CN115418632B - High-speed high-ductility chemical copper suitable for horizontal line equipment and preparation method thereof - Google Patents
High-speed high-ductility chemical copper suitable for horizontal line equipment and preparation method thereof Download PDFInfo
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- CN115418632B CN115418632B CN202210891636.4A CN202210891636A CN115418632B CN 115418632 B CN115418632 B CN 115418632B CN 202210891636 A CN202210891636 A CN 202210891636A CN 115418632 B CN115418632 B CN 115418632B
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- reducing agent
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- 239000010949 copper Substances 0.000 title claims abstract description 59
- 239000000126 substance Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 31
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims abstract description 24
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- -1 imidazoline compound Chemical class 0.000 claims abstract description 11
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 239000011591 potassium Substances 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000872 buffer Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 65
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 21
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 21
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 21
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 21
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 16
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 16
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 16
- CHENRKIAWPQCBU-UHFFFAOYSA-N 1-benzyl-3-methylimidazolidine Chemical compound C1N(C)CCN1CC1=CC=CC=C1 CHENRKIAWPQCBU-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UXGNDCFFVVYLPL-UHFFFAOYSA-N 1-(2-methoxyethyl)-3-methylimidazolidine Chemical compound COCCN1CCN(C)C1 UXGNDCFFVVYLPL-UHFFFAOYSA-N 0.000 claims description 2
- GYDNNJQLBOPSBD-UHFFFAOYSA-N 1-butyl-3-methylimidazolidine Chemical compound CCCCN1CCN(C)C1 GYDNNJQLBOPSBD-UHFFFAOYSA-N 0.000 claims description 2
- JOTQIXXCBHIDKJ-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidine Chemical compound CCN1CCN(C)C1 JOTQIXXCBHIDKJ-UHFFFAOYSA-N 0.000 claims description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- 230000036541 health Effects 0.000 abstract description 2
- 230000000711 cancerogenic effect Effects 0.000 abstract 1
- 231100000315 carcinogenic Toxicity 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- MNYOKDIIUJDYBM-UHFFFAOYSA-N 1-benzyl-3-methyl-2h-imidazole Chemical compound C1=CN(C)CN1CC1=CC=CC=C1 MNYOKDIIUJDYBM-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003138 coordinated effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides high-speed high-ductility chemical copper suitable for horizontal line equipment and a preparation method thereof, wherein the high-speed high-ductility chemical copper comprises the following raw materials in parts by weight: copper salt, complexing agent, reducing agent, imidazoline compound, buffer, stabilizer, hydroxyethyl ethylenediamine, thiosemicarbazide and the balance of water. The high-speed high-ductility chemical copper adopts the composition of potassium borohydride, hydroxylamine sulfate and hydroxylamine as the reducing agent, replaces the traditional formaldehyde reducing agent, has weak reducibility of formaldehyde and is a high-risk cancerogenic substance, and brings great health threat to the environment and operators.
Description
Technical Field
The invention relates to the technical field of electroless copper plating, in particular to high-speed high-ductility chemical copper suitable for horizontal line equipment and a preparation method thereof.
Background
The chemical copper is widely applied in chemical production, and the earliest time of the chemical copper is published in 1957 by Kaschin (Cahill), and the first similar modern chemical copper plating solution is alkaline copper tartrate plating solution, and formaldehyde is reducing agent. With the development of printed circuit boards, a great market is provided for the development of electroless copper plating technology, and in the production of printed circuit boards, electroless copper plating is used to precipitate copper on the wall surfaces of through holes and on the underlying circuit paths. Electroless copper plating is also useful in the decorative plastics industry to deposit copper, nickel, gold, silver and other metals as a foundation on non-conductive surfaces as desired.
The chemical copper plating comprises horizontal line chemical copper plating and vertical line chemical copper plating, and the substrate is horizontally placed during operation of the horizontal line chemical copper plating, so that compared with the vertical line chemical copper plating, the horizontal line chemical copper plating can solve the defects of uneven pore diameter plating layers of the multilayer board, and the like, can well improve the production environment, and realizes continuous automatic mass production operation and the like.
In practice, it can be seen that electroless copper plating requires longer processing times, meaning that the production process requires longer horizontal line production equipment, and that the enterprise requires more equipment investment and site space requirements. Therefore, how to improve the efficiency of electroless copper plating and shorten the reaction time becomes a problem to be solved in the industry.
