CN104955281B - A kind of method for making in three-dimensional polymer surface or repairing stereo circuit - Google Patents
A kind of method for making in three-dimensional polymer surface or repairing stereo circuit Download PDFInfo
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- CN104955281B CN104955281B CN201510418346.8A CN201510418346A CN104955281B CN 104955281 B CN104955281 B CN 104955281B CN 201510418346 A CN201510418346 A CN 201510418346A CN 104955281 B CN104955281 B CN 104955281B
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Classifications
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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
- H05K3/10—Apparatus 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
- H05K3/18—Apparatus 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
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
Abstract
The present invention proposes a kind of method for making stereo circuit in three-dimensional polymer surface, and using synchronous powder feeding system technology, last layer solid powder is covered in the line pattern position that polymer surface is pre-designed；At the same time, the region covered with metal or metallic compound is processed using laser, to improve the roughness of area to be machined on polymer surface, and metal or metallic compound is introduced into or be embedded into simultaneously in the region being lasered；Above-mentioned high polymer material is put into chemical plating fluid and carries out chemical plating, you can obtains stereoscopic circuit board.Method provided by the invention, processing step is simple, efficiency high, cost is cheap, flexibility degree is high, precision is high, easily realize three dimensional wiring, obtained conducting wire good conductivity and basal body binding force is high, and used high polymer material itself does not have platability, to molding process planning also without particular/special requirement, it is not required that specific electric slurry.
Description
Technical field
The invention belongs to the production field of stereoscopic circuit board, more precisely, is related to one kind in three-dimensional high polymer material table
Face makes or repaired the technology of stereo circuit.
Background technology
In recent years, with the fast development of electronics industry and the extensive use of high polymer material, polymer surface office
Field selectivity metallization has attracted increasing concern in fields such as the making, reparation and encapsulation of electronic device.Electronic apparatus
Product continues to directions such as digitlization, lightweight, small lot, flexibility, multifunction, intellectuality, high reliability, low energy consumption
Development, further promote and make and repair the rapid advances of conducting wire technology in polymer surface.
Traditional polymer surface local metallization technology, such as inject complex technique, hot press printing technology and tradition
Print circuit plates making technology etc., generally there is complex manufacturing technology, raw material loss is big, environmental pollution is serious,
And the requirement of the manufactures such as small lot, high accuracy and flexibility can not be met.Therefore, researcher attempts soft one after another both at home and abroad
Property degree is high, laser processing technology without mask is applied to surface of polymer material three-dimensional conductive circuit making and reparation
In.
Three dimensional mold interconnecting device (three dimensional molded interconnect devices, 3D-
MID), refer to using the moulded component with mechanical function as substrate, by the direct arranging electronic circuit of piece surface, three
Dimension space connects discrete electronic component, and the function of machinery and electronics is integrated into the device of an organic whole.3D-
MID technologies can be by the electric interconnection function of common circuit board, the support of the function of supporting component and plastic casing, protection
It is integrated in etc. function on a device, forms solid, circuit carrier that integrate electromechanical function, its application field is related to vapour
Car, communication, household appliances etc., and also have extensive development prospect in medical field.3D-MID technical process can divide
For the assembling three parts of injecting forming structure part, generation metallic circuit and electronic component.Wherein, the life of metallic conduction circuit
It is always the research emphasis of academia into mode.The laser three-D circuit straight forming technology developed such as German LPKF D. O. O.
(Laser Direct Structuring, LDS) develop in recent years it is very rapid, its core process be by a kind of plastics batch mixing with
Some special laser activation metal components are compound, are molded into thermoplastic processed element, when the element is exposed to sharp
When in light, the laser activation metal component will be broken down into elemental metals (such as copper, palladium, nickel or its mixture) and remnants are organic
Thing tissue, at the same time, in the position of laser beam flying, the rough surface containing elemental metals particle can be left, these gold
Metal particles, as catalytic active center, finally make the plating that deposit thickness is 5~8 μm on circuit using in follow-up chemical plating process
Layer metal.The advantages of this technology is that technique is convenient, reliable, and laser beam can be according to CAD data direct write, and production process flexibility
Degree is high, and at present, the technology has realized commercialization, and has successfully produced the products such as audiphone, car antenna, antenna for mobile phone.
