CN114921819B - Method for improving stability of hole-filling copper plating solution of phosphorus copper anode - Google Patents
Method for improving stability of hole-filling copper plating solution of phosphorus copper anode Download PDFInfo
- Publication number
- CN114921819B CN114921819B CN202210508649.9A CN202210508649A CN114921819B CN 114921819 B CN114921819 B CN 114921819B CN 202210508649 A CN202210508649 A CN 202210508649A CN 114921819 B CN114921819 B CN 114921819B
- Authority
- CN
- China
- Prior art keywords
- hole
- copper plating
- plating solution
- filling
- aeration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/429—Plated through-holes specially for multilayer circuits, e.g. having connections to inner circuit layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for improving stability of a hole-filling copper plating solution of a phosphorus copper anode, which is simple to operate and eliminates Cu in an oxidation mode + And by-products brought by the method, the waste of additives and electric quantity caused by long-time heavy-current cylinder dragging in the traditional maintenance method is avoided, the activity of the hole filling plating solution is maintained through aeration under the condition of copper plating production, and when the plate is stopped, the redundant phosphorus element in the hole filling plating solution is removed through adding hydrogen peroxide and ferrous sulfate, and the activity of the hole filling plating solution can be recovered only by short-time heavy-current cylinder dragging, so that the production efficiency of products is improved, and the production cost of the products is greatly reduced.
Description
Technical Field
The invention relates to the technical field of electric appliance copper plating, in particular to a method for improving stability of a hole-filling copper plating solution of a phosphorus copper anode.
Background
With the daily and monthly updating of electronic products, the products tend to be miniaturized, high-density and visualized more and more. To meet the miniaturization requirements of circuit boards, HDI boards have been developed, and the plated hole fills in the HDI boards represent a significant portion of the cost of production. The acidic hole-filling copper plating solution is based on sulfuric acid and copper sulfate, and the perfect filling of blind holes is realized by adding a plurality of additives such as chloride ions, brightening agent, wetting agent and leveling agent.
The anode of the acidic pore-filling plating can be classified into an insoluble anode and a soluble anode. The insoluble anode mainly uses titanium as base material, and its surface is coated with oxide of noble metal of iridium and tantalum as its functional coating, and because the insoluble anode has fixed area, the anode itself is insoluble, and its surface is coated with noble metal, so that it has the characteristics of uniform current density, and can not produce Cu + The advantages are that the insoluble anode has the disadvantages of high price, high production cost and the like; another kind ofThe anode is a phosphorus copper anode and is also a mainstream anode at present, wherein the phosphorus content is 0.04% -0.065%, the phosphorus copper anode generates a layer of black anode film in the dissolving process, the anode can be normally dissolved to reduce the falling of tiny particles, the generation of copper powder is reduced, and the film comprises the main component of Cu 3 P, can accelerate Cu + Oxidation of Cu is reduced + Is not completely free of Cu + The existence of the phosphor-copper anode can effectively fill the holes at the beginning, but the hole filling effect is poorer and worse along with the time, particularly when the production line does not continuously plate, mainly because of the high concentration of Cu 2+ Reacts with phosphor copper to produce Cu + Cu in the plating solution, particularly without making a plate + The additive is destroyed by the plating solution, the performance of filling holes becomes worse and the burrs, i.e. the coarse copper and the non-bright plating layer, poor leveling property, poor running property, poor plating quality and the like, are caused to the cathode plating layer.
Disclosure of Invention
The invention aims to provide a method for improving stability of a hole-filling copper plating solution of a phosphorus copper anode, which aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a method for improving stability of a hole-filling copper plating solution of a phosphorus copper anode has the following characteristics that:
s1, during copper plating production, a plate to be plated is placed in a hole filling copper plating solution, hole filling is performed through electroplating, and during electroplating, aeration treatment is performed in the hole filling copper plating solution;
s2, after stopping plating, removing a phosphorus copper anode, adding ferrous sulfate into the hole-filling copper plating solution, and then slowly adding hydrogen peroxide;
s3, heating the hole-filling copper plating liquid to 60-75 ℃, preserving heat for 1-2h, and stirring by aeration;
s4, stopping heating, cooling the hole-filling copper plating solution to room temperature, stopping aeration, adding active carbon, settling and filtering;
s5, after the phosphorus copper anode is put back into the copper plating solution, formaldehyde is added, aeration is continued, and small current is applied to drag the cylinder so as to recover the activity of the hole filling electroplating solution.
