CN100424226C - Method for electroless metalisation of polymer substrate - Google Patents

Method for electroless metalisation of polymer substrate Download PDF

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CN100424226C
CN100424226C CNB038130629A CN03813062A CN100424226C CN 100424226 C CN100424226 C CN 100424226C CN B038130629 A CNB038130629 A CN B038130629A CN 03813062 A CN03813062 A CN 03813062A CN 100424226 C CN100424226 C CN 100424226C
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film
solution
alkaline solution
inoculation
metal
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CN1659310A (en
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桑尼尔·麦德修卡·班盖尔
彼得·麦尔康·莫伦
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Agency for Science Technology and Research Singapore
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/30Activating or accelerating or sensitising with palladium or other noble metal
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1603Process or apparatus coating on selected surface areas
    • C23C18/1605Process or apparatus coating on selected surface areas by masking
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1689After-treatment
    • C23C18/1692Heat-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073Multistep pretreatment
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073Multistep pretreatment
    • C23C18/2086Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/032Organic insulating material consisting of one material
    • H05K1/0346Organic insulating material consisting of one material containing N
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate

Abstract

A method of activating and metallising an aromatic polymer film including the steps of: treating a first surface of the film with a basic solution; applying to said first surface of the film an aqueous seeding solution comprising polymer-stabilised catalyst particles; and immersing the film in an electroless plating bath comprising ions of a desired metal so as to deposit a layer of said metal onto the first surface of said film.

Description

The method of the no electric metal spraying plating of polymeric matrix
Technical field
The present invention relates to a kind of activation and sputtering of metals polymeric matrix of being used for, particularly aromatic(based)polymer matrix improves one's methods.
Background technology
That make by aromatic(based)polymer or contain in the structure of matrix through being commonly used in some electronic unit of aromatic(based)polymer, assemble as microelectronics.Found that a large amount of polymkeric substance satisfies as these matrix.Found that polyimide is particularly suitable in this respect, in part because its splendid thermostability and solvent resistance.
Be widely used in during the electronics assembling uses as the aromatic(based)polymer of polyimide, as flexible (Flex) circuit (flexible circuits), soft or hard combined circuit (rigid-flex circuits), printed circuit board (PCB) (PCB ' s), multilayer flexible circuit (multi-layer flexible circuits), also have passivation layer on the silicon chip.But these aromatic(based)polymers self often have poor adhesivity to plating metal (as copper, nickel and gold) thereon.Therefore, must develop certain and be used to improve adhering technology between above-mentioned metal and these matrix.For the problem of attempting to overcome this poor adhesion has adopted many methods.
For example, tackiness agent often is used with bonding metal layer on these polymeric films, and thereby makes metalclad film.Lithography is normally used for forming pattern on metal level.But, because the etching of metal level causes in the undercutting of circuit electric wire (because etching under mask), and, therefore use these clad films to be difficult to obtain fine line circuitry because metal level need have the fact of the physical strength that is used for separating treatment and need make metal level thicker relatively (at least 15 microns).In addition, the tackiness agent of use makes the laser boring of micro through hole become difficult.And this also wastes metal.
Another method of attempting to improve viscosity is by going up applying liquid polyimide (or its precursor polyamic acid) in shaggy tinsel (for example Copper Foil), sclerosis then.But, because the thickness of tinsel is difficult to obtain once more fine line circuitry.
Another kind of known method of attempting to improve viscosity is a sputter chromium thin layer on polymer surfaces.Then, sputter copper lamina on the chromium thin layer.Then, this copper layer uses to electroplate and is thickeied.Though this method can production fine line circuitry (by use photo-resist before plating step), sputter step is expensive and expend time in.
And, in all aforesaid methods, be difficult to punching to the micro through hole of the polymeric film that passes metallizing.And after punching, this micro through hole need be electroplated respectively.
Another technology of making metal-clad polymer films is an electroless-plating.But polymer surfaces need use catalyst activation (inoculation) to cause electroless-plating.For example, found that palladium (Pd) is the most effective catalyzer that causes electroless-plating.
The invention relates to the improving one's methods of polymeric matrix that a kind of activation is used for electroless-plating, so that obtain in matrix and good adhesivity between with after-applied metallic coating.
Summary of the invention
According to first embodiment of the present invention, the method for a kind of activation and sputtering of metals aromatic polymer films is provided, comprise the steps:
Handle the first surface of this film with alkaline solution;
Afterwards, described first surface is used the inoculation aqueous solution that comprises polymer stabilised catalyst particles; With
Then, this film immersion is comprised in the ionic electroless-plating groove of required metal, so that on the first surface of described film, deposit the layer of described metal.
Preferred bases solution is sodium hydroxide (NaOH) solution, or more preferably potassium hydroxide (KOH) solution.Relatively the broad range of concentrations is suitable for this solution (for example 0.2~2M).This alkaline solution can be by being applied this membranes submerged in the alkaline solution groove.Selectively, alkaline solution can be used by spray solution layer on the first surface of this film.The surface that will be activated (or a plurality of surface) that should keep this film contacts for some time with alkaline solution, and this depends on the volumetric molar concentration and the temperature (for example at room temperature keeping 1~15 minute for 1M KOH solution) of alkaline solution the time length of contact.After submergence (or spraying), alkaline solution is washed off, preferably uses deionized water.Using typically of alkaline solution carried out under 20~60 ℃ of degrees centigrade of quilts.
In some cases, after handling polymeric film with alkaline solution (for example KOH), this polymeric film is handled with acid solution subsequently and is used for forming from the teeth outwards protonated carboxylate ion.Realize acid treatment by will in aqueous acid, immersing for some time (for example 2~20 minutes) with the polymeric film that KOH handles.Later, carry out drying with deionized water wash and the common flowing air of using.
The preferred inoculation aqueous solution contains polymer stabilizing palladium particle (polymer-stabilisedpalladium particles).This stabilization can for example polyvinylpyrrolidone (PVP) or polyvinyl alcohol (PVA) but preferred especially PVP work by water-soluble polymkeric substance.
Above-mentioned palladium particle typically has the diameter of 1~50nm, or more preferably diameter is 2~10nm.
The inoculation aqueous solution generally is applied by this film being immersed in the inoculation solution tank.This immerses process and generally carried out for 2~60 seconds.After this, this film is taken out from the inoculation solution tank, and preferably by remove superfluous inoculation solution with deionized water wash.
Required metal generally is selected from the group that comprises nickel, copper and gold.Therefore, the electroless-plating groove can contain the ion of the metal of special expectation.
After required layer metal deposition was to film, this film was preferably used deionized water wash, and is dry then.
After layer metal deposition, or after flushing and drying subsequently, this film can be heated the adhesivity of improving between this film and the metal level with further.
Aforesaid method can be used in the first surface of this film, the second surface of this film, or two surfaces.
Preferred especially aromatic polymer films is made (Kapton for example by polyimide TMFilm).
Found that before using alkaline solution, it is particularly preferred forming the micro through hole that passes (or passing substantially) this film.These micro through holes can use known laser boring method, mechanical punching method or by the chemical erosion method run through film or in film punching form these micro through holes.Then, this film available bases solution and inoculation solution-treated (as mentioned above).During these were handled, the sidewall and the film surface of micro through hole were activated simultaneously.During inoculation step, polymer stabilised catalyst particles is adsorbed on the surface of this film and on the sidewall of micro through hole.Similarly, during metallisation step, required metal is applied on the sidewall of the surface of this film and micro through hole.Therefore, this method has been eliminated micro through hole in the existing method and is usually holed after forming circuit pattern and need be independent of outside the other parts of circuit and carry out galvanized step.
