CN114318434B - Electrolytic copper plating solution and preparation method thereof - Google Patents
Electrolytic copper plating solution and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electrolytic copper plating solution and a preparation method thereof, wherein each 1 liter of electrolytic copper plating solution comprises the following components: copper ions: 70-90g/L; sulfuric acid: 200-250g/L; the carrier agent comprises the following components: 50-90mg/L; and (3) brightening agent: 25-45mg/L; inhibitors: 75-105mg/L; degreasing agent: 35-100mg/L; leveling agent: 15-45mg/L; deionized water: the balance. The electrolytic copper plating solution provided by the invention has good deep plating capability, the deep plating capability can reach more than 76%, and the electrolytic copper plating solution meets the electroplating requirement of a high-quality circuit board; the electroplating solution does not cause the anode film to drop during electroplating, thereby being beneficial to improving the production efficiency and reducing the cost; the formed coating is uniform, has excellent thermal shock performance, does not generate the conditions of fog and copper nodules, and can still reach more than 75% of deep plating capability under high current.
Description
Technical Field
The invention relates to the field of electroplating solutions, in particular to an electroplating copper solution and a preparation method thereof.
Background
The electroplating copper is an important process link in PCB production, electroplating is carried out by adopting electroplating solution, the use amount of the electroplating solution is large, the application range is wide, and the technical requirement is high. Any kind of circuit board must be plated with copper to thicken the copper layer in order to continue the subsequent process flow.
The deep plating capability is one of the most important indexes for measuring the quality of electroplated copper, and only 65-70% of the deep plating capability can be achieved for Kong Houjing holes with the ratio of 8:1 in the domestic market, while the foreign copper plating solution can achieve 75-80% of the deep plating capability, such as Robin Hasi, siring gas and other foreign medicinal liquid vendors. In the electroplating process, the anode film is easy to drop, the copper plating solution needs to be replaced again, so that the cost is increased, and the problems that the deep plating capacity of high current is reduced, copper nodules are easy to generate and the like are also caused. The existing copper plating solution generally comprises anhydrous copper sulfate, sulfuric acid, brightening agent and leveling agent, and has the problems of poor deep plating capability and uneven electroplating.
Disclosure of Invention
The invention provides an electroplating copper solution and a preparation method thereof, aiming at solving the problems of poor deep plating capability, easy generation of copper nodules and high cost of the existing copper plating solution.
An electrolytic copper plating solution comprising the following components per 1 liter of electrolytic copper plating solution:
copper ions: 70-90g/L;
sulfuric acid: 200-250g/L;
the carrier agent comprises the following components: 50-90mg/L;
and (3) brightening agent: 25-45mg/L;
inhibitors: 75-105mg/L;
degreasing agent: 35-100mg/L;
leveling agent: 15-45mg/L;
deionized water: the balance.
Alternatively, the copper ions are provided by a copper sulfate solution.
Optionally, the carrier comprises a compound capable of providing chloride ions, and a compound capable of providing selenium ions.
Optionally, the carrier is hydrochloric acid or selenium dioxide.
Optionally, the brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof.
Optionally, the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid.
Optionally, the inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of polyethylenimine quaternary ammonium salt to sodium polynaphtholsulfonate is 3:1.
Optionally, the oil removing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2.
Optionally, the leveling agent is an amide quaternary ammonium salt compound.
A method for preparing an electrolytic copper plating solution, comprising the steps of:
preparing a base solution: mixing a carrier, a copper ion compound and sulfuric acid, uniformly stirring, and preparing a base solution;
preparation of agent A: mixing a brightening agent, a copper ion compound, sulfuric acid and deionized water, uniformly stirring, and preparing to obtain an agent A;
preparing a preparation B: mixing the leveling agent, the inhibitor, the degreasing agent and deionized water, uniformly stirring, and preparing to obtain a preparation B;
preparing a C agent: mixing brightening agent, leveling agent, inhibitor, carrier, degreasing agent, copper ion compound, sulfuric acid and deionized water, stirring uniformly, and preparing agent C; the volumes of the solutions prepared by the agent A, the agent B and the agent C are the same;
mixing the base solution, the agent A and the agent B, stirring uniformly to obtain a mixed solution, tabletting in a 1.5L Halin tank, and adding 0.5ml of the agent C per liter of the mixed solution per hour.
