CN105274587A - Diphenyl methane dye system acid copper plating electroplating liquid and electroplating method thereof - Google Patents
Diphenyl methane dye system acid copper plating electroplating liquid and electroplating method thereof Download PDFInfo
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- CN105274587A CN105274587A CN201410229530.3A CN201410229530A CN105274587A CN 105274587 A CN105274587 A CN 105274587A CN 201410229530 A CN201410229530 A CN 201410229530A CN 105274587 A CN105274587 A CN 105274587A
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Abstract
The present invention discloses a diphenyl methane dye system acid copper plating electroplating liquid and electroplating method thereof, wherein the electroplating liquid contains CuSO4.5H2O, H2SO4, chlorine ions, a diphenyl methane dye, thiazolinyl dithiopropane sodium sulfonate, alcohol thio propane sodium sulfonate, sodium succinate, polyethylene glycol, a fatty amine ethoxy sulfonated matter and a polyethylene imine alkyl salt. According to the present invention, the diphenyl methane dye is adopted as the leveling agent, the thiazolinyl dithiopropane sodium sulfonate is adopted as the brightener, the alcohol thio propane sodium sulfonate is adopted as the grain refining agent, the compounding of the polyethylene imine alkyl salt and the fatty amine ethoxy sulfonated matter is adopted as the extension agent, and the compounding of the polyethylene glycol and the sodium succinate is adopted as the wetting agent, such that the plating liquid has good stability; and the plating layer obtained through the electroplating by using the plating liquid under the acid condition has characteristics of good leveling property and high brightening capacity.
Description
Technical field
The present invention relates to the technical field of copper plating process, particularly relate to a kind of electroplate liquid and electro-plating method of diphenyl methane dye system acid copper-plating.
Background technology
Copper has good electroconductibility and thermal conductivity, and comparatively soft, easy polishing, is soluble in nitric acid, is also soluble in the vitriol oil of heating, acts on very slow in hydrochloric acid and dilute sulphuric acid.Be easy in atmosphere be oxidized (especially in a heated condition), itself color and gloss will be lost after oxidation, in damp atmosphere, generating one deck ventilation breather with carbonic acid gas or oxide compound effect, when being subject to sulfide effect, brown or black thin film will be generated.
Due to the calibration of copper current potential, thus it is easy to deposit on other metal.Using copper as bottom, when using together with bright nickel and tiny crack chromium, very good corrosion stability coating can be obtained.Copper coating effectively can be protected the etch of zine pressure casting acid and alkali nickel plating solution and dissolve, and thus prevent displacement plating, and when electro-galvanizing die casting, copper is absolutely necessary as bottom.Equally, copper facing before steel part nickel plating chromium, is easily polished to very high surface luminous intensity, thus can reduce polishing and the polishing cost of some steel part.So copper coating is commonly used to the bottom as gold and silver, nickel and chromium coating.In addition, owing to having good electroconductibility, copper coating is also widely used on printed-wiring board (PWB).Copper can stop the scattering and permeating of carbon, nitrogen effectively, and the copper coating of low porosity, as a kind of blocking layer, is also widely used in nitriding and the carburization process of steel matrix part.
Acid copper-plating is as one of a kind of copper-plating technique be most widely used, and it generally fills a prescription based on sulfuric acid and copper sulfate, and it has following major advantages: (1) coating and matrix metal bonding force good, intensity is high; (2) ductility of electrodeposited film is good; (3) dark plating performance is good, and Surface flat is good; (4) easily polishing, conductivity is good; (5) easily weld; (6) special additive can be selected in decorative electroplating to obtain brightness effect, or plate out concavo-convex boldface type; (7) coating easily continue copper facing or plate other metals.
The less stable of existing acid copper-plating ubiquity plating solution, the technological deficiency that coating Surface flat is not good and the ability that exposes is lower, these seriously constrain the industrial applications of acid copper-plating.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of electroplate liquid of diphenyl methane dye system acid copper-plating, and the bath stability of this electroplate liquid is better, and coating Surface flat is good and the ability that exposes is higher.
