CN116288558A - Copper-dissolving type copper electroplating process adopting insoluble anode - Google Patents
Copper-dissolving type copper electroplating process adopting insoluble anode Download PDFInfo
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- CN116288558A CN116288558A CN202310106656.0A CN202310106656A CN116288558A CN 116288558 A CN116288558 A CN 116288558A CN 202310106656 A CN202310106656 A CN 202310106656A CN 116288558 A CN116288558 A CN 116288558A
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- 239000010949 copper Substances 0.000 title claims abstract description 99
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000009713 electroplating Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 113
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 41
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 25
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 22
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 11
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- -1 ferrous oxide ions Chemical class 0.000 claims description 8
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- 230000009469 supplementation Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000007086 side reaction Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 8
- 239000010802 sludge Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000024891 symptom Diseases 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a copper-dissolving type electrolytic copper plating process adopting an insoluble anode, wherein metal copper is placed in electroplating equipment, and plating solution comprises the following components of CuSO 4 ·5H 2 O is 100-300g/L, H 2 SO 4 20-150g/L, cl ‑ 0-180ppm FeSO 4 ·7H 2 O is 20-150g/L, and the current density of the plating solution is 2-30A/dm 2 The temperature is 10-55 ℃; ferrous sulfate ions are added into the plating solution to oxidize the ferrous ions into ferric ions on the surface of the insoluble anode; the plating solution containing ferric ions is sprayed on the metallic copper, the metallic copper is oxidized and electrolyzed through the ferric ions, so that the metallic copper is changed into bivalent copper ions, the bivalent copper ions are reduced, and the copper ions consumed in electroplating are replenished through reciprocating circulation. The invention adopts the copper plating of the insoluble anode and adopts the plating liquid chemical solution to supplement copper ions in the electrolytic copper way, thus greatly reducing the anode surfaceOxygen evolution of the surface greatly reduces the decomposition amount of the additive, thereby ensuring the purity of the plating solution.
Description
Technical Field
The invention relates to the technical field of chemical electroplating, in particular to a copper-dissolving type copper electroplating process.
Background
In the electrolytic copper plating industry, sulfate copper plating is one of the most dominant electroplating processes, and a phosphorus copper anode is commonly used in the traditional art. Since electrolytic copper produces copper powder when dissolved, resulting in low utilization, anodes containing phosphorus element (0.6-0.8%) are commonly used in anodes. However, the anode can generate a small amount of black insoluble substances of cuprous phosphide in the dissolution process, and the plating solution can still be polluted. Therefore, the anode titanium basket is required to be sleeved with an anode bag so as to improve the purity of the plating solution, but the mode still can treat the symptoms and the root causes, and the plating layer still is easy to generate the defects of burr points, pocks and the like. The industry has started to use insoluble anodic copper plating, and copper ion replenishment adopts a mode of adding copper oxide into a solution. However, in the mode, the copper plating additive adopting polyethylene glycol and polyether as carriers can be quickly oxidized and decomposed in the plating solution due to oxygen absorption of an insoluble anode, and the stability of the plating solution can not meet the requirements of industrial application, so that the popularization and the application of the copper plating additive are restricted.
Disclosure of Invention
The invention aims to solve the technical problem of providing a copper-dissolving type copper electroplating process which adopts an insoluble anode and has higher requirements and high practicability for the purity and industrial production of a plating solution by adding ferrous sulfate to supplement copper ions together with electrolytic copper.
In order to solve the technical problems, the invention adopts the following technical scheme: the copper-dissolving type copper electroplating process with insoluble anode includes setting metal copper inside electroplating equipment, and features that: the plating solution used was the following composition, cuSO 4 ·5H 2 O is 100-300g/L, H 2 SO 4 20-150g/L, cl - 0-180ppm FeSO 4 ·7H 2 O is 20-150g/L, and the current density of the plating solution is 2-30A/dm 2 The temperature is 10-55 ℃; ferrous sulfate ions are added into the plating solution to oxidize the ferrous ions into ferric ions on the surface of the insoluble anode; the plating solution containing ferric ions is sprayed on the metallic copper, the metallic copper is oxidized and electrolyzed through the ferric ions, so that the metallic copper is changed into bivalent copper ions, the bivalent copper ions are reduced, and the copper ions consumed in electroplating are replenished through reciprocating circulation.
