CN114703468A - Method for plating nickel layer on silicon substrate and preparation method of solar cell nickel electrode - Google Patents
Method for plating nickel layer on silicon substrate and preparation method of solar cell nickel electrode Download PDFInfo
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- CN114703468A CN114703468A CN202210278052.XA CN202210278052A CN114703468A CN 114703468 A CN114703468 A CN 114703468A CN 202210278052 A CN202210278052 A CN 202210278052A CN 114703468 A CN114703468 A CN 114703468A
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- Prior art keywords
- nickel
- plating
- electroplating
- silicon substrate
- layer
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 291
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 143
- 238000007747 plating Methods 0.000 title claims abstract description 82
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 66
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 230000006911 nucleation Effects 0.000 claims abstract description 43
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000009713 electroplating Methods 0.000 claims description 62
- 150000001875 compounds Chemical class 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- 238000007772 electroless plating Methods 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 7
- 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 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 6
- 238000010899 nucleation Methods 0.000 claims description 6
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 claims description 6
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229910052763 palladium Inorganic materials 0.000 description 16
- 238000002161 passivation Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000010453 quartz Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 description 5
- 230000005641 tunneling Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000080590 Niso Species 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910015845 BBr3 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- AIOWANYIHSOXQY-UHFFFAOYSA-N cobalt silicon Chemical compound [Si].[Co] AIOWANYIHSOXQY-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910005883 NiSi Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/011—Electroplating using electromagnetic wave irradiation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
-
- 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
Abstract
The invention relates to a method for plating a nickel layer on a silicon substrate and a preparation method of a solar cell nickel electrode, belongs to the technical field of solar cells, and solves the problems of low nickel plating speed, poor effect and high cost of the silicon substrate in the prior art. The method comprises the following steps: step A: forming a metal nickel nucleation center on the surface of the silicon substrate; and B: and B, putting the product obtained in the step A into a chemical nickel plating solution for chemical plating, and forming a nickel metal layer by using the metal nickel nucleation center obtained in the step A. The nickel plating method for the silicon substrate has the advantages of high speed and good plating effect.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for plating a nickel layer on a silicon substrate and a method for preparing a nickel electrode of a solar cell.
Background
The passivation contact solar cell adopts a thin oxide layer as a tunneling layer, prevents minority carrier transmission, adopts a doped poly layer as field passivation, has higher voltage and FF, is easy to realize PERC (permanent resistance capacitance) upgrading, is a key direction of current research, but uses silver paste on two sides, uses more silver paste, has higher non-silicon cost ratio, and is not beneficial to popularization.
At present, the solar cell uses 20-30% of the silver storage amount, the capacity is continuously expanded, and the situation of insufficient silver exists. The conductivity of copper is close to that of silver, and the copper electroplating technology has great industrial significance for replacing silver paste, but because copper is easy to diffuse, traps are easy to form to capture minority carriers, and nickel is generally adopted as a barrier layer to block the diffusion of copper.
The deposition of nickel is usually carried out by PVD nickel, electroless nickel, electrolytic nickel and LIP nickel (light induced nickel). The chemical nickel plating deposition is slow, particles are fine, full coverage of nickel is facilitated, and subsequent bonding force is facilitated.
Disclosure of Invention
In view of the above analysis, the embodiments of the present invention are directed to providing a method for plating a nickel layer on a silicon substrate and a method for preparing a nickel electrode of a solar cell, so as to solve the problems of slow nickel plating speed and poor nickel plating effect on the silicon substrate in the prior art.
In one aspect, embodiments of the present invention provide a method for plating a nickel layer on a silicon substrate, including the following steps:
step A: forming a metal nickel nucleation center on the surface of the silicon substrate;
and B: and B, putting the product obtained in the step A into a chemical nickel plating solution for chemical plating, and forming a nickel metal layer by using the metal nickel nucleation center obtained in the step A.
Preferably, in step a, the method for forming the metal nickel nucleation centers on the surface of the silicon substrate is electroplating or light-induced electroplating.
Preferably, in step a, the electroplating solution for electroplating or light-induced electroplating comprises: 10-100g/L of nickel sulfate, 5-20g/L of nickel chloride, 25-40g/L of boric acid, 0.2-3mL/L of wetting agent and 20-50g/L of conductive compound; or
In step a, the electroplating solution for electroplating or light-induced electroplating comprises: 20-200g/L of nickel sulfamate, 5-35g/L of nickel chloride, 30-50g/L of boric acid, 0.2-3mL/L of wetting agent and 20-50g/L of conductive compound.
