CN103572334A - Copper plating solution for PCB (printed circuit board) through holes and PCB blind holes, as well as preparation method and plating method of copper plating solution - Google Patents
Copper plating solution for PCB (printed circuit board) through holes and PCB blind holes, as well as preparation method and plating method of copper plating solution Download PDFInfo
- Publication number
- CN103572334A CN103572334A CN201310585153.2A CN201310585153A CN103572334A CN 103572334 A CN103572334 A CN 103572334A CN 201310585153 A CN201310585153 A CN 201310585153A CN 103572334 A CN103572334 A CN 103572334A
- Authority
- CN
- China
- Prior art keywords
- pcb
- blind hole
- electroplating solution
- hole
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to the technical field of PCB (printed circuit board) plating, in particular to a copper plating solution for PCB through holes and PCB blind holes, and a preparation method and a plating method of the copper plating solution. Each liter of the copper plating solution comprises the following components according to contents: 100-250g of copper sulfate pentahydrate, 100-200g of sulfuric acid, 30-100ppm of chlorine ions, 5-50g of brightener, 3-30g of carrier, 2-20g of leveling agent and the balance of deionized water, wherein the concentration ratio of the copper sulfate pentahydrate to the sulfuric acid is (1-1.25) : 1. The plating method comprises the following steps: putting a PCB with through holes and blind holes into a plating bath with the copper plating solution; plating during air agitation to obtain a copper plating layer. The copper plating layer formed by the plating method has a good deep plating capability as high as 92% above, has a hole-filling rate as high as 96% above, and is dense, smooth, relatively good in malleability, good in gloss, high in toughness and low in internal stress.
Description
Technical field
The present invention relates to PCB electroplating technology field, be specifically related to a kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method.
Background technology
Printed circuit board (pcb) is in making processes, can carry out the making of through hole and blind hole, through hole comes outbreak out with machine dimensions drill and drill point, blind hole is with the laser ablation of laser drill out, through hole is used for realizing the interconnection of the conducting between random layer in multi-ply wood, and blind hole is used for realizing the conducting interconnection between multi-ply wood mesectoderm and sublevel.
In the follow-up copper sulfate electroplating technology of printed circuit board (pcb), requiring while electroplating for through hole on circuit card and blind hole is different, for high plate thickness aperture ratio through hole liquid medicine component, conventionally adopt the low copper of peracid, to improve covering power (though power); For laser micro blindness hole liquid medicine component, conventionally adopt the low acid of high-copper, to improve blind hole throwing power.The liquid medicine component that hence one can see that the electroplates in hole and blind hole are electroplated is contrary.
When high plate thickness aperture ratio through hole and laser micro blindness hole are electroplated simultaneously, can there is following problem:
When guaranteeing high plate thickness aperture ratio through hole quality, need to adopt the low copper of peracid to electroplate, often there is the problem of the thick deficiency of blind hole copper in this, and in thermal stresses and thermal shock test process, easily to produce copper disconnected for blind hole, and resistance becomes large and lost efficacy;
When guaranteeing laser micro blindness hole electroplating quality, need to adopt the low acid of high-copper to electroplate, often there is through hole " dog bone " phenomenon, namely Kong Biantong is thick, hole central copper is led to thick deficiency, in thermal stresses and thermal shock test process mesopore copper, easily produces fracture, and resistance becomes greatly even open failure.
When filling perforation is electroplated, not only to consider blind hole filling perforation, also to consider the electroplates in hole simultaneously.Blind hole is electroplated effective under the low acid of high-copper, and through hole covering power is better under the low copper bar part of peracid, both are opposition phenomenon, so in actual production, to copper sulfate and sulfuric acid concentration, to find a trim point, make blind hole fill quality and through hole copper is thick reaches requirement simultaneously.
Electroplating liquid medicine of the prior art can only be to a kind of plating the in PCB through hole or PCB blind hole, in the market also not to PCB through hole and PCB blind hole electroplate can be general liquid medicine.Therefore, be necessary to develop a kind of can plating PCB through hole, can electroplate PCB blind hole again, can also make the copper plate degree of depth ability that obtains good, filling perforation rate is high, copper plate is smooth, the good PCB through hole of ductility, gloss and toughness blind hole copper electroplating solution and preparation method thereof and using method.
Summary of the invention
In order to overcome the shortcoming and defect existing in prior art, the object of the present invention is to provide a kind of PCB through hole blind hole copper electroplating solution and preparation method thereof, this copper electroplating solution can be electroplated PCB through hole, can electroplate PCB blind hole again, can also make the copper plate degree of depth ability that obtains good, filling perforation rate is high, and copper plate is smooth, ductility, gloss and toughness are better, and bath stability, life-span are long; This preparation method is simple to operate, has reduced production cost, is applicable to suitability for industrialized production.
Another object of the present invention is to provide a kind of using method of PCB through hole blind hole copper electroplating solution, by the method, form copper plate degree of depth ability good, filling perforation rate is high, fine and close smooth, nothing is empty, seamless, surface deposition thickness is low, ductility is better, has good gloss, high tenacity, low internal stress.
Object of the present invention is achieved through the following technical solutions: a kind of PCB through hole blind hole copper electroplating solution, and each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 100 ~ 250g/L
Sulfuric acid: 100 ~ 200g/L
Chlorion: 30 ~ 100ppm
Brightening agent: 5 ~ 50g/L
Carrying agent: 3 ~ 30g/L
Leveling agent: 2 ~ 20g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1 ~ 1.25:1.
Preferably, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 140 ~ 220g/L
Sulfuric acid: 120 ~ 180g/L
Chlorion: 45 ~ 80ppm
Brightening agent: 15 ~ 35g/L
Carrying agent: 10 ~ 20g/L
Leveling agent: 5 ~ 15g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.17 ~ 1.22:1.
More preferred, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 180g/L
Sulfuric acid: 150g/L
Chlorion: 60ppm
Brightening agent: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.2:1.
Cupric sulfate pentahydrate is the main salt of copper electroplating solution, is Cu in solution
2+source, concentration is wanted appropriateness.The too low sedimentation rate of cupric sulfate pentahydrate concentration is slower, and too high sedimentation rate is too fast, and crystalline particle is thick, and affects the covering power of plating solution, and in plate face and hole, the difference of thickness of coated copper layer is excessive.Cupric sulfate pentahydrate of the present invention is defined as 100 ~ 250g/L, can guarantee sedimentation rate, does not affect again the covering power of plating solution, and preferred, cupric sulfate pentahydrate is defined as 140 ~ 220g/L, and more preferred, cupric sulfate pentahydrate is defined as 180g/L.