In the acidic copper plating solution, when pure copper is used as an anode, the phenomenon that the pure copper of the anode is dissolved too fast under the action of electric power often occurs, and the phenomenon that copper powder or burrs are generated due to too fast deposition speed on a cathode affects the surface smoothness and bonding strength of a PCB (printed circuit board), and finally the quality of a product is reduced. In the phosphorus-copper anode, 0.040-0.065% of phosphorus element is mixed in pure copper crystal, when electroplating is carried out, copper ions in the phosphorus-copper anode can not directly lose electrons and become divalent cations to enter electroplating solution, but can react with phosphorus element to generate Cu containing monovalent copper ions 3 P, and forming a black film to cover the phosphor copper anode, separating the anode from the electroplating solution like a fence, thereby changing the current efficiency of the anode, enabling the current efficiency of the anode to approach that of the cathode, controlling the dissolution speed of the anode copper, and keeping the concentration of bivalent copper ions in the hole-filling copper plating solution balanced.
Although the copper powder and burrs generated by the phosphor-copper anode during the production of the board are greatly reduced compared with the pure copper anode, the Cu cannot be completely avoided + Is generated, and Cu in the plating solution is generated along with the prolonging of the service time of the plating solution + The additive is destroyed by the plating solution, the pore filling performance becomes worse and worse, burrs, non-brightness, poor leveling property, poor running property, poor coating quality and other defects are caused to the cathode coating, and as the anode slime is hardly generated by the phosphor copper anode, substances in the phosphor copper anode can be fully fused into the plating solution, and as copper elements in the phosphor copper anode are gradually dissolved into the plating solution, the doped phosphor elements in the phosphor copper anode can also be used as impurities to enter the plating solution.
The leveling agent is a high-strength inhibitor, and can move towards the cathode and be adsorbed on the surface of the cathode due to polarization phenomenon generated by electroplating, the adsorption thickness of the leveling agent is related to the current density of the cathode, and the high-current density area can adsorb more leveling agent particles, so that the reaction resistance of the high-current density area is increased, and Cu is reduced 2+ Deposit, while the low current density region is free of excessive leveler particles, cu 2+ Can be rapidly piled up, thereby achieving the purpose of leveling. However, when too much phosphorus is contained in the copper plating solution, P 3- The negative charge in the anode can prevent the concentration of the leveler particles in the anode region due to the electric effect, so that the sensitivity of the leveler particles to the anode is reduced, the accumulation amount of the leveler particles in the anode is reduced, and Cu cannot be absorbed 2+ The effect of the accumulation rate is reduced, and the leveling effect is reduced.
In order to maintain the stability of the copper plating solution and enhance the working performance, hydrogen peroxide and ferrous sulfate are added into the copper plating solution during discontinuous production of the hole-filling copper plating solution, and in the electrolyte, the hydrogen peroxide can oxidize Cu in the copper plating solution + And P 3- Respectively oxidize it to Cu 2+ And phosphate ions, and hydrogen peroxide can also react with Fe in the added ferrous sulfate 2+ Oxidation is carried out to oxidize the Fe 3+ And then forms ferric phosphate precipitate with phosphate ions, thereby avoiding directly using ferric sulfate with serious toxicity and achieving the effect of purifying phosphorus element in the hole-filling copper plating solution.
The invention also carries out heating treatment on the copper plating solution, the temperature of the copper plating solution is increased to 60-75 ℃, hydrogen peroxide can be gradually decomposed into water and oxygen at the temperature, the oxidizing property is further enhanced, and meanwhile, the influence of residual hydrogen peroxide in the copper plating solution on the subsequent hole filling copper plating operation is avoided.
When the production is resumed, 0.3 to 1 percent of leveling agent, wetting agent and brightening agent can be additionally added into the hole-filling copper plating solution according to the situation of hole-filling copper plating.
