CN116936689A - Method for metallizing copper of silicon heterojunction solar cell - Google Patents
Method for metallizing copper of silicon heterojunction solar cell Download PDFInfo
- Publication number
- CN116936689A CN116936689A CN202310885236.7A CN202310885236A CN116936689A CN 116936689 A CN116936689 A CN 116936689A CN 202310885236 A CN202310885236 A CN 202310885236A CN 116936689 A CN116936689 A CN 116936689A
- Authority
- CN
- China
- Prior art keywords
- solar cell
- heterojunction solar
- silicon heterojunction
- copper
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 89
- 239000010949 copper Substances 0.000 title claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 88
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 87
- 239000010703 silicon Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000009713 electroplating Methods 0.000 claims abstract description 34
- 238000007747 plating Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000009472 formulation Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001465 metallisation Methods 0.000 claims description 16
- 206010070834 Sensitisation Diseases 0.000 claims description 14
- 230000008313 sensitization Effects 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920004890 Triton X-100 Polymers 0.000 claims description 3
- 239000013504 Triton X-100 Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- -1 polydithio-dipropyl Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000007788 roughening Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000001235 sensitizing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000005240 physical vapour deposition Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
Classifications
-
- 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
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Development (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a method for metallizing copper of a silicon heterojunction solar cell, which relates to the technical field of manufacturing of crystalline silicon solar cells and semiconductors and comprises the following steps of S1, carrying out pre-plating treatment on a patterned silicon heterojunction solar cell; s2, preparing a seed layer by performing an electroless copper plating process on the transparent conductive film of the patterned silicon heterojunction solar cell by an electroless copper plating method; and S3, performing copper electroplating process treatment on the patterned silicon heterojunction solar cell to obtain the metal copper electrode. The method for metallizing the silicon heterojunction solar cell, which is characterized by firstly electroless copper plating and then electroplating copper, has reasonable design, can control the width of the copper grid line to be less than 30 mu m, and truly realizes cost reduction and synergy of the silicon heterojunction solar cell.
Description
Technical Field
The invention relates to the technical field of crystalline silicon solar cells and semiconductor manufacturing, in particular to the technical field of a method for copper metallization of a silicon heterojunction solar cell.
Background
Amorphous silicon/crystalline silicon Heterojunction (HJT) solar cells have the advantages of high conversion efficiency, low process temperature, simplified process, high stability and the like, and become important points for research in the field of current solar cells. However, the current method for preparing the metal electrode by screen printing low-temperature silver paste and low-temperature sintering is generally adopted for metallization of the silicon heterojunction solar cell, and the paste cost is increased by 0.1-0.2 yuan/W compared with the conventional passivation emitter and back cell technology (PERC). In addition, the width and the aspect ratio of the silver electrode are limited by the screen printing process, which prevents further improvement of the battery efficiency.
In order to reduce the cost of the silicon heterojunction solar cell and improve the cell efficiency, an electroplated copper grid line technology is introduced in the industry to replace a screen printing low-temperature silver paste technology, and the method comprises five steps, namely, prefabricating a copper seed layer on a transparent conductive film of the silicon heterojunction solar cell, then adopting a dry film to expose and develop the copper seed layer to form a pattern, then electroplating the copper grid line, and finally removing the dry film and the copper seed layer through etching and cleaning to complete a copper metallization process. However, since expensive Physical Vapor Deposition (PVD) equipment is required in the process, and the etching back step of the seed layer increases the complexity and cost of the process, it is difficult to achieve the cost reduction effect. In addition, the prior patent discloses the following technology:
patent publication No. CN115084289A, entitled "heterojunction solar cell Metal electrode and preparation method thereof, heterojunction solar cell", discloses the following: a method for paving conductive metal wires to replace electroplated copper by a heterojunction solar cell; patent publication number CN113571606a entitled "method and apparatus for making heterojunction solar cell electrodes" discloses the following: a heterojunction battery metallization method comprises the steps of prefabricating a nickel-chromium alloy and copper seed layer by using vacuum coating equipment, and then welding a tin alloy grid line; patent publication No. CN113066897B, entitled "maskless preparation method of heterojunction solar cell copper electrode", discloses the following: a maskless preparation method of a laser-assisted heterojunction solar cell copper electrode.