Forming micro through hole before the chemical treatment of this film in this polymeric film is particularly advantageous.For example, when two surfaces of polymeric film during subsequently all by required washing, micro through hole also will be by required washing, thereby connects the electrodeposition of metals on the apparent surface of polymeric film.
About a preferred aspect of the present invention, before handling this film with alkaline solution, this film can be used photic resist-coating.Then, required circuit can be determined by use mask on photo-resist.Then, photo-resist can be developed so that expose the surface portion of this film corresponding to the circuit pattern of expectation.Then, the film surface of this exposure as mentioned above can processed and metallize, thereby makes the selective metal spraying plating of carrying out forming on can film required circuit pattern.Therefore, photo-resist and subsequently mask auxiliary down, can on polymeric film, form required circuit by selecting Metal plating.
Description of drawings
To be described with reference to the accompanying drawings preferred implementation of the present invention.
Fig. 1 is the synoptic diagram according to the method on two opposites of a kind of activation of the preferred embodiment of the invention and sputtering of metals aromatic polymer films.
Fig. 2 has formed the amplifier section of photo of the Kapton of a series of nickel pads thereon for expression the method according to this invention.
Fig. 3 is the further part enlarged photograph of the coated Kapton shown in Fig. 2.
Fig. 4 is the polyimide general formula, and (or oxygen-pentanoic 0DA) is made by pyromellitic acid dianhydride (PMDA) and 4-4 ' diamino-diphenyl ether for it.
Embodiment
Fig. 1 schematically represents the formation according to the double-sided flex circuit of preferred embodiment of the invention manufacturing.
As shown, the Kapton of cleaning TMFilm has the micro through hole 2 that passes it and be formed.Two of film 1 facing surfaces 3a then, 3b use strong base solution (for example KOH) to carry out chemical treatment, activate with polymer stabilizing palladium particulate colloidal suspension subsequently.The sidewall of film 1 (or several sidewall) 4 is simultaneously by chemical treatment and activation.
Then, this activatory film is positioned over the surperficial 3a that makes at this film, forms in the electroless nickel plating groove (for example not having the electrolytic copper groove) of metal copper layer 5 on the sidewall 4 of the last and micro through hole 2 of 3b.
Then, electrical treating coating is so that apply circuit pattern.In order to realize this purpose, use photo-resist 6 with required pattern.Selectively, patternless photo anti-corrosion agent material band can be used in the surface, this band that develops then (for example passing through to use mask and etching step so that produce the required pattern of photo-resist).
Then, electroplating film is carried out metallide so that on copper layer 5, form metallic circuit 7.
Then, photo-resist 6 for example can be removed by known engraving method.
Then, can carry out further etching so that remove electroless-plating copper layer between the metallic circuit 7 to laminar film.
According to foregoing invention, polymeric film can not use any photoresist mask to be electroplated with the regular pattern form with required metal by using miniature dispersion machine.In this embodiment, the aqueous solution of potassium hydroxide is dispersed on the polymeric film of cleaning with the form of small droplets.After about 5~10 minutes, next this polymeric film deionized water wash uses compressed air drying.Then, with this film of inoculation solution-treated, afterwards with deionized water wash and dry.This causes this film optionally to be inoculated in potassium hydroxide solution dispersive place.Then, the electroless-plating of one section grace time of this film experience makes the metal deposition of aequum to this film.This is only optionally electroplated metal in the region of activation of this film.As shown in Figures 2 and 3, can utilize the simplification of this metal Butut,, form the metal gasket in ball grid matrix (the ball grid array BGA) encapsulation with the form of the thin circumference 10 on the polymeric film.
The present invention also can be applicable to redistribute connection gasket on silicon chip.Aromatic polymer films is used as the passivation layer on the silicon chip widely.The application of the invention, the connection gasket of chip periphery can be reallocated in its surface.
Therefore, the invention provides the method on the surface of the required metal electroless-plating of a kind of selectable use aromatic polymer films.Method of the present invention also makes the circuit with required micro through hole can be simpler than existing method, manufactured more easily.
Embodiment
Embodiment:
(i), use the thick Kapton of 5 mils (mil) for serve exemplary purposes
Figure C0381306200111
Film, it is the commercial polyimide of representing with general formula shown in Figure 4, (or oxygen-pentanoic ODA) is made by pyromellitic acid dianhydride (PMDA) and 4-4 ' diamino-diphenyl ether for it.At room temperature handled this film 10 minutes with 1M potassium hydroxide (KOH) aqueous solution.KOH attacks the imide group in the polyimide and forms the sylvite of polyamic acid.This film washs to remove excessive KOH up hill and dale with deionized water (DI), uses the air stream drying of compression then.Then, at room temperature keep the Kapton film of this usefulness alkaline purification to contact 10 minutes, use DI water washing and dry subsequently with 0.2M hydrochloric acid (HCl).This chemical treatment forms polyamic acid on the surface of Kapton, thereby introduces carboxyl.
How to prepare by the embodiment of the stable palladium particulate waterborne suspension of polyvinylpyrrolidone (PVP) as follows:
150mg PVP (weight average molecular weight=50,000 are even this weight average molecular weight can be about 10,000~500,000) is dissolved in the DI water.
With 150mg PdCl 2Be dissolved among the 5.25ml HCl (purity about 37%).
With PVP and PdCl 2Solution mixes.
Hypophosporous Acid, 50 (the H that 10ml~35ml 50% is pure 3O 2P) slowly join in this solution.
Adding DI water is 1 liter up to the cumulative volume of this solution.
Then, will apply in the aqeous suspension of palladium particulate polyvinylpyrrolidone (PVP) 30 seconds of submergence, next use DI water washing and dry through chemically treated Kapton film.
Then, this palladium catalyst activatory Kapton film stands not have electrolytic copper plating 15~60 minutes under 25 ℃.Copper lamina (1~2 μ m) is plated on the Kapton.
(ii) except the electroless nickel plating groove is used to electronickelling thin layer (1-2 μ m) about 15-30 minute under 80 ℃, carry out according to the step of embodiment (i).
Do not break away from the spirit and scope of the invention and, be conspicuous for a person skilled in the art many variants and modifications of the present invention.
In specification sheets, except context has the requirement in addition, " comprising " " the meaning be " comprising ".In other words,, be interpreted as the present invention (at least) and comprise these features or component when the present invention is described or defined as when comprising some feature or component, but also can (except context have in addition point out) comprise other features or component.

