WO2018176828A1 - Metal glass-ceramics powder, manufacturing method thereof, and conductive paste - Google Patents
Metal glass-ceramics powder, manufacturing method thereof, and conductive paste Download PDFInfo
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- WO2018176828A1 WO2018176828A1 PCT/CN2017/108275 CN2017108275W WO2018176828A1 WO 2018176828 A1 WO2018176828 A1 WO 2018176828A1 CN 2017108275 W CN2017108275 W CN 2017108275W WO 2018176828 A1 WO2018176828 A1 WO 2018176828A1
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- Prior art keywords
- parts
- glass
- metal
- conductive paste
- powder
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 35
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000006121 base glass Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000006060 molten glass Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical group CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims 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 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000000859 sublimation Methods 0.000 claims 1
- 230000008022 sublimation Effects 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001947 lithium oxide Inorganic materials 0.000 abstract description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 6
- 239000011787 zinc oxide Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004327 boric acid Substances 0.000 abstract description 4
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 9
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910004205 SiNX Inorganic materials 0.000 description 3
- 230000003667 anti-reflective effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021418 black silicon Inorganic materials 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 bismuth-lead-bismuth-lithium Chemical compound 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic 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
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- 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
-
- 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 invention relates to a metal microcrystalline glass powder, a preparation method thereof and a conductive paste, and belongs to the technical field of functional materials of solar cells.
- photovoltaic cells have achieved rapid development in recent years. Photovoltaic cell technology is also changing with each passing day. The entire industry chain is actively promoting the conversion efficiency of photovoltaic cells and reducing costs through technological innovation, striving to achieve parity online and replacing traditional high pollution. energy.
- Crystalline silicon photovoltaic cells are the most important type of photovoltaic cells, accounting for more than 90%.
- the principle of photoelectric conversion is: boron-doped P-type silicon and phosphorus-doped N-type silicon form PN junction, when sunlight is irradiated, PN The junction absorbs photon energy to excite electron transitions, forming electron-hole pairs, which generate carriers.
- a conductive metal paste is coated on the light-receiving surface (front surface) and the backlight surface (back surface) of the photovoltaic cell, and after sintering, a metal electrode can be formed, and the PN junction generates carriers which are led out through the metal electrode to form a current.
- the metal electrode forms a good ohmic contact with the silicon substrate, has a low ohmic contact resistance and bulk resistance, reduces current loss, and improves solar cell conversion efficiency.
- the glass plays an important role.
- the glass reacts with the anti-reflective layer (SiNx), corrodes the anti-reflective layer and contacts the silicon-based layer, and the liquid glass dissolves the silver, and the silver-based contact crystallizes the silver particles upon cooling to lower the ohmic contact resistance.
- the present invention provides a metal microcrystalline glass powder and a conductive paste which are more excellent in electrical properties.
- the present invention relates to a metal microcrystalline glass powder, in parts by weight, comprising the following components:
- the metal microcrystalline glass powder of the present application further comprises one or more of lead, magnesium, aluminum, vanadium, cobalt, strontium, barium, sodium, potassium, indium, calcium, titanium and nickel oxide, and the number is 1 -10 servings.
- the metal microcrystalline glass powder of the present application has a particle diameter D50 of 0.3 to 2 ⁇ m.
- the application also provides a method for preparing a metal microcrystalline glass powder:
- Step 1 Mixing the materials of any one of claims 1 to 3 in parts by weight, raising the temperature to 900 to 1000 ° C under mixing of H 2 and argon, holding the glass for 10 to 60 minutes, and then forming the glass. The liquid is quenched on a steel plate or a stainless steel roll machine to obtain a base glass;
- Step 2 the base glass is kept at 200-400 ° C for 20 to 60 minutes in an oxygen-free atmosphere, and then slowly cooled at room temperature or with the furnace temperature to obtain a metal crystallized glass;
- Step 3 then crushing the metal crystallized glass obtained in the second step and then ball milling with a planetary ball mill to obtain a metal microcrystalline glass powder.
- the application further provides a conductive paste for a solar cell, the conductive paste comprising the following parts by weight:
- the metal glass ceramic powder is the above metal glass ceramic powder.
- the conductive paste for a solar cell of the present application has a spherical shape, a polyhedral shape, a short rod shape, a dendritic shape or a sheet shape.
- the conductive paste for solar cells of the present application wherein the organic solvent is terpineol, butyl carbitol, propylene glycol phenyl ether, propylene glycol methyl ether, dimethyl glutarate, dimethyl succinate One or more.
- the organic carrier is butyl carbitol acetate, ethyl cellulose, acrylate, oleic acid, polypropylene glycol, polyamide wax according to (50-80): 1-10): (0-15): (0-5): (0-3): (0.5-6) by weight mixing.
- the conductive paste for solar cells of the present application is formed by heating and stirring at a temperature of 50 to 90 degrees.
- the present invention has the following advantages and effects compared with the prior art:
- the present invention relates to a metal microcrystalline glass and a conductive paste for a solar cell, which comprises 10 to 50 parts of cerium oxide, 15 to 70 parts of cerium oxide, 2 to 10 parts of zinc oxide, and 1 to 15 parts of tungsten oxide. 5 to 20 parts of lithium oxide, which can precipitate "metal microcrystalline glass" when cooled.
