CN115074789B - Circuit board blind hole rapid filling electrolytic copper plating solution and rapid filling method - Google Patents
Circuit board blind hole rapid filling electrolytic copper plating solution and rapid filling method Download PDFInfo
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- CN115074789B CN115074789B CN202211003055.9A CN202211003055A CN115074789B CN 115074789 B CN115074789 B CN 115074789B CN 202211003055 A CN202211003055 A CN 202211003055A CN 115074789 B CN115074789 B CN 115074789B
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/421—Blind plated via connections
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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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
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Abstract
The invention discloses a rapid filling electrolytic copper plating solution for blind holes of a circuit board and a rapid filling method, and relates to the technical field of printed circuit board production. The circuit board blind hole rapid filling electro-coppering solution comprises the following components in mass concentration: 30-80g/L of sulfuric acid, 100-240g/L of copper sulfate, 30-80ppm of chloride ions, 0.004-0.02g/L of brightening agent, 0.1-0.3g/L of carrier and 0.04-0.2g/L of quick filling agent, wherein the quick filling agent is a mixture consisting of leveling agent, catalyst and stabilizer. The circuit board blind hole rapid filling electro-coppering solution can rapidly fill the blind hole, thereby improving the blind hole filling efficiency, and the hole filling rate reaches more than 95%. Effectively reduces the thickness of the copper on the blind hole surface and the cost of the etching process, and simultaneously can save the copper ball and the production time.
Description
Technical Field
The invention relates to the technical field of printed circuit board production, in particular to a quick filling electrolytic copper plating solution for a blind hole of a circuit board and a quick filling method.
Background
With the development of electronic products toward short, thin, light, small and high performance, the wiring density and the hole density of the printed wiring board used for bearing electronic devices are higher and higher, so that the manufacturing process of the printed wiring board is more and more complicated. In order to comply with the requirement of printed circuit manufacturing, on one hand, enterprises continuously update equipment, on the other hand, savings measures are issued inside the enterprises, potentials are continuously excavated, and new processes are researched and introduced to meet the requirement of process manufacturing. The research shows that: one of the most effective ways to realize high-density wiring of printed circuit boards is to reduce the number of vias on the board and increase the number of blind vias, and the blind via electroplating and filling technology is a key technology for realizing interlayer interconnection and becomes one of the important issues of research in the industry. Under the continuous development of high-speed, high-capacity, cloud computing and high-performance servers, the design requirements of the PCB are also continuously upgraded, such as the application of high-layer number, large size, high aspect ratio, high density and high-speed materials, the application of lead-free welding and the like.
As market demand increases, demand for HDI (high density interconnect) PCBs also increases. However, the conventional process flow has some disadvantages including complexity, high cost, long production cycle and low OTD (on-time delivery). In order to reduce the cost, reduce the process flow and shorten the production period, the blind hole filling technology is developed from the prior point plating blind hole filling technology to the prior plating blind hole filling technology. The novel blind hole electroplating technology can reduce the production cost and improve the quality of the HDI board. Furthermore, it may even facilitate the increase of OTD, providing the manufacturer with the opportunity to serve more customers with short time limit requirements.
The problem of low efficiency of blind hole filling copper plating generally exists in the prior art, for example:
1) The Chinese patent application CN112899737A solves the problem that the side reaction of the phosphor-copper anode in the dissolving process can affect the plating solution and further affect the stability of the hole filling additive, but the stability of the filling solution can not be ensured, the electroplating efficiency can not be improved, and the copper thickness of the blind hole surface can be reduced.
2) In the Chinese patent application CN113502512A, the electro-coppering additive can effectively solve the problem that the cost of the additive in using materials is high, and the filled blind holes can meet the general production requirements, but the blind hole surface has thicker copper and long electro-coppering time, so the aim of saving the production cost cannot be achieved.
When the aperture of a blind hole is 50-400um and the depth of the blind hole is 50-150um, the traditional blind hole electro-coppering solution needs to use the current density of 1.5-2.5A/dm 2 And the blind hole can be filled only after the electroplating time is 45-90 min. Meanwhile, the problems of low hole filling rate, large depression, poor hole filling effect, poor surface smoothness of the copper layer and the like exist. The blind hole is inevitably thicker in the production board surface copper, low in production efficiency, seriously influenced in the production quality of the etching process and the like due to overlong electroplating filling time. And the consumption of copper balls is high, great waste is generated, the cost is not saved, and the clean production is not facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention provides a circuit board blind hole rapid filling electro-coppering solution which can rapidly fill the blind hole, thereby improving the blind hole filling efficiency, and the hole filling rate reaches more than 95%; meanwhile, the thickness of copper on the blind hole surface and the cost of an etching process can be effectively reduced, and copper balls and production time can be saved.
