CN115602355A - Conductive paste and solar cell prepared from same - Google Patents
Conductive paste and solar cell prepared from same Download PDFInfo
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- CN115602355A CN115602355A CN202211262614.8A CN202211262614A CN115602355A CN 115602355 A CN115602355 A CN 115602355A CN 202211262614 A CN202211262614 A CN 202211262614A CN 115602355 A CN115602355 A CN 115602355A
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- conductive paste
- glass frit
- solar cell
- glass
- silver
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- 239000011521 glass Substances 0.000 claims abstract description 71
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 21
- 239000004332 silver Substances 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- -1 silver-aluminum Chemical compound 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001465 metallisation Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 3
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 3
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 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
- 238000007650 screen-printing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/142—Silica-free oxide glass compositions containing boron containing lead
-
- 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
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
- H01B3/087—Chemical composition of glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the technical field of solar cells, in particular to conductive paste and a solar cell prepared from the conductive paste. The conductive paste comprises glass frit, silver powder and an organic carrier, and does not contain aluminum powder; the weight ratio of the glass frit to the silver powder to the organic carrier is 1:15-45:1.5-5; the glass material contains PbO, znO and Bi 2 O 3 And B 2 O 3 (ii) a In the glass material, the weight percentage of PbO is 20-40%, pbO and Bi 2 O 3 In a weight ratio of 0.6-4:1; znO and B 2 O 3 15-40% of total weight of ZnO and B 2 O 3 The weight ratio of (1-5): 1. according to the invention, through specially designed glass frit components, the silver paste can better protect the emitter and the junction in the sintering process, obtain higher open-circuit voltage, enable the solar cell to obtain excellent contact performance and fully exert the efficiency advantage of the TOPCon cell.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to conductive paste and a solar cell prepared from the conductive paste.
Background
The N-type TOPCon battery (Tunnel Oxide Passivated Contact solar cell) has the advantages of high theoretical photoelectric conversion efficiency, high compatibility with PERC equipment, high double-sided rate, good low-temperature coefficient, low attenuation and the like, and the market share of the N-type TOPCon battery is rapidly increased in recent years. The front surface of the N-type TOPCon battery is doped by adopting boron diffusion, and ohmic contact is difficult to form compared with phosphorus diffusion. At present, silver-aluminum paste is generally used as front paste of the N-type TOPCon battery, and silver-aluminum spikes are formed in the sintering process to form a direct contact channel so as to realize better ohmic contact. Specifically, during sintering, as the temperature increases, the glass in the paste begins to soften and flow, contacting the silicon substrate and corroding the surface passivation layer. Meanwhile, the glass contacts with the aluminum powder to erode the aluminum oxide film on the surface of the aluminum powder, so that the aluminum flows to the surface of the silicon substrate along with the glass. Silver and aluminum form silver aluminum alloy, the silver aluminum alloy is deposited on the surface of the emitter, and silver aluminum spikes are generated by downward growth along with the increase of the temperature. The silver-aluminum spikes are helpful for forming contacts, but can damage an emitter and even a junction due to deeper pinning, so that the metallization recombination is increased, and the open-circuit voltage is reduced.
Relevant researches show that the large front-side metallization composition of the N-type TOPCon battery is a key factor for restricting the efficiency improvement. Researches show that when aluminum powder is not added into the slurry and pure silver slurry is adopted, the damage of silver crystals formed during sintering to an emitter and a junction is small, high open-circuit voltage can be obtained, but the contact resistance of the battery is greatly improved, and the efficiency is reduced.
In the prior art, CN109673171A describes a method for improving ohmic contact resistance between a metal electrode and an emitter. The current pulse is utilized to cause obvious power reduction in a region with larger contact resistance, so that the contact surface is obviously heated, the metal electrode is further sintered, the passivation layer is corroded, the contact area is increased, and the contact resistance is reduced. The situation of the slurry used is not disclosed in this patent.
How to provide a conductive paste which can better protect an emitter and a junction and enable a solar cell to have excellent contact performance so as to improve the efficiency of an N-type TOPCon cell becomes one of the technical problems to be solved urgently in the field.
