CN110689991A - Conductive paste - Google Patents
Conductive paste Download PDFInfo
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- CN110689991A CN110689991A CN201810722850.0A CN201810722850A CN110689991A CN 110689991 A CN110689991 A CN 110689991A CN 201810722850 A CN201810722850 A CN 201810722850A CN 110689991 A CN110689991 A CN 110689991A
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- Prior art keywords
- oxide
- conductive paste
- weight percentage
- amount
- conductive
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- 239000011521 glass Substances 0.000 claims abstract description 20
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- -1 Diethylene glycol butyl ether acetate (2- (2-butyl) Ethyl acetate) Chemical compound 0.000 claims description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 10
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 9
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 9
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 7
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229940116411 terpineol Drugs 0.000 claims description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 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 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000003760 tallow Substances 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 235000001968 nicotinic acid Nutrition 0.000 claims 1
- 239000011664 nicotinic acid Substances 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 abstract description 3
- 238000010344 co-firing Methods 0.000 description 29
- 239000004065 semiconductor Substances 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 238000002161 passivation Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002390 adhesive tape Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a conductive slurry comprising an organic medium, a conductive material and a glass medium, wherein the glass medium comprises vanadium oxide in an amount between 6 wt% and 35 wt%, boron oxide in an amount between 20 wt% and 53 wt%, zinc oxide in an amount between 5 wt% and 30 wt%, aluminum oxide or silicon dioxide in an amount between 1 wt% and 15 wt%, and an alkali metal oxide and/or an alkali earth oxide in an amount between 0.1 wt% and 35 wt%. The conductive paste can be applied to the electrode manufacture of a battery, and an electrode formed by using the conductive paste has low resistance value, no surface defect, good ohmic contact and high adhesion and strength.
Description
Technical Field
The invention relates to the technical field of conductive paste, in particular to conductive paste with good ohmic contact.
Background
A typical solar cell includes a semiconductor substrate having a P-type semiconductor layer and an N-type semiconductor layer, an anti-reflection layer, a front electrode and a back electrode, wherein the front electrode and the back electrode respectively form the N-type semiconductor layer and the P-type semiconductor layer, and form ohmic contact with the N-type semiconductor layer and the P-type semiconductor layer. The front electrode and the back electrode are usually formed on the N-type semiconductor layer and the P-type semiconductor layer by screen printing, coating or vacuum deposition. The front electrode is generally made of silver paste, and since the area of light incidence needs to be increased as much as possible to increase the photoelectric conversion efficiency of the solar cell, the surface area of the electrode on the light incidence side needs to be reduced as much as possible to increase the area of sunlight incidence. Since the back electrode is not irradiated to the back surface of the P-type semiconductor layer, the back electrode can cover the whole back surface of the P-type semiconductor layer and is usually made of aluminum paste and silver-aluminum paste. After the front electrode and the back electrode are formed, a co-firing process can be carried out, aluminum atoms of the back electrode are diffused into the P-type semiconductor layer by using high-temperature co-firing, and a back electric field is formed between the back electrode and the P-type semiconductor layer, so that the open-circuit voltage value in a circuit can be increased, and the conversion efficiency of the solar cell is increased. It should be noted that the front electrode and the back electrode need to maintain good ohmic contact with the semiconductor substrate, and the resistance value thereof also needs to be kept low, so as to increase the photoelectric conversion efficiency of the solar cell.
The front electrode and the back electrode have a large influence on the stability of the conversion efficiency of the solar cell. As a standard for electrode performance, there is a Fill Factor (FF) of a solar cell. When the series resistance of the solar cell is high, FF tends to be small, and the components of the series resistance are the resistance value of ohmic contact between the P-type semiconductor layer and the N-type semiconductor layer and the corresponding conductive electrode, and the resistance value of the conductive electrode itself.
Currently, in order to improve the conversion efficiency of solar cells, back passivated solar cells have become the mainstream of solar cell development due to their excellent electrochemical properties. Compared with the common solar cell, the back passivation solar cell carries out passivation treatment on the back surface of the semiconductor substrate, and simultaneously utilizes laser to carry out slotting/hole forming, and coating aluminum paste and silver-aluminum paste to carry out high-temperature co-firing. In this way, the aluminum paste and the silver-aluminum paste only form a local back surface electric field at the trench/hole. The passivated surface film can reduce the recombination of carriers, improve the conversion efficiency and simultaneously have the function of increasing reflection. The groove/hole is used as the joint of the back electrode and the semiconductor substrate, and whether the back electrode can have good ohmic contact with the semiconductor substrate is very important; on the other hand, the width of the laser trench/hole also affects the open circuit voltage of the cell, and only the width of the trench can be strictly controlled in order to obtain higher cell conversion efficiency.
