CN112126952A - Copper electroplating solution for heterojunction solar cell and preparation method thereof - Google Patents
Copper electroplating solution for heterojunction solar cell and preparation method thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- 239000010949 copper Substances 0.000 title claims abstract description 74
- 238000009713 electroplating Methods 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 45
- 230000008025 crystallization Effects 0.000 claims abstract description 45
- 239000003381 stabilizer Substances 0.000 claims abstract description 43
- 150000001879 copper Chemical class 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 239000008139 complexing agent Substances 0.000 claims abstract description 35
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims abstract description 15
- WYWHKKSPHMUBEB-UHFFFAOYSA-N tioguanine Chemical compound N1C(N)=NC(=S)C2=C1N=CN2 WYWHKKSPHMUBEB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 12
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000005282 brightening Methods 0.000 claims description 12
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- 239000001472 potassium tartrate Substances 0.000 claims description 3
- 229940111695 potassium tartrate Drugs 0.000 claims description 3
- 235000011005 potassium tartrates Nutrition 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- VJSWPZHJBUHZGI-UHFFFAOYSA-L dipotassium;chloride;hydroxide Chemical compound [OH-].[Cl-].[K+].[K+] VJSWPZHJBUHZGI-UHFFFAOYSA-L 0.000 claims description 2
- 229960001367 tartaric acid Drugs 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 32
- 230000008021 deposition Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 30
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- JTEQZWNDYJRHSC-UHFFFAOYSA-N C1(=CC=CC=C1)OS(=S)(=S)CCC.[Na] Chemical compound C1(=CC=CC=C1)OS(=S)(=S)CCC.[Na] JTEQZWNDYJRHSC-UHFFFAOYSA-N 0.000 description 9
- 229960003512 nicotinic acid Drugs 0.000 description 9
- 235000001968 nicotinic acid Nutrition 0.000 description 9
- 239000011664 nicotinic acid Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 7
- 125000005619 boric acid group Chemical group 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 4
- 229940081974 saccharin Drugs 0.000 description 4
- 235000019204 saccharin Nutrition 0.000 description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- MRGUSFYIQDLKNZ-UHFFFAOYSA-M sodium;prop-1-yne-1-sulfonate Chemical compound [Na+].CC#CS([O-])(=O)=O MRGUSFYIQDLKNZ-UHFFFAOYSA-M 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 230000008859 change 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
- 238000005238 degreasing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LWLVRCRDPVJBKL-UHFFFAOYSA-M sodium;prop-2-ynoate Chemical compound [Na+].[O-]C(=O)C#C LWLVRCRDPVJBKL-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention belongs to the technical field of metal surface treatment, and particularly relates to a copper electroplating solution for a heterojunction solar cell and a preparation method thereof. The copper electroplating solution for the heterojunction solar cell comprises copper salt, a complexing agent, conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer. The crystallization refiner consists of saccharin, sodium propynyl sulfonate and polyvinyl alcohol according to the mass ratio of 8-10:4-6: 1-2. The stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 11-13:4-7: 1. The copper plating film obtained after the copper electroplating solution for the heterojunction solar cell is adopted for electroplating has small deposition stress, and the reliability of a plated part is obviously improved. The copper plating film obtained by electroplating with the copper electroplating solution for the heterojunction solar cell is uniform, compact and bright, and the quality of the plating layer is obviously improved.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a copper electroplating solution for a heterojunction solar cell and a preparation method thereof.
Background
Since the 21 st century, the world's industries have rapidly developed and the earth has undergone a change from one month to another. The economic development, the living standard is gradually improved, and the life is more comfortable and faster. But advances have been made at the cost of energy consumption at an alarming rate. The limited non-renewable energy resources on the earth, mainly fossil energy resources such as petroleum, coal and natural gas, are consumed every day. The fossil energy is essentially a part of energy radiated to the earth by solar energy over tens of thousands of years or even longer, and is stored in ancient plants, and the energy is changed into the energy mineral deposit on the earth today through the change of Canghai mulberry field. These fossil energy sources have been consumed in significant proportions over thousands of years in humans, especially in the last hundred years of explosive industrial development.