Preferably, the nickel sulfate is NiSO4·7H2O, nickel chloride is NiCl6H2O, the conductive compound is sulfonate.
Preferably, the conductive compound is one or more of sulfamic acid, methanesulfonic acid, sodium sulfamate and sodium methylsulfonate.
Preferably, the plating conditions include: pH of 3.8-6.5, temperature of 40-55 deg.C, and current density of 0.1-2A/dm2The electroplating time is 5-60 s;
preferably, the conditions of the light-induced plating include: the pH value is 3.8-6.5, the temperature is 40-55 ℃, the illumination intensity is 0.1-2sun, the light is white light and/or green light, and the light-induced electroplating time is 5-60 s.
Preferably, in the step B, the electroless plating solution for electroless plating includes: NiSO4·H2O 15-40g/L，NaH2PO2·H210-30g/L of O and 10-25g/L of sodium citrate.
Preferably, in step B, the electroless plating conditions include: the pH value is 8-10, the temperature is 35-99 ℃, and the time is 1-20 min.
In another aspect, the present invention further provides a method for preparing a nickel electrode of a solar cell, including:
step a: the method for plating the nickel layer on the silicon substrate is adopted to plate the nickel layer on the surface of the solar cell silicon substrate on which the grid needs to be manufactured;
step b: and c, forming a copper layer on the surface of the nickel layer formed in the step a.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
1. the method forms the nickel nucleation center on the surface of the silicon substrate, then utilizes the metal nickel nucleation center, and adopts the chemical plating method to accumulate nickel metal atoms near the metal nickel nucleation center to form the nickel metal layer, thereby not only having low cost, but also having good stability of the nickel solution and being easy to control when the nucleation center is formed;
2. the metal element of the nucleation center and the outer layer element are made of the same material (such as nickel), so that the depth of the nickel-silicon alloy can be controlled; the contact performance is good, and the adhesive force of nickel and silicon is higher.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings, in which like reference numerals refer to like parts throughout, are for the purpose of illustrating particular embodiments only and are not to be considered limiting of the invention.
FIG. 1 is a schematic illustration of the nucleation of electroplating/photo-induced electroplating of the present invention;
FIG. 2 is a schematic view of an electroless nickel plating layer of the present invention;
FIG. 3 is a drawing of an electroplating apparatus;
FIG. 4 is a drawing of an apparatus for light-induced electroplating;
fig. 5 is a schematic structural diagram of a solar cell substrate.
Reference numerals:
1-a silicon substrate; 11-N type silicon substrate; a 12-P + emitter; 13-tunneling through a silicon oxide film; 14-a polycrystalline silicon thin film; 15-front passivation antireflection layer; 16-a back side passivation layer; 2-metallic nickel nucleation centers; 3-nickel metal atoms; 4-an anode; 5-plating solution; 6-plating bath; 7-a power supply; 8-light source.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The deposition of nickel is usually carried out by PVD nickel, electroless nickel, electroplating nickel, LIP nickel (light induced nickel plating) and the like. The inventor of the invention finds out through research that: the PVD nickel is used in a vacuum system, the cost is high, the pure nickel is too strong in magnetism, other metals are required to be added, the contact resistance is likely to rise, the PVD can only be used for the whole surface, a mask process and an etching process are required to be added, the cost is high, and nickel etching is difficult; directly electroplating nickel on silicon, because silicon is a semiconductor, the resistance of a slotted area is still relatively high, after electrification, electron transmission is difficult, electron distribution is uneven, so that electroplating is uneven, the local area is thick and thin, the coverage is incomplete, the nickel particles are large, the nickel layer is not compact, and a local cavity or plating leakage is caused; LIP nickel is generated by utilizing a photovoltaic cell of the LIP nickel under illumination, an n + pole (a phosphorus expanded face corresponding to a PERC cell) of the cell serves as a negative pole, and a p + pole of the cell serves as a positive pole, so that only an n + face can be plated with nickel, and the p + face cannot be plated with nickel, and because the LIP nickel is generated by utilizing a p-n junction of the LIP nickel, nickel grows unevenly at places with uneven sheet resistance; the chemical nickel plating deposition is slow, the particles are fine, the full coverage of nickel is facilitated, and the subsequent binding force is facilitated. The direct chemical nickel plating on silicon adopts palladium or gold as a catalytic center because nickel has no autocatalysis effect, and can be beneficial to the deposition of nickel after the catalytic center is available. However, palladium or gold is a noble metal, and particularly when palladium is adopted, the minimum concentration of ionic palladium needs to be 150-300mg/l, so that the cost is high, and the overall cost is influenced; also, the palladium solution has poor stability.
