lower than 370 ° C.
On the other hand, the glass frit can be produced by a conventional method. For example, the main components are lead oxide (PbO), thallium oxide (Tl 2 O 3 ), bismuth oxide (Bi 2 O 3 ), and tellurium oxide (TeO 2 ) The components are mixed so as to include different glass frit raw materials, with each component satisfying a specified content range. The mixing at this time may be performed using a ball mill, a planetary mill, or the like.
Thereafter, the mixed composition is melted in a temperature range of 900 ° C to 1300 ° C, quenched at room temperature (25 ° C), and then pulverized using a disk mill, a planetary mill or the like, To obtain a glass frit having a controlled particle diameter.
Specifically, the finally obtained glass frit may have a D50 particle diameter of 0.1 to 10 탆, and the shape thereof may be spherical or amorphous.
For electrode formation of solar cell Paste paste composition
In another embodiment of the present invention, a conductive powder; Glass frit; And an organic vehicle, wherein the glass frit is a paste composition for forming an electrode of a solar cell, wherein the glass frit is a lead (Pb) -thallium (Tl) -bismuth (Bi) .
Specifically, 27 to 37 wt% of lead oxide (PbO) as the first metal oxide and 27 to 37 wt% of thallium oxide (Tl 2 O 3 ) as the second metal oxide are contained in the total amount of the glass frit (100 wt% (Bi 2 O 3 ) as a third metal oxide, 5 to 18 wt% as a third metal oxide, 20 to 26 wt% as a fourth metal oxide, tellurium (TeO 2 ) The fifth metal oxide includes a glass frit raw material different from the first to fourth metal oxides. More specifically, the paste composition is a paste composition using the above-described glass frit, which is mixed with a conductive powder and an organic vehicle.
The glass frit may be contained in an amount of 1 to 5% by weight, specifically, 1.5 to 3% by weight based on the total amount (100% by weight) of the paste composition. When the glass frit is contained within the above content range, the adhesion between the electrode and the semiconductor substrate is improved, and a solar cell having excellent efficiency can be realized.
Hereinafter, the overlapping description of the glass frit will be omitted, and the remaining constitution of the paste composition will be described in detail.
The conductive powder is not particularly limited as long as it is conductive and capable of performing the function of collecting the photogenerated charge.
For example, the conductive powder may be at least one selected from the group consisting of Ag powder, Ag powder, Al powder, Al powder, Cu powder, Ni powder, And a nickel (Ni) -containing alloy powder. The conductive powder may be at least one selected from the group consisting of nickel (Ni) -based alloy powder. However, it is not limited to this, and it may be a different kind of metal powder, and may include other additives besides the metal powder.
In addition, the conductive powder may be a collection of conductive particles having different particle diameters, and the average particle diameter may be 0.01 to 50 탆. More specifically, when the conductive powder is a silver (Ag) powder, it may have an average particle diameter of 0.1 to 5 μm. At this time, the shape of the conductive particles may be spherical, plate-like, or amorphous.
The conductive powder may be contained in an amount of 80 to 95% by weight, specifically, 86 to 90% by weight based on the total amount (100% by weight) of the paste composition. When the conductive powder is contained within the above content range, it can have excellent electrical conductivity due to proper filling density of the conductive powder during firing, and can be excellent in dispersibility in the production of paste composition.
The organic vehicle may include an organic binder and an organic solvent for dissolving the organic binder, which is blended with the conductive powder to impart an appropriate viscosity to the paste.
Specifically, as the organic binder, ethyl cellulose, ethylhydroxyethyl cellulose, nitrocellulose, acrylic ester resin, etc. may be used alone or in combination of two or more, but not limited thereto.