- This metal microcrystalline glass is applied to the front electrode silver paste of crystalline silicon photovoltaic cell, which has superior performance and performance compared with conventional amorphous glass. Improve the conversion efficiency of the battery, and also have the characteristics of high temperature viscosity and large surface tension. When the slurry is sintered, the molten glass does not easily flow and maintains a fine line shape;
- the metal cermet glass powder and the conductive paste of the present application have the highest conversion efficiency.
- the series resistance is reduced by 0.2-0.4m ⁇
- the fill factor is increased by up to 1%
- the ohmic contact resistance is reduced by about half.
- the conductive paste for solar cells of the present invention wherein the organic carrier is butyl carbitol acetate, ethyl cellulose, acrylate, oleic acid, polypropylene glycol, polyamide wax according to (50-80): 1-10): (0-15): (0-5): (0-3): (0.5-6) by weight mixing, not only helps to improve the infiltration of the paste and stainless steel screen, which is beneficial to The paste is evenly spread during the printing process; moreover, it overcomes the defect that the silver powder and the metal microcrystalline glass powder in the conductive paste are relatively easy to agglomerate and settle, and forms a slurry in which the silver powder and the metal microcrystalline glass powder are uniformly dispersed.
- the organic carrier is butyl carbitol acetate, ethyl cellulose, acrylate, oleic acid, polypropylene glycol, polyamide wax according to (50-80): 1-10): (0-15): (0-5): (0-3): (0.5-6) by weight mixing
- Examples 1-18 provide a metal microcrystalline glass frit, respectively, and the metal frit glass powder of each example consists of the components of Table 1:
- Example 16 Example 17
- Example 18 Cerium oxide 50 copies 25 copies 15 copies Yttrium oxide 15 copies 50 copies 70 copies
- Embodiments 19-36 respectively provide a method for preparing a metal microcrystalline glass powder
- Step 1 Mix the materials in Examples 1-18 according to the ratio in Table 1, heat up to T1 °C under the mixture of H 2 and argon, heat the M1 minutes to form a glass solution, and then place the glass solution on the steel plate or stainless steel. Rapidly forming a base glass on a roller machine;
- Step 2 The base glass is kept at T2 ° C for 2 minutes in an oxygen-free atmosphere, and then slowly cooled at room temperature or with the furnace temperature to obtain a metal crystallized glass;
- Step 3 then crushing the metal crystallized glass obtained in the second step and then ball milling with a planetary ball mill to obtain a metal microcrystalline glass powder.
- the oxygen-free atmosphere is vacuum, inert gas or nitrogen.
- T1, M1, T2 and M2 are shown in Table 2.
- Embodiments 37-54 respectively provide a conductive paste for a solar cell
- the semiconductor substrate is selected from a boron-doped P-type silicon substrate, which is 180-250 ⁇ m thick 125*125 mm or 156*156 mm or other typical size silicon wafer.
- the side of the silicon substrate is etched with an alkali solution to form a pyramidal (single crystal) or rugged (polycrystalline) anti-reflective suede, and the black silicon nano-sue can also be formed by a wet black silicon technique.
- an N-type diffusion layer is formed on the other side of the P-type silicon substrate to form a PN junction
- the N-type diffusion layer may be a gas phase thermal diffusion method using gaseous phosphorus oxychloride as a diffusion source, or a phosphorus ion implantation method, or The slurry containing phosphorus pentoxide is coated with a thermal diffusion method or the like.
- a layer of 80 nm thick SiNx anti-reflection layer is deposited on the side of the silicon substrate, which is also a similar coating with good anti-reflection effect.
- the Al electrode layer and the main gate silver electrode layer are printed or coated on one side of the P-type silicon substrate, and a passivation layer may be formed on the back surface of the battery by using SiNx or Al2O3 as a back reflector to increase long-wavelength light. Absorption.
- the slurry of Examples 37 to 54 is formed on the N-type silicon substrate side antireflection film by screen printing, coating or inkjet printing to form a vertical and horizontal main gate and a fine gate at a certain sintering temperature.
- the electrode body is formed by co-firing.
- the recommended temperature sintering procedure is 250-350-450-550-600-700-800-900 °C.
- the contact resistance test method the contact resistance is tested using a commonly used TLM (line transmission line model).
- the experimental conditions used in the comparison group were as follows: the glass powder was a bismuth-lead-bismuth-lithium system glass powder.
- the formulation contains 10 to 50 parts of cerium oxide, 15 to 70 parts of cerium oxide, 2 to 10 parts of zinc oxide, 1 to 15 parts of tungsten oxide, and 5 to 20 parts of lithium oxide.
- metal microcrystalline glass can be precipitated. This metal microcrystalline glass is applied to the front electrode silver paste of the crystalline silicon photovoltaic cell, which has superior performance than the conventional amorphous glass, and effectively improves the conversion efficiency of the battery.
- the high temperature viscosity is large and the surface tension is large.