In the prior art and the method disclosed in the patent, expensive equipment still cannot be avoided in the process, the electrode width is still larger, and the purposes of reducing the cost of the heterojunction solar cell and improving the cell efficiency cannot be really achieved.
Disclosure of Invention
The invention aims at: the invention provides a method for metallizing copper of a silicon heterojunction solar cell, which aims to solve the technical problems that expensive equipment is required to be used in copper electroplating of the heterojunction solar cell, the process complexity is high, the electrode grid line width is difficult to achieve cost reduction.
The invention adopts the following technical scheme for realizing the purposes:
the invention provides a method for metallizing copper of a silicon heterojunction solar cell, which comprises the following steps:
s1, carrying out pre-plating treatment on a patterned silicon heterojunction solar cell;
s2, preparing a seed layer by performing an electroless copper plating process on the transparent conductive film of the patterned silicon heterojunction solar cell by an electroless copper plating method;
and S3, performing copper electroplating process treatment on the patterned silicon heterojunction solar cell to obtain the metal copper electrode.
Specifically, the method for metallizing the silicon heterojunction solar cell by electroless copper plating and then electroplating copper can control the width of the copper grid line to be less than 30 mu m, and truly realize cost reduction and synergy of the silicon heterojunction solar cell.
In one embodiment, in step S1, the pre-plating treatment of the patterned silicon heterojunction solar cell is performed according to the following method:
s11, cleaning: placing the patterned silicon heterojunction solar cell in absolute ethyl alcohol with the temperature of 20-40 ℃ for cleaning for 1-10 minutes;
s12, oil removal: placing the cleaned patterned silicon heterojunction solar cell in an oil removing liquid at 20-40 ℃ for oil removal for 1-8 minutes, and then cleaning the patterned silicon heterojunction solar cell with tap water or deionized water for 1-3 minutes;
s13, etching: the patterned silicon heterojunction solar cell after oil removal is placed in etching solution at 20-40 ℃ for roughening treatment for 1-8 minutes, and then is washed by deionized water for 1-3 minutes;
s14, sensitization: placing the etched patterned silicon heterojunction solar cell in a sensitization solution at 20-40 ℃ for sensitization for 3-10 minutes;
s15, activating: the sensitized patterned silicon heterojunction solar cell is placed in an activating solution at 20-40 ℃ for sensitization for 3-10 minutes, and then is washed by deionized water for 1-3 minutes;
s16, reduction: placing the activated patterned silicon heterojunction solar cell at 20-40 ℃ and 10-20 g/L NaH 2 PO 2 ·H 2 The O is reduced in the reducing solution for 1 to 5 minutes, and then is washed by deionized water for 1 to 3 minutes.
In one embodiment, as shown in table 1, in step S12, the degreasing fluid formulation includes the following components: 10-30 g/L NaOH, 20-30 g/L Na 2 CO 3 、20～30g/L Na 3 PO 4 ·12H 2 O、10～15Na 2 SiO 3 1-3 g/L of triton X-100.
Table 1 deoiling liquid formulation for silicon heterojunction solar cell
In one embodiment, as shown in table 2, in step S13, the formulation of the etching solution includes the following components: 20-30 ml/L H 2 O 2 、35～45g/L Na 2 SO 4 、10～15g/L NH 4 F. 15-25 g/L citric acid and 1-2 ml/L H 2 SO 4 。
Table 2 etching solution formulation for silicon heterojunction solar cell
In one embodiment, as shown in table 3, in step S14, the formulation of the sensitizing solution comprises the following components: 4-6 g/L NaCN, 8-12 g/L ethylenediamine and 8-12 g/L CuCl.