The invention also adds active carbon components in the copper plating solution, the active carbon surface is loose and porous, and can adsorb ferric phosphate precipitate suspended in the copper plating solution, thereby achieving the aim of clarification, and the P element in the pore-filling copper plating solution can be removed after filtration and separation.
Further, the aeration is microporous aeration, and the aeration rate is 5-10L/min.
Further, the mixing amount of the ferrous sulfate is 0.1-3mmol/L.
Further, the concentration of the hydrogen peroxide is 30% -50%, and the doping amount is 0.02-0.3L of hydrogen peroxide per 10L.
Further, the addition amount of the activated carbon is 20-30g/L.
In step S5, the formaldehyde addition amount and the stopping days are in positive correlation, and 0.3-0.6mL/L formaldehyde is required to be added into the hole filling electroplating solution every 1 day of stopping.
In the step S5, when the small current is used for pulling the cylinder, the plate is stopped for 8 hours, the current density is 1ASD when the cylinder is pulled, the electroplating duration is 30 minutes, and then the plate is stopped for 24 hours each time, the current density is kept at 1ASD, and the electroplating time is increased by 0.3-0.6 hours.
Compared with the prior art, the invention has the following beneficial effects:
the method is simple to operate, and the traditional method for recovering the activity of the hole filling plating solution comprises the following steps: the long-time heavy-current drawing cylinder consumes monovalent copper and byproducts brought by monovalent copper, so that production stagnation is caused, the productivity of a client is affected, in addition, the long-time heavy-current drawing cylinder also causes waste of light agent and electric quantity, a large amount of phosphor copper anodes are consumed, and the production cost of the client is increased. The method can maintain the activity of the hole filling plating solution under the condition of continuously making the plate, can remove redundant phosphorus elements in the hole filling copper plating solution under the condition of discontinuously making the plate, and can recover the activity of the hole filling copper plating solution only by a drawing cylinder with short time and small current, thereby improving the production efficiency of the client and greatly reducing the production cost of the client.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of example 1 of the present invention;
FIG. 2 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of example 2 of the present invention;
FIG. 3 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of example 3 of the present invention;
FIG. 4 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of example 4 of the present invention;
FIG. 5 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of example 5 of the present invention;
FIG. 6 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of comparative example 1 of the present invention;
FIG. 7 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of comparative example 2 of the present invention;
FIG. 8 is a graph showing the effect of hole-filling copper plating on the fifth week of the hole-filling copper plating solution of comparative example 3 of the present invention;
FIG. 9 is a graph showing the effect of the fifth week hole-filling copper plating of the hole-filling copper plating solution of comparative example 4 of the present invention;
FIG. 10 is a graph showing the effect of hole-filling copper plating on the fifth week of the hole-filling copper plating solution of comparative example 5 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into the hole-filling copper plating solution, slowly adding 0.1L of 45% hydrogen peroxide into each 10L of the hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Example 2
Compared with example 1, the present example has an extended downtime.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted every 2 weeks:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into the hole-filling copper plating solution, slowly adding 0.1L of 45% hydrogen peroxide into each 10L of the hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Example 3
In this example, the amount of ferrous sulfate added was increased as compared with example 1.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 2mmol/L into a hole-filling copper plating solution, slowly adding 0.1L of 45% hydrogen peroxide into each 10L of hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Example 4
Compared with the embodiment, the embodiment increases the doping amount of the hydrogen peroxide.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into the hole-filling copper plating solution, slowly adding 0.3L of 45% hydrogen peroxide into each 10L of the hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Example 5
The present invention increases the doping amount of activated carbon as compared with example 1.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into the hole-filling copper plating solution, slowly adding 0.1L of 45% hydrogen peroxide into each 10L of the hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 30g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Comparative example 1
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
The liquid medicine is used for continuous production, and the rest operation is not carried out on the liquid medicine.