- the metal cermet glass powder and the conductive paste of the above embodiment have a conversion efficiency of up to about 0.5%, a series resistance of 0.2-0.4 m ⁇ , a fill factor of up to 1%, and an ohmic contact resistance of about half.
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Abstract
Metal glass-ceramics powder, a manufacturing method thereof, and conductive paste. The conductive paste comprises, in parts by weight, the following components: 75-92 parts of silver powder, 5-12 parts of an organic solvent, 2-3 parts of an organic vehicle, 0.5-1 parts of a dispersant, and 0.8-5.3 parts of metal glass-ceramics powder. The particle diameter D50 of the metal glass-ceramics powder is 0.3-2 μm. The metal glass-ceramics powder comprises: 10-50 parts of tellurium dioxide, 15-70 parts of bismuth oxide, 2-10 parts of zinc oxide, 1-15 parts of tungsten oxide, 5-20 parts of lithium oxide, 0.4-2 parts of boric acid, 1-6 parts of molybdenum chloride, 1-4 parts of silicon oxide, and 1-2 parts of barium carbonate. The conductive paste can effectively improve the cell conversion efficiency, reduce the series resistance, increase the fill factor, and lower the ohmic contact resistance.
Description
本发明涉及一种金属微晶玻璃粉及其制备方法及导电浆料，属于太阳能电池功能材料技术领域。The invention relates to a metal microcrystalline glass powder, a preparation method thereof and a conductive paste, and belongs to the technical field of functional materials of solar cells.
光伏电池作为新型清洁能源重要分支，近几年已经取得突飞猛进发展，光伏电池技术也是日新月异，全产业链都在积极通过技术创新提升光伏电池转化效率并降低成本，努力实现平价上网，替代传统高污染能源。As an important branch of new clean energy, photovoltaic cells have achieved rapid development in recent years. Photovoltaic cell technology is also changing with each passing day. The entire industry chain is actively promoting the conversion efficiency of photovoltaic cells and reducing costs through technological innovation, striving to achieve parity online and replacing traditional high pollution. energy.
晶硅光伏电池是目前光伏电池最主要类型，占比90％以上，其光电转换原理为：硼掺杂的P型硅和磷掺杂的N型硅形成PN结，当太阳光照射时，PN结就会吸收光子能量激发电子跃迁，形成电子-空穴对，从而产生载流子。Crystalline silicon photovoltaic cells are the most important type of photovoltaic cells, accounting for more than 90%. The principle of photoelectric conversion is: boron-doped P-type silicon and phosphorus-doped N-type silicon form PN junction, when sunlight is irradiated, PN The junction absorbs photon energy to excite electron transitions, forming electron-hole pairs, which generate carriers.
在光伏电池受光面(正面)和背光面(背面)涂覆导电金属浆料，经过烧结后能够形成金属电极，PN结产生载流子通过金属电极导出，形成电流。金属电极要与硅基底形成良好欧姆接触，有较低的欧姆接触电阻和体电阻，降低电流损失，提高太阳能电池转化效率。A conductive metal paste is coated on the light-receiving surface (front surface) and the backlight surface (back surface) of the photovoltaic cell, and after sintering, a metal electrode can be formed, and the PN junction generates carriers which are led out through the metal electrode to form a current. The metal electrode forms a good ohmic contact with the silicon substrate, has a low ohmic contact resistance and bulk resistance, reduces current loss, and improves solar cell conversion efficiency.
为了实现良好的欧姆接触，提高电极导电性，业内技术人员已经做了大量研究，其中玻璃扮演重要角色。比如，玻璃要与减反射层(SiNx)反应，腐蚀掉减反层后与硅基接触，并且，液态玻璃能够溶解银，在冷却时在硅基接触层析出银颗粒，降低欧姆接触电阻。如前人研究的氧化铅、氧化碲作用原理。为获得转化效率更高、电性性能更加优异的太阳能电池的导电浆料是本领域技术人员的一致追求，而现有的氧化铅、氧化碲系导电浆料的提升空间有限，急需开发一种全新的导电浆料体系。In order to achieve good ohmic contact and improve electrode conductivity, a lot of research has been done by those skilled in the art, in which glass plays an important role. For example, the glass reacts with the anti-reflective layer (SiNx), corrodes the anti-reflective layer and contacts the silicon-based layer, and the liquid glass dissolves the silver, and the silver-based contact crystallizes the silver particles upon cooling to lower the ohmic contact resistance. As the predecessors studied the principle of the action of lead oxide and antimony oxide. In order to obtain a conductive paste of a solar cell having higher conversion efficiency and more excellent electrical properties, it is a common pursuit of those skilled in the art, and the existing lead oxide and yttrium oxide-based conductive paste have limited space for improvement, and it is urgent to develop a kind. A new conductive paste system.
发明内容Summary of the invention
为进一步提高太阳能电池的导电浆料的电性性能，本发明提供一种电性性能更加优良的金属微晶玻璃粉及导电浆料。In order to further improve the electrical properties of the conductive paste of the solar cell, the present invention provides a metal microcrystalline glass powder and a conductive paste which are more excellent in electrical properties.
