CN115117186A - TOPCon battery and preparation method thereof - Google Patents
TOPCon battery and preparation method thereof Download PDFInfo
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- CN115117186A CN115117186A CN202211050233.3A CN202211050233A CN115117186A CN 115117186 A CN115117186 A CN 115117186A CN 202211050233 A CN202211050233 A CN 202211050233A CN 115117186 A CN115117186 A CN 115117186A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910000521 B alloy Inorganic materials 0.000 claims abstract description 60
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910001096 P alloy Inorganic materials 0.000 claims abstract description 58
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 claims abstract description 58
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000000151 deposition Methods 0.000 claims description 101
- 238000004070 electrodeposition Methods 0.000 claims description 66
- 239000003792 electrolyte Substances 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- 230000008021 deposition Effects 0.000 claims description 38
- 229910052796 boron Inorganic materials 0.000 claims description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 18
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 9
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 9
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 9
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 9
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 9
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 9
- 238000010329 laser etching Methods 0.000 claims description 8
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 7
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 17
- 239000004332 silver Substances 0.000 abstract description 17
- 239000011574 phosphorus Substances 0.000 description 23
- 229910052698 phosphorus Inorganic materials 0.000 description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- AJQLEJAVGARHGQ-UHFFFAOYSA-N dithiosalicylic acid Chemical compound OC1=CC=CC=C1C(S)=S AJQLEJAVGARHGQ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910005883 NiSi Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
Images
Classifications
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction 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
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
Abstract
The invention provides a TOPCon battery and a preparation method thereof, wherein the TOPCon battery comprises a battery substrate, and the two side surfaces of the battery substrate are respectively an N surface and a P surface; the N surface and the P surface are respectively and independently provided with wire grooves, and grid lines are arranged in the wire grooves; the grid line of the N surface comprises a nickel-phosphorus alloy layer and a first copper-tin alloy layer which are arranged in a stacked mode, and the nickel-phosphorus alloy layer is in contact with the bottom of the N surface line groove; the grid line of the P face comprises a nickel-boron alloy layer and a second copper-tin alloy layer which are stacked, and the nickel-boron alloy layer is in contact with the bottom of the P face wire groove. The preparation method provided by the invention replaces the traditional silver paste process, reduces the contact resistance and improves the battery efficiency as much as possible.
Description
Technical Field
The invention belongs to the technical field of solar cells, relates to a TOPCon cell, and particularly relates to a TOPCon cell and a preparation method thereof.
Background
With the proposal of carbon neutralization and carbon peak-reaching targets in China, the solar cell is taken as a green conversion scheme, the market quantity is greatly increased, and the solar cell has larger development space in the future. The current new solar cell mainly uses percon cell as the main stream, but as the technology improves, percon cell has been slowly replaced by TOPCon cell because of its theoretical efficiency problem. In the incremental market, TOPCon batteries take a significant advantage, with theoretical efficiencies of 28.7% being possible. The TOPCon cell is a novel solar cell, and a very important step in the manufacturing process of the TOPCon cell is a grid line metallization process, and the size of the grid line influences the light absorption area of the solar cell panel, so that the TOPCon cell is also a key direction for improving the cell efficiency.
At present, the technology of screen printing silver paste is mainly adopted in industry to prepare the grid line electrode, and then organic matters in the silver paste volatilize through rapid sintering, and the silver is solidified to form the metal electrode. The process method is simple and mature and is applied in a large scale. However, the process has the following defects: (1) for sintering and forming, a glass phase is generally required to be added into the silver paste, and after sintering, the glass phase can sink to the interface of metal and silicon, so that the contact resistance is increased; meanwhile, the existence of the glass phase can also cause the volume resistance of the grid line to be obviously increased; (2) the screen printing has certain requirements on line width and line height, is limited by the size of a screen template, and is increasingly difficult to further reduce the line width of grid lines to improve the effective area of a battery; (3) silver belongs to precious metals, and reserves are limited, and with the further expansion of the solar market, the silver can certainly not meet the market demand.
In order to reduce the silver consumption, from the equipment perspective, methods of steel plate printing and laser transfer printing are mainly adopted; from the process perspective, silver-coated copper slurry is mainly adopted to replace silver paste, which aims to reduce the consumption of silver, but still cannot fundamentally solve the problem that the market demand cannot be met due to limited silver reserve.
Copper is a good candidate for replacing silver due to its close electrical conductivity to silver. However, since copper has a high melting point and is easily oxidized, the formed copper oxide cannot be decomposed by a high temperature, thereby limiting the use of copper paste. The other process route for preparing the copper grid line is an electroplating Ni-Cu-Ag scheme, Ni is adopted as a bottom layer in the scheme, the effect of preventing copper from migrating to a silicon substrate is achieved, and meanwhile NiSi alloy can be formed through heat treatment to improve the binding force. However, the NiSi alloy layer, which is an intermediate layer between Si and Ni, still has a large resistance, thereby significantly affecting the cell efficiency.
Therefore, how to provide a new grid line preparation method to replace the traditional silver paste process, reduce the contact resistance and improve the battery efficiency as much as possible becomes a problem to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a TOPCon battery and a preparation method thereof, wherein the preparation method replaces the traditional silver paste process, reduces the contact resistance and improves the battery efficiency as much as possible.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a TOPCon battery, which includes a battery substrate, and two side surfaces of the battery substrate are an N-plane and a P-plane, respectively.
The N face and the P face are respectively and independently provided with wire grooves, and grid lines are arranged in the wire grooves.
The grid line of N face includes nickel phosphorus alloy-layer and the first copper tin alloy-layer of range upon range of setting, and the nickel phosphorus alloy-layer contacts with the tank bottom of N face wire casing.
