CN103338596A - Manufacturing method of whole addition circuit board without photoresist - Google Patents
Manufacturing method of whole addition circuit board without photoresist Download PDFInfo
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- CN103338596A CN103338596A CN201310239609XA CN201310239609A CN103338596A CN 103338596 A CN103338596 A CN 103338596A CN 201310239609X A CN201310239609X A CN 201310239609XA CN 201310239609 A CN201310239609 A CN 201310239609A CN 103338596 A CN103338596 A CN 103338596A
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Abstract
The invention discloses a manufacturing method of a whole addition circuit board. The method comprises the following steps: covering conductive macromolecule on the insulation base material surface, radiating by vacuum ultraviolet with the wavelength of 100 to 200 nm, irradiating the conductive macromolecule through masks, damaging the conjugated structure of the conductive macromolecule, enabling the conductive macromolecule to be an insulator, forming conductive patterns on the base material surface, converting the conductive patterns on the base material surface into copper wire patterns through electrochemical electroless plating copper, and manufacturing the circuit board. The method has the characteristics that photoresist and photolithography technique are not needed, and copper wire patterns are manufactured on the surface of the insulation base material through the electrochemical electroless plating copper directly.
Description
Technical field
The invention belongs to wiring board (printing circuit board PCB) technical field, be specifically related to the manufacture method of full addition wiring board.
Background technology
Wiring board is one of topmost parts in semiconductor electronic device, it is applied to nearly all electronic product, little of electronic watch, calculator, PC, arrive greatly electromechanical equipment control assembly, data handling machine, communication electronic equipment and military armament systems.As long as the place of integrated circuit and other electronic devices and components is arranged, just need use wiring board.
The Main Function one of wiring board is the electric interconnection of realizing between integrated circuit and various electronic devices and components; The 2nd, load chip and other various electronic devices and components, the mechanical support be mounted with is provided; In addition, it also needs to provide the desired electrical characteristic of product electric insulation as impedance, withstand voltage, dielectric etc., and provides components and parts to assemble, check, keep in repair required identification character and figure.The technology quality index of wiring board directly has influence on function and the performance of electronic product.
Wiring board is combined into mainly with conductor and organic substrate.Along with the development of electronics industry, conductor develops into Copper Foil from electrically conductive ink, and conductor width drops to tens microns from grade; Base material has also experienced by cardboard, has strengthened the transition of phenolic aldehyde/epoxy resin to high performance engineering plastics; Wiring board also expands to high density flexible and toughness wiring board from rigid plate, to meet the needs of mobile communication product and flat-panel screens development.People not only wish that base material has high thermomechanical property and electrical insulation properties, also wish that it has low dielectric constant, reduce impedance between circuit and on the impact of high frequency electrical signal; Wish little copper cash spacing, high copper cash density simultaneously.
At present, high performance wiring board is that raw material is made mainly with Copper Foil and organic substrate.Manufacture craft can be divided into and subtracts layer method or semi-additive process.In manufacturing process, Copper Foil, by applying light-sensitive emulsion, exposure, development, etching and removing the photoetching process that glue cleans, changes into required copper cash figure line.High-density flexible circuit board also useful so-called semi-additive process is made.The technique of high-density flexible circuit board has first with sputter Cr/Cu or other method, form metal film as thin as a wafer at surface of polymer substrates, then by photoresist and photoetching process, the metallized polymer surfaces of major part is covered, stay small part and contact with electroplate liquid, by electrochemistry, sink copper thickening.Remove again photoresist layer, dissolve away the metallic diaphragm of polymer surfaces, form required copper cash figure line.Sputter Cr/Cu will use equipment or the specific process of semiconductor manufacture use, and cost is higher.Photoetching process consumes a large amount of chemical solutions and water, produces many accessory substances containing heavy metal ion, easily contaminated environment.
People are exploring the new technology that can make the surface of polymer material selective metallization always, directly make copper cash figure line on insulating body, save traditional photoetching process.Physical vapour deposition (PVD), chemical vapour deposition (CVD) or plated film can make surface metallation of insulator, but can not meet optionally requirement, all need to make the substrate surface selective metallization with photoetching process with photoresist.
Summary of the invention
The objective of the invention is make to need with photoresist the shortcoming with photoetching process in order to overcome the existing line plate, provides that a kind of cost is low, technique is simple, eco-friendly, not with photoresist with the method for manufacturing circuit board of photoetching process.The present invention is achieved through the following technical solutions:
A kind of not full addition method for manufacturing circuit board with photoresist, it sees through mask with vacuum ultraviolet light source, irradiates the conducting polymer film that invests substrate surface, at substrate surface structure conductive pattern line, through the heavy copper of electrochemistry, changes into copper cash figure line, makes described wiring board.
Further preferred, described conducting polymer is the compound of one or both in polythiophene and polypyrrole.
Further preferred, described conducting polymer film generates by the following method: have the base material of oxidant to immerse in monomer solution absorption, the monomer in monomer solution is deposited to substrate surface and oxidant reaction generates described conducting polymer film; After perhaps by the mixed solution of monomer and oxidant, being coated on substrate surface, intensification oxidation polymerization generates.
Further preferred, the conducting polymer of described conducting polymer film in the conducting polymer dispersion liquid is attached to substrate surface and generates; Dispersion in described conducting polymer dispersion liquid is thiofuran polymer or pyroles polymer.
Further optimize, the sheet resistance of described conducting polymer film is 10-10
4ohm.
Further optimize, the radiation wavelength of described vacuum ultraviolet light source output is 100～200 nm.
Further optimize, described vacuum ultraviolet light source is one or more in the semiconductor element of 172 nm xenon excimer ultraviolet lamps, 146 nm krypton Excimer UV light modulations, emission wavelength 100～200 nm; The vacuum ultraviolet (VUV) energy density of described vacuum ultraviolet light source output is 5-500 mW/cm
2.
Further preferred, described base material is thin polymer film, reinforced composite, clear glass or opaque pottery.
Further preferred, described oxidant is one or more of ammonium persulfate, potassium metaperiodate, potassium bichromate, potassium permanganate, manganese dioxide, copper nitrate, ferric iron compound, hydrogen peroxide, organic peroxide, macromolecule peroxide; Described ferric iron compound is one or more of ferric trichloride, ferric sulfate, p-methyl benzenesulfonic acid iron.
Further preferred, described monomer is one or more of thiophene, pyrroles, alkylthrophene, alkoxy thiophene.
Below principle of the present invention is described further:
The present invention sees through mask with vacuum ultraviolet light source, irradiates the conducting polymer film that invests substrate surface, destroys the conjugated structure of conductive polymer subchain, at substrate surface, stays the conductive pattern line.On this basis, the method for recycling Cu electroplating, plated metal copper on the conductive pattern line, make copper cash figure line.
Thiofuran polymer, pyroles polymer belong to structural conductive macromolecular, and the long strand of conjugation is arranged.This is the inherent feature of structural conductive macromolecular.When conducting polymer is exposed to vacuum ultraviolet, high-octane electromagnetic radiation meeting destroys the conjugation long-chain of conducting polymer, makes it lose conductive capability, and the formation sheet resistance differs millionfold electricity and leads the figure line.Even under electromotive force drives, the vacuum ultraviolet (VUV) illuminated portion effectively transmission electronic with induce electrochemistry to sink copper.
High molecular performance and its structure are closely related.High molecular conductivity requires the planar conjugate strand of rigidity, and high molecular processability requires flexible atactic molecule chain.High molecular conductivity and processability objectionable intermingling.Therefore, the conducting polymer bulk material is insoluble not molten, is difficult to the processing film forming.But under proper condition, the monomer of conducting polymer, at the substrate surface in-situ oxidizing-polymerizing, can form conducting polymer film at substrate surface, can overcome the insoluble not molten defect of conducting polymer.The method of in-situ polymerization can 1) after being adsorbed in to substrate surface, oxidant immerses again monomer solution, and the monomer that oxidation is deposited to substrate surface becomes conducting polymer film; 2) mixed liquor of oxidant and monomer is coated to substrate surface, in substrate surface oxidation polymerization, become the conduction conducting polymer film.
Conducting polymer film also can adopt the method preparation of physical absorption, and the conducting polymer in the conducting polymer dispersion liquid is attached to substrate surface and forms conducting polymer film.The dispersion liquid of this conducting polymer can be the dispersion of conducting polymer and electrolyte complex compound, as the poly-ethylenedioxy thiophene of Bayer company and the aqueous dispersion of poly-p styrene sulfonic acid salt complex; Can be also the emulsion of conducting polymer, or in solution newly-generated conducting polymer.No matter adopt which kind of mode to prepare conducting polymer film, as long as the sheet resistance of conducting polymer film is at 10-10
4ohm, just can complete copper ion and be reduced to the copper atom process to the copper ion conveying electronic in copper plating bath, the crystallization of formation metallic copper.
Thiophene monomer, pyrrole monomer, alkylated substituted thiazoline thiophene monomer or alkoxyl substituted thiophene monomer, as 3-hexyl thiophene, 3,4-ethylene dioxythiophene, not only reactivity is high, and filming performance is good, and gained conducting film sheet resistance is low.Easily generate smooth densification, the good polythiophene of conductivity and polypyrrole film under the oxidant effect.Copolymerization or the compound heavy copper of electrochemistry that can not affect, as long as the sheet resistance of conducting polymer film is at 10-10
4ohm, just can complete copper ion and be reduced to the copper atom process to the copper ion conveying electronic in copper plating bath, the crystallization of formation metallic copper.
Thiophene monomer, pyrrole monomer reactivity are high, and the oxidant of oxidation of thiophene or pyrrole monomer polymerization can be one or more of ammonium persulfate, potassium permanganate, manganese dioxide, potassium metaperiodate, potassium bichromate, copper nitrate, ferric iron compound, hydrogen peroxide, organic peroxide, polymeric peroxide.Ferric iron compound comprises ferric trichloride, ferric sulfate, p-methyl benzenesulfonic acid iron.Can be according to monomer used, the above-mentioned oxidant of optional use one or more.Multiple oxidant is also used and can be reduced the trend that oxidant is reunited at substrate surface, or increases the total solvability of oxidant in solution.The large molecule peroxy-radical of substrate surface particularly, constantly ferrous oxide or cuprous ion, to high valence state, recycle iron, copper ion, obtain thicker and more uniform conducting polymer film.For the benefit of electricity is led high molecular regular arrangement and is mixed ion and infiltrate, solution with faint acidity for well.
Preparing conductive polymer membrane at base material does not have special requirement to base material, as long as the mixed solution of oxidizing agent solution or oxidant monomer can moistening substrate surface.When wettability is not good enough, can adopt surface treatment to improve surface energy and the adsorptivity of base material.Physics or chemical method are processed surface energy and the adsorptivity that all can improve base material.Physical method commonly used has, and vacuum plasma is processed, corona treatment, and high-energy ray irradiates and vacuum ultraviolet (VUV) is irradiated.Wherein high-energy ray or vacuum ultraviolet (VUV) irradiation are little to the base material damage, and surperficial extra coarse degree changes little.
Base materials employed can being processed by engineering plastics, as polyimides, polytetrafluoroethylene, poly terephthalic acid diol ester, PEN; Reinforced composite, as glass/epoxy composite material, glass strengthen BT resin, the strong engineering plastic modification thermoset plastics of glass, can be also clear glass or opaque pottery.
Vacuum ultraviolet (VUV) is the electromagnetic radiation that wavelength is 100～200 nm.The photon energy of this electromagnetic radiation, at 6.2～12.4 eV, is greater than the bond energy of carbon-to-carbon, carbon-hydrogen, carbon-oxygen, can excite the structural change of conducting polymer conjugated chain.After vacuum ultraviolet (VUV) is irradiated, conducting polymer becomes insulator.The semiconductor element of 172 nm xenon excimer ultraviolet lamps, 146 nm krypton Excimer UV light modulations or emission wavelength 100～200 nm, all emission wavelength, can be as exposure conducting polymer vacuum ultraviolet light source lower than the vacuum ultraviolet of 200nm for they.The exposure vacuum ultraviolet light source can with above-mentioned light source one or more the composition hybrid light sources.But no matter be single light source or combined light source, the total energy density of its vacuum ultraviolet output should be at 5-500mW/cm
2.
By mask, after vacuum ultraviolet (VUV) is irradiated, conducting polymer becomes insulator, and effectively conveying electronic is given the bivalent cupric ion surperficial at it.And be not subject to the part that vacuum ultraviolet (VUV) is irradiated to be still electric conductor, and under electromotive force drives, can continuously by electron transport, give the bivalent cupric ion on the electric conductor surface, make copper ion constantly be reduced to copper atom, be deposited as metallic copper crystal grain.The heavy copper of electrochemistry can adopt constant-current supply or the pulse power.
Compared with prior art, the present invention has following advantage and technique effect: the present invention directly makes copper cash figure line at surface of polymer substrates, without photoresist and etching technics, reduces the waste of copper material and the energy, reduces wiring board and makes the pollution to environment; Shorten the making flow process of wiring board, reduce the production process of wiring board, reduce the cost of manufacture of wiring board.
Embodiment
Below in conjunction with embodiment, be to further illustrate of the present invention, but the present invention is not limited only to following embodiment.
Embodiment 1
Polyimides (PI) film is immersed to the 10%(mass percent) sodium hydroxide solution 15 minutes, after taking-up, with distilled water flushing and with nitrogen, dry up.The polyimide film of alkali cleaning is immersed to 70 mM/ls of ferric trichloride chloroformic solution absorption ferric trichlorides 3 minutes, and the adsorbance of ferric trichloride chlorine is at 1.5-1.7 g/m.The polyimide film of absorption ferric trichloride chlorine is taken out and dries, hang on again 50 mM/ls 3, in 4-ethylenedioxy thiophene (EDOT) chloroformic solution, static 10 hours of room temperature, the EDOT monomer constantly spreads from solution the retention layer that is deposited to the PI film, be oxidized to PEDOT by ferric ion, until the ferric ion approach exhaustion.Take out the PEDOT/PI composite membrane, with absolute ethyl alcohol, clean and dry up with nitrogen, the sheet resistance of PEDOT/PI composite membrane is about 5k Ω
.block the PEDOT/PI composite membrane with mask, use 8mW/cm
2the 172nm vacuum ultraviolet irradiate 3 minutes, the sheet resistance of exposure PEDOT part is greater than 10
5k Ω, and the sheet resistance of unexposed portion is constant.The PEDOT/PI composite membrane of exposure resistance pattern is put into to the Ha Shi electroplating bath that acid copper plating bath is housed, with the PEDOT/PI composite membrane, make negative electrode, the electrolysis phosphor-copper is made anode, and constant current density is at 0.05A/dm
2, voltage 5-6V, copper ion is deposited as metal copper foil at the conductive PEDOT surface reduction, the copper metal pattern on PEDOT/PI film surface occurs.
Embodiment 2
Polyimides (PI) film is immersed to 10% sodium hydroxide solution 15 minutes, use distilled water flushing after taking out, immerse again 1% hydrogenperoxide steam generator 10min, after taking-up 50 ℃ of oven dry, the polyimide film of processing is immersed to 50 mM/ls of ferric trichloride chloroformic solution absorption ferric trichlorides 3 minutes, the adsorbance of ferric trichloride chlorine is at 1.8-1.9 g/m, and the content of peroxide active oxygen is at 0.9-1.1 mM/square metre.To hang on containing the polyimide film of ferric trichloride chlorine and peroxide 50 mM/ls 3, in 4-ethylenedioxy thiophene (EDOT) chloroformic solution, static 10 hours of room temperature, the EDOT monomer constantly spreads from solution the retention layer that is deposited to the PI film, be oxidized to PEDOT by ferric ion, ferric ion becomes ferrous ion, through the active oxygen oxidation of peroxy-radical, becomes again ferric ion, continue the EDOT monomer of oxidation polymerization sedimentation, until ferric ion and active oxygen exhaust.Take out the PEDOT/PI composite membrane, with absolute ethyl alcohol, clean and dry up with nitrogen, the sheet resistance of PEDOT/PI composite membrane is about 0.5k Ω
.conductive PEDOT/PI composite membrane is put into to the Ha Shi electroplating bath that acid copper plating bath is housed, with the PEDOT/PI composite membrane, made negative electrode, the electrolysis phosphor-copper is made anode, and current constant is at 0.05A/dm
2, voltage 5-6V, copper ion reduce deposition on conductive PEDOT becomes metal copper foil, forms glue-free flexible copper-clad plate.
Embodiment 3
Polyimides (PI) film is immersed to 10% sodium hydroxide solution 15 minutes, use distilled water flushing after taking out, immerse again 5% hydrogenperoxide steam generator 10min, after taking-up 50 ℃ of oven dry, the polyimide film of processing is immersed to 50 mM/ls of ferric trichloride chloroformic solution absorption ferric trichlorides 3 minutes, the adsorbance of ferric trichloride chlorine is at 0.9-1.0 g/m, and the content of peroxide active oxygen is at 2.0-2.5 mM/square metre.To hang on containing the polyimide film of ferric trichloride chlorine and peroxide in the EDOT chloroformic solution of 50 mM/ls, static 10 hours of room temperature, the EDOT monomer constantly spreads from solution the retention layer that is deposited to the PI film, be oxidized to PEDOT by ferric ion, ferric iron becomes ferrous iron, active oxygen through peroxy-radical is oxidized to ferric iron, continues the EDOT monomer of oxidation polymerization sedimentation, until ferric ion and active oxygen exhaust.Take out the PEDOT/PI composite membrane, with absolute ethyl alcohol, clean and dry up with nitrogen, the sheet resistance of PEDOT/PI composite membrane is about 0.4k Ω
.block the PEDOT/PI composite membrane with mask, use 8mW/cm
2the 172nm vacuum ultraviolet (VUV) irradiate 3 minutes, the sheet resistance of exposure PEDOT part is greater than 10
5k Ω.Exposing patterns PEDOT/PI composite membrane is put into to the Ha Shi electroplating bath that acid copper plating bath is housed, with the PEDOT/PI composite membrane, made negative electrode, the electrolysis phosphor-copper is made anode, and current constant is at 0.05A/dm
2, voltage 5-6V, copper ion reduce deposition on conductive PEDOT becomes metal copper foil, the copper metal pattern on PEDOT/PI film surface occurs.
Embodiment 4
By the acetonitrile solution of 100 mM/ls of 3,4-ethylene dioxythiophenes (EDOT) and 100 mM/ls of p-methyl benzenesulfonic acid iron Fe (OTs)
3acetonitrile solution and imidazoles mix.EDOT and Fe (OTs) in mixed liquor
3mol ratio be 1:2.2, imidazoles content is 2%.By mixed liquor coating and PI film, 100 ℃ of reactions 10 minutes, make EDOT oxidation polymerization become PEDOT.Take out the PEDOT/PI composite membrane, with absolute ethyl alcohol, clean and dry up with nitrogen, the sheet resistance of PEDOT/PI composite membrane is about 1.0 k Ω
.block the PEDOT/PI composite membrane with mask, use 8mW/cm
2the 172nm vacuum ultraviolet (VUV) irradiate 5 minutes, the sheet resistance of exposure PEDOT part is greater than 10
5k Ω.Exposing patterns PEDOT/PI composite membrane is put into to the Ha Shi electroplating bath that acid copper plating bath is housed, with the PEDOT/PI composite membrane, made negative electrode, the electrolysis phosphor-copper is made anode, and current constant is at 0.05A/dm
2, voltage 5-6V, copper ion reduce deposition on conductive PEDOT becomes metal copper foil, on PEDOT/PI film surface, forms metallic copper line chart line.
Embodiment 5
To gather the butanols-aqueous dispersions of 3,4-ethylene dioxythiophene and poly-p styrene sulfonic acid (PEDOT:PSS) complex compound and coat polyimide film, 120
oc obtains the PEDOT/PI composite membrane in dry 10 minutes, and the sheet resistance of composite membrane is about 2 k Ω.Block the PEDOT/PI composite membrane with mask, use 8mW/cm
2the 172nm vacuum ultraviolet (VUV) irradiate 5 minutes, the sheet resistance of exposure PEDOT part is greater than 10
5k Ω.Exposing patterns PEDOT/PI composite membrane is put into to the Ha Shi electroplating bath that acid copper plating bath is housed, with the PEDOT/PI composite membrane, made negative electrode, the electrolysis phosphor-copper is made anode, and current constant is at 0.05A/dm
2, voltage 5-6V, copper ion reduce deposition on conductive PEDOT becomes metal copper foil, on PEDOT/PI film surface, forms metallic copper line chart line.
Claims (10)
1. a full addition method for manufacturing circuit board with photoresist not, it is characterized in that seeing through mask with vacuum ultraviolet light source, irradiate the conducting polymer film that invests substrate surface, at substrate surface structure conductive pattern line, change into copper cash figure line through the heavy copper of electrochemistry, make described wiring board.
2. full addition method for manufacturing circuit board according to claim 1, is characterized in that described conducting polymer is the compound of one or both in polythiophene and polypyrrole.
3. full addition method for manufacturing circuit board according to claim 1, it is characterized in that described conducting polymer film generates by the following method: have the base material of oxidant to immerse in monomer solution absorption, the monomer in monomer solution is deposited to substrate surface and oxidant reaction generates described conducting polymer film; After perhaps by the mixed solution of monomer and oxidant, being coated on substrate surface, intensification oxidation polymerization generates.
4. full addition method for manufacturing circuit board according to claim 1, is characterized in that the conducting polymer of described conducting polymer film in the conducting polymer dispersion liquid is attached to substrate surface and generates; Dispersion in described conducting polymer dispersion liquid is thiofuran polymer or pyroles polymer.
5. full addition method for manufacturing circuit board according to claim 1, the sheet resistance that it is characterized in that described conducting polymer film is 10-10
4ohm.
6. full addition method for manufacturing circuit board according to claim 1, is characterized in that the radiation wavelength of described vacuum ultraviolet light source output is 100～200 nm.
7. full addition method for manufacturing circuit board according to claim 1, is characterized in that described vacuum ultraviolet light source is one or more in the semiconductor element of 172 nm xenon excimer ultraviolet lamps, 146 nm krypton Excimer UV light modulations, emission wavelength 100～200 nm; The vacuum ultraviolet (VUV) energy density of described vacuum ultraviolet light source output is 5-500 mW/cm
2.
8. described full addition method for manufacturing circuit board according to claim 1, is characterized in that described base material is thin polymer film, reinforced composite, clear glass or opaque pottery.
9. described full addition method for manufacturing circuit board according to claim 3, is characterized in that described oxidant is one or more of ammonium persulfate, potassium metaperiodate, potassium bichromate, potassium permanganate, manganese dioxide, copper nitrate, ferric iron compound, hydrogen peroxide, organic peroxide, macromolecule peroxide; Described ferric iron compound is one or more of ferric trichloride, ferric sulfate, p-methyl benzenesulfonic acid iron.
10. full addition method for manufacturing circuit board according to claim 3, is characterized in that described monomer is one or more of thiophene, pyrroles, alkylthrophene, alkoxy thiophene.
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Cited By (5)
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| CN103613281A (en) * | 2013-11-01 | 2014-03-05 | 深圳市海富莱电子有限公司 | Graphical method capable of forming conductive function pattern and application |
| CN105244283A (en) * | 2015-10-26 | 2016-01-13 | 华南理工大学 | Preparation method for UV micro graphical oxide film and film transistor |
| JP2016216770A (en) * | 2015-05-18 | 2016-12-22 | アキレス株式会社 | Method of manufacturing plated article having patterned metal plating film formed |
| CN108445666A (en) * | 2018-04-17 | 2018-08-24 | 深圳市华星光电技术有限公司 | A kind of production method and display panel of display panel |
| CN112654136A (en) * | 2020-12-16 | 2021-04-13 | 深圳市景旺电子股份有限公司 | Reinforcement deviation detection plate and detection method of flexible circuit board |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613281A (en) * | 2013-11-01 | 2014-03-05 | 深圳市海富莱电子有限公司 | Graphical method capable of forming conductive function pattern and application |
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| CN108445666A (en) * | 2018-04-17 | 2018-08-24 | 深圳市华星光电技术有限公司 | A kind of production method and display panel of display panel |
| CN112654136A (en) * | 2020-12-16 | 2021-04-13 | 深圳市景旺电子股份有限公司 | Reinforcement deviation detection plate and detection method of flexible circuit board |
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Application publication date: 20131002 |