The specific steps of the copper electroplating process are as follows,
1) Setting titanium-based iridium tantalum insoluble anode in a plating tank, and pumping plating solution;
2) Placing the workpieceThe plating solution is immersed in the workpiece, the current is started, and copper ions perform reduction reaction on the surface of the workpiece serving as a cathode: cu (Cu) 2+ +2e=cu, so that a large amount of ferric ions and ferrous ions exist in the plating solution at the same time;
3) The anode is subjected to oxidation reaction, ferrous oxide ions are taken as main materials, and electrolytic water reaction is taken as auxiliary materials; the reaction of ferrous oxide ions is Fe 2+ -e＝Fe 3+ The electrolyzed water reacts to H 2 O-2e＝2H + +O 2 ；
4) As electroplating proceeds, copper ions in the plating solution are reduced due to the gradual reduction of the copper sulfate concentration, the concentration of ferrous ions is also gradually reduced, and the concentration of ferric ions is gradually increased; when the concentration of copper ions is lower than the set lower limit, the equipment injects the plating solution into a copper dissolver containing metallic copper at high speed, so that the metallic copper is contacted with the newly injected plating solution to react Cu+2Fe 3+ ＝Cu 2+ +2Fe 2+ ；
5) As the reaction continues, the concentrations of copper ions and ferrous ions in the solution gradually rise, and the concentrations of ferric ions gradually fall; and when the concentration of copper ions is higher than the set upper limit, stopping injecting the plating solution into the copper dissolver by the equipment to complete the supplementation of copper ions in the plating solution.
In the step 3), the surface of the anode is simultaneously accompanied with oxygen evolution side reaction, namely, the oxidation reaction of oxygen and ferrous ions occurs, namely 2Fe 2+ +1/2O 2 +2H + ＝2Fe 3+ +H 2 O。
In the step 4), oxygen generated by oxygen evolution of the anode is dissolved in the plating solution to enable the oxygen in the plating solution to react with copper to form Cu+O 2 =2cuo, cuo+2h + ＝Cu 2+ +H 2 O。
Wherein the metal copper adopts one or a mixture of a plurality of copper blocks, copper balls and copper corners.
The process is characterized in that ferrous sulfate is added according to the current density of a cathode and the stirring speed of a plating solution (ferrous sulfate plays a role in dissolving copper balls in the process, the content of the ferrous sulfate is influenced by the size of plating current, meanwhile, ferrous ions need to be oxidized on an anode, the stirring speed can improve the contact probability of the ferrous ions with the anode. Thus, expensive copper oxide is not required to be added, or the traditional copper dissolving process is adopted to cause too high temperature to be suitable for cold plating, and the emulsified plating solution generates a large amount of oxygen in the copper dissolving process, so that the consumption of the additive is too high. In the conventional electroplating process, although ferrous sulfate is added in the plating process, the ferrous sulfate is used for purifying the plating solution, only a small amount of ferrous sulfate is needed, copper plating is replaced, an anode is not needed, and a small amount of ferrous sulfate does not generate oxidation-reduction reaction in the plating solution.
The invention adopts the copper plating of the insoluble anode and adopts the plating solution chemical dissolution electrolytic copper to supplement copper ions, thereby greatly reducing the oxygen evolution on the surface of the anode and greatly reducing the decomposition amount of the additive, thereby ensuring the purity of the plating solution and the feasibility of industrial production.