本申请一种金属微晶玻璃粉，以重量份计，包括以下组分：The present invention relates to a metal microcrystalline glass powder, in parts by weight, comprising the following components:
本申请的金属微晶玻璃粉，还包括铅、镁、铝、钒、钴、锗、锶、钠、钾、铟、钙、钛、镍氧化物中的一种或多种，份数为1-10份。The metal microcrystalline glass powder of the present application further comprises one or more of lead, magnesium, aluminum, vanadium, cobalt, strontium, barium, sodium, potassium, indium, calcium, titanium and nickel oxide, and the number is 1 -10 servings.
本申请的金属微晶玻璃粉，所述金属微晶玻璃粉的粒径D50为0.3-2μm。The metal microcrystalline glass powder of the present application has a particle diameter D50 of 0.3 to 2 μm.
本申请还提供一种金属微晶玻璃粉的制备方法：The application also provides a method for preparing a metal microcrystalline glass powder:
包括以下步骤：Includes the following steps:
步骤一、以重量份计，将权利要求1-3中任一项中的物质混合，在H2和氩气混合下升温至900～1000℃，保温10～60分钟形成玻璃液，然后将玻璃液在钢板或不锈钢对辊机上急冷成型得到基体玻璃；Step 1: Mixing the materials of any one of claims 1 to 3 in parts by weight, raising the temperature to 900 to 1000 ° C under mixing of H 2 and argon, holding the glass for 10 to 60 minutes, and then forming the glass. The liquid is quenched on a steel plate or a stainless steel roll machine to obtain a base glass;
步骤二、将基体玻璃在无氧气氛下200～400℃保温20～60分钟，然后常温或随炉温缓慢冷却，得到金属微晶玻璃；Step 2, the base glass is kept at 200-400 ° C for 20 to 60 minutes in an oxygen-free atmosphere, and then slowly cooled at room temperature or with the furnace temperature to obtain a metal crystallized glass;
步骤三、然后将步骤二获得的金属微晶玻璃破碎后用行星式球磨机球磨，得到金属微晶玻璃粉。Step 3, then crushing the metal crystallized glass obtained in the second step and then ball milling with a planetary ball mill to obtain a metal microcrystalline glass powder.
本申请再提供一种用于太阳能电池的导电浆料，所述导电浆料包括下列重量份的组分：The application further provides a conductive paste for a solar cell, the conductive paste comprising the following parts by weight:
所述金属微晶玻璃粉为上述的金属微晶玻璃粉。The metal glass ceramic powder is the above metal glass ceramic powder.
本申请的用于太阳能电池的导电浆料，所述银粉形状为球型、多面体型、短棒形、树枝型或者片型。The conductive paste for a solar cell of the present application has a spherical shape, a polyhedral shape, a short rod shape, a dendritic shape or a sheet shape.
本申请的用于太阳能电池的导电浆料，所述有机溶剂为松油醇、丁基卡必醇、丙二醇苯醚、丙二醇甲醚、戊二酸二甲酯、丁二酸二甲酯中的一种或多种。The conductive paste for solar cells of the present application, wherein the organic solvent is terpineol, butyl carbitol, propylene glycol phenyl ether, propylene glycol methyl ether, dimethyl glutarate, dimethyl succinate One or more.
本申请的用于太阳能电池的导电浆料，所述有机载体为丁基卡必醇醋酸酯、乙基纤维素、丙烯酸酯、油酸、聚丙二醇、聚酰胺蜡按(50-80)：(1-10)：(0-15)：(0-5)：(0-3)：(0.5-6)重量比混合而成。The conductive paste for solar cells of the present application, the organic carrier is butyl carbitol acetate, ethyl cellulose, acrylate, oleic acid, polypropylene glycol, polyamide wax according to (50-80): 1-10): (0-15): (0-5): (0-3): (0.5-6) by weight mixing.
本申请的用于太阳能电池的导电浆料，所述有机载体在50-90度温度条件下加热搅拌混合而成。
The conductive paste for solar cells of the present application is formed by heating and stirring at a temperature of 50 to 90 degrees.
