CN115522188A - High-speed chemical copper plating solution and copper plating process thereof - Google Patents

High-speed chemical copper plating solution and copper plating process thereof Download PDF

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Publication number
CN115522188A
CN115522188A CN202211069335.XA CN202211069335A CN115522188A CN 115522188 A CN115522188 A CN 115522188A CN 202211069335 A CN202211069335 A CN 202211069335A CN 115522188 A CN115522188 A CN 115522188A
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copper plating
pcb
plating solution
electroless copper
solution
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Chinese (zh)
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刘政
刘波
陈伟长
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Nantong Circuit Electronic Co ltd
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Nantong Circuit Electronic Co ltd
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Priority to CN202211069335.XA priority Critical patent/CN115522188A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1669—Agitation, e.g. air introduction
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1676—Heating of the solution
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first

Abstract

The invention discloses a high-speed electroless copper plating solution, which comprises the following components: 10-30g/L of blue vitriol; 15-22g/L of compounding agent; 20-35g/L of reducing agent; 1-3g/L of stabilizer; 10-20mg/L of brightener; 10-40mg/L accelerator. The invention also discloses a high-speed chemical copper plating process. According to the invention, the PCB chemical copper plating system which is mainly prepared from sodium hypophosphite and assisted by formaldehyde and is used as a reducing agent is configured, so that the deposition rate, the reaction controllability and the service life of a copper plating solution can be effectively improved, harmful formaldehyde steam generated in the traditional copper plating process is greatly reduced, and the thickness and the quality of a product coating are ensured. The complexing agent prepared by mixing the disodium ethylene diamine tetraacetate and the tetrahydroxypropyl ethylenediamine can greatly improve the deposition rate of the copper plating solution by utilizing the excellent performance of the tetrahydroxypropyl ethylenediamine, and the mixed disodium ethylene diamine tetraacetate can reduce the cost on the premise of ensuring the deposition rate and the coating quality of the copper plating solution.

Description

High-speed chemical copper plating solution and copper plating process thereof
Technical Field
The invention relates to the technical field of chemical copper plating, in particular to a high-speed chemical copper plating solution and a copper plating process thereof.
Background
Electroless copper plating has wide application in the metallization of holes in Printed Circuit Boards (PCB), the metallization of plastic and ceramic surfaces, the preparation of electromagnetic shielding materials, and the like. Electroless plating is a metal deposition process in which metal ions are reduced by the autocatalytic action of the metal surface by means of a suitable reducing agent in solution, and electroless plating can only be carried out on catalytically active surfaces.
Compared with the electroplating process, the chemical plating process has the following characteristics:
(1) The plating layer has very uniform thickness, the dispersion capacity of the chemical plating solution is close to 100 percent, no obvious edge effect exists, and the method is suitable for plating on the surfaces of workpieces, cavity parts, deep hole parts, pipe fitting inner walls and the like with complicated shapes. The electroplating method is difficult to be performed due to the limitation of uneven distribution of power lines. Because the chemical plating layer has uniform thickness, easy control and smooth and clean surface, the plating layer does not need to be processed again.
(2) Chemical plating can be carried out on the surfaces of non-metal (non-conductor) materials such as plastics, glass, ceramics and semiconductor materials through pretreatment such as sensitization, activation and the like, and electroplating can be carried out on the surfaces of conductors only, so the chemical plating process is a common method for metalizing the non-metal surfaces and is also a common method for preparing a conductive bottom layer before electroplating of the non-conductor materials.
(3) The chemical plating process has simple equipment, does not need a power supply, a power transmission system and an auxiliary electrode, and only needs to correctly suspend the workpiece in the plating solution during operation.
(4) The chemical plating is carried out on a base material with autocatalysis activity, and the binding force is very good. The coating has bright appearance, compact crystal grains and low porosity.
