CN103491727A - Method using printed circuit board graphite oxide reduction method to carry out hole conductivity - Google Patents
Method using printed circuit board graphite oxide reduction method to carry out hole conductivity Download PDFInfo
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- CN103491727A CN103491727A CN201310455237.4A CN201310455237A CN103491727A CN 103491727 A CN103491727 A CN 103491727A CN 201310455237 A CN201310455237 A CN 201310455237A CN 103491727 A CN103491727 A CN 103491727A
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Abstract
The invention relates to printed circuit board manufacturing, in particular to a method using a printed circuit board graphite oxide reduction method to carry out hole conductivity. The method solves the technical problems that dispersion liquid of carbon black or graphite dispersion liquid hole conductivity process is poor in stability and prone to being invalid and a carbon film layer formed on a hole wall is large in thickness. The method comprises the steps of firstly placing a printed circuit board into preprocessing liquid to process the hole wall of the PCB to improve the adhesion capacity of the hole wall to graphite oxide, then immersing the PCB into graphite oxide water solution to enable graphite oxide to be absorbed on a PCB face and the hole wall, forming a non-conductive graphite oxide layer after being dried, using a reducing agent to reduce the graphite oxide to obtain conductive reduced graphite oxide in a hole, cleaning and drying the PCB after micro copper etching, and directly electroplating the PCB. The method uses graphite oxide to carry out online reduction on the hole wall to enable the hole to be conductive, and is simple in component and good in processing liquid stability. Furthermore, a processed conductive film layer cannot affect follow-up copper plating binding force.
Description
Technical field
This paper relates to the printed circuit board (PCB) manufacture, relates in particular to a kind of method of printed circuit board aperture conductionization.
Background technology
Printed circuit board (PCB) be take nonconducting insulation board as base material, at least has a conductive pattern on it.In the Design and manufacture process, for the area that increases conductive pattern is just separated formation multi-layer sheet compressed together by the multilayer conductive figure with insulation board.And the connection that will realize conductive pattern between multi-layer sheet will be holed, and by nonconducting hole metallization.Hole metallization is the important technology during printed circuit board (PCB) is manufactured.And catalytic chemistry copper facing after the colloid palladium that tradition adopts activation, last electroplating hole copper completes hole metallization.This technological process is long, difficult in maintenance, pollution is heavy.
Mai Demei company is applied to carbon black hole metallization Direct Electroplating technology at first, by surfactants such as dispersants, carbon black is dispersed in the aqueous solution.To through the PCB adjusted, immerse in the carbon black dispersion liquid, carbon black granules is adsorbed on the dry rear carbon black layer that forms conduction on hole wall, can directly carry out sour copper plating.And this technique is named as black hole.And U.S. ElectroChem utilizes the micron order graphite dispersing solution as conductive processing liquid, the hole electricity conduction technique of formation is called shadow.This process using graphite rate is higher than carbon black, but because the graphite flake layer particle diameter is large, need to be at the thickness of controlling rete.Therefore to add the photographic fixing step after shadow technique, its essence is the contact acid solution, remove in conjunction with tight not graphite particulate and form uniform conductive layer.And above-mentioned two kinds of techniques add other component auxiliary agent in solution, can be mixed in carbon-coating and reduce conductance after film forming, to reach certain thickness in order to reach the required conductivity carbon-coating of plating, this will cause the adhesion of copper plate to descend.Carbon black or graphite are all hydrophobics on the other hand, need to add surfactant to envelope carbon granule hydrophilic radical is formed to colloid or suspension-turbid liquid towards the aqueous solution, itself be exactly on thermodynamics metastable state unstable, too low too high or sneak into impurity and all can destroy the stability of solution when solution temperature, cause that the coagulation of particle lost efficacy.
Summary of the invention
For the carbon dispersion stability that solves existing carbon black or graphite dispersing solution hole electricity conduction technique is poor, be easy to lose efficacy, the carbon film layer thickness formed at hole wall is large, affects the technical problem of adhesion.And proposition printed circuit board (PCB) graphite oxide reducing process is carried out the method for hole electricity conduction.