Examples of the organic solvent include 2,2,4-trimethyl-monoisobutyrate (Texanol, Texanol), butyl carbitol acetate (diethylene glycol monobutyl ether acetate), toluene, ethyl cellosolve, butyl cellosolve A solvent of a glycol ether such as sorb, butyl carbitol (diethylene glycol monobutyl ether), dibutyl carbitol (diethylene glycol dibutyl ether), propylene glycol monomethyl ether and the like, hexylene glycol, terpineol ), Methyl ethyl ketone, 3-pentanediol, etc. may be used singly or in combination of two or more, but the present invention is not limited thereto.
For the total amount (100% by weight) of the paste composition, the organic vehicle may be included in an amount of 5 to 40% by weight, specifically 5 to 15% by weight. When the organic vehicle is contained within the above content range, a paste composition having an appropriate viscosity can be prepared.
The conductive powder is contained in an amount of 86 to 90% by weight, the glass frit is contained in an amount of 1.5 to 3.0% by weight based on the total amount of the paste composition (100% by weight) The vehicle may be comprised between 7 and 12.5 wt%.
On the other hand, the paste composition may further comprise an additive.
The additive may be used alone or as a mixture of two or more, if necessary, with a dispersant, a thixotropic agent, a plasticizer, a viscosity stabilizer, a defoamer, an ultraviolet stabilizer, an antioxidant and a coupling agent.
At this time, the additive may be contained in an amount of 0.1 to 5% by weight based on the total amount of the paste composition (100% by weight).
Electrode of solar cell
Another embodiment of the present invention provides an electrode for a solar cell manufactured using the glass frit composition or the paste composition comprising the glass frit composition described above. The electrode may be a front electrode or a rear electrode, By using the glass frit composition or the paste composition containing the glass frit composition, thermal stability can be ensured while improving the efficiency of the solar cell.
A detailed description of the glass frit composition or the paste composition containing the glass frit composition described above will be omitted, and the method of forming the electrode and the paste composition will be described below.
Solar cell
In yet another embodiment of the present invention, there is provided a semiconductor device comprising: a semiconductor substrate; And an electrode disposed on at least one side of the semiconductor substrate, the electrode being formed using the glass frit composition or a paste composition comprising the glass frit composition.
1 is a cross-sectional view of the solar cell.
Hereinafter, a solar cell according to one embodiment will be described with reference to FIG. However, this is merely an example, and the solar cell is not limited to Fig.
Hereinafter, the positional relationship between the
Referring to FIG. 1, a solar cell according to an embodiment includes a
The
At this time, one of the
On the other hand, on at least one surface of the
Also, an
The
The
On the
At this time, the
A bus bar electrode (not shown) may be formed on the front electrode 21. The bus bar electrode is for connecting neighboring solar cells when assembling a plurality of solar cells.
A
The solar cell having the above structure can be manufactured according to the following procedure, but is not limited thereto.
First, the
Then, the
Thereafter, the
Next, the glass frit composition or the paste composition containing the glass frit composition described above may be coated on the
More specifically, when the
The firing may be performed in the firing furnace and may be performed to raise the temperature to a temperature higher than the melting temperature of the conductive powder in each of the compositions. For example, the firing can be performed at a temperature range of about 700 to 900 ° C.
Hereinafter, preferred embodiments of the present invention, comparative examples thereof, and evaluation examples in which these are compared and evaluated will be described. However, the following examples are only a few of preferred embodiments of the present invention, and the present invention is not limited to the following examples.
Example 1 to 14
(1) Glass Frit Produce
Tables 1 and 2, lead oxide so as to satisfy the (PbO), oxidizing thallium (Tl 2 O 3), bismuth oxide (Bi 2 O 3), oxide tellurium (TeO 2), silicon oxide (SiO 2), zinc oxide (ZnO), tungsten oxide (WO 3), lithium (Li 2 O) oxide, sodium oxide (Na 2 O), and a mixture of aluminum oxide (Al 2 O 3), subjected to the glass frit compositions of examples 1 to 14 Respectively.
The mixing at this time was carried out for a sufficient time, using a zero-gravity mixer, so that all components in the glass frit composition were thoroughly mixed.