The electroless plating method has the remarkable advantages, so that the electroless plating method is increasingly widely applied to the industry. The most widely used electroless plating techniques currently include electroless nickel plating and electroless copper plating. The electroless copper plating is a technology of reducing copper ions in a plating solution by adopting a reducing agent and directionally depositing the copper ions on the surface of a substrate with catalytic activity to form a metal copper layer with certain thickness and function.
At present, the chemical copper plating process using formaldehyde (HCHO) as a reducing agent is still a relatively common method applied in industry, but formaldehyde has great harm to human bodies and environment, and the use of a large amount of formaldehyde can cause poor stability of plating solution, so that the stability of the copper plating solution, the complexity of process operation, the long copper plating time in the production process and the like become the bottleneck of the copper plating process. In recent years, therefore, neutral or acidic electroless copper plating solutions have been developed which use phosphates, traps or boron compounds as reducing agents. The hypophosphite chemical copper plating is an electroless copper plating system which has a good development prospect and is most likely to replace formaldehyde, the system can effectively avoid the defects of the existing chemical copper plating, but can affect the deposition rate of copper plating, and is difficult to ensure the application of large-scale industrialization, so that a more excellent additive composition needs to be found, and a plating layer with better performance (appearance, ductility, resistivity and tensile strength) can be obtained while the plating rate is ensured.
An effective solution to the problems in the related art has not been proposed yet.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a high-speed electroless copper plating solution and a copper plating process thereof, which are used for overcoming the technical problems in the prior related art.
Therefore, the invention adopts the following specific technical scheme:
according to one aspect of the present invention, there is provided a high-speed electroless copper plating solution comprising the following components:
10-30g/L of copper sulfate pentahydrate;
15-22g/L of compounding agent;
20-35g/L of reducing agent;
1-3g/L of stabilizer;
10-20mg/L of brightener;
10-40mg/L accelerator.
Further, the compounding agent comprises a mixture of disodium ethylene diamine tetraacetate and tetrahydroxypropyl ethylenediamine, and the concentration ratio of the disodium ethylene diamine to the tetrahydroxypropyl ethylenediamine is 1:1.2.
further, the reducing agent is a mixture of sodium hypophosphite and formaldehyde, and the concentration ratio of the reducing agent to the formaldehyde is 10:1.
further, the brightener is a mixture of a heterocyclic compound and alkyl aryl sulfonate and has a concentration ratio of 1:3.
further, the heterocyclic compound comprises at least one of mercaptobenzothiazole, mercaptothiazole, mercaptobenzimidazole, mercaptoimidazole, tetrahydrothiazolethione and mercaptothiadiazoline;
the alkyl aryl sulfonate comprises at least one of sodium dodecyl benzene sulfonate, sodium phenyl dithiopropane sulfonate, sodium allyl sulfonate and sodium dodecyl naphthalene sulfonate.
Further, the stabilizer is at least two of alpha-alpha' bipyridyl, maleic acid, L-arginine, nickel sulfate, triethanolamine and polyethylene glycol.
Further, the accelerator comprises at least one of nickel sulfate, nickel chloride, fatty amine polyoxyethylene ether and ethylene thiourea.
Further, the pH value of the electroless copper plating solution is between 11.5 and 13.
According to another aspect of the present invention, there is also provided a high-speed electroless copper plating process, comprising the steps of:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, enabling the chemical copper plating solution to completely immerse the PCB, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20-40 min;
and S5, cleaning and drying the PCB to obtain the PCB with copper plated.
Further, the pretreatment of the PCB board comprises the following steps:
s11, washing the PCB with water, and soaking in a solution containing 8% of alkaline cleaning agent for 5min to remove oil;
s12, placing the PCB after oil removal into the water containing 8 percent 2 O 2 Soaking in 8% concentrated sulfuric acid solution for 3min for coarsening;
s13, placing the roughened PCB in a solution containing a pre-immersion liquid for immersion for 3min;
s14, placing the PCB after being soaked in a solution of a colloidal palladium activating solution for soaking for 6min for activation;
s15, placing the activated PCB in a 10-percent HCl solution for soaking for 1min for dispergation;
and S16, washing the PCB after the glue is dissolved, and realizing pretreatment.
The invention has the beneficial effects that:
1. by configuring the PCB chemical copper plating system which is mainly composed of sodium hypophosphite and is assisted by formaldehyde, the deposition rate, the reaction controllability and the service life of a copper plating solution can be effectively improved, harmful formaldehyde steam generated in the traditional copper plating process is greatly reduced, and the thickness and the quality of a product coating are ensured.
2. The complexing agent prepared by mixing the disodium ethylene diamine tetraacetate and the tetrahydroxypropyl ethylenediamine can greatly improve the deposition rate of the copper plating solution by utilizing the excellent performance of the tetrahydroxypropyl ethylenediamine, and the production cost of the complexing agent can be effectively reduced on the premise of ensuring the deposition rate and the coating quality of the copper plating solution by using the disodium ethylene diamine tetraacetate in a mixing manner, so that the requirements of mass production and batch operation are met.
3. The brightener prepared by mixing the heterocyclic compound and the alkyl aryl sulfonate can effectively improve the ion density and the migration speed in the copper plating solution, can accelerate the copper plating speed, and effectively improve the brightness of a surface copper film.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram showing the comparison of plating rates of examples and comparative examples in a high-rate electroless copper plating solution according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a PCB anti-separation test in a high-speed electroless copper plating solution according to an embodiment of the invention;
figure 3 is a flow diagram of a high speed electroless copper plating process in accordance with an embodiment of the invention.
Detailed Description
According to embodiments of the present invention, a high-speed electroless copper plating solution and a copper plating process thereof are provided.
Example one
A high speed electroless copper plating solution comprising the following components:
10g/L of copper sulfate pentahydrate;
15g/L of compounding agent;
20g/L of reducing agent;
1g/L of stabilizer;
brightener 10mg/L;
the accelerator is 10mg/L.
The compounding agent comprises a mixture of disodium ethylene diamine tetraacetate (EDTA & 2 Na) and Tetrahydroxypropylethylenediamine (THPED) and the concentration ratio of the mixture is 1:1.2.
the reducing agent is sodium hypophosphite (NaH) 2 PO 2 ) Mixture with formaldehyde (HCHO) in a concentration ratio of 10:1.
the brightener is a mixture consisting of a heterocyclic compound and alkyl aryl sulfonate and has a concentration ratio of 1:3.
the heterocyclic compound is mercapto benzothiazole;
the alkyl aryl sulfonate is sodium dodecyl benzene sulfonate.
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The accelerator is nickel sulfate.
The electroless copper plating solution has a pH of between 12.5.
Selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps as shown in figure 3:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, enabling the chemical copper plating solution to completely immerse the PCB, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with copper plated.
The PCB preprocessing comprises the following steps:
s11, washing the PCB with water, and soaking in a solution containing 8% of alkaline cleaning agent for 5min to remove oil;
s12, placing the PCB after degreasing in a solution containing 8% 2 O 2 Soaking in 8% concentrated sulfuric acid solution for 3min for coarsening;
s13, placing the roughened PCB in a solution containing a pre-immersion liquid for immersion for 3min;
s14, placing the PCB after being soaked in a solution of a colloidal palladium activating solution for soaking for 6min for activation;
s15, placing the activated PCB in a 10-percent HCl solution for soaking for 1min for dispergation;
and S16, washing the PCB after the glue is dissolved, and realizing pretreatment.
Example two
A high speed electroless copper plating solution comprising the following components:
18g/L of copper sulfate pentahydrate;
16g/L of compounding agent;
20g/L of reducing agent;
2g/L of stabilizer;
brightener 14mg/L;
the accelerator is 20mg/L.
The compounding agent comprises a mixture of disodium ethylene diamine tetraacetate (EDTA & 2 Na) and Tetrahydroxypropylethylenediamine (THPED) and the concentration ratio of the mixture is 1:1.2.
the reducing agent is sodium hypophosphite (NaH) 2 PO 2 ) Mixture with formaldehyde (HCHO) and concentration ratio 10:1.
the brightener is a mixture consisting of a heterocyclic compound and alkyl aryl sulfonate and has a concentration ratio of 1:3.
the heterocyclic compound is mercapto benzothiazole;
the alkyl aryl sulfonate is sodium dodecyl benzene sulfonate.
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The accelerator is nickel sulfate.
The electroless copper plating solution has a pH of between 12.5.
Selecting and preparing the raw material components according to the concentration ratio to prepare a chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, completely immersing the PCB with the electroless copper plating solution, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with the copper plated.
The PCB preprocessing comprises the following steps:
s11, washing the PCB with water, and soaking in a solution containing 8% of alkaline cleaning agent for 5min for oil removal;
s12, placing the PCB after oil removal into the water containing 8 percent 2 O 2 Soaking in 8% concentrated sulfuric acid solution for 3min for coarsening;
s13, placing the roughened PCB in a solution containing a pre-immersion liquid for immersion for 3min;
s14, placing the PCB after being soaked in a solution of a colloidal palladium activating solution for soaking for 6min for activation;
s15, placing the activated PCB in a 10-percent HCl solution for soaking for 1min for dispergation;
and S16, washing the PCB after the glue is dissolved, and realizing pretreatment.
EXAMPLE III
A high speed electroless copper plating solution comprising the following components:
25g/L of blue vitriol;
20g/L of compounding agent;
26g/L of reducing agent;
2g/L of stabilizer;
17mg/L of brightener;
30mg/L accelerator.
The compounding agent comprises a mixture of disodium ethylene diamine tetraacetate (EDTA-2 Na) and tetrahydroxypropyl ethylenediamine (THPED) in a concentration ratio of 1:1.2.
the reducing agent is sodium hypophosphite (NaH) 2 PO 2 ) Mixture with formaldehyde (HCHO) in a concentration ratio of 10:1.
the brightener is a mixture consisting of a heterocyclic compound and alkyl aryl sulfonate and has a concentration ratio of 1:3.
the heterocyclic compound is mercapto benzothiazole;
the alkyl aryl sulfonate is sodium dodecyl benzene sulfonate.
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The accelerator is nickel sulfate.
The electroless copper plating solution has a pH between 12.5.
Selecting and preparing the raw material components according to the concentration ratio to prepare a chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, enabling the chemical copper plating solution to completely immerse the PCB, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with copper plated.
The PCB preprocessing comprises the following steps:
s11, washing the PCB with water, and soaking in a solution containing 8% of alkaline cleaning agent for 5min for oil removal;
s12, placing the PCB after degreasing in a solution containing 8% 2 O 2 And immersing in 8% concentrated sulfuric acid solution for 3min for coarsening;
s13, placing the roughened PCB in a solution containing a pre-immersion liquid for immersion for 3min;
s14, placing the PCB after the impregnation in a solution of a colloid palladium activating solution for impregnation for 6min for activation;
s15, placing the activated PCB in a 10-percent HCl solution for soaking for 1min for dispergation;
and S16, washing the PCB after the glue is dissolved, and realizing pretreatment.
Example four
A high speed electroless copper plating solution comprising the following components:
30g/L of blue vitriol;
22g/L of compounding agent;
35g/L of reducing agent;
3g/L of stabilizer;
20mg/L of brightener;
the accelerator is 40mg/L.
The compounding agent comprises a mixture of disodium ethylene diamine tetraacetate (EDTA & 2 Na) and Tetrahydroxypropylethylenediamine (THPED) and the concentration ratio of the mixture is 1:1.2.
the reducing agent is sodium hypophosphite (NaH) 2 PO 2 ) Mixture with formaldehyde (HCHO) and concentration ratio 10:1.
the brightener is a mixture consisting of a heterocyclic compound and alkyl aryl sulfonate, and the concentration ratio of the brightener to the alkyl aryl sulfonate is 1:3.
the heterocyclic compound is mercapto benzothiazole;
the alkyl aryl sulfonate is sodium dodecyl benzene sulfonate.
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The accelerator is nickel sulfate.
The electroless copper plating solution has a pH between 12.5.
Selecting and preparing the raw material components according to the concentration ratio to prepare a chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, enabling the chemical copper plating solution to completely immerse the PCB, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with the copper plated.
The PCB preprocessing comprises the following steps:
s11, washing the PCB with water, and soaking in a solution containing 8% of alkaline cleaning agent for 5min for oil removal;
s12, placing the PCB after oil removal into the water containing 8 percent 2 O 2 Soaking in 8% concentrated sulfuric acid solution for 3min for coarsening;
s13, placing the roughened PCB in a solution containing a pre-immersion liquid for immersion for 3min;
s14, placing the PCB after being soaked in a solution of a colloidal palladium activating solution for soaking for 6min for activation;
s15, placing the activated PCB in a 10-percent HCl solution for soaking for 1min for dispergation;
and S16, washing the PCB after the glue is dissolved, and realizing pretreatment.
Comparative example 1
25g/L of blue vitriol;
20g/L of compounding agent;
26g/L of reducing agent;
2g/L of stabilizer;
the compounding agent comprises a mixture of disodium ethylene diamine tetraacetate (EDTA & 2 Na) and Tetrahydroxypropylethylenediamine (THPED) and the concentration ratio of the mixture is 1:1.2.
the reducing agent is sodium hypophosphite (NaH) 2 PO 2 ) Mixture with formaldehyde (HCHO) and concentration ratio 10:1.
the heterocyclic compound is mercapto benzothiazole;
the alkyl aryl sulfonate is sodium dodecyl benzene sulfonate.
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The electroless copper plating solution has a pH between 12.5.
Selecting and preparing the raw material components according to the concentration ratio to prepare a chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, enabling the chemical copper plating solution to completely immerse the PCB, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with the copper plated.
Comparative example No. two
A high speed electroless copper plating solution comprising the following components:
25g/L of blue vitriol;
20g/L of compounding agent;
26g/L of reducing agent;
2g/L of stabilizer;
the compounding agent comprises a mixture of disodium ethylene diamine tetraacetate (EDTA & 2 Na) and Tetrahydroxypropylethylenediamine (THPED) and the concentration ratio of the mixture is 1:1.2.
the reducing agent is formaldehyde (HCHO).
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The electroless copper plating solution has a pH between 12.5.
Selecting and preparing the raw material components according to the concentration ratio to prepare a chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, completely immersing the PCB with the electroless copper plating solution, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with copper plated.
Comparative example No. three
A high speed electroless copper plating solution comprising the following components:
25g/L of blue vitriol;
20g/L of compounding agent;
26g/L of reducing agent;
2g/L of stabilizer;
wherein the compounding agent is disodium ethylene diamine tetraacetate (EDTA & 2 Na).
The reducing agent is formaldehyde (HCHO).
The stabilizer is a mixture of alpha-alpha' bipyridyl, maleic acid, L-arginine and nickel sulfate.
The electroless copper plating solution has a pH of between 12.5.
Selecting and preparing the raw material components according to the concentration ratio to prepare a chemical copper plating solution, and plating copper on the PCB by a high-speed chemical copper plating process, wherein the process comprises the following steps:
s1, preprocessing a PCB;
s2, placing the PCB subjected to pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, enabling the chemical copper plating solution to completely immerse the PCB, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20 min;
and S5, cleaning and drying the PCB to obtain the PCB with copper plated.
Examples of the experiments
Preparing 1L of chemical copper plating solution according to the concentration of each component in seven groups of the first, second, third and fourth embodiments and the first, second and third comparative embodiments, placing the PCB with the same specification and size in the copper plating solution for copper plating by using the corresponding copper plating process, removing the PCB after the copper plating is finished, performing quality and adhesion test (dividing the surface of the PCB into a plurality of grids with the size of 1 multiplied by 1mm by using a cutter, and observing whether grids fall off in the grids as shown in figure 2), and recording experimental data in the copper plating process in real time, as shown in Table 1 and figure 1:
table 1: performance test meter for chemical copper plating solution
Figure 212689DEST_PATH_IMAGE002
As can be seen from Table 1, the electroless copper plating solution disclosed by the invention can form a fine, smooth and bright coating on the surface of a PCB, the coating efficiency is greatly improved, and meanwhile, the internal components have the characteristics of environmental protection, high efficiency and long service life, and the electroless copper plating solution can be used in the fields of industrial processing, high-quality preparation of PCB and the like.
In conclusion, by means of the technical scheme of the invention, 1, the PCB chemical copper plating system which is mainly provided with sodium hypophosphite and takes formaldehyde as an auxiliary reducing agent is configured, so that the deposition rate, the reaction controllability and the service life of the copper plating solution can be effectively improved, harmful formaldehyde steam generated in the traditional copper plating process is greatly reduced, and the thickness and the quality of a product coating are ensured. The complexing agent prepared by mixing the disodium ethylene diamine tetraacetate and the tetrahydroxypropyl ethylenediamine can greatly improve the deposition rate of the copper plating solution by utilizing the excellent performance of the tetrahydroxypropyl ethylenediamine, and the production cost of the complexing agent can be effectively reduced on the premise of ensuring the deposition rate and the coating quality of the copper plating solution by using the disodium ethylene diamine tetraacetate in a mixing manner, so that the requirements of mass production and batch operation are met. The brightener prepared by mixing the heterocyclic compound and the alkyl aryl sulfonate can effectively improve the ion density and the migration speed in the copper plating solution, can accelerate the copper plating speed, and effectively improve the brightness of a surface copper film.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A high speed electroless copper plating solution, characterized in that the solution comprises the following components:
10-30g/L of copper sulfate pentahydrate;
15-22g/L of compounding agent;
20-35g/L of reducing agent;
1-3g/L of stabilizer;
10-20mg/L of brightener;
the accelerator is 10-40mg/L.
2. The high-speed electroless copper plating solution according to claim 1, wherein the complexing agent comprises a mixture of disodium ethylenediaminetetraacetate and tetrahydroxypropylethylenediamine in a concentration ratio of 1:1.2.
3. a high speed electroless copper plating solution according to claim 1, wherein the reducing agent is a mixture of sodium hypophosphite and formaldehyde in a concentration ratio of 10:1.
4. a high speed electroless copper plating solution according to claim 1 wherein the brightener is a mixture of a heterocyclic compound and an alkyl aryl sulfonate in a concentration ratio of 1:3.
5. the high speed electroless copper plating solution of claim 4 wherein the heterocyclic compound comprises at least one of mercaptobenzothiazole, mercaptothiazole, mercaptobenzimidazole, mercaptoimidazole, tetrahydrothiazolethione, and mercaptothiadiazoline;
the alkyl aryl sulfonate comprises at least one of sodium dodecyl benzene sulfonate, sodium phenyl dithiopropane sulfonate, sodium allyl sulfonate and sodium dodecyl naphthalene sulfonate.
6. The high speed electroless copper plating solution according to claim 1 wherein the stabilizer is at least two of alpha-alpha' bipyridine, maleic acid, L-arginine, nickel sulfate, triethanolamine and polyethylene glycol.
7. The high-speed electroless copper plating solution and the copper plating process thereof according to claim 1, wherein the accelerator comprises at least one of nickel sulfate, nickel chloride, fatty amine polyoxyethylene ether and ethylene thiourea.
8. A high speed electroless copper plating solution according to claim 1, characterised in that the pH of the electroless copper plating solution is between 11.5 and 13.
9. A high speed electroless copper plating process for use with a high speed electroless copper plating solution as claimed in claims 1 to 8, the process comprising the steps of:
s1, preprocessing a PCB;
s2, placing the PCB after the pretreatment in a constant-temperature water bath kettle at 65 ℃ for plating;
s3, completely immersing the PCB with the electroless copper plating solution, and stirring by using an air compressor;
s4, taking out the PCB after electroless copper plating for 20-40 min;
and S5, cleaning and drying the PCB to obtain the PCB with copper plated.
10. The high-speed electroless copper plating process according to claim 1, wherein the pre-treatment of the PCB board comprises the steps of:
s11, washing the PCB with water, and soaking in a solution containing 8% of alkaline cleaning agent for 5min for oil removal;
s12, placing the PCB after degreasing in a solution containing 8% 2 O 2 And immersing in 8% concentrated sulfuric acid solution for 3min for coarsening;
s13, placing the coarsened PCB in a solution containing a pre-immersion liquid for immersion for 3min;
s14, placing the PCB after being soaked in a solution of a colloidal palladium activating solution for soaking for 6min for activation;
s15, placing the activated PCB in a 10-percent HCl solution for dipping for 1min for dispergation;
and S16, washing the PCB after the glue is dissolved, and realizing pretreatment.
CN202211069335.XA 2022-09-02 2022-09-02 High-speed chemical copper plating solution and copper plating process thereof Pending CN115522188A (en)

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Publication number Priority date Publication date Assignee Title
CN1730724A (en) * 2005-08-19 2006-02-08 广东东硕科技有限公司 Chemical bronze plating liquid of mixing type non-formaldehyde reducer
CN104651814A (en) * 2014-11-28 2015-05-27 广东致卓精密金属科技有限公司 Chemical copper plating solution and chemical copper plating method
CN105296976A (en) * 2015-10-21 2016-02-03 深圳市发斯特精密技术有限公司 Chemical-copper solution and chemical copper plating method
KR101660520B1 (en) * 2015-04-08 2016-09-29 한국생산기술연구원 Method of performing continuous electroless plating of copper and nickel and plating layer using the same
CN112899666A (en) * 2021-01-19 2021-06-04 广州三孚新材料科技股份有限公司 Chemical copper plating brightener and preparation method thereof
CN113388829A (en) * 2021-06-11 2021-09-14 惠州金晟新电子科技有限公司 Electroless copper plating solution and method for plating copper on substrate by using electroless copper plating solution
CN114774899A (en) * 2022-04-28 2022-07-22 合肥工业大学 Copper nanocrystalline thin film material and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1730724A (en) * 2005-08-19 2006-02-08 广东东硕科技有限公司 Chemical bronze plating liquid of mixing type non-formaldehyde reducer
CN104651814A (en) * 2014-11-28 2015-05-27 广东致卓精密金属科技有限公司 Chemical copper plating solution and chemical copper plating method
KR101660520B1 (en) * 2015-04-08 2016-09-29 한국생산기술연구원 Method of performing continuous electroless plating of copper and nickel and plating layer using the same
CN105296976A (en) * 2015-10-21 2016-02-03 深圳市发斯特精密技术有限公司 Chemical-copper solution and chemical copper plating method
CN112899666A (en) * 2021-01-19 2021-06-04 广州三孚新材料科技股份有限公司 Chemical copper plating brightener and preparation method thereof
CN113388829A (en) * 2021-06-11 2021-09-14 惠州金晟新电子科技有限公司 Electroless copper plating solution and method for plating copper on substrate by using electroless copper plating solution
CN114774899A (en) * 2022-04-28 2022-07-22 合肥工业大学 Copper nanocrystalline thin film material and preparation method and application thereof

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