Disclosure of Invention
The invention provides a conductive paste, which comprises glass frit, silver powder and an organic carrier, and does not contain aluminum powder; the weight ratio of the glass frit to the silver powder to the organic carrier is 1:15 to 45:1.5 to 5;
the glass material contains PbO, znO and Bi 2 O 3 And B 2 O 3 ；
In the glass material, the weight percentage of PbO is 20-40%, pbO and Bi 2 O 3 In a weight ratio of 0.6-4:1; znO and B 2 O 3 15-40% of total weight of ZnO and B 2 O 3 The weight ratio of (1-5): 1.
according to the conductive paste, the glass frit further comprises a variable valence metal oxide with the weight percentage of 5-15%.
According to the conductive paste of the invention, the valence-variable metal oxide is TeO 2 、V 2 O 5 、CeO 2 、WO 3 、As 2 O 5 、Cr 2 O 3 、Fe 2 O 3 Preferably TeO 2 。
According to the conductive paste, the glass frit further comprises 1-10 wt% of alkaline earth metal oxide.
According to the conductive paste of the present invention, the alkaline earth metal oxide is at least one of oxides of magnesium, calcium, strontium, and barium.
According to the conductive paste, the particle size D50 of the silver powder is 1.0-1.5 microns;
and/or the tap density of the silver powder is 5.0-6.0 g per square centimeter;
and/or the specific surface area of the silver powder is 0.3-1.0 square meter per gram;
and/or the silver powder is spherical or spheroidal.
According to the conductive paste of the present invention, the organic vehicle contains an organic solvent, a resin, a surfactant, and a thixotropic agent.
Further, the present invention provides a method for manufacturing a solar cell, comprising: the conductive paste of any of the above embodiments was applied to the front side of a plated N-type topocon cell and then sintered.
The preparation method of the solar cell further comprises the following steps: after the sintering, a laser is used to scan a local surface of the front side of the cell while applying a positive bias to the solar cell.
According to the method for manufacturing the solar cell, the voltage of the positive bias is 5-15V.
Further, the invention also provides a solar cell prepared by the preparation method.
The invention has the beneficial effects that:
through specially designed glass frit components, the silver paste can better protect an emitter and a junction in the sintering process, obtain higher open-circuit voltage, enable the solar cell to obtain excellent contact performance and fully exert the efficiency advantage of the TOPCon cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As an embodiment of the present invention, the present embodiment provides a conductive paste including a glass frit, a silver powder, and an organic vehicle, and not containing an aluminum powder; the weight ratio of the glass frit to the silver powder to the organic carrier is 1:15-45:1.5-5; the glass material contains PbO, znO and Bi 2 O 3 And B 2 O 3 (ii) a In the glass material, the weight percentage of PbO is 20-40%, pbO and Bi 2 O 3 In a weight ratio of 0.6-4:1; znO and B 2 O 3 15-40% of total weight of ZnO and B 2 O 3 The weight ratio of (1-5): 1.
the glass material in the conductive paste has lower glass transition temperature, and can etch off silicon nitride and aluminum oxide dielectric layers in the sintering stage to enable the silver electrode to be in contact with the silicon substrate. Meanwhile, silver is dissolved in the glass in the form of silver ions, and in the cooling stage, the silver in the glass is deposited on the silicon surface to form a current transmission channel. Therefore, the conductive paste disclosed by the invention can better protect the emitter and the junction and can ensure that the solar cell obtains excellent contact performance.
Moreover, silver crystal grains generated in the sintering of the conductive paste are far smaller than the size of silver-aluminum spikes formed by silver-aluminum paste, so that the damage of the paste sintering to an emitter and a junction is greatly reduced.
Wherein, in the above PbO and Bi 2 O 3 The glass powder has proper corrosion capability, so that the slurry can react with silicon nitride in the sintering process, and a passivation layer is corroded to enable the silver electrode to be in contact with the silicon substrate. The proportion of the components and the PbO content have important influence on the corrosion capability of the glass frit, and if the proportion or the PbO content is controlled improperly, the corrosion capability is too small, so that the corrosion capability of the glass is weak, silicon nitride cannot be opened, and ohmic contact is difficult to form; if the etching capability is too strong, the emitter will be damaged after etching the silicon nitride. At the same time, znO and B in the above ratio 2 O 3 Can significantly lower the glass transition temperature of the glass, and B 2 O 3 And Bi 2 O 3 The glass has the effect of improving the stability of the glass in a synergistic manner, and the flow of the glass during sintering is controlled through crystallization.
