CN118048603B - A conductive carbon coating anode for copper electroplating process and its preparation method and application - Google Patents
A conductive carbon coating anode for copper electroplating process and its preparation method and application Download PDFInfo
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- CN118048603B CN118048603B CN202410120214.6A CN202410120214A CN118048603B CN 118048603 B CN118048603 B CN 118048603B CN 202410120214 A CN202410120214 A CN 202410120214A CN 118048603 B CN118048603 B CN 118048603B
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- 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
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- 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
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Abstract
本发明公开了一种用于电镀铜工艺的导电碳涂层阳极及其制备方法和应用。该用于电镀铜工艺的导电碳涂层阳极是以钛板为基底，在其表面上以真空溅射的方式涂敷一层导电碳涂层。导电碳涂层阳极的制备方法是先对钛板进行粗化，然后以高纯度的碳材料为靶材，在真空中以溅射的方式在钛基材上涂敷致密的导电碳涂层；再在隔绝空气的条件下对上述碳涂层钛阳极进行通电，使其加热到1000‑1500℃，通电5‑10小时，冷却后便得到用于电镀铜工艺的导电碳涂层阳极。本发明的导电碳涂层阳极价格低廉，膜厚均匀性更好，导电性更好。
The present invention discloses a conductive carbon coating anode for copper electroplating process and its preparation method and application. The conductive carbon coating anode for copper electroplating process is based on a titanium plate, and a layer of conductive carbon coating is applied on the surface of the titanium plate by vacuum sputtering. The preparation method of the conductive carbon coating anode is to first roughen the titanium plate, and then use a high-purity carbon material as a target material to apply a dense conductive carbon coating on the titanium substrate in a vacuum by sputtering; then, the carbon coating titanium anode is energized under air-tight conditions to heat it to 1000-1500°C, energize it for 5-10 hours, and obtain a conductive carbon coating anode for copper electroplating process after cooling. The conductive carbon coating anode of the present invention is low in price, has better film thickness uniformity, and better conductivity.
Description
Technical Field
The invention relates to the field of electroplating, in particular to a conductive carbon coating anode for an electroplating copper process, and a preparation method and application thereof.
Background
In the process of manufacturing a printed wiring board, copper electroplating is one of the extremely important process links.
The copper plating device mainly comprises a cathode, an anode and an electrolytic tank. The anodes on the market mainly comprise two types, namely 1) phosphorus copper is adopted as an anode, the soluble anode is used as a supplement of copper ions, a cylinder is required to be dragged frequently to maintain an anode film and activity, so that a large amount of phosphorus copper anode is wasted, in addition, the phosphorus copper anode can generate anode mud, periodic maintenance and cleaning are required, phosphorus copper is wasted, a large amount of waste water is generated, and manpower is wasted. More importantly, with the popularization of high-density fine circuits, the requirements on copper plating uniformity are higher and higher, and the phosphorus copper anode cannot meet the current requirements. 2) An insoluble anode is used, which is mainly a noble metal oxide titanium anode, and is mainly prepared by coating a precursor solution of a metal complex of one or more metals such as iridium, tantalum and the like on a titanium substrate, and forming a layer of noble metal oxide coating with catalytic activity on the surface of titanium through the technological processes of drying and thermal decomposition. It is well known that IrO 2-Ta2O5 oxide coated titanium anodes commonly used in anodes for circuit board copper plating processes can address the deficiencies of phosphor copper anodes, such as poor uniformity, e.g., periodic maintenance, etc. However, the price of the noble metal iridium oxide in the insoluble anode coating is high, the current market price of the insoluble anode per square meter is up to 3 ten thousand RMB, and the insoluble anode is replaced every two years by a common VCP line. The cost of the insoluble anode for two years will reach over 200 tens of thousands, which greatly increases the manufacturing cost of the client.
Therefore, a new anode material is needed.
Disclosure of Invention
In view of the above, the technical problem to be solved by the application is mainly to provide a conductive carbon coating anode for an electroplating copper process, and simultaneously, the application also provides a preparation method and application of the anode.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
The invention relates to a conductive carbon coating anode for an electrolytic copper plating process, which uses titanium as a substrate, and a conductive carbon coating layer is coated on the surface of the conductive carbon coating layer to replace an insoluble anode which uses noble metal iridium oxide tantalum oxide as a coating layer. The anode has the advantages of 1) simple manufacturing process, 2) low price, 3) better conductivity and further improvement of copper plating uniformity. The conductive carbon coating is made of carbon black, graphite, carbon nano tube, graphene and the like, and the purity is over 99.9 percent.