One major technical problem facing the back passivated solar cell technology is: the back electrode interdiffuses with the semiconductor substrate during the sintering process, and due to Kirkendall effect, a hole is generated on the local back electric field, so that the back electrode cannot have good ohmic contact with the semiconductor substrate or fall off. In order to reduce the kirkendall effect, and the corrosion of the conventional aluminum paste and silver-aluminum paste to the grooves/holes or the passivation layer is too strong, the conversion efficiency of the solar cell is reduced, and therefore the high-temperature co-firing temperature is reduced when the solar cell is manufactured. However, the cofiring temperature is regulated to make the back passivated solar cell face another serious technical problem: a low softening point lead-containing glass frit must be used to achieve good ohmic contact, and defects such as aluminum beads or peeling of the back electrode may occur.
In view of the above, the double-sided back-passivated solar cell has high photoelectric conversion efficiency, and the double-sided back-passivated solar cell does not need to change the cell production process to a large extent, but only needs to change the fully covered back electrode into a local back electrode, and the aluminum paste/silver-aluminum paste is covered on the groove/hole region on the back surface of the semiconductor substrate, and the back surface of the semiconductor substrate is kept partially not covered by the back electrode, so that the purposes of double-sided light transmission, power generation and improvement of the conversion efficiency of the solar cell can be achieved. Therefore, the double-sided back passivated solar cell will become the development trend of the solar cell.
The main technical problems faced by the double-sided back-passivated solar cell technology are: 1. due to ohm's law, the resistance of the back electrode will increase obviously after the thinning, resulting in the reduction of the power generation efficiency of the solar cell; 2. in order to improve the back surface power generation efficiency of the solar cell, reduce the effect of the increase of the resistance of the local back surface electrode, and reduce the coverage area of the back surface electrode to increase the light input amount, the local back surface electrode needs to have a good aspect ratio, but the strength of the thinned back surface electrode is greatly weakened.
In order to be widely applied to three mainstream solar cell processes, suitable glass powder is required to solve the disadvantages of the prior art: 1. avoiding the direct or indirect harm caused by lead-containing materials and human bodies. 2. Ohmic bonding of the aluminum silicon is enhanced to reduce the resistance of the back electrode. 3. Wide application range of co-firing temperature, low resistance, reduced defects of the back electrode and enhanced strength of the back electrode.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the conductive paste.
In order to solve the above problems, the present invention discloses a conductive slurry comprising an organic medium, a conductive material and a glass medium, wherein the glass medium comprises vanadium oxide in an amount of 6 wt% and 35 wt%, boron oxide in an amount of 20 wt% and 53 wt%, zinc oxide in an amount of 5 wt% and 30 wt%, aluminum oxide or silicon dioxide in an amount of 1 wt% and 15 wt%, and an alkali metal oxide and/or an alkali earth oxide in an amount of 0.1 wt% and 35 wt%.
According to an embodiment of the present invention, the alkali metal oxide and/or the alkali earth oxide is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide.
According to an embodiment of the present invention, the alkali metal oxide and/or the alkali earth oxide includes barium oxide, and the weight percentage of the barium oxide is between 21 wt% and 32 wt%.
According to an embodiment of the present invention, the alkali metal oxide and/or the alkali earth oxide further includes sodium oxide and potassium oxide, wherein the weight percentage of the sodium oxide is between 1 wt% and 2 wt%, and the weight percentage of the potassium oxide is between 1 wt% and 2 wt%.
According to an embodiment of the present invention, the alkali metal oxide and/or the alkali earth oxide includes lithium oxide and magnesium oxide, wherein the weight percentage of lithium oxide is between 10 wt% and 12 wt%, and the weight percentage of magnesium oxide is between 0.2 wt% and 0.5 wt%.
According to an embodiment of the present invention, the weight percentage of the alumina is between 1.5 wt% and 7.5 wt%.
According to an embodiment of the present invention, the weight percentage of the silica is between 4 wt% and 12 wt%.
According to an embodiment of the present invention, the organic carrier is selected from at least one of Ethyl 32406, vitamin (Ethyl cellulose), Polyacrylic acid (Polyacrylic acid), Polyvinyl butyral (Polyvinyl butyral), Polyvinyl alcohol (Polyvinyl alcohol), polyalkene (polyofin), Polyamide (Polyamide), carboxylic acid (carboxylic acid), Oleic acid (Oleic acid), Tallow diamine dioleate salt (N-Tallow-1, 3-diaminopropane), Diethylene glycol butyl ether (Diethylene glycol butyl ether), Diethylene glycol butyl ether acetate (2- (2-butyl) Ethyl acetate), Ester alcohol (Ester alcohol), dimethyl linoleate (methyl salicylate), Terpineol (Terpineol) and derivatives thereof.