The mixed glass composition was put into a platinum crucible and melted at a temperature of 950 to 1,250 ° C. The melting time was 30 minutes (min). The molten glass composition in the melting step was quenched by dry and wet quenching. The quenched glass melt was pulverized to a powder state using a jet mill and a pin mill to finally obtain a glass frit.
(2) Paste Preparation of composition
To each of the glass frit of Examples 1 to 14, conductive powder, organic vehicle, and additives were added and mixed to prepare respective paste compositions.
Specifically, for the total amount (100 wt.%) Of each paste composition, the amount of the glass frit was 2.5 wt%, the conductive powder was 88.5 wt%, the organic vehicle was 6.5 wt%, and the additive was 2.5 wt%.
In this case, silver (Ag) powder (D50 particle diameter: 2.0 m) was used as the conductive powder, and ethylcellulose as an organic binder and 2,2,4-trimethyl-monoisobutyrate as an organic solvent (Organic binder: organic solvent) at a weight ratio of 3:97 (CRYVALLAC) and a dispersing agent (Duomeen TDO) were used as the additives.
(3) Production of solar cell
Before forming the front electrode, an aluminum paste composition was applied to the rear surface of a silicon wafer (sheet resistance: 85 Ω / sq.), Which is a kind of semiconductor substrate, and dried to form a rear electrode.
Specifically, the aluminum paste composition was printed-dried using a commercial product DSCP-A151 (Dongjin Semichem) paste, and then a front electrode was formed. The drying was carried out by keeping in an infrared drying furnace at 130 캜 for 4 minutes (min) and cooling.
Thereafter, front electrodes were formed by using the paste compositions of Examples 1 to 14 prepared in (2), respectively.
Specifically, the respective paste compositions were applied to the entire surface of the silicon wafer on which the rear electrodes were formed. The application was performed by screen printing and printing in a predetermined pattern.
In a state in which both the rear electrode and the front surface were formed, the temperature was raised to 770 ° C at a rate of 245 inches / min using a belt-type sintering furnace and firing was performed.
Comparative Example 1 to 20
A paste composition and a front electrode were prepared in the same manner except that glass frit compositions were prepared in the respective compositions of Comparative Examples 1 to 20 instead of Examples 1 to 14 in Tables 1 and 2, Respectively.
([PbO] + [Bi 2 O 3 ]) / [Tl 2 O 3 ]
[TeO 2 ] / [Tl 2 O 3 ]
The adhesion, the line resistivity and the contact resistivity were evaluated for each glass frit, paste composition, or solar cell, and the evaluation results are shown in Table 3 below. At this time, the specific evaluation conditions are as follows.
Adhesion : A ribbon (1.5 mm in width, 0.2 mm in thickness) was aligned on an island-type bus bar of the front electrode of each of the above solar cells, and then, using a tabletting machine, And bonding was carried out while hot air of the resin was applied. Each of the bonded wafers was subjected to peel test (180 degree condition) using a universal material testing machine (NTS technology). In this connection, the adhesive force recorded in Table 3 below is the peak of the measured value in the peeling test.
Line Resistivity : The line resistance was measured using a multimeter (Tektronix DMM 4020 device) after printing, drying and firing an electrode paste composition containing the angular silver powder on a printed plate having a length of 20000 탆 and a width of 60 탆 . Separately, the area was measured using a laser microscope (KEYENCE VK-X100). Then, the line resistivity was calculated by adding the respective measured values to the following equation 1, and recorded in Table 3.
[Expression 1] Line resistivity = (resistance x area) / length
Contact Resistance: Contact resistance was measured using the TLM (Transfer Length Method), one of the well known methods. Specifically, the electrode paste composition containing the angular silver powder is printed on a wafer in a bar pattern (L * Z, 500 μm * 3000 μm), followed by drying and firing.