The manufacturing process of the conductive carbon coating anode for the copper electroplating process is as follows:
1) Coarsening the titanium substrate, namely putting the titanium substrate into 8-12% hydrochloric acid solution, treating for 1 hour at 60 ℃, washing with water and drying. Coarsening the titanium substrate is beneficial to enhancing the binding force of the carbon coating and the substrate.
2) And (3) taking a high-purity carbon material as a target material, and coating a compact carbon coating on the treated titanium substrate in a sputtering manner in vacuum. The carbon coating plated by adopting the vacuum sputtering method has the characteristics of high hardness, high wear resistance (low friction coefficient), good corrosion resistance, chemical stability and the like, and has the advantages of high bonding force between the carbon coating and the titanium substrate, good coating uniformity and longer service life of the film.
3) And electrifying the carbon-coated titanium anode under the condition of air isolation, heating the carbon-coated titanium anode to 1000-1500 ℃, electrifying for 5-10 hours, and cooling to obtain the conductive carbon-coated anode for the copper electroplating process. The effect of carrying out thermal oxidation treatment on the anode of the conductive carbon coating is mainly to remove impurities, so that the binding force between the conductive carbon coating and the substrate is further enhanced, and the coating and the substrate are firmly combined together.
The anode can be widely used for various copper electroplating processes of circuit boards, such as direct current through hole electroplating, direct current hole filling electroplating, pulse electroplating, electroplating of a copper-dissolving system and the like.
Compared with the prior art, the invention has the following beneficial effects:
1) The price is low, the price of the conductive carbon is about 100 yuan/kg, the price of the iridium oxide is about 500 yuan/g, and the price difference is about 5000 times;
2) The film thickness uniformity is better, the preparation of the iridium tantalum anode is mainly carried out by the traditional coating process, the coating uniformity is poor mainly due to manual operation, and the carbon coating anode obtained by vacuum sputtering has more uniform film thickness and more uniform power line distribution, thereby being beneficial to improving the uniformity of electroplated copper.
3) The conductivity is better, the conductivity of the conductive carbon coating is better than that of the noble metal oxide coating, and the voltage is lower, which further improves the uniformity of copper plating.
Drawings
FIG. 1 is a graph showing the effect of the anode of the conductive carbon coating for hole-filling copper plating according to example 1 of the present invention;
FIG. 2 is a copper pattern of a conductive carbon coated anode for use in a copper-dissolving system according to example 1 of the present invention;
FIG. 3 is a graph showing the effect of the conductive carbon coated anode of example 2 of the present invention on plating copper through holes;
FIG. 4 is a graph showing the effect of the anode of the conductive carbon coating for pulse copper plating according to example 2 of the present invention;
FIG. 5 is a graph showing the pore-filling effect of the conductive carbon coated anode of comparative example 1 for pore-filling copper plating according to the present invention;
Fig. 6 is a graph showing a comparison of tape stripping test of the conductive carbon coated anode of comparative example 2 according to the present invention and the conductive carbon coated anode prepared in example 2.
Detailed Description
The present invention will be further described with reference to the accompanying drawings for a clear and intuitive understanding to those skilled in the art.
Example 1
The preparation process of the conductive carbon coating anode of this embodiment is as follows:
1) Coarsening the titanium substrate, namely putting the titanium substrate into 8-12% hydrochloric acid solution, treating for 1 hour at 60 ℃, washing with water and drying.
2) The method comprises the steps of taking a high-purity graphite rod material as a target material, taking 99.9% argon as a protective gas in a vacuum environment with the vacuum degree of 0.2pa, controlling the temperature of vacuum coating to be 65 ℃, controlling the coating time to be 250 seconds, controlling the coating thickness to be 4 micrometers, and coating a compact graphite coating on a treated titanium substrate in a sputtering mode.
3) And electrifying the graphite-coated titanium anode under the condition of air isolation, heating to 1000 ℃, electrifying for 5 hours, and cooling to obtain the conductive carbon-coated anode for the copper electroplating process.
The conductive carbon coating anode is used in a hole filling copper plating process, and the electroplating solution is stirred into air according to the following electroplating solution configuration, the temperature is 25 ℃, the aperture of a blind hole on a test board is 125um, and the level is 70um. Electroplating parameters are current density 1.5ASD and electroplating time 50min.
250G/L of copper sulfate pentahydrate;
35g/L sulfuric acid;
Chloride ion 60mg/L;
Accelerator 2mg/L;
0.8g/L of wetting agent;
0.5g/L leveling agent.
The conductive carbon coating anode is used in the hole filling copper plating process, the hole filling effect obtained according to the parameters is shown in fig. 1, the brightness of the electroplating plate surface is uniform, no chromatic aberration exists, the blind hole surface is controlled to be about 15 microns, the recess is 0, and the hole filling effect is consistent with that obtained by the iridium tantalum titanium net commonly used in the market, namely, the hole filling electroplating effect cannot be influenced by the carbon coating anode.