According to one embodiment of the present invention, the conductive material is selected from one of nickel, mercury, copper, gold, , and one of the alloys described above.
Compared with the prior art, the invention can obtain the following technical effects:
the invention provides a conductive paste, which mainly improves the composition of a glass medium of the conductive paste, when the conductive paste is applied to an electrode of a battery, the formed electrode does not use a lead-containing material and has low resistance value, surface defects such as aluminum beads or aluminum packets and the like are not generated, and simultaneously, the conductive paste has good ohmic contact and high adhesion and strength, so that the electrode formed by the conductive paste has high reliability.
Detailed Description
In the following description, numerous implementation details are set forth in order to provide a thorough understanding of the various embodiments of the invention. It should be understood, however, that these implementation details are not to be interpreted as limiting the invention. That is, in some embodiments of the invention, such implementation details are not necessary.
The terms "first," "second," and the like, as used herein, are not intended to be limited to the specific order or sequence presented, nor are they intended to be limiting, but rather are intended to distinguish one element from another or from another element or operation described by the same technical term.
The present invention provides a conductive slurry, which comprises an organic carrier, a conductive material and a glass medium, wherein the glass medium at least comprises 6 wt% and 35 wt% of vanadium oxide, 20 wt% and 53 wt% of boron oxide, 5 wt% and 30 wt% of zinc oxide, 1 wt% and 15 wt% of aluminum oxide or silicon dioxide, and 0.1 wt% and 35 wt% of alkali metal oxide and/or alkali earth oxide.
The alkali metal oxide and/or the alkali earth oxide is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. In one embodiment of the present invention, the alkali metal oxide and/or the alkali earth oxide is barium oxide, and the weight percentage of the barium oxide is between 21 wt% and 32 wt%; in another embodiment of the present invention, the alkali metal oxide and/or the alkali earth oxide is barium oxide, sodium oxide and potassium oxide, wherein the weight percentage of barium oxide is between 21 wt% and 32 wt%, the weight percentage of sodium oxide is between 1 wt% and 2 wt%, and the weight percentage of potassium oxide is between 1 wt% and 2 wt%; in another embodiment of the present invention, the composition comprises between 2 wt% and 3 wt% of lithium oxide and magnesium oxide, wherein the weight percentage of lithium oxide is between 10 wt% and 12 wt%, and the weight percentage of magnesium oxide is between 0.2 wt% and 0.5 wt%.
The conductive paste does not use a lead-containing material, so that environmental pollution and harm to human bodies are avoided. When the conductive paste containing the glass medium is used for manufacturing electrodes of batteries, the conductive paste has good ohmic contact and a wide co-firing temperature range, has a low resistance value compared with electrodes formed by the conventional conductive paste, does not generate surface defects, and has high adhesion and high strength, and particularly, the conductive paste is applied to manufacturing the electrodes of solar batteries.
The organic carrier is at least one selected from Ethyl 32406vitamin (Ethyl cellulose), polyacrylic acid (polyacrylic acid), Polyvinyl butyral (Polyvinyl butyral), Polyvinyl alcohol (Polyvinyl alcohol), polyalkene (polyofin), Polyamide (Polyamide), Carboxylic acid (Carboxylic acid), Oleic acid (Oleic acid), Tallow diamine dioleate salt (N-tall-1, 3-diaminopropane diol), diethylene glycol butyl ether (diethylene glycol butyl ether), diethylene glycol butyl ether acetate (2- (2-butyl) Ethyl acetate), Ester alcohol (Ester alcohol), dimethyl nylon oleate (dimethyl benzoate), Terpineol (Terpineol) and derivatives thereof. The conductive material is selected from one of nickel, mercury, aluminum, copper, palladium, gold, and .