Comparative example 2
In contrast to example 1, the present invention did not add ferrous sulfate to the solution.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, slowly adding 0.1L of 45% hydrogen peroxide into every 10L of hole-filling copper plating solution, opening an air pump, performing microporous aeration at a rate of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Comparative example 3
In contrast to example 1, no hydrogen peroxide was added.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into a hole-filling copper plating solution, opening an air pump, performing microporous aeration at the rate of 10L/min, and performing auxiliary electroplating solution stirring to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Comparative example 4
In this comparative example, the temperature of the pore-filling copper plating solution was not raised as compared with example 1.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into the hole-filling copper plating solution, slowly adding 0.1L of 45% hydrogen peroxide into each 10L of the hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, after the copper plating solution is cooled to room temperature, adding active carbon particles into the hole-filling copper plating solution according to the amount of 20g/L, filtering the hole-filling copper plating solution after the active carbon particles are adsorbed and settled, and pouring the filtrate into a copper plating tank again;
s3, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s4, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Comparative example 5
In comparison with example 1, this comparative example was not spiked with activated carbon.
The parameters of the liquid medicine of the hole-filling copper plating solution are as follows:
copper sulfate pentahydrate: 230g/L
Sulfuric acid: 40g/L
Chloride ions: 70ppm of
Leveling agent a:25ml/L
Brightening agent B:1ml/L
Wetting agent C:15ml/L
During copper plating production, a plate to be plated is placed in the hole filling copper plating liquid, hole filling is performed through electroplating, during electroplating, aeration treatment is performed in the hole filling copper plating liquid, an aeration pump is opened, and microporous aeration is performed according to the speed of 10L/min.
The stability improvement method of the phosphorus copper anode pore-filling copper plating solution is adopted for improving every other week:
s1, adding ferrous sulfate with the addition amount of 1mmol/L into the hole-filling copper plating solution, slowly adding 0.1L of 45% hydrogen peroxide into each 10L of the hole-filling copper plating solution, opening an air pump, performing microporous aeration according to the speed of 10L/min, and stirring the auxiliary electroplating solution to react for 10-20min;
s2, heating the hole-filling copper plating solution to 70 ℃, preserving heat for 1.5 hours, ending heating, and stopping aeration;
s3, after the copper plating solution is cooled to room temperature, filtering the hole-filling copper plating solution, and pouring the filtrate back into the copper plating tank again;
s4, adding formaldehyde into the hole-filling copper plating solution, wherein the addition amount is 0.5mL/L, adding 0.5mL/L of formaldehyde for each additional day of plate stopping time, adding 1mL/L of formaldehyde solution for 2 days of plate stopping time, starting a gas pumping machine, continuing micropore aeration, applying small current to drag a cylinder, wherein the current of the cylinder is 1ASD, and the duration of the cylinder dragging is 90min;
s5, continuing construction by using the hole-filling copper plating solution treated by the stability method.
Electroplating experiments were performed on the electroplating solutions of examples 1 to 5, which were used for 5 weeks, for blind holes with a pore diameter of 125um and a level of 60 um. Wherein the current density: 1.7ASD, electroplating time 50min, stirring: jet flow + air stirring, temperature: 25 degrees; the pore-filling effect is shown in the following table:
electroplating experiments were performed on the electroplating solutions of comparative examples 1 to 5, which were used for 5 weeks, for blind holes with a pore diameter of 125um and a level of 60 um. Wherein the current density: 1.7ASD, electroplating time 50min, stirring: jet flow + air stirring, temperature: 25 degrees; the pore-filling effect is shown in the following table:
by comparing examples 1-5 with comparative example 1, the method for improving the stability of the hole-filling copper plating solution of the phosphorus copper anode greatly improves the continuous workability of the copper plating solution, can effectively improve the working performance of the copper plating solution with longer service time, ensures stable performance, and ensures that the produced hole-filling copper plating plate has smooth surface and meets the working performance.
By comparing the example 1 with the comparative example 2, it was found that the phosphorus element in the copper plating solution is accumulated without adding ferrous sulfate, which affects the hole filling effect;
by comparing the embodiment 1 with the comparative example 3, the fact that the element in the copper plating solution is not oxidized enough only by aeration operation without adding hydrogen peroxide can not eliminate the influence of the element on the additive in the copper plating solution, and finally the hole filling effect of the copper plating solution is not ideal is found;
by comparing the embodiment 1 with the comparative example 4, the hydrogen peroxide in the copper plating solution is remained when not heated, and the hydrogen peroxide damages organic matters in the additive under the electrochemical influence in the process of hole filling and copper plating, so that the hole filling effect is reduced;
by comparing example 1 with comparative example 5, activated carbon can adsorb ferric phosphate floc suspended in the solution, and can help the pore-filling copper plating solution to be further clarified, thereby improving the working effect.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for improving stability of a hole-filling copper plating solution for a phosphor copper anode, comprising the steps of:
s1, during copper plating production, a plate to be plated is placed in a hole filling copper plating solution, hole filling is performed through electroplating, and during electroplating, aeration treatment is performed in the hole filling copper plating solution;
s2, after stopping plating, removing a phosphorus copper anode, adding ferrous sulfate into the hole-filling copper plating solution, and then slowly adding hydrogen peroxide;
s3, heating the hole-filling copper plating liquid to 60-75 ℃, preserving heat for 1-2h, and stirring by aeration;
s4, stopping heating, cooling the hole-filling copper plating solution to room temperature, stopping aeration, adding active carbon, settling and filtering;
s5, after the phosphorus copper anode is put back into the copper plating solution, formaldehyde is added, aeration is continued, and small current is applied to drag the cylinder so as to recover the activity of the hole filling electroplating solution.
2. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: the aeration is microporous aeration, and the aeration rate is 5-10L/min.
3. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: the mixing amount of the ferrous sulfate is 0.1-3mmol/L.
4. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: the concentration of the hydrogen peroxide is 30% -50%, and the doping amount is 0.02-0.3L of hydrogen peroxide added to each 10L of electroplating solution.
5. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: the addition amount of the activated carbon is 20-30g/L.
6. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: in the step S5, the addition amount of formaldehyde is 1 day after each plate stopping, and 0.3-0.6mL/L formaldehyde is required to be added into the hole filling electroplating liquid.
7. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: in the step S5, when the small current is used for pulling the cylinder, the plate is stopped for 8 hours, the current density is 1ASD when the cylinder is pulled, the electroplating duration is 30 minutes, then the plate is stopped for 24 hours each time, the current density is kept at 1ASD, and the electroplating time is increased by 0.3-0.6 hours.
8. The method for improving the stability of a hole-filling copper plating solution for a phosphor copper anode according to claim 1, wherein: the pore-filling copper plating solution comprises the following components: 200-250g/L of copper sulfate pentahydrate, 30-50g/L of sulfuric acid, 40-80ppm of chloride ions, 10-30ml/L of leveling agent, 0.5-1.5ml/L of brightening agent and 5-15ml/L of wetting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210508649.9A CN114921819B (en) | 2022-05-10 | 2022-05-10 | Method for improving stability of hole-filling copper plating solution of phosphorus copper anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210508649.9A CN114921819B (en) | 2022-05-10 | 2022-05-10 | Method for improving stability of hole-filling copper plating solution of phosphorus copper anode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114921819A CN114921819A (en) | 2022-08-19 |
| CN114921819B true CN114921819B (en) | 2023-08-29 |
Family
ID=82808332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210508649.9A Active CN114921819B (en) | 2022-05-10 | 2022-05-10 | Method for improving stability of hole-filling copper plating solution of phosphorus copper anode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114921819B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179736A (en) * | 2003-12-19 | 2005-07-07 | Shinko Electric Ind Co Ltd | Electrolytic copper plating method and electrolytic copper plating device |