An electroplate liquid for diphenyl methane dye system acid copper-plating, comprises the CuSO of content 190 ~ 220g/L
45H
2o, content are the H of 50 ~ 70g/L
2sO
4, content is the chlorion of 0.050 ~ 0.080g/L, content is the diphenyl methane dye of 0.15 ~ 0.25g/L, content is the thiazolinyl dithio propane sulfonic acid sodium of 0.010 ~ 0.018g/L, content is the alcohol mercapto propyl-sulfonate of 0.20 ~ 0.30g/L, content is the succinate sodium salt of 0.19 ~ 0.28g/L, content is the polyoxyethylene glycol of 0.048 ~ 0.06g/L, content is the aliphatic amide oxyethyl group sulfonated bodies of 0.016 ~ 0.028g/L and content is 0.03 ~ 0.045g/L polymine alkyl salt.
Wherein, the CuSO that content is 208g/L is comprised
45H
2o, content are the H of 61g/L
2sO
4, the content chlorion that is 0.067g/L, the content diphenyl methane dye that is 0.18g/L, content is the thiazolinyl dithio propane sulfonic acid sodium of 0.013g/L, content is 0.26g/L alcohol mercapto propyl-sulfonate, the content succinate sodium salt that is 0.22g/L, content is the polyoxyethylene glycol of 0.057g/L, content is 0.020g/L aliphatic amide oxyethyl group sulfonated bodies and content is 0.036g/L polymine alkyl salt.
Wherein, described victoria blue B and/or auramine; Described molecular weight polyethylene glycol is 2000 ~ 8000.
In the technical scheme of above electroplate liquid, diphenyl methane dye is selected to be leveling agent.Diphenyl methane dye refers to the general name of the dyestuff containing ditane group in molecular structure.Diphenyl methane dye can be victoria blue B and/or auramine.No. CAS of victoria blue B is 2580-56-5, and the present invention's victoria blue B used is fastened the purple chemical reagent work in sea and produced.No. CAS of auramine is 2465-27-2, and the present invention's Methylene blue used is fastened Hai Hu space bio tech ltd and produced.The mechanism of action of leveling agent is specific as follows: become smooth to make rough matrix originally, the sedimentation velocity of recess in electroplating process just must be made to be greater than the sedimentation velocity at convex place, the realization of this process is called leveling, and it realizes by adding leveling agent in the plating solution.Leveling agent can be attracted on negative electrode, and can be consumed because of reduction, has the effect of the galvanic deposit hindering metal ion.Because the diffusion mass transfer speed of the recess on microcosmic is slower than convex place, therefore, do not supplemented in time after the leveling agent of recess exhausts, so that the amount of absorption is fewer, thus less to the Inhibition of deposition, sedimentation velocity is very fast; Just in time contrary then with recess of the situation of high spot.Therefore, the growth of the coating of recess will be faster than convex place, and the original concavo-convex gap of microcosmic of matrix is reduced gradually, so that finally eliminates, thus reaches the leveling to coating surface.
Using thiazolinyl dithio propane sulfonic acid sodium as brightening agent.Brightening agent has the effect of certain increase polarization, it passes through adsorption, local growth when suppressing copper simple substance to deposit, promote the miniaturization of crystallization, the size of crystal grain is made to be less than visible wavelength, and it is directed to have certain arrangement, be formed at the structural plane being parallel to surface thus, thus reach the visible ray making to incide surface and diffuse-reflectance does not occur.Thiazolinyl dithio propane sulfonic acid sodium system light yellow crystal, closes mesophytization Manufacturing Co., Ltd by Wuhan and is produced.
Using alcohol mercapto propyl-sulfonate as grain-refining agent.It can cause the factor producing dislocation and nucleation increase all can play the effect of refinement product grain.Product grain fining agent, by increasing polarization, produces high overpotential and ensures the former saturation ratio of high absorption, or has caused absorption former to enter the randomness of character to increase by this in surface adsorption, thus hinders and adsorbed former to spread to growth centre.Alcohol mercapto propyl-sulfonate is white crystals body, is that Jiangsu Meng get Plating chemistry company limited produced.
