CN101580953A - Electroless copper plating solution composition and preparation method thereof - Google Patents
Electroless copper plating solution composition and preparation method thereof Download PDFInfo
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- CN101580953A CN101580953A CNA2008100671462A CN200810067146A CN101580953A CN 101580953 A CN101580953 A CN 101580953A CN A2008100671462 A CNA2008100671462 A CN A2008100671462A CN 200810067146 A CN200810067146 A CN 200810067146A CN 101580953 A CN101580953 A CN 101580953A
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Abstract
The invention provides an electroless copper plating solution composition and a preparation method thereof. The electroless copper plating solution comprises bluestone, formaldehyde, EDTA, sodium citrate, sodium hydroxide, pyridine substances, alkynol polymer and polyethylene glycol. The preparation method of the electroless copper plating solution comprises preparing four copper precipitation stock solutions and adding the four stock solutions according to a certain proportion and a certain sequence to obtain the copper precipitation solution. The electroless copper plating solution is stable, has simple operation, can obtain a favourable sediment layer, and is especially suitable for galvanization of a multiple-layer circuit board.
Description
Technical field
The present invention relates to a kind of electroless copper plating solution, relate in particular to a kind of galvanized electroless copper plating solution of multilayer circuit board that is used for.
Background technology
Plating is to utilize electrolysis principle to plate the process of other metal or alloy of skim in some metallic surface.During plating, coated metal is done anode, is oxidized to positively charged ion and enters electroplate liquid; Metal products to be plated is done negative electrode, and the positively charged ion of coated metal is reduced formation coating in the metallic surface.For getting rid of other cationic interference, and make coating evenly, firmly, need cook electroplate liquid, to keep the cationic concentration of coated metal constant with containing the cationic solution of coated metal.Galvanized purpose is to plate metal plating on base material, changes substrate surface character or size.Plating can strengthen metal erosion resistance, increase hardness, prevent abrasion, improve electroconductibility, oilness, thermotolerance and surface aesthetic.
In the circuit card manufacturing technology, most critical be exactly heavy copper process.Its main effect is to make two-sided and nonmetal hole multilayer printed circuit board deposit the layer of even conductive layer by redox reaction on hole wall, thickeies copper facing through electroplating again, reaches the purpose in loop.Reaching this purpose just must select stable performance, reliable electroless copper plating solution and formulate correct, feasible and effective processing sequence.
Summary of the invention
The invention provides a kind of electroless copper plating solution, this electroless copper plating solution is solution-stabilized, simple to operate, can obtain good settled layer, is particularly suited for multilayer circuit board and electroplates.
The composition of this electroless copper plating solution comprises copper sulfate, formaldehyde, EDTA, Trisodium Citrate, sodium hydroxide, pyridines material, alkynol polymkeric substance and polyoxyethylene glycol, and the effect of main moiety is as follows:
Copper sulfate is the main salt in the solution, and the bivalent cupric ion source is provided;
Formaldehyde is reductive agent;
EDTA and Trisodium Citrate are complexing agents, and main effect is to make copper be the dissolved complex status to exist, and prevents that bivalent cupric ion from producing Cu (OH) in alkaline medium
2Precipitation, the while can also be controlled the concentration of bivalent cupric ion.Has shock absorption, to keep the pH value of solution.
Sodium hydroxide makes solution keep certain pH value, because formaldehyde under alkaline condition, just has reductive action.
Pyridines material, alkynol polymkeric substance and polyoxyethylene glycol are stablizers, have to make heavy copper liquid stable and improve copper layer performance, prevent to produce side reaction.
This electroless copper plating solution is made up of four kinds of heavy copper stostes, before using four kinds of heavy copper stostes is reached order according to a certain percentage and is mixed with heavy copper liquid.This method is simple to operate, and is easy to use.Heavy copper liquid stability is high, and through after repeatedly adding, solution still has highly stable ability.
Electroless copper plating solution provided by the invention can deposit 2.5～3.0 microns copper layer in 30 minutes, settled layer is pure fine and closely woven, good conductivity, there is not internal stress, and good in oxidation resistance is all having good hiding power on the resin or on the glass fibre, especially is suitable for multilayer circuit board and electroplates.
Mode by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Embodiment
The specific embodiment of a kind of electroless copper plating solution provided by the invention is as follows:
Copper sulfate 10g/L
Formaldehyde 3.9g/L
EDTA and Trisodium Citrate 42.0～48.5g/L
Wherein, EDTA: Trisodium Citrate is 1: 1.15～1: 1.2 (weight ratio)
Sodium hydroxide 8.0～12.0g/L
Pyridines material 1.2mg/L
Alkynol polymkeric substance 0.33g/L
Polyoxyethylene glycol 32mg/L
Electroless copper plating solution provided by the invention is made up of four kinds of heavy copper stostes, and is as follows respectively:
Stoste A: copper content 44g/L contains the strong solution of formaldehyde amount 65g/L;
Stoste M: the strong solution that contains free sub-EDTA 18～20g/L;
Stoste B: the strong solution that contains sodium hydroxide 250g/L;
Stoste C: the solution that contains dipyridyl 4g/L.
Before using these four kinds heavy copper stostes are mixed with heavy copper liquid in following ratio (weight ratio) and sequencing, embodiment is as follows: remove ionized water (80%), add stoste M (10%) earlier, add stoste A (6%) then, add stoste B (4%) again, add stoste C (0.3ml/L) at last
Prepare this electroless copper plating solution, at first need to prepare four kinds of heavy copper stostes, the specific implementation process of the heavy copper stoste of preparation 1000L is as follows:
Stoste A: 1L sulfuric acid is dissolved in the 35L pure water, adds 180kg copper sulfate, 180kg formaldehyde, 85kg Trisodium Citrate and 5L alkynol polymkeric substance successively, circulating filtration;
Stoste B: 270kg sodium hydroxide and water are dissolved with 1: 1 (weight ratio), be cooled to room temperature, add 100kgEDTA, add the 800g polyoxyethylene glycol again;
Stoste M: 20kg sodium hydroxide and water are dissolved with 1: 1 (weight ratio), add 170kg Trisodium Citrate and 200kg EDTA successively;
Stoste C: the 500L industrial spirit is soluble in water with 1: 1 (volume ratio), add the 4kg dipyridyl.
Secondly, four kinds of heavy copper stostes are pressed column weight amount and order interpolation respectively: in the 80L deionized water, add stoste M 10L earlier, add stoste A 6L then, add stoste B 4L again, add stoste C0.3ml/L at last.
When four kinds of heavy copper stostes being mixed with heavy copper liquid, initial temperature should be at 36～42 ℃, but needed to promote temperature to 42～44 ℃ at first day that newly opens cylinder, and Yin Xinkai cylinder active degree is low, so require to promote on liquor strength.PH value in the preparation process is 12.8～13, but optimal ph is 13.
In order to form the initiation center, make copper deposition uniformity, the nonmetallic surface deposition layer of even active center core particle that need plated.The present invention adopts the colloidal palladium activation, excellent property, thus make the settled layer bonding strength that is obtained good, duration of service is long.
When using this electroless copper plating solution copper facing, the principal element of the heavy copper speed of influence has:
The pH value of solution value: improve the pH value, the copper sedimentation velocity is accelerated, but also will accelerate Red copper oxide formation reaction speed simultaneously, thereby the solution inside deposition is speeded up, and bivalent cupric ion reduces, and causes the decomposition of copper solutions; When the pH value was less than or equal to 11, electroless copper plating speed was very slow; The pH value sharply stops less than 10.5 o'clock heavy copper.So the pH value that adopts is 12.8～13 usually, but optimal ph is 13.
The concentration of solution: improve bivalent cupric ion concentration in the solution, obvious especially to heavy copper speed influence, but neither infinitely increase, the bivalent cupric ion scope should be controlled at 1.8～2.8g/L, and optimum concn is 2.3g/L.If working fluid is when clocklike controlling as the basis with the titrimetry of copper, the content of copper is 2.0g/L.
The concentration sodium hydroxide scope is at 8.0～12.0g/L, and optimum concn is 10.0g/L.
The concentration of formaldehyde: improve concentration of formaldehyde, heavy copper speeds up, but too much easily causes heavy copper layer coarse, and the formaldehyde scope should be controlled at 2.8～4.2g/L, and optimum concn is 3.5g/L.To 4.0g/L, Yin Xinkai cylinder active degree is low, so require to promote on liquor strength at first day need lifting formaldehyde content newly opening cylinder.
Solution temperature: improve the activation energy that solution temperature can increase copper, improve heavy copper speed; But temperature raises, and the katalysis of cupric ion is strengthened in the solution, and the Red copper oxide formation speed is accelerated, and heavy copper mass is poor, impels solution to decompose.Therefore suitable temperature range is at 40～45 ℃, and optimum temps is 43 ℃.
Lifting capacity: 2～3.5dm
2/ rising working fluid, the optimum load amount is 2.5dm
2/ rising working fluid, when exceeding this scope, heavy copper speed descends.
Influence the factor of electroless copper plating solution stability:
Have the active substance of graininess in the solution, it is mainly derived from the colloid that has catalytic in koniology or the employed chemical reagent, cleans improper bringing into during the activated processing of substrate in addition and produces the plating bath instability.
The disproportionation reaction of formaldehyde is unavoidable, so the formaldehyde consumption is big, when formaldehyde is not enough, just may make solution aging, causes a large amount of Red copper oxide, and the result causes solution self to decompose and lost efficacy.
The formation of Red copper oxide: the formed Red copper oxide of the disproportionation reaction of formaldehyde is easy to produce disproportionation reaction, forms Cu and Cu
2+, and random being dispersed in the solution of small-particle of the copper that it generates becomes little active center, causes whole plating bath to react as heavy copper, causes solution natural decomposition rapidly.
In order to guarantee the stability of heavy copper liquid, should control copper ion concentration in the electroless copper plating solution at 1.8～2.8g/L, thus the heavy copper speed of control; The pH value wants strictness to control, and it is best selecting pH value 13; Must add and the strong complexing agent of copper complexing; Other as purity of raw materials, prevent that catalytic metal from bringing into, filtering solution.
The variation that is appreciated that a lot of details is possible, and therefore this do not run counter to scope and spirit of the present invention.
Claims (10)
1, a kind of electroless copper plating solution comprises copper sulfate, formaldehyde, EDTA, Trisodium Citrate, sodium hydroxide, pyridines material, alkynol polymkeric substance and polyoxyethylene glycol, and concentration is as follows:
Copper sulfate 6.8～10.6g/L
Formaldehyde 2.8～4.2g/L
EDTA and Trisodium Citrate 42.0～48.5g/L
Sodium hydroxide 8.0～12.0g/L
Pyridines material 1.2mg/L
Alkynol polymkeric substance 0.33g/L
Polyoxyethylene glycol 32mg/L
2, a kind of electroless copper plating solution comprises four kinds of heavy copper stostes:
Stoste A: copper content 30～47g/L contains the strong solution of formaldehyde amount 47～70g/L;
Stoste M: the strong solution that contains free sub-EDTA 18～20g/L;
Stoste B: the strong solution that contains sodium hydroxide 250～260g/L;
Stoste C: the solution that contains pyridines material 4g/L.
3, according to claim 2 described electroless copper plating solutions, it is characterized in that, the mixed solution that described heavy copper liquid is described four kinds of heavy copper stostes, weight ratio is as follows:
Deionized water 80%
Stoste M 10%
Stoste A 6%
Stoste B 4%
Stoste C 0.3ml/L
According to claim 2 described electroless copper plating solutions, it is characterized in that 4, the working temperature of described heavy copper liquid is 40～45 ℃.
According to claim 2 described electroless copper plating solutions, it is characterized in that 5, the lifting capacity of described heavy copper liquid is 2～3.5dm
2/ rise working fluid.
6, a kind of preparation method of electroless copper plating solution comprises the preparation of four kinds of heavy copper stostes:
Stoste A: 1L sulfuric acid is dissolved in the 35L pure water, adds 178～183kg copper sulfate, 177～182kg formaldehyde, 80～90kg Trisodium Citrate and 4.9～5.1L alkynol polymkeric substance successively, circulating filtration;
Stoste B: 265～275kg sodium hydroxide and water are dissolved with 1: 1 (weight ratio), be cooled to room temperature, add 95～105kg EDTA, add 798～802g polyoxyethylene glycol again;
Stoste M: 19.5～21kg sodium hydroxide and water are dissolved with 1: 1 (weight ratio), add 168～172kg Trisodium Citrate and 195～205kg EDTA successively;
Stoste C: the 500L industrial spirit is soluble in water with 1: 1 (volume ratio), add the 4kg dipyridyl.
According to the preparation method of claim 6 described electroless copper plating solutions, it is characterized in that 7, the preparation of described heavy copper liquid is that described four kinds of heavy copper stostes are added by following deal: deionized water 80L, stoste M 10L, stoste A 6L, stoste B 4L, stoste C 0.3ml/L.
According to the preparation method of claim 6 described electroless copper plating solutions, it is characterized in that 8, the preparation of described heavy copper liquid is that described four kinds of heavy copper stostes are added in the following order successively: in deionized water, add stoste M earlier, add stoste A then, add stoste B again, add stoste C at last.
According to the preparation method of claim 6 described electroless copper plating solutions, it is characterized in that 9, described heavy copper liquid initial temperature in the preparation is 36～42 ℃.
According to the preparation method of claim 6 described electroless copper plating solutions, it is characterized in that 10, described heavy copper liquid is in preparation process, the pH value is 12.8～13.
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| CN2008100671462A CN101580953B (en) | 2008-05-14 | 2008-05-14 | Electroless copper plating solution composition and preparation method thereof |
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Cited By (1)
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| CN106676502A (en) * | 2017-01-17 | 2017-05-17 | 广东成德电子科技股份有限公司 | Palladium-free copper deposition preparation process of printed circuit board |
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| US4684550A (en) * | 1986-04-25 | 1987-08-04 | Mine Safety Appliances Company | Electroless copper plating and bath therefor |
| CN1236839A (en) * | 1998-05-21 | 1999-12-01 | 刘绍之 | Electromagnetically shielding fabrics and production method thereof |
| CN1173092C (en) * | 1999-07-07 | 2004-10-27 | 刘绍芝 | Fabric for shielding electromagnetic wave and its producing method |
| US6749660B2 (en) * | 2001-06-04 | 2004-06-15 | Geovation Technologies, Inc. | Solid-chemical composition and method of preparation for the anaerobic bioremediation of environmental contaminants coupled to denitrification |
| TWI341889B (en) * | 2006-09-06 | 2011-05-11 | Formosa Taffeta Co Ltd | Color-coated, fouling-resistant conductive clothes and manufacturing method thereof |
| CN101067201A (en) * | 2007-06-12 | 2007-11-07 | 江苏大学 | Method for promoting preprocessing of copper-clad zirconium tungstate composite powder |
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| CN106676502A (en) * | 2017-01-17 | 2017-05-17 | 广东成德电子科技股份有限公司 | Palladium-free copper deposition preparation process of printed circuit board |
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