Disclosure of Invention
In order to solve the problem of how to improve the chemical copper plating efficiency and shorten the reaction time in the prior art, the invention adopts high-speed stable chemical copper plating solution which is compounded by a plurality of components, has high plating speed, deposition speed of more than 20 mu m/h, stable plating solution, flat and uniform copper plating layer and high ductility due to the interaction among the components, and meets the requirements of functional chemical copper plating.
The specific scheme is as follows: high-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: copper salt 5-10g/L, complexing agent 10-80g/L, reducing agent 15-25g/L, imidazoline compound 2-4g/L, buffer 10-50g/L, stabilizer 0.01-0.05g/L, hydroxyethyl ethylenediamine 0.1-5g/L, thiosemicarbazide 0.02-0.05g/L, and water in balance.
In carrying out the above embodiments, preferably, the copper salt is one or more of copper sulfamate, copper chloride, copper nitrate, copper sulfate, and basic copper carbonate.
In carrying out the above embodiments, preferably, the complexing agent is one or more of potassium sodium tartrate, ethylenediamine tetraacetic acid sodium salt, and cyclohexanediamine tetraacetic acid.
In practicing the above embodiments, preferably, the reducing agent is a combination of potassium borohydride, hydroxylamine sulfate, and hydroxylamine.
In practicing the above examples, it is preferred that the mass ratio of potassium borohydride, hydroxylamine sulfate, and hydroxylamine is 1:3:3.
In practicing the above embodiments, preferably, the imidazoline compound is one or more of 1- (2-methoxyethyl) -3-methylimidazoline alcohol, 1-benzyl-3-methylimidazoline alcohol, 1-ethyl-3-methylimidazoline alcohol, 1-aryl-methylimidazoline alcohol, and 1-butyl-3-methylimidazoline alcohol.
In practicing the above embodiments, preferably, the buffer is sodium carbonate or potassium carbonate.
In carrying out the above embodiments, preferably, the stabilizer is water-soluble polyvinyl alcohol or polyvinylpyrrolidone.
In carrying out the above examples, it is preferred that the ratio of hydroxyethyl ethylenediamine to thiocarbamide be 10:1.
The preparation method of the high-speed high-ductility chemical copper suitable for horizontal line equipment comprises the following steps: and (3) mutually dissolving copper salt and water, fully stirring until the solution is clarified, adding complexing agent, reducing agent, imidazoline compound, buffer, stabilizer, hydroxyethyl ethylenediamine and thiosemicarbazide, fully stirring until the solution is clarified, and fixing the volume with water to obtain the high-speed high-ductility chemical copper suitable for horizontal line equipment.
Compared with the prior art, the invention has the advantages that:
1. the raw material components of the invention are added with the reducing agent and the imidazoline compound, and the specific reducing agent combination, namely the combination of potassium borohydride, hydroxylamine sulfate and hydroxylamine, is matched with the imidazoline compound to improve the copper deposition rate on the substrate, so that copper ions can be rapidly reduced and rapidly deposited for plating, and high-speed chemical copper is obtained.
2. According to the invention, the ethyl ethylenediamine and the thiosemicarbazide are added into the raw material components, and when potassium sodium tartrate is selected as a complexing agent, the copper deposition rate can be improved, and the plating solution can be stabilized.
3. The raw material components of the invention do not contain formaldehyde reducer, and the invention has little threat to the environment and the health of operators, and the ductility of the copper coating is high.
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 in the embodiments of the present invention will be clearly and completely described in the following in conjunction with 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. 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.
The experimental drugs and reagents used in examples 1-6 and comparative examples of the present invention are described below:
the copper salt is anhydrous copper sulfate;
complexing agent is potassium sodium tartrate or ethylenediamine tetraacetic acid;
the reducing agent is a composition of potassium borohydride, hydroxylamine sulfate and hydroxylamine, and the mass ratio of the potassium borohydride to the hydroxylamine sulfate to the hydroxylamine is 1:3:3.
The imidazoline compound is 1-benzyl-3-methylimidazoline alcohol;
the buffering agent is potassium carbonate;
the stabilizer is water-soluble polyvinyl alcohol.
It should be noted that, in the examples, specific techniques or conditions are not noted, and the reagents or apparatuses used, which are carried out according to techniques or conditions described in the literature in the field or according to the specifications of the products, are conventional products commercially available, and are not noted to manufacturers.
Example 1
High-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: 5g/L of anhydrous copper sulfate, 80g/L of ethylenediamine tetraacetic acid, 25g/L of reducing agent, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the high-speed high-ductility chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding ethylenediamine tetraacetic acid, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to a specified solution volume.