Using aliphatic amide oxyethyl group sulfonated bodies and polymine alkyl salt as extension agent.Extension agent eliminates coating internal stress, improves the ductility of coating.Ductility refers to the elasticity that metal or other rete crackle do not occur and show or plastic deformation ability.In addition, the effect of polymine alkyl salt also its brightening agent, low current density coating luminance brightness in can improving.In the present invention, aliphatic amide oxyethyl group sulfonated bodies used is brown liquid, and pH is 4 ~ 7, and by Jiangsu, Meng get Plating chemistry company limited is produced.The present invention's polymine alkyl salts contg used is 50%, and outward appearance is weak yellow liquid, and pH is 5 ~ 7, and it is that Jiangsu Meng get Plating chemistry company limited produced.
Composite polyoxyethylene glycol and succinate sodium salt are wetting agent.Wetting agent can improve the wetting effect of plating solution, eliminates the pin hole of coating, improves quality of coating.Polyoxyethylene glycol also can make carrier, and leveling agent is by the effect of its Surface flat of carrier competence exertion.In addition, polyoxyethylene glycol can form complex compound with bivalent cupric ion coordination under the existence of chlorion, and to make, copper sedimentation potential is negative moves, thus is beneficial to the deposition of cupric ion.The present invention's polyoxyethylene glycol used is produced by Hai'an, Jiangsu petroleum chemical plant, and specification is PEG2000, PEG3000, PEG4000, PEG6000 and PEG8000, and be preferably PEG6000, its molecular-weight average is 6000, and range of molecular weight distributions is 5400 ~ 6600.Succinate sodium salt system colourless transparent liquid, the present invention Jiangsu Meng get Plating chemistry company limited of succinate sodium salt system used produced, and code name is MT-200.
Take chlorion as activator, katalysis is played to the galvanic deposit of bivalent cupric ion; And only when chlorion exists, anode copper coin can normally dissolve, otherwise positive terminal there will be the copper powder produced because not exclusively dissolving.When chloride ion content is lower, complex ion is dsp2 type mainly, the activation energy that bivalent cupric ion is reduced to copper simple substance to be needed increases, detrimentally affect is produced to branch's reduction of bivalent cupric ion, increase the possibility that bivalent cupric ion directly becomes Cu, coating is caused easily to occur striped, in addition with burning and pin hole.Reason is the too stable of dsp2 type, causes polarization value excessive; When content is too high, complex compound is sp3d2 type, to Cu
2++ e=Cu
+with Cu
++ e=Cu all serves restraining effect, cathodic polarization effect is declined, hinders Cu
2+galvanic deposit, the bright property of coating weakens, low district does not even work.Now, also can there is passivation in anode, electric current declines thereupon, and the black film of anode surface can change canescence into.In a word, the effect of chlorion is the electron reaction of balance negative electrode, mediation energy transformation, thus regulates cathodic polarization and bivalent cupric ion to be reduced into the speed of response of univalent copper ion.
With CuSO
45H
2o is main salt, with H
2sO
4as conducting salt.H
2sO
4can the hydrolysis of bivalent cupric ion always, the acidic conditions needed for plating solution can also be provided.The reaction mechanism of the acid copper of acid copper-plating is reaction in two steps, and first bivalent cupric ion is reduced to univalent copper ion, and then monovalence is reduced to copper metal simple-substance.
The present invention provides a kind of electro-plating method on the other hand, and the coating Surface flat that the method can make this electroplate liquid plating preferably of employing stability obtain is good and the ability that exposes is higher.
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, comprises the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains 190 ~ 220gCuSO
45H
2o, 50 ~ 70gH
2sO
4, 0.050 ~ 0.080g chlorion, 0.15 ~ 0.25g diphenyl methane dye, 0.010 ~ 0.018g thiazolinyl dithio propane sulfonic acid sodium, 0.20 ~ 0.30g alcohol mercapto propyl-sulfonate, 0.19 ~ 0.28g succinate sodium salt, 0.048 ~ 0.06g polyoxyethylene glycol, 0.016 ~ 0.028g aliphatic amide oxyethyl group sulfonated bodies and 0.03 ~ 0.045g polymine alkyl salt;
(2) insert with pretreated negative electrode and anode and pass into electric current in described electroplate liquid and electroplate.
Wherein, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 0.5 ~ 1ms, and dutycycle is 5 ~ 30%, and average current density is 2 ~ 4A/dm
2.
Wherein, the temperature of electroplate liquid is 15 ~ 35 DEG C.
Wherein, the time of plating is 20 ~ 60min.
Wherein, the material of described anode is the copper containing 0.35 ~ 0.05wt% phosphoric.
Wherein, in described step (2), plating is carried out under pneumatic blending negative electrode stirs, and the gas flow density of described pneumatic blending is 12 ~ 15m
3/ (h.m
2), the speed of described movable cathode is 20 ~ 30 times/min.
Wherein, in described step (2), the area ratio of negative electrode and positive electrode is (1/3 ~ 2): 1.
In the technical scheme of above electro-plating method, monopulse rectangular wave current is defined as at t
1passing into current density in time is J
pelectric current, at t
2without passing into electric current in time, it is a kind of intermittent pulse current.Dutycycle is defined as t
1/ (t
1+ t
2), frequency is 1/ (t
1+ t
2), mean current is defined as J
pt
1/ (t
1+ t
2).Compare with DC electrodeposition, thickness and the ion concentration distribution of electrostatic double layer all change; While adding electrochemical polarization, reduce concentration polarization, the direct effect of generation is, the coating that pulse plating obtains than DC electrodeposition coating evenly, crystallization is finer and closely woven.Moreover, pulse plating also has: hardness and the wear resistance of (1) coating are all high; (2) solution dispersibility and covering power good; (3) decrease the super plating of part edge, coating distributing homogeneity is good, can save plating solution consumption.
With phosphorous copper coin for anode, be preferably the copper coin containing 4wt% phosphoric.In the reaction of acid copper plating Anodic, monovalence copper reduction is that the speed that the speed ratio bivalent cupric ion of elemental copper is reduced to univalent copper ion wants slow, so, have little time the Cu reacted
+disproportionation reaction will be there is and generate copper powder formation " anode sludge ".Because the stirring of electroplating process in the present invention makes these copper powders just be easy to move to negative electrode and enter among coating, thus cause the appearance of burr.Use phosphorous copper as anode, during plating, the surface of anode can form the black membranoid substance Cu of one deck densification
3p, prevents the generation of copper powder, and its principle is: P and Cu
+combine, generate Cu
3p, and Cu
3p is to Cu
+oxidizing reaction have katalysis, it makes Cu
+rapid oxidation becomes Cu
2+, thus restrained effectively the generation of copper powder, again because of Cu
3p has excellent conductivity, although therefore anode is covered by a skim, and can not passivation.But phosphorus content is not The more the better, when phosphorous too time, black film naturally can be thickening, causes the bonding force of film and anode to reduce, so that be shed in solution, make electroplate liquid contaminated.
Using the steel plate of low-carbon (LC) as negative electrode.Anticathode pre-treatment is by comprising anticathode sand papering, oil removing, pickling, preimpregnation copper after elder generation successively.This use sand papering can polish twice, and first time with flint paper such as 200 object sand paperings, can be used fine sandpaper, such as, can use WC28 abrasive paper for metallograph for the second time.This oil removing can first adopt chemical alkali liquor oil removing then to adopt the dehydrated alcohol oil removing of 95%.Wherein, chemical alkali lye consists of: 50 ~ 80g/LNaOH, 15 ~ 20g/LNa
3pO
4, 15 ~ 20g/LNa
2cO
3and 5g/LNa
2siO
3with 1 ~ 2g/LOP-10.Electrochemical deoiling detailed process is through treating oil removing negative electrode 15 ~ 40 DEG C of dipping 30s in chemical alkali lye.The pickling time is 1 ~ 2min, and the object of pickling is activation, specifically, removes the oxide film on plating piece top layer, makes the lattice of matrix completely exposed, be in active state.Pickling solution composition used is: 100g/L sulfuric acid and 0.15 ~ 0.20g/L thiocarbamide.The preimpregnation copper time is 1 ~ 2min, and solution composition used is: 100g/L sulfuric acid, 50g/L anhydrous cupric sulfate and 0.20g/L thiocarbamide.
In step (2), the area ratio of negative electrode and positive electrode is preferably 1:1.5.Ratio of cathodic to anodic area is crossed conference and is made it more easily passivation occur, and even can produce mantoquita or cuprous oxide compound; Otherwise, then cathode copper sedimentation rate can be caused too small, thus reduce current efficiency.
In the present invention, electroplate liquid carries out pneumatic blending in energising electroplating process, and electroplate and carry out under the condition of pneumatic blending and movable cathode, the gas flow density of pneumatic blending is 12 ~ 15m
3/ (h.m
2), be understandable that here, gas flow density refers to the volume flowing through unit surface gas within the unit time.Air needed for pneumatic blending is by the low-pressure oil-free air pump supply being provided with strainer, and air-inflating tube is 30 ~ 80mm from the distance of bottom land, itself and the same direction of negative electrode copper rod.Tracheae need be drilled with the aperture that two row's internal diameters are about 3mm, is 45 jiaos with the inclination angle of bottom land, and two row's apertures answer staggered relative, every limit spacing 80 ~ 100mm (aperture interlock spacing 40 ~ 50mm).Coating bath is provided with the air-inflating tube of more than 2 or 2, and tracheae can be polyvinyl chloride or polythene material, internal diameter 20 ~ 40mm, and two pipe distances are 150 ~ 250mm.Movable cathode can be transverse shifting, also can be vertical mobile.Using one back and forth as once, the stroke of transverse shifting is 100mm, and speed is 20 ~ 25 times/min; The stroke of vertical movement is 60mm, and speed is 25 ~ 30 times/min.Pneumatic blending and movable cathode can make plating solution realize stirring.Stirring can reduce copper complexing ion and concentration gradient, thickness of diffusion layer and a large amount of liberation of hydrogen near electrode surface and cause the increase of cathodic area pH value, is conducive to the deposition of metal ion; Can promote that again coating thickens the uniform composition with coating continuously; The copper complexing ion that the electrolysis initial stage can also be made to produce shifts out cathodic area rapidly, thus improves quality of coating.
Plating solution of the present invention take diphenyl methane dye as leveling agent, using thiazolinyl dithio propane sulfonic acid sodium as brightening agent, using alcohol mercapto propyl-sulfonate as grain-refining agent, composite polymine alkyl salt and aliphatic amide oxyethyl group sulfonated bodies are as extension agent, composite polyoxyethylene glycol and succinate sodium salt are wetting agent, make plating solution have good stability thus, the Surface flat of the coating of acquisition is good and the ability that exposes is higher to adopt this plating solution to electroplate in acid condition.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
According to formulated electroplate liquid described in embodiment 1 ~ 6, specific as follows: the quality taking each feed composition according to formula electronic balance.Fully mix then after each feed composition is dissolved in appropriate deionized water respectively, add water move to pre-determined volume.
The electroplate liquid of formulated described in embodiment 1 ~ 6 and comparative example is used to carry out electric plating method:
(1) negative electrode adopts the Q235 steel plate of 10mm × 10mm × 0.2mm specification.Metalluster is exposed with the polishing of WC28 abrasive paper for metallograph to surface again after first tentatively being polished with 200 order waterproof abrasive papers by steel plate.Successively through temperature be 50 ~ 70 DEG C chemical alkali liquor oil removing, distilled water flushing, 95% dehydrated alcohol oil removing, distilled water flushing, pickling 1 ~ 2min, preimpregnation copper 1 ~ 2min, redistilled water rinse.Wherein, the formula of chemical alkali lye is 50 ~ 80g/LNaOH, 15 ~ 20g/LNa
3pO
4, 15 ~ 20g/LNa
2cO
3and 5g/LNa
2siO
3with 1 ~ 2g/LOP-10.Pickling solution composition used is: 100g/L sulfuric acid and 0.15 ~ 0.20g/L thiocarbamide.The solution composition used of preimpregnation copper is: 100g/L sulfuric acid, 50g/L anhydrous cupric sulfate and 0.20g/L thiocarbamide.
(2) with the phosphorous copper coin of 15mm × 10mm × 0.2mm specification for anode, by level and smooth for sand papering, deionized water rinsing and oven dry before plating.
(3) by the electroplate liquid in pretreated anode and negative electrode immersion plating groove, just plating tank is placed in thermostat water bath, and the power set of air stirrer and movable cathode is installed for plating tank, the structural parameter of air stirrer and installation parameter are described in summary of the invention.Regulate movable cathode to be that laterally (i.e. left and right) swings, flutter rate is 20 ~ 25 times/min, and swing single direction stroke is 60mm.Bath temperature to be regulated makes temperature of electroplating solution maintain 15 ~ 30 DEG C, opens air pump switch, make pulse power supply, and the pulsewidth of pulsed current is 0.5 ~ 1ms, and dutycycle is 5 ~ 30%, and average current density is 2 ~ 4A/dm
2.After 20 ~ 60min to be energised, cut off the power supply of electroplanting device.Take out steel plate, use distilled water cleaning, drying.
Embodiment 1
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.5ms, and dutycycle is 30%, and average current density is 2A/dm
2; Temperature is 35 DEG C, and electroplating time is 60min.
Embodiment 2
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.6ms, and dutycycle is 25%, and average current density is 4A/dm
2; Temperature is 15 DEG C, and electroplating time is 50min.
Embodiment 3
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.7ms, and dutycycle is 20%, and average current density is 3A/dm
2; Temperature is 25 DEG C, and electroplating time is 30min.
Embodiment 4
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.9ms, and dutycycle is 15%, and average current density is 2.5A/dm
2; Temperature is 20 DEG C, and electroplating time is 40min.
Embodiment 5
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 1ms, and dutycycle is 5%, and average current density is 3.5A/dm
2; Temperature is 30 DEG C, and electroplating time is 35min.
Embodiment 6
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.8ms, and dutycycle is 10%, and average current density is 3A/dm
2; Temperature is 25 DEG C, and electroplating time is 40min.
With reference to following methods, stability test is carried out to the plating solution of embodiment 1 ~ 6:
The stability of plating solution is reflected with the ability of continuous electroplating number of times.Adopt the Hull groove of the HullCell267ml model of Kocour company of the U.S. at 3A/dm
2dC current density is electroplated at 25 DEG C of temperature.The tinsel of workpiece to be plated to be specification be 10cm × 6.5cm, these tinsels are inserted continuous electroplating in electroplate liquid, and each tinsel plating 5min terminates.Record until coating occur send out mist tinsel institute occur plating number of times, net result represents with electroplating time, i.e. electroplating time=plating number of times × 5 (unit is min).
With reference to following methods, dispersive ability test is carried out to the plating solution of embodiment 1 ~ 6:
The dispersive ability of plating solution adopts far and near cathode method (Haring-Blue method) to measure.Measure the Hull groove that groove adopts the HullCell267ml model of Kocour company of the U.S., interior dimensions is 150mm × 50mm × 70mm.Negative electrode selects thickness to be the copper sheet of 0.5mm, and working face is of a size of 50mm × 50mm; Anode is plating nickel plate with holes; Plating electric current 1A, electroplating time 30min.
The dispersive ability calculation formula of plating solution is:
Dispersive ability=[K-(the Δ M of plating solution
1/ Δ M
2)]/(K-1) (result represents with percentage);
In formula, K is negative electrode far away to the distance of anode and nearly negative electrode to the ratio of distances constant of anode, and in this test, K gets 2; Δ M
1for the increment (g) after plating on nearly negative electrode; Δ M
2for the increment (g) after plating on negative electrode far away.
With reference to following methods, covering power test is carried out to the plating solution of embodiment 1 ~ 6:
Endoporus method is adopted to measure.Negative electrode selects internal diameter l10mm, and pipe range is the copper pipe of 50mm, and one end is closed.During test, the distance of the mouth of pipe and anode is fixed on 80mm, test current 0.2A, electroplating time 30min.According to following formulae discovery:
Covering power=endoporus coating length/pipe range (result represents with percentage).
With reference to following methods, current efficiency test is carried out to the plating solution of embodiment 1 ~ 6:
Copper voltameter method is adopted to measure.Negative electrode to be tested and copper voltameter cleaned and dry up rear electronic scale weighing, then insert in electrodeposit groove by two negative electrodes simultaneously, be energized 10 ~ 30min, take out and clean dry up after use electronic scale weighing.According to following formulae discovery:
Current efficiency=(1.186 × cathode quality to be measured)/(electrochemical equivalent of copper voltameter quality × cathodic deposition metal to be measured) × 100%.Here, electrochemical equivalent=molar mass ÷ (depositing ions valency × 26.8), unit is g.A
-1.h
-1.In the embodiment of the present invention, cupric electrochemical equivalent is 1.186g.A
-1.h
-1.
Speed test is plated with reference to the plating solution of following methods to embodiment 1 ~ 6:
Mass method is adopted to measure sedimentation rate.Be 10 with sensitivity
-4electronic balance weighing sample plating before and after quality.By the acquisition sedimentation rate of poor quality of unit time, unit surface, press formulae discovery below:
Plating speed=(after plating before sample mass-plating sample mass)/(specimen surface to be plated long-pending × plating time).Each Data duplication is measured three times and is got its mean value.
Test with reference to the bonding force of following methods to the coating of embodiment 1 ~ 6:
The method adopting line to draw lattice measures the bonding force of coating, is specially: being 30 degree with one cutting edge by electrodeposition cladding, converted steel draws parallel lines or the 1mm that 2mm of being separated by drawn by cutter
2square lattice.Whether the coating observing line tilts or peels off.Should master the dynamics during line, a cutter just can scratch coating, arrives matrix metal.Adopt quench to measure the bonding force of coating, be specially: the test piece of having plated is placed in retort furnace quenching in the cold water being heated to 300 DEG C of insulation 30min taking-up immersion 10 DEG C immediately, observe coating and whether occur bubble and decortication phenomenon.
With reference to following methods, toughness test is carried out to the coating of embodiment 1 ~ 6:
Coating is stripped down, is bent to 180 °, and extrudes knee, observe coating and whether occur fracture.
With reference to following methods, porosity test is carried out to the coating of embodiment 1 ~ 6:
The large young pathbreaker of porosity is directly connected to the corrosion resisting property of coating, adopts paster method to press GB5935-86 standard detection.The etchant solution that the potassium ferricyanide solution of 10g/L and the sodium chloride solution of 20g/L are tested as porosity.Operation steps is: after wiped clean of being deoiled by coating surface, is close to coating surface with the filter paper soaking into etchant solution, and the two can not have gap.Buy the fully wetting filter paper of etchant solution solution by glass stick or degreasing swab stick, supplement a solution at interval of lmin, taken off by filter paper after 5min, dry after clean with distilled water flushing, record hole is counted.Be placed on cleaned glass plate and dry, the number of number Bluepoint.Substitute into formulae discovery voidage below:
Number/tested area (individual/the cm of porosity=spot
2);
When calculating number of apertures, do following calculating by spot diameter size: hot spot diameter is less than lmm, and with a porosimeter at often; Be greater than lmm and be less than 3mm often o'clock with three porosimeters; Be greater than 3mm and be less than 5mm, often with ten porosimeters.
With reference to following methods, Surface flat test is carried out to the coating of embodiment 1 ~ 6:
By the Hull groove of the HullCell267ml model with the Kocour company of the test piece U.S. after 200 order sand paperings evenly at 3A/dm
2dC current density carries out plating 10min at 25 DEG C of temperature, and whether then observe test piece has scratch.
To expose aptitude tests with reference to the coating of following methods to embodiment 1 ~ 6:
Adopt the Hull groove of the HullCell267ml model of Kocour company of the U.S. at 3A/dm
2after DC current density carries out plating 10min at 25 DEG C of temperature, observe the surface luminous intensity of coating.
The test result of the coating of embodiment 1 ~ 6 and comparative example and the performance of plating solution is as follows:
As can be seen from the above table, in embodiment 1 ~ 6, consider from the integration test effect of plating solution and coating, the dispersive ability of the formula plating solution of embodiment 6, covering power, current efficiency and plating speed, the porosity of coating and bonding force will be got well compared with other embodiment.Thus, this formula is screening formulation of the present invention, and the preferred plating conditions of its correspondence is the pulsewidth of monopulse rectangular wave current is 0.8ms, and dutycycle is 10%, and average current density is 3A/dm
2; Temperature is 25 DEG C, and electroplating time is 40min, and negative and positive area ratio is 2:3, the phosphorous 4wt% of cathode plate.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. an electroplate liquid for diphenyl methane dye system acid copper-plating, is characterized in that, comprises the CuSO that content is 190 ~ 220g/L
45H
2o, content are the H of 50 ~ 70g/L
2sO
4, content is the chlorion of 0.050 ~ 0.080g/L, content is the diphenyl methane dye of 0.15 ~ 0.25g/L, content is the thiazolinyl dithio propane sulfonic acid sodium of 0.010 ~ 0.018g/L, content is the alcohol mercapto propyl-sulfonate of 0.20 ~ 0.30g/L, content is the succinate sodium salt of 0.19 ~ 0.28g/L, content is the polyoxyethylene glycol of 0.048 ~ 0.06g/L, content is the aliphatic amide oxyethyl group sulfonated bodies of 0.016 ~ 0.028g/L and content is 0.03 ~ 0.045g/L polymine alkyl salt.