Compared with the prior art, the invention has the beneficial effects that: the invention provides an electrolytic copper plating solution and a preparation method thereof, wherein the electrolytic copper plating solution has good deep plating capability, the deep plating capability can reach more than 76 percent, and the electrolytic copper plating solution meets the electroplating requirement of a high-quality circuit board; the electroplating solution does not cause the anode film to drop during electroplating, thereby being beneficial to improving the production efficiency and reducing the cost; the formed coating is uniform, has excellent thermal shock performance, does not generate fog and copper nodules, and can still reach more than 75% of deep plating capacity under high current (45 ASF).
Drawings
FIG. 1 is a first diagram of a plated layer formed by electroplating with an electrolytic copper plating solution according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a plating layer formed by electroplating with a conventional electrolytic copper plating solution;
FIG. 3 is a second diagram of a plated layer formed by electroplating with the electrolytic copper plating solution according to the embodiment of the present application;
FIG. 4 is a second view of a plated layer formed by electroplating using a conventional electrolytic copper plating solution;
FIG. 5 is a third view of a plated layer formed by electroplating with the electrolytic copper plating solution according to the embodiment of the present application;
FIG. 6 is a third view of a plated layer formed by electroplating using a conventional electrolytic copper plating solution;
Detailed Description
In order to describe the technical solution of the present invention in detail, the technical solution of the embodiments of the present invention will be clearly and completely described below.
An electrolytic copper plating solution, example 1:
each 1 liter of the electrolytic copper plating solution comprises the following components:
copper ions: 70g/L; sulfuric acid: 200g/L; the carrier agent comprises the following components: 50mg/L; and (3) brightening agent: 25mg/L; inhibitors: 75mg/L; degreasing agent: 35mg/L; leveling agent: 15mg/L; deionized water: the balance. The electrolytic copper plating solution can be used at normal temperature, the deep plating capacity can reach 76%, the appearance is free from fogging after copper plating, the orifice copper layer is free from cracking after thermal shock, and the pH value of the electrolytic copper plating solution is 4+/-0.5.
The copper ions are provided by a copper sulfate solution. The sulfuric acid may be industrial concentrated sulfuric acid.
The carrier includes a compound capable of providing chloride ions, and a compound capable of providing selenium ions. In some embodiments, the carrier is hydrochloric acid and selenium dioxide. The carrier agent improves the electroplating efficiency, promotes the three-dimensional continuous nucleation of copper crystals, and the obtained electroplated copper layer has very high compactness and brightness.
The brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof. In some embodiments, the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid, and phosphoric acid. The mixing ratio of N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid was 2:1. The carrier and the brightening agent are matched to realize normal brightening growth under high current, and the mechanism is that organic nitrogen propane sulfonic acid is introduced into a high current distribution area to realize reduction under the help of phosphoric acid to generate nitrogen-containing amine compounds, and the compounds are acidified into ions under acidic conditions, so that the compounds are easier to adsorb in the high current area, and the flatness of a coating is realized.
The inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of the polyethylenimine quaternary ammonium salt to the sodium polynaphtholsulfonate is 3:1. The mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate forms an organic layer on the electric double layer of the electroplated copper surface, plays a role in bridging and selective permeation, adjusts potential difference of each position of a plating layer, and greatly improves the uniformity of the plating layer.
The degreasing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2. The polyoxyethylene tallow amine is polyoxyethylene tallow amine produced by Shenzhen New source technology Co. In the electroplating process, a part of the degreasing agent is adsorbed on the anode film, diglycolamine and polyoxyethylene tallow amine are adsorbed on the anode to form a film net, and the N, O and P elements are conjugated with electrons mutually in space due to the organic molecular structure to generate adsorption force.
The leveling agent is an amide quaternary ammonium salt compound. In some embodiments, the leveling agent is a quaternary ammonium salt of fatty amidopropyl-N, N-dimethyl tertiary amine, oleamidopropyl dimethyl tertiary amine under acidic conditions. The leveler can enhance the deep plating ability. The leveling agent and the degreasing agent are matched, so that the penetration of impurities in the plating holes can be improved, the adsorption of copper ions in the holes can be accelerated, and the deep plating capacity can be greatly improved.
