CN103491727B - Printed circuit board (PCB) graphite oxide reducing process carries out the method for hole electricity conduction - Google Patents
Printed circuit board (PCB) graphite oxide reducing process carries out the method for hole electricity conduction Download PDFInfo
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- CN103491727B CN103491727B CN201310455237.4A CN201310455237A CN103491727B CN 103491727 B CN103491727 B CN 103491727B CN 201310455237 A CN201310455237 A CN 201310455237A CN 103491727 B CN103491727 B CN 103491727B
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Abstract
Printed circuit board (PCB) graphite oxide reducing process carries out the method for hole electricity conduction, and it relates to printed circuit board (PCB) manufacture, particularly relates to a kind of method of printed circuit board aperture conductionization.The present invention is that the dispersion stability difference for solving carbon black or graphite dispersing solution hole electricity conduction technique is easy to lose efficacy, in the technical problem that the carbon film layer thickness of hole wall formation is large.This method: first printed circuit board (PCB) is put into pretreatment fluid, the hole wall of process pcb board, makes the Adhering capacity of hole wall increase to graphite oxide; Immerse in the graphite oxide aqueous solution again, graphite oxide is adsorbed on pcb board face and hole wall, forms the nonconducting aluminum oxide/graphite layer of one deck after dry; Utilize reductant solution, graphite oxide is reduced, in hole, obtain the reduction-oxidation graphite conducted electricity; Microetch copper cleaning post-drying: carry out Direct Electroplating again.The method utilizes graphite oxide online reduction on hole wall to make hole electricity conduction, and component is simple, treatment fluid good stability, conductive film layer is thin after process does not affect follow-up copper plate adhesion.
Description
Technical field
Relate to printed circuit board (PCB) manufacture herein, particularly relate to a kind of method of printed circuit board aperture conductionization.
Background technology
Printed circuit board (PCB) for base material, it at least has a conductive pattern with nonconducting insulation board.In Design and manufacture process, in order to multilayer conductive figure is just separated formation multi-layer sheet compressed together with insulation board by the area increasing conductive pattern.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) manufactures.And catalytic chemistry copper facing after the colloid palladium activation that tradition adopts, last electroplating hole copper completes hole metallization.This technological process is long, difficult in maintenance, pollution is heavy.
Carbon black is applied to hole metallization Direct Electroplating technology by Mai Demei company at first, by surfactants such as dispersants by black dispersion in aqueous.Immerse in carbon black dispersion by the PCB through adjustment, carbon black granules is adsorbed on the dry rear carbon black layer forming conduction on hole wall, can directly carry out sour copper plating.And this technique is named as black holes.And ElectroChem of the U.S. utilizes micron order graphite dispersing solution as conductive processing liquid, the hole electricity conduction technique of formation is called shadow.This technique adopts graphite rate higher than carbon black, but due to graphite flake layer particle diameter large, need at the thickness controlling rete.Therefore will add fix steps after shadow technique, its essence is contact acid solution, removing combines graphite particulate tight not and forms 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, in order to the conductivity carbon-coating reached needed for plating will reach certain thickness, this will cause the adhesion of copper plate to decline.On the other hand carbon black or graphite is all hydrophobic, need to add surfactant and envelope carbon granule by hydrophilic radical towards aqueous solution formation colloid or suspension-turbid liquid, it itself is exactly metastable state instability on thermodynamics, when solution temperature is too low too high or be mixed into the stability that impurity all can destroy solution, the coagulation of particle is caused to lose efficacy.
Summary of the invention
In order to the carbon dispersion stability difference solving existing carbon black or graphite dispersing solution hole electricity conduction technique is easy to lose efficacy, the carbon film layer thickness formed at hole wall is large, affects the technical problem of adhesion.And the method that printed circuit board (PCB) graphite oxide reducing process carries out hole electricity conduction is proposed.
The method that printed circuit board (PCB) graphite oxide reducing process of the present invention carries out hole electricity conduction is carried out according to the following steps:
One, the printed circuit board (PCB) of boring is put into pretreatment fluid immersion treatment;
Wherein pretreatment fluid is dissolved in solvent by binding agent, then formed after regulating pH to 9 ~ 10 by pH adjusting agent;
Binding agent is a kind of or wherein several composition in potassium silicate, hydroxyethylcellulose, carboxymethyl cellulose, Sodium Polyacrylate, polyacrylamide, benzene emulsion, epoxy resin latex and poly-amino resins;
Solvent is a kind of or wherein several composition in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, acetone and water;
Two, dry after the printed circuit board (PCB) processed through step one being put into the process of graphite oxide aqueous solution soaking;
Wherein the graphite oxide aqueous solution is prepared according to the following steps: be under agitation added to the water by graphite oxide, then adds pH to 9 ~ 10 that pH adjusting agent regulates solution, then solution is carried out ultrasonic disperse and obtain the graphite oxide aqueous solution;
Three, again by the use in printed circuit board reducing agent aqueous solution soaking process through step 2 process;
Wherein reducing agent is a kind of or wherein several composition in hydrazine hydrate, inferior sodium phosphate, ascorbic acid and sodium borohydride;
Four, by the use in printed circuit board copper etching solution immersion treatment through step 3 process;
Wherein to be that a kind of or wherein several composition in monoethanolamine, sulfuric acid, sodium peroxydisulfate and hydrogen peroxide is soluble in water make copper etching solution;
Five, by after the printed circuit board (PCB) cleaning after step 4 process, oven dry, in sour copper solution, carry out Direct Electroplating copper, in hole, obtain copper conductive layer.
The present invention is a kind of method that graphite oxide is adsorbed on in-situ reducing conductionization after hole wall, namely first printed circuit board (PCB) is put into pretreatment fluid, the hole wall of process pcb board, makes hole wall increase sticking graphite oxide.Immersed by printed circuit board (PCB) in the graphite oxide aqueous solution, graphite oxide is adsorbed on pcb board copper surface and hole wall, forms the nonconducting aluminum oxide/graphite layer of one deck after dry again; Utilize reductant solution, graphite oxide is reduced, obtain the reduction-oxidation graphite conducted electricity; Printed circuit board (PCB) being dissolved the solution of microetch role by having copper, peeling off the reduction-oxidation graphite linings on copper surface, making fresh copper face out exposed, for follow-up copper facing is ready, and reduction-oxidation graphite guide electric layer in hole is unaffected.Cleaning post-drying, can carry out Direct Electroplating copper, plated with copper conductive layer in hole in sour copper solution.
Graphite itself be hydrophobicity, be difficult to stable dispersion in aqueous.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 is formed layer structure between plane with Van der Waals force.By processing graphite with strong oxidizer, graphite layer by layer between key oxidizedly open stripping, nano level graphite oxide can be formed.Graphite oxide has good hydrophily.Without in any dispersant aid interpolation situation, stable suspension-turbid liquid can be formed in water.But graphite oxide itself is nonconducting, graphite to be reduced into by reducing agent.After graphite oxide is reduced, can reunite in the solution, then be difficult to dispersed.Therefore want first on hole wall, to adsorb nonconducting graphite oxide, the online reduction-oxidation graphite of original position realizes at hole inner conducting layer.
The present invention utilizes the hole electricity conduction of graphite oxide online reduction in printed circuit board (PCB) hole wall, and the method compares former carbon black or graphite dispersing solution process component is simple; Treatment fluid good stability, can using in the scope of temperature 5-65 DEG C, can not there is apparent coagulation in excessive temperature solution, is only that solution concentration and viscosity easily change.Finely disseminated graphite solution, after leaving standstill February, solution is without lamination; After process, electrically conductive graphite rete is thin, and rete gross thickness is no more than 0.2 μm.
Accompanying drawing explanation
Fig. 1 is the process chart that printed circuit board (PCB) graphite oxide reducing process of the present invention carries out the method for hole electricity conduction;
Fig. 2 is the photo after 5 thermal shocks of the plating metapore that test 1 obtains;
The backlight experiment photo completing the hole of the brassboard of hole metallization of Fig. 3 to be through-hole aperture be 0.20mm;
The backlight experiment photo completing the hole of the brassboard of hole metallization of Fig. 4 to be through-hole aperture be 0.25mm;
The backlight experiment photo completing the hole of the brassboard of hole metallization of Fig. 5 to be through-hole aperture be 0.30mm;
The backlight experiment photo completing the hole of the brassboard of hole metallization of Fig. 6 to be through-hole aperture be 0.50mm;
The backlight experiment photo completing the hole of the brassboard of hole metallization of Fig. 7 to be through-hole aperture be 0.80mm;
The backlight experiment photo completing the hole of the brassboard of hole metallization of Fig. 8 to be through-hole aperture be 1.00mm;
Embodiment
Embodiment one: the method that the printed circuit board (PCB) graphite oxide reducing process of present embodiment carries out hole electricity conduction is carried out according to the following steps:
One, the printed circuit board (PCB) with through hole is put into pretreatment fluid immersion treatment; Wherein pretreatment fluid is dissolved in solvent by binding agent, then formed after regulating pH to 9 ~ 10 by pH adjusting agent; Binding agent is a kind of or wherein several composition in potassium silicate, hydroxyethylcellulose, carboxymethyl cellulose, Sodium Polyacrylate, polyacrylamide, benzene emulsion, epoxy resin latex and poly-amino resins; Solvent is a kind of or wherein several composition in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, acetone and water;
The hole wall of this step process printed circuit board (PCB), makes hole wall increase sticking graphite oxide;
Two, dry again after the printed circuit board (PCB) processed through step one being put into the process of graphite oxide aqueous solution soaking; Wherein the graphite oxide aqueous solution is prepared according to the following steps: be under agitation added to the water by graphite oxide, then adds pH to 9 ~ 10 that pH adjusting agent regulates solution, then solution is carried out ultrasonic disperse and obtain the graphite oxide aqueous solution;
Through the process of this step, graphite oxide is adsorbed on printed circuit board (PCB) face and hole wall, forms the nonconducting aluminum oxide/graphite layer of one deck after dry;
Three, again by the use in printed circuit board reducing agent aqueous solution soaking process through step 2 process; Wherein reducing agent is a kind of or wherein several composition in hydrazine hydrate, inferior sodium phosphate, ascorbic acid and sodium borohydride;
Reducing agent in this step can hydroxyl, the carboxyl of special groups of reduction-oxidation graphite, obtains the reduction-oxidation graphite conducted electricity after reduction;
Four, by the use in printed circuit board copper etching solution immersion treatment through step 3 process; Wherein to be that a kind of or wherein several composition in monoethanolamine, sulfuric acid, sodium peroxydisulfate and hydrogen peroxide is soluble in water make copper etching solution;
Copper etching solution has corrosion dissolution effect to copper, and plastic base and conductive carbon layer are not affected, by the effect of copper etching solution, peel off the reduction-oxidation graphite linings on copper surface, make fresh copper face out exposed, for follow-up copper facing is ready, and reduction-oxidation graphite guide electric layer in hole is unaffected.
Five, by after the printed circuit board (PCB) cleaning after step 4 process, oven dry, in sour copper solution, carry out Direct Electroplating copper, in hole, obtain copper conductive layer.
Embodiment two: present embodiment and embodiment one are 0.01% ~ 1.00% unlike the mass percentage concentration of binding agent in pretreatment fluid in step one; Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are a kind of or wherein several composition in potassium hydroxide, potassium silicate, potassium sulfate, potash and saleratus unlike pH adjusting agent in step one; Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are 0.5 ~ 10min unlike soak time in step one; Other are identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are adopt Hummer or Staudenmaier method to carry out oxidation intercalation to crystalline flake graphite or pyrolytic graphite by chemical method to obtain graphite oxide unlike graphite oxide in step 2, or adopt dilatometry preparation; Other are identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are one in potassium hydroxide, potassium silicate, potassium sulfate, potash and saleratus or wherein several composition unlike pH adjusting agent in step 2; Other are identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are 20 ~ 40min unlike the time of ultrasonic disperse when preparing the graphite oxide aqueous solution in step 2; Other are identical with one of embodiment one to six.
It is more even that ultrasonic process makes graphite oxide disperse.
Embodiment eight: one of present embodiment and embodiment one to seven are 0.05% ~ 2.00% unlike the mass percent concentration of graphite oxide in the graphite oxide aqueous solution in step 2; Other are identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are 0.5 ~ 10min unlike soak time in step 2; Other are identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine are 0.1% ~ 4.0% unlike the mass percentage concentration of reducing agent in the reducing agent aqueous solution in step 3; Other are identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten are 5 ~ 40min unlike soak time in step 3; Other are identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one are 0.1 ~ 5min unlike soak time in step 4; Other are identical with one of embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two are the through hole copper plating solution with the low copper feature of peracid unlike copper solution sour in step 5; Other are identical with one of embodiment one to ten two.
The through hole copper plating solution with the low copper feature of peracid of present embodiment is prior art.
Embodiment 14: one of present embodiment and embodiment one to ten three unlike the Parameter Conditions of electro-coppering in step 5 are: with air stirring, current density is 2A/dm
2, plating time is 60min.Other is identical with one of embodiment one to ten three.
With following verification experimental verification beneficial effect of the present invention:
The double-sided copper-clad epoxy resin fiberglass layer pressing plate chosen with through hole is experiment sheet material, and board size is 100mm × 80mm, thickness of slab 1.5mm, through-hole aperture is respectively 1.00,0.80,0.50,0.30,0.25,0.20mm.
Test 1: the method that the printed circuit board (PCB) graphite oxide reducing process of the present embodiment carries out hole electricity conduction is carried out according to the following steps:
One, hydroxyethylcellulose and each 1g of polyacrylamide is taken, with the mixed solution of second alcohol and water for solvent, wherein in solvent, the mass percentage of ethanol is 10%, under agitation, hydroxyethylcellulose and polyacrylamide are added in 500mL solvent, be stirred to and dissolve completely, then add potassium hydroxide and regulate pH to 10, be made into pretreatment fluid; The printed circuit board (PCB) of boring is put into pretreatment fluid and soaks 4min;
Two, 5g graphite oxide is under agitation slowly added in 500mL water; Then adding potassium hydroxide regulates pH to be 10, then solution is carried out ultrasonic disperse 30min, obtains the graphite oxide aqueous solution; The printed circuit board (PCB) processed through step one is put into graphite oxide aqueous solution soaking 4min, then uses the lower hot-air seasoning of 80 DEG C;
Wherein graphite oxide adopts Hummer method to obtain crystalline flake graphite oxidation intercalation by chemical method.Concrete technological process: the there-necked flask putting into 250mL in the water-bath of ice, adds the concentrated sulfuric acid of 100mL, keeps temperature lower than 20 DEG C, 2g crystalline flake graphite ink powder is slowly added under stirring, gradation adds 6g potassium permanganate again, and maintains reaction temperature lower than 20 DEG C, reaction 1h.Be warmed up to 35 DEG C, continue to stir 45min, add the deionized water of 500mL, continue after mixing 40min, 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, till being detected until sulfate radical-free ion.The vacuum drying chamber finally filter cake being placed in 60 DEG C is fully dry, obtains graphite oxide, saves backup.
Three, sodium borohydride 5g is added in 500ml water be mixed with the reducing agent aqueous solution, then by the use in printed circuit board reducing agent aqueous solution soaking 10min through step 2 process;
Four, by the concentration of sodium peroxydisulfate be 150g/L, the concentration of the concentrated sulfuric acid is that sodium peroxydisulfate and the concentrated sulfuric acid add in deionized water by 10g/L, mix, obtain copper etching solution; Use in printed circuit board copper etching solution through step 3 process is soaked 0.5min;
Five, by after graphite remaining for the use in printed circuit board washed with de-ionized water removing after step 4 process, then dry, being then placed in PCB through hole copper plating solution, is 2A/dm in current density
2condition under carry out Direct Electroplating copper 10min, in hole, obtain copper conductive layer, complete hole metallization.
PCB through hole copper plating solution is sour copper 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/LCuSO
45H
2o, 200 ~ 260g/LH
2sO
4, 50 ~ 80mg/LCl
-, add sour copper open cylinder agent, brightening agent for acid copper electroplating and sour copper leveling agent.
Thermal shock experiment reference standard IPC-TM-650.Tin furnace temperature rises to 288 DEG C, and leaching scaling powder is placed on molten tin surface with ventilating hole plate, takes out and is cooled to room temperature, repeat five times after each ten seconds.The photo after 5 thermal shocks of the plating metapore that this test obtains as shown in Figure 2, copper coating thickness reaches 25 μm as can be seen from Figure 2, after thermal shock 5 times, making sample sections can be observed in hole and all be coated with uniform copper plate, and atresia copper is broken and hole wall segregation phenomenon.
To be through-hole aperture be respectively Fig. 3 ~ Fig. 8 0.20,0.25,0.30,0.50,0.80 and the backlight experiment photo completing the hole of the brassboard of hole metallization of 1.00mm, the concrete grammar of backlight experiment is exactly breadboard is cut one piece of porose baseplate material of band to make sample, through sawing or grind center, hole (namely on center line).Utilize light to inject from bottom surface during test, then use magnifying glass to carry out checking.As can be seen from Fig., occur after the plating of 10min without large area plating leakage and pin hole, layers of copper the hole wall of complete covering different pore size can block light privately.
After this method hole electricity conduction technique (plating), be adjusted to the resistance of the conductive copper layer instrument connection reduction-oxidation graphite guide electric layer of the both sides of ohms range two test pencil difference contact print circuit board with universal instrument, single hole resistance value is 10000 ~ 50000 Ω.
The graphite oxide aqueous solution in this test procedure two at room temperature left standstill after 2 months, and solution obviously without deposition lamination, illustrates that this aqueous stability is fabulous.
Test 2: the method that the printed circuit board (PCB) graphite oxide reducing process of this test carries out hole electricity conduction is carried out according to the following steps:
One, hydroxyethylcellulose and each 1g of polyacrylamide is taken, with the mixed solution of second alcohol and water for solvent, wherein in solvent, the mass percentage of ethanol is 10%, under agitation, hydroxyethylcellulose and polyacrylamide are added in 500mL solvent, be stirred to and dissolve completely, then add potassium hydroxide and regulate pH to 10, be made into pretreatment fluid; The printed circuit board (PCB) of boring is put into pretreatment fluid and soaks 4min;
Two, 2.5g graphite oxide is under agitation added in 500mL water; Then adding potassium hydroxide regulates pH to be 10, then solution is carried out ultrasonic disperse 30min, obtains the graphite oxide aqueous solution; The printed circuit board (PCB) processed through step one is put into graphite oxide aqueous solution soaking 4min, then uses the lower hot-air seasoning of 80 DEG C;
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 be mixed with the reducing agent aqueous solution, then by the use in printed circuit board reducing agent aqueous solution soaking 10min through step 2 process;
Four, by the concentration of sodium peroxydisulfate be 150g/L, the concentration of the concentrated sulfuric acid is that sodium peroxydisulfate and the concentrated sulfuric acid add in deionized water by 10g/L, mix, obtain copper etching solution; Use in printed circuit board copper etching solution through step 3 process is soaked 0.5min;
Five, by after graphite remaining for the use in printed circuit board washed with de-ionized water removing after step 4 process, then dry, being then placed in sour copper solution, is 2A/dm in current density
2condition under carry out Direct Electroplating copper 20min, in hole, obtain copper conductive layer, complete hole metallization.
Sour copper solution wherein in step 5 is purchased from Guangdong Zhizhuo Precision Metal Technology Co., Ltd.;
The making sample sections can observe in hole and be all coated with uniform copper plate after 5 thermal shocks of plating metapore, atresia copper is broken and hole wall segregation phenomenon.Plate face occurs without large area plating leakage and pin hole through plating back optical tests after conductionization in copper plating solution, and layers of copper can the hole wall of complete covering different pore size.
Test 3: the method that the printed circuit board (PCB) graphite oxide reducing process of this test carries out hole electricity conduction is carried out according to the following steps:
One, hydroxyethylcellulose and each 1g of polyacrylamide is taken, with the mixed solution of second alcohol and water for solvent, wherein in solvent, the mass percentage of ethanol is 10%, under agitation, hydroxyethylcellulose and polyacrylamide are added in 500mL solvent, be stirred to and dissolve completely, then add potassium hydroxide and regulate pH to 10, be made into pretreatment fluid; The printed circuit board (PCB) of boring is put into pretreatment fluid and soaks 4min;
Two, 2.5g graphite oxide is under agitation added in 500mL water; Then adding potassium hydroxide regulates pH to be 10, then solution is carried out ultrasonic disperse 30min, obtains the graphite oxide aqueous solution; The printed circuit board (PCB) processed through step one is put into graphite oxide aqueous solution soaking 4min, then uses the lower hot-air seasoning of 80 DEG C;
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 be mixed with the reducing agent aqueous solution, then by the use in printed circuit board reducing agent aqueous solution soaking 5min through step 2 process;
Four, by the concentration of sodium peroxydisulfate be 150g/L, the concentration of the concentrated sulfuric acid is that sodium peroxydisulfate and the concentrated sulfuric acid add in deionized water by 10g/L, mix, obtain copper etching solution; Use in printed circuit board copper etching solution through step 3 process is soaked 0.5min;
Five, by after graphite remaining for the use in printed circuit board washed with de-ionized water removing after step 4 process, then dry, being then placed in sour copper solution, is 2A/dm in current density
2condition under carry out Direct Electroplating copper 60min, in hole, obtain copper conductive layer, complete hole metallization.
Sour copper solution wherein in step 5 is purchased from Guangdong Zhizhuo Precision Metal Technology Co., Ltd.;
The making sample sections can observe in hole and be all coated with uniform copper plate after 5 thermal shocks of plating metapore, atresia copper is broken and hole wall segregation phenomenon.Plate face occurs without large area plating leakage and pin hole through plating back optical tests after conductionization in copper plating solution, and layers of copper can the hole wall of complete covering different pore size.
Claims (10)
1. printed circuit board (PCB) graphite oxide reducing process carries out the method for hole electricity conduction, it is characterized in that the method is carried out according to the following steps:
One, the printed circuit board (PCB) of boring is put into pretreatment fluid immersion treatment; Wherein pretreatment fluid is dissolved in solvent by binding agent, then formed after regulating pH to 9 ~ 10 by pH adjusting agent; Binding agent is a kind of or wherein several composition in potassium silicate, hydroxyethylcellulose, carboxymethyl cellulose, Sodium Polyacrylate, polyacrylamide, benzene emulsion, epoxy resin latex and poly-amino resins; Solvent is a kind of or wherein several composition in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, monoethanolamine, diethanol amine, triethanolamine, acetone and water;
Two, dry again after the printed circuit board (PCB) processed through step one being put into the process of graphite oxide aqueous solution soaking; Wherein the graphite oxide aqueous solution is prepared according to the following steps: be under agitation added to the water by graphite oxide, then adds pH to 9 ~ 10 that pH adjusting agent regulates solution, then solution is carried out ultrasonic disperse and obtain the graphite oxide aqueous solution;
Three, again by the use in printed circuit board reducing agent aqueous solution soaking process through step 2 process; Wherein reducing agent is a kind of or wherein several composition in hydrazine hydrate, inferior sodium phosphate, ascorbic acid and sodium borohydride;
Four, by the use in printed circuit board copper etching solution immersion treatment through step 3 process; Wherein to be that a kind of or wherein several composition in monoethanolamine, sulfuric acid, sodium peroxydisulfate and hydrogen peroxide is soluble in water make copper etching solution;
Five, by after the printed circuit board (PCB) cleaning after step 4 process, oven dry, in sour copper solution, carry out Direct Electroplating copper, in hole, obtain copper conductive layer.
2. printed circuit board (PCB) graphite oxide reducing process according to claim 1 carries out the method for hole electricity conduction, it is characterized in that the mass percentage concentration of binding agent in pretreatment fluid in step one is 0.01% ~ 1.00%.
3. printed circuit board (PCB) graphite oxide reducing process according to claim 1 and 2 carries out the method for hole electricity conduction, it is characterized in that in step one, pH adjusting agent is a kind of or wherein several composition in potassium hydroxide, potassium silicate, potassium sulfate, potash and saleratus.
4. printed circuit board (PCB) graphite oxide reducing process according to claim 3 carries out the method for hole electricity conduction, it is characterized in that in step one, soak time is 0.5 ~ 10min.
5. printed circuit board (PCB) graphite oxide reducing process according to claim 3 carries out the method for hole electricity conduction, and when it is characterized in that preparing the graphite oxide aqueous solution in step 2, the time of ultrasonic disperse is 20 ~ 40min.
6. printed circuit board (PCB) graphite oxide reducing process according to claim 3 carries out the method for hole electricity conduction, it is characterized in that the mass percent concentration of graphite oxide in the graphite oxide aqueous solution in step 2 is 0.05% ~ 2.00%.
7. printed circuit board (PCB) graphite oxide reducing process according to claim 3 carries 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 carries out the method for hole electricity conduction, it is characterized in that the mass percentage concentration of reducing agent in the reducing agent aqueous solution in step 3 is 0.1% ~ 4.0%.
9. printed circuit board (PCB) graphite oxide reducing process according to claim 3 carries 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 carries 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684560A (en) * | 1985-11-29 | 1987-08-04 | Olin Hunt Specialty Products, Inc. | Printed wiring board having carbon black-coated through holes |
| CN102142317A (en) * | 2011-01-14 | 2011-08-03 | 天津师范大学 | Solar battery with graphite interface layer and manufacturing method thereof |
-
2013
- 2013-09-29 CN CN201310455237.4A patent/CN103491727B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684560A (en) * | 1985-11-29 | 1987-08-04 | Olin Hunt Specialty Products, Inc. | Printed wiring board having carbon black-coated through holes |
| CN102142317A (en) * | 2011-01-14 | 2011-08-03 | 天津师范大学 | Solar battery with graphite interface layer and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 以石墨为导电基质的黑孔化新技术;遇世友 等;《印制电路信息》;20120731(第7期);全文 * |
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