2. electroplate liquid according to claim 1, is characterized in that, comprises the CuSO that content is 208g/L
45H
2o, content are the H of 61g/L
2sO
4, the content chlorion that is 0.067g/L, the content diphenyl methane dye that is 0.18g/L, content is the thiazolinyl dithio propane sulfonic acid sodium of 0.013g/L, content is 0.26g/L alcohol mercapto propyl-sulfonate, the content succinate sodium salt that is 0.22g/L, content is the polyoxyethylene glycol of 0.057g/L, content is 0.020g/L aliphatic amide oxyethyl group sulfonated bodies and content is 0.036g/L polymine alkyl salt.
3. electroplate liquid according to claim 1, is characterized in that, described diphenyl methane dye is victoria blue B and/or auramine; Described molecular weight polyethylene glycol is 2000 ~ 8000.
4. use the electroplate liquid electric plating method described in claim 1, it is characterized in that, comprise the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains 190 ~ 220gCuSO
45H
2o, 50 ~ 70gH
2sO
4, 0.050 ~ 0.080g chlorion, 0.15 ~ 0.25g diphenyl methane dye, 0.010 ~ 0.018g thiazolinyl dithio propane sulfonic acid sodium, 0.20 ~ 0.30g alcohol mercapto propyl-sulfonate, 0.19 ~ 0.28g succinate sodium salt, 0.048 ~ 0.06g polyoxyethylene glycol, 0.016 ~ 0.028g aliphatic amide oxyethyl group sulfonated bodies and 0.03 ~ 0.045g polymine alkyl salt;
(2) insert with pretreated negative electrode and anode and pass into electric current in described electroplate liquid and electroplate.
5. method according to claim 4, is characterized in that, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 0.5 ~ 1ms, and dutycycle is 5 ~ 30%, and average current density is 2 ~ 4A/dm
2.
6. method according to claim 4, is characterized in that, the temperature of electroplate liquid is 15 ~ 35 DEG C.
7. method according to claim 4, is characterized in that, the time of plating is 20 ~ 60min.
8. method according to claim 4, is characterized in that, the material of described anode is the copper containing 0.35 ~ 0.05wt% phosphoric.
9. method according to claim 4, is characterized in that, in described step (2), plating is carried out under pneumatic blending and negative electrode stir, and the gas flow density of described pneumatic blending is 12 ~ 15m
3/ (h.m
2), the speed of described movable cathode is 20 ~ 30 times/min.
10. method according to claim 4, is characterized in that, in described step (2), the area ratio of negative electrode and positive electrode is (1/3 ~ 2): 1.
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| CN111748087A (en) * | 2020-07-20 | 2020-10-09 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | Dye modified PEG and application thereof in acid bright copper plating |
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| 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 |
| CN109137012A (en) * | 2018-11-14 | 2019-01-04 | 江西旭昇电子有限公司 | A kind of PCB electroplating gold liquid and its preparation method and application |
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| CN111424296A (en) * | 2020-05-18 | 2020-07-17 | 深圳市创智成功科技有限公司 | Electroplating copper solution for filling through holes of IC carrier plate and electroplating method |
| CN111424296B (en) * | 2020-05-18 | 2021-06-29 | 深圳市创智成功科技有限公司 | Electroplating copper solution for filling through holes of IC carrier plate and electroplating method |
| CN111748087A (en) * | 2020-07-20 | 2020-10-09 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | Dye modified PEG and application thereof in acid bright copper plating |
| CN111748087B (en) * | 2020-07-20 | 2022-06-21 | 国科温州研究院(温州生物材料与工程研究所) | Dye modified PEG and application thereof in acid bright copper plating |
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