The method that printed circuit board (PCB) graphite oxide reducing process of the present invention is carried out hole electricity conduction is carried out according to the following steps:
One, the printed circuit board (PCB) of boring is put into to the pretreatment fluid immersion treatment;
Wherein pretreatment fluid is that binding agent is dissolved in solvent, then regulates pH to 9～10 rear formation by pH adjusting agent;
Binding agent is a kind of in potassium silicate, hydroxyethylcellulose, carboxymethyl cellulose, Sodium Polyacrylate, polyacrylamide, benzene emulsion, epoxy resin latex and poly-amino resins or several composition wherein;
Solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, acetone and water or several composition wherein;
Two, the printed circuit board (PCB) that will process through step 1 is dry after putting into the graphite oxide aqueous solution soaking and processing;
Wherein prepared by the graphite oxide aqueous solution according to the following steps: graphite oxide under agitation is added to the water, then adds the pH to 9 of pH adjusting agent regulator solution～10, then solution is carried out to ultrasonic dispersion and obtain the graphite oxide aqueous solution;
Three, immersion treatment in the use in printed circuit board reducing agent aqueous solution that will process through step 2 again;
Wherein reducing agent is a kind of in hydrazine hydrate, inferior sodium phosphate, ascorbic acid and sodium borohydride or several composition wherein;
Four, the use in printed circuit board copper etching solution immersion treatment that will process through step 3;
Wherein the copper etching solution is a kind of in monoethanolamine, sulfuric acid, sodium peroxydisulfate and hydrogen peroxide or several soluble in water the making of composition wherein;
Five, after the printed circuit board (PCB) after the step 4 processing is cleaned to post-drying, carry out Direct Electroplating copper in sour copper solution, obtain the copper conductive layer in hole.
The present invention is a kind of method that graphite oxide is adsorbed on in-situ reducing conductionization after hole wall, first printed circuit board (PCB) is put into to pretreatment fluid, processes the hole wall of pcb board, makes hole wall increase sticking graphite oxide.Printed circuit board (PCB) is immersed in the graphite oxide aqueous solution, graphite oxide is adsorbed on pcb board copper surface and hole wall again, the dry rear nonconducting aluminum oxide/graphite layer of one deck that forms; Utilize reductant solution, by the graphite oxide reduction, obtain the reduction-oxidation graphite of conduction; Printed circuit board (PCB), by copper being had to the solution that dissolves microetch role, is peeled off to the reduction-oxidation graphite linings on copper surface, make fresh copper face out exposed, ready for follow-up copper facing, and the reduction-oxidation graphite layer in hole is unaffected.Clean post-drying, can carry out Direct Electroplating copper in sour copper solution, plated with copper conductive layer in hole.
Graphite itself be hydrophobicity, be difficult to stable dispersion in the aqueous solution.In graphite-structure, carbon atom all forms three covalent single bonds with sp2 hybridized orbit and three contiguous carbon atoms and is arranged in the network structure of two dimensional surface hexagonal, is unified into plane parallel to each other with Van der Waals force between plane and forms layer structure.By with strong oxidizer, processing graphite, oxidized the opening of key graphite between layer by layer peeled off, and can form nano level graphite oxide.Graphite oxide has good hydrophily.In any dispersant aid interpolation situation, can in water, form stable suspension-turbid liquid.Yet graphite oxide itself is nonconducting, it is reduced into to graphite by reducing agent.After graphite oxide is reduced, can reunites in solution, then be difficult to dispersed.Therefore want the first nonconducting graphite oxide of absorption on hole wall, the online reduction-oxidation graphite of original position is realized at the hole inner conducting layer.
The present invention utilizes the hole electricity conduction of graphite oxide online reduction in the printed circuit board (PCB) hole wall, and the method compares former carbon black or graphite dispersing solution technique component is simple; The treatment fluid good stability can be used in the scope of temperature 5-65 ℃, and excessive temperature solution apparent coagulation can not occur, and is only that solution concentration and viscosity easily change.Finely disseminated graphite solution, after standing February, solution is without lamination; After processing, the electrically conductive graphite rete is thin, and the rete gross thickness is no more than 0.2 μ m.