But the technology there is also it is obvious the shortcomings that, i.e., the technology must use with LDS performances particular plastic, it is expensive, and
The laser activation metal component on moulding surface has only been used, has caused the waste of most of activated metal.
Patent document (the patent No.：ZL200810197225.5) also disclose one kind and utilize laser direct-writing and micro- melting and coating technique
The method for making and repairing conductive circuit of three dimensional mold interconnecting device.Its general principle is to utilize micro-pen or micro- spray direct write work
Skill, or the mode such as spraying, mask plate silk-screen printing, according to designed line pattern, preset one layer on molded structural member surface
The electric slurry of 0.1~50 μ m-thick, after low temperature drying slurry organic solvent, then using infrared laser (such as ND:YAG laser and CO2
Laser etc.) along the track of electric slurry pulp layer is irradiated, the preliminary profile of conductive circuit pattern is formed, then by chemical plating work
Skill forms the conducting wire with high-bond and superior electrical conductivity, wearability, oxidative resistance and corrosion resistance.Utilize this kind of skill
Art can be respectively on ten several polymeric matrixs such as polystyrene (PS), polyethylene (PE), polypropylene (PP), polyimides (PI)
Metallic circuit is produced, and various complicated conducting wires quickly can be prepared and repair, flexibility without platability requirement to matrix material
Change degree is high.But the major defect of this method is that processing efficiency is low, it is difficult to which high-volume makes；In addition, infrared laser can be to base
Body causes certain damage in itself, and the selectivity of figure reduces when its heat affected area can cause the subsequent chemistry to plate；And electric slurry
The raw material essential as this method, also have impact on the application of the technology.
In laser-induced deposition technical field, laser-induced chemical gas phase deposition technology can be a variety of in a variety of deposited on substrates
Metal, but vacuum condition is needed, equipment manufacturing cost is expensive, and gas toxicity is big；The shortcomings that induced with laser solid precipitation technology is deposition
Conductive line is in uneven thickness than relatively thin, poor with basal body binding force；Laser-induced chemical liquid-phase deposition technique has operation letter
It is single, the advantages that technological process is few, but there is also deposited metal thickness degree it is too thin the shortcomings that.
On laser induction chemical plating technology, its key is how to exist using laser technology according to the line pattern of design
Matrix surface desired zone produces catalytic active center, and then conducting wire is formed after chemical plating.Urged around how to be formed
Changing activated centre, researcher proposes serial of methods, such as H.Niino (Appl.Phys.Lett., 1993, vol.63,
pp.3527-3529:surface modification and metall ization of fluorocarbon polymers
By excimer laser processing) in hydrazine atmosphere, polytetrafluoroethylene (PTFE) (PTFE) and PEP are copolymerized
Thing (FEP) first carries out surface modification, introduces amino, is then sensitized, activates again, finally realize chemical plating, but this process
It is complex；G.A.Shafeev et al. (Appl.Surf.Sci.1999, vol.138-139, pp.455-460:Light-
Enhanced electroless Cudeposition on laser-treated polyimide surface) proposition Ar
The defects of+laser radiates to PI materials, and irradiated area produces, crackle, free radical etc. can turn into catalytic active center, enter
And electroless copper is realized, but the binding force of cladding material that this method obtains is difficult to ensure；Chen Hengwu of Zhejiang University et al. (patent Shens
Please number：200510050716.3) propose using low pressure mercury lamp as radiation source, by quartz/chromium plate mask to PC surfaces local
Selective light chemical modification, afterwards carboxyl caused by light area by directly adsorb silver ammino solution in silver ammino ion,
By the reduction of the reducing agent in chemical plating fluid, silver ammino ion is reduced into metal Ag, is consequently formed in catalytic activity
The heart, and then optionally prepare gold microelectrode in PC surfaces local.For the method using low pressure mercury lamp as light source, equipment is simple, is easy to grasp
Make, but due to using there is mask plate, therefore be suitable only for two dimension, simple conductive circuit pattern making, and make week
Phase is grown, and flexibility degree is low.
The content of the invention
It is an object of the present invention to provide a kind of the side of stereo circuit is made or repairs in three-dimensional polymer surface
The new solution of method.