由于上述技术方案运用，本发明与现有技术相比具有下列优点和效果：Due to the application of the above technical solutions, the present invention has the following advantages and effects compared with the prior art:
1.本发明为金属微晶玻璃及用于太阳能电池的导电浆料，其配方中含有二氧化碲10～50份、氧化铋15～70份、氧化锌2～10份、氧化钨1～15份、氧化锂5～20份，在冷却时可以析出“金属微晶玻璃”，这种金属微晶玻璃应用于晶硅光伏电池正面电极银浆，取得了比常规无定型玻璃优异的性能，有效提高电池转化效率，也具有高温粘度大、表面张力大特点，浆料在烧结时熔融玻璃不易流动，保持精细线型；1. The present invention relates to a metal microcrystalline glass and a conductive paste for a solar cell, which comprises 10 to 50 parts of cerium oxide, 15 to 70 parts of cerium oxide, 2 to 10 parts of zinc oxide, and 1 to 15 parts of tungsten oxide. 5 to 20 parts of lithium oxide, which can precipitate "metal microcrystalline glass" when cooled. This metal microcrystalline glass is applied to the front electrode silver paste of crystalline silicon photovoltaic cell, which has superior performance and performance compared with conventional amorphous glass. Improve the conversion efficiency of the battery, and also have the characteristics of high temperature viscosity and large surface tension. When the slurry is sintered, the molten glass does not easily flow and maintains a fine line shape;
其次，其在玻璃粉中进一步添加硼酸0.4～2份、氧化硅1～4份、碳酸钡1～2份，可以降低玻璃熔点，并且在高于熔点较大温度窗口内保持高粘度，可以在降低电极烧结温度同时拓宽烧结窗口，增大烧结稳定性，提高电池成品率；再次，其基于二氧化碲10～50份、氧化铋15～70份、氧化锌2～10份、氧化钨1～15份、氧化锂5～20份体系中进一步添加氯化钼，实现了金属微晶玻璃与硅基形成良好欧姆接触，最终，本申请的金属微晶玻璃粉及导电浆料，转化效率最高提升0.5％左右，串联电阻降低了0.2-0.4mΩ，填充因子提高了最多1％，欧姆接触电阻降低了一半左右。Secondly, it further adds 0.4 to 2 parts of boric acid, 1 to 4 parts of silicon oxide, and 1 to 2 parts of cesium carbonate to the glass powder, which can lower the melting point of the glass and maintain a high viscosity in a temperature window higher than the melting point. Reduce the sintering temperature of the electrode while widening the sintering window, increase the sintering stability, and improve the battery yield; again, it is based on 10 to 50 parts of cerium oxide, 15 to 70 parts of cerium oxide, 2 to 10 parts of zinc oxide, and 1 to 10 parts of tungsten oxide. 15 parts and 5 to 20 parts of lithium oxide are further added with molybdenum chloride to achieve good ohmic contact between the metal crystallized glass and the silicon base. Finally, the metal cermet glass powder and the conductive paste of the present application have the highest conversion efficiency. Around 0.5%, the series resistance is reduced by 0.2-0.4mΩ, the fill factor is increased by up to 1%, and the ohmic contact resistance is reduced by about half.
2.本发明用于太阳能电池的导电浆料，其有机载体采用丁基卡必醇醋酸酯、乙基纤维素、丙烯酸酯、油酸、聚丙二醇、聚酰胺蜡按(50-80)：(1-10)：(0-15)：(0-5)：(0-3)：(0.5-6)重量比混合而成，不仅有利于改善膏体与不锈钢丝网网版浸润性，利于印刷过程中膏体均匀铺展；而且，克服了导电浆料中银粉和金属微晶玻璃粉较容易团聚沉降的缺陷，形成银粉和金属微晶玻璃粉均匀分散的浆料。2. The conductive paste for solar cells of the present invention, wherein the organic carrier is butyl carbitol acetate, ethyl cellulose, acrylate, oleic acid, polypropylene glycol, polyamide wax according to (50-80): 1-10): (0-15): (0-5): (0-3): (0.5-6) by weight mixing, not only helps to improve the infiltration of the paste and stainless steel screen, which is beneficial to The paste is evenly spread during the printing process; moreover, it overcomes the defect that the silver powder and the metal microcrystalline glass powder in the conductive paste are relatively easy to agglomerate and settle, and forms a slurry in which the silver powder and the metal microcrystalline glass powder are uniformly dispersed.
下面结合实施例对本发明作进一步描述：The present invention is further described below in conjunction with the embodiments:
实施例1-18Example 1-18
实施例1-18分别提供一种金属微晶玻璃粉，各实施例的金属微晶玻璃粉由表1中的组分组成：Examples 1-18 provide a metal microcrystalline glass frit, respectively, and the metal frit glass powder of each example consists of the components of Table 1:
表1实施例1-18的金属微晶玻璃粉成分表Table 1 Composition of metal glass ceramic powder of Examples 1-18
续表1Continued Table 1
续表1Continued Table 1
续表1Continued Table 1
| 组分Component | 实施例16Example 16 | 实施例17Example 17 | 实施例18Example 18 |
| 二氧化碲Cerium oxide | 50份50 copies | 25份25 copies | 15份15 copies |
| 氧化铋Yttrium oxide | 15份15 copies | 50份50 copies | 70份70 copies |
| 氧化锌Zinc oxide | 2份2 servings | 5份5 servings | 10份10 copies |
| 氧化钨Tungsten oxide | 1份1 serving | 8份8 servings | 15份15 copies |
| 氧化锂Lithium oxide | 20份20 copies | 12份12 copies | 5份5 servings |
| 硼酸Boric acid | 2份2 servings | 1.2份1.2 servings | 0.4份0.4 parts |
| 氯化钼Molybdenum chloride | 1份1 serving | 2.5份2.5 servings | 6份6 servings |
| 氧化硅Silicon oxide | 4份4 parts | 2份2 servings | 1份1 serving |
| 碳酸钡Barium carbonate | 2份2 servings | 1.5份1.5 servings | 1份1 serving |
| 其它氧化物Other oxide | 无no | 无no | 无no |
实施例19-36Example 19-36
实施例19-36分别提供一种金属微晶玻璃粉的制备方法，Embodiments 19-36 respectively provide a method for preparing a metal microcrystalline glass powder,
包括以下步骤：Includes the following steps:
步骤一、将实施例1-18中各物质按表1中的比例进行混合，在H2和氩气混合下升温至T1℃，保温M1分钟形成玻璃液，然后将玻璃液在钢板或不锈钢对辊机上急冷成型得到基体玻璃；Step 1. Mix the materials in Examples 1-18 according to the ratio in Table 1, heat up to T1 °C under the mixture of H 2 and argon, heat the M1 minutes to form a glass solution, and then place the glass solution on the steel plate or stainless steel. Rapidly forming a base glass on a roller machine;
步骤二、将基体玻璃在无氧气氛下T2℃保温M2分钟，然后常温或随炉温缓慢冷却，得到金属微晶玻璃；Step 2: The base glass is kept at T2 ° C for 2 minutes in an oxygen-free atmosphere, and then slowly cooled at room temperature or with the furnace temperature to obtain a metal crystallized glass;
步骤三、然后将步骤二获得的金属微晶玻璃破碎后用行星式球磨机球磨，得到金属微晶玻璃粉。Step 3, then crushing the metal crystallized glass obtained in the second step and then ball milling with a planetary ball mill to obtain a metal microcrystalline glass powder.