The glass frit formed by the proportioning components can open the passivation layer during sintering, so that the silver electrode is in contact with the silicon substrate, and the contact resistance is reduced.
As a preferred embodiment of the invention, the glass frit comprises the following components in parts by weight: 20-40 parts of PbO,10-30 parts of ZnO and 10-30 parts of Bi 2 O 3 And 5-15 parts of B 2 O 3 。
As an embodiment of the invention, the glass material also comprises a variable valence metal oxide with the weight percentage of 5-15%.
As a preferred embodiment of the invention, the glass frit comprises the following components in parts by weight: 20-40 parts of PbO,10-30 parts of ZnO and 10-30 parts of Bi 2 O 3 5-15 parts of B 2 O 3 And 5-15 parts of a valence-variable metal oxide.
As an embodiment of the present invention, the variable valence metal oxide is TeO 2 、V 2 O 5 、CeO 2 、WO 3 、As 2 O 5 、Cr 2 O 3 、Fe 2 O 3 Preferably TeO 2 。
The invention discovers that when the variable valence metal oxide with the content is added into the glass material with the proportion, the variable valence metal oxide can generate gas in the glass melting stage, and the uniformity and the clarification of the glass are promoted. More importantly, in the sintering stage of the slurry, the valence-variable metal oxide is changed from high valence to low valence, and the released oxygen can enable more silver to be fused into the glass melt, so that more silver grains are separated out on the silicon surface in the cooling stage, more current transmission channels are provided, and the efficiency of the TOPCon battery is further improved.
As an embodiment of the invention, the glass material also comprises 1-10 wt% of alkaline earth metal oxide.
As a preferred embodiment of the invention, the glass frit comprises the following components in parts by weight:
20-40 parts of PbO,10-30 parts of ZnO and 10-30 parts of Bi 2 O 3 5-15 parts of B 2 O 3 5-15 parts of variable valence metal oxide and 1-10 parts of alkaline earth metal oxide.
In a preferred embodiment of the present invention, the alkaline earth metal oxide is at least one of oxides of magnesium, calcium, strontium, and barium.
In a specific implementation process, the alkaline earth metal oxide can also be prepared by taking a substance which generates the alkaline earth metal oxide through high-temperature sintering as a raw material.
As an embodiment of the present invention, the silver powder has a particle size D50 of 1.0 to 1.5 μm;
and/or the tap density of the silver powder is 5.0-6.0 g per square centimeter;
and/or the specific surface area of the silver powder is 0.3-1.0 square meter per gram;
and/or the silver powder is spherical or spheroidal.
As an embodiment of the present invention, this embodiment provides a preparation method for preparing the glass frit, including:
(1) Weighing and mixing raw materials for preparing the glass frit;
(2) Heating the mixed raw materials at 900-1100 ℃ to prepare a melt, preferably heating for 30-60 minutes;
(3) Mixing the melt with water and cooling to obtain glass slag;
(4) And ball-milling the glass slag to prepare the glass material with the granularity D50 of 1.0-1.5 mu m.
In specific implementations, the heating process includes, but is not limited to, using a high temperature resistance furnace and the container includes, but is not limited to, using a platinum crucible.
As an embodiment of the present invention, the organic vehicle contains an organic solvent, a resin, a surfactant, and a thixotropic agent.
As a preferred embodiment of the present invention, the organic vehicle comprises: butyl carbitol, butyl carbitol acetate, alcohol ester dodeca, acrylic resin, ethyl cellulose, a surfactant and a thixotropic agent.
The organic vehicle uniformly mixes the silver powder and the glass frit therein, so that the paste can be transferred to the surface of the silicon wafer through screen printing. The organic vehicle largely determines the printing performance of the paste and the aspect ratio of the grid lines.
As an embodiment of the present invention, this embodiment provides a method for preparing a conductive paste, including:
and mixing the glass frit, the silver powder and the organic carrier in proportion, and then grinding to a fineness of less than 5 microns.