The method specifically comprises the following technical scheme:
on one hand, the invention provides a circuit board blind hole rapid filling electrolytic copper plating solution, which comprises the following components in mass concentration:
30-80g/L of sulfuric acid,
100-240g/L of copper sulfate,
30-80ppm of chloride ions are added,
0.004-0.02g/L of brightener,
0.1-0.3g/L of carrier,
0.04-0.2g/L of fast filler,
the rapid filling agent is a mixture consisting of a leveling agent, a catalyst and a stabilizer;
the brightener is selected from at least one of 2-mercaptobenzimidazole, 1,2-ethylene thiourea, N-dimethyl dithioformamide propane sodium sulfonate and 3,3' -dithiobis (1-propanesulfonic acid) disodium salt;
the carrier is selected from at least one of diallyl dimethyl ammonium chloride-acrylamide copolymer and diallyl dimethyl ammonium bromide copolymer.
Preferably, the fast filler consists of the following components in mass concentration: leveling agent 0.04-0.08g/L, catalyst 0.02-0.04g/L, stabilizer 0.008-0.012g/L; the leveling agent is selected from at least one of 2,2-dithiodipyridine, 1-azapyridin-3-yl pyrrolidine, 4,6-dimethyl-2-mercaptopyrimidine, 1- (3-acetamide) phenyl 5-mercaptotetrazole, and 2-mercaptopyridine; the catalyst is a mixture of 4-butanediol diglycidyl ether and 1-vinylimidazole; the stabilizer is at least one of isooctyl dimercaptoacetate di-n-octyl tin and dimethyl isooctyl dimercaptoacetate tin.
Preferably, in the catalyst, the mass ratio of 4-butanediol diglycidyl ether to 1-vinylimidazole is 1: (1-4).
Preferably, in the fast filler, the leveling agent: catalyst: the mass ratio of the stabilizer is 1: (0.3-0.5): (0.05-0.2).
Preferably, the mass concentration of the copper sulfate is 180-220g/L, the mass concentration of the sulfuric acid is 40-60g/L, and the mass concentration of the chloride ions is 40-70 ppm.
Preferably, the mass concentration of the brightener is 0.008-0.012g/L.
Preferably, the mass concentration of the carrier is 0.15-0.25g/L.
The preparation method for quickly filling the blind hole of the circuit board with the electro-coppering solution comprises the following steps:
s1, mixing a leveling agent, a catalyst and a stabilizer to obtain a rapid filling agent;
s2, mixing sulfuric acid, copper sulfate and chloride ions to obtain an aqueous solution;
and S3, adding the brightener, the carrier and the quick filling agent prepared in the step S1 into the aqueous solution obtained in the step S2, stirring and mixing to obtain the circuit board blind hole quick filling electro-coppering solution.
On the other hand, the invention also provides a method for quickly filling the blind holes of the circuit board, wherein the circuit board with the blind holes is continuously electroplated by VCP;
wherein, the circuit board blind hole is adopted to quickly fill the electro-coppering solution, the phosphor-copper alloy anode is taken as a soluble anode, and the phosphor content is 0.04-0.063%; the technological parameters of VCP continuous electroplating are as follows: the solution temperature is 15-40 deg.C, and the current density is 0.5-6A/dm 2 The electroplating time is 15-40min.
Preferably, in the circuit board, the blind hole size is the blind hole of aperture 50-400um, hole depth 50-150 um.
The invention has the beneficial effects that:
(1) The circuit board blind hole is filled with the quick filling agent contained in the copper electroplating solution. The quick filling agent consists of a leveling agent, a catalyst and a stabilizer, wherein micromolecular nitrogen-containing heterocyclic compounds such as sulfydryl, pyridine and the like in the leveling agent are adsorbed on the surface of the PCB under the coordination of chloride ions, and meanwhile, nitrogen-containing group substances have extremely strong polarity and are easy to absorb in a high-potential area of a blind hole orifice, so that the quick filling agent has stronger inhibiting effect on copper deposition, can obviously improve the filling capacity of electroplating solution and can effectively inhibit the growth of surface copper; the brightener and the catalyst mainly contain mercaptan micromolecule substances, and accelerate the permeation filling of the inner position of the blind hole while copper on the surface of the blind hole is inhibited. Meanwhile, in a copper sulfate system, effective components such as a rapid filling agent, a brightening agent, a carrier and the like interact with each other, so that the blind hole filling efficiency can be improved, the copper thickness of the blind hole surface can be reduced, the copper surface brightness can be improved, and copper balls can be saved.