The grid line of the P face comprises a nickel-boron alloy layer and a second copper-tin alloy layer which are stacked, and the nickel-boron alloy layer is in contact with the bottom of the P face wire groove.
According to the TOPCon battery provided by the invention, the N-side nickel layer of the traditional battery substrate is doped with phosphorus elements, and the P-side nickel layer is doped with boron elements, so that the nickel layer and the silicon layer of the substrate form nickel-silicon alloy at the interface, meanwhile, the contact position of an N-side grid line forms phosphorus-rich doping, and the contact position of a P-side grid line forms boron-rich doping, thereby forming electron hole transmission, further reducing the contact resistance and remarkably improving the battery efficiency.
Preferably, the phosphorus content of the nickel-phosphorus alloy layer is 1-5 wt.%, for example 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.% or 5 wt.%, but is not limited to the recited values, and other values not recited within this range are equally applicable.
In the invention, the content of phosphorus in the nickel-phosphorus alloy layer needs to be controlled within a reasonable range. When the content of the phosphorus is lower than 1wt%, the electron transmission effect is not obvious and is close to the effect of directly depositing the metal nickel layer; when the content of phosphorus is more than 5wt%, the resistivity of the underlying nickel-phosphorus alloy layer may be increased, thereby increasing the contact resistance of the battery.
Preferably, the boron content of the nickel-boron alloy layer is 0.8-4 wt.%, for example 0.8 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.% or 4 wt.%, but is not limited to the recited values, and other values not recited within this range are equally applicable.
In the invention, the content of boron in the nickel-boron alloy layer needs to be controlled within a reasonable range. When the content of boron is lower than 0.8wt%, the hole transport effect is not obvious and is close to the effect of directly depositing a metallic nickel layer; when the content of boron is more than 4wt%, the resistivity of the nickel-boron alloy layer of the bottom layer is increased, and the contact resistance of the battery is increased.
Preferably, the thickness of the nickel-phosphorus alloy layer and the nickel-boron alloy layer is 0.1 to 1 μm, respectively, and may be, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the tin content in the first and second copper-tin alloy layers is independently 0.01-0.5wt%, such as 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, or 0.5wt%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
In a second aspect, the present invention provides a method for preparing the TOPCon battery according to the first aspect, the method comprising the steps of:
(1) respectively and independently arranging wire grooves on the N surface and the P surface of the battery substrate;
(2) sequentially depositing a nickel-phosphorus alloy layer and a first copper-tin alloy layer in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer and a second copper-tin alloy layer in the wire groove on the P surface;
(4) carrying out heat treatment on the battery substrate to obtain a TOPCon battery;
wherein, the steps (2) and (3) are not in sequence.
Preferably, the method for opening the wire groove in the step (1) includes laser etching, and the wire groove is cleaned by hydrofluoric acid after being opened.
Preferably, the deposition method of the nickel-phosphorus alloy layer of step (2) includes a first electrochemical deposition.
Preferably, the deposition method of the nickel-boron alloy layer in the step (3) comprises a second electrochemical deposition.
Preferably, the deposition methods of the first copper-tin alloy layer of step (2) and the second copper-tin alloy layer of step (3) each independently comprise a third electrochemical deposition.
Preferably, the electrolyte used in the first electrochemical deposition includes nickel sulfamate, nickel chloride, phosphoric acid and additives, and the electrolyte is adjusted to a pH of 1.0 to 2.0 with sulfamic acid, which may be, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0, but is not limited to the recited values, and other values within the range are equally applicable.
In the present invention, the additive is a conventional additive in the art, and may be, for example, sulfonic acid, sulfonamide, sulfimide, etc., as long as it can perform the corresponding function of the additive, and thus, it is not particularly limited herein.
Preferably, the concentration of the nickel sulfamate is 450-500g/L, for example 450g/L, 455g/L, 460g/L, 465g/L, 470g/L, 475g/L, 480g/L, 485g/L, 490g/L, 495g/L or 500g/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the concentration of nickel chloride is 15-20g/L, and may be, for example, 15g/L, 15.5g/L, 16g/L, 16.5g/L, 17g/L, 17.5g/L, 18g/L, 18.5g/L, 19g/L, 19.5g/L, or 20g/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the phosphoric acid is present in a concentration of 1 to 2g/L, for example 1g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L, 1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L or 2g/L, but not limited to the values listed, and other values not listed in this range of values are equally suitable.
Preferably, the concentration of the additive is 20-30g/L, for example 20g/L, 21g/L, 22g/L, 23g/L, 24g/L, 25g/L, 26g/L, 27g/L, 28g/L, 29g/L or 30g/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the first electrochemical deposition comprises: firstly, the concentration is 0.8-1.2A/dm 2 Depositing for 25-35s until the thickness of the nickel-phosphorus alloy layer is 0.08-0.12 μm, and then depositing for 4-6A/dm 2 The following deposition is performed for 20-40s to a thickness of the nickel-phosphorus alloy layer of 0.4-0.6 μm and at a deposition temperature of 60-70 deg.C, such as 60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C, 65 deg.C, 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C or 70 deg.C, but not limited to the values listed, and other values not listed in the range of values are also applicable.
According to the invention, the first electrochemical deposition is limited to the sectional deposition under specific conditions, an alloy layer with higher phosphorus content can be formed on the contact surface of the silicon layer of the substrate, and the electron transport capability between the silicon layer and the nickel-phosphorus alloy layer can be improved after heat treatment; meanwhile, the overall phosphorus content in the plating layer can be reduced, and the resistivity of the nickel-phosphorus alloy layer is reduced, so that the overall resistance of the nickel-phosphorus alloy layer in the grid line is reduced.