A solar cell may also be referred to as a photovoltaic cell, which is a novel power generation technology for directly converting solar radiation into electric energy by using a photovoltaic effect, and is considered as one of the most promising renewable energy technologies due to its advantages of sufficient resources, cleanliness, safety, long service life, and the like. The crystalline silicon solar cell includes a single crystalline silicon solar cell, a polycrystalline silicon solar cell, a high efficiency crystalline silicon solar cell, and the like. The single crystal silicon solar cell has high conversion efficiency and mature technology, but the manufacturing cost of the cell is high due to the fact that a high-purity single crystal silicon rod is required to be used as a raw material, and the cell is difficult to popularize and apply on a large scale. The manufacturing process of the polycrystalline silicon solar cell is similar to that of the monocrystalline silicon solar cell, and the manufacturing cost of the polycrystalline silicon solar cell is lower than that of the monocrystalline silicon solar cell. However, the photoelectric conversion efficiency of the polycrystalline silicon solar cell is lower than that of the single crystalline silicon solar cell, and the service life of the polycrystalline silicon solar cell is also shorter than that of the single crystalline silicon solar cell.
The heterojunction solar cell is a novel efficient cell technology, integrates the advantages of the monocrystalline silicon solar cell and the amorphous silicon solar cell, and has the characteristics of simple structure, low temperature of the preparation process, higher conversion efficiency, good high-temperature characteristic and the like, so that the heterojunction solar cell has great market potential. The main structure of the heterojunction solar cell is as follows: depositing a thin film intrinsic amorphous silicon layer and an amorphous silicon emitter layer on the light receiving surface of the silicon substrate in sequence to form a heterojunction with a thin film intrinsic amorphous silicon interlayer; and depositing a transparent conductive oxide layer on the amorphous silicon thin layer with the two doped surfaces by a sputtering method, and finally forming a grid-shaped metal electrode on the transparent conductive oxide layer. Forming a grid-shaped metal electrode as a key step for manufacturing the heterojunction solar cell, wherein the conventional method comprises the following steps: and manufacturing a first electroplated copper lamination of the metal grid line by electroplating, wherein the first electroplated copper lamination is used as a main conducting layer of the metal grid line, and manufacturing a second electroplated tin lamination as a welding assistant layer of the metal grid line. Electroplating is a process of plating a thin layer of metal or alloy on the surface of a material by using an electrolysis method, and can be designed to produce an extremely thin plating layer with excellent performance, so that the electroplating method is widely applied to rare and precious metal plating layers. However, the plating layer electroplated by the copper electroplating solution for the existing heterojunction solar cell has the problems of large stress, brittle plating layer, unsatisfactory plating layer quality and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a copper electroplating solution for a heterojunction solar cell and a preparation method thereof. The copper plating film obtained after the copper electroplating solution for the heterojunction solar cell is adopted for electroplating has small deposition stress, and the reliability of a plated part is obviously improved. The copper plating film obtained by electroplating with the copper electroplating solution for the heterojunction solar cell is uniform, compact and bright, and the quality of the plating layer is obviously improved.
The technical scheme of the invention is as follows:
the copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer.
Further, the copper electroplating solution for the heterojunction solar cell comprises 28-35 g/L of copper salt, 52-60 g/L of complexing agent, 40-46 g/L of conductive salt, 2-4 g/L of crystallization refiner, 1-3 g/L of stress remover, 0.4-1 g/L of brightener and 35-45 g/L of pH stabilizer.
Further, the content of the copper salt is 33g/L, the content of the complexing agent is 54g/L, the content of the conductive salt is 45g/L, the content of the crystallization refiner is 3g/L, the content of the stress remover is 2g/L, the content of the brightener is 0.7g/L, and the content of the pH stabilizer is 38 g/L.
Further, the copper salt is copper chloride, copper sulfate or copper citrate.
Further, the complexing agent is one or more of citric acid, tartaric acid, potassium citrate and potassium tartrate.
Further, the crystallization refiner consists of saccharin, sodium propynyl sulfonate and polyvinyl alcohol according to the mass ratio of 8-10:4-6: 1-2.
Further, the crystallization refiner consists of saccharin, sodium propynyl sulfonate and polyvinyl alcohol according to the mass ratio of 10:5: 1.
