CN103874344A - Vias of a circuit board and method for depositing conducting polymers into through-holes - Google Patents
Vias of a circuit board and method for depositing conducting polymers into through-holes Download PDFInfo
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- CN103874344A CN103874344A CN201310659203.7A CN201310659203A CN103874344A CN 103874344 A CN103874344 A CN 103874344A CN 201310659203 A CN201310659203 A CN 201310659203A CN 103874344 A CN103874344 A CN 103874344A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0055—After-treatment, e.g. cleaning or desmearing of holes
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- Microelectronics & Electronic Packaging (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
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Abstract
The present invention relates to a method for depositing a conductive polymer layer on the printed circuit board through holes and vias. The method comprises the steps of: providing a through-hole or through-hole printed circuit board substrate; utilizing solution with first oxidizing agent to form a oxide layer on the holes or vias, and utilizing solution with second oxidizing agent and conductive polymer units to form a conductive polymer layer.
Description
Technical field
The present invention relates to a kind of pass through CNC (computer numerical control) boring or laser drill at printed circuit board (PCB) and process the method that forms electric conductive polymer layer on the resin of inwall of the through hole (through-hole) that obtains or via hole (via-hole), particularly, relate on a kind of resin of the inwall at through hole or via hole and form the method for electric conductive polymer layer as the conductive layer of plated metal.
Background technology
Printed circuit board (PCB) is to utilize printing, plating or etching and the substrate on insulated substrate with interconnection pattern, and can be divided into one-sided printed circuit board (PCB), double-sided printed or multilayer board according to the structure that forms interconnection pattern.In multilayer board, will hole by CNC or laser drill is processed the through hole or the via hole that obtain and is formed as connecting the interconnection pattern on different layers, and adopted the whole bag of tricks to form conductive material on the resin of the inwall of through hole or via hole.
On resin as the inwall at through hole or via hole, form the conventional method of conductive material, adopted electroless plating copper method and the method for utilizing carbon granule.Electroless plating copper method is that one has obtained long-term widely used technology, and uses formalin as reducing agent.But formalin is carcinogenicity material, therefore according to environmental legislation, it will start in 2014 forbidding.Therefore, the electroless plating copper medicine that does not contain formalin of Application and Development alternative material is just being attempted by medicament company, but the substitute of formalin not yet develops so far.In addition, utilize as the carbon granule such as carbon black or graphite provides conductivity method to hole inwall can be limited because of the size of carbon granule in the time of manufacture high-density base board, due to the surface roughness of carbon granule, on the surface of gained copper electroplating layer, form inhomogeneous dietary fibres, and the pollution of the plating liquid that causes of the desorption of carbon granule can make the lost of life of plating liquid.Therefore, as electroless plating copper method or utilize the alternative method of the method for carbon granule, there is the trial that uses electric conductive polymer.
As using electric conductive polymer to form the prior art of conductive material on the inwall of through hole, TOHKEMY 1995-321461 communique and United States Patent (USP) are comprised No. 6007866, but these prior aries run into following difficulty: for example, be difficult to guarantee that electric conductive polymer has conductivity enough as copper; Electric conductive polymer is coated in through hole unevenly, and the operation (electro-coppering) after causing is difficult to carry out for minor diameter through hole; With in the process of diameter through hole being carried out to electro-coppering, in hole, produce space (void), cause reproducibility reduce.
It is polyethylene dioxythiophene (PEDOT) conductive layer more than 4000 Ω/cm that Blasberg etc. have formed resistance by following manner: permanganic acid oxidant is doped on glass epoxy substrate (FR-4 substrate), and this doped substrate is immersed in the combination solution that comprises 3,4-rthylene dioxythiophene (EDOT), polystyrolsulfon acid (PSSA) and emulsifying agent; But, because resistance is relatively high, the method is difficult to the inwall of plating through hole equably in operation (substrate surfaces) subsequently.
Atotech etc. have covered the inwall of minor diameter through hole equably and reproducibly by following manner: working concentration is than the permanganic acid oxidant doped-glass epoxy substrate of the high 10g/L used such as Blasberg, and doped substrate are immersed in the combination solution that comprises ethene dioxythiophene, Loprazolam and surfactant the resistance of PEDOT is reduced to 2000 Ω (No. 2004-0112755th, U.S. Patent Application Publication); But, compared with electroless plating copper method as conventional method, the too high in resistance of electric conductive polymer layer, and metallic growth speed is very low, is difficult to thus obtain uniform thickness and obtains volume production ability.