The conductive carbon coating anode is used in a hole-filling copper plating process of a ferric iron copper dissolution system, and the electroplating solution is stirred into air according to the following electroplating solution configuration, wherein the temperature is 25 ℃. The aperture of the blind hole on the test board is 125um, and the level is 70um. Electroplating parameters are current density 1.6ASD and electroplating time 50min.
250G/L of copper sulfate pentahydrate;
35g/L sulfuric acid;
Chloride ion 60mg/L;
Total Fe 3g/L;
Ferric ion 0.7g/L;
Accelerator 2mg/L;
0.8g/L of wetting agent;
0.5g/L leveling agent.
The conductive carbon coating anode is used in the hole filling copper plating process of a copper dissolving system, the hole filling effect obtained according to the parameters is shown in fig. 2, the brightness of a plating plate surface is uniform and no chromatic aberration, the surface hole of a blind hole is controlled to be about 16 microns, the recess is 0, and the hole filling effect is consistent with that obtained by an iridium tantalum titanium net commonly used in the market, namely, the carbon coating anode is applied to a ferric iron hole filling copper plating system, and the effect of hole filling electroplating is not influenced.
Example 2
The preparation process of the conductive carbon coating anode of this embodiment is as follows:
1) Coarsening the titanium substrate, namely putting the titanium substrate into 8-12% hydrochloric acid solution, treating for 1 hour at 60 ℃, washing with water and drying.
2) The method comprises the steps of taking a high-purity carbon rod material as a target material, taking 99.9% argon as vacuum gas in a vacuum environment with the vacuum degree of 0.1pa, controlling the temperature of vacuum coating to be 75 ℃, controlling the coating time to be 280 seconds and the coating thickness to be 8 micrometers, and coating a compact graphite coating on the treated titanium substrate in a sputtering mode.
3) And electrifying the graphite-coated titanium anode under the condition of air isolation, heating the graphite-coated titanium anode to 1500 ℃, electrifying for 8 hours, and cooling to obtain the conductive carbon-coated anode for the copper electroplating process.
The conductive carbon coating anode is used in a direct current through hole copper plating process, and the electroplating solution is stirred into air stirring and spraying according to the following electroplating solution configuration, and the temperature is 25 ℃. The aperture of the through hole on the test board is 250um, the thickness of the board is 1500um, and the thickness-to-diameter ratio is 6:1. Electroplating parameters are current density of 2ASD and electroplating time of 60min.
75G/L of copper sulfate pentahydrate;
230g/L sulfuric acid;
Chloride ion 60mg/L;
accelerator 1mg/L;
0.8g/L of wetting agent;
0.5g/L leveling agent.
The conductive carbon coating anode is used in a through hole copper plating process, the through hole effect obtained according to the parameters is shown in fig. 3, the plated plate surface is bright and uniform without chromatic aberration, the through hole deep plating capacity is more than 75%, and the through hole electroplating effect is consistent with that of a common iridium tantalum titanium net in the market, namely, the through hole electroplating effect is not affected by the carbon coating anode.
The conductive carbon coating anode is used in a pulse copper plating process, and the electroplating solution is stirred into air stirring and spraying according to the following electroplating solution configuration, wherein the temperature is 25 ℃. The aperture of the through hole on the test board is 250um, and the thickness of the board is 3000um thickness-diameter ratio of 12:1. Electroplating parameters are current density of 2.5ASD and electroplating time of 85min.
75G/L of copper sulfate pentahydrate;
230g/L sulfuric acid;
Chloride ion 60mg/L;
accelerator 1.5mg/L;
0.8g/L of wetting agent.
The through hole effect obtained by adopting the conductive carbon coating anode in the pulse copper plating process according to the parameters is shown in fig. 4, the surface of the electroplated plate is bright and uniform without chromatic aberration, the deep plating capacity of the through hole is more than 110 percent, and the pulse plating effect is consistent with that of the iridium tantalum titanium net commonly used in the market, namely the effect of pulse plating is not affected by adopting the carbon coating anode.
Uniformity comparison
It can be seen from the above table that the coated anodes of examples 1 and 2 had better plating uniformity due to their good conductivity.
Comparative example 1
The preparation process of the conductive carbon coating anode of the comparative example is as follows:
1) Coarsening the titanium substrate, namely putting the titanium substrate into 8-12% hydrochloric acid solution, treating for 1 hour at 60 ℃, washing with water and drying.
2) Uniformly dispersing graphite in a solution by using a solvent acetone and an adhesive methyl acrylate, uniformly coating the dispersed graphite slurry on the surface of the roughened titanium substrate, putting the roughened titanium substrate into an oven, setting 120 ℃, and baking for 4H to remove redundant solvents.