In practice, this includes, but is not limited to, grinding with a three-roll mill.
As an embodiment of the present invention, this embodiment provides a method for manufacturing a solar cell, including: the conductive paste of any of the above embodiments was applied to the front side of a plated N-type topocon cell and then sintered.
As an embodiment of the present invention, the method for manufacturing a solar cell further includes: after the sintering, a laser is used to scan a partial surface of the front surface of the cell while applying a positive bias to the solar cell, preferably at a voltage of 5 to 15V.
The invention further discovers that the conductive paste is applied to the front surface of the coated N-type TOPCon battery, after the conductive paste is sintered in an infrared chain type sintering furnace, carriers are induced in a depletion region by scanning the local surface of the battery through laser, and meanwhile, positive bias is applied to the battery to generate local current, so that the contact resistance can be reduced. Meanwhile, the temperature of the action surface of the slurry is raised by laser, silver crystal grains generated in the sintering stage can continue to grow, and the contact area with silicon is increased, so that the contact resistance is further reduced.
Moreover, the laser can cause the temperature of the electrode to rise, further promote the sintering shrinkage of the silver powder, reduce the shielding area of the front surface, improve the short-circuit current and finally obtain the N-type TOPCon battery with high conversion efficiency.
Through the synergistic effect of the Laser Enhanced Contact Optimization (LECO) technology and the silver paste, the emitter and the junction can be well protected, and excellent contact performance can be obtained, so that the efficiency advantage of the N-type TOPCon battery is fully exerted. The silver paste provides appropriate corrosivity in the sintering stage, passivation layers such as silicon nitride and aluminum oxide are opened, contact resistance is reduced, and fine silver grains are generated on the surface of the silicon. And then, a laser-enhanced contact optimization technology is applied to reduce the contact resistance between the metal and the emitter, improve the filling factor and achieve the optimal ohmic contact, so that the conversion efficiency of the N-type TOPCon battery is obviously improved.
This example also provides, as an embodiment of the present invention, a solar cell prepared by the above-described preparation method.
The solar cell prepared by the conductive paste has the advantages of reduced metallization composition and increased open-circuit voltage, so that the conversion efficiency of the prepared solar cell is obviously improved.
The technical solution and the advantages thereof will be described with reference to more specific embodiments.
The specific techniques or conditions not indicated in the examples are all conventional methods or techniques or conditions described in the literature of the field or according to the product specifications. The reagents and instruments used are conventional products which are available from normal commercial vendors, not indicated by manufacturers.
The particle sizes D50 of the silver powder and the aluminum powder of the following examples and comparative examples were 1.0 μm and 1.5. Mu.m, respectively.
The compositions of the frits of the following examples and comparative examples are shown in table 1.
TABLE 1 glass frit composition and weight (g)
| Item | PbO | Bi 2 O 3 | ZnO | TeO 2 | SrO | B 2 O 3 |
| Example 1 | 20 | 30 | 20 | 5 | 10 | 15 |
| Example 2 | 35 | 20 | 20 | 5 | 10 | 10 |
| Example 3 | 40 | 30 | 10 | 10 | 5 | 5 |
| Example 4 | 30 | 27 | 25 | 5 | 1 | 12 |
| Example 5 | 35 | 10 | 30 | 10 | 5 | 10 |
| Example 6 | 25 | 25 | 20 | 15 | 5 | 10 |
| Example 7 | 40 | 10 | 25 | 10 | 10 | 5 |
Example 1
The embodiment provides a conductive paste, and the preparation method comprises the following steps:
the glass raw materials are accurately weighed according to the mixture ratio shown in the table 1, the total weight is 100 g, and the glass raw materials are fully mixed and then put into a platinum crucible. The crucible is placed in a resistance furnace to be heated, the heating temperature is 1000 ℃, and the heat preservation time is 30 minutes. And then quickly pouring the melt into deionized water for quenching to obtain the glass slag. And grinding the glass slag by using a ball mill to obtain glass powder with the granularity D50 of 1.0 mu m.