Further, the brightening agent consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 2-5: 9-15.
Further, the brightening agent consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 3: 14.
Further, the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 11-13:4-7: 1.
Further, the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 12:5: 1.
In addition, the invention also provides a preparation method of the copper electroplating solution for the heterojunction solar cell, which comprises the following steps:
s1, adding a pH stabilizer into water, stirring until the pH stabilizer is completely dissolved, adding a complexing agent, and stirring until the pH stabilizer is completely dissolved to obtain a solution A;
s2, under the condition of stirring, adding copper salt into the solution A obtained in the step S1, and stirring until the copper salt is completely dissolved to obtain a solution B;
s3, under the condition of stirring, adding conductive salt into the solution B obtained in the step S2, and stirring until the conductive salt is completely dissolved to obtain a solution C;
s4, adding a brightening agent, a crystallization refiner and a stress remover into the solution C obtained in the step S3 under the stirring condition, and stirring until the brightening agent, the crystallization refiner and the stress remover are completely dissolved to obtain a solution D;
and S5, under the stirring condition, adding potassium hydroxide into the solution D obtained in the step S4, and adjusting the pH value to 8-9 to obtain the potassium hydroxide-potassium chloride solution.
In the invention, the crystallization refiner consisting of saccharin, sodium propiolate and polyvinyl alcohol according to a certain mass ratio can not only prevent the growth of crystals, but also improve the dispersion capacity and deep plating capacity of the plating solution and enhance the surface compactness of the plating layer.
According to the invention, the stress remover consisting of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to a certain mass ratio can improve the cathode polarization of copper electroplating solution for the heterojunction solar cell, reduce the internal stress of a plating layer, solve the problem of easy cracking of the plating layer and enable the obtained plating layer to be more uniform and fine.
Compared with the prior art, the invention has the following advantages:
(1) the copper plating film obtained by electroplating with the copper electroplating solution for the heterojunction solar cell is uniform, compact and bright, and the quality of the plating layer is obviously improved.
(2) The copper plating film obtained after the copper electroplating solution for the heterojunction solar cell is adopted for electroplating has small deposition stress, the toughness of the plating layer is improved, and the reliability of a plated part is obviously improved.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
In the invention, the polyvinyl alcohol can be purchased from Shenzhen Shenchun chemical Co., Ltd, and the model is as follows: PVA 217; polyethyleneimine is available from basf (china) ltd, type: loxanol MI 6735.
EXAMPLE 1 copper electroplating bath for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 28g/L, the content of the complexing agent is 52g/L, the content of the conductive salt is 40g/L, the content of the crystallization refiner is 2g/L, the content of the stress remover is 1g/L, the content of the brightener is 0.4g/L, and the content of the pH stabilizer is 35 g/L; the copper salt is copper sulfate; the complexing agent is potassium citrate; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin, sodium propiolate and polyvinyl alcohol according to the mass ratio of 8:6: 2; the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 11:7: 1; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 2: 15; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell comprises the following steps:
s1, adding a pH stabilizer into water, stirring until the pH stabilizer is completely dissolved, adding a complexing agent, and stirring until the pH stabilizer is completely dissolved to obtain a solution A;
s2, under the condition of stirring, adding copper salt into the solution A obtained in the step S1, and stirring until the copper salt is completely dissolved to obtain a solution B;
s3, under the condition of stirring, adding conductive salt into the solution B obtained in the step S2, and stirring until the conductive salt is completely dissolved to obtain a solution C;
s4, adding a brightening agent, a crystallization refiner and a stress remover into the solution C obtained in the step S3 under the stirring condition, and stirring until the brightening agent, the crystallization refiner and the stress remover are completely dissolved to obtain a solution D;
s5 adding potassium hydroxide into the solution D obtained in the step S4 under the stirring condition, and adjusting the pH value to 8 to obtain the compound.