The accompanying drawing explanation
Fig. 1 is the process chart that printed circuit board (PCB) graphite oxide reducing process of the present invention is carried out the method for hole electricity conduction;
Fig. 2 is the photo after 5 thermal shocks of the test 1 plating metapore obtained;
Fig. 3 is the experiment photo backlight in the hole of the through-hole aperture brassboard that completes hole metallization that is 0.20mm;
Fig. 4 is the experiment photo backlight in the hole of the through-hole aperture brassboard that completes hole metallization that is 0.25mm;
Fig. 5 is the experiment photo backlight in the hole of the through-hole aperture brassboard that completes hole metallization that is 0.30mm;
Fig. 6 is the experiment photo backlight in the hole of the through-hole aperture brassboard that completes hole metallization that is 0.50mm;
Fig. 7 is the experiment photo backlight in the hole of the through-hole aperture brassboard that completes hole metallization that is 0.80mm;
Fig. 8 is the experiment photo backlight in the hole of the through-hole aperture brassboard that completes hole metallization that is 1.00mm;
Embodiment
Embodiment one: the printed circuit board (PCB) graphite oxide reducing process of present embodiment is carried out the method for hole electricity conduction and is carried out according to the following steps:
One, will put into the pretreatment fluid immersion treatment with the printed circuit board (PCB) of through hole; Wherein pretreatment fluid is that binding agent is dissolved in solvent, then regulates pH to 9～10 rear formation by pH adjusting agent; Binding agent is a kind of in potassium silicate, hydroxyethylcellulose, carboxymethyl cellulose, Sodium Polyacrylate, polyacrylamide, benzene emulsion, epoxy resin latex and poly-amino resins or several composition wherein; Solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, acetone and water or several composition wherein;
The hole wall of this step process printed circuit board (PCB), make hole wall increase sticking graphite oxide;
Two, the printed circuit board (PCB) that will process through step 1 is dry again after putting into the graphite oxide aqueous solution soaking and processing; Wherein prepared by the graphite oxide aqueous solution according to the following steps: graphite oxide under agitation is added to the water, then adds the pH to 9 of pH adjusting agent regulator solution～10, then solution is carried out to ultrasonic dispersion and obtain the graphite oxide aqueous solution;
Through the processing of this step, graphite oxide is adsorbed on printed circuit board (PCB) face and hole wall, the dry rear nonconducting aluminum oxide/graphite layer of one deck that forms;
Three, immersion treatment in the use in printed circuit board reducing agent aqueous solution that will process through step 2 again; Wherein reducing agent is a kind of in hydrazine hydrate, inferior sodium phosphate, ascorbic acid and sodium borohydride or several composition wherein;
Reducing agent in this step can reduction-oxidation graphite hydroxyl, the carboxyl of special groups, obtain the reduction-oxidation graphite of conduction after reduction;
Four, the use in printed circuit board copper etching solution immersion treatment that will process through step 3; Wherein the copper etching solution is a kind of in monoethanolamine, sulfuric acid, sodium peroxydisulfate and hydrogen peroxide or several soluble in water the making of composition wherein;
The copper etching solution has the corrosion dissolution effect to copper, and on plastic base and not impact of conductive carbon layer, effect by the copper etching solution, peel off the reduction-oxidation graphite linings on copper surface, make fresh copper face out exposed, ready for follow-up copper facing, and the reduction-oxidation graphite layer in hole is unaffected.
Five, after the printed circuit board (PCB) after the step 4 processing is cleaned to post-drying, carry out Direct Electroplating copper in sour copper solution, obtain the copper conductive layer in hole.