The organic carrier is prepared by putting 25 g of organic solvent butyl carbitol, 25 g of butyl carbitol acetate, twelve 28 g of alcohol ester, 10 g of acrylic resin, 5 g of ethyl cellulose, 1 g of surfactant glyceryl monostearate and 5 g of thixotropic agent polyamide wax into a heater, heating at a constant temperature of 60 ℃, and stirring for 20 minutes.
2 g of the glass powder, 10 g of the organic carrier and 88 g of the silver powder are weighed, mixed uniformly and ground by a three-roll grinder to obtain conductive slurry with the fineness of less than 5 mu m, and the conductive slurry is numbered as P1.
Example 2
This example provides a conductive paste, which is prepared by a method different from that of example 1 only: the glass raw materials are different in proportion; the melting temperature of the glass is 900 ℃, and the holding time is 60 minutes. The conductive paste obtained in example 2 was numbered P2.
Examples 3 to 7
This example provides a conductive paste, which is prepared by a method different from that of example 1 only: the glass raw materials are different in proportion; the obtained conductive pastes were numbered P3-P7.
Example 8
This example provides a conductive paste, which is prepared by a method different from that of example 1 only:
5 g of glass powder, 7.5 g of organic carrier and 87.5 g of silver powder are weighed, evenly mixed and ground by a three-roll grinder to obtain conductive slurry with the fineness less than 5 mu m, and the conductive slurry is numbered as P8.
Example 9
This example provides a conductive paste, which is prepared by a method different from that of example 1 only:
2 g of glass powder, 8 g of organic carrier and 90 g of silver powder are weighed, mixed uniformly and ground by a three-roll grinder to obtain conductive paste with the fineness less than 5 mu m, and the conductive paste is numbered as P9.
Example 10
This example provides a conductive paste, which is prepared by a method different from that of example 1 only:
5.6 g of glass powder, 10.4 g of organic carrier and 84 g of silver powder are weighed, evenly mixed and ground by a three-roll grinder to obtain conductive paste with the fineness less than 5 mu m, which is numbered as P10.
Comparative example 1
This comparative example provides a conductive paste, which was prepared by a method different from that of example 1 only:
3.5 g of the prepared glass powder, 7.5 g of the organic carrier, 87 g of the silver powder and 2 g of the aluminum powder are weighed, and are uniformly mixed and ground by a three-roll grinder to obtain conductive paste with the fineness of less than 5 mu m, wherein the number of the conductive paste is P11.
Comparative example 2
This comparative example provides a conductive paste, glass frit, organic vehicle and paste prepared in the same manner as in example 1, except that: replacing glass raw materials with PERC battery silver paste by using conventional PbO-SiO 2 -TeO 2 -Bi 2 O 3 -WO 3 -Li 2 O 3 Glass system, wherein PbO is 35 g, siO 2 Is 10 g, teO 2 35 g of Bi 2 O 3 Is 10 g, WO 3 Is 5 g, li 2 O 3 5 grams, thus obtaining the conductive paste with the number P12.
Test examples
The conductive paste prepared in the examples and the comparative examples is applied to the front surface of a coated N-type TOPCon battery, and after the conductive paste is sintered in an infrared chain type sintering furnace, a laser-enhanced contact optimization process is used, carriers are induced in a depletion region by scanning the local surface of the front surface of the battery through laser, and meanwhile, a positive bias voltage of 10V is applied to the surface of the battery to generate local current. Wherein the sintering peak temperature is 750 ℃, the wavelength of the laser is 1062nm, the laser power is 0.5W, and the laser processing time is 3 seconds.
The efficiency was then tested using an I-V tester, with test results including photoelectric conversion efficiency (Eta), open circuit voltage (Voc), short circuit current (Isc), fill Factor (FF), series resistance (Rs), and parallel resistance (Rsh).
Meanwhile, the P13 group was set without being subjected to the laser-enhanced contact optimization process, and the preparation method of the conductive paste was the same as that of example 1. Specifically, the conductive paste prepared in example 1 was applied to the front surface of a coated N-type TOPCon cell, and after sintering in an infrared chain sintering furnace, I-V electrical performance testing was performed without a laser enhanced contact optimization process.
The test results are shown in table 2.