Detailed Description
In this example, the plating solution composition is shown in the following table:
| composition or process conditions | Range | Standard of |
| CuSO 4 ·5H 2 O | 100-300g/L | 220g/L |
| H 2 SO 4 | 20-150g/L | 60g/L |
| Cl - | 0-180ppm | 80ppm |
| FeSO 4 ·7H 2 O | 20-150g/L | 60g/L |
| Anode | Insoluble anode | Titanium-based iridium tantalum anode |
| Current density | 2-30A/dm 2 | 16-20A/dm 2 |
| Temperature (temperature) | 10-55℃ | 38-42℃ |
The implementation process of the copper electroplating process is as follows:
1. the workpiece is hoisted into the plating tank body, the plating solution is pressed into the filter through the liquid feeding pump, and the plating solution enters the plating tank body after being filtered. When the plating solution submerges the workpiece, the current is started, and copper ions are reduced on the surface of the cathode workpiece.
Cathode counterThe method comprises the following steps: cu (Cu) 2+ +2e＝Cu
Since a large amount of ferric ions and ferrous ions exist in the plating solution, but the reduction potential of the ferric ions is much lower than that of copper ions and hydrogen ions, the ferric ions and the ferrous ions cannot be reduced on the surface of the cathode;
2. the anode is subjected to oxidation reaction, ferrous oxide ions are taken as main materials, and electrolytic water reaction is taken as auxiliary materials;
anode reaction: fe (Fe) 2+ -e＝Fe 3+ (Main reaction)
H 2 O-2e＝2H + +O 2 (auxiliary reaction)
The surface of the anode has oxygen evolution side reaction, so that the oxidation reaction of oxygen and ferrous ions also occurs:
2Fe 2+ +1/2O 2 +2H + ＝2Fe 3+ +H 2 O
when the flow of the plating solution is larger, ferrous ions in the plating solution have more contact opportunities with the anode, the higher the reaction ratio of the ferrous ions oxidized into ferric ions at the anode is, the less oxygen evolution reaction is;
3. the concentration of ferric ions near the anode is gradually increased along with the continuous operation of the liquid feeding pump, and overflows to flow back into the liquid storage tank along with the flow of the plating solution through the plating solution overflow port;
4. as electroplating proceeds: the copper ion concentration in the plating solution is gradually reduced (copper sulfate concentration is gradually reduced), the ferrous ion concentration is also gradually reduced, and the ferric ion concentration is gradually increased. Meanwhile, in the cathode reaction, the potential of ferric ions reduced to ferrous ions is far lower than that of cupric ions reduced to metallic copper, so that the reaction of ferric ions reduced to ferrous ions does not exist in the cathode reaction; unless by changing the process conditions (too high current density, too low cathode movement speed, too low bath agitation capacity, too low bath temperature, too low copper ion concentration or too high iron ion concentration, or using very high complexing additives), it is possible to reduce the ferric ions, causing a very large concentration change;
5. as the plating continues, the copper ions gradually decrease, and when the copper ion concentration is below a set lower limit, the plating solution detects that the copper ion concentration is too low via the copper ion detector. The copper ion detector transmits a concentration signal to a controller (PLC), the PLC sends a command to enable the copper dissolution pump to work, plating solution is injected into a solution cavity at the bottom of the copper dissolution device at a high speed, then is sprayed into the copper dissolution cavity through a through hole of a partition plate above the solution cavity, and when metal copper contacts with the newly injected plating solution, the following reaction occurs:
Cu+2Fe 3+ ＝Cu 2+ +2Fe 2+ (Main reaction)
Since the solution is also rich in oxygen (the anode will have a small amount of oxygen evolution and dissolve in the bath), the oxidation reaction of copper will also occur:
Cu+O 2 ＝2CuO
CuO+2H + ＝Cu 2+ +H 2 O；
6. as the reaction continues, the concentration of copper ions and ferrous ions in the solution gradually increases, and the concentration of ferric ions gradually decreases. When the concentration of copper ions is higher than the set upper limit, the PLC sends out a command to stop the copper dissolving pump, so that the supplementation of copper ions is completed.
In addition, the loading capacity of the metal copper in the copper dissolver is related to factors such as the size of the metal copper, plating current, flow rate of a copper dissolving pump, content of trivalent chromium iron ions and the like, and the smaller the size of the metal copper is, the larger the surface area is, and the dissolution speed is higher; the larger the plating current, the larger the required load; the larger the flow of the copper dissolving pump, the higher the ferric iron content, and the faster the metallic copper is dissolved.