Example 2 copper electroplating solution for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 35g/L, the content of the complexing agent is 60g/L, the content of the conductive salt is 46g/L, the content of the crystallization refiner is 4g/L, the content of the stress remover is 3g/L, the content of the brightener is 1g/L, and the content of the pH stabilizer is 45 g/L; the copper salt is copper chloride; the complexing agent consists of citric acid and potassium tartrate according to the mass ratio of 1: 4; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin, sodium propiolate and polyvinyl alcohol according to the mass ratio of 10:4: 1; the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 13:4: 1; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 5: 9; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell comprises the following steps:
s1, adding a pH stabilizer into water, stirring until the pH stabilizer is completely dissolved, adding a complexing agent, and stirring until the pH stabilizer is completely dissolved to obtain a solution A;
s2, under the condition of stirring, adding copper salt into the solution A obtained in the step S1, and stirring until the copper salt is completely dissolved to obtain a solution B;
s3, under the condition of stirring, adding conductive salt into the solution B obtained in the step S2, and stirring until the conductive salt is completely dissolved to obtain a solution C;
s4, adding a brightening agent, a crystallization refiner and a stress remover into the solution C obtained in the step S3 under the stirring condition, and stirring until the brightening agent, the crystallization refiner and the stress remover are completely dissolved to obtain a solution D;
s5 adding potassium hydroxide into the solution D obtained in the step S4 under the stirring condition, and adjusting the pH value to 9 to obtain the product.
Example 3 copper electroplating solution for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 33g/L, the content of the complexing agent is 54g/L, the content of the conductive salt is 45g/L, the content of the crystallization refiner is 3g/L, the content of the stress remover is 2g/L, the content of the brightener is 0.7g/L, and the content of the pH stabilizer is 38 g/L; the copper salt is copper citrate; the complexing agent consists of citric acid and tartaric acid according to the mass ratio of 2: 7; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin, sodium propiolate and polyvinyl alcohol according to the mass ratio of 10:5: 1; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 3: 14; the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 12:5: 1; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell comprises the following steps:
s1, adding a pH stabilizer into water, stirring until the pH stabilizer is completely dissolved, adding a complexing agent, and stirring until the pH stabilizer is completely dissolved to obtain a solution A;
s2, under the condition of stirring, adding copper salt into the solution A obtained in the step S1, and stirring until the copper salt is completely dissolved to obtain a solution B;
s3, under the condition of stirring, adding conductive salt into the solution B obtained in the step S2, and stirring until the conductive salt is completely dissolved to obtain a solution C;
s4, adding a brightening agent, a crystallization refiner and a stress remover into the solution C obtained in the step S3 under the stirring condition, and stirring until the brightening agent, the crystallization refiner and the stress remover are completely dissolved to obtain a solution D;
s5 adding potassium hydroxide into the solution D obtained in the step S4 under the stirring condition, and adjusting the pH value to 8.5 to obtain the product.
Comparative example 1 copper electroplating solution for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 33g/L, the content of the complexing agent is 54g/L, the content of the conductive salt is 45g/L, the content of the crystallization refiner is 3g/L, the content of the stress remover is 2g/L, the content of the brightener is 0.7g/L, and the content of the pH stabilizer is 38 g/L; the copper salt is copper citrate; the complexing agent consists of citric acid and tartaric acid according to the mass ratio of 2: 7; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin and sodium propynyl sulfonate according to the mass ratio of 10: 5; the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 12:5: 1; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 3: 14; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell is similar to that of example 3.
The difference from the example 3 is that the crystallization refiner consists of saccharin and sodium propynyl sulfonate in a mass ratio of 10: 5.
Comparative example 2 copper electroplating solution for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 33g/L, the content of the complexing agent is 54g/L, the content of the conductive salt is 45g/L, the content of the crystallization refiner is 3g/L, the content of the stress remover is 2g/L, the content of the brightener is 0.7g/L, and the content of the pH stabilizer is 38 g/L; the copper salt is copper citrate; the complexing agent consists of citric acid and tartaric acid according to the mass ratio of 2: 7; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin and sodium propiolate according to the mass ratio of 1: 1; the stress remover consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine according to the mass ratio of 12:5: 1; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 3: 14; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell is similar to that of example 3.
The difference from the example 3 is that the crystallization refiner consists of saccharin and sodium propynyl sulfonate in a mass ratio of 1: 1.
Comparative example 3 copper electroplating solution for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 33g/L, the content of the complexing agent is 54g/L, the content of the conductive salt is 45g/L, the content of the crystallization refiner is 3g/L, the content of the stress remover is 2g/L, the content of the brightener is 0.7g/L, and the content of the pH stabilizer is 38 g/L; the copper salt is copper citrate; the complexing agent consists of citric acid and tartaric acid according to the mass ratio of 2: 7; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin, sodium propiolate and polyvinyl alcohol according to the mass ratio of 10:5: 1; the stress remover consists of 2-amino-6-mercaptopurine and 1, 4-butynediol in a mass ratio of 12: 5; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 3: 14; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell is similar to that of example 3.
The difference from example 3 is that the destressing agent consists of 2-amino-6-mercaptopurine and 1, 4-butynediol in a mass ratio of 12: 5.
Comparative example 4 copper electroplating solution for heterojunction solar cell
The copper electroplating solution for the heterojunction solar cell comprises a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer; the content of the copper salt is 33g/L, the content of the complexing agent is 54g/L, the content of the conductive salt is 45g/L, the content of the crystallization refiner is 3g/L, the content of the stress remover is 2g/L, the content of the brightener is 0.7g/L, and the content of the pH stabilizer is 38 g/L; the copper salt is copper citrate; the complexing agent consists of citric acid and tartaric acid according to the mass ratio of 2: 7; the conductive salt is sodium chloride; the crystallization refiner consists of saccharin, sodium propiolate and polyvinyl alcohol according to the mass ratio of 10:5: 1; the stress remover consists of 2-amino-6-mercaptopurine and 1, 4-butynediol in a mass ratio of 1: 1; the brightener consists of nicotinic acid and sodium phenyl dithiopropane sulfonate according to the mass ratio of 3: 14; the pH stabilizer is boric acid.
The preparation method of the copper electroplating solution for the heterojunction solar cell is similar to that of example 3.
The difference from example 3 is that the destressing agent consists of 2-amino-6-mercaptopurine and 1, 4-butynediol in a mass ratio of 1: 1.
Test example I, evaluation of coating quality
1. Test samples: examples 1, 2, 3, 1 and 2 were prepared from the copper plating solutions for heterojunction solar cells.
2. Test subjects:
and sputtering and depositing a layer of copper layer with the thickness not more than 1 mu m into a round silicon wafer by a magnetron sputtering method.
3. The test method comprises the following steps:
the copper plating solutions for heterojunction solar cells prepared in examples 1 and 2 and 3 and comparative examples 1 and 2 were plated by an electroplating method using electrolytic copper as an anode and a test object as a cathode after chemical degreasing and cleaning, respectively, under the following plating conditions: the temperature is 25 ℃, and the cathode current density is 3.0A/dm2Anode current density 1.0A/dm2Electroplating time is 30 min. And observing the appearance of the plating layer after the electroplating is finished, and evaluating the quality of the plating layer.
4. And (3) test results:
the test results are shown in table 1.
Table 1: evaluation result of plating quality
As can be seen from Table 1, the appearance of the plated layer after being electroplated by the copper electroplating solution for the heterojunction solar cell provided by the invention is uniform, compact and bright, while the appearance of the plated layer after being electroplated by the copper electroplating solution for the heterojunction solar cell of the comparative examples 1-2 has the problems of nonuniform plated layer, pores and the like. Therefore, the copper electroplating solution for the heterojunction solar cell, which is prepared by the invention, can obviously improve the quality of a plating layer.
Test example two, plating stress detection
1. Test samples: copper plating solutions for heterojunction solar cells prepared in example 3, comparative example 3, and comparative example 4.
2. Test subjects:
and sputtering and depositing a layer of copper layer with the thickness not more than 1 mu m into a round silicon wafer by a magnetron sputtering method.
3. The test method comprises the following steps:
the copper plating solutions for heterojunction solar cells prepared in example 3, comparative example 3 and comparative example 4 were plated by an electroplating method after chemical degreasing and cleaning with electrolytic copper as an anode and a test object as a cathode, under the following conditions: the temperature is 25 ℃, and the cathode current density is 3.0A/dm2Anode current density 1.0A/dm2Electroplating time is 30 min. And after the electroplating is finished, measuring the deposition stress of the electroplated copper film by adopting a spiral stress tester.