Omecon etc. by adding the conductivity that has significantly improved electric conductive polymer as the method for 1-METHYLPYRROLIDONE (NMP) isopolarity solvent in the PEDOT solution that comprises micro-polyaniline, but, electric conductive polymer can not be formed uniformly on the inwall of small through hole (No. 2010-0297337th, U.S. Patent Application Publication) in the time utilizing spin coating.
Summary of the invention
The present invention relates to a kind of holing by CNC or laser drill is processed the method that forms electric conductive polymer layer on the resin of inwall of the through hole that obtains or via hole, the low resistance, the resistance deviation that approach metal to make it have be low, without burn (burnt) phenomenon and productivity ratio higher.
The present invention relates to a kind of method that uses the method manufacture printed circuit board (PCB) that forms electric conductive polymer layer.
The present invention relates to a kind of printed circuit board (PCB) making according to the manufacture method of above-mentioned printed circuit board (PCB).
According to an aspect of the present invention, a kind of method that forms electric conductive polymer layer on resin of the inwall at through hole or via hole is provided, said method comprising the steps of: use in printed circuit board substrate is provided, and described substrate has by CNC holes or laser drill is processed the through hole or the via hole that obtain; The solution that use comprises the first oxidant forms oxide layer on the inwall of through hole or via hole; The solution that comprises the second oxidant and electric conductive polymer monomer with use forms electric conductive polymer layer in oxide layer.
According to an exemplary embodiment of the present invention, the second oxidant can be slaine or persulfate.
According to another illustrative embodiments of the present invention, slaine can be iron (III) salt or copper (II) salt.
According to another illustrative embodiments of the present invention, electric conductive polymer can be ethene dioxythiophene with monomer.
According to an illustrative embodiments more of the present invention, the second oxidant can be ferric sulfate, electric conductive polymer can be ethene dioxythiophene with monomer, and the concentration of ferric sulfate can be 100mg/L～600mg/L, and the concentration of ethene dioxythiophene can be 0.15 % by weight～1.0 % by weight.
According to another illustrative embodiments of the present invention, the solution that comprises the second oxidant and electric conductive polymer monomer can also comprise organic acid.
According to a further aspect in the invention, provide a kind of manufacture method of printed circuit board (PCB), said method comprising the steps of: use in printed circuit board substrate is provided, and described substrate has by CNC has holed or laser drill is processed the through hole or the via hole that obtain; The solution that use comprises the first oxidant forms oxide layer on the inwall of through hole or via hole; The solution that use comprises the second oxidant and electric conductive polymer layer monomer forms electric conductive polymer layer in oxide layer; On electric conductive polymer layer, form metal with utilizing to electroplate.
According to another aspect of the invention, provide a kind of printed circuit board (PCB) that uses the manufacture method of this printed circuit board (PCB) to make.
Accompanying drawing explanation
By describe illustrative embodiments of the present invention in detail with reference to accompanying drawing, above and other object of the present invention, Characteristics and advantages will be more obvious to those skilled in the art, in accompanying drawing:
Fig. 1 is the flow chart that the manufacturing process of the printed circuit board (PCB) of an exemplary embodiment of the present invention has been described.
Embodiment
Describe below with reference to accompanying drawings illustrative embodiments of the present invention in detail.Although the present invention only describes and shows its illustrative embodiments, be apparent that to those skilled in the art, can carry out various modifications and not depart from the spirit and scope of the invention.
According to an exemplary embodiment of the present invention, holing by CNC or laser drill is processed the method that forms electric conductive polymer layer on the resin of inwall of the through hole that obtains or via hole and comprised the following steps: the use in printed circuit board substrate with through hole or via hole is provided; On the inwall of through hole or via hole, form oxide layer, use the solution that comprises the first oxidant to form oxide layer on the inwall of through hole or via hole; The solution that comprises the second oxidant and electric conductive polymer monomer with use forms electric conductive polymer layer in oxide layer.
According to the present invention, on the substrate for the manufacture of printed circuit board (PCB), holing by CNC or laser drill is processed on the resin of inwall of the through hole that obtains or via hole and formed electric conductive polymer layer, on the inwall of through hole or via hole, forming thus conductive material to carry out electro-coppering.
Fig. 1 is the flow chart that the manufacturing process of the printed circuit board (PCB) of an exemplary embodiment of the present invention has been described.With reference to Fig. 1, hole or laser drill is processed the method that forms the illustrative embodiments of electric conductive polymer layer on the inwall of the through hole that obtains or via hole being described in detail in by CNC.
First, hole or laser drill is processed the through hole that obtains or the use in printed circuit board substrate of via hole carries out swelling (S1) to having by CNC.The swelling solution that can comprise 1-METHYLPYRROLIDONE (NMP) 55 ℃ of uses carries out 10 minutes.Subsequently, carry out etching (S2) through the substrate of swelling treatment.As etching solution, can use the etching solution that comprises permanganate, and etching can be carried out 10 minutes at 80 ℃.Subsequently, will be through etched substrate neutralization (S3).In N-process, can use the combination solution of sulfuric acid and hydrogen peroxide (oxygenated water).
Subsequently, be oxidized (S4) by the substrate of said procedure decontamination (desmear).In order to be oxidized, can use permanganate solution, this solution can be neutral, or the pH subacidity that is 6～7.Permanganate solution can be potassium permanganate (KMnO
4) or sodium permanganate (NaMnO
4) solution, and the liquor potassic permanganate that oxidation can be 5 % by weight～11 % by weight at 75 ℃～98 ℃ working concentrations carries out 5 minutes～20 minutes, the liquor potassic permanganate that is preferably 7 % by weight～9 % by weight at 80 ℃～95 ℃ working concentrations carries out 7 minutes～15 minutes, and the liquor potassic permanganate that is more preferably 7.5 % by weight～8.5 % by weight at 90 ℃ of working concentrations carries out 10 minutes.By manganese dioxide (MnO
2) the above-mentioned oxide layer that forms plays the effect of anchor layer (anchor), this anchor layer provides layer that can attached electric conductive polymer in operation subsequently.
Subsequently, on the solution-treated through hole that comprises 3,4-rthylene dioxythiophene (EDOT) by use or the inwall of via hole, be formed with the substrate of oxide layer, form electric conductive polymer layer (S5).The solution that is used to form electric conductive polymer layer can comprise monomer for electric conductive polymer, the second oxidant and organic acid.Electric conductive polymer can become electric conductive polymer by polymerization with monomer, and electric conductive polymer can be EDOT or derivatives thereof with monomer, and the electric conductive polymer forming is thus polyethylene dioxythiophene (PEDOT).The second oxidant can be slaine, persulfate or peroxysulphate, and slaine can be iron (III) salt or copper (II) salt, and iron (III) salt can be iron chloride (FeCl
3), ferrous perchlorate (II) (Fe (ClO
4)
2) or ferric sulfate (Fe
2(SO
4)
3), copper (II) salt can be copper chloride (CuCl
2), persulfate can be ammonium persulfate, and peroxysulphate can be peroxo disulfate acid ammonium.Organic acid can play and improve rate of polymerization and the stable effect of the polymer of polymerization, and can be polyacrylic acid, polymethylacrylic acid or the poly as polymerization of carboxylic acid series, or as polystyrolsulfon acid (PSSA) or the polyvinylsulfonic acid of polymerization sulfonic acid series.It is that 100mg/L～1000mg/L, preferred concentration are 130mg/L～800mg/L and the ferric sulfate of 200mg/L～600mg/L more preferably that the solution that is used to form electric conductive polymer layer can comprise concentration.The solution that is used to form electric conductive polymer layer can comprise 0.1 % by weight～1.1 % by weight, preferably 0.2 % by weight～0.5 % by weight and the more preferably ethene dioxythiophene of 0.22 % by weight～0.40 % by weight.The time that uses this solution-treated electric conductive polymer layer can be to use the ethene dioxythiophene solution of 0.1 % by weight～1.1 % by weight to carry out more than 5 minutes, preferably use the ethene dioxythiophene solution of 0.2 % by weight～0.5 % by weight to carry out more than 7 minutes, and more preferably use 0.22 % by weight～0.40 % by weight ethene dioxythiophene solution to carry out more than 10 minutes.Being used to form in the solution of electric conductive polymer layer the concentration of the second oxidant and the resistance uniformity of electric conductive polymer and inhibition, to burn phenomenon relevant.When the concentration of ferric sulfate is during lower than 100mg/L, attach to densely manganese dioxide (MnO
2) ethene dioxythiophene of layer can not be completely fixed as PEDOT by polystyrolsulfon acid, presents thus the inhomogeneous of color, for example, be mixed with dirty-green and skipper, and the electrical resistance region recording in sample and changing on a large scale.Meanwhile, when the concentration of ferric sulfate is during higher than 600mg/L, ethene dioxythiophene attaches to manganese dioxide layer densely, thereby promotes over oxidation, also there will be and burns phenomenon thus on the surface of PEDOT.In addition, according to an illustrative embodiment of the invention, the solution that is used to form electric conductive polymer layer does not comprise emulsifying agent, thus the conductivity that prevents electric conductive polymer layer because of emulsifying agent deteriorated.
Subsequently, utilize electrocoppering that copper is plated on and is had on the through hole of use in printed circuit board substrate of electric conductive polymer layer or the inwall of via hole (S6), and dry (S7).Although do not describe in the explanation of each operation, after carrying out the operation shown in Fig. 1, can comprise the operation of washing substrate.
In the printed circuit board (PCB) of manufacturing by above operation, conductive material is coated on by CNC and holes or laser drill is processed on the resin of inwall of the through hole that obtains or via hole.Herein, on the electric conductive polymer layer forming on the inwall of conductive material by through hole or via hole and this electric conductive polymer layer, the coat of metal of plating forms.
With reference to embodiment and comparative example, illustrative embodiments of the present invention is described below.
Embodiment 1 (preliminary treatment of substrate)
FR-4 substrate carries out swelling 10 minutes with 1-METHYLPYRROLIDONE solution at 55 ℃, uses permanganic acid etching solution to carry out etching 10 minutes at 80 ℃, then uses sulfuric acid/hydrogen peroxide solution to neutralize.
Embodiment 2 (formation of oxide layer)
To pretreated processing substrate as described in example 1 above 10 minutes, and form oxide layer at 90 ℃ of liquor potassic permanganates that are 80g/L by working concentration on the inwall of through hole or via hole.
Embodiment 3-1 (formation of electric conductive polymer layer)
Under room temperature, use 0.24 % by weight ethene dioxythiophene, 50mg/L ferric sulfate and the 0.36 % by weight polystyrolsulfon acid aqueous solution to being formed with the processing substrate 10 minutes of oxide layer on the inwall of through hole or via hole described in embodiment 1 or embodiment 2, in oxide layer, form thus electric conductive polymer layer.
Embodiment 3-2 (formation of electric conductive polymer layer)
By to form electric conductive polymer layer with the similar method of embodiment 3-1, difference is, the concentration of ferric sulfate is 250mg/L.
Embodiment 3-3 (formation of electric conductive polymer layer)
By to form electric conductive polymer layer with the similar method of embodiment 3-1, difference is, the concentration of ferric sulfate is 500mg/L.
Embodiment 3-4 (formation of electric conductive polymer layer)
By to form electric conductive polymer layer with the similar method of embodiment 3-1, difference is, the concentration of ferric sulfate is 750mg/L.
Comparative example 3-1 (formation of electric conductive polymer layer)
Under room temperature, use 0.24 % by weight ethene dioxythiophene and the 0.36 % by weight polystyrolsulfon acid aqueous solution to being formed with the processing substrate 10 minutes of oxide layer on the inwall of through hole or via hole described in embodiment 1 or embodiment 2, in oxide layer, form thus electric conductive polymer layer.
Comparative example 3-2 (formation of electric conductive polymer layer)
Under room temperature, use 0.24 % by weight ethene dioxythiophene, 100mg/L lauryl sodium sulfate (as levelling agent) and the 0.36 % by weight polystyrolsulfon acid aqueous solution to being formed with the processing substrate 10 minutes of oxide layer on the inwall of through hole or via hole described in embodiment 1 or embodiment 2, in oxide layer, form thus electric conductive polymer layer.
Comparative example 3-3 (formation of electric conductive polymer layer)
Under room temperature, use 0.24 % by weight ethene dioxythiophene, 50mg/L catechol and the 0.36 % by weight polystyrolsulfon acid aqueous solution to being formed with the processing substrate 10 minutes of oxide layer on the inwall of through hole or via hole described in embodiment 1 or embodiment 2, in oxide layer, form thus electric conductive polymer layer.
Evaluation Example (resistance and the evaluation that occurs burning phenomenon)
Use 4 point probes to measure the resistance of the electric conductive polymer layer (PEDOT) of the treated substrate described in embodiment and comparative example, and evaluate the appearance of burning phenomenon.According to tape stripping test, burn the appearance of phenomenon by the residual quantity evaluation of electric conductive polymer layer on adhesive tape after also peeling off from it on the surface adhesive tape being adhered to electric conductive polymer layer.Result is summarised in table 1.