At this time, in order to suppress the interference phenomenon in the measurement of the contact resistance, a laser with a frequency of 200 kHz and a pulse width of 50% was irradiated twice with a laser etching machine (hardram) And the edges of the bar pattern were isolated. After this, the resistance was measured with a multimeter (Tektronix DMM 4020 device), and the effective length (L T ) was obtained by measuring the slope and the slope of the resistance with the interval. Also, the sheet resistance (rho s) of each silicon wafer was measured by putting the slope of the resistance and the Z-axis value of the pattern into the equation (2). The contact resistivity is calculated by adding the effective length and the sheet resistance value to the equation 3 and recorded in Table 3 below.
[Equation 2]]
[Equation 3]
(Unit: u? 占) m)
(Unit: m? 占 ㎠ 2)
(Unit: N)
Example
According to the above Table 3, in Comparative Examples 1 to 20, the low adhesiveness was not exhibited in Examples 1 to 14, the line resistivity was high, and the contact resistivity was high. In particular, in the case of Comparative Examples 6 and 16, the glass frit could not be produced and was broken, and the experiment could not proceed.
On the other hand, in Examples 1 to 14, all exhibited excellent adhesiveness exceeding 3 N, while exhibiting a low line resistance of less than 3.1 u? 占 및 m and a low contact resistance of less than 2 m? ㎠.
This is due to the difference in glass frit composition. Unlike Comparative Examples 1 to 20, in Examples 1 to 14, the adhesiveness between the electrode and the semiconductor substrate was excellent because both Tables 1 and 2 were satisfied. Which means that the line resistance and contact resistance are lowered.
Evaluation example 2: Evaluation of softening point and crystallization temperature
For each of the glass frit, the softening point and the crystallization temperature were evaluated, and the respective evaluation results are shown in Table 4 below. At this time, the specific evaluation conditions are as follows.
Softening point: Each glass frit was applied to an aluminum pen and measured while increasing the temperature to 580 DEG C at a heating rate of 10 DEG C / min using a differential scanning calorimeter (DSC, TA Corporation) Respectively. The peak point at which the endothermic reaction ends in the measurement was analyzed to determine the Tdsp temperature and recorded in Table 4 below.
Crystallization temperature : The same apparatus used in the above softening point measurement was used, and the same heating rate and temperature conditions were applied, and the peak point at the end of the exothermic reaction in the measurement was analyzed to determine the Tc temperature and recorded in Table 4 below .
(Tdsp, ° C)
(Tc, ° C)
According to Table 4, in the case of Comparative Examples 1 to 20, a low softening point of 230 DEG C or less or a high softening point of 350 DEG C or more was measured, or a crystallization temperature of 260 DEG C or more and 370 DEG C or less was measured. In particular, in the case of Comparative Examples 6 and 16, as mentioned above, the glass frit could not be produced, and the glass frit could not be produced, and the experiment could not proceed.
On the other hand, in Examples 1 to 14, the crystallization temperature exceeding 260 占 폚 but lower than 370 占 폚 was measured while a suitable range of softening point exceeding 230 占 폚 and lower than 350 占 폚 was measured.
This is also due to the difference in the composition of the glass frit. Unlike Comparative Examples 1 to 20, in Examples 1 to 14, satisfying both Tables 1 and 2 leads to an effect of softening at a proper softening point to lower the firing temperature And has an effect of exhibiting excellent thermal stability.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
10:
12: antireflection film 20: front electrode 30: rear electrode
Claims (20)
For the total amount of glass frit (100% by weight)
27 to 37% by weight of lead oxide (PbO), which is the first metal oxide,
(Tl 2 O 3 ), which is a second metal oxide, is contained in an amount of 5.5 to 30 wt%
And 5 to 18% by weight of bismuth oxide (Bi 2 O 3 ), which is a third metal oxide,
A fourth metal oxide, tellurium oxide (TeO 2 ), in an amount of 20 to 26 wt%
The remainder includes a fifth metal oxide,
The fifth metal oxides, silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), boron oxide (B 2 O 3 ), And aluminum oxide (Al 2 O 3 ).