Table 3 sensitization solution formulation for silicon heterojunction solar cells
In one embodiment, as shown in table 4, in step S15, the activating solution formulation includes the following components: 0.2-0.8 g/L PdCl 2 And 3-7 ml/L concentrated hydrochloric acid.
Table 4 activating solution formulation for silicon heterojunction solar cell
In one embodiment, as shown in table 5, in step S15, the reducing solution formulation includes the following components: 10-20 g/L NaH 2 PO 2 ·H 2 O。
Table 5 reducing solution formulation for silicon heterojunction solar cell
In one embodiment, in step S2, a seed layer is prepared by performing an electroless copper plating process on a transparent conductive film of a patterned silicon heterojunction solar cell by an electroless copper plating method, which comprises the following specific steps:
and placing the reduced patterned silicon heterojunction solar cell in an electroless plating solution at 60-90 ℃ for chemical plating for 2-10 minutes, and then cleaning with tap water or deionized water for 1-3 minutes.
In one embodiment, as shown in table 6, the electroless copper plating solution formulation includes the following components: 5-30 g/LCuSO 4 ·5H 2 O、5～30g/L NaH 2 PO 2 ·H 2 O, 5-30 g/L citric acid, 2-20 g/LNaCH 3 COO·3H 2 O, 1-8 g/L sodium dodecyl benzene sulfonate and 1-5 mg/L thiourea.
Table 6 chemical copper plating solution formulation for silicon heterojunction solar cell
In one embodiment, in step S3, the patterned silicon heterojunction solar cell is subjected to a copper electroplating process to obtain a metal copper electrode, which specifically comprises the following steps:
and placing the patterned silicon heterojunction solar cell subjected to electroless copper plating in an electroplating solution to be connected with a power supply cathode, placing a phosphorus copper plate in the electroplating solution to be connected with a power supply anode, electroplating for 5-30 minutes at 20-40 ℃, then washing with deionized water for 1-3 minutes, and finally drying or baking to obtain the metal copper electrode with good adhesive force and conductivity on the patterned silicon heterojunction solar cell.
Specifically, the copper electroplating mode is horizontal electroplating, the mode of connecting the graphical silicon heterojunction solar cell with the power supply negative electrode is multipoint contact type, and the current density is 1-10A/dm 2 。
In one embodiment, as shown in Table 7, the formulation of the plating solution includes the following components: 150-220 g/LCuSO 4 ·5H 2 O, 50-100 ml/L concentrated sulfuric acid, 0.02-0.08 g/L chloride ion, 0.001-0.01 g/L sodium polydithio-dipropyl sulfonate, 0.1-0.3 ml/L polyethylene glycol and 0.001-0.02 ml/L5-amino-1, 3, 4-thiadiazole-2-mercaptan.
Table 7 silicon heterojunction solar cell electroplated copper solution formulation
The beneficial effects of the invention are as follows:
forming a seed layer by electroless copper plating on the patterned silicon heterojunction solar cell transparent conductive film, and then electroplating copper to realize metallization; compared with the traditional five-step copper electroplating technology, the method only needs four steps, omits the steps of prefabricating the copper seed layer and finally back-engraving the seed layer by using high-end equipment such as PVD (physical vapor deposition) and the like, simplifies the production process route and reduces the production cost. In addition, compared with the common screen printing low-temperature silver paste technology, the method can limit the width of the copper metal grid line to be less than 30 mu m, increase the illumination area of the heterojunction battery and further improve the battery efficiency.
