CN115011952B - Method for preventing chemical silver plating and plating leakage on surface of ceramic copper-clad substrate - Google Patents
Method for preventing chemical silver plating and plating leakage on surface of ceramic copper-clad substrate Download PDFInfo
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- CN115011952B CN115011952B CN202210652018.4A CN202210652018A CN115011952B CN 115011952 B CN115011952 B CN 115011952B CN 202210652018 A CN202210652018 A CN 202210652018A CN 115011952 B CN115011952 B CN 115011952B
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
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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
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- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
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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
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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Abstract
The invention discloses a method for preventing chemical silver plating from leaking plating on the surface of a ceramic copper-clad substrate; selecting proper ink, printing the ink on the surface of the metal copper foil, protecting the surface of the copper foil and grain boundaries from being corroded by liquid medicine, removing the ink protecting layer after finishing the related pattern etching and other processes, and then performing chemical silver plating on the surface of the metal copper foil. Thus, the crystal boundary of the metal copper foil is prevented from being corroded by liquid medicine in other working procedures, and foreign matters and residual medicine stains in the crystal boundary are avoided. Meanwhile, nano silver particles are added into the plating solution, so that the occurrence of the phenomenon of crystal boundary plating leakage is further reduced, the compactness of the plating layer is improved, and the surface of the plating layer is smooth and flat.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a method for preventing chemical silver plating and plating leakage on the surface of a ceramic copper-clad substrate.
Background
The chemical silver plating on the surface of the AMB ceramic copper-clad substrate is serious in local 'skip plating', and mainly the ceramic substrate and the metal copper foil cannot obtain good compactness and can generate fine 'grain boundary' due to the influence of various uncontrollable factors in the vacuum brazing (high-temperature sintering) process.
In the post-treatment process, the grain boundary is corroded by strong acid liquid medicine in a plurality of different processes, and particularly, various patterns meeting the requirements of related drawings are required to be etched on the surface of the metal copper foil, so that the over-corrosion by the chemical liquid medicine is unavoidable, and the grain boundary is obvious after partial copper foil is subjected to vacuum brazing, so that the liquid medicine remains in the grain boundary, the over-corrosion phenomenon on the surface of the metal copper foil is accelerated, and other foreign matters are easily mixed in the grain boundary and are difficult to clean in the subsequent process. Over time, slow over-corrosion is more severe. The metal silver ions cannot normally contact with copper grain boundaries in the chemical silver plating process, so that the metal silver ions cannot normally deposit, and finally grain boundary 'skip plating' is generated.
Disclosure of Invention
The invention aims to provide a method for preventing chemical silver plating from leaking on the surface of a ceramic copper-clad substrate, so as 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 preventing the surface of a ceramic copper-clad substrate from being plated with chemical silver and leaking comprises the following steps:
s1: carrying out chemical pretreatment on the ceramic copper-clad substrate; performing ink protection on the ceramic copper-clad substrate by using composite ink; after solidification, forming an ink protection layer and step etching; removing the printing ink protective layer by sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: carrying out chemical pretreatment on the ceramic copper-clad substrate A; and performing alignment exposure and development, plating silver to obtain a silver-plated ceramic copper-clad substrate, removing film, cleaning, performing laser cutting, performing post-treatment, inspecting and packaging to obtain a finished product.
Further, in the step S1, the thickness of the composite ink coating is 10-20 μm; the concentration of sodium hydroxide is 30-50 g/L.
Further, in the step S1, the chemical pretreatment is performed as follows:
placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning the ceramic copper-clad substrate for 10-20 min at 45-50 ℃, taking out the ceramic copper-clad substrate and drying the ceramic copper-clad substrate.
Further, in the step S2, the chemical pretreatment is performed as follows:
coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film; the thickness is 10-20 mu m.
Further, in the step S1, the composite ink is prepared as follows:
adding trioctyl trimellitate and diisononyl phthalate, stirring uniformly, adding white carbon black, titanium white, a defoaming agent and a heat stabilizer, mixing uniformly, adding high-molecular polyvinyl chloride and low-molecular polyvinyl chloride into the system, and stirring to obtain the composite printing ink.
130-135 parts of trioctyl trimellitate, 46-50 parts of diisononyl phthalate, 3-4 parts of white carbon black, 7-8 parts of titanium dioxide, 3-4 parts of defoamer, 9-10 parts of heat stabilizer, 250-281 parts of high molecular weight polyvinyl chloride and 85-95 parts of low molecular weight polyvinyl chloride; wherein the molecular weight of the high molecular weight polyvinyl chloride is 3000-4000, and the molecular weight of the low molecular weight polyvinyl chloride is 800-900.
Further, in the step S2, the plating solution for silver plating includes the following four parts: silver ammonia complexing solution, glucose solution, dispersant solution and nanoparticle suspension; wherein the nanoparticle suspension is a silver nanoparticle suspension, and the dispersing agent solution is a polyvinylpyrrolidone solution.
Further, the silver ammonia complex solution is prepared as follows:
placing silver nitrate into a container, and adding deionized water for dissolution; slowly adding the triethylene tetramine solution into a container, stirring, and obtaining the silver ammonia complex solution after the precipitation disappears.
The nano silver particle suspension is prepared according to the following method:
respectively dissolving glycerol, silver nitrate and polyvinylpyrrolidone in absolute ethyl alcohol with different volumes to obtain a solution A, a solution B and a solution C, mixing the solution A, the solution B and the solution C, putting into a water bath, stirring, and heating for reaction to obtain nano silver particles; and ultrasonically dispersing the nano silver particles in deionized water to obtain nano silver particle suspension.
Further, the concentration of the solution A is 46-50 g/L, the concentration of the solution B is 85-90 g/L, the concentration of the solution C is 0.75-0.81 g/L, the heating reaction temperature is 85-90 ℃, and the reaction time is 1.5-2 h.
Further, the concentration of the silver ammonia complex solution is 0.36-0.40 mol/L, the concentration of the glucose solution is 0.42-0.45 mol/L, the concentration of the dispersing agent solution is 4-5 g/L, and the concentration of the nanoparticle suspension is 1-3 g/L.
Further, in the step S2, silver plating is performed as follows: placing the ceramic copper-clad substrate A in deionized water, and carrying out constant-temperature ultrasonic cleaning; and respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath, and washing and drying to obtain the silver-plated ceramic copper-clad substrate.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the printing ink protection process is utilized to serve as a protection layer on the copper surface, so that the over-corrosion of the copper surface caused by corrosive liquid medicine is avoided, and meanwhile, the cleanliness and the smoothness of the copper surface of the copper substrate are improved. Meanwhile, the composite ink has the characteristics of corrosion resistance and easy stripping, and the ink protection layer on the surface of the copper-clad substrate can be removed by using sodium hydroxide, so that compared with the traditional process for removing the ink by using acid or physics, the secondary corrosion and damage to the grain boundary are avoided. Therefore, the crystal boundary of the metal copper foil is prevented from being corroded by liquid medicine in other working procedures, foreign matters and residual medicine stains in the crystal boundary are avoided, and the phenomenon of crystal boundary plating leakage is avoided.
According to the invention, by adding the additional nano silver particles, the nano silver and the reduced nano silver are deposited together to form a composite coating, so that the coating is complete, and the compactness of the silver-plated coating is improved; in the deposition process, nano silver particles are adsorbed on the activation position of the metal surface of the substrate, active particles are added, crystal grains are refined, and grain boundary pores are filled by utilizing the characteristic of small size of the nano silver particles, so that the surface of the plating layer is flat and smooth.
Compared with the traditional surface chemical silver plating, the method has the advantages that the nano particles are added, silver ions are deposited around particles to form atomic beams in a reduced mode, the atomic beams grow to form crystal particles, but the surface active particles of the copper-clad substrate in the traditional mode are limited, so that the plating layer is not compact and smooth enough. The nano particles can be used as active particles to be enriched on the surface of the copper-clad substrate, so that the overpotential of silver nucleation reaction is reduced, the nucleation rate is increased, and a new atomic beam is formed. In the crystal growth process of two atomic beams, expansion in the plane is blocked, so that crystal particles are further reduced, the crystal grains of the coating are refined, and the surface of the coating is denser and smoother.
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 schematic illustration of the surface of a ceramic copper clad substrate of the present invention;
FIG. 2 is a schematic view of a ceramic copper clad substrate of the present invention with a 5-fold partial enlargement of the surface;
FIG. 3 is a schematic view of the surface of the ceramic copper-clad substrate of comparative example 1 after silver plating without ink protection;
FIG. 4 is a schematic view of the surface of the ceramic copper-clad substrate after ink protection silver plating in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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.
The composite ink in the following examples was prepared as follows:
133 parts of trioctyl trimellitate and 47 parts of diisononyl phthalate were added to a reaction vessel, followed by 3 parts of white carbon black, 7 parts of titanium white, 4 parts of a defoaming agent and 10 parts of a heat stabilizer, and stirred at a speed of 100n/min for 20 minutes. 250 parts of high molecular weight polyvinyl chloride and 85 parts of low molecular weight polyvinyl chloride are added, and the mixture is stirred for 1.5 hours at the speed of 300n/min, so as to obtain the composite ink.
Nanoparticle suspensions were prepared as follows:
4.6g of glycerol is dissolved in 100mL of absolute ethanol to obtain a solution A; 17g of silver nitrate is dissolved in 200mL of absolute ethyl alcohol to obtain solution B; 0.4g of polyvinylpyrrolidone was dissolved in 40mL of absolute ethanol to obtain solution C. Mixing the solution A, B with the solution C, heating to 90 ℃ in a water bath, stirring and reacting for 1.5 hours to obtain nano silver particles, and ultrasonically dispersing the nano silver particles in deionized water to obtain a nano particle suspension.
Example 1
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 1g/L.
Example 2
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 2g/L.
Example 3
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 3g/L.
Comparative example 1
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; step etching; obtaining a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 1g/L.
Comparative example 2
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using traditional printing ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using nitric acid to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 1g/L
Comparative example 3
The nano particles in the nano particle suspension are nano cerium oxide.
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 1g/L.
Comparative example 4
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complex solution and the glucose solution into a reaction container at a constant speed, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing and drying at 50 ℃ for 8h, and thus obtaining the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product.
Comparative example 5
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 0.5g/L.
Comparative example 6
S1: placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning for 10min at 50 ℃, and drying for later use; performing ink protection on the ceramic copper-clad substrate by using composite ink, wherein the thickness of the ink protection layer is 10 mu m; step etching after solidification; removing the composite ink on the surface of the ceramic copper-clad substrate by using sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film, wherein the thickness of the exposure film is 15 mu m; after para-position exposure and development, placing the ceramic copper-clad substrate A in a reaction container, adding deionized water, and carrying out ultrasonic cleaning at a constant temperature of 50 ℃ for 30min; respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution into a reaction container at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath at 50 ℃ for 30min, performing ultrasonic reaction in a constant-temperature water bath at 60 ℃ for 30min, washing at 50 ℃ and drying for 8h to obtain the silver-plated ceramic copper-clad substrate. Removing film, cleaning, laser cutting, post-processing, inspecting and packaging to obtain the finished product. Wherein the nanoparticle suspension concentration is 4g/L.
And (3) testing:
leveling: the measurement was carried out according to the standard JB/T7704.5-1995 "leveling test for plating solution test method", using a roughness meter method, see Table below.
Contact resistance: the contact resistance test was carried out according to GB/T15078-1994 method for measuring the contact resistance of noble metal electric contact materials, see Table below.
Adhesion strength: the evaluation was carried out according to the bending test in GB/T5270-2005 test method for adhesion strength of metal coating on metal substrate by electrodeposition and chemical deposition, see Table below.
Conclusion:
in examples 1 to 3 and comparative example 1, it can be seen from fig. 3 and 4 that the copper-clad substrate without ink protection has a remarkable grain boundary gap, severe plating leakage and roughness of the plating layer. After the ink is protected, the grain boundary is normal after silver plating, and the surface of the plating layer is smooth and flat
In comparative example 2, after the ink is removed by nitric acid, the surface grain boundary corrosion of the copper-clad substrate is serious, the subsequent silver plating process is not facilitated, and the plating leakage is easy to occur; meanwhile, the grain boundary is easy to remain, the subsequent working procedures are difficult to clean, and slow over-corrosion is more serious along with the extension of time. Resulting in the inability of metallic silver ions to normally contact copper grain boundaries during electroless silver plating processes, resulting in the inability of metallic silver ions to normally deposit.
| Average roughness R a (μm) | Contact resistance value (mΩ) | Adhesion strength | |
| Example 1 | 0.321 | 0.045 | Good (good) |
| Example 2 | 0.338 | 0.046 | Good (good) |
| Example 3 | 0.341 | 0.048 | Good (good) |
| Comparative example 1 | 0.387 | 0.051 | Difference of difference |
| Comparative example 2 | 0.393 | 0.052 | Difference of difference |
| Comparative example 3 | 0.397 | 0.062 | Difference of difference |
| Comparative example 4 | 0.418 | 0.051 | Difference of difference |
| Comparative example 5 | 0.388 | 0.050 | Difference of difference |
| Comparative example 6 | 0.398 | 0.052 | Difference of difference |
In comparative example 3, cerium oxide can fill the grain boundary gap, but the resistance of cerium oxide is excessively increased, the conductivity is poor, and the cerium oxide is doped in the plating layer to have a certain influence on the conductivity of the plating layer.
In comparative example 4, no nano silver particles are added, so that the density of the surface of the plating layer is reduced, gaps of grain boundaries are not fully filled, the grain growth is larger, and the surface of the plating layer is rougher.
In comparative example 5, the concentration of nanoparticle suspension was lower, resulting in a decrease in active spots on the surface of the copper-clad substrate, resulting in an insufficiently dense, flat and smooth coating.
In comparative example 6, the concentration of the nanoparticle suspension is high, which results in serious agglomeration of nanoparticles on the surface of the copper-clad substrate, and prevents effective deposition of matrix silver; part of silver is directly deposited and grown on the surface of the aggregate, so that the surface shape of a plating layer is irregular, and the plating effect is poor.
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 preventing electroless silver plating from leaking plating on the surface of a ceramic copper-clad substrate is characterized by comprising the following steps: the prevention is carried out according to the following steps:
s1: carrying out chemical pretreatment on the ceramic copper-clad substrate; performing ink protection on the ceramic copper-clad substrate by using composite ink; after solidification, forming an ink protection layer and step etching; removing the printing ink protective layer by sodium hydroxide to obtain a ceramic copper-clad substrate A;
s2: carrying out chemical pretreatment on the ceramic copper-clad substrate A; performing alignment exposure and development, plating silver to obtain a silver-plated ceramic copper-clad substrate, removing film, cleaning, laser cutting, performing post-treatment, inspecting and packaging to obtain a finished product;
in the step S1, the thickness of the composite ink coating is 10-20 mu m; the concentration of sodium hydroxide is 30-50 g/L;
in step S1, the composite ink is prepared as follows:
adding trioctyl trimellitate and diisononyl phthalate, uniformly stirring, adding white carbon black, titanium white, a defoaming agent and a heat stabilizer, uniformly mixing, adding high-molecular polyvinyl chloride and low-molecular polyvinyl chloride into a system, and stirring to obtain composite printing ink;
130-135 parts of trioctyl trimellitate, 46-50 parts of diisononyl phthalate, 3-4 parts of white carbon black, 7-8 parts of titanium dioxide, 3-4 parts of defoamer, 9-10 parts of heat stabilizer, 250-281 parts of high molecular weight polyvinyl chloride and 85-95 parts of low molecular weight polyvinyl chloride; wherein the molecular weight of the high molecular weight polyvinyl chloride is 3000-4000, and the molecular weight of the low molecular weight polyvinyl chloride is 800-900.
2. The method for preventing electroless silver plating leakage on a surface of a ceramic copper-clad substrate according to claim 1, wherein the method comprises the following steps: in step S1, the chemical pretreatment is performed as follows:
placing the ceramic copper-clad substrate in an acetone solution, ultrasonically cleaning the ceramic copper-clad substrate for 10-20 min at 45-50 ℃, taking out the ceramic copper-clad substrate and drying the ceramic copper-clad substrate.
3. The method for preventing electroless silver plating leakage on a surface of a ceramic copper-clad substrate according to claim 1, wherein the method comprises the following steps: in step S2, the chemical pretreatment is performed as follows:
coating a layer of photosensitive polyimide photoresist on the surface of the ceramic copper-clad substrate A to form an exposure film; the thickness is 10-20 mu m.
4. The method for preventing electroless silver plating leakage on a surface of a ceramic copper-clad substrate according to claim 1, wherein the method comprises the following steps: in step S2, the plating solution for silver plating comprises the following four parts: silver ammonia complexing solution, glucose solution, dispersant solution and nanoparticle suspension; wherein the nanoparticle suspension is a silver nanoparticle suspension, and the dispersing agent solution is a polyvinylpyrrolidone solution.
5. The method for preventing electroless silver plating on a surface of a ceramic copper-clad substrate according to claim 4, wherein the method comprises the steps of: the silver ammonia complexing solution is prepared according to the following method:
placing silver nitrate into a container, and adding deionized water for dissolution; slowly adding the triethylene tetramine solution into a container, stirring, and obtaining a silver ammonia complexing solution after precipitation disappears;
the nano silver particle suspension is prepared according to the following method:
respectively dissolving glycerol, silver nitrate and polyvinylpyrrolidone in absolute ethyl alcohol with different volumes to obtain a solution A, a solution B and a solution C, mixing the solution A, the solution B and the solution C, putting into a water bath, stirring, and heating for reaction to obtain nano silver particles; and ultrasonically dispersing the nano silver particles in deionized water to obtain nano silver particle suspension.
6. The method for preventing electroless silver plating leakage on a surface of a ceramic copper-clad substrate according to claim 5, wherein the method comprises the steps of: the concentration of the solution A is 46-50 g/L, the concentration of the solution B is 85-90 g/L, the concentration of the solution C is 0.75-0.81 g/L, the heating reaction temperature is 85-90 ℃, and the reaction time is 1.5-2 h.
7. The method for preventing electroless silver plating on a surface of a ceramic copper-clad substrate according to claim 4, wherein the method comprises the steps of: the concentration of the silver ammonia complex solution is 0.36-0.40 mol/L, the concentration of the glucose solution is 0.42-0.45 mol/L, the concentration of the dispersing agent solution is 4-5 g/L, and the concentration of the nanoparticle suspension is 1-3 g/L.
8. The method for preventing electroless silver plating leakage on a surface of a ceramic copper-clad substrate according to claim 1, wherein the method comprises the following steps: in step S2, silver plating is performed as follows: placing the ceramic copper-clad substrate A in deionized water, and carrying out constant-temperature ultrasonic cleaning; and respectively adding the dispersing agent solution, the silver ammonia complexing solution and the glucose solution at a constant speed, adding the nanoparticle suspension in the dripping process, performing ultrasonic reaction in a constant-temperature water bath, and washing and drying to obtain the silver-plated ceramic copper-clad substrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3269861A (en) * | 1963-06-21 | 1966-08-30 | Day Company | Method for electroless copper plating |
| US5058799A (en) * | 1986-07-24 | 1991-10-22 | Zsamboky Kalman F | Metallized ceramic substrate and method therefor |
| EP3681256A1 (en) * | 2019-01-09 | 2020-07-15 | BGT Materials Limited | A method for forming trace of circuit board |
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| CN101699931B (en) * | 2009-11-02 | 2011-07-06 | 广东达进电子科技有限公司 | Method for manufacturing high-heat conduction ceramic circuit board |
| CN103687319A (en) * | 2012-09-25 | 2014-03-26 | 昆山联滔电子有限公司 | Manufacturing method for forming conductor circuit on non-conductive substrate |
| CN103131261B (en) * | 2013-03-08 | 2015-01-21 | 番禺南沙殷田化工有限公司 | Printing strippable protective ink, and preparation method and application thereof |
| CN105670382A (en) * | 2015-05-26 | 2016-06-15 | 华南农业大学 | Thermal-curable peelable print ink, preparation method and construction method thereof |
| CN114525500B (en) * | 2021-12-28 | 2023-05-05 | 南通威斯派尔半导体技术有限公司 | Local silver plating method for copper-clad ceramic substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3269861A (en) * | 1963-06-21 | 1966-08-30 | Day Company | Method for electroless copper plating |
| US5058799A (en) * | 1986-07-24 | 1991-10-22 | Zsamboky Kalman F | Metallized ceramic substrate and method therefor |
| EP3681256A1 (en) * | 2019-01-09 | 2020-07-15 | BGT Materials Limited | A method for forming trace of circuit board |
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