Preferably, the electrolyte used for the second electrochemical deposition comprises nickel chloride, sodium borohydride, ethylenediamine, sodium potassium tartrate and additives, and the electrolyte is adjusted to a pH of 13.0-14.0 with ammonia, for example, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9 or 14.0, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
In the present invention, the additive is a conventional additive in the art, and may be, for example, salicylic acid, dithiosalicylic acid, etc., as long as it can perform the corresponding function of the additive, and thus is not particularly limited herein.
Preferably, the concentration of nickel chloride is 30-50g/L, for example 30g/L, 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L or 50g/L, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the concentration of sodium borohydride is 0.2-0.5g/L, such as 0.2g/L, 0.25g/L, 0.3g/L, 0.35g/L, 0.4g/L, 0.45g/L, or 0.5g/L, but not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the concentration of ethylenediamine is 30-50g/L, for example 30g/L, 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L or 50g/L, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the concentration of potassium sodium tartrate is 30 to 50g/L, and may be, for example, 30g/L, 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L or 50g/L, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the concentration of the additive is 0.5 to 1g/L, and may be, for example, 0.5g/L, 0.55g/L, 0.6g/L, 0.65g/L, 0.7g/L, 0.75g/L, 0.8g/L, 0.85g/L, 0.9g/L, 0.95g/L or 1g/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the second electrochemical deposition comprises: firstly, 0.4-0.6A/dm 2 Depositing 55-65s till the thickness of the nickel-boron alloy layer is 0.08-0.12 mu m and then 1-3A/dm 2 The thickness of the nickel-boron alloy layer is 0.4-0.6 μm after 50-70s deposition, and the deposition temperature is 50-60 deg.C, such as 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C, and 55 deg.C56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃, but are not limited to the recited values, and other values not recited within the numerical range are equally applicable.
According to the invention, the second electrochemical deposition is limited to the sectional deposition under specific conditions, an alloy layer with higher boron content can be formed on the contact surface of the silicon layer of the substrate, and the hole transport capability between the silicon layer and the nickel-boron alloy layer can be improved after heat treatment; meanwhile, the whole boron content in the plating layer can be reduced, and the resistivity of the nickel-boron alloy layer is reduced, so that the whole resistance of the nickel-boron alloy layer in the grid line is reduced.
Preferably, the electrolyte used in the third electrochemical deposition includes copper pyrophosphate, tin pyrophosphate, potassium pyrophosphate and potassium dihydrogen phosphate, and the electrolyte is adjusted to pH 9.0-9.2, for example, 9.0, 9.05, 9.1, 9.15 or 9.2 with ammonia, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the concentration of copper pyrophosphate is 20-30g/L, for example 20g/L, 21g/L, 22g/L, 23g/L, 24g/L, 25g/L, 26g/L, 27g/L, 28g/L, 29g/L or 30g/L, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the concentration of the tin pyrophosphate is 0.05-0.15g/L, such as 0.05g/L, 0.06g/L, 0.07g/L, 0.08g/L, 0.09g/L, 0.10g/L, 0.11g/L, 0.12g/L, 0.13g/L, 0.14g/L or 0.15g/L, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the potassium pyrophosphate concentration is 40-60g/L, such as 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L, 56g/L, 58g/L or 60g/L, but not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the concentration of the potassium dihydrogen phosphate is 50-70g/L, such as 50g/L, 52g/L, 54g/L, 56g/L, 58g/L, 60g/L, 62g/L, 64g/L, 66g/L, 68g/L or 70g/L, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the current density of the third electrochemical deposition is 1.0-1.5A/dm 2 For example, it may be 1.0A/dm 2 、1.1A/dm 2 、1.2A/dm 2 、1.3A/dm 2 、1.4A/dm 2 Or 1.5A/dm 2 However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
Preferably, the deposition temperature of the third electrochemical deposition is 20-30 ℃, and may be, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the deposition time of the third electrochemical deposition is 5-10min, such as 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferable technical solution of the second aspect of the present invention, the preparation method comprises the steps of:
(1) respectively and independently forming wire grooves on the N surface and the P surface of the battery substrate by adopting laser etching, and cleaning by using hydrofluoric acid;
(2) sequentially depositing a nickel-phosphorus alloy layer and a first copper-tin alloy layer in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer and a second copper-tin alloy layer in the wire groove on the P surface;
(4) carrying out heat treatment on the battery substrate to obtain the TOPCon battery;
wherein, the steps (2) and (3) are not in sequence; step (2) the method of depositing the nickel-phosphorus alloy layer comprises a first electrochemical deposition, step (3) the method of depositing the nickel-boron alloy layer comprises a second electrochemical deposition, and step (2) the method of depositing the first copper-tin alloy layer and step (3) the second copper-tin alloy layer each independently comprises a third electrochemical deposition;
the first electricityThe electrolyte used for chemical deposition comprises 450-500g/L nickel sulfamate, 15-20g/L nickel chloride, 1-2g/L phosphoric acid and 20-30g/L additive, and the pH of the electrolyte is adjusted to 1.0-2.0 by adopting sulfamic acid; the first electrochemical deposition comprises: firstly, the concentration is 0.8-1.2A/dm 2 Depositing for 25-35s until the thickness of the nickel-phosphorus alloy layer is 0.08-0.12 μm, and then depositing for 4-6A/dm 2 Depositing for 20-40s until the thickness of the nickel-phosphorus alloy layer is 0.4-0.6 mu m, and the deposition temperature is 60-70 ℃;
the electrolyte adopted by the second electrochemical deposition comprises 30-50g/L of nickel chloride, 0.2-0.5g/L of sodium borohydride, 30-50g/L of ethylenediamine, 30-50g/L of sodium potassium tartrate and 0.5-1g/L of additive, and the pH of the electrolyte is adjusted to 13.0-14.0 by adopting ammonia water; the second electrochemical deposition comprises: firstly, 0.4-0.6A/dm 2 Depositing 55-65s till the thickness of the nickel-boron alloy layer is 0.08-0.12 mu m and then 1-3A/dm 2 Depositing for 50-70s till the thickness of the nickel-boron alloy layer is 0.4-0.6 mu m, and the deposition temperature is 50-60 ℃;
the electrolyte adopted by the third electrochemical deposition comprises 20-30g/L of copper pyrophosphate, 0.05-0.15g/L of tin pyrophosphate, 40-60g/L of potassium pyrophosphate and 50-70g/L of potassium dihydrogen phosphate, and the pH of the electrolyte is adjusted to 9.0-9.2 by adopting ammonia water; the current density of the third electrochemical deposition is 1.0-1.5A/dm 2 The deposition temperature is 20-30 deg.C, and the deposition time is 5-10 min.