A glass frit composition for forming an electrode of a solar cell.
Wherein the glass frit satisfies the following formula (1)
A glass frit composition for forming an electrode of a solar cell.
[Formula 1] 1 <([PbO] + [Bi 2 O 3 ]) / [Tl 2 O 3 ] <10
(PbO), [Bi 2 O 3 ] and [Tl 2 O 3 ] in the above formula (1) are the contents (% by weight) of the lead oxide (PbO) , The content (% by weight) of the bismuth oxide (Bi 2 O 3 ) and the content (% by weight) of the thallium oxide (Tl 2 O 3 ).
Wherein the glass frit satisfies the following formula (2)
A glass frit composition for forming an electrode of a solar cell.
[Formula 2] 0.65 < [TeO 2 ] / [Tl 2 O 3 ] < 4.8
(TeO 2 ) and [Tl 2 O 3 ] in the above formula 2 are the contents (wt%) of tellurium oxide (TeO 2 ) relative to the total amount of the glass frit (100 wt% 2 O 3 ) (% by weight).
The fifth metal oxide comprising the silicon oxide (SiO 2),
With respect to the glass frit total amount (100 wt%), and the silicon oxide (SiO 2) and contains 8 to 11% by weight, and the balance part is zinc oxide (ZnO), tungsten (WO 3), lithium oxide (Li 2 O oxide ), At least one metal oxide selected from the group consisting of sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
Wherein the fifth metal oxide comprises the zinc oxide (ZnO)
(SiO 2 ), tungsten oxide (WO 3 ), lithium oxide (Li 2 O), and the like are contained in an amount of 0.4 to 3 wt% based on the total amount of the glass frit (100 wt% ), At least one metal oxide selected from the group consisting of sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
Wherein the fifth metal oxide comprises the tungsten oxide (WO 3 )
With respect to the glass frit total amount (100 wt%), the oxide containing tungsten (WO 3) is 2 to 3% by weight, the remainder portion is a silicon oxide (SiO 2), zinc oxide (ZnO), lithium oxide (Li 2 O ), At least one metal oxide selected from the group consisting of sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
Wherein the fifth metal oxide comprises the lithium oxide (Li 2 O)
The glass frit total amount of the lithium (Li 2 O) oxide containing 0.7 to 2% by weight, the remainder portion is a silicon oxide on the (100 weight%) (SiO 2), zinc (ZnO), tungsten oxide (WO 3 ), At least one metal oxide selected from the group consisting of sodium oxide (Na 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
Wherein the fifth metal oxide comprises the sodium oxide (Na 2 O)
The glass frit is the total amount (100 weight%) for the sodium (Na 2 O) oxide containing 0.05 to 2% by weight, the remainder portion is a silicon oxide (SiO 2), zinc oxide (ZnO), tungsten oxide (WO 3 ), At least one metal oxide selected from the group consisting of lithium oxide (Li 2 O), boron oxide (B 2 O 3 ), and aluminum oxide (Al 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
Wherein the fifth metal oxide comprises the boron oxide (B 2 O 3 )
(B 2 O 3 ) is contained in an amount of 0.5 to 2% by weight based on the total amount of the glass frit (100% by weight), and the remainder is silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide 3 ), at least one metal oxide selected from the group consisting of lithium oxide (Li 2 O), sodium oxide (Na 2 O), and aluminum oxide (Al 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
Wherein the fifth metal oxide comprises the aluminum oxide (Al 2 O 3 )
0.7 to 2% by weight of the aluminum oxide (Al 2 O 3 ) is contained in the total amount of the glass frit (100% by weight), and the remainder is silicon oxide (SiO 2 ), zinc oxide (ZnO), tungsten oxide 3 ), at least one metal oxide selected from the group consisting of lithium oxide (Li 2 O), sodium oxide (Na 2 O), and boron oxide (B 2 O 3 )
A glass frit composition for forming an electrode of a solar cell.