Claims (29)

1. the method for activation and sputtering of metals aromatic polymer films comprises the steps:
Handle the first surface of this film with alkaline solution;
Afterwards, use the inoculation aqueous solution that comprises polymer stabilised catalyst particles at the described first surface of this film; With
Then, this film immersion is comprised in the ionic electroless-plating groove of required metal, so that on the first surface of described film, deposit the layer of described metal.
2. according to the process of claim 1 wherein that alkaline solution is a potassium hydroxide solution.
3. according to the method for claim 1 or 2, wherein after the alkaline solution treatment step, described first surface is used acid solution.
4. according to the method for claim 3, wherein said acid solution is a protonic acid.
5. according to the method for claim 4, wherein said acid solution is hydrochloric acid or acetum
6. according to the process of claim 1 wherein that the inoculation aqueous solution comprises polymer stabilizing palladium particle.
7. according to the process of claim 1 wherein that granules of catalyst stablized by water-soluble polymers.
8. according to the method for claim 7, wherein water-soluble polymers is polyvinylpyrrolidone or polyvinyl alcohol.
9. method according to Claim 8, wherein water-soluble polymers is a polyvinylpyrrolidone.
10. according to the method for claim 6, wherein the palladium particle has the diameter of 1~50 nanometer.
11. according to the process of claim 1 wherein that required metal is selected from the group that comprises nickel, copper and gold.
12. according to the method for claim 11, wherein required metal is nickel or copper.
13. according to the process of claim 1 wherein that alkaline solution is applied by this film is immersed in this alkaline solution groove.
14. according to the process of claim 1 wherein that alkaline solution is applied by spray this solution of one deck on the first surface of described film.
15. according to the method for claim 13 or 14, wherein keep this film to contact 1~15 minute with alkaline solution, this alkaline solution is washed off afterwards.
16. according to the process of claim 1 wherein that the inoculation aqueous solution is applied by this film is immersed in this inoculation solution tank.
17. according to the method for claim 16, wherein said immersion reaches for some time of 5~60 seconds.
18. according to the process of claim 1 wherein, after using this inoculation aqueous solution, with this film of washed with de-ionized water to remove excessive granules of catalyst.
19. according to the process of claim 1 wherein, after the required metal level of deposition, with this film of deionized water wash and dry.
20. according to the process of claim 1 wherein, after the required metal level of deposition, this film is heated to improve the adhesivity between this film and the metal level.
21., before using the alkaline solution step, form basically or pass completely through the through hole of this film according to the process of claim 1 wherein.
22., wherein use laser drilling to form this through hole according to the method for claim 21.
23. according to the process of claim 1 wherein, before using the alkaline solution step, photo anti-corrosion agent material is used to this film, and described photo anti-corrosion agent material is developed to promote to form the pattern of required circuit on described film.
24. according to the process of claim 1 wherein, before executing the step of all alkaline solutions, this film is cleaned and is dry.
25. according to the method for claim 24, wherein this cleaning is by carrying out ultrasonic the realization in acetone and deionized water.
26., wherein further clean and realize by the ozonize under elevated temperature according to the method for claim 25.
27. according to the method for claim 26, wherein this ozonize was carried out 3~10 minutes under about 80 ℃ of temperature.
28. according to the process of claim 1 wherein that aromatic polymer films is formed by polyimide.
29. the aromatic polymer films of a washing of making according to each method of claim 1~28.
CNB038130629A 2002-06-04 2003-06-03 Method for electroless metalisation of polymer substrate Expired - Fee Related CN100424226C (en)

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SG200233140 2002-06-04
SG200203314A SG107593A1 (en) 2002-06-04 2002-06-04 Method for electroless metalisation of polymer substrate
SG20023314-0 2002-06-04

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CN100424226C true CN100424226C (en) 2008-10-08

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EP2078607B1 (en) * 2006-10-23 2018-09-12 FUJIFILM Corporation Process for producing a metal film coated material, process for producing a metallic pattern bearing material and use of a composition for polymer layer formation
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TW201505493A (en) 2013-07-17 2015-02-01 Ichia Tech Inc Precursor substrate, flexible circuit board and process for producing the same
TW201529885A (en) * 2014-01-24 2015-08-01 Taiwan Uyemura Co Ltd Polyimide substrate metallization method
JP6328575B2 (en) * 2015-02-23 2018-05-23 東京エレクトロン株式会社 Catalyst layer forming method, catalyst layer forming system, and storage medium
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CN113893876B (en) * 2021-09-10 2023-07-21 浙江鑫柔科技有限公司 Electroless copper plating catalyst and method for forming metal mesh using the same
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AU2003239102A8 (en) 2003-12-19
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CN1659310A (en) 2005-08-24
WO2003102267A1 (en) 2003-12-11

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