Compared with the prior art, the invention has the following beneficial effects:
according to the TOPCon battery provided by the invention, the N-side nickel layer of the traditional battery substrate is doped with phosphorus elements, and the P-side nickel layer is doped with boron elements, so that the nickel layer and the silicon layer of the substrate form nickel-silicon alloy at the interface, meanwhile, the contact position of an N-side grid line forms phosphorus-rich doping, and the contact position of a P-side grid line forms boron-rich doping, thereby forming electron hole transmission, further reducing the contact resistance, remarkably improving the battery efficiency, and reducing the contact resistance to 0.1m omega/cm at the lowest 2 The efficiency of the battery can be raised to 24.6 percent at most.
Drawings
Fig. 1 is a schematic diagram of a TOPCon battery according to the present invention;
fig. 2 is a flow chart of a method for preparing a TOPCon battery provided by the present invention.
Wherein: a 1-TOPCon substrate; 2-tunneling oxide layer; 3-phosphorus heavily doped polysilicon layer; 4-boron heavily doped polysilicon layer; 5-an aluminum oxide layer; a 6-silicon nitride layer; a 7-nickel-phosphorus alloy layer; 8-a first copper-tin alloy layer; a 9-nickel-boron alloy layer; 10-second copper-tin alloy layer.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this embodiment, as shown in fig. 1, the TOPCon battery includes a battery substrate, and two side surfaces of the battery substrate are an N-plane and a P-plane, respectively. The center of the battery substrate is a TOPCon substrate 1, a tunneling oxide layer 2, a phosphorus heavily doped polycrystalline silicon layer 3 and a silicon nitride layer 6 are stacked towards the N surface, and a boron heavily doped polycrystalline silicon layer 4, an aluminum oxide layer 5 and a silicon nitride layer 6 are stacked towards the P surface.
As shown in fig. 1, the N-plane and the P-plane are respectively and independently provided with a wire slot, and a grid line is arranged in the wire slot; the grid line of the N surface comprises a nickel-phosphorus alloy layer 7 and a first copper-tin alloy layer 8 which are arranged in a stacked mode, and the nickel-phosphorus alloy layer 7 is in contact with the bottom of the wire groove of the N surface; the grid line of the P surface comprises a nickel-boron alloy layer 9 and a second copper-tin alloy layer 10 which are stacked, and the nickel-boron alloy layer 9 is in contact with the bottom of the P surface line groove.
In this embodiment, the content of phosphorus in the nickel-phosphorus alloy layer 7 is 2.5wt%, the content of boron in the nickel-boron alloy layer 9 is 2wt%, and the thicknesses of the nickel-phosphorus alloy layer 7 and the nickel-boron alloy layer 9 are respectively and independently 0.5 μm. The tin content in the first copper-tin alloy layer 8 and the second copper-tin alloy layer 10 is 0.25wt% respectively and independently.
As shown in fig. 2, the preparation method comprises the following steps:
(1) respectively and independently forming wire grooves on the N surface and the P surface of the battery substrate by adopting laser etching, and cleaning by using hydrofluoric acid;
(2) sequentially depositing a nickel-phosphorus alloy layer 7 and a first copper-tin alloy layer 8 in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer 9 and a second copper-tin alloy layer 10 in the wire groove on the P surface;
(4) annealing the battery substrate in argon atmosphere at 350 ℃ for 2min to obtain the TOPCon battery;
wherein the deposition method of the nickel-phosphorus alloy layer 7 in the step (2) is a first electrochemical deposition, the deposition method of the nickel-boron alloy layer 9 in the step (3) is a second electrochemical deposition, and the deposition methods of the first copper-tin alloy layer 8 in the step (2) and the second copper-tin alloy layer 10 in the step (3) are respectively and independently a third electrochemical deposition.
Specifically, the electrolyte adopted by the first electrochemical deposition comprises 480g/L of nickel sulfamate, 18g/L of nickel chloride, 1.5g/L of phosphoric acid and 25g/L of sulfimide, and the pH of the electrolyte is adjusted to 1.5 by adopting sulfamic acid; the first electrochemical deposition comprises: firstly, 1.0A/dm 2 Depositing for 30s to the thickness of the nickel-phosphorus alloy layer of 0.1 μm, and then depositing at 5.0A/dm 2 The thickness of the nickel-phosphorus alloy layer is 0.5 μm after 30s of bottom deposition, and the deposition temperature is 65 ℃.
Specifically, the electrolyte adopted by the second electrochemical deposition comprises 40g/L of nickel chloride, 0.3g/L of sodium borohydride, 40g/L of ethylenediamine, 40g/L of sodium potassium tartrate and 0.8g/L of dithiosalicylic acid, and the pH of the electrolyte is adjusted to 13.5 by adopting ammonia water; the second electrochemical deposition comprises: firstly, 0.5A/dm 2 Depositing 60s to the thickness of the nickel-boron alloy layer of 0.1 μm and then 2.0A/dm 2 The thickness of the lower deposited 60s to nickel-boron alloy layer was 0.5 μm, and the deposition temperature was 55 ℃.