Drawings
FIG. 1 is a schematic diagram of a process flow for copper metallization of a silicon heterojunction solar cell according to the present invention;
FIG. 2 is a graphical silicon heterojunction solar cell physical diagram;
FIG. 3 is an SEM image of example 1 for preparing dense metal copper grid lines on the surface of a complex patterned silicon heterojunction solar cell;
FIG. 4 is an SEM image of a patterned silicon heterojunction solar cell after electroless copper plating;
fig. 5 is an SEM image of a patterned silicon heterojunction solar cell after electroless copper plating and then electroplating.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In describing embodiments of the present invention, it should be noted that the directions or positional relationships indicated by the terms "inner", "outer", "upper", etc. are directions or positional relationships based on those shown in the drawings, or those that are conventionally put in place when the inventive product is used, are merely for convenience of description and simplification of description, and are not indicative or implying that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Example 1
As shown in fig. 1, the embodiment provides a method for copper metallization of a silicon heterojunction solar cell, which includes the following steps:
s001, cleaning: the patterned silicon heterojunction solar cell (figure 2) was placed in absolute ethanol at 25 ℃ for 3 minutes;
s002, degreasing: placing the cleaned patterned silicon heterojunction solar cell in a degreasing liquid at 25 ℃ for degreasing for 5 minutes, and then cleaning the patterned silicon heterojunction solar cell with deionized water for 1 minute, wherein the degreasing liquid comprises the following components: 20g/LNaOH, 25g/L Na 2 CO 3 、25g/L Na 3 PO 4 ·12H 2 O、10g/L Na 2 SiO 3 And 1g/L triton X-100;
s003, etching: the patterned silicon heterojunction solar cell after oil removal is placed in etching solution at 25 ℃ for roughening treatment3 minutes, then washing with deionized water for 1 minute, wherein the etching solution comprises the following components: 20ml/L H 2 O 2 、40g/L Na 2 SO 4 、10g/L NH 4 F. 20g/L citric acid and 1ml/L H 2 SO 4 ；
S004, sensitization: placing the etched patterned silicon heterojunction solar cell in a sensitization solution at 25 ℃ for sensitization for 5 minutes, wherein the sensitization solution comprises the following components: 4g/L NaCN, 8g/L ethylenediamine and 10g/LCuCl;
s005, activation: the sensitized graphical silicon heterojunction solar cell is placed in an activating solution at 25 ℃ for sensitization for 5 minutes and then is washed by deionized water for 1 minute, and the formula of the activating solution is 0.3g/L PdCl 2 And 3ml/L concentrated hydrochloric acid;
s006, reduction: placing the activated patterned silicon heterojunction solar cell at 25 ℃ for 10g/LNaH 2 PO 2 ·H 2 Reducing in the O reducing solution for 3 minutes, and then cleaning with deionized water for 1 minute;
s007, electroless copper plating: placing the reduced patterned silicon heterojunction solar cell in an electroless plating solution at 75 ℃ for electroless plating for 3 minutes, and then cleaning the patterned silicon heterojunction solar cell for 1 minute by tap water, wherein the electroless plating solution comprises the following components: 15g/L CuSO 4 ·5H 2 O、15g/L NaH 2 PO 2 ·H 2 O, 5g/L citric acid, 2g/LNaCH 3 COO·3H 2 O, 2g/L sodium dodecyl benzene sulfonate, and 2mg/L thiourea;
s008, electroplated copper: the patterned silicon heterojunction solar cell subjected to electroless copper plating is placed in an electroplating solution and is connected with the negative electrode of a power supply, a phosphorus copper plate is placed in the electroplating solution and is connected with the positive electrode of the power supply, the electroplating mode is horizontal electroplating, the connection mode of the patterned silicon heterojunction solar cell and the negative electrode of the power supply is multipoint contact type, and the current density is 1A/dm 2 Electroplating for 10 minutes at 25 ℃, then washing for 1 minute by deionized water, and finally drying or baking to obtain the metal copper electrode with good adhesion and conductivity on the patterned silicon heterojunction solar cell. Wherein the formula of the electroplating solution comprises the following components: 180g/L CuSO 4 ·5H 2 O, 70ml/L concentrated sulfuric acid, 0.05g/L chloride ion, 0.005g +.Sodium L polydithio-dipropyl sulfonate, 0.2ml/L polyethylene glycol and 0.005 ml/L5-amino-1, 3, 4-thiadiazole-2-thiol.