Embodiment two: present embodiment is different from embodiment one be in step 1 in pretreatment fluid the mass percentage concentration of binding agent be 0.01%～1.00%; Other are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is that in step 1, pH adjusting agent is a kind of in potassium hydroxide, potassium silicate, potassium sulfate, potash and saleratus or several composition wherein; Other are identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that in step 1, soak time is 0.5～10min; Other are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four is that in step 2, graphite oxide is by chemical method, to adopt Hummer or Staudenmaier method to carry out the oxidation intercalation to crystalline flake graphite or pyrolytic graphite to obtain graphite oxide, or adopts the dilatometry preparation; Other are identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five is that in step 2, pH adjusting agent is a kind of in potassium hydroxide, potassium silicate, potassium sulfate, potash and saleratus or several compositions wherein; Other are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six be while preparing the graphite oxide aqueous solution in step 2 the time of ultrasonic dispersion be 20～40min; Other are identical with one of embodiment one to six.
It is more even that ultrasonic processing disperses graphite oxide.
Embodiment eight: present embodiment is different from one of embodiment one to seven be in step 2 in the graphite oxide aqueous solution mass percent concentration of graphite oxide be 0.05%～2.00%; Other are identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is that in step 2, soak time is 0.5～10min; Other are identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine be in step 3 in the reducing agent aqueous solution mass percentage concentration of reducing agent be 0.1%～4.0%; Other are identical with one of embodiment one to nine.
Embodiment 11: what present embodiment was different from one of embodiment one to ten is that in step 3, soak time is 5～40min; Other are identical with one of embodiment one to ten.
Embodiment 12: what present embodiment was different from one of embodiment one to 11 is that in step 4, soak time is 0.1～5min; Other are identical with one of embodiment one to 11.
Embodiment 13: what present embodiment was different from one of embodiment one to 12 is that in step 5, sour copper solution is the through hole copper plating solution with the low copper feature of peracid; Other are identical with one of embodiment one to 12.
The through hole copper plating solution with the low copper feature of peracid of present embodiment is prior art.
Embodiment 14: present embodiment is different from one of embodiment one to 13 is that the Parameter Conditions of electro-coppering in the step 5 step 5 is: use air stirring, current density is 2A/dm
2, plating time is 60min.Other is identical with one of embodiment one to 13.
With following verification experimental verification beneficial effect of the present invention:
Choosing with the double-sided copper-clad epoxy resin fiberglass layer pressing plate of through hole is experiment sheet material, and board size is 100mm * 80mm, thickness of slab 1.5mm, and through-hole aperture is respectively 1.00,0.80,0.50,0.30,0.25,0.20mm.
Test 1: the printed circuit board (PCB) graphite oxide reducing process of the present embodiment is carried out the method for hole electricity conduction and is carried out according to the following steps:
One, take each 1g of hydroxyethylcellulose and polyacrylamide, the mixed solution of second alcohol and water of take is solvent, wherein in solvent, the quality percentage composition of ethanol is 10%, under stirring condition, hydroxyethylcellulose and polyacrylamide are added in the 500mL solvent, be stirred to fully and dissolve, then add potassium hydroxide to regulate pH to 10, be made into pretreatment fluid; The printed circuit board (PCB) of boring is put into to pretreatment fluid and soak 4min;
Two, by the 5g graphite oxide, under agitation slowly add in 500mL water; Then adding potassium hydroxide to regulate pH is 10, then solution is carried out to ultrasonic dispersion 30min, obtains the graphite oxide aqueous solution; The printed circuit board (PCB) that to process through step 1 is put into graphite oxide aqueous solution soaking 4min, then uses the lower hot-air seasoning of 80 ℃;
Wherein graphite oxide adopts the Hummer method to obtain crystalline flake graphite oxidation intercalation by chemical method.Concrete technological process: put into the there-necked flask of 250mL in the water-bath of ice, add the concentrated sulfuric acid of 100mL, keep temperature lower than 20 ℃, slowly add 2g crystalline flake graphite ink powder under stirring, gradation adds 6g potassium permanganate again, and maintains reaction temperature lower than 20 ℃, reaction 1h.Be warmed up to 35 ℃, continue stir 45min, add the deionized water of 500mL, continuous mix 40min after, and add 100mL hydrogen peroxide and 1.5L deionized water, 24h is stirred in reaction.Filtering reacting solution, and with 5%HCl cyclic washing product three times, with until the sulfate radical-free ion be detected.The vacuum drying chamber that finally filter cake is placed in to 60 ℃ is fully dry, obtains graphite oxide, saves backup.