Table 2 cell electrical performance test results
As shown in table 2, the silver paste of the present invention, together with the laser enhanced contact optimization technique, can achieve higher efficiency of the battery, i.e., higher open-circuit voltage and fill factor, indicating that the metallization composition of the battery is lower and the contact resistance is smaller.
In comparative example 1, aluminum powder is added into the conductive paste, and the battery obtains a good filling factor, but the silver-aluminum spikes have great damage to the emitter, so that the metallization composition is large, the open-circuit voltage is low, and the battery efficiency is low.
The cell efficiency of the P13 group is reduced compared to P1-P10, and since no laser enhanced contact optimization technique is used, the open circuit voltage is higher, but the series resistance is also higher, indicating that the contact resistance is larger. As can be seen from comparison with example 1, the series resistance was significantly reduced after laser scanning, and a high open circuit voltage could be maintained.
In comparative example 2, the conventional glass system for silver paste of PERC cell was used as the conductive paste, the components of the glass paste were not properly selected, and during the sintering process, silver grains were not sufficiently formed and grown, resulting in poor contact performance and higher series resistance, and therefore, the cell efficiency was the worst.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The conductive paste is characterized by comprising glass frit, silver powder and an organic carrier, wherein the conductive paste does not contain aluminum powder;
the weight ratio of the glass frit to the silver powder to the organic carrier is 1:15-45:1.5-5;
the glass material contains PbO, znO and Bi 2 O 3 And B 2 O 3 ；
In the glass frit, a glass frit is used,20-40% of PbO, pbO and Bi 2 O 3 In a weight ratio of 0.6-4:1; znO and B 2 O 3 15-40% of total weight of ZnO and B 2 O 3 The weight ratio of (1-5): 1.
2. the conductive paste according to claim 1, further comprising 5 to 15 wt% of a variable valence metal oxide in the glass frit.
3. The conductive paste according to claim 2, wherein the valence-change metal oxide is TeO 2 、V 2 O 5 、CeO 2 、WO 3 、As 2 O 5 、Cr 2 O 3 、Fe 2 O 3 Preferably TeO 2 。
4. The conductive paste according to any one of claims 1 to 3, further comprising 1 to 10% by weight of an alkaline earth metal oxide in the glass frit.
5. The conductive paste according to claim 4, wherein the alkaline earth metal oxide is at least one of oxides of magnesium, calcium, strontium, and barium.
6. The electroconductive paste according to any one of claims 1 to 5, wherein the organic vehicle contains an organic solvent, a resin, a surfactant, and a thixotropic agent.
7. A method for manufacturing a solar cell, comprising: the conductive paste according to any one of claims 1 to 6 is coated on the front surface of a coated N-type topon cell and then sintered.
8. The method for manufacturing a solar cell according to claim 7, further comprising: after the sintering, a laser is used to scan a local surface of the front side of the cell while applying a positive bias to the solar cell.
9. The method according to claim 8, wherein the voltage of the positive bias is 5 to 15 volts.
10. A solar cell, characterized in that it is produced by the production method according to any one of claims 7 to 9.
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| CN117174357A (en) * | 2023-09-27 | 2023-12-05 | 江苏索特电子材料有限公司 | Conductive paste composition, preparation method of solar cell and solar cell |
| CN117374153A (en) * | 2023-09-28 | 2024-01-09 | 帝尔激光科技(无锡)有限公司 | Laser-induced sintering method for solar cell and solar cell |
| CN117650184A (en) * | 2024-01-30 | 2024-03-05 | 晶澜光电科技(江苏)有限公司 | TOPCON solar cell metallization method using silver-coated copper paste and solar cell |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117174357A (en) * | 2023-09-27 | 2023-12-05 | 江苏索特电子材料有限公司 | Conductive paste composition, preparation method of solar cell and solar cell |
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| CN117650184A (en) * | 2024-01-30 | 2024-03-05 | 晶澜光电科技(江苏)有限公司 | TOPCON solar cell metallization method using silver-coated copper paste and solar cell |
| CN117650184B (en) * | 2024-01-30 | 2024-04-05 | 晶澜光电科技(江苏)有限公司 | TOPCON solar cell metallization method using silver-coated copper paste and solar cell |
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