As shown in fig. 3, embodiment 1 can prepare a dense metal copper grid line on the surface of a complex patterned silicon heterojunction solar cell, the width of the copper grid line can be customized along with the patterning specification, expensive PVD equipment and the like are not required, and the copper metallization is realized only by a simple pretreatment-electroless copper plating-copper electroplating process, so that the cost reduction purpose of the silicon heterojunction solar cell is realized.
Example 2
In this embodiment, in step S007, the electroless copper plating time is 5 minutes, and the patterned silicon heterojunction solar cell after electroless copper plating is shown in fig. 4; step 8 copper electroplating current density of 2A/dm 2 Electroplating time is 15 minutes; the rest of the arrangement in this embodiment is the same as that in embodiment 1.
As shown in fig. 4, the width of the copper metal gate line prepared in example 2 is only 27 μm, which is significantly smaller than the currently mainstream 40 μm copper electroplating process. Taking a 6-inch silicon wafer with a side length of 156.75mm as shown in fig. 2 as an example, a single-sided 160 grid line can save 32.5% of silver paste consumption, and meanwhile, the photoelectric conversion efficiency is improved by 0.33%, so that the cost reduction and efficiency improvement of the silicon heterojunction solar cell are truly realized.
Example 3
In this example, in step S007, electroless copper plating time was 8 minutes; step 8 copper electroplating current density of 3A/dm 2 Electroplating time is 20 minutes; the rest of the settings in this example are the same as those in example 1; the metal copper electrode produced on the patterned silicon heterojunction solar cell is shown in fig. 5.
As shown in fig. 5, the width of the copper metal gate line prepared in example 2 is only 32 μm, which is significantly smaller than the currently mainstream 40 μm copper electroplating process. Taking a 6-inch silicon wafer with a side length of 156.75mm as shown in fig. 2 as an example, a single-sided 160 grid line can save 20% of silver paste consumption, and meanwhile, the photoelectric conversion efficiency is improved by 0.21%, so that the cost reduction and efficiency improvement of the silicon heterojunction solar cell are realized.
Comparative example
In the background art, patent publication No. CN113571606a, entitled "method and apparatus for manufacturing heterojunction solar cell electrode" is used as a comparative example.
The heterojunction battery metallization method disclosed by the comparative example comprises the steps of prefabricating the nickel-chromium alloy and the copper seed layer by using vacuum coating equipment, then welding the tin alloy grid line, wherein the width of the prepared metal grid line is 40 mu m at the minimum, and the expensive vacuum coating equipment is used, so that the process is complex, and obviously the cost reduction and synergy effects of the patent are not achieved.
Claims (10)
1. A method for copper metallization of a silicon heterojunction solar cell, comprising the steps of:
s1, pre-plating treatment: carrying out pre-plating treatment on the patterned silicon heterojunction solar cell;
s2, electroless copper plating treatment: preparing a seed layer by performing an electroless copper plating process on the transparent conductive film of the patterned silicon heterojunction solar cell by an electroless copper plating method;
s3, electroplating copper treatment: and then carrying out copper electroplating process treatment on the patterned silicon heterojunction solar cell to obtain the metal copper electrode.
2. The method of copper metallization of a silicon heterojunction solar cell as claimed in claim 1, wherein in step S1, the pre-plating treatment is performed as follows:
s11, cleaning: placing the patterned silicon heterojunction solar cell in absolute ethyl alcohol with the temperature of 20-40 ℃ for cleaning for 1-10 minutes;
s12, oil removal: placing the cleaned patterned silicon heterojunction solar cell in an oil removing liquid at 20-40 ℃ for oil removal for 1-8 minutes, and then cleaning the patterned silicon heterojunction solar cell with tap water or deionized water for 1-3 minutes;
s13, etching: the patterned silicon heterojunction solar cell after oil removal is placed in etching solution at 20-40 ℃ for roughening treatment for 1-8 minutes, and then is washed by deionized water for 1-3 minutes;
s14, sensitization: placing the etched patterned silicon heterojunction solar cell in a sensitization solution at 20-40 ℃ for sensitization for 3-10 minutes;
s15, activating: the sensitized patterned silicon heterojunction solar cell is placed in an activating solution at 20-40 ℃ for sensitization for 3-10 minutes, and then is washed by deionized water for 1-3 minutes;
s16, reduction: placing the activated patterned silicon heterojunction solar cell at 20-40 ℃ and 10-20 g/L NaH 2 PO 2 ·H 2 The O is reduced in the reducing solution for 1 to 5 minutes, and then is washed by deionized water for 1 to 3 minutes.