Based on this, the present invention provides a method for plating a nickel layer on a silicon substrate, as shown in fig. 1 and 2, the method comprising the steps of:
step A: forming a metallic nickel nucleation center 2 on the surface of a silicon substrate 1;
and B, step B: and B, putting the product obtained in the step A into a chemical nickel plating solution for chemical plating, and forming a nickel metal layer by using the metal nickel nucleation center 2 obtained in the step A.
According to the invention, the metal nickel nucleation center 2 is formed on the surface of the silicon substrate 1, the metal nickel nucleation center 2 is utilized, the nickel metal atoms 3 are accumulated near the metal nickel nucleation center 2 by adopting a chemical plating method to form a nickel metal layer, and the metal nickel nucleation center 2 is adopted, so that the cost is low, the stability of a nickel solution is superior to that of a palladium solution, and the control is easier when the nucleation center is formed.
When palladium is adopted to prepare the palladium nucleation center, colloidal palladium is needed to be used as an activation solution, the colloidal palladium contains divalent tin ions, the divalent tin ions are unstable and easily form tetravalent tin ions, so that the solution is turbid or precipitates, and the precipitates can influence the formation of a subsequent nickel layer; in addition, the active center substance of the ionic palladium activation solution has the conditions that the adhesive force on the substrate is poor and only a small part of ionic palladium can be adsorbed on the substrate, when the method for plating the nickel layer on the silicon substrate is adopted to prepare the nickel electrode, in addition, the ionic palladium activation treatment easily causes the problems of diffusion plating or plating leakage, and the distribution is uneven, so that the problems of plating leakage, plating overflow, pinholes, bubbles and the like easily occur on the chemical plating layer at the rear section; meanwhile, palladium is a noble metal, and a palladium solution is expensive and large in consumption, so that cost control is not facilitated; soluble palladium salts such as palladium sulfate, palladium chloride and tetraamminepalladium dichloride are unstable.
Moreover, the metal element of the nucleation center and the metal element of the nickel layer obtained by subsequent chemical plating are made of the same material (both nickel), which is beneficial to controlling the depth of the nickel-silicon alloy, the nickel-silicon alloy is usually formed in a sintering process after the nickel layer is formed, the bonding force with silicon is improved, the material of the nucleation center is different, the depths of the formed alloy layers are different, for example, cobalt usually needs to be sintered at a temperature higher than 600 ℃ to form the cobalt-silicon alloy, and the depth of the cobalt-silicon alloy is very deep, so that p-n junctions are easy to burn through, the nickel-silicon alloy can be realized at a low temperature (200-; because the nickel-silicon alloy is formed with low depth and consumes less volume, Ni is formed2Si or NiSi, one or two nickel atoms consume one silicon atom, so nickel consumes less silicon atoms, whereas cobalt silicon compounds are one cobalt two silicon atoms; in addition, the adhesive force of nickel and silicon is good (when the nickel and silicon are used for electrodes, the average value of electrode tension can reach 1.45-1.46 newtons or more), and the contact resistance can be realized<1mohmcm2The photoelectric conversion efficiency is high, and the silver paste can be printed with a screenKeeping the level.
In the invention, the nickel nucleation center is well combined with silicon, and when the metal nickel nucleation center is used for preparing an electrode, the nucleation center only needs to grow at the electrode, and the whole surface of the metal nickel nucleation center is not required to deposit, so that the method for forming the metal nickel nucleation center 2 on the surface of the silicon substrate 1 is preferably electroplating or photoinduction electroplating. The nickel nucleation center is formed by electroplating or photoinduction electroplating, the operation is simple, the nucleation efficiency is high, and the cost is low. Compared with the PVD method, the method has the advantages that when the metal nickel nucleation center 2 is formed on the surface of the silicon substrate 1 by electroplating or photo-induced electro-plating, the technological process of laying a mask on a cell sheet in advance and then etching is not needed, the process is simple, and the equipment cost is low; other techniques, such as printing, are difficult to achieve at the atomic layer level, are very thin, and form nickel oxides; the ALD method is too expensive.