Example 2
High-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: 10g/L of anhydrous copper sulfate, 10g/L of ethylenediamine tetraacetic acid, 25g/L of reducing agent, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the high-speed high-ductility chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding ethylenediamine tetraacetic acid, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to a specified solution volume.
Example 3
High-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: 10g/L of anhydrous copper sulfate, 80g/L of potassium sodium tartrate, 15g/L of reducing agent, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the high-speed high-ductility chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding potassium sodium tartrate, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to a specified solution volume.
Example 4
High-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: 10g/L of anhydrous copper sulfate, 80g/L of potassium sodium tartrate, 25g/L of reducing agent, 2g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the high-speed high-ductility chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding potassium sodium tartrate, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to a specified solution volume.
Example 5
High-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: 10g/L of anhydrous copper sulfate, 80g/L of potassium sodium tartrate, 25g/L of reducing agent, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 10g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the high-speed high-ductility chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding potassium sodium tartrate, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to a specified solution volume.
Example 6
High-speed high ductility chemical copper suitable for horizontal line equipment, the raw materials are constituteed and are included: 10g/L of anhydrous copper sulfate, 80g/L of potassium sodium tartrate, 25g/L of reducing agent, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.01g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the high-speed high-ductility chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding potassium sodium tartrate, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to a specified solution volume.
Comparative example 1
Commercial electroless copper plating solutions.
Comparative example 2
Chemical copper, the raw materials are composed of: 5g/L of anhydrous copper sulfate, 80g/L of ethylenediamine tetraacetic acid, 10g/L of potassium borohydride, 15g/L of hydroxylamine sulfate, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiocarbamide and the balance of water.
The preparation method of the chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at 20rpm, fully stirring until the solution is clear, adding ethylenediamine tetraacetic acid, potassium borohydride, hydroxylamine sulfate, 1-benzyl-3-methylimidazoline alcohol, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at 100rpm for 10 minutes, and adding water to the solution to obtain the final product.
Comparative example 3
Chemical copper, the raw materials are composed of: 5g/L of anhydrous copper sulfate, 80g/L of ethylenediamine tetraacetic acid, 25g/L of reducing agent, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 5g/L of hydroxyethyl ethylenediamine, 0.05g/L of thiosemicarbazide and the balance of water.
The preparation method of the chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding ethylenediamine tetraacetic acid, a reducing agent, potassium carbonate, polyvinyl alcohol, hydroxyethyl ethylenediamine and thiosemicarbazide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to set the volume of the solution.
Comparative example 4
Chemical copper, the raw materials are composed of: 5g/L of anhydrous copper sulfate, 80g/L of potassium sodium tartrate, 25g/L of reducing agent, 4g/L of 1-benzyl-3-methylimidazoline alcohol, 50g/L of potassium carbonate, 0.05g/L of polyvinyl alcohol, 0.05g/L of thiocarbamide and the balance of water.
The preparation method of the chemical copper comprises the following steps of:
adding anhydrous copper sulfate into a stirring kettle filled with water, stirring at a stirring speed of 20rpm, fully stirring until the solution is clear, adding potassium sodium tartrate, a reducing agent, 1-benzyl-3-methylimidazole alcohol, potassium carbonate, polyvinyl alcohol and thiocarbamide into the stirring kettle, stirring at a stirring speed of 100rpm for 10 minutes, and adding water to set the volume of the solution.
To verify the effect of the improved high speed of this ductile chemical copper of the present invention, the following tests were performed for each of the examples and comparative test groups, respectively:
1. deposition rate test, the deposition rate is measured by a weight gain method, and the calculation formula is as follows:
v＝(m 1 －m 0 )×10000/(ρ×A×t)
wherein v is the deposition rate, μm/h; m is m 0 And m 1 G, the mass of the plating piece before plating and the mass of the plating piece after plating are respectively shown in g; ρ is the relative density of copper, 8.93g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the A is the surface area of the plating piece, cm 2 The method comprises the steps of carrying out a first treatment on the surface of the t is plating time and h.
2. Ductility test: the titanium is coated with an iridium oxide anode, a polished stainless steel plate is adopted as a cathode, 50-80 microns is electroplated, a plating layer is peeled off after baking for 2 hours at 120 ℃, a 1cm wide strip is manufactured, and the elongation and tensile strength of the plating layer are tested on a pull-up tester when the plating layer breaks. The elongation is required to be more than 18%, and the higher the tensile strength is, the better the tensile strength is, and the tensile strength is required to be 200-500MPa.