上述步骤二中无氧气氛为真空、惰性气体或者氮气。In the above step two, the oxygen-free atmosphere is vacuum, inert gas or nitrogen.
T1、M1、T2、M2的值见表2The values of T1, M1, T2 and M2 are shown in Table 2.
表2实施例19-36中T1、M1、T2、M2的值及最终产物的粒径D50Table 2 The values of T1, M1, T2, M2 and the particle size D50 of the final product in Examples 19-36
实施例37-54Example 37-54
实施例37-54分别提供一种用于太阳能电池的导电浆料，Embodiments 37-54 respectively provide a conductive paste for a solar cell,
表3实施例37-54中各组分的值Table 3 Values of the components in Examples 37-54
表4实施例37-54中有机载体的组分表(重量比)
Table 4 Table of components of organic carriers in Examples 37-54 (weight ratio)
效果实施例Effect embodiment
应用到太阳能电池装置后电性性能测试：Electrical performance test after application to solar cell devices:
太阳能电池装置制备：Solar cell device preparation:
半导体衬底选择掺杂硼的P型硅基底，P型硅基底为180-250μm厚的125*125mm或156*156mm或其它典型尺寸的硅片。The semiconductor substrate is selected from a boron-doped P-type silicon substrate, which is 180-250 μm thick 125*125 mm or 156*156 mm or other typical size silicon wafer.
第一步，用碱溶液对硅基底一侧进行腐蚀职称金字塔形(单晶)或凹凸不平(多晶)减反射绒面，也可以用湿法黑硅技术制成黑硅纳米绒面。In the first step, the side of the silicon substrate is etched with an alkali solution to form a pyramidal (single crystal) or rugged (polycrystalline) anti-reflective suede, and the black silicon nano-sue can also be formed by a wet black silicon technique.
第二步，在P型硅基底另一侧形成N型扩散层制成PN结，N型扩散层可以是以气态三氯氧磷作为扩散源的气相热扩散法，或者磷离子注入法，或者含有五氧化二磷的浆料涂覆热扩散法等。In the second step, an N-type diffusion layer is formed on the other side of the P-type silicon substrate to form a PN junction, and the N-type diffusion layer may be a gas phase thermal diffusion method using gaseous phosphorus oxychloride as a diffusion source, or a phosphorus ion implantation method, or The slurry containing phosphorus pentoxide is coated with a thermal diffusion method or the like.
第三步，在硅基底绒面一侧沉覆一层80nm厚的SiNx减反层，也可以是相近的其它具有良好减反射效果的涂层。In the third step, a layer of 80 nm thick SiNx anti-reflection layer is deposited on the side of the silicon substrate, which is also a similar coating with good anti-reflection effect.
第四步，在P型硅基底一侧印刷或涂覆Al电极层和主栅银电极层，另外，也可以利用SiNx或Al2O3在电池背面形成钝化层，作为背反射器，增加长波光
的吸收。In the fourth step, the Al electrode layer and the main gate silver electrode layer are printed or coated on one side of the P-type silicon substrate, and a passivation layer may be formed on the back surface of the battery by using SiNx or Al2O3 as a back reflector to increase long-wavelength light.
Absorption.
第五步，将实施例37～54的浆料在N型硅基底一侧减反膜上通过丝网印刷、涂覆或喷墨打印等方式形成纵横的主栅和细栅，在一定烧结温度程序下，共烧形成电极体。推荐使用的温度烧结程序为250-350-450-550-600-700-800-900℃。In the fifth step, the slurry of Examples 37 to 54 is formed on the N-type silicon substrate side antireflection film by screen printing, coating or inkjet printing to form a vertical and horizontal main gate and a fine gate at a certain sintering temperature. Under the program, the electrode body is formed by co-firing. The recommended temperature sintering procedure is 250-350-450-550-600-700-800-900 °C.