| CN103088396A (en) * | 2013-01-29 | 2013-05-08 | 惠州中京电子科技股份有限公司 | Chemical water treatment method for PCB (printed circuit board) electro-coppering trough |
| EP2716795A1 (en) * | 2012-10-04 | 2014-04-09 | Rohm and Haas Electronic Materials LLC | Electrolytic copper plating liquid, the electrolytic copper plating method and product obtained |
| CN106435664A (en) * | 2016-08-16 | 2017-02-22 | 广东工业大学 | Electro-coppering solution of soluble anode for hole filling |
| CN108411353A (en) * | 2018-04-04 | 2018-08-17 | 鹰潭江南铜业有限公司 | A kind of galvanic anode phosphorous copper balls and preparation method thereof |
| CN112011822A (en) * | 2019-05-31 | 2020-12-01 | 王美华 | Application of ferric iron copper dissolving system in vertical continuous electroplating line |
| CN113151880A (en) * | 2021-04-26 | 2021-07-23 | 王美华 | Application of ferric iron copper dissolving technology in vertical continuous electroplating line and device thereof |
-
2022
- 2022-05-10 CN CN202210508649.9A patent/CN114921819B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179736A (en) * | 2003-12-19 | 2005-07-07 | Shinko Electric Ind Co Ltd | Electrolytic copper plating method and electrolytic copper plating device |
| EP2716795A1 (en) * | 2012-10-04 | 2014-04-09 | Rohm and Haas Electronic Materials LLC | Electrolytic copper plating liquid, the electrolytic copper plating method and product obtained |
| CN103088396A (en) * | 2013-01-29 | 2013-05-08 | 惠州中京电子科技股份有限公司 | Chemical water treatment method for PCB (printed circuit board) electro-coppering trough |
| CN106435664A (en) * | 2016-08-16 | 2017-02-22 | 广东工业大学 | Electro-coppering solution of soluble anode for hole filling |
| CN108411353A (en) * | 2018-04-04 | 2018-08-17 | 鹰潭江南铜业有限公司 | A kind of galvanic anode phosphorous copper balls and preparation method thereof |
| CN112011822A (en) * | 2019-05-31 | 2020-12-01 | 王美华 | Application of ferric iron copper dissolving system in vertical continuous electroplating line |
| CN113151880A (en) * | 2021-04-26 | 2021-07-23 | 王美华 | Application of ferric iron copper dissolving technology in vertical continuous electroplating line and device thereof |
Non-Patent Citations (1)
| Title |
|---|
| 酸性光亮铜镀层不亮因素;奚兵;电镀与环保;31(06);48-50 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114921819A (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3455709B2 (en) | Plating method and plating solution precursor used for it | |
| JP4551994B2 (en) | Method for recovering tin, tin alloy or lead alloy from printed circuit board | |
| CN106435664A (en) | Electro-coppering solution of soluble anode for hole filling | |
| CA1220759A (en) | Regeneration of plating bath by acidification and treatment of recovered chelating agent in membrane cell | |
| CN112064026A (en) | Novel copper surface roughness corrosion stabilizer and preparation method thereof | |
| CN114921819B (en) | Method for improving stability of hole-filling copper plating solution of phosphorus copper anode | |
| CN1524132A (en) | Regeneration method for a plating solution | |
| CN103966442A (en) | Electro-deposition method for preparing high-purity copper from scrap copper | |
| JP2008266766A (en) | Method for producing sheet-form electrolytic copper from halide solution | |
| KR102297887B1 (en) | Method and apparatus for reducing ferric ion in sulfuric acid bath for eletroplating iron | |
| CN113774432A (en) | Continuous electrolytic refining process for high-purity copper | |
| CN112794544A (en) | Treatment method of high-chlorine palladium-containing wastewater | |
| IL98645A (en) | Alkaline etching solution | |
| JPH02254188A (en) | Method for electrolyzing copper chloride solution | |
| CN112210790B (en) | Treatment method of copper anode slime copper separating liquid | |
| JPH10237685A (en) | Method for preventing melting of steel strip in tinning bath | |
| EP4317537A1 (en) | Method for removing ferric ions from sulfate-based iron electroplating solution | |
| JPH05311484A (en) | Reflow tin or tin alloy plating bath | |
| US8801916B2 (en) | Recovery method of nickel from spent electroless nickel plating solutions by electrolysis | |
| JPH05125582A (en) | Method for electroplating steel sheet with tin | |
| JPH0438834B2 (en) | ||
| JPH05106085A (en) | Method for preventing elution of fe ion into electroplating solution | |
| JP3316606B2 (en) | Tin plating apparatus and tin plating method | |
| JP3481378B2 (en) | Method for suppressing formation of tin sludge by iron (III) ions in plating bath | |
| JP3056594B2 (en) | Iron-zinc alloy electroplating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |