CN100428871C - Method for forming plain conductor pattern by means of ink-jet - Google Patents
Method for forming plain conductor pattern by means of ink-jet Download PDFInfo
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- CN100428871C CN100428871C CNB2003101218250A CN200310121825A CN100428871C CN 100428871 C CN100428871 C CN 100428871C CN B2003101218250 A CNB2003101218250 A CN B2003101218250A CN 200310121825 A CN200310121825 A CN 200310121825A CN 100428871 C CN100428871 C CN 100428871C
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Abstract
The present invention relates to an ink-jet method for forming a metal conducting wire pattern. A catalyst is sprayed at a position of a basal plate in a microdroplet spraying manner, and a metal conducting wire is formed at the position. Then electroless plating procedure is carried out to form the metal conducting wire. In order to make the catalyst effective absorbed on the basal plate and improve the surface property of the basal plate, the basal plate needs proper surfaction process before the microdroplet spraying is carried out.
Description
Technical field
The present invention relates to a kind of plain conductor formation method, relate in particular to a kind of method that forms metal conductive line pattern with ink-jet method.
Background technology
Along with the design concept of electronic product trend " compact ", printed circuit board (PCB) (Printed CircuitBoard, PCB) also towards the small-bore, high density, multilayer number, the development of fine rule road.General printed circuit board (PCB), the plane substrate that uses glass fabric or flexible substrate to form usually utilizes solid and hot pressing mode, attaches metal level or Copper Foil and is etched with the formation plain conductor again.But need to add in the prescription of solid and contain the incombustible agent of halogen, and be difficult to meet the regulation that European Union's electronic product in 2004 is forbidden halogen comprehensively, will limit its future development.And often add ionic impurity in the solid, make the dielectric and the insulation characterisitic variation of substrate, and at high temperature cause the substrate torsional deformation easily, these all can reduce the reliability of substrate.Therefore should in circuit board, avoid the use of solid as far as possible.
Therefore, can form metal level at substrate surface, etch required plain conductor in the light lithography mode again by the mode of metal deposition.Electroless plating (electroless plating) or be called chemical plating, it is a kind of mode of depositing metal layers, under need not the situation of applied voltage,, deposit metal on the surface of solids the chemical reaction mode of solution metal ion by autocatalysis (autocatalytic).This response procedures and plating (electroplating) are very similar, electron transport when different is the reaction generation is not via external circuit, but the material in the solution is when surface of solids generation redox reaction, directly transmits from the teeth outwards and is different from the plating of additional circuit.Be the wide requirement of the fine rule of coincident circuit plate, thereby increased light shield manufacture and the etched difficulty of metal level, and the plain conductor of variety classes and size all needs to utilize different light shields to make, relative increase on manufacturing cost.
Thereby develop by electroless characteristic and directly on substrate, to form metal pattern with method as plain conductor, because electroless plating need just can be carried out on the surface through overactivation or catalysis, can be optionally form Catalytic Layer, and then carry out electroless plating in the substrate surface plain conductor part of need growing up.As described in No. 6521285 patent of the U.S., disclose a kind of optionally electroless process, carve printed panel in advance with metal conductive line pattern, again its printed panel is stained with catalyst, in the mode of impressing the printed panel aligning is pressed on the substrate, the predetermined plain conductor part that forms of substrate surface is stamped after the Catalytic Layer, have the surface growth conducting metal of catalyst again in the electroless plating mode at substrate.This method need cooperate the catalyst of the plain conductor of variety classes and size to make different printed panels equally, and the live width of circuit need depend on the accessible engraving precision of printed panel.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that forms metal conductive line pattern with ink-jet method, be to form plain conductor part spraying catalyst in the substrate desire with little drop spraying method, and then carry out the electroless plating program to form plain conductor, avoided the use of solid.And for making catalyst effectively be adsorbed in substrate, and improve the surface nature of substrate, substrate carries out suitable surfaction at the preceding need that carry out little drop spraying to be handled.
To achieve these goals, the invention provides a kind of method with ink-jet method formation metal conductive line pattern, its characteristics are that step includes:
One substrate is provided;
This substrate is soaked by two kinds of electrical polyeletrolyte solution of difference,, this substrate surface is formed from forming the film interface this substrate surface is carried out a upgrading step;
Form the plain conductor part with little drop spraying method in this substrate surface desire and spray a catalyst to form a metal catalytic pattern; And
Have this metal catalytic pattern part in the electroless plating mode at this substrate surface and deposit a metal to form a plain conductor.
Above-mentioned form the method for metal conductive line pattern with ink-jet method, its characteristics are, described with this substrate by the step that two kinds of electrical polyeletrolyte solution of difference soak, comprise:
Step a, with this substrate immersion in an anionic polyelectrolyte solution;
Step b, with this substrate immersion in a cationic polymerization electrolyte solution;
Step c, repeat once above step a to step b; And
Steps d, with this substrate immersion in this anionic polyelectrolyte solution.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that this anionic polyelectrolyte solution is selected from polyacrylic acid solution, polymethylacrylic acid and poly-match fen-3-acetic acid.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that this cationic polymerization electrolyte solution is selected from polypropylene amine hydrogen chloride solution, poly-ethyl pyrazoles, poly-N-ethyl pyrrole N-ketone and polyaniline.
Above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that this substrate is selected from glass substrate, polyester substrate, polymethyl methacrylate fibre base plate, pliability polymethyl methacrylate fibre base plate and Polyimide substrate.
Above-mentioned form the method for metal conductive line pattern with ink-jet method, its characteristics are, described with this substrate by the step that two kinds of electrical polyeletrolyte solution of difference soak, comprise:
Step a, with this substrate immersion in a cationic polymerization electrolyte solution;
Step b, with this substrate immersion in an anionic polyelectrolyte solution;
Step c, repeat once above step a to step b; And
Steps d, with this substrate immersion in this anionic polyelectrolyte solution.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that this anionic polyelectrolyte solution is selected from polyacrylic acid solution, polymethylacrylic acid and poly-match fen-3-acetic acid.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that this cationic polymerization electrolyte solution is selected from polypropylene amine hydrogen chloride solution, poly-ethyl pyrazoles, poly-N-ethyl pyrrole N-ketone and polyaniline.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that also comprising one provides the step of a fluctuation to this substrate, with this metal catalytic pattern of this substrate surface of planarization.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that the principal component material of this metal is a copper.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are that this catalyst is selected from tetrachloro-palladium acid sodium solution and four hydrazine dichloride palladium solution.
Above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are, also comprise the following step:
Spray another layer metal catalytic pattern with ink-jetting style on this first plain conductor surface; And
Carry out another layer of electroless deposition metal to form another plain conductor at this another metal catalytic patterned surfaces.
The above-mentioned method with ink-jet method formation metal conductive line pattern, its characteristics are, the principal component material difference of these two kinds of metals.
By substrate surface is formed from forming film (Self-Assembled Monolayer, SAM) interface carries out surfaction, what substrate surface was handled is back formed from forming the film interface, utilize atom chemical kinetics difference to each other, cause from forming (self-assembly) and form special nanometer interface structure, this nanometer interface structure has the thickness of nano-scale.Can on substrate, form the compact arranged sequential 2 D monolayer of atom by the chemisorbed between the solid-liquid interface from the membrane formation mechanism of forming film with chemical bond connection.This can form nano level multilayer film interface structure from forming film to repeat control formation, and can change the surface nature of substrate by composition, structure, physics and the chemical property of this film interface, and make substrate surface have optionally adsorption capacity for some material, can make the effective adsoption catalyst of substrate whereby.
By form plain conductor part spraying catalyst in the substrate desire, can effectively reduce and the formed plain conductor live width of the stable follow-up electroless plating of control, based on electroless characteristic, more can control the thickness of plain conductor and the resistance that reduces plain conductor easily.Cooperate spraying of little drop and electroless process can finish the making of plain conductor, raising productive rate fast compared to existing light lithography and etch process.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Fig. 1 forms the flow chart of the method for metal conductive line pattern with ink-jet method for the present invention;
Fig. 2 the present invention is with the device schematic diagram of ink-jet method spray metal catalysis pattern;
Fig. 3 is the circuit board generalized section of first embodiment of the invention; And
Fig. 4 is the circuit board generalized section of second embodiment of the invention.
Embodiment
Please refer to Fig. 1, it is the flow chart that forms the method for metal conductive line pattern with ink-jet method, at first, step 110, clean substrate, the ultraviolet light ozone (UV-ozone) that carried out 10 minutes is handled.Step 120, with substrate immersion in anionic polyelectrolyte solution, anionic polyelectrolyte solution be 10 millimolar concentrations (M) polyacrylic acid (poly (acrylic acid), PAA).Step 130 is with the washed with de-ionized water substrate.Step 140, with substrate immersion in the cationic polymerization electrolyte solution, the cationic polymerization electrolyte solution be 10 millimolar concentrations (M) polypropylene amine hydrogen chloride (poly (allylamine hydrochloride), PAH).Step 150, again with substrate immersion in anionic polyelectrolyte solution.Step 160 forms plain conductor part spraying catalyst with little drop spraying method in the substrate desire, and catalyst is not sodium tetrachloropalladate (Na2PdCl4) solution of ear concentration (M) of 10 millis.Step 170 is with the washed with de-ionized water substrate.Again with the hydrogen chloride solution of substrate immersion between pH value 2.5 to 3 30 seconds; Then, step 180 is carried out electroless plated metal.At last, step 190 is again with the washed with de-ionized water substrate.
Wherein, step 120 of the present invention to step 140 is the surfaction processing that are used for carrying out substrate, carry out surfaction by substrate surface is formed from forming the film interface, cooperate different materials substrate its soak the order of cation and anionic polymerization electrolyte solution also possibility be opposite.Substrate can form from forming the film interface on its surface through the immersion treatment of the electrical polyeletrolyte solution of two kinds of differences.In above-mentioned technology, be effectively to change its surface nature, but also repeating step 120 to step 140 at substrate surface storehouse PAH/PAA double-decker (bilayers) repeatedly, and then carry out step 150 to form nano level multilayer from the component film interface.Can select from the structure of forming the film interface based on the character of different materials substrate, above-mentioned PAH/PAA bilayers baseplate material applicatory can be glass substrate, polyester (PET) substrate, polymethyl methacrylate fiber (FR-4) substrate, pliability polymethyl methacrylate fibre base plate (Flexible FR-4) and Polyimide substrate (Polyimide).In addition, its cationic polymerization electrolyte solution is optional from polypropylene amine hydrogen chloride solution (PAH), poly-ethyl pyrazoles (PVI+), poly-N-ethyl pyrrole N-ketone (PVP+) and polyaniline (PAN); The anionic polyelectrolyte solution of the use of arranging in pairs or groups is optional from polyacrylic acid solution (PAA), polymethylacrylic acid (PMA) and poly-match fen-3-acetic acid (PTAA).
The present invention forms plain conductor part spraying catalyst with inkjet printing methods in the substrate desire, because catalyst is generally salt, can almost completely be dissolved in water and forms homogeneous solution, therefore has good ink-jet stability.Because ink-jet resolution is depended in the formed plain conductor of follow-up electroless plating system, and present ink-jet technology can reach high-resolution, so the present invention can be in order to make high density, the wide plain conductor of fine rule.In addition, for increasing the flatness of the catalyst drop that sprays, in ink-jet is carried out, can provide the fluctuation of appropriate frequency and amplitude to destroy the surface tension of the little drop that is attached to substrate, and obtain more smooth uniformity of film.
Please refer to Fig. 2, be device schematic diagram with ink-jet method spray metal catalysis pattern.Include ink gun module 10, motion carrying platform 20, bracing frame 21 and fluctuation generation module 30, ink gun module 10 has more than one spray orifice 11, and is fixed in a nozzle regulating mechanism 12 substrate 40 is carried out 13 sprayings of catalyst drop.Motion carrying platform 20 is that bearing substrate 40 also can be adjusted its position for ink gun module 10 spraying catalyst drops 13, and has bracing frame 21 substrate settings, makes substrate 40 and motion carrying platform 20 keep a segment distance.And fluctuation generation module 30 is a piezoelectric element, is attached at substrate 40 belows, and fluctuation generation module 30 does not contact with motion carrying platform 20, can avoid unnecessary energy attenuation.The fluctuation that 30 starts of fluctuation generation module produce appropriate frequency when spray orifice 11 is sprayed at substrate 40 with formation metal catalytic pattern with a plurality of catalyst drops 13, treats that the solvent evaporates of catalyst drop can obtain the metal catalytic pattern of planarization afterwards.Above-mentioned technology is to carry out the catalysis of metals such as electroless copper as catalyst by separating out palladium with tetrachloro-palladium acid sodium (Na2PdCl4) solution or four hydrazine dichloride palladiums (Pd (NH3) 4Cl2) solution.
Electroless plating is called chemical plating (chemical plating) again or autocatalysis is electroplated (autocatalyticplating).Electroless plating is meant metal ion in the aqueous solution by under the plating bath environment of control, gives electronation and forms coating at substrate.General electroless plating liquid composition mainly need include the metal ion (metal ions) as the source of coated metal; Metal ion is reduced into metallic reducing agent (reducing agent); Make substrate surface have the catalyst (catalyst) of catalytic.Secondly in order to keep the stability of plating bath, also need comprise misfit agent (complexing agent), make plating bath stable to prevent precipitation of hydroxide, regulate precipitation rate, to prevent that plating bath from decomposing; The sorption granulometric impurity prevents the plating bath natural decomposition, to prolong the stabilization agent (stabilizer) of bath life; And in order to the buffer (buffer) of control pH value in opereating specification.And, need to add making the good wetting agent of surface action (wetting agent) in order to increase composite coating properties; Make coating have the polishing material (brightener) of good gloss.
Electroless plating liquid need be stabilized, need be inoperative when not using, only when the contact of the surface of catalytic, just begin to act on precipitating metal coating.The present invention earlier carries out surfaction at substrate to handle, and forms plain conductor part spraying catalyst in the substrate desire again, then, carry out the electroless plating alternative only at surface deposition metal with catalyst to form plain conductor.Please refer to Fig. 3, it is the circuit board generalized section of first embodiment of the invention.Be to have multilayer that PAA layer 211 and PAH layer 212 formed through surfaction on substrate 200 surfaces from forming film interface 210, metal catalytic pattern 220 is to be attached to multilayer through spraying to be formed on the metal catalytic pattern 220 from forming 230 of film interface 210, the first plain conductors.
Because electroless plating is after after a while, the speed that its metal is separated out deposition can descend, and therefore, uses the inventive method, and as shown in Figure 4, it is the circuit board generalized section of second embodiment of the invention.Can above first plain conductor, spray another layer metal catalytic pattern 221 again, and carry out the electroless plating second time once more to form the two or two plain conductor 231.Except using identical catalyst and electroless plating bath to increase the thickness of metal conductive line pattern, more can select different catalyst and electroless plating liquid simultaneously, make first plain conductor and second plain conductor can be identical or different metal material and form.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (15)
1, a kind of method with ink-jet method formation metal conductive line pattern is characterized in that step includes:
One substrate is provided;
This substrate is soaked by two kinds of electrical polyeletrolyte solution of difference, this substrate surface is carried out a upgrading step, this substrate surface is formed certainly form the film interface, and this substrate also comprises the step that substrate is cleaned between two kinds of electrical polyeletrolyte solution of difference soak;
Form the plain conductor part with little drop spraying method in this substrate surface desire and spray a catalyst to form a metal catalytic pattern; And
Have this metal catalytic pattern part in the electroless plating mode at this substrate surface and deposit a metal to form a plain conductor.
2, according to claim 1ly form the method for metal conductive line pattern, it is characterized in that with ink-jet method, described with this substrate by the step that two kinds of electrical polyeletrolyte solution of difference soak, comprise:
Step a, with this substrate immersion in an anionic polyelectrolyte solution;
Step b, substrate is cleaned;
Step c, with this substrate immersion in a cationic polymerization electrolyte solution;
Steps d, repeat once above step a to step c; And
Step e, with this substrate immersion in this anionic polyelectrolyte solution.
3, the method with ink-jet method formation metal conductive line pattern according to claim 2 is characterized in that, this anionic polyelectrolyte solution is selected from polyacrylic acid solution, polymethylacrylic acid and poly-match fen-3-acetic acid.
4, the method with ink-jet method formation metal conductive line pattern according to claim 2 is characterized in that, this cationic polymerization electrolyte solution is selected from polypropylene amine hydrogen chloride solution, poly-ethyl pyrazoles, poly-N-ethyl pyrrole N-ketone and polyaniline.
5, the method with ink-jet method formation metal conductive line pattern according to claim 2 is characterized in that this substrate is selected from glass substrate, polyester substrate, polymethyl methacrylate fibre base plate and Polyimide substrate.
6, the method with ink-jet method formation metal conductive line pattern according to claim 5 is characterized in that this polymethyl methacrylate fibre base plate is a pliability polymethyl methacrylate fibre base plate.
7, according to claim 1ly form the method for metal conductive line pattern, it is characterized in that with ink-jet method, described with this substrate by the step that two kinds of electrical polyeletrolyte solution of difference soak, comprise:
Step a, with this substrate immersion in a cationic polymerization electrolyte solution;
Step b, substrate is cleaned;
Step c, with this substrate immersion in an anionic polyelectrolyte solution;
Steps d, repeat once above step a to step c; And
Step e, with this substrate immersion in this anionic polyelectrolyte solution.
8, the method with ink-jet method formation metal conductive line pattern according to claim 7 is characterized in that, this anionic polyelectrolyte solution is selected from polyacrylic acid solution, polymethylacrylic acid and poly-match fen-3-acetic acid.
9, the method with ink-jet method formation metal conductive line pattern according to claim 7 is characterized in that, this cationic polymerization electrolyte solution is selected from polypropylene amine hydrogen chloride solution, poly-ethyl pyrazoles, poly-N-ethyl pyrrole N-ketone and polyaniline.
10, the method with ink-jet method formation metal conductive line pattern according to claim 1 is characterized in that, also comprising one provides the step of a fluctuation to this substrate, with this metal catalytic pattern of this substrate surface of planarization.
11, the method with ink-jet method formation metal conductive line pattern according to claim 1 is characterized in that the principal component material of this metal is a copper.
12, the method with ink-jet method formation metal conductive line pattern according to claim 1 is characterized in that this catalyst is selected from tetrachloro-palladium acid sodium solution and four hydrazine dichloride palladium solution.
13, the method with ink-jet method formation metal conductive line pattern according to claim 1 is characterized in that, also comprises the following step:
Spray another layer metal catalytic pattern with ink-jetting style on this first plain conductor surface; And
Carry out another layer of electroless deposition metal to form another plain conductor at this another metal catalytic patterned surfaces.
14, the electroless process with ink-jet method formation metal catalytic pattern according to claim 13 is characterized in that the principal component material difference of these two kinds of metals.
15, according to claim 1,2 or 7 described methods, it is characterized in that this carries out with deionized water the step that substrate cleans with ink-jet method formation metal conductive line pattern.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101218250A CN100428871C (en) | 2003-12-19 | 2003-12-19 | Method for forming plain conductor pattern by means of ink-jet |
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| CNB2003101218250A CN100428871C (en) | 2003-12-19 | 2003-12-19 | Method for forming plain conductor pattern by means of ink-jet |
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| CN1630458A CN1630458A (en) | 2005-06-22 |
| CN100428871C true CN100428871C (en) | 2008-10-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1988251B (en) * | 2005-12-20 | 2012-02-08 | 财团法人工业技术研究院 | Method for producing radio frequency identifying antenna and its antenna structure |
| CN101754585B (en) * | 2008-11-27 | 2011-09-21 | 富葵精密组件(深圳)有限公司 | Method for manufacturing conductive circuit |
| CN102883543B (en) * | 2012-10-08 | 2016-04-13 | 复旦大学 | A kind of method adopting additive process to prepare conducting wire |
| CN103476199B (en) * | 2013-09-27 | 2016-02-03 | 电子科技大学 | Based on the printed circuit addition preparation method of copper self-catalysis and electroless copper |
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| JPH06108297A (en) * | 1991-10-08 | 1994-04-19 | Tokyo Kakoki Kk | Chemical treatment device |
| US5492613A (en) * | 1987-01-27 | 1996-02-20 | Zhang; Shaoxian | Process for electroless plating a metal on non-conductive materials |
| CN1119879A (en) * | 1994-01-05 | 1996-04-03 | 蓝片控股公司 | Polymeric resin for depositing catalytic palladium on a substrate |
| JPH10150278A (en) * | 1996-11-19 | 1998-06-02 | Toppan Printing Co Ltd | Multilayer interconnection board and its manufacture |
| JP2000312068A (en) * | 1999-04-27 | 2000-11-07 | Kyocera Corp | Wiring board and manufacture thereof |
| CN1302179A (en) * | 1999-10-28 | 2001-07-04 | 味之素株式会社 | Method for producing multilayer printed circuit board using adhesive film |
| CN1459824A (en) * | 2002-03-27 | 2003-12-03 | 精工爱普生株式会社 | Surface treating method and film pattern forming method |
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2003
- 2003-12-19 CN CNB2003101218250A patent/CN100428871C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492613A (en) * | 1987-01-27 | 1996-02-20 | Zhang; Shaoxian | Process for electroless plating a metal on non-conductive materials |
| JPH06108297A (en) * | 1991-10-08 | 1994-04-19 | Tokyo Kakoki Kk | Chemical treatment device |
| CN1119879A (en) * | 1994-01-05 | 1996-04-03 | 蓝片控股公司 | Polymeric resin for depositing catalytic palladium on a substrate |
| JPH10150278A (en) * | 1996-11-19 | 1998-06-02 | Toppan Printing Co Ltd | Multilayer interconnection board and its manufacture |
| JP2000312068A (en) * | 1999-04-27 | 2000-11-07 | Kyocera Corp | Wiring board and manufacture thereof |
| CN1302179A (en) * | 1999-10-28 | 2001-07-04 | 味之素株式会社 | Method for producing multilayer printed circuit board using adhesive film |
| CN1459824A (en) * | 2002-03-27 | 2003-12-03 | 精工爱普生株式会社 | Surface treating method and film pattern forming method |
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