Practical tests prove that under the copper dissolution mode, the maximum dissolution efficiency of the copper balls can reach 3g/kg. For example, if the copper balls are loaded at 800kg, the amount of copper ions dissolved per hour is 2400g, i.e., the amount of copper ions required for current consumption of 2020A can be satisfied.
In contrast, the copper ball utilization rate in the traditional phosphor copper anode copper plating process is low, in order to reduce the generation of phosphor copper anode copper powder, 0.04-0.06% of phosphor element is generally added into the copper anode, black sludge is generated in the production process, the main component is a mixture of cuprous phosphide and copper powder, the copper anode utilization rate is reduced, and the traditional copper ball utilization rate is generally 80-90%. The copper anode and cathode of the insoluble anode adopt iridium tantalum coating anode, so that no sludge is generated, meanwhile, copper ion supplementation adopts a copper dissolution method, electrolytic copper balls or copper corners are chemically dissolved in a copper dissolution device, no sludge is generated, and the utilization rate of the copper balls is nearly 100%;
in the traditional process, because the phosphor copper balls, phosphor copper corners or phosphor copper plates are adopted, and the conductive uniformity of the anode is different in the production process, the cathode-anode distance needs to be enlarged to overcome the problem of poor plating capability. Meanwhile, due to the existence of anode mud, an anode sleeve is generally adopted, and the reasons of the anode sleeve and the anode sleeve are that the tank voltage in the electroplating process is increased, so that the energy consumption is increased. According to the invention, the insoluble anode copper plating adopts the iridium tantalum coating anode, the electric conduction of the anode surface is more uniform, the closer cathode-anode distance can be adopted in the production process, the cell voltage in the production process can be effectively reduced, and the energy consumption is lower;
in the traditional copper plating process, the components of the plating solution are unstable, the current efficiency of the anode is influenced by the area of the anode, the plating current, the quality of the phosphorus copper anode, the sulfuric acid content in the plating solution, the chloride ion content, the type of additives and the like, so that the components of the copper sulfate and the like in the plating solution are changed, and unstable factors are brought to the production quality. In the insoluble anode copper plating process, the replenishment of copper ions is controlled, and other components are relatively stable, so that the components of plating solution are stable, and the production quality is stable;
the traditional copper plating process is complex to maintain: because the anode can generate sludge in the production process and the plating solution components are unstable, the anode needs to be periodically disassembled and washed in production, the frequency of plating solution detection, test and adjustment is increased, and the complexity of process maintenance is increased. According to the insoluble anode copper plating process, on one hand, anode sludge is not generated, meanwhile, plating solution components are more stable, process maintenance is simpler, and labor is saved;
in the production process of the traditional copper plating process, due to the generation of anode sludge, the plating solution cannot be absolutely pure, the plating defects such as pits, burrs and the like are inevitably generated, and particularly, the plating layer with the plating thickness of more than 50um is higher in probability of occurrence of problems. The insoluble anode copper plating process can be used for absolute purity of plating solution, so that the probability of generating electroplating defects in the production process is low, and the insoluble anode copper plating process is more suitable for the field with high requirements on the thickness of an electroplated layer;
the traditional copper plating process adopts a phosphor copper anode for acid copper plating, the current distribution of the anode is uneven, and the distribution of a plating layer is uneven, so that the uniform plating capability is poor; the insoluble anode adopts the iridium tantalum coating anode, the electric conduction of the anode is more uniform, the current distribution is uniform, the plating layer distribution is more uniform for round roll shafts with regular shapes, and the iridium tantalum coating anode can design a pictographic anode with better anode laminating degree according to the shape of a workpiece, so that the uniform plating capability of the plating layer is more beneficial to improvement.
The foregoing detailed description of the invention has been presented for purposes of illustration and description, but is not intended to limit the scope of the invention, i.e., the invention is not limited to the details shown and described.