Sulfuric acid mainly increases the conductive capability of copper electroplating solution, and prevents Cu
2+hydrolysis, it is appropriate that concentration is also wanted.The too high meeting of sulfuric acid concentration makes copper electroplating solution dispersive ability poor, and too low meeting increases copper plate fragility, and toughness declines.Sulfuric acid of the present invention is defined as 100 ~ 200g/L, both can guarantee the dispersive ability of copper electroplating solution, again can be so that the copper plate toughness arriving be higher, and preferred, sulfuric acid is defined as 120 ~ 180g/L, and more preferred, sulfuric acid is defined as 150g/L.
When filling perforation is electroplated, not only to consider blind hole filling perforation, also to consider the electroplates in hole simultaneously.Blind hole is electroplated effective under the low acid of high-copper, and through hole covering power is better under the low copper bar part of peracid, both are opposition phenomenon, so in actual production, to copper sulfate and sulfuric acid concentration, to find a trim point, make blind hole fill quality and through hole copper is thick reaches requirement simultaneously.Cupric sulfate pentahydrate of the present invention: the concentration ratio of sulfuric acid is defined as 1 ~ 1.25:1, both there is dark plating effect preferably, there is again good filling perforation rate, preferably, cupric sulfate pentahydrate: the concentration ratio of sulfuric acid is defined as 1.56 ~ 1.88:1, more preferred, cupric sulfate pentahydrate: the concentration ratio of sulfuric acid is defined as 1.67:1.
Chlorion can improve the activity of anode, promotes that anode normally dissolves, and prevents anode passivation; Can also reduce " copper powder " that because of anode dissolution, not exclusively produce, improve light and the leveling ability of copper plate, improve copper plate quality.Chlorion of the present invention is defined as 30 ~ 100ppm, can make copper plate densification smooth, and preferred, chlorion is defined as 45 ~ 80ppm, and more preferred, chlorion is defined as 60ppm.
In tradition, electroplate in theory, blind hole bottom is low current region, and liquid medicine exchange is few, and its electroplating effect is often difficult to reach perfect condition.Blind hole is electroplated process for filling hole along with the development of filling perforation photo etching and optimization and ripe gradually, in HDI plate making processes, is playing the part of key player.On market, filling perforation photo etching kind is more, but its cardinal principle is close.Filling perforation photo etching main component has three kinds: brightening agent, carrying agent, leveling agent.
Brightening agent (Hrightener): meeting can produce a kind of " depolarize " or force down the action of " overpotential " under chlorion is assisted, thereby there will be the copper-plated effect of acceleration, therefore be called again accelerator (Accelerator).Brightening agent itself can also enter in copper plate and participate in crystalline texture, and impact or intervention, to the spontaneous nucleation mode of copper atom deposition, impel and become more fine and smooth tissue, therefore be called again grain-refining agent (GrainRefiner).In filling perforation is electroplated, brightening agent is mainly adsorbed in blind hole bottom, utilizes thio-alcohol organism and Cu
2+form complex compound, to accelerate copper in the deposition of blind hole bottom; Brightening agent of the present invention is defined as 5 ~ 50g/L, can make copper plate densification smooth, and preferred, brightening agent is defined as 15 ~ 35g/L, and more preferred, brightening agent is defined as 25g/L.
Preferably, the mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 1.5 ~ 3.5:1 by weight ratio and ethylene thiourea form.
3-sulfydryl-1-propane sulfonic acid sodium (MPS) is white or buff powder, and easily the moisture absorption, water-soluble strong; 3-sulfydryl-1-propane sulfonic acid sodium, as acid copper plating brightening agent, can make copper plate light, and have smooth effect, also can improve working current density.Normal and copper brightener N etc. is used in conjunction with.
Ethylene thiourea (N) is white powder, and fusing point is 198 ℃.Ethylene thiourea is used as copper brightener, normal and acid copper plating brightening agent M, and MPS etc. are used in conjunction with.
The present invention adopts 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea to be used in conjunction with, and the weight ratio that limits 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea is 1.5 ~ 3.5:1, can make copper plate smooth, preferably, the weight ratio of 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea is 2 ~ 3:1, more preferred, the weight ratio of 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea is 2.5:1.
Carrying agent (Carrier): with Cl
-under acting in conjunction, can strengthen the inhibition to copper deposition, can assist brightening agent to go to negative electrode depression distributed throughout, therefore be called carrying agent.Carrying agent can present " increasing polarization " or increase the effect of " overpotential " in groove in liquid reaction, to copper facing deposition, can produce the phenomenon of " deceleration ", has namely showed the effect of " constraining ", therefore be called again repressor (Suppresser).But carrying agent yet separately has the capillary effect of the tank liquor of reduction, or increases its moistening effect, so be often called again wetting agent (Wetting Agent or Wetter).Carrying agent can assist gloss-imparting agent in the distribution of surfacing, also can make copper face increase glossiness.In filling perforation is electroplated, carrying agent is mainly macro-radical, is adsorbed in copper surface, utilizes Adsorption of Organic Cu
2+, play the effect that suppresses surface copper ion deposition; Carrying agent of the present invention is defined as 3 ~ 30g/L, can increase the gloss of copper plate, and preferred, carrying agent is defined as 10 ~ 20g/L, more preferred, and carrying agent is defined as 15g/L.
Preferably, the mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 5000 ~ 15000 by molecular weight and molecular weight are 500 ~ 1500 forms by weight 1.8 ~ 2.6:1.
Polyoxyethylene glycol (PEG), along with the increase of PEG molecular weight, the micropore filling power of copper electroplating solution obviously improves.When current density is 2A/dm
2, additive PEG molecular weight surpasses at 6000 o'clock, and plating solution can be filled blind hole completely, and there is not any cavity and gap in copper plate.This is because additive PEG can obviously be strengthened the cathodic polarization of electro-coppering plating solution, has suppressed the deposition of electro-coppering; Meanwhile, the spread coefficient of PEG in plating solution also reduces with the increase of its molecular weight, thereby increased the adsorptive power of M in micropore bottom, accelerated the deposition of electro-coppering in micropore bottom; Further, increase the table of PEG molecular weight depositing copper film and roughness, copper film degree of crystallinity and resistivity all decrease.Therefore, the molecular weight of polyoxyethylene glycol of the present invention is defined as 5000 ~ 15000, can increase filling perforation rate, and makes copper plate densification smooth.