3. The method of claim 2, wherein in step S12, the degreasing liquid comprises the following components: 10-30 g/L NaOH, 20-30 g/L Na 2 CO 3 、20～30g/L Na 3 PO 4 ·12H 2 O、10～15Na 2 SiO 3 1-3 g/L of triton X-100.
4. The method of claim 2, wherein in step S13, the etching solution comprises the following components: 20-30 ml/L H 2 O 2 、35～45g/L Na 2 SO 4 、10～15g/L NH 4 F. 15-25 g/L citric acid and 1-2 ml/L H 2 SO 4 。
5. The method of claim 2, wherein in step S14, the formulation of the sensitizing solution comprises the following components: 4-6 g/L NaCN, 8-12 g/L ethylenediamine and 8-12 g/L CuCl.
6. The method of copper metallization of a silicon heterojunction solar cell according to claim 2, wherein in step S15, the activating solution formulation comprises the following components: 0.2-0.8 g/L PdCl 2 And 3-7 ml/L concentrated hydrochloric acid.
7. The method of copper metallization of a silicon heterojunction solar cell as claimed in claim 2, wherein in step S2, the electroless copper plating process comprises the following specific steps:
and placing the reduced patterned silicon heterojunction solar cell in an electroless plating solution at 60-90 ℃ for chemical plating for 2-10 minutes, and then cleaning with tap water or deionized water for 1-3 minutes.
8. The method of copper metallization of a silicon heterojunction solar cell of claim 7, wherein the electroless copper plating solution formulation comprises the following components: 5-30 g/L CuSO 4 ·5H 2 O、5～30g/L NaH 2 PO 2 ·H 2 O, 5-30 g/L citric acid, 2-20 g/L NaCH 3 COO·3H 2 O, 1-8 g/L sodium dodecyl benzene sulfonate and 1-5 mg/L thiourea.
9. The method for copper metallization of a silicon heterojunction solar cell as claimed in claim 8, wherein in the step S3, the specific steps of the electroplated copper treatment are as follows:
and placing the patterned silicon heterojunction solar cell subjected to electroless copper plating in an electroplating solution to be connected with a power supply cathode, placing a phosphorus copper plate in the electroplating solution to be connected with a power supply anode, electroplating for 5-30 minutes at 20-40 ℃, then washing with deionized water for 1-3 minutes, and finally drying or baking to obtain the metal copper electrode with good adhesive force and conductivity on the patterned silicon heterojunction solar cell.