Specifically, the electrolyte adopted by the third electrochemical deposition comprises 25g/L of copper pyrophosphate, 0.10g/L of tin pyrophosphate, 50g/L of potassium pyrophosphate and 60g/L of potassium dihydrogen phosphate, and the pH of the electrolyte is adjusted to 9.1 by ammonia water; the current density of the third electrochemical deposition is 1.2A/dm 2 The deposition temperature is 25 ℃, and the deposition is carried outThe product time is 8 min.
Example 2
In this embodiment, as shown in fig. 1, the TOPCon battery includes a battery substrate, and two side surfaces of the battery substrate are an N-plane and a P-plane, respectively. The center of the battery substrate is a TOPCon substrate 1, a tunneling oxide layer 2, a phosphorus heavily doped polycrystalline silicon layer 3 and a silicon nitride layer 6 are stacked towards the N surface, and a boron heavily doped polycrystalline silicon layer 4, an aluminum oxide layer 5 and a silicon nitride layer 6 are stacked towards the P surface.
As shown in fig. 1, the N-plane and the P-plane are respectively and independently provided with a wire slot, and a grid line is arranged in the wire slot; the grid line of the N surface comprises a nickel-phosphorus alloy layer 7 and a first copper-tin alloy layer 8 which are arranged in a stacked mode, and the nickel-phosphorus alloy layer 7 is in contact with the bottom of the wire groove of the N surface; the grid line of the P surface comprises a nickel-boron alloy layer 9 and a second copper-tin alloy layer 10 which are stacked, and the nickel-boron alloy layer 9 is in contact with the bottom of the P surface line groove.
In this embodiment, the content of phosphorus in the nickel-phosphorus alloy layer 7 is 1wt%, the content of boron in the nickel-boron alloy layer 9 is 0.8wt%, and the thicknesses of the nickel-phosphorus alloy layer 7 and the nickel-boron alloy layer 9 are respectively and independently 0.4 μm. The tin content in the first copper-tin alloy layer 8 and the second copper-tin alloy layer 10 is 0.01wt% respectively and independently.
As shown in fig. 2, the preparation method comprises the following steps:
(1) respectively and independently forming wire grooves on the N surface and the P surface of the battery substrate by adopting laser etching, and cleaning by using hydrofluoric acid;
(2) sequentially depositing a nickel-phosphorus alloy layer 7 and a first copper-tin alloy layer 8 in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer 9 and a second copper-tin alloy layer 10 in the wire groove on the P surface;
(4) annealing the battery substrate in argon atmosphere at 350 ℃ for 2min to obtain a TOPCon battery;
wherein the deposition method of the nickel-phosphorus alloy layer 7 in the step (2) is a first electrochemical deposition, the deposition method of the nickel-boron alloy layer 9 in the step (3) is a second electrochemical deposition, and the deposition methods of the first copper-tin alloy layer 8 in the step (2) and the second copper-tin alloy layer 10 in the step (3) are respectively and independently a third electrochemical deposition.
Specifically, the electrolyte adopted by the first electrochemical deposition comprises 450g/L nickel sulfamate, 15g/L nickel chloride, 1g/L phosphoric acid and 20g/L sulfimide, and the pH of the electrolyte is adjusted to 1.0 by sulfamic acid; the first electrochemical deposition comprises: firstly, 0.8A/dm 2 Depositing a nickel-phosphorus alloy layer with a thickness of 0.08 μm for 25s, and then depositing a nickel-phosphorus alloy layer with a thickness of 4.0A/dm 2 The thickness of the nickel-phosphorus alloy layer is 0.4 μm after the lower deposition for 20s, and the deposition temperature is 60 ℃.
Specifically, the electrolyte adopted by the second electrochemical deposition comprises 30g/L of nickel chloride, 0.2g/L of sodium borohydride, 30g/L of ethylenediamine, 30g/L of sodium potassium tartrate and 0.5g/L of salicylic acid, and the pH of the electrolyte is adjusted to 13.0 by adopting ammonia water; the second electrochemical deposition comprises: firstly, 0.4A/dm 2 Depositing 55s to nickel-boron alloy layer with thickness of 0.08 μm and then 1.0A/dm 2 The thickness of the lower deposition 50s to nickel-boron alloy layer is 0.4 μm, and the deposition temperature is 50 ℃.
Specifically, the electrolyte adopted by the third electrochemical deposition comprises 20g/L of copper pyrophosphate, 0.05g/L of tin pyrophosphate, 40g/L of potassium pyrophosphate and 50g/L of potassium dihydrogen phosphate, and the pH of the electrolyte is adjusted to 9.0 by adopting ammonia water; the current density of the third electrochemical deposition is 1.0A/dm 2 The deposition temperature is 20 ℃ and the deposition time is 5 min.
Example 3
In this embodiment, as shown in fig. 1, the TOPCon battery includes a battery substrate, and two side surfaces of the battery substrate are an N-plane and a P-plane, respectively. The center of the battery substrate is a TOPCon substrate 1, a tunneling oxide layer 2, a phosphorus heavily doped polycrystalline silicon layer 3 and a silicon nitride layer 6 are stacked towards the N surface, and a boron heavily doped polycrystalline silicon layer 4, an aluminum oxide layer 5 and a silicon nitride layer 6 are stacked towards the P surface.
As shown in fig. 1, the N-plane and the P-plane are respectively and independently provided with a wire slot, and a grid line is arranged in the wire slot; the grid line of the N surface comprises a nickel-phosphorus alloy layer 7 and a first copper-tin alloy layer 8 which are arranged in a stacked mode, and the nickel-phosphorus alloy layer 7 is in contact with the bottom of the wire groove of the N surface; the grid line of the P surface comprises a nickel-boron alloy layer 9 and a second copper-tin alloy layer 10 which are stacked, and the nickel-boron alloy layer 9 is in contact with the bottom of the P surface line groove.
In this embodiment, the content of phosphorus in the nickel-phosphorus alloy layer 7 is 5wt%, the content of boron in the nickel-boron alloy layer 9 is 4wt%, and the thicknesses of the nickel-phosphorus alloy layer 7 and the nickel-boron alloy layer 9 are respectively and independently 0.6 μm. The tin content in the first copper-tin alloy layer 8 and the second copper-tin alloy layer 10 is 0.5wt% respectively and independently.
As shown in fig. 2, the preparation method comprises the following steps:
(1) respectively and independently forming wire grooves on the N surface and the P surface of the battery substrate by adopting laser etching, and cleaning by using hydrofluoric acid;
(2) sequentially depositing a nickel-phosphorus alloy layer 7 and a first copper-tin alloy layer 8 in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer 9 and a second copper-tin alloy layer 10 in the wire groove on the P surface;
(4) annealing the battery substrate in argon atmosphere at 350 ℃ for 2min to obtain a TOPCon battery;
wherein the deposition method of the nickel-phosphorus alloy layer 7 in the step (2) is a first electrochemical deposition, the deposition method of the nickel-boron alloy layer 9 in the step (3) is a second electrochemical deposition, and the deposition methods of the first copper-tin alloy layer 8 in the step (2) and the second copper-tin alloy layer 10 in the step (3) are respectively and independently a third electrochemical deposition.
Specifically, the electrolyte adopted by the first electrochemical deposition comprises 500g/L of nickel sulfamate, 20g/L of nickel chloride, 2g/L of phosphoric acid and 30g/L of sulfamide, and the pH of the electrolyte is adjusted to 2.0 by adopting sulfamic acid; the first electrochemical deposition comprises: firstly, 1.2A/dm 2 Depositing 35s to the thickness of the nickel-phosphorus alloy layer of 0.12 μm, and then depositing at 6A/dm 2 The thickness of the lower deposited 40s to nickel-phosphorus alloy layer is 0.6 μm, and the deposition temperature is 70 ℃.
Specifically, the first stepThe electrolyte adopted by the second electrochemical deposition comprises 50g/L of nickel chloride, 0.5g/L of sodium borohydride, 50g/L of ethylenediamine, 50g/L of sodium potassium tartrate and 1g/L of dithiosalicylic acid, and the pH of the electrolyte is adjusted to 14.0 by adopting ammonia water; the second electrochemical deposition comprises: firstly, 0.6A/dm 2 Depositing 65s to nickel-boron alloy layer with thickness of 0.12 μm and then 3.0A/dm 2 The thickness of the lower deposition 70s to nickel-boron alloy layer is 0.6 μm, and the deposition temperature is 60 ℃.
Specifically, the electrolyte adopted by the third electrochemical deposition comprises 30g/L of copper pyrophosphate, 0.15g/L of tin pyrophosphate, 60g/L of potassium pyrophosphate and 70g/L of potassium dihydrogen phosphate, and the pH of the electrolyte is adjusted to 9.2 by adopting ammonia water; the current density of the third electrochemical deposition is 1.5A/dm 2 The deposition temperature is 30 ℃ and the deposition time is 10 min.
Example 4
This embodiment provides a TOPCon battery and a method for manufacturing the same, except that the content of phosphorus in the nickel-phosphorus alloy layer 7 is changed to 0.5wt%, and the concentration of phosphoric acid in the manufacturing method is adaptively adjusted, and the remaining structure and conditions are the same as those in embodiment 1, and therefore, the details are not repeated herein.
Example 5
This example provides a TOPCon battery and a method for manufacturing the same, except that the content of phosphorus in the nickel-phosphorus alloy layer 7 is changed to 6wt%, and the concentration of phosphoric acid in the manufacturing method is adaptively adjusted, and the remaining structure and conditions are the same as those in example 1, and thus the description thereof is omitted.
Example 6
This embodiment provides a topon battery and a method for manufacturing the same, except that the content of boron in the nickel-boron alloy layer 9 is changed to 0.6wt%, and the concentration of sodium borohydride in the method for manufacturing is adaptively adjusted, and the remaining structures and conditions are the same as those in embodiment 1, and thus are not described herein again.
Example 7
This embodiment provides a TOPCon battery and a method for manufacturing the same, except that the content of boron in the nickel-boron alloy layer 9 is changed to 5wt%, and the concentration of sodium borohydride in the manufacturing method is adaptively adjusted, and the remaining structure and conditions are the same as those in embodiment 1, and therefore, the detailed description thereof is omitted.
Comparative example 1
This comparative example provides a TOPCon battery and a method for manufacturing the same, except that the nickel-phosphorus alloy layer 7 is replaced by a pure nickel layer having the same thickness, and the manufacturing method is adaptively adjusted, and the remaining structure and conditions are the same as those in example 1, and thus the description thereof is omitted.
Comparative example 2
This comparative example provides a TOPCon battery and a method for manufacturing the same, except that the nickel-boron alloy layer 9 is changed to a pure nickel layer with the same thickness, and the manufacturing method is adaptively adjusted, and the remaining structure and conditions are the same as those in example 1, and thus, the details thereof are not repeated herein.
Comparative example 3
This comparative example provides a TOPCon battery and a method for manufacturing the same, except that the nickel-phosphorus alloy layer 7 and the nickel-boron alloy layer 9 were respectively and correspondingly changed to pure nickel layers of the same thickness, and the manufacturing method was adaptively adjusted, and the remaining structures and conditions were the same as those in example 1, and thus are not described herein again.
Comparative example 4
The preparation method adopts the traditional Ni/Cu/Ag electroplating process, firstly carries out laser etching on a grid line graph on a battery substrate, then carries out hydrofluoric acid cleaning, sequentially electroplates Ni, Cu and Ag on an N surface, and sequentially electroplates Ni, Cu and Ag on a P surface; finally annealing for 2min in argon atmosphere at 350 ℃ to obtain the TOPCon battery.
Comparative example 5
The preparation method adopts a traditional Ag process of screen printing, and after a layer of silver paste is printed, the TOPCon battery is obtained by sintering at 850 ℃ for 30 s.
The results of the performance tests of the TOPCon cells obtained in examples 1-7 and comparative examples 1-5 are shown in Table 1 below.
TABLE 1
In the above table, the test method of the contact resistance is: a rectangular transmission line method (TLM method); the method for testing the battery efficiency comprises the following steps: I-V test methods.
As can be seen from Table 1: the doping of phosphorus element in the N-side nickel layer and the doping of boron element in the P-side nickel layer can increase the electron/hole transmission between the silicon layer and the nickel layer of the substrate, reduce the contact resistance of the grid line and improve the battery efficiency. The doping amount of phosphorus and boron also affects the efficiency of the battery, and if the doping amount is too small, the influence on electrons/holes of the nickel-silicon alloy is small; if the doping amount is too high, the resistivity of the grid lines is increased, and the efficiency of the battery is reduced. Therefore, the invention adopts the method of heavily doping the contact layer and lightly doping the conducting layer, thereby obtaining better technical effect.
Therefore, the TOPCon battery provided by the invention has the advantages that the N-side nickel layer of the traditional battery substrate is doped with phosphorus elements, and the P-side nickel layer is doped with boron elements, so that the nickel layer and the silicon layer of the substrate form nickel-silicon alloy at the interface, meanwhile, the contact position of an N-side grid line is doped with phosphorus, and the contact position of a P-side grid line is doped with boron, thereby forming electron hole transmission, further reducing the contact resistance, remarkably improving the battery efficiency, and reducing the contact resistance to 0.1m omega/cm at the lowest 2 The battery efficiency can be improved to 24.6 percent at most.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A TOPCon battery is characterized by comprising a battery substrate, wherein the two side surfaces of the battery substrate are an N surface and a P surface respectively;
the N surface and the P surface are respectively and independently provided with wire grooves, and grid lines are arranged in the wire grooves;
the grid line of the N surface comprises a nickel-phosphorus alloy layer and a first copper-tin alloy layer which are stacked, and the nickel-phosphorus alloy layer is contacted with the bottom of the N surface wire groove;
the grid line of the P face comprises a nickel-boron alloy layer and a second copper-tin alloy layer which are stacked, and the nickel-boron alloy layer is in contact with the bottom of the P face wire groove.
2. The TOPCon cell of claim 1, wherein the phosphorous content in the nickel phosphorous alloy layer is 1-5 wt%;
the content of boron in the nickel-boron alloy layer is 0.8-4 wt%;
the thicknesses of the nickel-phosphorus alloy layer and the nickel-boron alloy layer are respectively and independently 0.1-1 mu m;
the tin content in the first copper-tin alloy layer and the second copper-tin alloy layer is 0.01-0.5wt% respectively and independently.
3. A method of manufacturing a TOPCon cell as claimed in claim 1 or 2, characterized in that it comprises the following steps:
(1) respectively and independently arranging wire grooves on the N surface and the P surface of the battery substrate;
(2) sequentially depositing a nickel-phosphorus alloy layer and a first copper-tin alloy layer in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer and a second copper-tin alloy layer in the wire groove on the P surface;
(4) carrying out heat treatment on the battery substrate to obtain a TOPCon battery;
wherein, the steps (2) and (3) are not in sequence.
4. The preparation method of claim 3, wherein the method for opening the wire grooves in the step (1) comprises laser etching, and the wire grooves are cleaned by hydrofluoric acid after being opened.
5. The method according to claim 3, wherein the deposition method of the nickel-phosphorus alloy layer of step (2) comprises a first electrochemical deposition;
the deposition method of the nickel-boron alloy layer in the step (3) comprises a second electrochemical deposition.
6. The method of claim 5, wherein the deposition of the first copper-tin alloy layer of step (2) and the second copper-tin alloy layer of step (3) each independently comprises a third electrochemical deposition.
7. The method according to claim 5, wherein the electrolyte used in the first electrochemical deposition includes nickel sulfamate, nickel chloride, phosphoric acid and additives, and the electrolyte is adjusted to a pH of 1.0 to 2.0 using sulfamic acid;
the concentration of the nickel sulfamate is 450-500 g/L;
the concentration of the nickel chloride is 15-20 g/L;
the concentration of the phosphoric acid is 1-2 g/L;
the concentration of the additive is 20-30 g/L;
the first electrochemical deposition comprises: firstly, the concentration is 0.8-1.2A/dm 2 Depositing for 25-35s until the thickness of the nickel-phosphorus alloy layer is 0.08-0.12 μm, and then depositing for 4-6A/dm 2 The thickness of the nickel-phosphorus alloy layer is 0.4-0.6 mu m after 20-40s of lower deposition, and the deposition temperature is 60-70 ℃.
8. The preparation method according to claim 5, wherein the electrolyte used in the second electrochemical deposition comprises nickel chloride, sodium borohydride, ethylenediamine, sodium potassium tartrate and additives, and the electrolyte is adjusted to pH 13.0-14.0 by ammonia water;
the concentration of the nickel chloride is 30-50 g/L;
the concentration of the sodium borohydride is 0.2-0.5 g/L;
the concentration of the ethylenediamine is 30-50 g/L;
the concentration of the potassium sodium tartrate is 30-50 g/L;
the concentration of the additive is 0.5-1 g/L;
the second electrochemical deposition comprises: firstly, 0.4-0.6A/dm 2 Depositing 55-65s to nickelThe thickness of the boron alloy layer is 0.08-0.12 μm, and then 1-3A/dm 2 Depositing 50-70s till the thickness of the nickel-boron alloy layer is 0.4-0.6 μm, and the deposition temperature is 50-60 ℃.
9. The preparation method according to claim 6, wherein the electrolyte used in the third electrochemical deposition comprises copper pyrophosphate, tin pyrophosphate, potassium pyrophosphate and potassium dihydrogen phosphate, and the electrolyte is adjusted to pH 9.0-9.2 with ammonia water;
the concentration of the copper pyrophosphate is 20-30 g/L;
the concentration of the tin pyrophosphate is 0.05-0.15 g/L;
the concentration of the potassium pyrophosphate is 40-60 g/L;
the concentration of the monopotassium phosphate is 50-70 g/L;
the current density of the third electrochemical deposition is 1.0-1.5A/dm 2 The deposition temperature is 20-30 deg.C, and the deposition time is 5-10 min.
10. The method of manufacturing according to claim 3, comprising the steps of:
(1) respectively and independently forming wire grooves on the N surface and the P surface of the battery substrate by adopting laser etching, and cleaning by using hydrofluoric acid;
(2) sequentially depositing a nickel-phosphorus alloy layer and a first copper-tin alloy layer in the wire groove on the N surface;
(3) sequentially depositing a nickel-boron alloy layer and a second copper-tin alloy layer in the wire groove on the P surface;
(4) carrying out heat treatment on the battery substrate to obtain a TOPCon battery;
wherein, the steps (2) and (3) are not in sequence; step (2) the method of depositing the nickel-phosphorus alloy layer comprises a first electrochemical deposition, step (3) the method of depositing the nickel-boron alloy layer comprises a second electrochemical deposition, and step (2) the method of depositing the first copper-tin alloy layer and step (3) the second copper-tin alloy layer each independently comprises a third electrochemical deposition;
the first isThe electrolyte used for electrochemical deposition comprises 450-500g/L nickel sulfamate, 15-20g/L nickel chloride, 1-2g/L phosphoric acid and 20-30g/L additive, and the pH of the electrolyte is adjusted to 1.0-2.0 by adopting sulfamic acid; the first electrochemical deposition comprises: firstly, the concentration is 0.8-1.2A/dm 2 Depositing for 25-35s to the thickness of the nickel-phosphorus alloy layer of 0.08-0.12 μm, and further depositing at 4-6A/dm 2 Depositing for 20-40s until the thickness of the nickel-phosphorus alloy layer is 0.4-0.6 mu m, and the deposition temperature is 60-70 ℃;
the electrolyte adopted by the second electrochemical deposition comprises 30-50g/L of nickel chloride, 0.2-0.5g/L of sodium borohydride, 30-50g/L of ethylenediamine, 30-50g/L of sodium potassium tartrate and 0.5-1g/L of additive, and the pH of the electrolyte is adjusted to 13.0-14.0 by adopting ammonia water; the second electrochemical deposition comprises: firstly, the concentration is 0.4-0.6A/dm 2 Depositing 55-65s to nickel-boron alloy layer with thickness of 0.08-0.12 μm, and further depositing at 1-3A/dm 2 Depositing for 50-70s till the thickness of the nickel-boron alloy layer is 0.4-0.6 mu m, and the deposition temperature is 50-60 ℃;
the electrolyte adopted by the third electrochemical deposition comprises 20-30g/L of copper pyrophosphate, 0.05-0.15g/L of tin pyrophosphate, 40-60g/L of potassium pyrophosphate and 50-70g/L of potassium dihydrogen phosphate, and the pH of the electrolyte is adjusted to 9.0-9.2 by adopting ammonia water; the current density of the third electrochemical deposition is 1.0-1.5A/dm 2 The deposition temperature is 20-30 deg.C, and the deposition time is 5-10 min.
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| JP2004193337A (en) * | 2002-12-11 | 2004-07-08 | Sharp Corp | Method for forming electrode for solar cell and solar cell manufactured thereby |
| TW201933618A (en) * | 2018-01-23 | 2019-08-16 | 茂迪股份有限公司 | Solar cell and method for manufacturing the same |
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| CN114597270A (en) * | 2022-05-09 | 2022-06-07 | 苏州晶洲装备科技有限公司 | Heterojunction solar cell and preparation method and application thereof |
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|---|---|---|---|---|
| JP2004193337A (en) * | 2002-12-11 | 2004-07-08 | Sharp Corp | Method for forming electrode for solar cell and solar cell manufactured thereby |
| TW201933618A (en) * | 2018-01-23 | 2019-08-16 | 茂迪股份有限公司 | Solar cell and method for manufacturing the same |
| CN114203834A (en) * | 2021-12-06 | 2022-03-18 | 苏州晶洲装备科技有限公司 | Solar cell with double-sided electrode structure and preparation method thereof |
| CN114551609A (en) * | 2021-12-31 | 2022-05-27 | 天合光能股份有限公司 | Solar cell and preparation method and application thereof |
| CN114597270A (en) * | 2022-05-09 | 2022-06-07 | 苏州晶洲装备科技有限公司 | Heterojunction solar cell and preparation method and application thereof |
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