3) And electrifying the graphite-coated titanium anode under the condition of air isolation, heating to 1000 ℃, electrifying for 5 hours, and cooling to obtain the conductive carbon-coated anode for the copper electroplating process.
The conductive carbon coating anode is used in a hole filling copper plating process, and the electroplating solution is stirred into air according to the following electroplating solution configuration, the temperature is 25 ℃, the aperture of a blind hole on a test board is 125um, and the level is 70um. Electroplating parameters are current density 1.5ASD and electroplating time 50min.
250G/L of copper sulfate pentahydrate;
35g/L sulfuric acid;
Chloride ion 60mg/L;
Accelerator 2mg/L;
0.8g/L of wetting agent;
0.5g/L leveling agent.
The conductive carbon coating anode is used in the hole filling copper plating process, the hole filling effect obtained according to the parameters is shown in fig. 5, the surface holes of the blind holes are controlled to be about 15 micrometers, the recesses are 18 micrometers, the hole filling effect is far lower than that of the anode in embodiment 1, and the poor electroplating effect is probably caused by poor coating conductivity due to the mode of coating slurry.
Comparative example 2
The preparation process of the conductive carbon coating anode of the comparative example 2 is as follows:
1) The method comprises the steps of taking a high-purity carbon rod material as a target material, taking 99.9% argon as vacuum gas in a vacuum environment with the vacuum degree of 0.1pa, controlling the temperature of vacuum coating to be 75 ℃, controlling the coating time to be 280 seconds and the coating thickness to be 8 micrometers, and coating a compact graphite coating on the treated titanium substrate in a sputtering mode.
2) And electrifying the graphite-coated titanium anode under the condition of air isolation, heating the graphite-coated titanium anode to 1500 ℃, electrifying for 8 hours, and cooling to obtain the conductive carbon-coated anode for the copper electroplating process.
Comparative example 2 compared with example 2, the roughening process of the titanium substrate was reduced, and it was found through the tape stripping experiment that the anode obtained in comparative example 2 was stripped off with more black carbon substance remained on the tape, while the anode obtained in example 2 was stripped off with less black carbon substance remained on the tape, as shown in fig. 6. It is explained that the binding force between the titanium substrate and the carbon coating can be enhanced by coarsening the titanium substrate (the coarsening process is to put the titanium substrate into 8-12% hydrochloric acid solution, treat the titanium substrate for 1 hour at 60 ℃, wash the titanium substrate with water and dry the titanium substrate).
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art, based on the present disclosure, should make improvements and modifications within the scope of the present invention.
Claims (8)
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| EP1454651B1 (en) * | 2003-03-03 | 2009-09-09 | Greatbatch Ltd. | Low polarization coatings for implantable electrodes |
| US20050089711A1 (en) * | 2003-10-23 | 2005-04-28 | Joachim Hossick-Schott | Methods of producing carbon layers on titanium metal |
| JP5108976B2 (en) * | 2011-02-14 | 2012-12-26 | 株式会社神戸製鋼所 | Fuel cell separator |
| KR101571844B1 (en) * | 2013-01-11 | 2015-11-26 | 재단법인 포항산업과학연구원 | Method for manufacturing anode for electroplating or electrolysis having cnt-ti combined structure with improved adhesion |
| CN105734526B (en) * | 2016-03-11 | 2018-06-29 | 天津理工大学 | A kind of method that graphene is prepared using Titanium as substrate |
| CN206289329U (en) * | 2016-08-25 | 2017-06-30 | 先丰通讯股份有限公司 | Insoluble anode |
| CN109585581A (en) * | 2018-12-03 | 2019-04-05 | 江苏中宇光伏科技有限公司 | A kind of preparation method of solar battery sheet electrode |
| FR3093112A1 (en) * | 2019-02-21 | 2020-08-28 | Saft | Metal foil for an electrochemical element electrode comprising a material based on Ti, C and H |
| CN115354384A (en) * | 2022-08-31 | 2022-11-18 | 西北大学 | Coating titanium anode for electrodeposited copper and preparation method thereof |
| CN116727927A (en) * | 2023-07-31 | 2023-09-12 | 重庆大学 | Multi-size copper particle composite soldering paste doped with copper-plated carbon nano tube and preparation method thereof |
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| CN210104115U (en) * | 2019-04-26 | 2020-02-21 | 广东天承科技有限公司 | Composite anode plate for electro-coppering |
| CN114464818A (en) * | 2022-01-18 | 2022-05-10 | 哈尔滨工业大学 | A low-cost surface treatment method for improving the surface properties of titanium and titanium alloys for proton exchange membrane fuel cell plates |
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