Table 1 below and the glass media of the thirteen examples and nine comparative examples were formulated according to the above disclosed compositions and the weight percentages of the compositions of each glass medium are listed.
| Examples | 01 | 02 | 03 | 04 | 05 | 06 | 07 | 08 | 09 | 10 | 11 | 12 | 13 |
| V2O5 | 32.1 | 32.1 | 32.6 | 26.9 | 21.2 | 8.6 | 26.5 | 15.1 | 18.1 | 22.3 | 16.2 | 20.3 | 25.9 |
| B2O3 | 31.3 | 28.8 | 31.8 | 32.5 | 33.6 | 36.3 | 36.3 | 34.9 | 44.2 | 21.1 | 45.9 | 49.4 | 23.8 |
| SiO2 | 4.2 | 4.0 | 11.8 | ||||||||||
| Al2O3 | 1.6 | 1.6 | 1.6 | 1.6 | 1.7 | 1.8 | 1.6 | 1.8 | 1.7 | 1.8 | 7.1 | 6.8 | |
| ZnO | 7.9 | 7.9 | 8.0 | 11.0 | 14.4 | 21.9 | 8.0 | 18.0 | 7.6 | 24.4 | 15.1 | 10.6 | 26.5 |
| Li2O | 11.1 | 10.6 | 11.6 | ||||||||||
| Na2O | 1.1 | 1.1 | |||||||||||
| K2O | 1.4 | 1.4 | |||||||||||
| MgO | 0.4 | 0.3 | 0.4 | ||||||||||
| BaO | 27.1 | 27.1 | 21.2 | 28.0 | 29.1 | 31.4 | 27.6 | 30.2 | 28.4 | 28.2 |
TABLE 1
TABLE 2
Then, the glass media of the thirteen groups of embodiments and the nine groups of comparative examples are respectively prepared into conductive paste with a conductive material and an organic carrier, the conductive paste is printed on a back passivation layer of a semiconductor substrate in a screen printing mode, a plurality of conductive wires are formed on the back passivation layer, the back passivation layer printed with the plurality of conductive wires is sintered at high temperature, finally, four-point probes are adopted to measure the resistance value of each conductive wire, two probes provide current to each conductive wire, the voltage of each conductive wire is measured by the other two probes, and then the resistance value of each conductive wire is calculated. The conductive material uses aluminum powder, the organic carrier uses terpineol and ethyl cellulose, the material of the semiconductor substrate uses silicon, the material of the back passivation layer uses silicon nitride, the line width of the conductive line printed on the back passivation layer is controlled to be 100-200 mu m, the length of the conductive line is controlled to be 3 cm, and the final sintering temperature is controlled to be between 700 ℃ and 900 ℃.
After the above tests, the resistance of the conductive line formed on the back passivation layer by the conductive paste made of the glass medium of the above group 1 embodiment is the resistance reference value, and the resistance of the conductive line formed on the back passivation layer by the conductive paste made of the glass medium of other embodiments is between 70% and 120% of the resistance reference value, wherein the lower the resistance value, the better. The conductive paste made of the glass media of the comparative examples was tested as described above, and it was found that the resistance value of the glass media containing lead could reach 90% to 120% of the reference resistance value, as in comparative examples 8 to 9. The resistance values of the other comparative examples were all greater than the resistance reference value, even far greater than the resistance reference value. As described above, it is understood that the resistance value of the electrode can be effectively reduced by using the conductive paste of the present invention without using a lead-containing material.
TABLE 3
As can be seen from table 3, when the electrical property test is performed on the conductive pastes of the above-mentioned ten three sets of examples and nine sets of comparative examples, and the simulation is mainly performed to manufacture a general solar cell and a back-passivated solar cell, three co-firing temperatures are controlled to manufacture the general solar cell, the first co-firing temperature is the standard co-firing temperature, the second co-firing temperature is the standard co-firing temperature minus 15 ℃, and the third co-firing temperature is the standard co-firing temperature minus 30 ℃. The method comprises the following steps of controlling three co-firing temperatures for manufacturing the back passivation solar cell, wherein the first co-firing temperature is a reference co-firing temperature, the second co-firing temperature is the reference co-firing temperature plus 15 ℃, and the third co-firing temperature is the reference co-firing temperature minus 15 ℃.
When the conductive pastes of the thirteen sets of examples and the nine sets of comparative examples are co-fired at different co-firing temperatures, the electrical properties of the electrodes formed by co-firing the conductive pastes of the thirteen sets of examples are below 125%, and the electrical properties of the electrodes formed by co-firing the conductive pastes of the nine sets of comparative examples are above 125%. Therefore, the electrode formed by co-firing the conductive paste of the present invention has good electrical properties in a wide co-firing temperature range.