The softening point (Tdsp) of the glass frit,
Lt; RTI ID = 0.0 > 230 C < / RTI > to <
A glass frit composition for forming an electrode of a solar cell.
The crystallization temperature (Tc) of the glass frit,
Lt; RTI ID = 0.0 > 260 C < / RTI > to <
A glass frit composition for forming an electrode of a solar cell.
The line resistivity of the glass frit is,
3.1 mu OMEGA .cm (but excluding 0 mu OMEGA .cm)
A glass frit composition for forming an electrode of a solar cell.
The contact resistivity of the glass frit is determined by the following equation:
Cm < 2 > (but excluding 0 m <
A glass frit composition for forming an electrode of a solar cell.
Adhesion of the glass frit may be determined by,
3 < / RTI > N,
A glass frit composition for forming an electrode of a solar cell.
Glass frit; And
An organic vehicle;
The glass frit is a lead (Pb) - thallium (Tl) - bismuth (Bi) - tellurium (Te) glass frit,
For the total amount of glass frit (100% by weight)
27 to 37% by weight of lead oxide (PbO), which is the first metal oxide,
(Tl 2 O 3 ), which is a second metal oxide, is contained in an amount of 5.5 to 30 wt%
And 5 to 18% by weight of bismuth oxide (Bi 2 O 3 ), which is a third metal oxide,
A fourth metal oxide, tellurium oxide (TeO 2 ), in an amount of 20 to 26 wt%
The remainder includes a fifth metal oxide,
The fifth metal oxides, silicon oxide (SiO 2), zinc (ZnO), tungsten oxide (WO 3), lithium oxide (Li 2 O), sodium (Na 2 O), boron oxide (B 2 O 3 ), And aluminum oxide (Al 2 O 3 ).
A paste composition for forming an electrode of a solar cell.
The conductive powder,
(Al) -containing alloy powder, a copper (Cu) powder, a nickel (Ni) powder, and a nickel (Ni) -containing alloy powder And at least one conductive powder selected from the group consisting of the conductive powder and the conductive powder.
A paste composition for forming an electrode of a solar cell.
Wherein the organic vehicle comprises:
An organic binder, and an organic solvent.
A paste composition for forming an electrode of a solar cell.
≪ / RTI > further comprising an additive.
A paste composition for forming an electrode of a solar cell.
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| KR20180133166A (en) * | 2017-06-05 | 2018-12-13 | 삼성에스디아이 주식회사 | Composition for forming solar cell electrode and electrode prepared using the same |
| WO2019017519A1 (en) * | 2017-07-21 | 2019-01-24 | 주식회사 휘닉스소재 | Glass frit for forming solar cell electrode and paste composition comprising glass frit |
| CN110590168A (en) * | 2019-10-28 | 2019-12-20 | 四川东树新材料有限公司 | Glass material for crystalline silicon solar cell, preparation method thereof and silver paste |
| CN111630012A (en) * | 2017-10-31 | 2020-09-04 | LS-Nikko铜制炼株式会社 | Conductive paste for solar cell electrode, glass frit contained in conductive paste, and solar cell |
| KR20200123643A (en) * | 2019-04-22 | 2020-10-30 | 주식회사 휘닉스에이엠 | Glass frit composition for forming solar cell electrode, and paste composition including the same |
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| KR20200123643A (en) * | 2019-04-22 | 2020-10-30 | 주식회사 휘닉스에이엠 | Glass frit composition for forming solar cell electrode, and paste composition including the same |
| KR102183618B1 (en) * | 2019-04-22 | 2020-11-26 | 주식회사 휘닉스에이엠 | Glass frit composition for forming solar cell electrode, and paste composition including the same |
| CN110590168A (en) * | 2019-10-28 | 2019-12-20 | 四川东树新材料有限公司 | Glass material for crystalline silicon solar cell, preparation method thereof and silver paste |
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