An electrolytic copper plating solution, example 2:
each 1 liter of the electrolytic copper plating solution comprises the following components:
copper ions: 90g/L; sulfuric acid: 250g/L; the carrier agent comprises the following components: 90mg/L; and (3) brightening agent: 45mg/L; inhibitors: 105mg/L; degreasing agent: 100mg/L; leveling agent: 45mg/L; deionized water: the balance. The electrolytic copper plating solution can be used at normal temperature, the deep plating capacity can reach 76%, the appearance is free from fogging after copper plating, the orifice copper layer is free from cracking after thermal shock, and the pH value of the electrolytic copper plating solution is 4+/-0.5.
The copper ions are provided by a copper sulfate solution. The sulfuric acid may be industrial concentrated sulfuric acid.
The carrier includes a compound capable of providing chloride ions, and a compound capable of providing selenium ions. In some embodiments, the carrier is hydrochloric acid and selenium dioxide. The carrier agent improves the electroplating efficiency, promotes the three-dimensional continuous nucleation of copper crystals, and the obtained electroplated copper layer has very high compactness and brightness.
The brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof. In some embodiments, the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid, and phosphoric acid. The mixing ratio of N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid was 2:1. The carrier and the brightening agent are matched to realize normal brightening growth under high current, and the mechanism is that organic nitrogen propane sulfonic acid is introduced into a high current distribution area to realize reduction under the help of phosphoric acid to generate nitrogen-containing amine compounds, and the compounds are acidified into ions under acidic conditions, so that the compounds are easier to adsorb in the high current area, and the flatness of a coating is realized.
The inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of the polyethylenimine quaternary ammonium salt to the sodium polynaphtholsulfonate is 3:1. The mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate forms an organic layer on the electric double layer of the electroplated copper surface, plays a role in bridging and selective permeation, adjusts potential difference of each position of a plating layer, and greatly improves the uniformity of the plating layer.
The degreasing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2. The polyoxyethylene tallow amine is polyoxyethylene tallow amine produced by Shenzhen New source technology Co. In the electroplating process, a part of the degreasing agent is adsorbed on the anode film, diglycolamine and polyoxyethylene tallow amine are adsorbed on the anode to form a film net, and the N, O and P elements are conjugated with electrons mutually in space due to the organic molecular structure to generate adsorption force.
The leveling agent is an amide quaternary ammonium salt compound. In some embodiments, the leveling agent is a quaternary ammonium salt of fatty amidopropyl-N, N-dimethyl tertiary amine, oleamidopropyl dimethyl tertiary amine under acidic conditions. The leveler can enhance the deep plating ability. The leveling agent and the degreasing agent are matched, so that the penetration of impurities in the plating holes can be improved, the adsorption of copper ions in the holes can be accelerated, and the deep plating capacity can be greatly improved.
Copper electroplating solution, example 3:
each 1 liter of the electrolytic copper plating solution comprises the following components:
copper ions: 80g/L; sulfuric acid: 225g/L; the carrier agent comprises the following components: 70mg/L; and (3) brightening agent: 30mg/L; inhibitors: 90mg/L; degreasing agent: 65mg/L; leveling agent: 30mg/L; deionized water: the balance. The electrolytic copper plating solution can be used at normal temperature, the deep plating capacity can reach 76%, the appearance is free from fogging after copper plating, the orifice copper layer is free from cracking after thermal shock, and the PH of the electrolytic copper plating solution is 4+/-0.5.
The copper ions are provided by a copper sulfate solution. The sulfuric acid may be industrial concentrated sulfuric acid.
The carrier includes a compound capable of providing chloride ions, and a compound capable of providing selenium ions. In some embodiments, the carrier is hydrochloric acid and selenium dioxide. The carrier agent improves the electroplating efficiency, promotes the three-dimensional continuous nucleation of copper crystals, and the obtained electroplated copper layer has very high compactness and brightness.
The brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof. In some embodiments, the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid, and phosphoric acid. The mixing ratio of N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid was 2:1. The carrier and the brightening agent are matched to realize normal brightening growth under high current, and the mechanism is that organic nitrogen propane sulfonic acid is introduced into a high current distribution area to realize reduction under the help of phosphoric acid to generate nitrogen-containing amine compounds, and the compounds are acidified into ions under acidic conditions, so that the compounds are easier to adsorb in the high current area, and the flatness of a coating is realized.
The inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of the polyethylenimine quaternary ammonium salt to the sodium polynaphtholsulfonate is 3:1. The mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate forms an organic layer on the electric double layer of the electroplated copper surface, plays a role in bridging and selective permeation, adjusts potential difference of each position of a plating layer, and greatly improves the uniformity of the plating layer.
The degreasing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2. The polyoxyethylene tallow amine is polyoxyethylene tallow amine produced by Shenzhen New source technology Co. In the electroplating process, a part of the degreasing agent is adsorbed on the anode film, diglycolamine and polyoxyethylene tallow amine are adsorbed on the anode to form a film net, and the N, O and P elements are conjugated with electrons mutually in space due to the organic molecular structure to generate adsorption force.
The leveling agent is an amide quaternary ammonium salt compound. In some embodiments, the leveling agent is a quaternary ammonium salt of fatty amidopropyl-N, N-dimethyl tertiary amine, oleamidopropyl dimethyl tertiary amine under acidic conditions. The leveler can enhance the deep plating ability. The leveling agent and the degreasing agent are matched, so that the penetration of impurities in the plating holes can be improved, the adsorption of copper ions in the holes can be accelerated, and the deep plating capacity can be greatly improved.
An electrolytic copper plating solution, example 4:
each 1 liter of the electrolytic copper plating solution comprises the following components:
copper ions: 75g/L; sulfuric acid: 210g/L; the carrier agent comprises the following components: 60mg/L; and (3) brightening agent: 35mg/L; inhibitors: 85mg/L; degreasing agent: 80mg/L; leveling agent: 40mg/L; deionized water: the balance. The electrolytic copper plating solution can be used at normal temperature, the deep plating capacity can reach 76%, the appearance is free from fogging after copper plating, the orifice copper layer is free from cracking after thermal shock, and the PH of the electrolytic copper plating solution is 4+/-0.5.
The copper ions are provided by a copper sulfate solution. The sulfuric acid may be industrial concentrated sulfuric acid.
The carrier includes a compound capable of providing chloride ions, and a compound capable of providing selenium ions. In some embodiments, the carrier is hydrochloric acid and selenium dioxide. The carrier agent improves the electroplating efficiency, promotes the three-dimensional continuous nucleation of copper crystals, and the obtained electroplated copper layer has very high compactness and brightness.
The brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof. In some embodiments, the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid, and phosphoric acid. The mixing ratio of N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid was 2:1. The carrier and the brightening agent are matched to realize normal brightening growth under high current, and the mechanism is that organic nitrogen propane sulfonic acid is introduced into a high current distribution area to realize reduction under the help of phosphoric acid to generate nitrogen-containing amine compounds, and the compounds are acidified into ions under acidic conditions, so that the compounds are easier to adsorb in the high current area, and the flatness of a coating is realized.
The inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of the polyethylenimine quaternary ammonium salt to the sodium polynaphtholsulfonate is 3:1. The mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate forms an organic layer on the electric double layer of the electroplated copper surface, plays a role in bridging and selective permeation, adjusts potential difference of each position of a plating layer, and greatly improves the uniformity of the plating layer.
The degreasing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2. The polyoxyethylene tallow amine is polyoxyethylene tallow amine produced by Shenzhen New source technology Co. In the electroplating process, a part of the degreasing agent is adsorbed on the anode film, diglycolamine and polyoxyethylene tallow amine are adsorbed on the anode to form a film net, and the N, O and P elements are conjugated with electrons mutually in space due to the organic molecular structure to generate adsorption force.
The leveling agent is an amide quaternary ammonium salt compound. In some embodiments, the leveling agent is a quaternary ammonium salt of fatty amidopropyl-N, N-dimethyl tertiary amine, oleamidopropyl dimethyl tertiary amine under acidic conditions. The leveler can enhance the deep plating ability. The leveling agent and the degreasing agent are matched, so that the penetration of impurities in the plating holes can be improved, the adsorption of copper ions in the holes can be accelerated, and the deep plating capacity can be greatly improved.
An electrolytic copper plating solution, example 5:
each 1 liter of the electrolytic copper plating solution comprises the following components:
copper ions: 85g/L; sulfuric acid: 230g/L; the carrier agent comprises the following components: 80mg/L; and (3) brightening agent: 40mg/L; inhibitors: 100mg/L; degreasing agent: 50mg/L; leveling agent: 20mg/L; deionized water: the balance. The electrolytic copper plating solution can be used at normal temperature, the deep plating capacity can reach 76%, the appearance is free from fogging after copper plating, the orifice copper layer is free from cracking after thermal shock, and the PH of the electrolytic copper plating solution is 4+/-0.5.
The copper ions are provided by a copper sulfate solution. The sulfuric acid may be industrial concentrated sulfuric acid.
The carrier includes a compound capable of providing chloride ions, and a compound capable of providing selenium ions. In some embodiments, the carrier is hydrochloric acid and selenium dioxide. The carrier agent improves the electroplating efficiency, promotes the three-dimensional continuous nucleation of copper crystals, and the obtained electroplated copper layer has very high compactness and brightness.
The brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof. In some embodiments, the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid, and phosphoric acid. The mixing ratio of N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid was 2:1. The carrier and the brightening agent are matched to realize normal brightening growth under high current, and the mechanism is that organic nitrogen propane sulfonic acid is introduced into a high current distribution area to realize reduction under the help of phosphoric acid to generate nitrogen-containing amine compounds, and the compounds are acidified into ions under acidic conditions, so that the compounds are easier to adsorb in the high current area, and the flatness of a coating is realized.
The inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of the polyethylenimine quaternary ammonium salt to the sodium polynaphtholsulfonate is 3:1. The mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate forms an organic layer on the electric double layer of the electroplated copper surface, plays a role in bridging and selective permeation, adjusts potential difference of each position of a plating layer, and greatly improves the uniformity of the plating layer.
The degreasing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2. The polyoxyethylene tallow amine is polyoxyethylene tallow amine produced by Shenzhen New source technology Co. In the electroplating process, a part of the degreasing agent is adsorbed on the anode film, diglycolamine and polyoxyethylene tallow amine are adsorbed on the anode to form a film net, and the N, O and P elements are conjugated with electrons mutually in space due to the organic molecular structure to generate adsorption force.
The leveling agent is an amide quaternary ammonium salt compound. In some embodiments, the leveling agent is a quaternary ammonium salt of fatty amidopropyl-N, N-dimethyl tertiary amine, oleamidopropyl dimethyl tertiary amine under acidic conditions. The leveler can enhance the deep plating ability. The leveling agent and the degreasing agent are matched, so that the penetration of impurities in the plating holes can be improved, the adsorption of copper ions in the holes can be accelerated, and the deep plating capacity can be greatly improved.
A method for preparing an electrolytic copper plating solution, comprising the steps of:
preparing a base solution: mixing a carrier, a copper ion compound and sulfuric acid, uniformly stirring, and preparing a base solution;
preparation of agent A: mixing a brightening agent, a copper ion compound, sulfuric acid and deionized water, uniformly stirring, and preparing to obtain an agent A;
preparing a preparation B: mixing the leveling agent, the inhibitor, the degreasing agent and deionized water, uniformly stirring, and preparing to obtain a preparation B;
preparing a C agent: mixing brightening agent, leveling agent, inhibitor, carrier, degreasing agent, copper ion compound, sulfuric acid and deionized water, stirring uniformly, and preparing agent C; the volumes of the solutions prepared by the agent A, the agent B and the agent C are the same;
mixing the base solution, the agent A and the agent B, stirring uniformly to obtain a mixed solution, tabletting in a 1.5L Halin tank, and adding 0.5ml of the agent C per liter of the mixed solution per hour.
The concentration of each liter of solution of the components is as follows: copper ions: 70-90g/L; sulfuric acid: 200-250g/L; the carrier agent comprises the following components: 50-90mg/L; and (3) brightening agent: 25-45mg/L; inhibitors: 75-105mg/L; degreasing agent: 35-100mg/L; leveling agent: 15-45mg/L; deionized water: allowance of
In some embodiments, the copper ion providing compound is copper sulfate, with a copper sulfate concentration of 2g/L and a sulfuric acid concentration of 10ml/L. The preparation method can be carried out at normal temperature.
Comparing fig. 1 with fig. 2, comparing fig. 3 with fig. 4, comparing fig. 5 with fig. 6, and fig. 1, fig. 3 and fig. 5 are all plating layer diagrams formed by electroplating with the copper electroplating solution according to the invention, and fig. 2, fig. 4 and fig. 6 are all plating layer diagrams formed by electroplating with the existing copper electroplating solution, wherein the deep plating capacity of the copper electroplating solution is 77.3% and the deep plating capacity of the existing copper electroplating solution is 67.5%, so that the deep plating capacity of the copper electroplating solution is better, the plating layer of the copper electroplating solution is more uniform, brighter and clearer, and has better tolerance to thermal shock.
The invention provides an electrolytic copper plating solution and a preparation method thereof, wherein the electrolytic copper plating solution has good deep plating capability, the deep plating capability can reach more than 76 percent, and the electrolytic copper plating solution meets the electroplating requirement of a high-quality circuit board; the electroplating solution does not cause the anode film to drop during electroplating, thereby being beneficial to improving the production efficiency and reducing the cost; the formed coating is uniform, has excellent thermal shock performance, does not generate fog and copper nodules, and can still reach more than 75% of deep plating capacity under high current (45 ASF).
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but the present invention is described in detail with reference to the foregoing embodiments, and it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or that equivalents may be substituted for part of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present embodiment are included in the protection scope of the present invention.
Claims (7)
1. An electrolytic copper plating solution, characterized in that: each 1 liter of the electrolytic copper plating solution comprises the following components:
copper ions: 70-90g/L;
sulfuric acid: 200-250g/L;
the carrier agent comprises the following components: 50-90mg/L;
and (3) brightening agent: 25-45mg/L;
inhibitors: 75-105mg/L;
degreasing agent: 35-100mg/L;
leveling agent: 15-45mg/L;
deionized water: the balance;
the carrier comprises a compound capable of providing chloride ions and a compound capable of providing selenium ions;
the brightening agent is organic nitrogen propane sulfonic acid and derivatives thereof;
the inhibitor is a mixture of polyethylenimine quaternary ammonium salt and sodium polynaphtholsulfonate, and the mixing ratio of the polyethylenimine quaternary ammonium salt to the sodium polynaphtholsulfonate is 3:1.
2. An electrolytic copper plating solution according to claim 1, wherein: the copper ions are provided by a copper sulfate solution.
3. An electrolytic copper plating solution according to claim 1 or 2, wherein: the carrier is hydrochloric acid and selenium dioxide.
4. An electrolytic copper plating solution according to claim 1, wherein: the brightening agent comprises N-propane sulfonic acid, N-propane benzenesulfonic acid and phosphoric acid.
5. An electrolytic copper plating solution according to claim 1, wherein: the oil removing agent is a mixture of diglycolamine and polyoxyethylene tallow amine, and the mixing ratio of the diglycolamine to the polyoxyethylene tallow amine is 3:2.
6. An electrolytic copper plating solution according to claim 1, wherein: the leveling agent is an amide quaternary ammonium salt compound.
7. A method for producing the electrolytic copper plating solution according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
preparing a base solution: mixing a carrier, a copper ion compound and sulfuric acid, uniformly stirring, and preparing a base solution;
preparation of agent A: mixing a brightening agent, a copper ion compound, sulfuric acid and deionized water, uniformly stirring, and preparing to obtain an agent A;
preparing a preparation B: mixing the leveling agent, the inhibitor, the degreasing agent and deionized water, uniformly stirring, and preparing to obtain a preparation B;
preparing a C agent: mixing brightening agent, leveling agent, inhibitor, carrier, degreasing agent, copper ion compound, sulfuric acid and deionized water, stirring uniformly, and preparing agent C; the volumes of the solutions prepared by the agent A, the agent B and the agent C are the same;
mixing the base solution, the agent A and the agent B, stirring uniformly to obtain a mixed solution, tabletting in a 1.5L Halin tank, and adding 0.5ml of the agent C per liter of the mixed solution per hour.
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| CN101665962A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Alkaline non-cyanide plating solution for copper-plating used on iron and steel base and preparation method thereof |
| CN103290438A (en) * | 2013-06-25 | 2013-09-11 | 深圳市创智成功科技有限公司 | An electro-copper plating solution and an electroplating method for wafer level packaging |
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| WO2015190390A1 (en) * | 2014-06-11 | 2015-12-17 | 上村工業株式会社 | Tin electroplating bath and tin plating film |
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