(2) According to the method for quickly filling the blind holes of the circuit board, the blind holes are quickly filled by adopting the circuit board blind holes to quickly fill the electroplating copper solution, the filling efficiency of the blind holes can be improved, the hole filling rate can reach more than 95%, the copper thickness of the blind hole surface and the etching process cost are effectively reduced, and the copper balls and the production time can be saved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a diagram showing the effect of the Harlin trough test in example 1 of the present invention;
FIG. 2 is a diagram showing the effect of the Harlin trough test in embodiment 2 of the present invention;
FIG. 3 is a diagram showing the effect of the Harlin trough test in embodiment 3 of the present invention;
FIG. 4 is a diagram showing the effect of the Harlin trough test in embodiment 4 of the present invention;
FIG. 5 is a diagram showing the effect of the Harlin trough test in embodiment 5 of the present invention;
FIG. 6 is a diagram showing the effect of the Harlin trough test in embodiment 6 of the present invention;
FIG. 7 is a diagram showing the effect of the Harlin trough test in embodiment 7 of the present invention;
FIG. 8 is a diagram showing the effect of the Harlin trough test in embodiment 8 of the present invention;
FIG. 9 is a graph showing the effect of the Harlin trough test of comparative example 1 of the present invention;
FIG. 10 is a graph showing the effect of the Harlin trough test of comparative example 2 of the present invention;
FIG. 11 is a graph showing the effect of the Harlin trough test of comparative example 3 of the present invention;
FIG. 12 is a graph showing the effect of the Harlin trough test of comparative example 4 of the present invention;
FIG. 13 is a graph showing the effect of the Harlin trough test of comparative example 8 of the present invention;
FIG. 14 is a graph showing the effect of the Harlin trough test of comparative example 9 of the present invention;
FIG. 15 is a graph showing the effect of the Harlin bath test of comparative example 10 of the present invention;
FIG. 16 is a graph showing the effect of the Harlin trough test of comparative example 11 of the present invention;
FIG. 17 is a graph showing the effect of the Harlin trough test of comparative example 14 of the present invention;
FIG. 18 is a graph showing the effect of the Harlin trough test of comparative example 15 of the present invention;
FIG. 19 is a graph showing the effect of the Harlin bath test of comparative example 18 of the present invention;
FIG. 20 is a diagram showing the effect of the Harlin groove test for rapidly filling the blind hole with the electro-coppering solution according to the present invention;
FIG. 21 is a diagram showing the effect of the Harlin bath test of a conventional blind-hole electrolytic copper plating solution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that 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. As used in this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to specific embodiments.
A circuit board blind hole rapid filling electro-coppering solution comprises the following components in mass concentration:
30-80g/L of sulfuric acid,
100-240g/L of copper sulfate,
30-80ppm of chloride ions are added,
0.004-0.02g/L of brightener,
0.1-0.3g/L of carrier,
0.04-0.2g/L of fast filler,
specifically, in the examples and comparative examples of the present application, the brightener, the carrier, and the fast filler are prepared into a solution with a mass concentration of 10 ± 0.1 g/L; therefore, the mass concentration of 0.004-0.02g/L brightener is equivalent to 0.4-2.0 ml/L, the mass concentration of 0.1-0.3g/L carrier is equivalent to 10-30 ml/L, and the mass concentration of 0.04-0.2g/L fast filler is equivalent to 4-20 ml/L;
the rapid filling agent comprises the following components in percentage by mass: leveling agent 0.04-0.08g/L, catalyst 0.02-0.04g/L, stabilizer 0.008-0.012g/L; leveling agent: catalyst: the mass ratio of the stabilizer is 1: (0.3-0.5): (0.05-0.2); the leveling agent is selected from at least one of 2,2-dithiodipyridine, 1-azapyridin-3-yl pyrrolidine, 4,6-dimethyl-2-mercaptopyrimidine, 1- (3-acetamide) phenyl 5-mercaptotetrazole, and 2-mercaptopyridine; the catalyst is a mixture of 4-butanediol diglycidyl ether and 1-vinylimidazole, and the mass ratio of the 4-butanediol diglycidyl ether to the 1-vinylimidazole is 1: (1-4); the stabilizer is selected from at least one of isooctyl dithioglycolate di-n-octyl tin and dimethyl isooctyl dithioglycolate tin;
the brightener is selected from at least one of 2-mercaptobenzimidazole, 1,2-ethylene thiourea, N-dimethyl dithioformamide propane sodium sulfonate and 3,3' -dithiobis (1-propanesulfonic acid) disodium salt;
the carrying agent is selected from at least one of diallyl dimethyl ammonium chloride-acrylamide copolymer and diallyl dimethyl ammonium bromide copolymer.
The preparation method of the circuit board blind hole rapid filling electro-coppering solution comprises the following steps:
s1, mixing a leveling agent, a catalyst and a stabilizer to obtain a rapid filling agent;
s2, mixing sulfuric acid, copper sulfate and chloride ions to obtain an aqueous solution;
and S3, adding the brightener, the carrier and the quick filling agent prepared in the step S1 into the aqueous solution obtained in the step S2, stirring and mixing to obtain the circuit board blind hole quick filling electro-coppering solution.