The electrodes formed by co-firing the conductive paste of the thirteen embodiments do not have surface defects such as aluminum packets or aluminum beads and the like. The adhesion of the electrodes formed by co-firing the conductive pastes of the thirteen embodiments is tested by using an adhesive tape, the adhesive tape is adhered to the electrodes formed by co-firing the conductive pastes of the thirteen embodiments, and then the adhesive tape is torn off, so that no powder residue is found in the torn adhesive tape, and the electrodes cannot fall off along with the tearing of the adhesive tape. The electrodes formed by the conductive pastes of the thirteen groups of examples were subjected to the boiling-water resistance test, in which the conductive paste was boiled at 75 ℃ for more than 10 minutes, and the electrodes formed by the conductive pastes of the thirteen groups of examples could pass the test. The conductive paste of the present invention can form electrodes that pass the above-mentioned tests and are not affected by the variation of co-firing temperature, so that the conductive paste of the present invention has high reliability.
After the conductive pastes of the nine sets of comparative examples are co-fired, some surface defects such as aluminum clad or aluminum bead may be generated; or when the adhesive tape is tested, the nine groups of comparative examples partially discover that the powder remains in the torn adhesive tape, and even the electrode falls off along with the torn adhesive tape; or nine comparison examples have a partial boiling at 75 deg.C for 10 minutes test, so that each of the nine comparison examples also original gray level reliability is generated.
The results of the above tests are shown in Table 4 below, where ○ indicates compliance and gamma indicates non-compliance.
TABLE 4
In summary, in one or more embodiments of the present invention, the present invention provides a conductive paste, which mainly improves the composition of a glass medium of the conductive paste, and when the conductive paste is applied to a battery, an electrode formed by the conductive paste of the present invention has a low resistance value without using a lead-containing material, does not generate surface defects such as aluminum beads or aluminum packets, and has good ohmic contact to make the electrode have high adhesion and high strength, so that the electrode formed by the conductive paste of the present invention has high reliability.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (9)
1. A conductive paste comprising an organic substrate, a conductive material, and a glass medium, wherein the glass medium comprises vanadium oxide in an amount from 6 wt% to 35 wt%, boron oxide in an amount from 20 wt% to 53 wt%, zinc oxide in an amount from 5 wt% to 30 wt%, aluminum oxide or silicon dioxide in an amount from 1 wt% to 15 wt%, and an alkali metal oxide and/or an alkali metal oxide in an amount from 0.1 wt% to 35 wt%.
2. The conductive paste according to claim 1, wherein the alkali metal oxide and/or the alkali earth oxide is at least one selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide.
3. The conductive paste according to claim 2, wherein the alkali metal oxide and/or the alkali earth oxide comprises the barium oxide, and the weight percentage of the barium oxide is between 21 wt% and 32 wt%.
4. The conductive paste according to claim 3, wherein the alkali metal oxide and/or the alkali earth oxide further comprises the sodium oxide and the potassium oxide, the weight percentage of the sodium oxide is between 1 wt% and 2 wt%, and the weight percentage of the potassium oxide is between 1 wt% and 2 wt%.
5. The conductive paste according to claim 2, wherein the alkali metal oxide and/or the alkali earth oxide comprises the lithium oxide and the magnesium oxide, the weight percentage of the lithium oxide is between 10 wt% and 12 wt%, and the weight percentage of the magnesium oxide is between 0.2 wt% and 0.5 wt%.
6. The conductive paste of claim 1, wherein the weight percentage of the alumina is between 1.5 wt% and 7.5 wt%.
7. The conductive paste of claim 1, wherein the weight percentage of the silica is between 4 wt% and 12 wt%.
8. The conductive paste as claimed in claim 1, wherein the organic carrier is selected from at least one of Ethyl 32406vitamin (Ethyl cellulose), Polyacrylic acid (Polyacrylic acid), Polyvinyl butyral (Polyvinyl butyral), Polyvinyl alcohol (Polyvinyl alcohol), Polyolefin (polyofin), Polyamide (Polyamide), Carboxylic acid (Carboxylic acid), Oleic acid (Oleic acid), Tallow diamine dioleate (N-tall-1, 3-diaminopropane diolate), Diethylene glycol butyl ether (Diethylene glycol butyl ether), Diethylene glycol butyl ether acetate (2- (2-butyl) Ethyl acetate), Ester alcohol (Ester alcohol), dimethyl nicotinate (diesel), Terpineol (Terpineol), and derivatives thereof.
9. The conductive paste according to claim 1, wherein the conductive material is selected from one of nickel, mercury, alumina, copper, palladium, gold, , and one of the aforementioned alloys.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113362981A (en) * | 2021-06-15 | 2021-09-07 | 华中科技大学温州先进制造技术研究院 | Inorganic glass binder for P-type emitter silver-aluminum electrode slurry of N-type silicon solar cell |
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