Three, sodium borohydride 5g is added in 500ml water and is mixed with the reducing agent aqueous solution, then soak 10min in the use in printed circuit board reducing agent aqueous solution that will process through step 2;
Four, the concentration that is 150g/L, the concentrated sulfuric acid by the concentration of sodium peroxydisulfate is that 10g/L adds sodium peroxydisulfate and the concentrated sulfuric acid in deionized water, mixes, and obtains the copper etching solution; The use in printed circuit board copper etching solution that to process through step 3 soaks 0.5min;
Five, after the use in printed circuit board washed with de-ionized water after the step 4 processing is removed to remaining graphite, then drying,, in PCB through hole copper plating solution, is then 2A/dm in current density
2condition under carry out Direct Electroplating copper 10min, obtain the copper conductive layer in hole, complete hole metallization.
PCB through hole copper plating solution is sour ketone solution, and purchased from Guangdong Zhizhuo Precision Metal Technology Co., Ltd., its model is IMT-350H acid copper additives.Its basic components is 50～70g/L CuSO
45H
2o, 200～260g/L H
2sO
4, 50～80mg/L Cl
-, add sour copper to open cylinder agent, brightening agent for acid copper electroplating and sour copper leveling agent.
Thermal shock experiment reference standard IPC-TM-650.The tin furnace temperature rises to 288 ℃, will soak scaling powder and be placed on the molten tin surface with ventilating hole plate, after each ten seconds, takes out and is cooled to room temperature, repeats five times.The photo after 5 thermal shocks of the plating metapore that this test obtains as shown in Figure 2, copper coating thickness reaches 25 μ m as can be seen from Figure 2, after thermal shock 5 times, the section of making sample can be observed in hole and all be coated with uniform copper plate, and atresia copper is broken and the hole wall segregation phenomenon.
Fig. 3～Fig. 8 is respectively that through-hole aperture is 0.20,0.25,0.30,0.50,0.80 and the experiment photo backlight in the hole of the brassboard that completes hole metallization of 1.00mm, the concrete grammar of experiment backlight is exactly breadboard to be cut to one with porose baseplate material, make sample, passes through sawing or grinds center, hole (being on center line).During test, utilize light to inject from bottom surface, then use magnifying glass inspection to get final product.As can be seen from Fig., after the plating of 10min, without large tracts of land plating leakage and pin hole, occur, the hole wall that the copper layer can complete covering different pore size has blocked light privately.
(do not electroplate) after this method hole electricity conduction technique, with universal instrument, be adjusted to the ohms range two test pencils resistance of the conductive copper layer instrument connection reduction-oxidation graphite layer of the both sides of contact print circuit board respectively, the single hole resistance value is 10000～50000 Ω.
After the graphite oxide aqueous solution in this test procedure two at room temperature standing 2 months, solution obviously, without the deposition lamination, illustrates that this aqueous stability is fabulous.