Specifically, 1) the leveling agent, the catalyst and the stabilizer are weighed according to the required proportion to prepare 10 +/-0.1 g/L of aqueous solution as the rapid filling agent. Weighing brightener according to the required proportion to prepare 10 plus or minus 0.1g/L aqueous solution. Weighing the carrier according to the required proportion to prepare 10 +/-0.1 g/L aqueous solution;
2) Weighing sulfuric acid, copper sulfate and chloride ions according to the required proportion to prepare an aqueous solution. And then adding a rapid filling agent, a brightening agent and a carrying agent with required mass concentration, and stirring for 10-20min to obtain the circuit board blind hole rapid filling electro-coppering solution.
The method for quickly filling the blind hole of the circuit board comprises the following steps:
the method for quickly filling the blind hole of the circuit board comprises the following steps: s1, upper plate; s2, removing oil; s3, washing with water; s4, micro-etching; s5, washing with water; s6, acid washing; s7, plating copper on blind holes of the Harlin groove; s8, washing with water; s9, discharging the board; and S10, inserting a frame.
The step of plating copper on the blind holes of the Harlin groove comprises the following steps:
the prepared blind holes of the circuit board are quickly filled with an electro-coppering solution, the solution is added into a 1500mL Harlin groove, clean pure copper plates with the phosphorus content of 0.04-0.063 percent are placed at the two ends of the Harlin groove to be used as anodes (namely phosphorus-copper alloy anodes), and an electric inflating mode is adopted for stirring. The power supply of the inflating pump is 220-240V/50Hz, the power is 2W, the pressure is more than 0.012Mpa, and the air displacement is 3.2L/min.
A pre-plated copper smooth plate with blind holes (the specification is 50mm multiplied by 100mm, the diameter of the blind holes is 100mm, the hole depth is 50um, and the plate thickness is 1.6 mm) is subjected to oil removal, microetching and sulfuric acid solution pickling treatment, and then is placed into the liquid of the Harlin tank for electro-coppering (vertically placed in the middle position).
At the temperature of 15-40 ℃ and the current density of 0.5-6A/dm of the copper electroplating solution 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 15-40min and the automatic addition amount is 50-100ml/KA & H.
Verification test for effect of circuit board blind hole rapid filling electrolytic copper plating solution
And (3) respectively carrying out blind hole slicing on the printed circuit board with the electrolytic copper, grinding the printed circuit board to the middle position of the blind hole by using a slicing grinder, and respectively observing the copper surface section of the dissected slice of the measured sample by using a metallographic microscope. The values of the face copper thickness, the aperture, the hole depth and the dishing value of the sample were measured. Wherein, the recess value is qualified when less than 15 um.
Example 1
The circuit board blind hole rapid filling electro-coppering solution comprises the following components in concentration: 40g/L of sulfuric acid, 200g/L of copper sulfate pentahydrate, 60ppm of chloride ions, 0.8ml/L of brightening agent, 15ml/L of carrier and 8ml/L of quick filling agent. Wherein the brightener is a 2-mercaptobenzimidazole aqueous solution with the concentration of 10 +/-0.1 g/L; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.3:0.08, wherein the leveling agent is 2,2-dithiodipyridine, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a weight ratio of 1:1, and the stabilizer is isooctyl dimercaptoacetate di-n-octyl tin. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 20 ℃ and the current density of 2.5A/dm 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 20min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the plate thickness is 1.6mm, and obtaining the printed circuit board example 1 after electroplating.
Example 2
The circuit board blind hole rapid filling electro-coppering solution comprises the following components in concentration: 50g/L of sulfuric acid, 180g/L of copper sulfate pentahydrate, 60ppm of chloride ions, 0.8ml/L of brightening agent, 20ml/L of carrier and 8ml/L of quick filling agent. Wherein the brightener is 1,2-ethylene thiourea aqueous solution with the concentration of 10 +/-0.1 g/L; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.3:0.1, wherein the leveling agent is 1-azadin-3-yl pyrrolidine, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a weight ratio of 1:2, and the stabilizer is dimethyl tin dimercaptoacetate isooctyl ester. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 22 ℃ and the current density of 2.0A/dm 2 Electroplating the printed circuit board under the conditions that the copper electroplating time is 25min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, and the hole isA depth of 50um and a thickness of 1.6mm, and was plated to obtain a printed wiring board of example 2.
Example 3
The circuit board blind hole rapid filling electro-coppering solution comprises the following components in concentration: 60g/L of sulfuric acid, 220g/L of copper sulfate pentahydrate, 50ppm of chloride ions, 1.0ml/L of brightening agent, 15ml/L of carrier and 9ml/L of quick filling agent. Wherein the brightener is 10 +/-0.1 g/L of N, N-dimethyl dithioformamide sodium propane sulfonate aqueous solution; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.4:0.12, wherein the leveling agent is 4,6-dimethyl-2-mercaptopyrimidine, and the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a weight ratio of 1:3, and the stabilizer is dimethyl tin dimercaptoacetate isooctyl. The balance being deionized water.