Polypropylene glycol (PPG) can obviously be strengthened the cathodic polarization of electro-coppering plating solution, has suppressed the deposition of electro-coppering; Meanwhile, the spread coefficient of PPG in plating solution also reduces with the increase of its molecular weight, thereby increased the adsorptive power of SPS in micropore bottom, accelerated the deposition of electro-coppering in micropore bottom; Further, increase the table of PPG molecular weight depositing copper film and roughness, copper film degree of crystallinity and resistivity all decrease.Therefore, the molecular weight of polyoxyethylene glycol of the present invention is defined as 500 ~ 1500, can guarantee the spread coefficient of PPG in copper electroplating solution, and makes copper plate densification smooth.
The present invention adopts polyoxyethylene glycol and ethylene thiourea to be used in conjunction with, and the weight ratio that limits polyoxyethylene glycol and polypropylene glycol is 1.8 ~ 2.6:1, can increase filling perforation rate, preferably, the weight ratio of polyoxyethylene glycol and polypropylene glycol is 2 ~ 2.4:1, more preferred, the weight ratio of polyoxyethylene glycol and polypropylene glycol is 2.2:1.
Leveling agent (Leveler): with very strong positive polarity, be easy to be adsorbed on plating piece surface current density larger part, compete with cupric ion, make cupric ion at high electric current place, be difficult for deposition, but the copper that does not affect low current district deposits, make up-and-down surface originally become more smooth, be therefore called leveling agent.In filling perforation is electroplated, leveling agent Main Function is the distribution of current of balance aperture, high Current Zone and low current district angle of spot hole, modifies blind hole hole shape.Leveling agent of the present invention is defined as 2 ~ 20g/L, can guarantee the smooth of copper plate, and preferred, leveling agent is defined as 5 ~ 15g/L, and more preferred, leveling agent is defined as 10g/L.
Early 1970s, sour copper is electroplated and is progressively tending towards ripe.There is the patent of a large amount of discussion leveling agents this period, wherein used the product after the sub-limb alkylation of polyhexene, as a leveling agent, alkylating reagent used has benzyl chloride, methyl-sulfate, sulfuric acid two ester, propenyl bromine, propane sultone etc.This quaternary ammonium salt is compared with polyhexene imines in the past used, water-soluble better, with other the composite better effects if of additive, has expanded the range of current in bright district, and copper plate is bright, smooth, high tenacity, low internal stress.
The product of having used another synthetic leveling agent Epicholorohydrin and substance reaction gained containing one or more N functional group this period, the material containing N functional group of using has pyridine, quinoline, isoquinoline 99.9, benzoglyoxaline etc.The introducing of this additive is mainly the low problem of additive utilization ratio existing in original sour copper plating system in order to solve.Additive system originally makes plating piece surface irregularity, leveling poor effect, and new leveling agent has but made up this deficiency to a certain extent.In electroplating process, allow protruding local copper plate partially thin, partially thick at pit copper plate accordingly, and can not cause high internal stress, and both reached leveling object, make again copper plate possess good mechanical property.
Preferably, the mixture that the leveling agent A that described leveling agent is 1.2 ~ 2.4:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
Preferably, the structural formula of described leveling agent A is:
Wherein, R1 is that carbonatoms is the epoxy alkyl that 1 ~ 10 alkyl, aromatic base or the carbonatoms cycloalkyl that is 3 ~ 10 or carbonatoms are 2 ~ 10, and X is halogen atom or hydrogen sulfate ion, and n and m are greater than 2 and be less than 100 integer.
Preferably, R1 is ethyl group, propyl, butane group, phenyl, benzyl, cyclopropane base, propylene oxide base; X is chlorine, bromine, iodine or hydrogen sulfate ion.
More preferred, R1X is monochloroethane, N-PROPYLE BROMIDE, butyl iodide, benzyl chlorine, epoxy chloropropane.
Preferably, the structural formula of described leveling agent B is:
Wherein, R
2the epoxy alkyl that the cycloalkyl that alkyl, aromatic base, ether, ester group or the carbonatoms that is 1 ~ 10 for carbonatoms is 3 ~ 10 or carbonatoms are 2 ~ 10, X is halogen atom or hydrogen sulfate ion, n and m are greater than 2 and be less than 100 integer.
Preferably, R2 is ethyl group, propyl, butane group, phenyl, benzyl, cyclopropane base, propylene oxide base.
The present invention adopts polyvinyl imidazol quaternary ammonium compound and N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer with the composite use of weight ratio of 1.2 ~ 2.4:1, can make that copper plate is bright, smooth, high tenacity, low internal stress.
A preparation method for PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2 ~ 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 5 ~ 10min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 5 ~ 10min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
Another object of the present invention is achieved through the following technical solutions: a kind of electro-plating method of PCB through hole blind hole copper electroplating solution, the pcb board with through hole and blind hole is put into the plating tank that described copper electroplating solution is housed and under pneumatic blending, electroplate, obtain copper plate.
Preferably, described plating is divided into three sections:
First paragraph current density is 8 ~ 12ASF, and electroplating time is 15 ~ 35min;
Second segment current density is 10 ~ 14ASF, and electroplating time is 15 ~ 35min;
The 3rd section of current density is 16 ~ 24ASF, and electroplating time is 15 ~ 35min.
The influence factor that acid copper plating bath is electroplated has:
1, current density: when filling perforation is electroplated, often adopt low current density can obtain good blind hole filling perforation effect and through hole covering power, but the low current density production time is long, production efficiency is low, and cost is high.In existing market with keen competition, cost consciousness and production efficiency are rooted in the hearts of the people already.So reduce current density, to carry out guaranteed quality be not long-term plan, improve current density as far as possible, enhances productivity, and realizes the bumper harvests of cost and quality.
Prove by experiment, high current density blind hole filling effect is poor, for promoting electroplating efficiency, can take segmentation electric plating method, and current density progressively promotes, and can according to circumstances be divided into two sections or three sections, is the better method that solves filling perforation production efficiency and quality.The present invention adopts three sections of electrochemical plating, can effectively solve filling perforation production efficiency and quality.
2, through hole radius-thickness ratio: the radius-thickness ratio of through hole is larger on covering power impact, in order to make perforation plating also can have good covering power, radius-thickness ratio of the present invention is defined as 2 ~ 6, and preferred, radius-thickness ratio is defined as 2 ~ 5, and more preferred, radius-thickness ratio is defined as 4.
3, the shape of blind hole: the blind hole of waist-drum-shaped and vertical-type when filling perforation is electroplated, Shi Gao Current Zone, aperture, as control badly, its sedimentation velocity, higher than blind hole bottom sedimentation velocity, will produce filling perforation bubble.Ramp type liquid medicine circulation is good compared with the above two, is difficult for producing filling perforation bubble, and manufacture difficulty is easy compared with the above two.Good blind hole shape is the basis that filling perforation is electroplated, and to the quality of laser drill, will have strict monitoring, the quality that the filling perforation of guarantee blind hole is electroplated.The blind hole that the present invention adopts is ramp type, and specifically, for falling isosceles trapezoid, and top margin (long limit) is 1.5 ~ 2.5:1 with the Length Ratio on base (minor face), and preferred, the Length Ratio on top margin and base is 2:1.
4, blind hole radius-thickness ratio: use different filling perforation photo etchings, its blind hole aperture is different on the impact of filling perforation.But it is bigger than normal that major effect is radius-thickness ratio, aperture hour, when filling perforation is electroplated liquid medicine exchange poor, be prone to the defect in filling perforation cavity, the filling perforation time is long, production efficiency is low; When aperture is bigger than normal, blind hole bottom is difficult for absorption accelerator under the effect of jet flow, and its filling perforation effect is poor.So suitable aperture and aspect ratio are larger on the property impact of fine qualities of filling perforation.The blind hole radius-thickness ratio that the present invention adopts is 0.8 ~ 1.2:1, can reach good filling effect, and preferred, blind hole radius-thickness ratio is 1:1.
5, stir: in plating, liquid medicine circulation directly has influence on electroplating effect, blind hole is because one end is sealed, and liquid medicine circulation is than through hole difficulty, so liquid medicine agitation cycle effect when filling perforation is electroplated is extremely important.Liquid medicine circulation is poor, easily produces bubble in blind hole; Liquid medicine circulation is excessively strong, and blind hole bottom can not active adsorption accelerator, and filling perforation effect is not good on the contrary.Different photo etchings are different with the requirement of strength of jet flow to liquid medicine circulation, the blind hole of different pore size is to jet flow intensity also difference to some extent, so select suitable liquid medicine alr mode and intensity extremely important to filling perforation effect, the mode that the present invention adopts pressurized air to stir, via depth ability and blind hole filling perforation effect are all better.
6, anode material: in acidic copper-plating of bright, quality of anode is very important factor, generally should not use electrolytic copper, and the present invention adopts the phosphorous copper anode of anaerobic.When this is because uses oxygen containing electrolytic copper anode, surface easily produces Red copper oxide (copper powder), the consumption of brightening agent is increased, and reduce copper plate quality, when phosphorus can make the electrochemical dissolution of anode, surface produces one deck black rete, has avoided uneven dissolution.
Beneficial effect of the present invention is: the present invention adopts 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea as the composite use of brightening agent, can make copper plate smooth; The present invention adopts polyoxyethylene glycol and polypropylene glycol as carrying agent, can make copper plate densification smooth, the present invention adopts polyvinyl imidazol quaternary ammonium compound and N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer as the composite use of leveling agent, can make that copper plate is bright, smooth, high tenacity, low internal stress.
Copper electroplating solution of the present invention can be electroplated PCB through hole, can electroplate PCB blind hole again, can also make the copper plate degree of depth ability that obtains good, and filling perforation rate is high, and copper plate is smooth, and ductility, gloss and toughness are better, and bath stability, life-span are long.
The preparation method of a kind of PCB through hole blind hole copper electroplating solution of the present invention, simple to operate, reduced production cost, be applicable to suitability for industrialized production.
The using method of a kind of PCB through hole blind hole copper electroplating solution of the present invention, good by the method copper plate degree of depth ability, reach more than 92%, filling perforation rate is high, reaches more than 96%, and copper plate densification is smooth, nothing is empty, seamless, surface deposition thickness is low, ductility is better, has good gloss, high tenacity, low internal stress.
embodiment:
For the ease of those skilled in the art's understanding, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
A through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 100g/L
Sulfuric acid: 100g/L
Chlorion: 30ppm
Brightening agent: 5g/L
Carrying agent: 3g/L
Leveling agent: 2g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.
The mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 1.5:1 by weight ratio and ethylene thiourea form; The mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 5000 by molecular weight and molecular weight are 500 forms by weight 1.8:1.
The mixture that the leveling agent A that described leveling agent is 1.2:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
The structural formula of described leveling agent A is:
Wherein, R
1for ethyl group, X is chlorine atom, n=2, m=2.
The structural formula of described leveling agent B is:
Wherein, R
2for cyclopropane base, n=100, m=100.
A preparation method for PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 5min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 5min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
An electro-plating method for PCB through hole blind hole copper electroplating solution, puts into by the pcb board with through hole and blind hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
Described plating is divided into three sections:
First paragraph current density is 8ASF, and electroplating time is 15min;
Second segment current density is 10ASF, and electroplating time is 15min;
The 3rd section of current density is 16ASF, and electroplating time is 15min.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 2
A through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 140g/L
Sulfuric acid: 120g/L
Chlorion: 45ppm
Brightening agent: 15g/L
Carrying agent: 10g/L
Leveling agent: 5g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.17:1.
The mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 2:1 by weight ratio and ethylene thiourea form; The mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 8000 by molecular weight and molecular weight are 800 forms by weight 2:1.
The mixture that the leveling agent A that described leveling agent is 1.5:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
The structural formula of described leveling agent A is:
Wherein, R
1for propyl, X is bromine atoms, n=20, m=80.
The structural formula of described leveling agent B is:
Wherein, R
2for benzyl, n=80, m=20.
A preparation method for PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) in container, add the deionized water of deionized water volume 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 6min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 6min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
An electro-plating method for PCB through hole blind hole copper electroplating solution, puts into by the pcb board with through hole and blind hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
Described plating is divided into three sections:
First paragraph current density is 9ASF, and electroplating time is 20min;
Second segment current density is 11ASF, and electroplating time is 20min;
The 3rd section of current density is 18ASF, and electroplating time is 20min.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 3
A through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 220g/L
Sulfuric acid: 180g/L
Chlorion: 80ppm
Brightening agent: 35g/L
Carrying agent: 20g/L
Leveling agent: 15g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.22:1.
The mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 2.5:1 by weight ratio and ethylene thiourea form; The mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 10000 by molecular weight and molecular weight are 1000 forms by weight 2.2:1.
The mixture that the leveling agent A that described leveling agent is 1.8:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
The structural formula of described leveling agent A is:
Wherein, R
1for butane group, X is iodine atom, n=50, m=50.
The structural formula of described leveling agent B is:
Wherein, R
2for propyl, n=50, m=50.
A preparation method for PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 7min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 7min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
An electro-plating method for PCB through hole blind hole copper electroplating solution, puts into by the pcb board with through hole and blind hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
Described plating is divided into three sections:
First paragraph current density is 10ASF, and electroplating time is 25min;
Second segment current density is 12ASF, and electroplating time is 25min;
The 3rd section of current density is 20ASF, and electroplating time is 25min.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 4
A through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 180g/L
Sulfuric acid: 150g/L
Chlorion: 60ppm
Brightening agent: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.2:1.
The mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 3:1 by weight ratio and ethylene thiourea form; The mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 12000 by molecular weight and molecular weight are 1200 forms by weight 2.4:1.
The mixture that the leveling agent A that described leveling agent is 2.1:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
The structural formula of described leveling agent A is:
Wherein, R
1for benzyl, X is chlorine atom, n=80, m=20.
The structural formula of described leveling agent B is:
Wherein, R
2for ethyl group, n=20, m=80.
A preparation method for PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) in container, add the deionized water of deionized water volume 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 8min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 8min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
An electro-plating method for PCB through hole blind hole copper electroplating solution, puts into by the pcb board with through hole and blind hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
Described plating is divided into three sections:
First paragraph current density is 11ASF, and electroplating time is 30min;
Second segment current density is 13ASF, and electroplating time is 30min;
The 3rd section of current density is 22ASF, and electroplating time is 30min.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 5
A through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 250g/L
Sulfuric acid: 200g/L
Chlorion: 100ppm
Brightening agent: 50g/L
Carrying agent: 30g/L
Leveling agent: 20g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.25:1.
The mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 3.5:1 by weight ratio and ethylene thiourea form; The mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 15000 by molecular weight and molecular weight are 1500 forms by weight 2.6:1.
The mixture that the leveling agent A that described leveling agent is 2.4:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
The structural formula of described leveling agent A is:
Wherein, R
1for cyclopropane base, X is cyclopropane base atom, n=100, m=100.
The structural formula of described leveling agent B is:
Wherein, R
2for butane group, n=2, m=2.
A preparation method for PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 10min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 10min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
An electro-plating method for PCB through hole blind hole copper electroplating solution, puts into by the pcb board with through hole and blind hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
Described plating is divided into three sections:
First paragraph current density is 12ASF, and electroplating time is 35min;
Second segment current density is 14ASF, and electroplating time is 35min;
The 3rd section of current density is 24ASF, and electroplating time is 35min.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
The analytical test result of the copper plate that table 1 embodiment 1 ~ 5 obtains
| Test event | Standard value | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Degree of depth ability | 82% | 93% | 92% | 94% | 93% | 94% |
| Filling perforation rate | 88% | 97% | 98% | 99% | 97% | 96% |
| Ductility | 4% | 9% | 8% | 10% | 8% | 9% |
| Stretching force | 220 | 330 | 310 | 320 | 320 | 330 |
| Thermal shocking | Good | Outstanding | Outstanding | Outstanding | Outstanding | Outstanding |
| Planeness | Good | Outstanding | Outstanding | Outstanding | Outstanding | Outstanding |
| Brightness | Light | Light | Light | Light | Light | Light |
| Electroconductibility | 53.3 | 55.7 | 56.2 | 57.1 | 56.8 | 55.9 |
| Hardness | 140HV | 164HV | 166HV | 158HV | 162HV | 168HV |
Copper electroplating solution of the present invention has good degree of depth ability and dispersive ability, can improve copper layer in printed circuit board through hole hole and be uniformly distributed, and can also effectively reduce the ratio of surface copper layer thickness and hole central copper layer thickness, is applicable to low and middle-end printing plate the electroplates in hole.
The copper plate densification that the present invention obtains is smooth, and filling perforation rate is high, reaches more than 95%, and ductility is better, has good gloss, high tenacity, low internal stress.
Above-described embodiment is preferably implementation of the present invention, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. a PCB through hole blind hole copper electroplating solution, is characterized in that: each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 100 ~ 250g/L
Sulfuric acid: 100 ~ 200g/L
Chlorion: 30 ~ 100ppm
Brightening agent: 5 ~ 50g/L
Carrying agent: 3 ~ 30g/L
Leveling agent: 2 ~ 20g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1 ~ 1.25:1.
2. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, is characterized in that: each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 140 ~ 220g/L
Sulfuric acid: 120 ~ 180g/L
Chlorion: 45 ~ 80ppm
Brightening agent: 15 ~ 35g/L
Carrying agent: 10 ~ 20g/L
Leveling agent: 5 ~ 15g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.17 ~ 1.22:1.
3. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, is characterized in that: each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 180g/L
Sulfuric acid: 150g/L
Chlorion: 60ppm
Brightening agent: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1.2:1.
4. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, is characterized in that: the mixture that 3-sulfydryl-1-propane sulfonic acid sodium that described brightening agent is 1.5 ~ 3.5:1 by weight ratio and ethylene thiourea form; The mixture that the polypropylene glycol that the polyoxyethylene glycol that described carrying agent is 5000 ~ 15000 by molecular weight and molecular weight are 500 ~ 1500 forms by weight 1.8 ~ 2.6:1.
5. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, is characterized in that: the mixture that the leveling agent A that described leveling agent is 1.2 ~ 2.4:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-butyl imidazole-ethyl acrylate copolymer.
6. a kind of PCB through hole blind hole copper electroplating solution according to claim 5, is characterized in that: the structural formula of described leveling agent A is:
Wherein, R
1the epoxy alkyl that the cycloalkyl that alkyl, aromatic base or the carbonatoms that is 1 ~ 10 for carbonatoms is 3 ~ 10 or carbonatoms are 2 ~ 10, X is halogen atom or hydrogen sulfate ion, n and m are greater than 2 and be less than 100 integer.