3. And (3) binding force test: and (3) tearing by using a hundred-grid test method and using a 3M 610 adhesive tape, wherein the absence of falling is OK and the presence of falling is NG.
4. Plating solution stability test: because the plating solution is left to naturally decompose for a long time, an acceleration method is generally used to shorten the experimental time. The invention adopts palladium chloride acceleration test to test the stability of the plating solution: 15mL of PdCl was added to 50mL of the plating solution 2 (0.18 g/L) at 60℃and recording the bath decomposition time, i.e., the time required to produce a significant amount of red copper powder and hydrogen gas.
The test results are shown in Table 1:
TABLE 1
| Deposition Rate (μm/h) | Extensibility rate | Decomposition time (min) | Binding force of plating | |
| Example 1 | 20.8 | 38.5％ | 89 | OK |
| Example 2 | 21.7 | 37.8％ | 105 | OK |
| Example 3 | 26.9 | 39.3％ | 151 | OK |
| Example 4 | 27.3 | 38.9％ | 157 | OK |
| Example 5 | 27.1 | 39.6％ | 153 | OK |
| Example 6 | 26.5 | 39.1％ | 149 | OK |
| Comparative example 1 | 10.4 | 9.6％ | 26 | OK |
| Comparative example 2 | 15.7 | 23.7％ | 92 | OK |
| Comparative example 3 | 14.6 | 21.6％ | 96 | OK |
| Comparative example 4 | 12.4 | 31.9％ | 31 | OK |
As can be seen from the test results in Table 1, examples 1 and 2 have lower deposition rate and decomposition time than examples 3-6, because ethylenediamine tetraacetic acid is used as the complexing agent in examples 1 and 2, and potassium sodium tartrate is used as the complexing agent in examples 3-6, and because the components added with ethylenediamine and thiocarbamide can produce a coordinated effect with potassium sodium tartrate, not only can the copper deposition rate be improved, but also the plating solution can be stabilized.
The use of a combination of potassium borohydride and hydroxylamine sulfate as the reducing agent in the component of comparative example 2 and the absence of an imidazoline compound in the component of comparative example 3 resulted in inferior test results for both comparative example 2 and comparative example 3 to examples 1-6.
The absence of hydroxyethylethylenediamine in the component of comparative example 4 resulted in inferior test results to examples 1-6.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (2)
1. The high-speed high-ductility chemical copper suitable for horizontal line equipment is characterized in that the raw material composition comprises: copper salt 5-10g/L, complexing agent 10-80g/L, reducing agent 15-25g/L, imidazoline compound 2-4g/L, buffer 10-50g/L, stabilizer 0.01-0.05g/L, hydroxyethyl ethylenediamine 0.1-5g/L, thiosemicarbazide 0.02-0.05g/L, and water for the rest; the copper salt is one or more of copper sulfamate, copper chloride, copper nitrate, copper sulfate and basic copper carbonate; the complexing agent is one or more of potassium sodium tartrate, ethylenediamine tetraacetic acid sodium salt and cyclohexanediamine tetraacetic acid; the reducing agent is a composition obtained by mixing potassium borohydride, hydroxylamine sulfate and hydroxylamine in a mass ratio of 1:3:3; the imidazoline compound is one or more of 1- (2-methoxyethyl) -3-methylimidazoline alcohol, 1-benzyl-3-methylimidazoline alcohol, 1-ethyl-3-methylimidazoline alcohol, 1-aryl-methylimidazoline alcohol and 1-butyl-3-methylimidazoline alcohol; the buffer is sodium carbonate or potassium carbonate; the stabilizer is water-soluble polyvinyl alcohol or polyvinylpyrrolidone; the ratio of the hydroxyethyl ethylenediamine to the thiocarbamide is 10:1.
2. The method for preparing high-speed high-ductility chemical copper suitable for horizontal line equipment according to claim 1, wherein copper salt and water are mutually dissolved, after fully stirring until the solution is clarified, complexing agent, reducing agent, imidazoline compound, buffering agent, stabilizer, hydroxyethyl ethylenediamine and thiosemicarbazide are added, after fully stirring until the solution is clarified, water is used for constant volume, and the high-speed high-ductility chemical copper suitable for horizontal line equipment is obtained.
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| CN103422079A (en) * | 2012-05-22 | 2013-12-04 | 比亚迪股份有限公司 | Chemical copper plating solution and preparation method thereof |
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