Quickly filling the blind holes of the circuit board with an electro-coppering solution, and allowing the blind holes to have a current density of 1.5A/dm at a solution temperature of 25 deg.C 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 30min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the board thickness is 1.6mm, and obtaining the printed circuit board example 3 after electroplating.
Example 4
The circuit board blind hole rapid filling electro-coppering solution comprises the following components in concentration: 50g/L of sulfuric acid, 210g/L of copper sulfate pentahydrate, 60ppm of chloride ions, 1.2ml/L of brightening agent, 25ml/L of carrier and 12ml/L of quick filling agent. Wherein the brightener is 10 plus or minus 0.1 g/L3,3' -dithiobis (1-propanesulfonic acid) disodium aqueous solution; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.5:0.08, wherein the leveling agent is 1- (3-acetamide) phenyl 5-mercaptotetrazole, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a weight ratio of 1:4, and the stabilizer is dimethyl tin isooctyl dimercaptoacetate. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 24 ℃ and the current density of 2.5A/dm 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 25min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the board thickness is 1.6mm, and obtaining the printed circuit board example 4 after electroplating.
Example 5
The circuit board blind hole rapid filling electro-coppering solution comprises the following components in concentration: 40g/L of sulfuric acid, 220g/L of copper sulfate pentahydrate, 70ppm of chloride ions, 1.0ml/L of brightening agent, 20ml/L of carrier and 8ml/L of quick filling agent. Wherein the brightener is 1,2-ethylene thiourea aqueous solution with the concentration of 10 plus or minus 0.1 g/L; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.4:0.1, wherein the leveling agent is 2-mercaptopyridine, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a ratio of 1:1.5, and the stabilizer is dimethyl tin isooctyl dimercaptoacetate. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 26 ℃ and the current density of 3.5A/dm 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 15min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the board thickness is 1.6mm, and obtaining the printed circuit board example 5 after electroplating.
Example 6
The circuit board blind hole rapid filling electro-coppering solution comprises the following components in concentration: 60g/L of sulfuric acid, 190g/L of copper sulfate pentahydrate, 50ppm of chloride ions, 1.2ml/L of brightening agent, 25ml/L of carrier and 8ml/L of quick filling agent. Wherein the brightener is 10 +/-0.1 g/L of N, N-dimethyl dithioformamide sodium propane sulfonate aqueous solution; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filling agent is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is 1:0.45:0.12, wherein the leveling agent is 2-mercaptopyridine, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a ratio of 1:2.5, and the stabilizer is isooctyl dimercaptoacetate di-n-octyl tin. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 24 ℃ and the current density of 2.5A/dm 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 25min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the plate thickness is 1.6mm, and obtaining the printed circuit board embodiment 6 after electroplating.
Example 7
The circuit board blind hole fast filling electro-coppering solution comprises the following components in concentration: 40g/L of sulfuric acid, 200g/L of copper sulfate pentahydrate, 40ppm of chloride ions, 0.8ml/L of brightening agent, 20ml/L of carrier and 10ml/L of quick filling agent. Wherein the brightener is 10 +/-0.1 g/L3,3' -dithiobis (1-propanesulfonic acid) disodium water solution; the carrier is 10 plus or minus 0.1g/L of diallyl dimethyl ammonium bromide copolymer aqueous solution; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.5:0.15, wherein the leveling agent is 1- (3-acetamide) phenyl 5-mercaptotetrazole, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a weight ratio of 1:3.5, and the stabilizer is dimethyl tin dimercaptoacetate isooctyl ester. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 20 ℃ and the current density of 2.0A/dm 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 25min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the board thickness is 1.6mm, and obtaining the printed circuit board example 7 after electroplating.
Example 8
The circuit board blind hole fast filling electro-coppering solution comprises the following components in concentration: 60g/L of sulfuric acid, 220g/L of copper sulfate pentahydrate, 50ppm of chloride ions, 1.0ml/L of brightening agent, 20ml/L of carrier and 12ml/L of quick filling agent. Wherein the brightener is 10 +/-0.1 g/L3,3' -dithiobis (1-propanesulfonic acid) disodium water solution; the carrier is 10 plus or minus 0.1g/L of aqueous solution of diallyl dimethyl ammonium chloride-acrylamide copolymer; the fast filler is 10 +/-0.1 g/L of leveling agent: catalyst: the stabilizer is prepared from the following components in percentage by mass: 0.35:0.2, wherein the leveling agent is 2-mercaptopyridine, the catalyst is 4-butanediol diglycidyl ether and 1-vinylimidazole in a ratio of 1:1.8, and the stabilizer is dimethyl tin isooctyl dimercaptoacetate. The balance being deionized water.
Quickly filling the blind holes of the circuit board with the copper electroplating solution, and enabling the blind holes to be filled with the copper electroplating solution at the solution temperature of 23 ℃ and the current density of 2.0A/dm 2 And electroplating the printed circuit board under the conditions that the copper electroplating time is 30min and the automatic addition amount is 100ml/KA & H, wherein the diameter of a blind hole is 100mm, the hole depth is 50 mu m, and the plate thickness is 1.6mm, and obtaining the printed circuit board example 8 after electroplating.
The circuit board blind holes of examples 1 to 8 were quickly filled with the electrolytic copper plating solution to perform the harn bath test, and the test results are shown in table 1:
TABLE 1 results of the Harlin groove blind via fill electroplating test of examples 1-8
As can be seen from the test results in Table 1, the circuit board blind hole rapid filling electro-coppering solution provided by the invention is adopted for Harlin bath test, and has the advantages of simple proportioning, convenient operation, no toxicity, no harm, no other side effects and low economic cost from the aspects of proportioning dosage and application. The circuit board blind hole rapid filling electro-coppering solution is very effective in filling the blind hole, the blind hole is full and has no bubbles and holes, the depression value is stable within 5 mu m, and the hole filling rate reaches more than 95%; meanwhile, electroplating filling can be completed in 15-30min, the surface copper thickness is 8-12 um, and compared with the surface copper thickness used in 45-90min in the prior art, the surface copper thickness can be reduced by about 6-8um, and the electroplating time is shortened and the cost can be reduced.
1. Based on the influence of different mass concentrations of copper sulfate
Comparative examples 1 to 3 differ from example 1 in the mass concentration of copper sulfate and the remaining conditions were the same. Harlin groove blind hole filling electroplating tests are respectively carried out on the example 1 and the comparative examples 1 to 3, and the test results are shown in the table 2:
TABLE 2 Harlin groove blind via fill electroplating test results of example 1, comparative examples 1-3
As shown in the test results in Table 2, the circuit board blind hole is rapidly filled with the copper electroplating solution without adding copper sulfate (comparative example 1), and the test result of the Harlin groove is very unsatisfactory. The mass concentration of the copper sulfate is lower than 100 g/L (comparative example 2) or higher than 240g/L (comparative example 3), and the Harlin groove test result is not ideal. Therefore, the mass concentration of the copper sulfate in the circuit board blind hole rapid filling electrolytic copper plating solution is preferably 100-240g/L.
2. Based on the influence of different mass concentrations of sulfuric acid
Comparative examples 4 to 6 are different from example 1 in the mass concentration of sulfuric acid, and the other conditions are the same. The hardgrove blind via fill plating tests of example 1 and comparative examples 4-6, respectively, have the test results shown in table 3:
TABLE 3 Harlin groove blind via fill electroplating test results for example 1, comparative examples 4-6
As can be seen from the test results in Table 3, the sulfuric acid is not added in the copper electroplating solution for rapidly filling the blind holes of the circuit board (comparative example 4), and the test results of the Harlin bath are not ideal. The mass concentration of the sulfuric acid is lower than 30g/L (comparative example 5) or higher than 80g/L (comparative example 6), and the Harlin bath test result is not ideal. Therefore, the mass concentration of the sulfuric acid in the circuit board blind hole rapid filling electrolytic copper plating solution is preferably 30-80g/L.
3. Based on the combined effect of copper sulfate and sulfuric acid
Comparative example 1 differs from example 1 in that copper sulfate is not contained and the other conditions are the same. Comparative example 4 differs from example 1 in that no sulfuric acid is contained, and the other conditions are the same. Comparative example 7 is different from example 1 in that copper sulfate and sulfuric acid are not contained, and the other conditions are the same. Harlin groove blind hole filling electroplating tests are respectively carried out on the example 1, the comparative example 4 and the comparative example 7, and the test results are shown in a table 4:
table 4 harlin bath test results for example 1, comparative example 4, and comparative example 7
FIG. 15 is a graph showing the effect of the Harlin groove blind hole filling electroplating test of comparative example 7, and it can be seen from the test results in Table 4 that the Harlin groove test results are not ideal when no copper sulfate is added (comparative example 1), no sulfuric acid is added (comparative example 4) or no copper sulfate and sulfuric acid are added (comparative example 7) in the circuit board blind hole rapid filling electroplating copper solution. Among them, the test results of the absence of copper sulfate and various components in sulfuric acid (comparative example 7) are less effective than those of the absence of a single component (comparative example 1, comparative example 4).
4. Based on the influence of different mass concentrations of brightener
Comparative examples 8 to 10 are different from example 1 in the mass concentration of the brightener and the remaining conditions are the same. The test results for example 1 and comparative examples 8-10 in the Harlin cell test are shown in Table 5:
TABLE 5 Harlin cell test results for example 1, comparative examples 8-10
As can be seen from the test results in Table 5, the blind holes of the circuit board are quickly filled with the copper electroplating solution without adding a brightener (comparative example 8), and the test results of the Harlin groove are not ideal. The mass concentration of the brightener was less than 0.4ml/L (comparative example 9) or more than 2ml/L (comparative example 10), and the Harlin bath test results were not satisfactory. Therefore, the mass concentration of the brightener in the circuit board blind hole rapid filling copper electroplating solution is preferably 0.4ml/L-2ml/L.
5. Based on the influence of different mass concentrations of the carrier
Comparative examples 11 to 13 differ from example 1 in the mass concentration of the carrier, and the remaining conditions were the same. The harlin bath test was performed for example 1 and comparative examples 11-13, respectively, and the test results are shown in table 6:
TABLE 6 Harlin bath test results for example 1, comparative examples 11-13
Fig. 19 is a graph showing the effect of the harlin bath test of comparative example 11. As can be seen from the test results in Table 6, the circuit board blind hole is rapidly filled with the copper electroplating solution without adding a carrier (comparative example 11), and the test results of the Harlin groove are not ideal. The mass concentration of the carrier is lower than 15ml/L (comparative example 12) or higher than 25ml/L (comparative example 13), and the Harlin groove test result is not ideal. Therefore, the mass concentration of the carrying agent in the circuit board blind hole rapid filling electrolytic copper plating solution is preferably 10ml/L-30ml/L.
6. Effect of different mass concentrations based on fast fillers
Comparative examples 14 to 15 differ from example 1 in the mass concentration of the fast filler and the remaining conditions were the same. The test results of the Harlin cell test for example 1 and comparative examples 14 to 15 are shown in Table 7:
TABLE 7 Harlin cell test results for example 1, comparative examples 14-16
As can be seen from the test results in Table 7, the circuit board blind hole is rapidly filled with the copper electroplating solution without adding a rapid filling agent (comparative example 14), and the test results of the Harlin groove are not ideal. The mass concentration of the fast filler is lower than 4ml/L (comparative example 15) or higher than 20ml/L (comparative example 16), and the Harlin trough test result is not ideal. Therefore, the mass concentration of the carrying agent in the circuit board blind hole rapid filling copper electroplating solution is preferably 4ml/L-20ml/L.
7. Based on the influence of different mass ratios of levelling agent, catalyst and stabilizer in the fast-acting filler
Comparative examples 17 to 18 differ from example 1 in the different mass ratio concentrations of levelling agent, catalyst and stabilizer in the fast-acting filler, and the rest of the conditions were the same. The harlin bath test was performed for example 1 and comparative examples 17-18, respectively, and the test results are shown in table 8:
TABLE 8 Harlin cell test results for example 1, comparative examples 17-18
As is clear from the test results in Table 8, the Harlin trough test results were not satisfactory when the ratio of the leveler, the catalyst and the stabilizer in the mass ratio was small (comparative example 17) or the ratio of the leveler, the catalyst and the stabilizer in the mass ratio was large (comparative example 18) in the rapid filler for rapid filling of a blind via hole in a wiring board with an electrolytic copper plating solution. Therefore, the mass ratio of the leveling agent, the catalyst and the stabilizer in the rapid filling agent for rapidly filling the copper electroplating solution into the blind holes of the circuit board is preferably 1: (0.3-0.5): (0.05-0.2).
8. Based on the influence of different mass proportioning concentrations in 4-butanediol diglycidyl ether and 1-vinyl imidazole in the catalyst
Comparative examples 19 to 20 differ from example 1 in the different stoichiometric concentrations of 4-butanediol diglycidyl ether and 1-vinylimidazole in the catalyst, and the other conditions were the same. The harlin bath test was performed for example 1 and comparative examples 19 to 20, respectively, and the test results are shown in table 9:
TABLE 9 Harlin bath test results for example 1, comparative examples 19-20
From the test results in Table 9, it is found that the Harlin bath test results are not satisfactory when the ratio of 1-vinylimidazole content in the solution prepared by mass-mixing 4-butanediol diglycidyl ether and 1-vinylimidazole content in the catalyst for fast fillers is small (comparative example 19) or the ratio of 1-vinylimidazole content in the solution is large (comparative example 20). Therefore, the mass ratio of the 4-butanediol diglycidyl ether and the 1-vinyl imidazole solution in the mass ratio of the catalyst for quickly filling the quick filling agent in the copper electroplating solution into the blind holes of the circuit board is preferably 1: (1-4).
9. Harlin groove comparison test of rapid blind hole filling electro-coppering solution and common blind hole filling electro-coppering solution based on the invention
TABLE 10 Harlin bath test results for the inventive and conventional blind via electrocoppering solutions
Specifically, the solution prepared in example 1 was used to fill the blind via with the copper electroplating solution. The common blind hole copper electroplating solution is a solution with the concentration of 80-240 g/L of copper sulfate pentahydrate, 30-120 g/L of sulfuric acid, 40-80ppm of chloride ions, 0.5-1.5ml/L of sodium phenyl dithiopropane sulfonate, 10-20ml/L of alkoxy naphthol and 40-70% of deionized water.