7. a kind of PCB through hole blind hole copper electroplating solution according to claim 5, is characterized in that: the structural formula of described leveling agent B is:
Wherein, R
2the epoxy alkyl that the cycloalkyl that alkyl, aromatic base, ether, ester group or the carbonatoms that is 1 ~ 10 for carbonatoms is 3 ~ 10 or carbonatoms are 2 ~ 10, X is halogen atom or hydrogen sulfate ion, n and m are greater than 2 and be less than 100 integer.
8. the preparation method of a kind of PCB through hole blind hole copper electroplating solution described in claim 1 ~ 7 any one, is characterized in that: comprise the steps:
(1) in container, add the deionized water of deionized water volume 1/2 ~ 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 5 ~ 10min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 5 ~ 10min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB through hole blind hole copper electroplating solution.
9. the electro-plating method of a kind of PCB through hole blind hole copper electroplating solution described in claim 1 ~ 7 any one, it is characterized in that: the pcb board simultaneously with through hole and blind hole is put into the plating tank that described copper electroplating solution is housed and under pneumatic blending, electroplate, obtain one deck copper electroplating layer.
10. the electro-plating method of a kind of PCB through hole blind hole copper electroplating solution according to claim 9, is characterized in that: described plating is divided into three sections:
First paragraph current density is 8 ~ 12ASF, and electroplating time is 15 ~ 35min;
Second segment current density is 12 ~ 14ASF, and electroplating time is 15 ~ 35min;
The 3rd section of current density is 16 ~ 24ASF, and electroplating time is 15 ~ 35min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310585153.2A CN103572334B (en) | 2013-11-20 | 2013-11-20 | A kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310585153.2A CN103572334B (en) | 2013-11-20 | 2013-11-20 | A kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103572334A true CN103572334A (en) | 2014-02-12 |
| CN103572334B CN103572334B (en) | 2016-06-22 |
Family
ID=50045021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310585153.2A Expired - Fee Related CN103572334B (en) | 2013-11-20 | 2013-11-20 | A kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103572334B (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562102A (en) * | 2014-12-31 | 2015-04-29 | 苏州福莱盈电子有限公司 | High-depth blind hole electrocoppering solution |
| CN105316713A (en) * | 2015-10-26 | 2016-02-10 | 苏州福莱盈电子有限公司 | Copper electroplating dissolving solution and rapid high-depth blind hole filling process |
| CN105441993A (en) * | 2015-12-22 | 2016-03-30 | 苏州禾川化学技术服务有限公司 | Electroplating solution and electroplating method for electroplating through holes and blind holes of circuit boards |
| CN106119913A (en) * | 2016-06-30 | 2016-11-16 | 深圳市励高表面处理材料有限公司 | Copper electroplating liquid and using method thereof and the synthetic method of leveling agent therein |
| CN106132116A (en) * | 2016-07-05 | 2016-11-16 | 广州美维电子有限公司 | A kind of wiring board blind hole fills out process for copper |
| CN107217282A (en) * | 2017-07-24 | 2017-09-29 | 苏州天承化工有限公司 | A kind of high TP values soft board electroplate liquid and electro-plating method |
| CN107557826A (en) * | 2017-09-30 | 2018-01-09 | 广东骏亚电子科技股份有限公司 | A kind of acid electrochemical copper plating solution |
| CN107675218A (en) * | 2017-09-30 | 2018-02-09 | 广东骏亚电子科技股份有限公司 | A kind of acid electrochemical copper-plating technique |
| CN107922611A (en) * | 2015-08-31 | 2018-04-17 | 埃托特克德国有限公司 | Imidazole radicals urea polymers and its purposes in metal or metal alloy bath compositions |
| CN108026656A (en) * | 2015-09-25 | 2018-05-11 | 韩国生产技术研究院 | Electro-coppering organic additive comprising two kinds of leveling agents and the electrolytic copper plating solution comprising the additive |
| CN108203836A (en) * | 2016-12-19 | 2018-06-26 | 艾威尔电路（深圳）有限公司 | A kind of method for improving electro-coppering covering power |
| CN108350590A (en) * | 2016-03-18 | 2018-07-31 | 韩国生产技术研究院 | It is used to form the electro-coppering organic additive of high-flatness copper plating film and the electrolytic copper plating solution comprising the additive |
| CN110042444A (en) * | 2019-05-10 | 2019-07-23 | 九江德福科技股份有限公司 | A kind of additive formulations improving copper foil surface uniformity |
| JP2019525006A (en) * | 2016-08-15 | 2019-09-05 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Acidic aqueous composition for electrolytic copper plating |
| CN110284163A (en) * | 2019-07-31 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110331422A (en) * | 2019-08-16 | 2019-10-15 | 国网河南省电力公司桐柏县供电公司 | A kind of ceramic substrate copper electroplating layer thickening method |
| CN110373687A (en) * | 2019-08-30 | 2019-10-25 | 广州皓悦新材料科技有限公司 | A kind of pulse plating photo etching and preparation method thereof plating high aspect ratio through-hole and blind hole |
| CN111155153A (en) * | 2020-02-19 | 2020-05-15 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
| CN111270277A (en) * | 2020-03-23 | 2020-06-12 | 东莞市康迈克电子材料有限公司 | Blind hole filling electroplating process, plated part obtained by adopting blind hole filling electroplating process, application of plated part and electronic product |
| CN111945192A (en) * | 2020-08-11 | 2020-11-17 | 深圳市创智成功科技有限公司 | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board |
| CN112877739A (en) * | 2021-01-13 | 2021-06-01 | 苏州天承化工有限公司 | Electroplating solution and electroplating method and application thereof |
| CN112899736A (en) * | 2021-01-15 | 2021-06-04 | 深圳中科利尔科技有限公司 | PCB high-longitudinal-transverse-through-hole electro-coppering additive and preparation method thereof |
| CN113445086A (en) * | 2021-04-17 | 2021-09-28 | 珠海松柏科技有限公司 | Copper plating additive and copper electroplating solution suitable for printed circuit board |
| CN113784528A (en) * | 2021-09-13 | 2021-12-10 | 万安裕维电子有限公司 | Local thick copper plating of PCB and preparation method thereof |