太阳能电池片电性能测试，使用太阳能模拟电效率测试仪，在标准条件下测试(AM1.5，1000W/m2,25℃)。Solar cell electrical performance test, using a solar simulated electrical efficiency tester, tested under standard conditions (AM 1.5, 1000 W/m2, 25 ° C).
接触电阻测试方法，选用常用的TLM(线传输线模型)测试接触电阻。For the contact resistance test method, the contact resistance is tested using a commonly used TLM (line transmission line model).
测试结果如表5所示：The test results are shown in Table 5:
表6太阳能电池装置的接触电阻测试结果Table 6 Contact resistance test results of solar cell devices
对比组采用的实验条件为：玻璃粉为碲-铅-铋-锂体系玻璃粉。The experimental conditions used in the comparison group were as follows: the glass powder was a bismuth-lead-bismuth-lithium system glass powder.
采用上述用于太阳能电池的导电浆料时，其配方中含有二氧化碲10～50份、氧化铋15～70份、氧化锌2～10份、氧化钨1～15份、氧化锂5～20份，在冷却时可以析出“金属微晶玻璃”，这种金属微晶玻璃应用于晶硅光伏电池正面电极银浆，取得了比常规无定型玻璃优异的性能，有效提高电池转化效率，也具有高温粘度大、表面张力大特点，浆料在烧结时熔融玻璃不易流动，保持精细线型；其次，其在玻璃粉中进一步添加硼酸0.4～2份、氧化硅1～4份、碳酸钡1～2份，可以降低玻璃熔点，并且在高于熔点较大温度窗口内保持高粘度，可以在降低电极烧结温度同时拓宽烧结窗口，增大烧结稳定性，提高电池成品率；再次，其基于二氧化碲10～50份、氧化铋15～70份、氧化锌2～10份、氧化钨1～15份、氧化锂5～20份体系中进一步添加氯化钼，经研究发现氯化钼的添加可以实现金属微晶玻璃与硅基形成良好欧姆接触，降低了串联电阻。再次，其不仅有利于改善膏体与不锈钢丝网网版浸润性，利于印刷过程中膏体均匀铺展；而且，克服了导电浆料中银粉和金属微晶玻璃粉较容易团聚沉降的缺陷，形成银粉和金属微晶玻璃粉均匀分散的浆料。最终，上述实施例的金属微晶玻璃粉及导电浆料，转化效率最高提升0.5％左右，串联电阻降低了0.2-0.4mΩ，填充因子提高了最多1％，欧姆接触电阻降低了一半左右。When the conductive paste for a solar cell is used, the formulation contains 10 to 50 parts of cerium oxide, 15 to 70 parts of cerium oxide, 2 to 10 parts of zinc oxide, 1 to 15 parts of tungsten oxide, and 5 to 20 parts of lithium oxide. In the case of cooling, "metal microcrystalline glass" can be precipitated. This metal microcrystalline glass is applied to the front electrode silver paste of the crystalline silicon photovoltaic cell, which has superior performance than the conventional amorphous glass, and effectively improves the conversion efficiency of the battery. The high temperature viscosity is large and the surface tension is large. When the slurry is sintered, the molten glass does not flow easily and maintains a fine line shape. Secondly, it further adds 0.4 to 2 parts of boric acid, 1 to 4 parts of silicon oxide, and cesium carbonate 1 to the glass powder. 2 parts, can lower the melting point of glass, and maintain high viscosity in the temperature window higher than the melting point, can widen the sintering window while reducing the sintering temperature of the electrode, increase the sintering stability and improve the battery yield; again, it is based on dioxide Further, 10 to 50 parts, 15 to 70 parts of cerium oxide, 2 to 10 parts of zinc oxide, 1 to 15 parts of tungsten oxide, and 5 to 20 parts of lithium oxide are further added with molybdenum chloride. Glass and silicon metal crystallites to achieve a good ohmic contact, reducing the series resistance. Thirdly, it not only helps to improve the infiltration of the paste and the stainless steel screen, but also facilitates the uniform spreading of the paste during the printing process. Moreover, it overcomes the defects of the silver powder and the metal microcrystalline glass powder in the conductive paste which are relatively easy to agglomerate and settle. A slurry in which silver powder and metal crystallized glass powder are uniformly dispersed. Finally, the metal cermet glass powder and the conductive paste of the above embodiment have a conversion efficiency of up to about 0.5%, a series resistance of 0.2-0.4 mΩ, a fill factor of up to 1%, and an ohmic contact resistance of about half.
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。
The above embodiments are merely illustrative of the technical concept and the features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the present invention and to implement the present invention, and the scope of the present invention is not limited thereto. Equivalent variations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention.
Claims (9)
- 一种金属微晶玻璃粉，其特征在于，以重量份计，包括以下组分：A metal microcrystalline glass frit characterized by comprising the following components in parts by weight:
- 根据权利要求1所述的金属微晶玻璃粉，其特征在于，还包括铅、镁、铝、钒、钴、锗、锶、钠、钾、铟、钙、钛、镍氧化物中的一种或多种，份数为1-10份。The metal ceramsite powder according to claim 1, further comprising one of lead, magnesium, aluminum, vanadium, cobalt, strontium, barium, sodium, potassium, indium, calcium, titanium and nickel oxide. Or a variety of parts, the number of parts is 1-10.
- 根据权利要求1或2所述的金属微晶玻璃粉，其特征在于，所述金属微晶玻璃粉的粒径D50为0.3-2μm。The metal glass-ceramic powder according to claim 1 or 2, wherein the metal glass-ceramic powder has a particle diameter D50 of 0.3 to 2 μm.
- 一种金属微晶玻璃粉的制备方法：Preparation method of metal microcrystalline glass powder:包括以下步骤：Includes the following steps:步骤一、以重量份计，将权利要求1-3中任一项中的物质混合，在H2和氩气混合下升温至900～1000℃，保温10～60分钟形成玻璃液，然后将玻璃液在钢板或不锈钢对辊机上急冷成型得到基体玻璃；Step 1: Mixing the materials of any one of claims 1-3 in parts by weight, heating to 900-1000 ° C under mixing of H 2 and argon, holding for 10 to 60 minutes to form a molten glass, and then adding the molten glass. Sublimation molding on a steel plate or stainless steel counter roll machine to obtain a base glass;步骤二、将基体玻璃在无氧气氛下200～400℃保温20～60分钟，然后常温或随炉温缓慢冷却，得到金属微晶玻璃；Step 2, the base glass is kept at 200-400 ° C for 20 to 60 minutes in an oxygen-free atmosphere, and then slowly cooled at room temperature or with the furnace temperature to obtain a metal crystallized glass;步骤三、然后将步骤二获得的金属微晶玻璃破碎后用行星式球磨机球磨，得到金属微晶玻璃粉。Step 3, then crushing the metal crystallized glass obtained in the second step and then ball milling with a planetary ball mill to obtain a metal microcrystalline glass powder.
- 一种用于太阳能电池的导电浆料，其特征在于：所述导电浆料包括下列重量份的组分：A conductive paste for a solar cell, characterized in that the conductive paste comprises the following components by weight:
所述金属微晶玻璃粉为权利要求1或2或3中所述的金属微晶玻璃粉。The metal glass ceramic powder is the metal glass ceramic powder described in claim 1 or 2 or 3. - 根据权利要求5所述的用于太阳能电池的导电浆料，其特征在于：所述银粉形状为球型、多面体型、短棒形、树枝型或者片型。The conductive paste for a solar cell according to claim 5, wherein the silver powder has a spherical shape, a polyhedral shape, a short rod shape, a dendritic shape or a sheet shape.
- 根据权利要求5所述的用于太阳能电池的导电浆料，其特征在于：所述有机溶剂为松油醇、丁基卡必醇、丙二醇苯醚、丙二醇甲醚、戊二酸二甲酯、丁二酸二甲酯中的一种或多种。The conductive paste for a solar cell according to claim 5, wherein the organic solvent is terpineol, butyl carbitol, propylene glycol phenyl ether, propylene glycol methyl ether, dimethyl glutarate, One or more of dimethyl succinate.
- 根据权利要求5所述的用于太阳能电池的导电浆料，其特征在于：所述有机载体为丁基卡必醇醋酸酯、乙基纤维素、丙烯酸酯、油酸、聚丙二醇、聚酰胺蜡按(50-80)：(1-10)：(0-15)：(0-5)：(0-3)：(0.5-6)重量比混合而成。The conductive paste for a solar cell according to claim 5, wherein the organic carrier is butyl carbitol acetate, ethyl cellulose, acrylate, oleic acid, polypropylene glycol, polyamide wax. Press (50-80): (1-10): (0-15): (0-5): (0-3): (0.5-6) by weight mixing.
- 根据权利要求5所述的用于太阳能电池的导电浆料，其特征在于：所述有机载体在50-90度温度条件下加热搅拌混合而成。 The conductive paste for a solar cell according to claim 5, wherein the organic vehicle is heated and stirred at a temperature of 50 to 90 degrees.
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| JP2014031294A (en) * | 2012-08-03 | 2014-02-20 | Nippon Electric Glass Co Ltd | Glass for electrode formation and electrode formation material using the same |
| US20150075597A1 (en) * | 2013-09-16 | 2015-03-19 | Heraeus Precious Metals North America Conshohocken Llc | Electroconductive paste with adhension promoting glass |
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| JP2014031294A (en) * | 2012-08-03 | 2014-02-20 | Nippon Electric Glass Co Ltd | Glass for electrode formation and electrode formation material using the same |
| US20150075597A1 (en) * | 2013-09-16 | 2015-03-19 | Heraeus Precious Metals North America Conshohocken Llc | Electroconductive paste with adhension promoting glass |
| CN104867534A (en) * | 2014-01-17 | 2015-08-26 | 赫劳斯贵金属北美康舍霍肯有限责任公司 | Lead-bismuth-tellurium inorganic reaction system for electroconductive paste composition |
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