Table 1
With reference to table 1, the resistance measured value of the substrate that embodiment 3-2 and 3-3 manufacture is 200 Ω～270 Ω, and resistance uniformity is very high, do not exist and burn phenomenon, and the retentivity of resistance is very good while repeating the perparation of specimen.The substrate that embodiment 3-1 manufactures is slightly improved burning aspect phenomenon, but has relatively inhomogeneous outward appearance (exterior) and slightly high resistance deviation.The resistance of the substrate that embodiment 3-4 manufactures is relatively high, for example, be 300 Ω～350 Ω, and observe certain phenomenon of burning.The resistance of the substrate that comparative example 3-1, comparative example 3-2 and comparative example 3-3 manufacture is very low, but resistance uniformity is poor with the characteristic of burning phenomenon.
According to above trend, in the time that ferric sulfate is added into EDOT monomer solution as the second oxidant, resistance can improve slightly, but PEDOT changes into uniform dirty-green conductive layer, and the surface of electric conductive polymer does not remain in burns on the adhesive tape of peeling off in phenomenon evaluation, and can keep resistance through evaluating after removal adhesive tape.Although laurilsulfate impels the dissolving of EDOT monomer and make PEDOT surface become very even, it brings out the generation of burning phenomenon, and is removing resistance raising after adhesive tape.Although catechol makes PEDOT can have uniform resistance and prevent to a certain extent burning phenomenon, these characteristics are inferior to the characteristic in ferric sulfate situation.
Change the evaluation experimental of ethene dioxythiophene concentration
Prepare the ethene dioxythiophene solution of 200ml concentration as 0.15%～0.60% take the ratio of components shown in table 2, and room temperature by use six FR-4 samples of decontamination/oxidizer treatment immerse above solution in 10 minutes, and evaluate the characteristic of electric conductive polymer layer under differing ethylene dioxy thiophene concentration.
Table 2
With reference to table 2, when ethene dioxythiophene concentration is 0.48 % by weight when above, sample can keep low resistance while repeating to manufacture in same EDOT solution continuously.But, because the relative concentration of ethene dioxythiophene is higher, a large amount of ethene dioxythiophenes spontaneously react with the manganese dioxide anchor layer that attaches to FR-4, and part ethene dioxythiophene is not converted into PEDOT by polystyrolsulfon acid, cause thus ethene dioxythiophene not thoroughly desorption burn phenomenon, cause adhesive strength deteriorates in subsequent handling.But, although being ethene dioxythiophene solution below 0.2 % by weight, concentration do not there is the serious phenomenon of burning, and in the time that sample repeats to manufacture in same groove is bathed, resistance significantly improves, and the maintenance of solution is very difficult thus.
Change the evaluation experimental of the first oxidant concentration
The resistance of the measurement of concetration FR-4 sample by change the first oxidant as shown in table 3, result is summarised in table 3.
Table 3
With reference to table 3, as the first oxidant potassium permanganate (KMnO
4) concentration when lower, it easily dissolves, but the resistance of PEDOT is higher, and as potassium permanganate (KMnO
4) concentration when higher, the resistance of PEDOT significantly reduces, but needs additionally heat with complete dissolved oxidant.In addition, when the concentration of potassium permanganate is 80g/L when above, the resistance variations scope of the different piece of same sample reduces, but resistance does not significantly reduce.This is because be difficult to the resistance of the derivative of above material PEDOT to be reduced to ratio resistance 150 Ω lower than polythiophene.
Add the evaluation experimental of surfactant
For containing the impact of surfactant on PEDOT conductivity in the composition of the nertralizer solution that uses in assessment decontamination operation and EDOT solution, preparation 1L has the neutralization solution of concentration shown in table 4, and processes FR-4 sample, then analysis result with it.
Table 4
With reference to table 4, the resistance of PEDOT does not significantly change with the concentration of sulfuric acid in neutralization solution and hydrogen peroxide, but in the time comprising non-polar surfactant in ethene dioxythiophene solution, the resistance of PEDOT is slightly improved.This is because low reproducibility reagent hydrogen peroxide (H
2o
2) solution fully eluted in washing procedure, the oxidant potassium permanganate (KMnO using in not appreciable impact subsequent handling thus
4), but surfactant has suppressed the excessive FR-4 of attaching to of ethene dioxythiophene.Therefore, when holing by CNC or laser drill is processed while forming eco-friendly PEDOT as electric conductive polymer layer on the resin of inwall of the through hole that obtains or via hole, can be used as it is the decontamination operation adopting in conventional electroless plating process for copper line, therefore do not need independent equipment investment.
The evaluation experimental of immersion time in ethene dioxythiophene solution
Immerse for being evaluated at difference in the first oxidant and ethene dioxythiophene solution the impact that the time forms PEDOT conductive layer, in table 5, under listed treatment conditions, on FR-4 sample, form conductive layer, and evaluate its characteristic.
Table 5
With reference to table 5, along with immerse the increase of time in the first oxidant and ethene dioxythiophene solution, the resistance of PEDOT conductive layer reduces, and along with immerse the increase of time in ethene dioxythiophene solution, surface uniformity improves.But along with immersing the increase of time, what occur on PEDOT surface burns phenomenon variation, have more PEDOT to remain on adhesive tape, and after removing adhesive tape, resistance can improve again in adhesive tape test.
Holing by CNC or laser drill is processed and on the resin of inwall of the through hole that obtains or via hole, formed the method for the illustrative embodiments of electric conductive polymer layer, has following effect with method and printed circuit board (PCB) that the method is manufactured printed circuit board (PCB).
1. in the oxide layer forming on the resin of the inwall of through hole or via hole, form in the operation of electric conductive polymer layer, by making the electric conductive polymer layer that forms in oxide layer thereon attached securely with the second oxidant as complementary oxidant, the resistance of electric conductive polymer layer can be reduced to below 200 Ω, this is 1/10 of conventional resistance.
2. the resistance of electric conductive polymer layer and resistance deviation reduce, and subsequent handling (electro-coppering) can be carried out fast and equably thus, and can carry out substrate surfaces and not have space in the through hole inner side with minor diameter.
3. because do not adopt adjustment operation, thereby can significantly reduce the waste water generation that plant investment, the dose using and printed circuit board (PCB) consume in manufacturing.
4. method of the present invention can replace conventional electroless plating copper process, low cost and High-efficient Production can be provided thus, and do not use the carcinogenicity formalin or the ethylenediamine tetra-acetic acid (EDTA) that in waste water treatment, are difficult to disposal, can realize thus rolling type (roll-to-roll) volume production.
It is obvious to the skilled person that and can carry out various modifications to above-mentioned illustrative embodiments of the present invention, and do not depart from the spirit and scope of the invention.Therefore, the invention is intended to cover all these type of modifications in the scope of claims and equivalent thereof.
Claims (8)
1. a method that forms electric conductive polymer layer in through hole or via hole, described method comprises:
The use in printed circuit board substrate with through hole or via hole is provided;
The solution that use comprises the first oxidant forms oxide layer in described through hole or via hole; With
The solution that use comprises the second oxidant and electric conductive polymer monomer forms electric conductive polymer layer in described oxide layer.
2. the method for claim 1, wherein described the second oxidant is slaine or persulfate.
3. method as claimed in claim 2, wherein, described slaine is iron (III) salt or copper (II) salt.
4. the method for claim 1, wherein described electric conductive polymer monomer is ethene dioxythiophene or derivatives thereof.
5. the method for claim 1, wherein, described the second oxidant is ferric sulfate, and described electric conductive polymer monomer is ethene dioxythiophene, the concentration of described ferric sulfate is 100mg/L～1000mg/L, and the concentration of described ethene dioxythiophene is 0.1 % by weight～1.1 % by weight.
6. the described solution that the method for claim 1, wherein comprises described the second oxidant and described electric conductive polymer monomer also comprises organic acid.
7. a manufacture method for printed circuit board (PCB), described method comprises:
The use in printed circuit board substrate with through hole or via hole is provided;
The solution that use comprises the first oxidant forms oxide layer in described through hole or via hole;
The solution that use comprises the second oxidant and electric conductive polymer monomer forms electric conductive polymer layer in described oxide layer; With
By electroplating metal lining on described electric conductive polymer layer.
8. a printed circuit board (PCB), described printed circuit board (PCB) makes by the manufacture method of printed circuit board (PCB) claimed in claim 7.
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|---|---|---|---|
| KR10-2012-0142608 | 2012-12-10 | ||
| KR1020120142608A KR101294229B1 (en) | 2012-12-10 | 2012-12-10 | Method for depositing conducting polymers into through-holes and vias of a circuit board |
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| CN106686911A (en) * | 2017-03-21 | 2017-05-17 | 胜华电子（惠阳）有限公司 | Conducting film production method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101294229B1 (en) | 2013-08-07 |
| TW201444439A (en) | 2014-11-16 |
| CN103874344B (en) | 2017-11-21 |
| TWI517772B (en) | 2016-01-11 |
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