| CN114318434A (en) * | 2021-12-10 | 2022-04-12 | 胜宏科技（惠州）股份有限公司 | Copper electroplating solution and preparation method thereof |
| CN114990647A (en) * | 2022-08-01 | 2022-09-02 | 深圳市创智成功科技有限公司 | Environment-friendly through hole filling pulse copper electroplating solution and electroplating method thereof |
| CN115418686A (en) * | 2022-11-07 | 2022-12-02 | 深圳创智芯联科技股份有限公司 | Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296375A (en) * | 1999-11-12 | 2001-05-23 | 荏原优莱特科技股份有限公司 | Method for filling through hole |
| US20050072683A1 (en) * | 2003-04-03 | 2005-04-07 | Ebara Corporation | Copper plating bath and plating method |
| JP2008088524A (en) * | 2006-10-04 | 2008-04-17 | Ebara Udylite Kk | Copper sulfate plating solution for printed board |
| CN102036509A (en) * | 2009-09-25 | 2011-04-27 | 北大方正集团有限公司 | Method for electroplating blind hole and through hole of circuit board |
| US20120205250A1 (en) * | 2011-02-14 | 2012-08-16 | Samsung Electro-Mechanics Co., Ltd. | Electrolytic copper plating solution composition |
| CN102647862A (en) * | 2012-04-25 | 2012-08-22 | 博敏电子股份有限公司 | Blind via filling plating method using different current parameter combinations |
| CN102869206A (en) * | 2012-09-27 | 2013-01-09 | 电子科技大学 | Method for co-plating metallization of blind holes and through hole of printed circuit board |
| CN102995076A (en) * | 2012-12-05 | 2013-03-27 | 陕西师范大学 | Electrocoppering solution for filling blind microvia |
-
2013
- 2013-11-20 CN CN201310585153.2A patent/CN103572334B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296375A (en) * | 1999-11-12 | 2001-05-23 | 荏原优莱特科技股份有限公司 | Method for filling through hole |
| US20050072683A1 (en) * | 2003-04-03 | 2005-04-07 | Ebara Corporation | Copper plating bath and plating method |
| JP2008088524A (en) * | 2006-10-04 | 2008-04-17 | Ebara Udylite Kk | Copper sulfate plating solution for printed board |
| CN102036509A (en) * | 2009-09-25 | 2011-04-27 | 北大方正集团有限公司 | Method for electroplating blind hole and through hole of circuit board |
| US20120205250A1 (en) * | 2011-02-14 | 2012-08-16 | Samsung Electro-Mechanics Co., Ltd. | Electrolytic copper plating solution composition |
| CN102647862A (en) * | 2012-04-25 | 2012-08-22 | 博敏电子股份有限公司 | Blind via filling plating method using different current parameter combinations |
| CN102869206A (en) * | 2012-09-27 | 2013-01-09 | 电子科技大学 | Method for co-plating metallization of blind holes and through hole of printed circuit board |
| CN102995076A (en) * | 2012-12-05 | 2013-03-27 | 陕西师范大学 | Electrocoppering solution for filling blind microvia |
Non-Patent Citations (2)
| Title |
|---|
| 刘小平: "印制线路板酸性镀铜整平剂的合成与应用", 《中南大学硕士学位论文》 * |
| 张允诚等: "《电镀手册》", 31 January 2007, 国防工业出版社 * |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562102A (en) * | 2014-12-31 | 2015-04-29 | 苏州福莱盈电子有限公司 | High-depth blind hole electrocoppering solution |
| US11066553B2 (en) | 2015-08-31 | 2021-07-20 | Atotech Deutschland Gmbh | Imidazoyl urea polymers and their use in metal or metal alloy plating bath compositions |
| CN107922611B (en) * | 2015-08-31 | 2020-11-24 | 埃托特克德国有限公司 | Imidazoyl urea polymers and their use in metal or metal alloy plating bath compositions |
| CN107922611A (en) * | 2015-08-31 | 2018-04-17 | 埃托特克德国有限公司 | Imidazole radicals urea polymers and its purposes in metal or metal alloy bath compositions |
| CN108026656A (en) * | 2015-09-25 | 2018-05-11 | 韩国生产技术研究院 | Electro-coppering organic additive comprising two kinds of leveling agents and the electrolytic copper plating solution comprising the additive |
| CN108026656B (en) * | 2015-09-25 | 2019-10-01 | 韩国生产技术研究院 | Electro-coppering organic additive comprising two kinds of leveling agents and include the electrolytic copper plating solution of the additive |
| CN105316713A (en) * | 2015-10-26 | 2016-02-10 | 苏州福莱盈电子有限公司 | Copper electroplating dissolving solution and rapid high-depth blind hole filling process |
| CN105441993A (en) * | 2015-12-22 | 2016-03-30 | 苏州禾川化学技术服务有限公司 | Electroplating solution and electroplating method for electroplating through holes and blind holes of circuit boards |
| CN108350590A (en) * | 2016-03-18 | 2018-07-31 | 韩国生产技术研究院 | It is used to form the electro-coppering organic additive of high-flatness copper plating film and the electrolytic copper plating solution comprising the additive |
| CN106119913A (en) * | 2016-06-30 | 2016-11-16 | 深圳市励高表面处理材料有限公司 | Copper electroplating liquid and using method thereof and the synthetic method of leveling agent therein |
| CN106132116A (en) * | 2016-07-05 | 2016-11-16 | 广州美维电子有限公司 | A kind of wiring board blind hole fills out process for copper |
| JP2021185271A (en) * | 2016-08-15 | 2021-12-09 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングAtotech Deutschland GmbH | Acidic aqueous composition for electrolytic copper plating |
| JP7064115B2 (en) | 2016-08-15 | 2022-05-10 | アトテック ドイチュラント ゲー・エム・ベー・ハー ウント コー． カー・ゲー | Acidic aqueous composition for electrolytic copper plating |
| JP2019525006A (en) * | 2016-08-15 | 2019-09-05 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Acidic aqueous composition for electrolytic copper plating |
| JP7223083B2 (en) | 2016-08-15 | 2023-02-15 | アトテック ドイチュラント ゲー・エム・ベー・ハー ウント コー． カー・ゲー | Acidic aqueous composition for electrolytic copper plating |
| CN108203836A (en) * | 2016-12-19 | 2018-06-26 | 艾威尔电路（深圳）有限公司 | A kind of method for improving electro-coppering covering power |
| CN108203836B (en) * | 2016-12-19 | 2021-12-17 | 艾威尔电路（深圳）有限公司 | Method for improving deep plating capacity of electroplated copper |
| CN107217282A (en) * | 2017-07-24 | 2017-09-29 | 苏州天承化工有限公司 | A kind of high TP values soft board electroplate liquid and electro-plating method |
| CN107675218A (en) * | 2017-09-30 | 2018-02-09 | 广东骏亚电子科技股份有限公司 | A kind of acid electrochemical copper-plating technique |
| CN107557826A (en) * | 2017-09-30 | 2018-01-09 | 广东骏亚电子科技股份有限公司 | A kind of acid electrochemical copper plating solution |
| CN110042444A (en) * | 2019-05-10 | 2019-07-23 | 九江德福科技股份有限公司 | A kind of additive formulations improving copper foil surface uniformity |