4. And (3) test results:
the test results are shown in table 2.
Table 2: coating stress detection result
| Item | Example 3 | Comparative example 3 | Comparative example 4 |
| Deposition stress (Kg/mm)2) | 0.51 | 2.43 | 3.54 |
As can be seen from table 2, the deposition stress of the electroplated copper film obtained after electroplating with the copper electroplating solution for the heterojunction solar cell provided by the invention is as low as 0.51MPa, which is significantly lower than the deposition stress of the electroplated copper film obtained after electroplating with the copper electroplating solutions for the heterojunction solar cell of comparative examples 3 and 4; compared with comparative examples 3-4, the deposition stress of the electroplated copper film obtained after the electroplating is carried out by using the copper electroplating solution for the heterojunction solar cell is smaller, and the quality of the plated part is obviously improved.
Claims (10)
1. The copper electroplating solution for the heterojunction solar cell is characterized by comprising a copper salt, a complexing agent, a conductive salt, a crystallization refiner, a stress remover, a brightener and a pH stabilizer.
2. The copper electroplating solution for the heterojunction solar cell according to claim 1, wherein the content of the copper salt is 28 to 35g/L, the content of the complexing agent is 52 to 60g/L, the content of the conductive salt is 40 to 46g/L, the content of the crystallization refiner is 2 to 4g/L, the content of the stress remover is 1 to 3g/L, the content of the brightener is 0.4 to 1g/L, and the content of the pH stabilizer is 35 to 45 g/L.
3. The copper electroplating solution for heterojunction solar cells of claim 2, wherein the copper salt is 33g/L, the complexing agent is 54g/L, the conductive salt is 45g/L, the crystal refiner is 3g/L, the destressing agent is 2g/L, the brightener is 0.7g/L, and the pH stabilizer is 38 g/L.
4. The copper electroplating bath for a heterojunction solar cell of claim 1 wherein the copper salt is copper chloride, copper sulfate or copper citrate.
5. The copper electroplating bath for heterojunction solar cells of claim 1 wherein the complexing agent is one or more of citric acid, tartaric acid, potassium citrate and potassium tartrate.
6. The copper electroplating bath for a heterojunction solar cell as claimed in claim 1 wherein said crystallization refiner consists of saccharin, sodium propynyl sulfonate and polyvinyl alcohol in a mass ratio of 8-10:4-6: 1-2.
7. The copper electroplating bath for a heterojunction solar cell of claim 6 wherein said crystallization refiner consists of saccharin, sodium propynyl sulfonate and polyvinyl alcohol in a mass ratio of 10:5: 1.
8. The copper electroplating bath for heterojunction solar cells as claimed in claim 1 wherein said stress relief agent consists of 2-amino-6-mercaptopurine, 1, 4-butynediol and polyethyleneimine in a mass ratio of 11-13:4-7: 1.
9. The copper electroplating bath for heterojunction solar cells of claim 8 wherein said stress relief agent is comprised of 2-amino-6-mercaptopurine, 1, 4-butynediol, and polyethyleneimine in a mass ratio of 12:5: 1.
10. The method of preparing a copper electroplating bath for a heterojunction solar cell as claimed in any of claims 1 to 9, comprising the steps of:
s1, adding a pH stabilizer into water, stirring until the pH stabilizer is completely dissolved, adding a complexing agent, and stirring until the pH stabilizer is completely dissolved to obtain a solution A;
s2, under the condition of stirring, adding copper salt into the solution A obtained in the step S1, and stirring until the copper salt is completely dissolved to obtain a solution B;
s3, under the condition of stirring, adding conductive salt into the solution B obtained in the step S2, and stirring until the conductive salt is completely dissolved to obtain a solution C;
s4, adding a brightening agent, a crystallization refiner and a stress remover into the solution C obtained in the step S3 under the stirring condition, and stirring until the brightening agent, the crystallization refiner and the stress remover are completely dissolved to obtain a solution D;
and S5, under the stirring condition, adding potassium hydroxide into the solution D obtained in the step S4, and adjusting the pH value to 8-9 to obtain the potassium hydroxide-potassium chloride solution.
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