In the present invention, the electroplating may be performed in an apparatus as shown in fig. 3, with a silicon substrate 1 as a cathode, metallic nickel as an anode 4, the cathode and the anode 4 being placed in a plating solution 5 in a plating tank 6, and the electroplating process being controlled by a power supply 7.
In the present invention, the light-induced electroplating may be performed in an apparatus as shown in fig. 4, a silicon substrate 1 is used as a cathode, metallic nickel is used as an anode 4, the cathode is disposed above a plating solution 5, a surface to be plated is directly opposite to a light source 8 and is in contact with a liquid level of the plating solution 5, the anode 4 is disposed in the plating solution 5 in a plating tank 6, and the light-induced electroplating process is controlled by the light source 8.
In the invention, the electroplating or light-induced electroplating process only needs to grow the nickel nucleation center on the surface of the silicon substrate instead of forming the nickel layer, compared with the common electroplating or light-induced electroplating, the method is equivalent to pre-plating, and the amount of the adopted metal ions is very low. Therefore, preferably, in step a, the electroplating solution for electroplating or light-induced electroplating comprises: 10-100g/L (10 g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L and the like) of nickel sulfate, 5-20g/L (5 g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 10g/L, 20g/L and the like) of nickel chloride, 25-40g/L (25 g/L, 26g/L, 27g/L, 100g/L and the like) of boric acid, 28g/L, 29g/L, 30g/L, 31g/L, 32g/L, 33g/L, 34g/L, 35g/L, 36g/L, 37g/L, 38g/L, 39g/L, 40g/L, etc.), a wetting agent 0.2-3mL/L (which may be 0.2mL/L, 0.5mL/L, 1mL/L, 1.5mL/L, 2mL/L, 2.5mL/L, 3mL/L, etc.), a conductive compound 20-50g/L (which may be 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, etc.).
In the present invention, the electroplating or light-induced electroplating solution may be other electroplating solutions, and for example, in step a, the electroplating or light-induced electroplating solution includes: nickel sulfamate 20-200g/L (20/L, 40g/L, 60g/L, 80g/L, 100g/L, 120g/L, 140g/L, 160g/L, 180g/L, 200g/L, etc.), nickel chloride 5-35g/L (5 g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, etc.), boric acid 30-50g/L (30 g/L, 31g/L, 32g/L, 33g/L, 34g/L, 35g/L, 36g/L, 37g/L, 38g/L, 39g/L, 40g/L, 41g/L, etc.), 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 47g/L, 48g/L, 49g/L, 50g/L, etc.), a wetting agent 0.2-3mL/L (which may be 0.2mL/L, 0.5mL/L, 1mL/L, 1.5mL/L, 2mL/L, 2.5mL/L, 3mL/L, etc.), a conductive compound 20-50g/L (which may be 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, etc.).
In the present invention, the step of preparing the nickel nucleation center in step a corresponds to pre-plating of nickel, and too much nickel element cannot be plated, so that it is preferable to select a formulation with a low nickel ion concentration, which results in poor conductivity in the entire plating solution, and the conductive compound functions to reduce the resistance of the plating solution, thereby improving the plating quality.
Specifically, the nickel sulfate is NiSO4·7H2O, nickel chloride is NiCl6H2And O, the conductive compound is a compound containing a sulfonate group, and the sulfonate group is a strong ionization electrolyte and can effectively improve anions or cations in the solution, so that the conductivity of the plating solution is effectively improved. Further preferably, the conductive compound is one or more of sulfamic acid, methanesulfonic acid, sodium sulfamate and sodium methylsulfonate. Sulfamic acid, methanesulfonic acid, sodium sulfamate and sodium methylsulfonate have dual functions of conducting electricity and buffering agents.
Exemplary wetting agents are sodium lauryl sulfate and/or sodium diester succinate. Because the competitive reaction in the nickel electroplating process is a hydrogen evolution reaction, the wetting agent can adjust the surface tension of the surface, and avoid air bubbles and pinholes in the coating to influence the quality of the coating.
In the present invention, the plating conditions include: pH of 3.8-6.5 (3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.7, 5.9, 6.0, 6.5, etc.), temperature of 40-55 deg.C (40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C, 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C, 55 deg.C, etc.), and current density of 0.1-2A/dm2(may be 0.1A/dm)2、0.2A/dm2、0.4A/dm2、0.6A/dm2、0.8A/dm2、1A/dm2、1.2A/dm2、1.4A/dm2、1.6A/dm2、1.8A/dm2、2A/dm2Etc.) for 5-60s (5 s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, etc.);
in the present invention, the conditions of the light-induced plating include: the pH value is 3.8-6.5 (may be 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.7, 5.9, 6.0, 6.5, etc.), the temperature is 40-55 deg.C (may be 40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C, 50 deg.C, 51 deg.C, 52 deg.C, 54 deg.C, 55 deg.C, etc.), the illumination intensity is 0.1-2sun (may be 0.1sun, 0.2sun, 0.4sun, 0.8sun, 1.0sun, 1.2sun, 1.4sun, 1.6sun, 1.8sun, 2sun, etc.), the light is white light and/or green light (may be 5-5 s, 5.5 s, 5.5.5 s, 5.2 s, 5.7, 5.9, 6s, 5.5.5.5.5 s, 5s, etc.), and the like, 5s, 55s, etc.), and the like, 55s, and the like, 5s, etc., and the like, 5s, etc., and the like. White light simulates traditional sunlight because traditional solar cells are also directed to white light. The green light was chosen because the nickel plating solution was also green, which had a strong penetration in its solution
The plating solution formulation containing nickel sulfamate is preferable for the two plating solution formulations, because the plating solution containing nickel sulfamate has low stress and can prevent nickel-silicon from falling off due to stress.
In the invention, the metal nickel nucleation center is utilized, and the nickel metal atoms are accumulated near the metal nickel nucleation center by adopting a chemical plating method to form the nickel metal layer, so that the nickel metal layer can be crystallized finely by chemical plating, and the tensile force performance is better. Preferably, in the step B, the electroless plating solution for electroless plating includes: NiSO4·H2O15-40 g/L (15 g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, etc.), NaH2PO2·H2O10-30 g/L (10 g/L, 15g/L, 20g/L, 25g/L, 30g/L and the like can be selected), and sodium citrate 10-25g/L (10 g/L, 12g/L, 14g/L, 16g/L, 18g/L, 20g/L, 22g/L, 24g/L, 25g/L and the like can be selected).
Preferably, the chemical plating solution can also comprise sodium acetate and thiourea, wherein the dosage of the sodium acetate is 10-40g/L (10 g/L, 20g/L, 30g/L, 40g/L and the like), and the dosage of the thiourea is 20-120mg/L (20 mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 120mg/L and the like). The sodium acetate can play a buffering role, and the thiourea can be used as a stabilizer of the solution and has a function of accelerating the growth of nickel grains.
Further preferably, in step B, the electroless plating conditions include: the pH value is 8-10 (8, 8.5, 9, 9.5, 10, etc.), the temperature is 35-99 deg.C (35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 99 deg.C, etc.), and the time is 1-20min (1 min, 4min, 8min, 12min, 14min, 16min, 18min, 20min, etc.).
In the invention, the chemical plating is a redox reaction process, which comprises the following steps:
H2PO2 -+H2O→HPO3 -+2H+H+；
Ni2++2H→Ni+2H+。
in the present invention, the nickel layer obtained by electroless plating has a thickness of 10 to 500nm (which may be 10nm, 20nm, 30nm, 40nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, etc.).
In the present invention, the solvent of the plating solution is water.
On the other hand, the invention also provides a preparation method of the solar cell nickel electrode, which comprises the following steps:
step a: plating a nickel layer on the surface of the solar cell silicon substrate on which the grid needs to be manufactured by adopting the method for plating the nickel layer on the silicon substrate;
step b: and c, forming a copper layer on the surface of the nickel layer formed in the step a.
Preferably, the method for preparing the nickel electrode of the solar cell further comprises forming a silver layer on the surface of the copper layer.
As shown in fig. 5, the method for preparing the solar cell silicon substrate includes:
s1: texturing, namely placing an N-type silicon substrate 11 serving as a silicon substrate in texturing liquid for texturing;
the texturing solution comprises sodium hydroxide and an additive, wherein the concentration of the sodium hydroxide is 1-3 wt%, the additive is mainly organic micromolecules and can be preferentially adsorbed on a crystal face (111) to inhibit reaction, the texturing principle is that the principle of anisotropy of the sodium hydroxide on silicon corrosion is utilized, the density of the crystal face (100) is low and can be corroded preferentially, the density of the crystal face (111) is high, the corrosion rate is slow, so that a pyramid structure is formed, the crystal face (111) is equivalent to the middle diagonal of a cube, and the diagonals of several cubes form a structure similar to a tetrahedron.
S2: b diffusion, performing a boron diffusion process on the front surface of the silicon wafer to form a P-n junction to obtain a P + emitter 12;
taking the cell structure of an N-type passivated contact cell as an example, the cell structure is shown in fig. 5, the substrate is an N-type silicon wafer, and the p-N junction is on the front side, i.e. a positive junction structure; boron diffusion corresponds to boron doping of the substrate, the number of boron implanted into the silicon body per unit volume is about 1E19, is small relative to the number of silicon atoms per unit volume, the number of silicon atoms per unit volume is nE23 (n 1-10), boron is a trivalent element, silicon is tetravalent, and after pairing with four electrons of silicon, one hole remains, which is positively charged, corresponding to an acceptor, i.e. the p-region. The reaction equation:
BBr3+O2→B2O3；
B2O3+Si→B+SiO2。
BBr3is a liquid source, BBr3Is carried to a furnace tube by nitrogen, the reaction is carried out in the furnace tube, the reaction temperature is 800-1100 ℃, and the time is 1-4 h. The process comprises the following steps: firstly, loading a silicon wafer into a quartz boat, opening a furnace door, putting the quartz boat into a furnace tube, closing the furnace door, returning the temperature, detecting leakage, introducing required gas for reaction, blowing nitrogen after the reaction is finished, cooling, then discharging the quartz boat, and arranging the furnace tube with an air inlet system and a tail gas discharge device.
S3: etching to remove the p-n junction on the back and the borosilicate glass on the back;
s4: depositing a tunneling silicon oxide layer, namely depositing a layer of tunneling silicon oxide film 13 on both sides of a cleaned silicon wafer by using a thermal oxidation device, wherein the thickness of the tunneling silicon oxide film is 1-2 nm;
the deposition method can be a method for thermally growing silicon dioxide, and the specific process comprises the steps of loading a silicon wafer into a quartz boat, placing the quartz boat into a quartz tube, introducing oxygen, reacting the oxygen with silicon, and controlling the reaction temperature at 500-700 ℃;
Si+O2→SiO2；
s5: preparing a back polysilicon passivation layer, and depositing by adopting LPCVD equipment to form a polysilicon film 14 with the thickness of 80-200 nm;
s6: phosphorus diffusion, namely placing the silicon wafer in a phosphorus diffusion furnace tube at the diffusion temperature of 700-900 ℃, and forming an N-type doped polycrystalline silicon film on the back surface;
s7: performing winding plating cleaning, namely enabling the back of the silicon wafer to face upwards, passing through a chain type cleaning machine, taking borosilicate glass as a mask, removing the polysilicon film wound and plated on the front side, and removing the borosilicate glass on the front side by using hydrofluoric acid;
s8: preparing a front passivation film and a back passivation film, and depositing the passivation films on the front and back of the silicon wafer by using ALD (atomic layer deposition) and/or PECVD (plasma enhanced chemical vapor deposition) equipment to obtain a front passivation anti-reflection layer 15 and a back passivation layer 16;
s9: laser drilling or grooving is performed on the front passivation anti-reflection layer 15 and the back passivation layer 16 to open the gate region.
As shown in fig. 5, the prepared solar cell silicon substrate includes: the front passivation anti-reflection layer 15, the P + emitter 12, the N-type silicon substrate 11, the tunneling silicon oxide film 13, the polycrystalline silicon film 14 and the back passivation layer 16 are sequentially stacked, a groove forming region is arranged on the front passivation anti-reflection layer 15, and a gate region is formed on the back passivation layer 16 in a groove mode.