10. The method of copper metallization of a silicon heterojunction solar cell of claim 9, wherein the formulation of the electroplating solution comprises the following components: 150-220 g/L CuSO 4 ·5H 2 O, 50-100 ml/L concentrated sulfuric acid, 0.02-0.08 g/L chloride ion, 0.001-0.01 g/L sodium polydithio-dipropyl sulfonate, 0.1-0.3 ml/L polyethylene glycol and 0.001-0.02 ml/L5-amino-1, 3, 4-thiadiazole-2-mercaptan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310885236.7A CN116936689A (en) | 2023-07-18 | 2023-07-18 | Method for metallizing copper of silicon heterojunction solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310885236.7A CN116936689A (en) | 2023-07-18 | 2023-07-18 | Method for metallizing copper of silicon heterojunction solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116936689A true CN116936689A (en) | 2023-10-24 |
Family
ID=88392010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310885236.7A Pending CN116936689A (en) | 2023-07-18 | 2023-07-18 | Method for metallizing copper of silicon heterojunction solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116936689A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776495A (en) * | 2012-07-13 | 2012-11-14 | 南京航空航天大学 | Chemical nickel-plating method for capacitive touch screen indium tin oxide (ITO) wiring |
| CN103160817A (en) * | 2011-12-19 | 2013-06-19 | 李平 | Chemical copper plating solution |
| CN106435664A (en) * | 2016-08-16 | 2017-02-22 | 广东工业大学 | Electro-coppering solution of soluble anode for hole filling |
| CN108649077A (en) * | 2018-06-21 | 2018-10-12 | 苏州太阳井新能源有限公司 | A kind of two-sided galvanic metallization solar battery sheet of no main grid, production method and methods for using them |
-
2023
- 2023-07-18 CN CN202310885236.7A patent/CN116936689A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160817A (en) * | 2011-12-19 | 2013-06-19 | 李平 | Chemical copper plating solution |
| CN102776495A (en) * | 2012-07-13 | 2012-11-14 | 南京航空航天大学 | Chemical nickel-plating method for capacitive touch screen indium tin oxide (ITO) wiring |
| CN106435664A (en) * | 2016-08-16 | 2017-02-22 | 广东工业大学 | Electro-coppering solution of soluble anode for hole filling |
| CN108649077A (en) * | 2018-06-21 | 2018-10-12 | 苏州太阳井新能源有限公司 | A kind of two-sided galvanic metallization solar battery sheet of no main grid, production method and methods for using them |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105449014B (en) | The solar cell of metallic grid with plating | |
| CN113130671A (en) | Silicon heterojunction solar cell and preparation method thereof | |
| US8426236B2 (en) | Method and structure of photovoltaic grid stacks by solution based processes | |
| CN113066897B (en) | Maskless preparation method of copper electrode of heterojunction solar cell | |
| CN108649077A (en) | A kind of two-sided galvanic metallization solar battery sheet of no main grid, production method and methods for using them | |
| CN108400175A (en) | A kind of heterojunction solar battery and preparation method with electroplated electrode | |
| US9916936B2 (en) | Method for forming conductive electrode patterns and method for manufacturing solar cells comprising the same | |
| KR100757797B1 (en) | Manufacture method for rear contact in single crystal solar cell | |
| CN110137278A (en) | In-situ reducing prepares heterojunction solar battery of plating seed layer and preparation method thereof | |
| WO2023185350A1 (en) | Method for forming gate line electrode of photovoltaic device and photovoltaic device | |
| CN103236415A (en) | Thin film hybrid integrated circuit electroplating method | |
| TWI408253B (en) | Light induced electroless plating | |
| CN116936689A (en) | Method for metallizing copper of silicon heterojunction solar cell | |
| JPH05235387A (en) | Manufacture of solar cell | |
| CN104576824A (en) | Novel method for slotting front grid line electrode of crystalline silicon solar battery and manufacturing method of solar battery | |
| WO2013143350A1 (en) | Solar cell, module and method for manufacturing solar cell electrode | |
| KR20030088665A (en) | High efficient solar cell and fabrication method thereof | |
| CN112216766A (en) | Manufacturing method of crystalline silicon solar cell and crystalline silicon solar cell | |
| CN220208979U (en) | Gate line electrode of heterojunction solar cell | |
| CN116960199B (en) | Manufacturing method of metal grid line electrode on heterojunction solar cell | |
| CN218932348U (en) | Novel heterojunction solar cell grid line-based electroplating device | |
| CN115976588A (en) | Electrode preparation method based on micro-area metallization and solar cell | |
| TW202207485A (en) | Preparation method of double-sided P-type battery back structure which is allowed for the passage of large currents and can improve electroplating efficiency and product qualification rate | |
| CN117476802A (en) | Low-cost heterojunction solar cell and preparation method thereof | |
| CN115332398A (en) | Low-cost metal electrode preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |