CN109056002B - Acid copper electroplating process and device adopting through hole isolation method - Google Patents

Abstract

The invention discloses an acid copper electroplating process with a through-hole isolation method, comprising the following steps: (1) using a spacer with through-holes to separate an electroplating tank into an anode area and a cathode area, and setting an electroplating solution stirring device in the anode area (2) Prepare anodic electroplating solution and cathodic electroplating solution respectively, pour the anodic electroplating solution and cathodic electroplating solution into the anodic area and the cathodic area respectively, and add metallic copper and/or copper oxide in the anodic area; The insoluble anode is connected to the positive electrode of the power supply as a plating anode and is immersed in the anodic plating solution in the anode area, and the cathode plating piece is connected to the negative electrode of the power supply and immersed in the cathodic plating solution in the cathode area; The electroplating solution stirring device is used for electroplating. The process can solve the problems existing in the acid copper electroplating process of the existing insoluble anode, not only can improve the quality of electroplating, save the production cost of electroplating, but also be environmentally friendly. The invention also discloses a device suitable for the acid copper electroplating process of the through hole isolation method.

Description

A kind of through hole isolation method acid copper electroplating process and device

technical field

The invention relates to an acid copper electroplating process, in particular to a through hole isolation method acid copper electroplating process and a device thereof.

Background technique

The existing acid copper plating process is divided into two types: the use of soluble anodes and the use of insoluble anodes. Soluble anodes used in acid copper plating processes are typically phosphor bronze. According to the description on pages 84-85 of the book "Copper Plating", edited by Huo Shuancheng and published by Chemical Industry Press in August 2007: "In sulfate bright copper plating, the anode is one of the most important links. What kind of anode is used, people have done a lot of research work, the anode plate of sulfate bright copper plating is made of phosphorous copper plate. Phosphorus copper plate can be divided into two types, one is cast phosphorus-containing copper plate; the other is rolled phosphorus-containing copper plate , their phosphorus content is different. According to the copper plating process of different brighteners, the phosphorus content of the anode is also different, which can be roughly divided into two categories: one with a phosphorus content of 0.035% to 0.075%, and the other with a phosphorus content of 0.035% to 0.075%. The phosphorus content of the first type is 0.1% to 0.3%, which is determined according to the copper plating process of different brighteners, but no matter which anode is selected, the phosphorus content should not be too low. It is difficult to maintain, so that the dissolution rate of the anode is accelerated, the amount of monovalent copper is relatively large, and the balance of the concentration of divalent copper ions in the plating solution is changed, resulting in the deterioration of the plating solution and normal production." Therefore, in the general acidity In the electroplating copper industry, phosphorus copper with moderate phosphorus content is used for soluble anodes. However, the price of phosphorus copper is high, and the production and use of phosphorous copper will produce toxic phosphorus-containing wastewater, which is extremely harmful to the liver and other organs when it enters the human body.

Insoluble anodes refer to anodes that do not occur or rarely undergo anodic dissolution reactions during the electrochemical reaction process. Titanium, graphite, platinum or lead alloy materials coated with noble metal oxides are usually selected in the acid copper plating process.

A common acid copper plating process using an insoluble anode uses an aqueous solution of copper sulfate and sulfuric acid as the main components as the electroplating solution. The water reacts and decomposes at the anode to generate hydrogen ions and oxygen, and the copper ions in the electroplating solution are reduced to metallic copper at the cathode. . With the precipitation of copper electroplating, the concentration of sulfuric acid in the electroplating solution is getting higher and higher, and copper oxide can be added to react with it to supplement the copper ions lost in the electroplating solution and consume the corresponding amount of sulfuric acid:

Electrochemical reaction on anode: 2H ₂ O - 4e ^- → O ₂ ↑ + 4H ⁺

Electrochemical reactions on the cathode: Cu ²⁺ + 2e ^- → Cu↓

Reaction of copper sulfate electroplating bath regeneration: CuO + H ₂ SO ₄ → CuSO ₄ + H ₂ O

The disadvantage of this method is that due to the electrolysis of water on the anode to desorb oxygen, the oxygen dissolved in the electroplating solution will attach to the cathode plating and affect the quality of the coating.

Another common acid copper plating process using an insoluble anode is to add iron ions to the electroplating solution whose main components are copper sulfate and sulfuric acid aqueous solution, and the electrochemical reaction on the anode is the oxidation of ferrous ions to ferric ions. The copper ions are reduced to metallic copper at the cathode:

Electrochemical reactions on the anode: Fe ²⁺ - e ^- → Fe ³⁺

Electrochemical reactions on the cathode: Cu ²⁺ + 2e ^- → Cu↓

Reaction of copper sulfate electroplating bath regeneration: Cu + 2Fe ³⁺ → Cu ²⁺ +2 Fe ²⁺

This process utilizes the base of ferric ions to corrode metallic copper to increase copper ions in the electroplating solution, which can reduce the amount of oxygen dissolved in the electroplating solution and avoid quality problems caused by oxygen. However, the ferric ions present in the electroplating solution may etch back the metallic copper on the cathode, which will also affect the electroplating quality.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a through-hole isolation method acid copper electroplating process, which can solve the problems existing in the acid copper electroplating process of the existing insoluble anode, not only can improve the quality of electroplating, but also save the cost of electroplating production , and also green.

The second object of the present invention is to provide a device used in the acid copper electroplating process using the through hole isolation method.

The first object of the present invention can be achieved through the following technical solutions:

An acid copper electroplating process with a through-hole isolation method, comprising the following steps:

(1) Use a spacer with a through hole to separate the electroplating tank into an anode area and a cathode area, and set a plating solution stirring device in the anode area;

(2) Prepare an anodic electroplating solution and a cathodic electroplating solution respectively, the anodic electroplating solution and the cathodic electroplating solution contain sulfuric acid and/or copper sulfate, pour the anodic electroplating solution and the cathodic electroplating solution into the anodic area and the cathodic area, respectively, and place them in the anodic area and the cathodic area, respectively. Adding metallic copper and/or copper oxide to the anode area;

(3) Connect the insoluble anode as the electroplating anode to the positive electrode of the power supply and immerse it in the anodic plating solution in the anode area, connect the cathode plating piece to the negative electrode of the power supply and immerse it in the cathodic electroplating solution in the cathode area; turn on the power supply, and Turn on the electroplating solution stirring device in the anode area to carry out electroplating. During the electroplating process, the reaction between metal copper and oxygen and the reaction between copper oxide and sulfuric acid will occur in the anode area, so that the copper ions in the electroplating solution are replenished.

The concentrations of the anodic electroplating solution and the cathodic electroplating solution in step (2) of the present invention can be prepared according to the concentration of the conventional acid copper electroplating solution, and the sulfuric acid and/or copper sulfate in the anodic electroplating solution and the cathodic electroplating solution The concentrations can be the same or different.

The insoluble anode described in step (3) of the present invention refers to an anode that does not or rarely undergoes an anode dissolution reaction during the electrochemical reaction process, such as platinum electrodes, lead alloy electrodes, graphite electrodes, titanium electrodes, titanium alloy electrodes, Titanium-based electrodes with other metals or rare earth oxide coatings or metal alloys, etc.

In step (1) of the present invention, when a spacer with a through hole is used to separate the electroplating tank into an anode area and a cathode area, the number of anode areas and/or cathode areas may be one or more than one, and the cathode area and the anode area are alternated Setting; when there are one or more anode regions, one insoluble anode is soaked in each anode region, and the insoluble anodes can be made of different materials respectively.

The electrochemical reaction on the two poles of the process of the present invention is the same as that of the existing insoluble anode without iron ions.

The working principle of the invention is as follows: during the electroplating process of the acid copper electroplating process, as the copper ions in the cathode electroplating solution obtain electrons, they are continuously reduced to elemental copper and precipitated on the plated parts, and the concentration of copper ions continuously decreases, resulting in the cathode The acidity in the electroplating solution will also become higher and higher, which affects the electroplating reaction. Therefore, it is necessary to continuously replenish copper ions to stabilize the concentration of copper ions. In the copper plating process of the present invention, the sources of copper ions participating in the electrochemical reaction are mainly metal copper and/or copper oxides added to the anode region, metal copper and/or copper oxides and oxygen and sulfuric acid in the anodic plating solution A reaction occurs to generate copper sulfate, and the concrete reaction equation is as follows:

1) Reaction of metallic copper with sulfuric acid and oxygen: 1/2O ₂ + H ₂ SO ₄ + Cu → CuSO ₄ + H ₂ O;

2) Copper oxide reacts with sulfuric acid: H ₂ SO ₄ + CuO → CuSO ₄ + H ₂ O;

3) Cuprous oxide reacts with sulfuric acid: H ₂ SO ₄ + Cu ₂ O → Cu + CuSO ₄ + H ₂ O.

The copper ions generated by the above reaction will enter the cathode region through the through holes on the separator between the cathode and anode regions of the electroplating tank, so as to keep the copper ion concentration of the cathode plating solution stable; and the sulfuric acid in the cathode region will also enter the cathode region. In the anode region, it participates in the reaction of copper ion generation.

In the invention, an electroplating solution stirring device is arranged in the anode area to increase the contact between oxygen and metal copper, sulfuric acid and copper oxide, and at the same time improve the reaction rate, the electroplating tank is separated into an anode area and a cathode area by a spacer with a through hole , so that the anode area and the cathode area are in a relatively isolated state, that is, the electroplating solutions in the two pole areas can communicate with each other: ① The copper ions in the anode area enter the cathode area through the through holes on the spacer due to the attraction of the electric field, In order to maintain the stability of the copper ion concentration in the cathodic electroplating solution; ② the sulfuric acid in the cathode area can also enter the anode area to participate in the reaction of copper ion generation; but it is relatively independent: ① The use of spacers can effectively block the generation of copper ions in the anode area. The oxygen is directly close to the cathode plating part, which can effectively isolate the influence of the surging of the plating solution on the cathode area caused by stirring and gas movement, so as to avoid the corrosion of the outer metal of the plating part; ② At the same time, it can also effectively prevent the anode area The metal copper and/or copper oxides in the cathode area enter the cathode area and affect the plating quality.

During the electroplating operation in step (3) of the present invention, it is still necessary to intermittently add metallic copper and/or copper oxide to the anode region to supplement the source of copper ions.

The source of the metal copper and/or copper oxide added to the anode region in the steps (2) and (3) of the present invention can be one or more of copper metal, copper oxide and copper alloy. combination.

The present invention can also adopt the following improvement measures:

The through-holes on the spacer with through-holes of the present invention are fine pores uniformly distributed on the spacer and with a diameter in the range of 0.1-1000 μm, and the diameters of the through-holes may be the same or different. The spacer with through holes can be one or more of filter cloth, plastic plate with through holes, ceramic plate with microporous or microporous filter membrane, and the filter cloth can be woven cloth or Non-woven fabrics; plastic plates with through holes or ceramic plates with micro holes can be plastic plates with through holes or ceramic plates with micro holes for filtering.

The electroplating liquid stirring device described in step (1) of the present invention may adopt a pipeline liquid circulation return device, the pipeline liquid circulation return device is composed of a pump and a pipeline, and the liquid inlet of the pipeline liquid circulation return device is connected to the At the bottom of the anode area, the liquid outlet is placed in the anode area, so that the anodic plating solution can be circulated back into the anode area. The pipeline liquid circulation and return device can realize the circulation and return of the anodic plating solution in the anode area, so as to increase the contact between oxygen and metal copper, sulfuric acid and copper oxide, and improve the reaction rate.

The electroplating liquid stirring device described in step (1) of the present invention can also adopt a jet vacuum oxygenation device, the suction area of the jet vacuum oxygenation device is connected to the oxygen source, and the liquid inlet of the jet vacuum oxygenation device is connected to the oxygen source. The port is connected with a pump and the bottom of the anode area in turn through a pipeline, and the liquid outlet of the jet vacuum oxygenation device is placed in the anode area, so that the anodic plating solution is returned to the anode area.

In the present invention, it is further preferable to use an automatic detection control machine to perform real-time detection on one or more parameters of acidity, photoelectric colorimetry, oxidation-reduction potential, and specific gravity of the cathodic electroplating solution, and control the jet vacuum oxygenation respectively. When the device is turned on and off, when the acidity of the cathodic electroplating solution is higher than the set value, the redox potential is lower than the set value, the photoelectric colorimetric resistance value is lower than the set value, and the specific gravity is lower than the set value, or In many cases: turn on the jet vacuum oxygenation device to increase the oxygen content of the electroplating solution in the anode area, accelerate the formation reaction of copper sulfate, and further stabilize the composition of the cathode electroplating solution.

In the present invention, an anodic plating solution oxygenation device can be arranged in the anode area, so that oxygen can be rapidly increased in the anode area as required.

In the present invention, it is further preferable to use an automatic detection control machine to perform real-time detection on one or more of the parameters of acidity, photoelectric colorimetry, redox potential and specific gravity of the cathodic electroplating solution, and control the increase of the anodic electroplating solution separately. The opening and closing of the oxygen device, when the acidity of the cathode plating solution is higher than the set value, the redox potential is lower than the set value, the photoelectric colorimetric resistance value is lower than the set value, and the specific gravity is lower than the set value. In one or more cases: the anodic electroplating solution oxygenation device is turned on to increase the oxygen content of the electroplating solution in the anode area, accelerate the formation reaction of copper sulfate, and further stabilize the composition of the cathodic electroplating solution.

The present invention can also preferably use a pump and a pipeline to connect the cathode area and the anode area, a filter screen is arranged in front of the liquid inlet of the pump, and the liquid outlet is placed in the anode area. The cathodic electroplating solution is added to the anode area to quickly replenish the sulfuric acid concentration in the anodic electroplating solution.

In the present invention, a pump and a pipeline can also be used to connect the anode area and the cathode area, a filter screen is arranged in front of the liquid inlet of the pump, and the liquid outlet is placed in the cathode area. Concentrated anodic plating solution is added to the cathode area to quickly replenish the copper sulfate concentration in the cathodic plating solution. In the present invention, it is more preferable to use an automatic detection and control machine to detect one or more of the acidity, specific gravity, and photoelectric colorimetric parameters of the cathodic plating solution in real time, and to control the start and stop of the pump, so as to control the concentration of high sulfuric acid The start and stop of the action of adding copper concentration anodic plating solution to the cathode area: when the acidity of the cathodic plating solution is higher than the set value, the specific gravity is lower than the set value and the photoelectric colorimetric value is lower than the set value. In one or more cases, the pump is turned on to add an anodic electroplating solution with high copper sulfate concentration to the cathode region, so that the composition of the cathodic electroplating solution is kept stable.

In a preferred embodiment of the present invention, the level of the anodic plating solution is higher than that of the cathodic plating solution, so that the anodic plating solution containing high sulfuric acid concentration can more easily enter the cathode region through the through holes on the separator by utilizing the pressure difference. When the diameter of the through hole is in the range of 0.1-1000 μm, the liquid level difference between the anodic plating solution and the cathodic plating solution can be realized.

A preferred embodiment of the present invention may be that, in the step (3), an automatic detection and control machine is used to set the copper ion concentration parameter of the anodic plating solution, so as to monitor the metal copper and/or copper oxide in the anode region in real time Dosing: When the automatic detection and control machine detects that the copper ion concentration of the anode plating solution is lower than the set value, it will remind or control to start adding copper and/or copper oxide to the anode area.

Another preferred embodiment of the present invention is that an electroplating solution regeneration tank is arranged beside the anode area, the electroplating solution regeneration tank is connected with the anode area by a pipeline to form a circulation loop, and the electroplating solution regeneration tank is equipped with a pipeline. There is a regeneration tank oxygen-enhancing device, and the copper and/or copper oxides described in step (2) can be added to the regeneration tank of the electroplating solution, so that the reaction between metal copper and oxygen in the electroplating process, and copper oxides The reaction with sulfuric acid takes place in the electroplating bath regeneration tank instead, which reduces the amount of oxygen in the anode area while further supplementing the copper ions in the electroplating bath. In the case of a plating bath regeneration tank, copper and/or copper oxide can be selectively added or not added to the anode zone.

The regenerating tank oxygenation device can also adopt a jet vacuum oxygenation device, the suction area of the jet vacuum oxygenation device is connected with the oxygen source, and the liquid inlet of the jet vacuum oxygenation device is connected in turn through a pipeline. A pump and the bottom of the anode area, the liquid outlet of the jet vacuum oxygenation device is placed in the anode area, and the anodic plating solution is returned to the anode area.

Preferably, one or more of the acidity, photoelectric colorimetry, redox potential, and specific gravity parameters of the cathodic electroplating solution are detected in real time by an automatic detection control machine, and the opening and closing of the oxygen-enhancing device of the regeneration tank are respectively controlled. : When the acidity of the cathodic electroplating solution is higher than the set value, the redox potential is lower than the set value, the photoelectric colorimetric resistance value is lower than the set value and the specific gravity is lower than the set value, it will be turned on. The regeneration tank oxygen-enhancing device accelerates the formation reaction of copper sulfate, and further stabilizes the composition of the cathodic electroplating solution.

The oxygen source of the anode plating solution oxygenation device, the jet vacuum oxygenation device or the regeneration tank oxygenation device of the present invention is selected from the oxygen generated on the anode, the air, the external oxygen source and the oxygen emitted by the zeolite molecular sieve oxygen generator. one or more combinations.

The second object of the present invention is achieved through the following technical solutions:

A device suitable for the acid copper electroplating process of the through hole isolation method, comprising:

An electroplating tank, a spacer with a through hole is arranged in the electroplating tank, and the electroplating tank is divided into an anode area and a cathode area, and an electroplating solution stirring device is arranged in the anode area to increase oxygen and metal copper, sulfuric acid contact with copper oxide;

A power source, the positive electrode of the power source is connected to the insoluble anode, the insoluble anode is placed in the anode area, the negative electrode of the power source is connected to a cathode plating piece, and the cathode plating piece is placed in the cathode area.

The number of the anode area/cathode area in the present invention may be one or more than one, and the cathode area and the anode area are arranged alternately.

The present invention can be further improved:

The pore diameter of the through holes on the spacer with through holes is 0.1-1000 μm, and the pore diameters between the through holes may be the same or different. The spacer with through holes can be one or more of filter cloth, plastic plate with through holes, ceramic plate with microporous or microporous filter membrane, and the filter cloth can be woven cloth or Non-woven fabrics; plastic plates with through holes or ceramic plates with micro holes can be plastic plates with through holes or ceramic plates with micro holes for filtering.

The electroplating solution stirring device of the present invention can adopt a pipeline liquid circulation return device. The pipeline liquid circulation return device is composed of a pump and a pipeline, and the liquid inlet of the pipeline liquid circulation return device is connected to the bottom of the anode area. , the liquid outlet is placed in the anode area, so that the anodic plating solution can be circulated back into the anode area.

The electroplating solution stirring device of the present invention can also adopt a jet vacuum oxygenation device. The suction area of the jet vacuum oxygenation device is connected to the oxygen source, and the liquid inlet of the jet vacuum oxygenation device is sequentially connected through a pipeline. A pump is connected to the bottom of the anode area, the liquid outlet of the jet vacuum oxygenation device is placed in the anode area, and the anodic plating solution is returned to the anode area.

Preferably, the jet vacuum oxygenation device can be connected to an automatic detection and control machine for real-time detection and control of one or more parameters of acidity, photoelectric colorimetry, redox potential and specific gravity of the cathodic plating solution. The opening and closing of the jet vacuum oxygenation device: when the acidity of the cathodic electroplating solution is higher than the set value, the redox potential is lower than the set value, the photoelectric colorimetric resistance value is lower than the set value and the specific gravity is lower than the set value When one or more of the values are met, the jet vacuum oxygenation device is turned on to increase the oxygen content of the electroplating solution in the anode area, accelerate the formation reaction of copper sulfate, and further stabilize the composition of the cathodic electroplating solution.

The anode area of the present invention may also be provided with an anode plating solution oxygenation device, so as to rapidly increase oxygen in the anode area as required.

Preferably, the anodic electroplating solution oxygenation device can be connected to an automatic detection control machine for real-time detection of one or more parameters of acidity, photoelectric colorimetry, redox potential, and specific gravity of the cathodic electroplating solution, and respectively Control the opening and closing of the oxygenation device of the anode plating solution: when the acidity of the cathode plating solution is higher than the set value, the redox potential is lower than the set value, the photoelectric colorimetric resistance value is lower than the set value and the specific gravity is lower than the set value In the case of one or more of the set values, the anodic electroplating solution oxygenation device is turned on to increase the oxygen content of the electroplating solution in the anode area, accelerate the formation reaction of copper sulfate, and further stabilize the composition of the cathodic electroplating solution.

In the present invention, a pump and a pipeline can also be used to connect the cathode area and the anode area, a filter screen is arranged in front of the liquid inlet of the pump, and the liquid outlet is placed in the anode area, and the cathode containing a higher concentration of sulfuric acid is placed in the anode area. The electroplating solution is added to the anode area to quickly replenish the sulfuric acid concentration in the anode electroplating solution.

In the present invention, a pump and a pipeline can also be used to connect the anode area and the cathode area, a filter screen is arranged in front of the liquid inlet of the pump, and the liquid outlet is placed in the cathode area. The anodic plating solution is added to the cathode area to quickly replenish the copper sulfate concentration in the cathodic plating solution. Preferably, the pump can be connected to an automatic detection control machine for real-time detection of one or more of the acidity, specific gravity, and photoelectric colorimetric parameters of the cathodic plating solution and to control the start and stop of the pump , to control the start and stop of the action of adding the anodic plating solution containing high copper sulfate concentration to the cathode area: when the acidity of the cathodic plating solution is higher than the set value, the specific gravity is lower than the set value and the photoelectric colorimetric value is low In one or more of the set values, the pump is turned on to add an anodic electroplating solution with high copper sulfate concentration to the cathode region, so that the composition of the cathodic electroplating solution remains stable.

In the present invention, an automatic detection and control machine can also be set in the anode area to monitor the addition of metallic copper and/or copper oxide in the anode area in real time: when the automatic detection control machine detects the copper content of the anode plating solution When the ion concentration is lower than the set value, it is reminded or controlled to start adding copper and/or copper oxide to the anode area.

In the present invention, an electroplating solution regeneration tank can also be arranged beside the anode area, and the electroplating solution regeneration tank is connected with the anode area by pipelines to form a circulation loop. The reaction between metallic copper and oxygen, and the reaction between copper oxide and sulfuric acid in the process are changed to occur in the electroplating bath regeneration tank, so that the copper ions in the electroplating bath are further supplemented, and the amount of oxygen in the anode area is reduced. .

The regenerating tank oxygenation device can also adopt a jet vacuum oxygenation device, the suction area of the jet vacuum oxygenation device is connected with the oxygen source, and the liquid inlet of the jet vacuum oxygenation device is connected in turn through a pipeline. A pump and the bottom of the anode area, the liquid outlet of the jet vacuum oxygenation device is placed in the anode area, and the anodic plating solution is returned to the anode area.

More preferably, the regeneration tank oxygen-enhancing device is connected to an automatic detection control machine for real-time detection and control of one or more of the acidity, photoelectric colorimetry, redox potential, and specific gravity parameters of the cathodic electroplating solution. The opening and closing of the oxygen-enhancing device in the electroplating solution regeneration tank: when the acidity of the cathode electroplating solution is higher than the set value, the redox potential is lower than the set value, the photoelectric colorimetric resistance value is lower than the set value and the specific gravity When one or more of the set values are lower than the set value, the oxygen-enhancing device of the regeneration tank is turned on to accelerate the formation reaction of copper sulfate and further stabilize the composition of the cathodic electroplating solution.

The oxygen source of the anode plating solution oxygenation device, the jet vacuum oxygenation device or the regeneration tank oxygenation device of the present invention is selected from the oxygen generated on the anode, the air, the external oxygen source and the oxygen emitted by the zeolite molecular sieve oxygen generator. one or more combinations.

The present invention has the following beneficial effects:

1. High quality and high efficiency: the acid copper electroplating process of the present invention sets an electroplating solution stirring device in the anode area, and uses a spacer with a through hole to separate the electroplating solutions in the cathode and anode areas. The reaction rate of oxygen and metallic copper, sulfuric acid and copper oxide, thereby improving the current efficiency of electroplating; quality, to meet the quality requirements of acid copper plating;

2. Energy saving and low production cost: the acid copper electroplating process of the present invention can use copper metal that is cheaper than phosphorous copper, and utilize the oxygen precipitated from the anode and the outside air as an oxidant to realize the energy saving and environmental protection process of synthesizing copper sulfate in the electroplating tank, To achieve the purpose of reducing costs;

3. Simple and environmentally friendly: the electroplating device of the process of the present invention is simple and reliable, can completely replace the acid copper plating process using soluble phosphor copper anode, and reduce environmental pollution.

Description of drawings

The present invention will be further described below with reference to the accompanying drawings.

Figure 1 Schematic diagram of the apparatus of Example 1 (electroplating solution, power source, cathode and anode are not shown).

Figure 2 Schematic diagram of the apparatus of Example 2 (electroplating solution, power source, cathode and anode are not shown).

Figure 3 Schematic diagram of the apparatus of Example 3 (electroplating solution, power source, cathode and anode are not shown).

Figure 4 Schematic diagram of the apparatus of Example 4 (electroplating solution, power source, cathode and anode are not shown).

Figure 5 Schematic diagram of the apparatus of Example 5 (electroplating solution, power source, cathode and anode are not shown).

Figure 6 Schematic diagram of the apparatus of Example 6 (electroplating solution, power source, cathode and anode are not shown).

Figure 7 Schematic diagram of the jet vacuum oxygenation device.

FIG. 8 is a schematic diagram of a plastic plate with through holes in Example 3. FIG.

Reference numerals: 1 - cathode area; 2 - anode area; 3 - electroplating solution stirring device; 4 - spacer with through holes; 5 - anodic plating solution oxygenation device; 6 - automatic detection and control machine; 7 - jet vacuum Oxygenation device; 8-pump; 9-exhaust hood; 10-compressed oxygen cylinder; 11-electroplating solution regeneration tank; 12-liquid inlet; 13-suction area; 14-liquid outlet.

Detailed ways

The present invention will be further described below through specific embodiments.

In the described embodiment and comparative example, the copper sulfate used is the copper sulfate produced by Changzhou Hairun Chemical Co., Ltd., and the sulfuric acid used is the sulfuric acid produced by Guangzhou Chemical Reagent Factory; the metal copper used is Changsha Tianjiu Metal Materials Co., Ltd. The metal copper powder produced; the copper oxide used is preferably the copper oxide powder produced by Guangzhou Chemical Reagent Factory; the cuprous oxide used is preferably the cuprous oxide produced by Taihe Metal Industry Co., Ltd.; the copper alloy used is preferably The silver-copper alloy produced by Shanghai Xinxi Alloy Materials Co., Ltd.; the rare earth oxide-coated titanium anode used is preferably the rare earth oxide-coated titanium anode plate produced by Shaanxi Elad New Material Technology Co., Ltd.; the metal-coated titanium anode used It is preferably a platinum-plated titanium anode produced by Shaanxi E-Lide New Material Technology Co., Ltd.; the titanium anode used is preferably a titanium plate produced by Shaanxi E-Lide New Material Technology Co., Ltd.; the platinum anode used is preferably Shaanxi E-Lide New Material Technology Co., Ltd. Platinum electrodes produced by New Material Technology Co., Ltd.; the lead alloy anodes used are preferably chrome-plated lead-tin anode rods produced by Gaopeng Surface Treatment Technology Co., Ltd.; the graphite anodes used are preferably graphite electrodes produced by Haimen Xingda Graphite Products Factory plate; the cathode plating used is a commercially available pure copper plate; the microscope used is an electron microscope produced by Guangzhou Optical Instrument Factory. In addition to those listed above, those skilled in the art can also select other products with similar properties to those listed in the present invention according to routine selection, all of which can achieve the purpose of the present invention.

The current efficiency is calculated by the following equation (1):

Current efficiency η= m'÷m×100%=m'÷(I·t·k)×100% Equation-1

In formula-1:

m' is the quality of the actual product;

m Calculate the mass of the theoretical product by Faraday's law;

I current intensity (A);

T power-on time (h);

K Electrochemical equivalent (g·/(A·h)).

Example 1

The device suitable for the acid copper electroplating process of the through hole isolation method as shown in FIG. 1 is one of the embodiments of the present invention, and it includes:

An electroplating tank, in which a filter cloth with a pore size of 1000 μm is set as a spacer 4 with through holes, and the electroplating tank is divided into an anode area 2 and a cathode area 1, and the anode area 2 is provided with an electroplating solution stirring device 3;

A power supply (not shown in the figure), the positive pole of the power supply is connected to an insoluble anode (not shown in the figure), the insoluble anode is placed in the anode area 2, and the negative pole of the power supply is connected to a cathode plating piece (not shown in the figure), The cathode plating member is placed in the cathode area 1 .

The through hole isolation method acid copper electroplating process includes the following steps:

(1) Use a filter cloth with a pore size of 1000 μm as a spacer 4 with through holes to separate the electroplating tank into an anode area 2 and a cathode area 1, and set a plating solution stirring device 3 in the anode area 2 for stirring the anode plating solution. ;

(2) Prepare a mixed solution with a sulfuric acid concentration of 60 g/L and a copper sulfate concentration of 50 g/L as the anodic electroplating solution and the cathodic electroplating solution, and pour the anodic electroplating solution and the cathodic electroplating solution into the anodic area 2 and the cathodic area 1 respectively, And add metallic copper in the anode area 2;

(3) Weigh the initial mass of the plated part, connect the titanium anode with rare earth oxide layer as the electroplating anode to the positive electrode of the power supply and immerse it in the anodic plating solution in the anode area 2, connect the cathode plated part to the negative electrode of the power supply and immerse the cathode In the cathode electroplating solution in zone 1; turn on the power supply, turn on the electroplating solution stirring device 3 in the anode zone 2, carry out electroplating, and the electroplating time is 15 hours. After drying, the current efficiency was calculated according to formula-1, and the surface of the coating was observed with an electron microscope, and the results were recorded in Table-1.

Example 2

The device suitable for the acid copper electroplating process of the through hole isolation method as shown in FIG. 2 is one of the embodiments of the present invention, which includes:

An electroplating tank, in which a plastic plate with a through hole with a diameter of 400 μm and a microporous ceramic plate with a diameter of 0.1 μm, 50 μm and 100 μm are arranged as the spacer 4 with through holes. The electroplating tank is divided into two anode regions 2 and a cathode region 1 located between the two anode regions 2. The anode region 2 is provided with an electroplating solution stirring device 3, and the electroplating solution stirring device 3 is composed of a pump. The pipeline liquid circulation return device composed of the Purwa pipeline, the liquid inlet of the pipeline liquid circulation return device is connected to the bottom of the anode area, and the pipeline of the liquid outlet enters the anode area 2 from the top of the anode area 2, so that the anode The electroplating solution is circulated back to the anode area;

Each of the two anode regions 2 is provided with an anodic plating solution oxygenation device 5, and the oxygen source is the oxygen emitted by a zeolite molecular sieve oxygen generator. The photoelectric colorimetric parameters of the electroplating solution are detected in real time and the opening and closing of the anodic electroplating solution oxygenation device 5 are controlled respectively;

A power supply (not shown in the figure), the positive pole of the power supply is connected to an insoluble anode (not shown in the figure), one of the insoluble anodes is placed in each of the two anode regions 2, and the negative pole of the power supply is connected to a cathode plating piece (not shown in the figure) shown), the cathode plating is placed in the cathode area 1.

The through hole isolation method acid copper electroplating process includes the following steps:

(1) Use a plastic plate with a through hole with a diameter of 400 μm and a microporous ceramic plate with a hole diameter of 0.1 μm, 50 μm and 100 μm as the spacer 4 with through holes to separate the electroplating tank into two anode areas 2 and the cathode area 1 located between the two anode areas, and the two anode areas 2 are both provided with a pipeline liquid circulation return device as the electroplating solution stirring device 3, and the pipeline liquid circulation return device is controlled by a return pump. Puhe pipeline is composed, the liquid inlet of the pipeline liquid circulation return device is connected to the bottom of the anode area 2, and the pipeline of the liquid outlet enters the anode area 2 from the top of the anode area 2, so that the anode plating solution can be circulated back. In the anode area 2, an anodic electroplating solution oxygenation device 5 is provided in the two anode areas 2, the oxygen source is the oxygen emitted by the zeolite molecular sieve oxygen generator, and the photoelectric ratio of the cathodic electroplating solution is measured by the automatic detection controller 6. The color parameters are detected in real time and the opening and closing of the anodic plating solution oxygenation device 5 are controlled respectively;

(2) Prepare a 300g/L sulfuric acid solution as an anodic plating solution, prepare a mixed solution with a copper sulfate concentration of 150g/L and a hydrochloric acid concentration of 5000mg/L as a cathodic electroplating solution, and pour the anodic electroplating solution and the cathodic electroplating solution respectively into In the anode zone 2 and the cathode zone 1, the gas outlet of the anodic electroplating solution oxygenation device 5 is then placed in the anodic electroplating solution, and in the anode zone 2, a mixture of metallic copper, cupric oxide and cuprous oxide is added;

(3) Weigh the initial mass of the plated parts, connect the metal-clad titanium anode and the titanium anode as electroplating anodes to the positive electrode of the power supply and immerse them in the anodic plating solution in the two anode regions 2 respectively, and connect the cathode plated part to the negative electrode of the power supply. Connected and immersed in the cathode electroplating solution in the cathode area 1; turn on the power supply, turn on the automatic detection control machine 6, and open the electroplating solution stirring device 3, and set the automatic detection control machine according to the measured photoelectric colorimetric value of the cathode electroplating solution. The photoelectric colorimetric value of 6, electroplating, when the photoelectric colorimetric of the cathodic electroplating solution is lower than the set value, the automatic detection control machine 6 controls to open the anodic electroplating solution oxygenation device 5, and the electroplating time is 15 hours, every 5 hours. Add a mixture of metallic copper, copper oxide and cuprous oxide to the anode area 2 for hours. After the electroplating, take out the cathode plated parts, wash them with clean water and dry them with hot air, and then calculate the current efficiency according to formula-1, and use an electron microscope to calculate the current efficiency. The surface of the coating was observed, and the results were recorded in Table-1.

Example 3

The device suitable for the acid copper electroplating process of the through hole isolation method as shown in FIG. 3 is one of the embodiments of the present invention, which includes:

An electroplating tank, in which a through-hole plastic plate with a diameter of 800 μm is set as the spacer 4 with through-holes. The through-hole plastic plate is shown in FIG. Cathode region 1, described anode region 2 is provided with jet vacuum oxygenation device 7 as electroplating solution stirring device 3, jet vacuum oxygenation device 7 is shown in Figure 7, and the air extraction hood 9 located above anode region 2 is used as The oxygen source is connected to the suction region 13 of the jet vacuum oxygenation device 7, and the liquid inlet 12 of the jet vacuum oxygenation device 7 is connected to the pump 8 and the bottom of the anode region 2 through pipes in turn. The liquid outlet 14 of the vacuum oxygenation device 7 enters the anode area 2 from the top of the anode area 2, so that the anodic plating solution is returned to the anode area 2;

The anode area 2 and the cathode area 1 are connected by a pump 8a and a pipeline. The pump 8a is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the anode area 2 from the top of the anode area 2 , the liquid outlet enters the cathode area 1 from the top of the cathode area 1, and the anodic electroplating solution containing higher copper sulfate concentration is added into the cathode area 1;

A power supply (not shown in the figure), the positive pole of the power supply is connected to an insoluble anode (not shown in the figure), the insoluble anode is placed in the anode area 2, and the negative pole of the power supply is connected to a cathode plating piece (not shown in the figure), The cathode plating member is placed in the cathode area 1 .

The through hole isolation method acid copper electroplating process includes the following steps:

(1) Use a through-hole plastic plate with a hole diameter of 800 μm as the spacer 4 with through-holes, separate the electroplating tank into an anode area 2 and a cathode area 1, and set a jet vacuum in the anode area 2 as the plating solution stirring device 3 Oxygenation device 7, and a suction hood 9 is set above the anode area 2, the suction area 13 of the jet vacuum oxygenation device 7 is connected with the air outlet of the suction hood 9 to absorb air and the oxygen produced on the anode area 2, The liquid inlet 12 of the jet vacuum oxygenation device 7 is sequentially connected to the pump 8 and the bottom of the anode region 2 through a pipeline, and the liquid outlet 14 of the jet vacuum oxygenation device 7 enters the anode region 2 from the top of the anode region 2; 8a and the pipeline are connected to the anode area 2 and the cathode area 1, the pump 8a is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the anode area 2 from the top of the anode area 2, and the outlet is The liquid port enters the cathode area 1 from the top of the cathode area 1, and the anodic plating solution containing the higher copper sulfate concentration is added into the cathode area 1;

(2) Prepare a mixed solution with a sulfuric acid concentration of 200 g/L and a copper sulfate concentration of 90 g/L as an anode plating solution, and prepare a mixed solution with a sulfuric acid concentration of 150 g/L and a copper sulfate concentration of 150 g/L as the cathodic plating solution. The anodic electroplating solution and the cathodic electroplating solution are poured into the anodic area 2 and the cathodic area 1 respectively, and metallic copper is added in the anodic area 2;

(3) Weigh the initial mass of the plated part, connect the platinum electrode as the electroplating anode to the positive electrode of the power supply and immerse it in the anodic plating solution in the anode area 2, connect the cathode plated part to the negative electrode of the power supply and immerse it in the cathode area 1. In the cathodic electroplating solution; turn on the power supply, turn on the jet vacuum oxygenation device 7, the pump 8 and the pump 8a in the anode area 2, keep the liquid level of the anodic electroplating solution always higher than the cathodic electroplating solution, carry out electroplating, and the electroplating time is: After 15 hours, the cathode plated parts were taken out after electroplating, washed with clean water and dried with hot air, and then calculated the current efficiency according to formula-1, and observed the surface of the plating layer with an electron microscope, and recorded the results in Table-1.

Example 4

The device suitable for the acid copper electroplating process by the through hole isolation method as shown in FIG. 4 is one of the embodiments of the present invention, which includes:

An electroplating tank, in which a microporous ceramic plate with a diameter of 200 μm is set as a spacer 4 with through holes, and the electroplating tank is divided into an anode area 2 and a cathode area 1. In the anode area 2 There is a jet vacuum oxygenation device 7 as the electroplating solution stirring device 3, and the compressed oxygen cylinder 10 is connected with the suction area 13 of the jet vacuum oxygenation device 7 as an oxygen source. The liquid inlet 12 is connected to the pump 8 and the bottom of the anode region 2 in turn through a pipeline, and the liquid outlet 14 of the jet vacuum oxygenation device 7 enters the anode region 2 from the top of the anode region 2, so that the anode plating solution is returned to the anode. Zone 2;

The anode area 2 and the cathode area 1 are connected by a pump 8a and a pipeline. The pump 8a is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the anode area 2 from the top of the anode area 2 , the liquid outlet enters the cathode area 1 from the top of the cathode area 1, and the anodic electroplating solution containing higher copper sulfate concentration is added into the cathode area 1;

The pump 8a and the jet vacuum oxygenation device 7 are connected to an automatic detection control machine 6 for real-time detection of the acidity and redox potential parameters of the cathodic electroplating solution and to control the flow rate of the jet vacuum oxygenation device 7 and the pump 8a respectively. On and off, when the acidity of the cathodic electroplating solution is higher than the set value, the jet vacuum oxygenation device 7 is turned on, and when the redox potential value of the cathodic electroplating solution is lower than the set value, the pump 8a is turned on;

The cathode area 1 and the anode area 2 are connected by the pump 8b and the pipeline. The pump 8b is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the cathode area 1 from the top of the cathode area 1 , the liquid outlet is placed in the anode area 2 from the top of the anode area 2, and the cathodic electroplating solution containing higher sulfuric acid concentration is added into the anode area;

A power supply (not shown in the figure), the positive pole of the power supply is connected to an insoluble anode (not shown in the figure), the insoluble anode is placed in the anode area 2, and the negative pole of the power supply is connected to a cathode plating piece (not shown in the figure), The cathode plating member is placed in the cathode area 1 .

The through hole isolation method acid copper electroplating process includes the following steps:

(1) Using a microporous ceramic plate with a pore diameter of 200 μm as the spacer 4 with through holes, the electroplating tank is divided into an anode area 2 and a cathode area 1, and a jet vacuum oxygenation device 7 is set in the anode area 2, and the jet vacuum The suction area 13 of the oxygenation device 7 is connected to the compressed oxygen cylinder 10 as an oxygen source, the liquid inlet 12 is connected to the pump 8 and the bottom of the anode area 2 through pipelines in turn, and the liquid outlet 14 enters from the top of the anode area 2. In the anode area 2; the anode area 2 and the cathode area 1 are connected by the pump 8a and the pipeline, and the pump 8a is provided with a filter screen (not shown in the figure) before the liquid inlet of the pump 8a and is connected from the anode area 2. The top enters the anode area 2, the liquid outlet enters the cathode area 1 from the top of the cathode area 1, and the anode plating solution containing higher copper sulfate concentration is added to the cathode area 1; Cathode area 1 and anode area 2, the pump 8b is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the cathode area 1 from the top of the cathode area 1, and the liquid outlet is placed from the anode area. The top of 2 enters the anode area 2, and the cathodic electroplating solution containing higher sulfuric acid concentration is added into the anode area; the automatic detection control machine 6 is used to detect the acidity and redox potential parameters of the cathodic electroplating solution and control the jet vacuum respectively. On and off the oxygenation device 7 and the pump 8a;

(2) Prepare a mixed solution with a sulfuric acid concentration of 500 g/L and a copper sulfate concentration of 50 g/L as an anode plating solution, and prepare a mixed solution with a sulfuric acid concentration of 50 g/L, a copper sulfate concentration of 240 g/L, and a hydrochloric acid concentration of 10 mg/L. The solution is used as a cathodic electroplating solution, and the anodic electroplating solution and the cathodic electroplating solution are poured into the anode area 2 and the cathode area 1 respectively, and metallic copper is added in the anode area 2;

(3) Weigh the initial mass of the plated part, connect the aluminum alloy electrode as the electroplating anode to the positive electrode of the power supply and immerse it in the anodic plating solution in the anode area 2, connect the cathode plated part to the negative electrode of the power supply and immerse it in the cathode area 1 In the cathodic electroplating solution; turn on the power supply, turn on the automatic detection control machine 6, the pump 8b, and set the acidity and the redox potential value of the automatic detection control machine 6 according to the measured acidity and redox potential value of the cathodic electroplating solution. , keep the liquid level of the anodic electroplating solution always higher than the cathodic electroplating solution, carry out electroplating, when the acidity of the cathodic electroplating solution is higher than the set value, turn on the jet vacuum oxygenation device 7, when the redox potential value of the cathodic electroplating solution is lower than the set value Turn on the pump 8a when the value is fixed; use another automatic detection control machine (not shown in the figure) to set the standard value of the copper ion concentration in the anodic plating solution, when the copper ion concentration in the anodic plating solution is lower than the set value When the automatic detection control machine automatically adds metal copper to the anode area 2, the electroplating time is 15 hours. After the electroplating is completed, the cathode plated parts are taken out, washed with clean water and dried with hot air, and the current efficiency is calculated according to formula-1. , and the surface of the coating was observed with an electron microscope, and the results were recorded in Table-1.

Example 5

The device suitable for the acid copper electroplating process by the through hole isolation method as shown in FIG. 5 is one of the embodiments of the present invention, which includes:

an electroplating tank, in which a microporous filter membrane with a pore diameter of 10 μm is set as the spacer 4 with through holes, and the electroplating tank is divided into an anode area 2 and a cathode area 1;

A plating solution regeneration tank 11 is arranged beside the anode area 2, and the plating solution regeneration tank 11 is connected with the anode area 2 by pipelines to form a circulation loop. The plating solution regeneration tank 11 is provided with a jet vacuum oxygenation device 7 as a regeneration tank oxygenation device , the suction hood 9 located above the anode area 2 is connected with the suction area 13 of the jet vacuum oxygenation device 7 as an oxygen source, and the liquid inlet 12 of the jet vacuum oxygenation device 7 is connected to the pump 8 through a pipeline. and the bottom of the plating solution regeneration tank 11, the liquid outlet 14 of the jet vacuum oxygenation device 7 enters the plating solution regeneration tank 11 from the top of the plating solution regeneration tank 11, so that the plating solution in the plating solution regeneration tank 11 is returned to the plating solution in the regeneration tank 11;

The anode area 2 and the cathode area 1 are connected by a pump 8a and a pipeline. The pump 8a is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the anode area 2 from the top of the anode area 2 , the liquid outlet enters the cathode area 1 from the top of the cathode area 1, and the anodic electroplating solution containing higher copper sulfate concentration is added into the cathode area 1;

The cathode area 1 and the anode area 2 are connected by the pump 8b and the pipeline. The pump 8b is provided with a filter screen (not shown in the figure) before the liquid inlet and enters the cathode area 1 from the top of the cathode area 1 , the liquid outlet is placed in the anode area 2 from the top of the anode area 2, and the cathodic electroplating solution containing higher sulfuric acid concentration is added into the anode area;

A power supply (not shown in the figure), the positive pole of the power supply is connected to an insoluble anode (not shown in the figure), the insoluble anode is placed in the anode area 2, and the negative pole of the power supply is connected to a cathode plating piece (not shown in the figure), The cathode plating member is placed in the cathode area 1 .

The through hole isolation method acid copper electroplating process includes the following steps:

(1) Using a microporous filter membrane with a pore size of 10 μm as the spacer 4 with through holes, the electroplating tank is divided into an anode area 2 and a cathode area 1, and a plating solution regeneration tank 11 and an electroplating solution regeneration tank are set next to the anode area 2. 11 is connected with the anode area 2 by pipelines to form a circulation loop; the electroplating solution regeneration tank 11 is used as the jet vacuum oxygenation device 7 of the regeneration tank oxygenation device, and the air extraction hood 9 is set above the anode area 2, and the jet vacuum oxygenation device 7 The suction area 13 is connected with the air outlet of the air extraction hood 9 to absorb the oxygen generated on the air and the anode area 2, and the liquid inlet 12 of the jet vacuum oxygenation device 7 is connected to the pump 8 and the electroplating solution regeneration tank 11 through the pipeline in turn. At the bottom, the liquid outlet 14 of the jet vacuum oxygenation device 7 enters the plating solution regeneration tank 11 from the top of the plating solution regeneration tank 11, so that the plating solution in the plating solution regeneration tank 11 is returned to the plating solution regeneration tank 11; using automatic The detection and control machine 6 detects the specific gravity parameter of the cathodic electroplating solution and controls the opening and closing of the jet vacuum oxygenation device 7 respectively; Pu 8a is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the anode zone 2 from the top of the anode zone 2, and the liquid outlet enters the cathode zone 1 from the top of the cathode zone 1, which will contain higher sulfuric acid. The anodic plating solution of copper concentration is added into the cathode area 1; the pump 8b and the pipeline are connected to the cathode area 1 and the anode area 2, and the pump 8b is provided with a filter screen (not shown in the figure) before the liquid inlet. out) and enter the cathode area 1 from the top of the cathode area 1, the liquid outlet is placed in the anode area 2 from the top of the anode area 2, and the cathodic electroplating solution containing higher sulfuric acid concentration is added to the anode area;

(2) Prepare a mixed solution with a sulfuric acid concentration of 70 g/L and a copper sulfate concentration of 10 g/L as an anode plating solution, and prepare a mixed solution with a sulfuric acid concentration of 0.001 g/L and a copper sulfate concentration of 80 g/L as a cathodic plating solution, Pour the anodic electroplating solution and the cathodic electroplating solution into the anodic area 2 and the cathodic area 1 respectively, and add copper alloy in the anodic area 2;

(3) Weigh the initial mass of the plated piece, connect the graphite anode as the electroplating anode to the positive electrode of the power supply and immerse it in the anodic plating solution in the anode area 2, connect the cathode plated piece with the negative electrode of the power supply and immerse the anode in the cathode area 1. In the cathodic electroplating solution; turn on the power supply, turn on the automatic detection control machine 6, the pump 8a and the pump 8b, set the specific gravity value of the automatic detection control machine 6 according to the measured specific gravity of the cathodic electroplating solution, and keep the liquid of the anodic electroplating solution. The position is always higher than the cathode electroplating solution, and electroplating is carried out. When the specific gravity of the cathode electroplating solution is lower than the set value, the jet vacuum oxygenation device 7 is turned on. The electroplating time is 15 hours. After drying with hot air, the current efficiency was calculated according to formula-1, and the surface of the coating was observed with an electron microscope, and the results were recorded in Table-1.

Example 6

The device suitable for the acid copper electroplating process of the through hole isolation method as shown in FIG. 6 is one of the embodiments of the present invention, which includes:

An electroplating tank, in which a through-hole plastic plate with a diameter of 600 μm is set as the spacer 4 with through-holes, and the electroplating tank is divided into an anode area 2 and a cathode area 1, and the anode area 2 is provided with an anode Electroplating solution oxygenation device, the oxygen source is compressed oxygen cylinder 10;

A plating solution regeneration tank 11 is arranged next to the anode area 2, and the plating solution regeneration tank 11 is connected with the anode area 2 by pipelines to form a circulation loop. The plating solution regeneration tank 11 is provided with a regeneration tank oxygenation device, and the oxygen source is a compressed oxygen cylinder 10 ;

The anode area 2 and the cathode area 1 are connected by a pump 8a and a pipeline. The pump 8a is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the anode area 2 from the top of the anode area 2 , the liquid outlet enters the cathode area 1 from the top of the cathode area 1, and the anodic electroplating solution containing higher copper sulfate concentration is added into the cathode area 1;

The cathode area 1 and the anode area 2 are connected by the pump 8b and the pipeline. The pump 8b is provided with a filter screen (not shown in the figure) in front of the liquid inlet and enters the cathode area 1 from the top of the cathode area 1 , the liquid outlet is placed in the anode area 2 from the top of the anode area 2, and the cathodic electroplating solution containing higher sulfuric acid concentration is added into the anode area;

The pump 8a and the compressed oxygen cylinder 10 are connected to an automatic detection and control machine 6, which is used for real-time detection of the acidity, photoelectric colorimetry and redox potential parameters of the cathodic electroplating solution and controls the opening, closing and pumping of the valve of the compressed oxygen cylinder 10 respectively. Pu 8a is turned on and off, when the photoelectric colorimetric parameter or the redox potential parameter of the cathodic electroplating solution is lower than the set value, the valve of the compressed oxygen cylinder 10 is activated, and when the redox potential of the cathodic electroplating solution is lower than the set value Turn on the pump 8a;

A power supply (not shown in the figure), the positive pole of the power supply is connected to an insoluble anode (not shown in the figure), the insoluble anode is placed in the anode area 2, and the negative pole of the power supply is connected to a cathode plating piece (not shown in the figure), The cathode plating member is placed in the cathode area 1 .

The through hole isolation method acid copper electroplating process includes the following steps:

(1) Use a plastic plate with a through hole with a diameter of 600 μm as the spacer 4 with a through hole to separate the electroplating tank into an anode area 2 and a cathode area 1, and set the electroplating solution regeneration tank 11 next to the anode area 2. The electroplating solution is regenerated The tank 11 and the anode area 2 are connected by pipelines to form a circulation loop; the electroplating solution regeneration tank 11 and the anode area 2 are respectively connected with the compressed oxygen cylinder 10, and the gas outlet of the compressed oxygen cylinder 10 is respectively placed in the electroplating solution regeneration tank 17 and the electroplating solution. In the anode area 2 of the tank; the pump 8a and the pipeline are connected to the anode area 2 and the cathode area 1, and the pump 8a is provided with a filter screen (not shown in the figure) before the liquid inlet of the pump 8a and is connected from the anode area 2. The top enters the anode area 2, the liquid outlet enters the cathode area 1 from the top of the cathode area 1, and the anodic plating solution containing higher copper sulfate concentration is added to the cathode area 1; Use the pump 8b to connect the described The cathode area 1 and the anode area 2, the pump 8b is provided with a filter screen (not shown in the figure) before the liquid inlet and enters the cathode area 1 from the top of the cathode area 1, and the liquid outlet is placed from the anode. The top of the area 2 enters the anode area 2, and the cathodic electroplating solution containing higher sulfuric acid concentration is added into the anode area; the acidity, photoelectric colorimetry and redox potential parameters of the cathodic electroplating solution are checked in real time using the automatic detection control machine 6 Detect and respectively control the opening and closing of the valve of the compressed oxygen cylinder 10 and the opening and closing of the pump 8a, as shown in Figure 6;

(2) Prepare a mixed solution with a sulfuric acid concentration of 700 g/L and a copper sulfate concentration of 0.001 g/L as an anode plating solution, and prepare a mixed solution with a sulfuric acid concentration of 400 g/L and a copper sulfate concentration of 240 g/L as the cathodic plating solution, Pour the anodic electroplating solution and the cathodic electroplating solution into the anodic area 2 and the cathodic area 1 respectively, and add metallic copper in the anodic area 2;

(3) Weigh the initial mass of the plated part, connect the titanium anode with rare earth oxide layer as the electroplating anode to the positive electrode of the power supply and immerse it in the anodic plating solution in the anode area 2, connect the cathode plated part to the negative electrode of the power supply and immerse the cathode In the cathodic electroplating solution in zone 1; turn on the power supply, turn on the automatic detection control machine 6 and the pump 8b, and set the automatic detection control machine 6 according to the measured acidity, photoelectric colorimetry and redox potential parameters of the cathodic electroplating solution. The values of acidity, photoelectric colorimetry and redox potential, keep the level of the anodic plating solution always higher than that of the cathodic plating solution, and perform electroplating. When the photoelectric colorimetric parameter or the redox potential parameter of the cathodic plating solution is lower than the set value, start Compress the valve of the oxygen cylinder 10, turn on the pump 8a when the redox potential of the cathodic plating solution is lower than the set value; use another automatic detection control machine (not shown in the figure) to set the copper ion concentration in the anodic plating solution The standard value, when the copper ion concentration in the anode plating solution is lower than the set value, the automatic detection control machine automatically adds metal copper to the anode area 2, and the electroplating time is 15 hours. After the electroplating, the cathode is plated The parts were taken out, washed with clean water and dried with hot air, and the current efficiency was calculated according to formula-1, and the surface of the coating was observed with an electron microscope, and the results were recorded in Table-1.

Comparative Example 1

Units for the insoluble anodic acid copper electroplating process include:

an electroplating tank;

A power supply, the positive pole of the power supply is connected to the insoluble anode, the negative pole of the power supply is connected to a cathode plating piece, and the insoluble anode and the cathode plating piece are placed in the electroplating tank.

The insoluble anodic acid copper electroplating process consists of the following steps:

(1) Prepare a mixed solution with a sulfuric acid concentration of 60 g/L and a copper sulfate concentration of 50 g/L as an electroplating solution, and pour the obtained electroplating solution into an electroplating tank;

(2) Weigh the initial mass of the plated piece, connect the titanium metal as an insoluble electroplating anode to the positive electrode of the power supply and immerse it in the electroplating solution, connect the cathode plated piece to the negative electrode of the power supply and immerse it in the electroplating solution; turn on the power supply, and start the energization Carry out electroplating, the electroplating time is 15 hours, after the electroplating, the cathode plating parts are taken out, washed with water and dried with hot air, and the current efficiency is calculated according to formula-1, and the surface of the plating layer is observed with a computer microscope, and the results are recorded in Table-1 among.

Table 1

Cathode current efficiency/% Surface observation of plated parts Example 1 99 Flat and dense Example 2 98 Flat and dense Example 3 100 Flat and dense Example 4 99 Flat and dense Example 5 99 Flat and dense Example 6 98 Flat and dense Comparative Example 1 95 The thickness of the coating surface is uneven, and the metal particles are relatively loose

From the results in Table-1 above, it can be seen that the flatness of the surface of the plated parts obtained by the plating in Examples 1 to 6 is significantly higher than that of the pair that does not use a spacer with a through hole to separate the electroplating tank into an anode area and a cathode area. Example 1, and in terms of cathode current efficiency, Examples 1 to 6 are also improved compared to Comparative Example 1. This is precisely because Examples 1 to 6 use spacers with through holes to affect the electroplating solutions in the cathode and anode regions. The separation can overcome the influence of the surging of the electroplating solution in the anode area on the cathode area due to stirring and gas movement.

It should be pointed out that the above-mentioned embodiments are only further descriptions of the present invention, rather than limitations, and non-essential modifications and adjustments made by those skilled in the art according to the present invention still belong to the protection scope of the present invention.

Claims (26)

1. The acid copper electroplating process by using the through hole isolation method is characterized by comprising the following steps of:

(1) a spacer with a through hole is used for dividing the electroplating bath into an anode area and a cathode area, and an electroplating solution stirring device is arranged in the anode area;

(2) respectively preparing an anode electroplating solution and a cathode electroplating solution, wherein the anode electroplating solution contains sulfuric acid or contains sulfuric acid and copper sulfate, the cathode electroplating solution contains sulfuric acid and copper sulfate, respectively pouring the anode electroplating solution and the cathode electroplating solution into an anode area and a cathode area, and adding metal copper or metal copper and copper oxide into the anode area;

(3) connecting an insoluble anode serving as an electroplating anode with a positive electrode of a power supply and immersing the insoluble anode into anode electroplating solution in an anode area, and connecting a cathode electroplating piece with a negative electrode of the power supply and immersing the cathode electroplating solution in a cathode area; switching on a power supply to carry out electroplating, and starting an electroplating solution stirring device in an anode area in the electroplating process to increase the contact of oxygen with the metal copper and the sulfuric acid and accelerate the reaction of the metal copper with the oxygen and the sulfuric acid to generate copper sulfate so as to supplement copper ions in the electroplating solution;

the electroplating solution stirring device in the step (1) adopts a jet vacuum oxygenation device, an air suction area of the jet vacuum oxygenation device is communicated with an oxygen source, a liquid inlet of the jet vacuum oxygenation device is sequentially connected with the bottoms of a pump and an anode area through a pipeline, a liquid outlet of the jet vacuum oxygenation device is arranged in the anode area, and anode electroplating solution flows back to the anode area so as to increase the oxygen amount of the electroplating solution in the anode area and accelerate the reaction of metal copper in the electroplating process to generate copper sulfate;

the through holes on the spacer with the through holes in the step (1) are fine holes which are uniformly distributed on the spacer and have the aperture within the range of 0.1-1000 mu m, and the spacer with the through holes is one or more of filter cloth, a plastic plate with the through holes, a ceramic plate with micropores or a microporous filter membrane; the filter cloth is woven cloth/non-woven cloth; the plastic plate with the through holes or the ceramic plate with the micropores is used for filtering.

2. The isolated via acid copper plating process of claim 1, wherein in step (1), the plating bath is divided into an anode region and a cathode region by a spacer having a via hole, the number of the anode region and/or the cathode region is one or more, and the cathode region and the anode region are alternately arranged.

3. The process of acid electroplating copper by via isolation according to claim 1 or 2, wherein the insoluble anode is one or more of a platinum electrode, a lead alloy electrode, a graphite electrode, a titanium alloy electrode, a titanium-based electrode coated with other metal or rare earth oxide coating or metal alloy.

4. The process of claim 3, wherein the step (3) of electroplating is performed by intermittently adding copper metal and/or copper oxide to the anode region to replenish the source of copper ions.

5. The via isolation acid copper electroplating process according to claim 4, wherein the source of metallic copper or copper oxide added to the anode region in steps (2) and (3) is one or more of copper metal, copper oxide, and copper alloy.

6. The via isolation acid copper plating process of claim 5, wherein the via hole diameter of the via-hole spacer is the same or different from via hole to via hole.

7. The acid copper electroplating process by the through hole isolation method according to claim 6, wherein an automatic detection control machine is used for detecting one or more of acidity, photoelectric colorimetry, oxidation-reduction potential and specific gravity parameters of the cathode electroplating solution in real time and respectively controlling the on and off of the jet flow vacuum oxygenation device, and when one or more of the acidity of the cathode electroplating solution is higher than a set value, the oxidation-reduction potential is lower than the set value, the photoelectric colorimetry resistance is lower than the set value and the specific gravity is lower than the set value: and opening the jet flow vacuum oxygenation device to increase the oxygen amount of the electroplating solution in the anode area, accelerating the generation reaction of copper sulfate and further keeping the components of the cathode electroplating solution stable.

8. The process of claim 6, wherein the cathode region and the anode region are connected by a pump and a pipeline, a filter screen is arranged in front of a liquid inlet of the pump, a liquid outlet of the pump is arranged in the anode region, and the catholyte solution with higher sulfuric acid concentration is added into the anode region to rapidly supplement the sulfuric acid concentration in the anolyte solution.

9. The process of claim 6 or 8, wherein the anode region and the cathode region are connected by a pump and a pipeline, a filter screen is arranged in front of a liquid inlet of the pump, a liquid outlet is arranged in the cathode region, and anode electroplating solution with higher copper sulfate concentration is added into the cathode region to quickly supplement the copper sulfate concentration in the cathode electroplating solution.

10. The process of claim 9, wherein an automatic detection controller is used to detect one or more of acidity, specific gravity and photoelectric colorimetric parameters of the catholyte in real time and control the on and off of the pump to control the start and off of the feeding of the anolyte solution containing high copper sulfate concentration into the cathode region: when the condition of one or more of acidity of the cathodic electroplating solution is higher than a set value, specific gravity of the cathodic electroplating solution is lower than a set value and photoelectric colorimetric value of the cathodic electroplating solution is lower than a set value, the pump is started to add the anodic electroplating solution with high copper sulfate concentration to the cathode region, so that the components of the cathodic electroplating solution are kept stable.

11. The process of claim 6, wherein the anode plating solution is at a higher level than the cathode plating solution, so that the anode plating solution with high sulfuric acid concentration can more easily enter the cathode region through the through-hole on the separator by using the pressure difference.

12. The acid copper electroplating process according to claim 5, wherein in step (3), an automatic detection control machine is used to set the concentration parameter of copper ions in the anode electroplating solution so as to monitor the addition of copper metal in the anode region in real time: when the automatic detection control machine detects that the concentration of the copper ions in the anode electroplating solution is lower than a set value, the start of adding copper into the anode area is reminded or controlled.

13. The acid copper electroplating process according to claim 1 or 2, wherein an electroplating solution regeneration tank is arranged beside the anode region, the electroplating solution regeneration tank is connected with the anode region through a pipeline to form a circulation loop, the electroplating solution regeneration tank is provided with a regeneration tank oxygenation device, and metallic copper is added into the electroplating solution regeneration tank, so that the reaction of the metallic copper and oxygen in the electroplating process is generated in the electroplating solution regeneration tank to supplement copper ions in the electroplating solution.

14. The acid copper electroplating process by using through hole isolation method as claimed in claim 13, wherein the aeration device of the regeneration tank adopts a jet vacuum aeration device, the air suction area of the jet vacuum aeration device is communicated with an oxygen source, the liquid inlet of the jet vacuum aeration device is sequentially connected with a pump and the bottom of the electroplating solution regeneration tank through a pipeline, and the liquid outlet of the jet vacuum aeration device is arranged in the electroplating solution regeneration tank, so that the electroplating solution in the electroplating solution regeneration tank flows back to the electroplating solution regeneration tank.

15. The process of claim 14, wherein an automatic detection controller is used to detect one or more of acidity, photoelectric colorimetry, oxidation-reduction potential and specific gravity parameters of the cathode electroplating solution in real time and control the regeneration tank oxygenation device to turn on and off respectively: when the cathode electroplating solution has one or more of acidity higher than a set value, oxidation-reduction potential lower than a set value, photoelectric colorimetric resistance lower than a set value and specific gravity lower than a set value, the regeneration tank oxygenation device is started to accelerate the generation reaction of copper sulfate, and further the components of the cathode electroplating solution are kept stable.

16. An apparatus suitable for a through hole isolation method acid copper electroplating process, comprising: the electroplating bath is divided into an anode area and a cathode area by arranging a spacer with a through hole, and an electroplating solution stirring device is arranged in the anode area to increase the contact between oxygen and metal copper and between sulfuric acid and copper oxide; the anode of the power supply is connected with the insoluble anode, the insoluble anode is arranged in the anode area, the cathode of the power supply is connected with a cathode plating piece, and the cathode plating piece is arranged in the cathode area;

the electroplating solution stirring device adopts a jet vacuum oxygenation device, an air suction area of the jet vacuum oxygenation device is communicated with an oxygen source, a liquid inlet of the jet vacuum oxygenation device is sequentially connected with the bottom of a pump and the bottom of an anode area through a pipeline, and a liquid outlet of the jet vacuum oxygenation device is arranged in the anode area to enable anode electroplating solution to flow back into the anode area;

the through holes on the spacer with the through holes are fine holes which are uniformly distributed on the spacer and have the aperture within the range of 0.1-1000 mu m, and the spacer with the through holes is one or more of filter cloth, a plastic plate with the through holes, a ceramic plate with the micro holes or a micro-porous filter membrane; the filter cloth is woven cloth/non-woven cloth; the plastic plate with the through holes or the ceramic plate with the micropores is used for filtering.

17. The apparatus according to claim 16, wherein the number of the anode/cathode regions is one or more, and the cathode and anode regions are alternately arranged.

18. The apparatus of claim 17, wherein the through hole diameter of the through hole spacer is the same or different from one through hole to another through hole.

19. The apparatus of claim 18, wherein the jet vacuum aerator is connected to an automatic detection controller for detecting one or more of acidity, photoelectric colorimetry, oxidation-reduction potential, and specific gravity parameters of the cathode electroplating solution in real time and controlling the on/off of the jet vacuum aerator respectively: when the condition or the conditions of acidity of the cathode electroplating solution is higher than a set value, oxidation-reduction potential is lower than a set value, photoelectric colorimetric resistance is lower than a set value and specific gravity is lower than a set value occur, the jet flow vacuum oxygenation device is started to increase the oxygen amount of the electroplating solution in the anode area, accelerate the generation reaction of copper sulfate and further keep the components of the cathode electroplating solution stable.

20. The apparatus of any one of claims 16 to 19, wherein a pump and a pipe are used to connect the cathode region and the anode region, a filter screen is provided in front of the pump inlet, the pump outlet is disposed in the anode region, and the catholyte solution with higher sulfuric acid concentration is added to the anode region to rapidly replenish the sulfuric acid concentration in the anolyte solution.

21. The apparatus of claim 20, wherein the anode region and the cathode region are connected by a pump and a pipe, a filter screen is disposed in front of a liquid inlet of the pump, a liquid outlet of the pump is disposed in the cathode region, and an anode plating solution with a higher copper sulfate concentration is added to the cathode region to rapidly replenish the copper sulfate concentration in the cathode plating solution.

22. The apparatus of claim 20, wherein the pump is connected to an automatic detection controller for real-time detection of one or more of acidity, specific gravity and photoelectric colorimetric parameters of the cathode plating solution and controlling the on/off of the pump to control the start and stop of the feeding of the anode plating solution containing high copper sulfate concentration into the cathode region: when the condition of one or more of acidity of the cathodic electroplating solution is higher than a set value, specific gravity of the cathodic electroplating solution is lower than a set value and photoelectric colorimetric value of the cathodic electroplating solution is lower than a set value, the pump is started to add the anodic electroplating solution with high copper sulfate concentration to the cathode region, so that the components of the cathodic electroplating solution are kept stable.

23. An apparatus as claimed in any one of claims 16 to 19, wherein an automatic detection control machine is provided in the anode region for real-time monitoring of the copper metal addition in the anode region: when the automatic detection control machine detects that the concentration of the copper ions in the anode electroplating solution is lower than a set value, the start of adding copper into the anode area is reminded or controlled.

24. The apparatus of claim 23, wherein a plating solution regeneration tank is disposed beside the anode region, the plating solution regeneration tank is connected to the anode region via a pipeline to form a circulation loop, and the plating solution regeneration tank is provided with a regeneration tank oxygenation device for feeding copper metal into the plating solution regeneration tank, so that the reaction between the copper metal and oxygen during plating occurs in the plating solution regeneration tank to replenish copper ions in the plating solution.

25. The apparatus of claim 24, wherein the regeneration tank oxygenation device is a jet vacuum oxygenation device, an air suction region of the jet vacuum oxygenation device is connected to an oxygen source, a liquid inlet of the jet vacuum oxygenation device is sequentially connected to the bottom of a pump and an anode region through a pipeline, and a liquid outlet of the jet vacuum oxygenation device is disposed in the anode region to enable an anode plating solution to flow back into the anode region.

26. The apparatus of claim 25, wherein the oxygen-enriching device of the regeneration tank is connected to an automatic detection controller for detecting one or more of acidity, photoelectric colorimetry, oxidation-reduction potential and specific gravity parameters of the cathode electroplating solution in real time and controlling the on-off of the oxygen-enriching device in the electroplating solution regeneration tank respectively: when the cathode electroplating solution has one or more of acidity higher than a set value, oxidation-reduction potential lower than a set value, photoelectric colorimetric resistance lower than a set value and specific gravity lower than a set value, the regeneration tank oxygenation device is started to accelerate the generation reaction of copper sulfate, and further the components of the cathode electroplating solution are kept stable.

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