In one embodiment of the present invention, specifically, during electroplating or light-induced electroplating, the solar cell silicon substrate is placed in a plating solution, the P + emitter 12 is used as an anode, the polysilicon thin film 14 is used as a cathode, the gate region is electroplated, and the electroplating process is controlled by a power source or a light source.
In another embodiment of the present invention, specifically, during the electroplating or light-induced electroplating process, the solar cell silicon substrate is placed in a plating solution, the P + emitter 12 and the metal nickel are used as an anode together, the polysilicon thin film 14 is used as a cathode, the gate region is electroplated, and the electroplating process is controlled by a power supply or a light source.
In the present invention, the formation of the copper layer on the surface of the nickel layer formed in step a and the formation of the silver layer on the surface of the copper layer may be conventional methods in the art, and are not described herein again.
The process of the present invention is further illustrated by the following specific examples.
The electrode performance test methods in the following examples are as follows: and (3) testing the tension of the electrode: welding the electrode with a conventional welding strip, wherein the size of a contact point is 1.0mm x 0.6mm, the other end of the welding strip is fixed on a tension meter, a horizontal tension meter is adopted, the moving direction of the tension meter is 180 degrees to the direction of the welding strip, and the tension of the welding strip is measured; and (3) contact resistance testing: measuring the resistance of different thin grid lines by four probes, wherein the sheet resistance (measured value) among the thin grid lines comprises the line resistance of a metal layer, the transverse sheet resistance, the contact resistance and the line resistance, and measuring the contact resistance of the thin grid lines by conversion; testing the photoelectric conversion efficiency: and measuring the open-circuit voltage and the short-circuit current of the battery by using an IV tester under illumination, and calculating the photoelectric conversion efficiency of the battery.
Example 1
(1) Forming metal nickel nucleation centers on the surface of a solar cell silicon substrate needing to be provided with a grid electrode by adopting an electroplating method, wherein NiSO is contained in electroplating solution4·7H2Content of OIs 10g/L of NiCl2·6H2The content of O is 5g/L, H3BO3The content of (A) is 25g/L, the wetting agent (sodium dodecyl sulfate) is 1mL/L, the content of the conductive compound (sodium sulfamate) is 20g/L, the pH value is 3.8, the temperature is 50 ℃, and the current density is 1A/dm2The electroplating time is 60 s;
(2) utilizing a metal nickel nucleation center, loading the silicon wafer obtained in the step (1) into a flower basket, placing the flower basket into chemical plating solution for chemical plating, carrying out nickel metal atom accumulation near the metal nickel nucleation center to form a nickel metal layer, and carrying out NiSO (nickel oxide) in the chemical plating solution4·H2The content of O is 15g/L, NaH2PO2·H2The content of O is 20g/L, the content of sodium citrate is 10g/L, the pH value is 8.6, the temperature is 35 ℃, the time is 10min, and the nickel metal layer with the thickness of 200nm is obtained.
(3) And sequentially forming a copper layer and a silver layer outside the nickel metal layer.
The performance of the prepared electrode is measured, the mean value of the tensile force is 1.46N, and the contact resistance is 0.9mohm cm2The photoelectric conversion efficiency was 24%.
Example 2
(1) Forming a metal nickel nucleation center on the surface of a solar cell silicon substrate needing to be provided with a grid electrode by adopting a light-induced electroplating method, wherein NiSO is contained in electroplating solution4·7H2O content of 100g/L, NiCl2·6H2The content of O is 20g/L, H3BO3The content of (A) is 40g/L, the content of a wetting agent (sodium sulfosuccinate) is 3mL/L, the content of a conductive compound (sulfamic acid) is 50g/L, the pH value is 5.5, the temperature is 55 ℃, the illumination intensity is 1.5sun, and the electroplating time is 10 s;
(2) utilizing a metal nickel nucleation center, loading the silicon wafer obtained in the step (1) into a flower basket, placing the flower basket into chemical plating solution for chemical plating, carrying out nickel metal atom accumulation near the metal nickel nucleation center to form a nickel metal layer, and carrying out NiSO (nickel oxide) in the chemical plating solution4·H2O content of 40g/L, NaH2PO2·H2The content of O is 30g/L, the content of sodium citrate is 25g/L, the pH value is 10, the temperature is 99 ℃, the time is 10min, and a nickel metal layer with the thickness of 100nm is obtained.