According to the results of the Harlin groove test comparison between the circuit board rapid blind hole filling electro-coppering solution and the common blind hole filling electro-coppering solution, under the same blind hole aperture, hole depth and electro-coppering conditions, the circuit board rapid blind hole filling electro-coppering solution has the advantages that the blind hole filling efficiency is improved by 35.4% compared with the common blind hole filling electro-coppering solution, the blind hole filling efficiency is improved, the thickness of surface copper can be effectively reduced, and copper balls can be saved.
In conclusion, the circuit board rapid blind hole filling electro-coppering solution provided by the invention is simple in proportioning, convenient to operate, non-toxic and harmless, free of other side effects and low in economic cost from the aspects of proportioning dosage and application. The circuit board blind hole rapid filling electro-coppering solution can rapidly fill blind holes, thereby improving the blind hole filling efficiency, effectively reducing the blind hole surface copper thickness and the etching process cost, and simultaneously saving copper balls and production time.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The circuit board blind hole rapid filling electrolytic copper plating solution is characterized by comprising the following components in mass concentration:
30-80g/L of sulfuric acid,
100-240g/L of copper sulfate,
30-80ppm of chloride ions are added,
0.004-0.02g/L of brightener,
0.1-0.3g/L of carrier,
0.04-0.2g/L of rapid filling agent,
the rapid filling agent is a mixture consisting of a leveling agent, a catalyst and a stabilizer;
the brightener is selected from at least one of 2-mercaptobenzimidazole, 1,2-ethylene thiourea, N-dimethyl dithioformamide propane sodium sulfonate and 3,3' -dithiobis (1-propanesulfonic acid) disodium;
the carrying agent is selected from at least one of diallyl dimethyl ammonium chloride-acrylamide copolymer and diallyl dimethyl ammonium bromide copolymer;
the rapid filling agent comprises the following components in percentage by mass: leveling agent 0.04-0.08g/L, catalyst 0.02-0.04g/L, stabilizer 0.008-0.012g/L; the leveling agent is selected from at least one of 2,2-dithiodipyridine, 1-azapyridin-3-yl pyrrolidine, 4,6-dimethyl-2-mercaptopyrimidine, 1- (3-acetamide) phenyl 5-mercaptotetrazole, and 2-mercaptopyridine; the catalyst is a mixture of 4-butanediol diglycidyl ether and 1-vinylimidazole; the stabilizer is selected from at least one of isooctyl dimercaptoacetate di-n-octyl tin and dimethyl isooctyl dimercaptoacetate tin; in the catalyst, the mass ratio of 4-butanediol diglycidyl ether to 1-vinyl imidazole is 1: (1-4);
among the rapid filler, leveling agent: catalyst: the mass ratio of the stabilizer is 1: (0.3-0.5): (0.05-0.2).
2. The solution of claim 1, wherein the copper sulfate has a mass concentration of 180-220g/L, the sulfuric acid has a mass concentration of 40-60g/L, and the chloride ion has a mass concentration of 40-70 ppm.
3. The circuit board blind hole fast filling electro-coppering solution as claimed in claim 2, wherein the mass concentration of the brightener is 0.008-0.012g/L.
4. The circuit board blind hole rapid filling electrolytic copper plating solution according to claim 3, wherein the mass concentration of the carrying agent is 0.15-0.25g/L.
5. The method for preparing the circuit board blind hole rapid filling electrolytic copper plating solution according to any one of claims 1 to 4, characterized by comprising the following steps:
s1, mixing a leveling agent, a catalyst and a stabilizer to obtain a rapid filling agent;
s2, mixing sulfuric acid, copper sulfate and chloride ions to obtain an aqueous solution;
and S3, adding the brightener, the carrier and the quick filling agent prepared in the step S1 into the aqueous solution obtained in the step S2, stirring and mixing to obtain the circuit board blind hole quick filling electro-coppering solution.
6. A method for quickly filling blind holes of a circuit board is characterized in that VCP continuous electroplating is adopted for the circuit board with the blind holes;
the method comprises the steps of adopting the circuit board blind hole rapid filling electro-coppering solution as claimed in any one of claims 1 to 4, taking a phosphorus-copper alloy anode as a soluble anode, wherein the phosphorus content is 0.04-0.063%; the VCP continuous electroplating process parameters are as follows: the solution temperature is 15-40 deg.C, and the current density is 0.5-6A/dm 2 The electroplating time is 15-40min.
7. The rapid filling method according to claim 6, wherein the blind holes in the circuit board have a diameter of 50-400um and a depth of 50-150 um.
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| CN117512719A (en) * | 2023-10-13 | 2024-02-06 | 中山博美新材料科技有限公司 | Hole filling copper plating process and application |
| CN117488377B (en) * | 2023-12-29 | 2024-04-05 | 上海尚容电子科技有限公司 | Preparation method and application of leveling agent for electroplating |
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