Claims (5)
1. The copper-dissolving type copper electroplating process with insoluble anode includes setting metal copper inside electroplating equipment, and features that: the plating solution used was the following composition, cuSO 4 •5H 2 O is 100-300g/L, H 2 SO 4 20-150g/L, cl - 0-180ppm FeSO 4 •7H 2 O is 20-150g/L, and the current density of the plating solution is 2-30A/dm 2 The temperature is 10-55 ℃; ferrous sulfate ions are added into the plating solution to oxidize the ferrous ions into ferric ions on the surface of the insoluble anode; the plating solution containing ferric ions is sprayed on the metallic copper, the metallic copper is oxidized and electrolyzed through the ferric ions, so that the metallic copper is changed into bivalent copper ions, the bivalent copper ions are reduced, and the copper ions consumed in electroplating are replenished through reciprocating circulation.
2. The copper-dissolving electrolytic copper plating process using an insoluble anode according to claim 1, wherein: the specific steps are as follows,
1) Setting titanium-based iridium tantalum insoluble anode in a plating tank, and pumping plating solution;
2) Placing the workpiece into a plating tank, immersing the workpiece in the plating solution, starting current, and carrying out reduction reaction on the surface of the workpiece serving as a cathode by copper ions: cu (Cu) 2+ +2e=cu, so that a large amount of ferric ions and ferrous ions exist in the plating solution at the same time;
3) The anode is subjected to oxidation reaction, ferrous oxide ions are taken as main materials, and electrolytic water reaction is taken as auxiliary materials; the reaction of ferrous oxide ions is Fe 2+ - e =Fe 3+ The electrolyzed water reacts to H 2 O-2e=2H + +O 2 ；
4) As electroplating proceeds, copper ions in the plating solution are reduced due to the gradual reduction of the copper sulfate concentration, the concentration of ferrous ions is also gradually reduced, and the concentration of ferric ions is gradually increased; when the concentration of copper ions is lower than the set lower limit, the equipment injects the plating solution into a copper dissolver containing metallic copper at high speed, so that the metallic copper is contacted with the newly injected plating solution to react Cu+2Fe 3+ =Cu 2 + +2Fe 2+ ；
5) As the reaction continues, the concentrations of copper ions and ferrous ions in the solution gradually rise, and the concentrations of ferric ions gradually fall; and when the concentration of copper ions is higher than the set upper limit, stopping injecting the plating solution into the copper dissolver by the equipment to complete the supplementation of copper ions in the plating solution.
3. The copper-dissolving electrolytic copper plating process using an insoluble anode according to claim 2, wherein: in the step 3), the surface of the anode is simultaneously accompanied with oxygen evolution side reaction, namely, the oxidation reaction of oxygen and ferrous ions occurs, namely 2Fe 2+ +1/2O 2 +2H + = 2Fe 3+ + H 2 O。
4. A copper-dissolving electrolytic copper plating process using an insoluble anode according to claim 3, wherein: in the step 4), oxygen generated by oxygen evolution of the anode is dissolved in the plating solution to enable the oxygen in the plating solution to react with copper to form Cu+O 2 =2cuo, cuo+2h + =Cu 2+ +H 2 O。
5. The copper-dissolving electrolytic copper plating process using an insoluble anode according to claim 1, wherein: the metal copper adopts one or a plurality of copper blocks, copper balls and copper corners to be mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310106656.0A CN116288558A (en) | 2023-02-13 | 2023-02-13 | Copper-dissolving type copper electroplating process adopting insoluble anode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310106656.0A CN116288558A (en) | 2023-02-13 | 2023-02-13 | Copper-dissolving type copper electroplating process adopting insoluble anode |
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| Publication Number | Publication Date |
|---|---|
| CN116288558A true CN116288558A (en) | 2023-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310106656.0A Pending CN116288558A (en) | 2023-02-13 | 2023-02-13 | Copper-dissolving type copper electroplating process adopting insoluble anode |
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| Country | Link |
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| CN (1) | CN116288558A (en) |
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- 2023-02-13 CN CN202310106656.0A patent/CN116288558A/en active Pending
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