Test 2: the printed circuit board (PCB) graphite oxide reducing process of this test is carried out the method for hole electricity conduction and is carried out according to the following steps:
One, take each 1g of hydroxyethylcellulose and polyacrylamide, the mixed solution of second alcohol and water of take is solvent, wherein in solvent, the quality percentage composition of ethanol is 10%, under stirring condition, hydroxyethylcellulose and polyacrylamide are added in the 500mL solvent, be stirred to fully and dissolve, then add potassium hydroxide to regulate pH to 10, be made into pretreatment fluid; The printed circuit board (PCB) of boring is put into to pretreatment fluid and soak 4min;
Two, the 2.5g graphite oxide is under agitation added in 500mL water; Then adding potassium hydroxide to regulate pH is 10, then solution is carried out to ultrasonic dispersion 30min, obtains the graphite oxide aqueous solution; The printed circuit board (PCB) that to process through step 1 is put into graphite oxide aqueous solution soaking 4min, then uses the lower hot-air seasoning of 80 ℃;
Wherein graphite oxide adopts Hummer to obtain crystalline flake graphite oxidation intercalation by chemical method, and concrete grammar is with test 1;
Three, sodium borohydride 5g is added in 500ml water and is mixed with the reducing agent aqueous solution, then soak 10min in the use in printed circuit board reducing agent aqueous solution that will process through step 2;
Four, the concentration that is 150g/L, the concentrated sulfuric acid by the concentration of sodium peroxydisulfate is that 10g/L adds sodium peroxydisulfate and the concentrated sulfuric acid in deionized water, mixes, and obtains the copper etching solution; The use in printed circuit board copper etching solution that to process through step 3 soaks 0.5min;
Five, after the use in printed circuit board washed with de-ionized water after the step 4 processing is removed to remaining graphite, then drying,, in sour copper solution, is then 2A/dm in current density
2condition under carry out Direct Electroplating copper 20min, obtain the copper conductive layer in hole, complete hole metallization.
Wherein the sour copper solution in step 5 is purchased from Guangdong Zhizhuo Precision Metal Technology Co., Ltd.;
The making sample section after 5 thermal shocks of plating metapore can be observed in hole and all be coated with uniform copper plate, and atresia copper is broken and the hole wall segregation phenomenon.The plate face is through occurring without large tracts of land plating leakage and pin hole through electroplating the back optical tests in copper plating solution after conductionization, the hole wall that the copper layer can complete covering different pore size.
Test 3: the printed circuit board (PCB) graphite oxide reducing process of this test is carried out the method for hole electricity conduction and is carried out according to the following steps:
One, take each 1g of hydroxyethylcellulose and polyacrylamide, the mixed solution of second alcohol and water of take is solvent, wherein in solvent, the quality percentage composition of ethanol is 10%, under stirring condition, hydroxyethylcellulose and polyacrylamide are added in the 500mL solvent, be stirred to fully and dissolve, then add potassium hydroxide to regulate pH to 10, be made into pretreatment fluid; The printed circuit board (PCB) of boring is put into to pretreatment fluid and soak 4min;
Two, the 2.5g graphite oxide is under agitation added in 500mL water; Then adding potassium hydroxide to regulate pH is 10, then solution is carried out to ultrasonic dispersion 30min, obtains the graphite oxide aqueous solution; The printed circuit board (PCB) that to process through step 1 is put into graphite oxide aqueous solution soaking 4min, then uses the lower hot-air seasoning of 80 ℃;
Wherein graphite oxide adopts Hummer to obtain crystalline flake graphite oxidation intercalation by chemical method, and concrete grammar is with embodiment 1;
Three, sodium borohydride 10g is added in 500ml water and is mixed with the reducing agent aqueous solution, then soak 5min in the use in printed circuit board reducing agent aqueous solution that will process through step 2;
Four, the concentration that is 150g/L, the concentrated sulfuric acid by the concentration of sodium peroxydisulfate is that 10g/L adds sodium peroxydisulfate and the concentrated sulfuric acid in deionized water, mixes, and obtains the copper etching solution; The use in printed circuit board copper etching solution that to process through step 3 soaks 0.5min;
Five, after the use in printed circuit board washed with de-ionized water after the step 4 processing is removed to remaining graphite, then drying,, in sour copper solution, is then 2A/dm in current density
2condition under carry out Direct Electroplating copper 60min, obtain the copper conductive layer in hole, complete hole metallization.
Wherein the sour copper solution in step 5 is purchased from Guangdong Zhizhuo Precision Metal Technology Co., Ltd.;
The making sample section after 5 thermal shocks of plating metapore can be observed in hole and all be coated with uniform copper plate, and atresia copper is broken and the hole wall segregation phenomenon.The plate face is through occurring without large tracts of land plating leakage and pin hole through electroplating the back optical tests in copper plating solution after conductionization, the hole wall that the copper layer can complete covering different pore size.
Claims (10)
1. printed circuit board (PCB) graphite oxide reducing process is carried out the method for hole electricity conduction, it is characterized in that the method carries out according to the following steps:
One, the printed circuit board (PCB) of boring is put into to the pretreatment fluid immersion treatment; Wherein pretreatment fluid is that binding agent is dissolved in solvent, then regulates pH to 9～10 rear formation by pH adjusting agent; Binding agent is a kind of in potassium silicate, hydroxyethylcellulose, carboxymethyl cellulose, Sodium Polyacrylate, polyacrylamide, benzene emulsion, epoxy resin latex and poly-amino resins or several composition wherein; Solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, acetone and water or several composition wherein;
Two, the printed circuit board (PCB) that will process through step 1 is dry again after putting into the graphite oxide aqueous solution soaking and processing; Wherein prepared by the graphite oxide aqueous solution according to the following steps: graphite oxide under agitation is added to the water, then adds the pH to 9 of pH adjusting agent regulator solution～10, then solution is carried out to ultrasonic dispersion and obtain the graphite oxide aqueous solution;
Three, immersion treatment in the use in printed circuit board reducing agent aqueous solution that will process through step 2 again; Wherein reducing agent is a kind of in hydrazine hydrate, inferior sodium phosphate, ascorbic acid and sodium borohydride or several composition wherein;
Four, the use in printed circuit board copper etching solution immersion treatment that will process through step 3; Wherein the copper etching solution is a kind of in monoethanolamine, sulfuric acid, sodium peroxydisulfate and hydrogen peroxide or several soluble in water the making of composition wherein;
Five, after the printed circuit board (PCB) after the step 4 processing is cleaned to post-drying, carry out Direct Electroplating copper in sour copper solution, obtain the copper conductive layer in hole.
2. printed circuit board (PCB) graphite oxide reducing process according to claim 1 is carried out the method for hole electricity conduction, it is characterized in that in step 1 in pretreatment fluid that the mass percentage concentration of binding agent is 0.01%～1.00%.
3. printed circuit board (PCB) graphite oxide reducing process according to claim 1 and 2 is carried out the method for hole electricity conduction, it is characterized in that pH adjusting agent in step 1 is a kind of in potassium hydroxide, potassium silicate, potassium sulfate, potash and saleratus or several composition wherein.
4. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, it is characterized in that in step 1, soak time is 0.5～10min.
5. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, and while it is characterized in that in step 2 preparing the graphite oxide aqueous solution, the time of ultrasonic dispersion is 20～40min.
6. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, it is characterized in that in step 2 in the graphite oxide aqueous solution that the mass percent concentration of graphite oxide is 0.05%～2.00%.
7. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, it is characterized in that in step 2, soak time is 0.5～10min.
8. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, it is characterized in that in step 3 in the reducing agent aqueous solution that the mass percentage concentration of reducing agent is 0.1%～4.0%.
9. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, it is characterized in that in step 3, soak time is 5～40min.
10. printed circuit board (PCB) graphite oxide reducing process according to claim 3 is carried out the method for hole electricity conduction, it is characterized in that in step 4, soak time is 0.1～5min.
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| CN112888152A (en) * | 2014-11-21 | 2021-06-01 | 安费诺公司 | Mating backplane for high speed, high density electrical connectors |
| US11950356B2 (en) | 2014-11-21 | 2024-04-02 | Amphenol Corporation | Mating backplane for high speed, high density electrical connector |
| CN104818506A (en) * | 2015-05-28 | 2015-08-05 | 哈尔滨工业大学 | Solution for metalizing printed circuit board hole |
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| CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
| CN109811382A (en) * | 2019-03-28 | 2019-05-28 | 烟台恒诺新材料有限公司 | A kind of application of graphene oxide conductive paste in black holesization is directly electroplated |
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| CN110923771A (en) * | 2019-12-16 | 2020-03-27 | 电子科技大学 | Through hole electroplating method of printed circuit board |
| CN113207243A (en) * | 2021-05-08 | 2021-08-03 | 电子科技大学中山学院 | Preparation and application method of black hole liquid |
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