(3) And sequentially forming a copper layer and a silver layer outside the nickel metal layer.
The performance of the prepared electrode is measured, the mean value of the tensile force is 1.46N, and the contact resistance is 0.98mohm cm2The photoelectric conversion efficiency was 24%.
Example 3
A nickel electrode for a solar cell was prepared in the same manner as in example 1, except that the plating solution contained 100g/L of nickel sulfamate and NiCl6H2The content of O is 20g/L, the content of boric acid is 40g/L, the content of wetting agent (sodium dodecyl sulfate) is 2mL/L, the content of conductive compound (sodium sulfamate) is 30g/L, and the current density is 1A/dm2The plating time was 20 s.
Example 4
A solar cell nickel electrode was prepared as in example 2, except that the plating solution contained 20g/L of nickel sulfamate and NiCl6H2The content of O is 5g/L, the content of boric acid is 30g/L, the content of a wetting agent (sodium sulfosuccinate) is 1mL/L, the content of a conductive compound (sulfamic acid) is 10g/L, the illumination intensity is 1.5sun, and the electroplating time is 50 s.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A method of plating a nickel layer on a silicon substrate, the method comprising the steps of:
step A: forming a metal nickel nucleation center on the surface of the silicon substrate;
and B: and B, putting the product obtained in the step A into a chemical nickel plating solution for chemical plating, and forming a nickel metal layer by using the metal nickel nucleation center obtained in the step A.
2. The method of claim 1, wherein the step a, the metal nickel nucleation centers are formed on the surface of the silicon substrate by electroplating or light-induced electroplating.
3. The method as claimed in claim 2, wherein the electroplating or light-induced electroplating solution in step a comprises: 10-100g/L of nickel sulfate, 5-20g/L of nickel chloride, 25-40g/L of boric acid, 0.2-3mL/L of wetting agent and 20-50g/L of conductive compound; or
In step a, the electroplating solution for electroplating or light-induced electroplating comprises: 20-200g/L of nickel sulfamate, 5-35g/L of nickel chloride, 30-50g/L of boric acid, 0.2-3mL/L of wetting agent and 20-50g/L of conductive compound.
4. The method of claim 3, wherein the nickel sulfate is NiSO4·7H2O, nickel chloride is NiCl6H2And O, the conductive compound is a sulfonate-containing compound.
5. The method of claim 4, wherein the conductive compound is one or more of sulfamic acid, methanesulfonic acid, sodium sulfamate, and sodium methylsulfonate.
6. The method of claims 3-5, wherein the plating conditions comprise: pH of 3.8-6.5, temperature of 40-55 deg.C, and current density of 0.1-2A/dm2The plating time is 5-60 s.
7. The method of claims 3-5, wherein the conditions of light-induced plating comprise: the pH value is 3.8-6.5, the temperature is 40-55 ℃, the illumination intensity is 0.1-2sun, the light is white light and/or green light, and the light-induced electroplating time is 5-60 s.
8. The method according to claim 1, wherein in step B, the electroless plating solution for electroless plating comprises: NiSO4·H2O 15-40g/L，NaH2PO2·H210-30g/L of O and 10-25g/L of sodium citrate.
9. The method of claim 8, wherein in step B, the electroless plating conditions comprise: the pH value is 8-10, the temperature is 35-99 deg.C, and the time is 1-20 min.
10. A method for preparing a nickel electrode of a solar cell, the method comprising:
a, step a: plating a nickel layer on the surface of a solar cell silicon substrate needing grid manufacturing by adopting the method of any one of claims 1 to 9;
step b: and c, forming a copper layer on the surface of the nickel layer formed in the step a.
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| CN202210278052.XA Pending CN114703468A (en) | 2022-03-21 | 2022-03-21 | Method for plating nickel layer on silicon substrate and preparation method of solar cell nickel electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115332391A (en) * | 2022-08-19 | 2022-11-11 | 扬州大学 | Solar cell photo-assisted metallization manufacturing device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115332391A (en) * | 2022-08-19 | 2022-11-11 | 扬州大学 | Solar cell photo-assisted metallization manufacturing device and method |
| CN115332391B (en) * | 2022-08-19 | 2023-02-28 | 扬州大学 | Solar cell photo-assisted metallization manufacturing device and method |
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