CN108977862B - Method for electroplating metal on surface of insulating substrate - Google Patents
Method for electroplating metal on surface of insulating substrate Download PDFInfo
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- CN108977862B CN108977862B CN201811003652.5A CN201811003652A CN108977862B CN 108977862 B CN108977862 B CN 108977862B CN 201811003652 A CN201811003652 A CN 201811003652A CN 108977862 B CN108977862 B CN 108977862B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- 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
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
Abstract
The invention relates to a method for electroplating metal on the surface of an insulating substrate, which comprises the following steps: contacting the insulating substrate surface with a water-soluble anionic compound to produce a modified surface; contacting the modified surface with an aqueous solution containing permanganate ions to form a manganese dioxide adsorption layer on the modified surface; forming a conductive polymer layer on the surface of the manganese dioxide adsorption layer; and electroplating the surface of the conductive polymer layer to form a metal layer. The method utilizes the anionic compound to deposit on the surface of the insulating base material to form a coating layer which is tightly combined with the surface of the base material, and after the coating layer is modified and adsorbed to form a uniform film with a certain thickness on the surface, the deep plating capacity and the dispersion capacity of the electroplating solution can be greatly improved under the same metal electroplating solution and electroplating conditions, the obtained metal coating has the characteristics of flatness, uniformity and good backlight effect, and the phenomena of hole breakage and over-thinning of the electroplated metal layer at individual sites in the hole are avoided.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a method for electroplating metal on the surface of an insulating base material.
Background
With the rapid development of the electronic information industry, the Printed Circuit Board (PCB) industry, which is an electronic interconnection carrier, has also been developed at a high speed. From the conventional double-sided multilayer to High Density Interconnect (HDI) board to the conventional SLPCB (substrate interconnect printed circuit board) board, the process requirement is higher and higher. In the past, the chemical copper plating for interlayer conduction of the process adopts formaldehyde as a reducing agent, and the formaldehyde is a carcinogenic substance with high toxicity and poses great threat to the body health of operators. In addition, the process uses and discharges metal ions such as copper ions, nickel ions, palladium ions and the like, and more importantly, wastewater containing a large amount of complexing agents generated in the process is difficult to treat. Therefore, the current process uses a conductive polymer process to replace the conventional electroless copper plating process. Firstly, an organic conductive film is required to be deposited on a hole wall insulating layer of a circuit board, then chemical plating is carried out by utilizing the conductivity of the conductive film, and finally a permanent conductive copper layer is formed on the surface of the conductive film. The process has the advantages of environment-friendly operation process, shortened process flow, no use of formaldehyde, no use and discharge of heavy metal ions and complexing agents thereof, simple wastewater treatment step, low unit energy consumption and low operation cost. However, the process has a fatal weakness, because due to the charge characteristic of the treated substrate surface (such as pore walls), if the substrate is directly treated by using the permanganate-containing solution, the amount of manganese dioxide deposited on the substrate surface, especially on the pore wall surface, is very small, so that an organic conductive film formed on the substrate surface is relatively thin, the conductivity of the organic conductive polymer is relatively weak, the reaction is particularly poor at glass fiber sites in circuit board pores, and voids (Void) are frequently generated in the electroplating process, which are commonly called as copper breaking, and light transmission and voids can occur in a backlight test. In addition, even if light transmission and voids are not generated in the backlight test, if the copper thickness at a certain position in the hole is extremely thin, the conductivity and stability of the circuit board are still affected.
Thus, the prior art remains to be improved.
Disclosure of Invention
Based on this, the invention aims to provide a method for electroplating metal on the surface of an insulating substrate.
The specific technical scheme is as follows:
a method for electroplating metal on the surface of an insulating substrate comprises the following steps:
contacting the insulating substrate surface with a water-soluble anionic compound to form a modified surface;
contacting the modified surface with an aqueous solution containing permanganate ions to form a manganese dioxide adsorption layer on the modified surface;
forming a conductive polymer layer on the surface of the manganese dioxide adsorption layer;
and electroplating the surface of the conductive polymer layer to form a metal layer.
It will be appreciated that contacting the surface of the insulating substrate with an anionic compound may be by immersing the insulating substrate in an aqueous solution of an anionic compound, wherein the concentration of anions in the aqueous solution of an anionic compound is in the range 0.1g/L to 20 g/L. The treatment of the substrate with the anionic compound may be carried out at a temperature of 15 to 80 ℃ for 50 seconds to 5 minutes.
In some of these embodiments, the water-soluble anionic compound is selected from one or more of a sulfonate, a carboxylate, a sulfate, and a phosphate.
In some of these embodiments, the sulfonate is selected from one or more of sodium polybutadiene sulfonate, sodium dodecylbenzene sulfonate, sodium hexadecyl sulfonate, sodium allyl sulfonate, and lignosulfonic acid;
the carboxylic acids are selected from one or more of sodium oleate, sodium carboxymethylcellulose, sodium gluconate, sodium fatty alcohol polyoxyethylene ether carboxylate and sodium stearate;
the sulfate salt is selected from one or more of sodium laureth sulfate, sodium dodecyl sulfate and sodium lauroyl aminoethyl sulfate;
the phosphate salt is selected from one or more of sodium hexadecyl phosphate, potassium dodecyl phosphate and potassium fatty alcohol polyoxyethylene ether phosphate.
In some of these embodiments, the concentration of the water-soluble anionic compound is from 0.1g/L to 20 g/L.
In some of these embodiments, the manganese dioxide adsorbent layer has a density of 20 μ g/cm 2 -120μg/cm 2 。
In some embodiments, the metal layer is made of a material selected from copper, gold, silver, or nickel.
In some of these embodiments, the insulating substrate is selected from plastic, resin, fiberglass, ceramic, or stone.
The invention also aims to provide a preparation method of the printed wiring board, which comprises the method for electroplating metal on the surface of the insulating substrate.
The invention also aims to provide a printed wiring board obtained by the preparation method.
The principle and the advantages of the invention are as follows:
firstly, the surface of the insulating base material is contacted with a water-soluble anionic compound to obtain a modified surface; the water-soluble anionic compound has good binding force on the surface of the insulating base material, and a compact charged multilayer reducing film is deposited on the surface of the insulating base material after the treatment of the anionic compound aqueous solution. The thin film layer is effective for improving the surface characteristics of the insulating substrate, and can adsorb substances which cannot be effectively adsorbed on the surface of the substrate, such as an oxidizing agent in electroplating, by a redox reaction.
Then contacting the modified surface with an aqueous solution containing permanganate ions to form a manganese dioxide adsorption layer on the modified surface; the anionic compound deposited on the modified surface in this step acts as a reducing agent, promoting the adsorption of the oxidation product manganese dioxide. Moreover, the compact multilayer film deposited on the surface of the insulating base material by the anionic compound can enable manganese dioxide to be deposited more uniformly, and the phenomenon that a copper layer at a certain position is thinner during subsequent copper plating is avoided.
Finally, forming a conductive polymer layer on the surface of the manganese dioxide adsorption layer; and electroplating the surface of the conductive polymer layer to form a metal layer.
Compared with the prior insulating base material surface treatment technology, the method utilizes the deposition of anionic compounds on the surface of the insulating base material to form a coating layer which is tightly combined with the surface of the base material, and after the surface forms a uniform film with a certain thickness through the modification and adsorption, the deep plating capacity and the dispersion capacity of the electroplating solution can be greatly improved under the same metal electroplating solution and electroplating conditions, so that the surface of the insulating base material is very favorable for forming a flat metal coating with proper thickness in subsequent electroplating, the obtained metal coating has the characteristics of flatness, uniformity and good backlight effect, the thickness of the metal deposition is easy to control in the plating process, and the phenomenon that holes are broken or copper at a certain position in the holes is thin is avoided.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The "water-soluble anionic compound" according to the present invention may be, for example, a sulfonate, a carboxylate, a sulfate and a phosphate, and each salt type compound may be in a polymer form or a non-polymer form. The invention mainly utilizes the reductive covering layer formed on the surface of the insulating substrate to be used for reducing permanganate subsequently to generate a manganese dioxide adsorption layer.
"conductive polymers" are primarily polymers formed by chemical or electrochemical doping of polymers having conjugated pi bonds, and have conductivities that extend from the insulator to the conductor. For example, polythiophene, polyaniline, polyfuran, polypyrrole, polystyrene sulfonate, derivatives thereof, and the like, which are commonly used, may be used, and various metal ions, for example, lithium ion, aluminum ion, sodium ion, potassium ion, and the like, may be incorporated therein.
The TP value (turning power) used in the examples is an index for comprehensively evaluating the throwing power and the dispersing power of a copper plating solution. The TP values typically include TP according to various evaluation angles std And TP min . Wherein TP std Is to evaluate the overall condition of metal plating in the substrate hole, which is equal to the ratio of the hole copper center plating thickness (average) to the orifice copper plating thickness (average). TP min Is the case where the point of the substrate hole where the metal plating thickness is thinnest is evaluated, which is equal to the ratio of the copper plating thickness at that point to the via plating thickness (average). The invention uses the same copper plating solution and electroplating conditions to plate metal. Thus, the TP value of the final metal plating reflects the ability of the different water-soluble anionic compounds of the present invention to modify the surface of the insulating substrate. The backlight test is one of the methods for evaluating the effect of metal plating, and the detected results are expressed in terms of backlight scale and classified into 0-10 gradesThe 1mm thick section taken from each plate was observed at 50 times magnification in the transmission mode of a conventional optical microscope. The quality of the copper plating is obtained from the contrast of the brightness observed under the microscope with the backlight grade pictures commonly used in the industry. If no light is observed, the profile is completely black at a level of 10 of the backlight level, indicating complete copper coverage. If the light is completely transmitted without any dark areas, it means that little or no copper metal is deposited on the substrate surface, this portion is of the 0 grade. If there are both dark areas and areas that are transparent to light, the grading is from 1 to 9 according to comparison with the standard picture.
The experimental procedures in the following examples are conventional unless otherwise specified. The raw materials and reagent materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
Substrate surface modification: two plastic substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and 100 microns of medium thickness are generated on the plastic substrates by using laser, and the following same treatment is respectively carried out: the mixture was washed with water, then immersed in a 1g/L aqueous solution of sodium allylsulfonate at 50 ℃ for 4.5 minutes, washed with water, then immersed in a 60g/L aqueous solution of potassium permanganate (adjusted with 10g/L boric acid) at 80 ℃ for about 1.5 minutes, and washed with water after the completion of the treatment.
And (3) testing the adsorption quantity of manganese dioxide: one of the treated substrates was taken, manganese dioxide on the substrate was eluted with a sufficient amount of a mixed solution containing 3% (volume fraction) sulfuric acid and 3% (volume fraction) hydrogen peroxide, and the amount of adsorption (density) of manganese dioxide on the substrate was calculated to be 38.18. mu.g/cm 2 。
Copper electroplating: another treated substrate was immersed in a mixed solution of 10ml/L of 3, 4-ethylenedioxythiophene, 6g/L of p-toluenesulfonic acid, and 7ml/L of OP emulsifier for 3 minutes. After completion, the substrate was immersed in a copper plating solution containing 80g/L of copper sulfate pentahydrate, 1g/L of sulfuric acid (pH adjusted to 2), 40mg/L of chloride ions, 8mg/L of sodium polydithiodipropylsulfonate, and 1g/L of polyethylene glycol, and 2A/dm was applied 2 Electroplating for 60 minutes to form a plating layer on the substrateAnd plating copper on the surface of the plate, the through holes and the blind holes. Finally, the backlight test shows that the backlight grade reaches 9 grades and the electroplating effect TP is achieved std Value of 84%, TP min The value was 70%.
Example 2
Substrate surface modification: two pieces of glass fiber cloth with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and the aperture of 100 microns are generated on the glass fiber cloth by using laser, and the following same treatment is respectively carried out: the mixture is washed by water, then is immersed into 5g/L sodium dodecyl benzene sulfonate aqueous solution for about 2 minutes at 30 ℃, is immersed into 60g/L potassium permanganate aqueous solution (adjusted by 10g/L boric acid) for about 1.5 minutes at 80 ℃ after being washed by water, and is washed by water for standby after the treatment is finished.
And (3) testing the adsorption quantity of manganese dioxide: one of the treated glass fiber cloths was taken, manganese dioxide on the substrate was eluted with a sufficient amount of a mixed solution containing 3% (volume fraction) sulfuric acid and 3% (volume fraction) hydrogen peroxide, and the adsorption amount (density) of manganese dioxide on the glass fiber cloth was calculated to be 119.29. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another piece of modified glass fiber cloth under the same conditions, and backlight test showed that the backlight grade reached 9.5 grade and the electroplating effect TP std Value of 90%, TP min The value was 76%.
Example 3
Substrate surface modification: two epoxy resin substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the dielectric thickness of 75 mu m and the aperture of 100 mu m are generated on the epoxy resin substrates by using laser, and the following same treatment is respectively carried out: the mixture is washed by water, then is immersed into 10g/L aqueous solution of sodium oleate for about 1.5 minutes at 35 ℃, is immersed into 60g/L aqueous solution of potassium permanganate (adjusted by 10g/L boric acid) for about 1.5 minutes at 80 ℃ after being washed by water, and is washed by water for standby after the treatment is finished.
And (3) testing the adsorption quantity of manganese dioxide: one of the epoxy resin substrates was treated in the same manner as in example 1, and the adsorption of manganese dioxide on the substrate was calculatedThe amount was 64.47. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another modified substrate under the same conditions, and backlight test showed that the backlight level reached 9, and the electroplating effect TP was achieved std The value is 87%, TP min The value was 73%.
Example 4
Substrate surface modification: two 1.6 mm-thick polytetrafluoroethylene resin substrates were taken, through holes of 0.2mm in diameter and blind holes of 75 μm in dielectric thickness and 100 μm in diameter were formed thereon using laser, and the following same treatments were carried out, respectively: the method comprises the following steps of firstly washing, then immersing into 0.1g/L sodium fatty alcohol polyoxyethylene ether carboxylate aqueous solution at 60 ℃ for about 3 minutes, immersing into 60g/L potassium permanganate aqueous solution (adjusted by 10g/L boric acid) with pH value of 6 at 80 ℃ for about 1.5 minutes after washing, and washing after finishing treatment for standby.
And (3) testing the adsorption quantity of manganese dioxide: one of the above substrates was treated in the same manner as in example 1, and the amount of manganese dioxide adsorbed thereon was calculated to be 52.91. mu.g/cm 2 。
Copper electroplating: using the same copper electroplating solution as in example 1, another modified polytetrafluoroethylene resin substrate was electroplated under the same conditions, and finally, the backlight test showed that the backlight level reached 9, and the through hole electroplating effect TP std Value 86%, TP min The value was 71%.
Example 5
Substrate surface modification: two pieces of glass fiber cloth with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and the aperture of 100 microns are generated on the glass fiber cloth by using laser, and the following same treatment is respectively carried out: the mixture is washed by water, then is immersed into 0.5g/L aqueous solution of sodium laureth sulfate at 65 ℃ for about 50 seconds, is immersed into 60g/L aqueous solution of potassium permanganate (adjusted by 10g/L boric acid) at 80 ℃ for about 1.5 minutes after being washed by water, and is washed by water for standby after the treatment is finished.
And (3) testing the adsorption quantity of manganese dioxide: it was treated in the same manner as in example 1The amount of manganese dioxide adsorbed on one of the glass fiber cloths was calculated to be 44.05. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another piece of modified fiberglass cloth under the same conditions, and finally, backlight test showed that the backlight level reached 9, and the through hole electroplating effect TP was achieved std Value 85%, TP min The value was 70%.
Example 6
Substrate surface modification: two epoxy resin substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the dielectric thickness of 75 mu m and the aperture of 100 mu m are generated on the epoxy resin substrates by using laser, and the following same treatment is respectively carried out: the mixture was washed with water, then immersed in a 20g/L aqueous solution of sodium lauryl sulfate at 70 ℃ for about 4 minutes, washed with water, immersed in a 60g/L aqueous solution of potassium permanganate (adjusted with 10g/L boric acid) at 80 ℃ for about 1.5 minutes, and then washed with water after the completion of the treatment.
And (3) testing the adsorption quantity of manganese dioxide: one of the modified epoxy resin substrates was treated in the same manner as in example 1, and the amount of manganese dioxide adsorbed thereon was calculated to be 70.37. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another modified epoxy resin substrate under the same conditions, and backlight test showed that the backlight level reached 9.5 and the through hole electroplating effect TP std Value 88%, TP min The value was 73%.
Example 7
Substrate surface modification: two ceramic substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and 100 microns of dielectric thickness are generated on the ceramic substrates by using laser, and the following same treatment is respectively carried out: the mixture is washed with water, then immersed in a 15g/L aqueous solution of sodium hexadecylphosphate at 80 ℃ for about 3.5 minutes, then immersed in a 60g/L aqueous solution of potassium permanganate (adjusted with 10g/L boric acid) at 80 ℃ for about 1.5 minutes, and then washed with water for later use after the treatment is finished.
And (3) testing the adsorption quantity of manganese dioxide: one of the above substrates was treated in the same manner as in example 1, and the amount of manganese dioxide adsorbed thereon was calculated to be 63.12. mu.g/cm 2 。
Copper electroplating: using the same copper electroplating solution as in example 1, another modified ceramic substrate was electroplated under the same conditions, and finally, the backlight test showed that the backlight level reached 9, and the through hole electroplating effect TP std Value 88%, TP min The value was 72%.
Example 8
Substrate surface modification: two stone substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and the aperture of 100 microns are generated on the stone substrates by using laser, and the following same treatment is respectively carried out: the mixture was washed with water, then immersed in a 3g/L aqueous solution of lignosulfonic acid at 40 ℃ for about 3 minutes, washed with water, immersed in a 50g/L aqueous solution of potassium permanganate (adjusted with 10g/L boric acid) at 80 ℃ for about 1.5 minutes, and then washed with water for use.
And (3) testing the adsorption quantity of manganese dioxide: one of the substrates was treated in the same manner as in example 1, and the amount of manganese dioxide adsorbed thereon was calculated to be 71.05. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another modified stone substrate under the same conditions, and backlight test showed that the backlight level reached 9.5, and the through hole electroplating effect TP was achieved std Value 88%, TP min The value was 74%.
Example 9
Substrate surface modification: two epoxy resin substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the dielectric thickness of 75 mu m and the aperture of 100 mu m are generated on the epoxy resin substrates by using laser, and the following same treatment is respectively carried out: the mixture is washed by water, then is immersed into 18g/L sodium gluconate aqueous solution for about 5 minutes at 15 ℃, is washed by water, is immersed into 50g/L potassium permanganate aqueous solution (adjusted by 10g/L boric acid) for about 1.5 minutes at 80 ℃, and is washed by water for standby after the treatment.
And (3) testing the adsorption quantity of manganese dioxide: one of the above substrates was treated in the same manner as in example 1, and the amount of manganese dioxide adsorbed on the epoxy resin was calculated to be 20.15. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another piece of modified epoxy resin under the same conditions, and backlight test showed that the backlight grade reached 9 grade and the electroplating effect TP std Value of 81%, TP min The value was 68%.
Comparative example 10 (example 5 comparison)
Substrate surface modification: two pieces of glass fiber cloth with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and the aperture of 100 microns are generated on the glass fiber cloth by using laser, and the following same treatment is respectively carried out: the mixture was washed with water, then immersed in 0.5g/L aqueous polyquaternium-7 at 65 ℃ for about 50 seconds, washed with water, immersed in 60g/L aqueous potassium permanganate solution (adjusted with 10g/L boric acid) at 80 ℃ for about 1.5 minutes, and then washed with water after the completion of the treatment.
And (3) testing the adsorption quantity of manganese dioxide: one of the above-mentioned glass fiber cloths was treated in the same manner as in example 1, and the adsorption amount of manganese dioxide on the glass fiber cloth was calculated to be 8.31. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another piece of modified glass fiber cloth under the same conditions, and backlight test showed that the backlight grade reached 8.5 and the through hole electroplating effect TP was achieved std Value 80%, TP min The value was 44%.
Comparative example 11 (example 7 comparison)
Substrate surface modification: two ceramic substrates with the thickness of 1.6mm are taken, through holes with the aperture of 0.2mm and blind holes with the aperture of 75 microns and 100 microns of dielectric thickness are generated on the ceramic substrates by using laser, and the following same treatment is respectively carried out: the mixture is washed by water, then is immersed into 15g/L aqueous solution of polydiallyldimethylammonium chloride for about 3.5 minutes at 80 ℃, is immersed into 60g/L aqueous solution of potassium permanganate (adjusted by 10g/L boric acid) for about 1.5 minutes at 80 ℃, and is washed for standby after the treatment.
And (3) testing the adsorption quantity of manganese dioxide: one of the above ceramic substrates was treated in the same manner as in example 1, and the amount of manganese dioxide adsorbed thereon was calculated to be 12.76. mu.g/cm 2 。
Copper electroplating: the same copper electroplating solution as in example 1 was used to electroplate copper on another modified ceramic substrate under the same conditions, and backlight test showed that the backlight grade reached 9 grade and the electroplating effect TP std Value of 84%, TP min The value was 49%.
And (4) analyzing results:
examples 1 to 9 were obtained by treating an insulating base material with the solution of the present invention and then plating a metal by electroplating, and the results of examples 1 to 9 show that: the adsorption capacity of the base material surface modified by the technology of the invention to manganese dioxide is more than 20 mu g/cm 2 The backlight grade of the subsequent copper electroplating can reach more than 9 grade, TP std The value is not less than 81%, TP min The values are all not less than 68%. The technical scheme of the invention is used for treating the base material, and then the electroplated copper layer with uniform thickness, good backlight and no particularly thin points in the hole can be obtained, thereby ensuring the conductivity and stability of the subsequent circuit board.
Comparative example 10 and comparative example 11 are compared with example 5 and example 7, respectively, except that examples 5 and 7 are treated with an anionic compound, whereas comparative example 10 and comparative example 11 are treated with a cationic compound only. As a result, the manganese dioxide adsorption amounts of the substrates of comparative examples 10 and 11 were only 8.31. mu.g/cm, respectively 2 And 12.76. mu.g/cm 2 Although TP of both std None were less than 80%, but TP was obtained for both comparative examples min 44% and 49%, respectively, compared to the electrolytic copper plating TP of the insulating base material treated with the anionic compound in examples 1 to 9 min There is a clear difference in the numerical values. TP of comparative example 10 and comparative example 11 min Lower, indicating that the thickness of the plated layer in the hole after subsequent copper electroplating of the insulating substrate treated with the cationic compound aloneThe degree is not uniform, and the conductivity and the stability of the circuit board cannot be ensured due to the existence of a site with thinner copper.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A method for electroplating metal on the surface of an insulating substrate is characterized by comprising the following steps:
contacting the insulating substrate surface with a water-soluble anionic compound to form a modified surface;
contacting the modified surface with an aqueous solution containing permanganate ions to form a manganese dioxide adsorption layer on the modified surface;
forming a conductive polymer layer on the surface of the manganese dioxide adsorption layer;
electroplating the surface of the conductive polymer layer to form a metal layer;
the water-soluble anionic compound is selected from sodium allyl sulfonate, sodium dodecyl benzene sulfonate, sodium oleate, sodium fatty alcohol polyoxyethylene ether carboxylate, sodium laureth sulfate, sodium dodecyl sulfate, sodium hexadecyl phosphate, lignosulfonic acid or sodium gluconate.
2. The method of claim 1, wherein the concentration of the water-soluble anionic compound is 0.1g/L to 20 g/L.
3. The method of claim 1, wherein the manganese dioxide adsorption layer has a density of 20 μ g/cm 2 -120μg/cm 2 。
4. A method for electroplating metal onto a surface of an insulating substrate according to any of claims 1 to 3, wherein the metal layer is made of a material selected from the group consisting of copper, gold, silver and nickel.
5. A method for electroplating metal on the surface of an insulating substrate according to any of claims 1 to 3, wherein the insulating substrate is selected from the group consisting of plastic, resin, fiberglass, ceramic, and stone.
6. A method for producing a printed wiring board, comprising the method for plating a metal on the surface of the insulating substrate according to any one of claims 1 to 5.
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| CN110117803B (en) * | 2019-05-14 | 2020-10-23 | 广州超邦化工有限公司 | Potassium chloride cyanide-free cadmium titanium alloy plating solution, preparation method and electroplating process thereof |
| CN110029382B (en) * | 2019-05-22 | 2021-09-24 | 电子科技大学 | Surface treatment process for direct electroplating and related direct electroplating process |
| CN115110071B (en) * | 2022-07-29 | 2023-09-01 | 电子科技大学 | Method for treating insulating substrate before electroless plating and electroless plating method |
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| TW200618876A (en) * | 2004-12-08 | 2006-06-16 | Ind Tech Res Inst | Method of forming a metal thin film with micro holes by ink-jet printing |
| CN107723764A (en) * | 2017-10-31 | 2018-02-23 | 电子科技大学 | A kind of method of the Direct Electroplating on insulating substrate |
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| CN1612951A (en) * | 2001-05-18 | 2005-05-04 | 埃托特克德国有限公司 | Direct electrolytic metallization of non-conducting substrate |
| TW200618876A (en) * | 2004-12-08 | 2006-06-16 | Ind Tech Res Inst | Method of forming a metal thin film with micro holes by ink-jet printing |
| CN107723764A (en) * | 2017-10-31 | 2018-02-23 | 电子科技大学 | A kind of method of the Direct Electroplating on insulating substrate |
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