| CN110042444B (en) * | 2019-05-10 | 2022-03-08 | 九江德福科技股份有限公司 | Additive formula for improving surface uniformity of copper foil |
| CN110284163B (en) * | 2019-07-31 | 2020-08-04 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110284163A (en) * | 2019-07-31 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Copper plating solution for solar cell and preparation method thereof |
| CN110331422A (en) * | 2019-08-16 | 2019-10-15 | 国网河南省电力公司桐柏县供电公司 | A kind of ceramic substrate copper electroplating layer thickening method |
| CN110373687A (en) * | 2019-08-30 | 2019-10-25 | 广州皓悦新材料科技有限公司 | A kind of pulse plating photo etching and preparation method thereof plating high aspect ratio through-hole and blind hole |
| CN111155153A (en) * | 2020-02-19 | 2020-05-15 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
| CN111270277A (en) * | 2020-03-23 | 2020-06-12 | 东莞市康迈克电子材料有限公司 | Blind hole filling electroplating process, plated part obtained by adopting blind hole filling electroplating process, application of plated part and electronic product |
| CN111270277B (en) * | 2020-03-23 | 2021-05-25 | 东莞市康迈克电子材料有限公司 | Blind hole filling electroplating process, plated part obtained by adopting blind hole filling electroplating process, application of plated part and electronic product |
| CN111945192B (en) * | 2020-08-11 | 2021-08-06 | 深圳市创智成功科技有限公司 | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board |
| CN111945192A (en) * | 2020-08-11 | 2020-11-17 | 深圳市创智成功科技有限公司 | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board |
| CN112877739A (en) * | 2021-01-13 | 2021-06-01 | 苏州天承化工有限公司 | Electroplating solution and electroplating method and application thereof |
| CN112899736A (en) * | 2021-01-15 | 2021-06-04 | 深圳中科利尔科技有限公司 | PCB high-longitudinal-transverse-through-hole electro-coppering additive and preparation method thereof |
| CN113445086A (en) * | 2021-04-17 | 2021-09-28 | 珠海松柏科技有限公司 | Copper plating additive and copper electroplating solution suitable for printed circuit board |
| CN113784528A (en) * | 2021-09-13 | 2021-12-10 | 万安裕维电子有限公司 | Local thick copper plating of PCB and preparation method thereof |
| CN114318434A (en) * | 2021-12-10 | 2022-04-12 | 胜宏科技（惠州）股份有限公司 | Copper electroplating solution and preparation method thereof |
| CN114318434B (en) * | 2021-12-10 | 2023-08-08 | 胜宏科技（惠州）股份有限公司 | Electrolytic copper plating solution and preparation method thereof |
| CN114990647A (en) * | 2022-08-01 | 2022-09-02 | 深圳市创智成功科技有限公司 | Environment-friendly through hole filling pulse copper electroplating solution and electroplating method thereof |
| CN115418686A (en) * | 2022-11-07 | 2022-12-02 | 深圳创智芯联科技股份有限公司 | Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof |
| CN115418686B (en) * | 2022-11-07 | 2023-01-10 | 深圳创智芯联科技股份有限公司 | Through hole high-depth copper electroplating solution for glass substrate and copper electroplating process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103572334B (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103572334A (en) | Copper plating solution for PCB (printed circuit board) through holes and PCB blind holes, as well as preparation method and plating method of copper plating solution | |
| CN103572336B (en) | A kind of PCB blind hole copper electroplating solution and preparation method thereof and electro-plating method | |
| CN103572335B (en) | A kind of PCB the electroplates in hole copper solutions and preparation method thereof and electro-plating method | |
| CN111945192B (en) | Blind hole filling electro-coppering solution for HDI (high Density interconnect) board and carrier board | |
| CN102080241B (en) | Low-concentration weakly alkaline cyanide-free copper plating and bath solution preparing method | |
| CN103547711B (en) | Aqueous acid bath for the electrolytic deposition of copper | |
| CN105441993A (en) | Electroplating solution and electroplating method for electroplating through holes and blind holes of circuit boards | |
| US20090229986A1 (en) | Continuous copper electroplating method | |
| CN111424296B (en) | Electroplating copper solution for filling through holes of IC carrier plate and electroplating method | |
| CN103014787B (en) | A kind of copper electroplating liquid and electroplating technology thereof | |
| CN108118372A (en) | A kind of high dispersive acidic copper plating additive and preparation method and application | |
| JP6900621B2 (en) | Copper electroplating liquid and electroplating method used for copper wiring material for through silicon vias in wafer level packages | |
| CN106757194A (en) | A kind of method that PCB blind holes are filled out in utilization electro-coppering | |
| CN112899736A (en) | PCB high-longitudinal-transverse-through-hole electro-coppering additive and preparation method thereof | |
| CN115074789B (en) | Circuit board blind hole rapid filling electrolytic copper plating solution and rapid filling method | |
| JP6899062B1 (en) | Electrocopper plating solution for filling through holes of IC boards and its electroplating method | |
| CN110424030A (en) | Cyanide-free alkaline copper electroplating solution, preparation thereof and application thereof in flexible printed circuit board | |
| WO2023246889A1 (en) | Acid sulfate electroplating copper combination additive for dense filling of pcb through hole metal | |
| CN101070604B (en) | Electroplating method | |
| CN105951137A (en) | HDI laminated plate blind buried hole copper plating bath | |
| CN110106536A (en) | A kind of printed circuit board blind hole fills out copper and fills out copper method with acid copper plating bath and its blind hole | |
| CN114990647A (en) | Environment-friendly through hole filling pulse copper electroplating solution and electroplating method thereof | |
| CN108315781A (en) | Fill plating system and filling method for plating | |
| TWI683931B (en) | Anode for electrolytic copper plating and electrolytic copper plating device using the same | |
| CN104388989A (en) | Trivalent chromium electroplating liquid and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160622 Termination date: 20171120 |