According to the first aspect of the invention, there is provided a kind of side that stereo circuit is made in three-dimensional polymer surface
Method, comprise the following steps：
A, using synchronous powder feeding system technology, in the line pattern position that polymer surface is pre-designed covering last layer gold
The solid powder of category or/and metallic compound；
B, at the same time, the region for covering solid powder is processed using laser, to improve high polymer material
The roughness of area to be machined on surface, and metal or/and metallic compound are introduced or be embedded into what is be lasered simultaneously
In region；
C, above-mentioned high polymer material is put into chemical plating fluid and carries out chemical plating, you can obtain stereoscopic circuit board.
Preferably, the solid powder be containing in element palladium, silver, platinum, gold, nickel, copper, zinc, aluminium, tin, chromium, iron at least
A kind of simple substance, compound and/or mix powder.
Preferably, the particle diameter of the solid powder is 5nm~100 μm.
Preferably, the thickness of the solid powder layer is 10nm~100 μm.
Preferably, described high polymer material be isoprene rubber, it is butadiene-styrene rubber, makrolon, poly- titanate esters, poly- to benzene two
Formic acid butanediol ester, polymethyl methacrylate, liquid crystal polymer, nylon, acrylonitrile-butadiene-styrene (ABS) plastics, poly- second
Alkene plastics, polystyrene plastics, polystyrene-acrylonitrile plastics, polypropylene plastics, PC- glass fiber compound materials, epoxy
At least one of resin-glass fiber compound material, Melamine-glass fiber compound material.
Preferably, between the step b) and step c), in addition to the surface of high polymer material is cleaned, will
The solid powder of excessive residual washes.
A kind of method for making stereo circuit in three-dimensional polymer surface provided by the invention, first in macromolecule material
Layer of metal or/and metallic compound are covered on material, it is next to strengthen by laser to improve the roughness on processed surface
Bond strength between the electroless deposited metal and matrix material of step；Simultaneously by laser by specific metallic element introduce and it is embedding
Enter to these positions so that metallic element and high polymer material are combined and consolidated, can be as the catalytic activity of next step chemical plating
Center；The processing step of this method is simple, efficiency high, cost is cheap, flexibility degree is high, precision is high, easily realizes three-dimensional cloth
Line, obtained conducting wire good conductivity and basal body binding force are high, and used high polymer material itself does not have and can plated
Property, to molding process planning also without particular/special requirement, it is not required that specific electric slurry.
The process of the present invention, has further the advantage that：
(1) compared with the LDS technologies of LPKF D. O. O., the molding process planning of used high polymer material is wanted without special
Ask, such three dimensional mold interconnecting device material cost will substantially reduce；
(2) with forming the method phase of conducting wire using infrared, the micro- cladding electric slurry of Submillineter Wave Technology and then chemical plating
Than the present invention does not need the specific electric slurry of outsourcing, it is not required that silk-screen printing, micro-pen direct write or the preset electronics slurry of micro- spray
The bed of material；
(3) by the application of synchronous powder feeding system technology in process, high score is embedded it in using laser while powder is covered
The surface of sub- material so that can be covered on the 3 D stereo surface of high polymer material using solid powder.
It was found by the inventors of the present invention that in the prior art, realizing the complex process of stereo circuit method, cost is high, and
And fabrication cycle is long, effect is poor.Therefore, the technical assignment or technical problem to be solved that the present invention to be realized are abilities
It is that field technique personnel never expect or it is not expected that, therefore the present invention is a kind of new technical scheme.
Embodiment
The various exemplary embodiments of the present invention are will be described in now.It should be noted that：Unless specifically stated otherwise, otherwise
Part and the positioned opposite of step that illustrates in these embodiments, numerical expression and numerical value do not limit the scope of the invention.
The description only actually at least one exemplary embodiment is illustrative to be never used as to the present invention below
And its application or any restrictions that use.
It may be not discussed in detail for technology, method and apparatus known to person of ordinary skill in the relevant, but suitable
In the case of, the technology, method and apparatus should be considered as part for specification.
In shown here and discussion all examples, any occurrence should be construed as merely exemplary, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
The invention provides the method for making in three-dimensional polymer surface or repairing stereo circuit, its step is：
Such as can be under the cooperation of linkage work-table and synchronous powder feeding system device, in the line that polymer surface is pre-designed
Road graph position covering last layer metal or/and metallic compound solid powder；Using synchronous powder feeding system technology, in covering solid powder
While last, using laser, by laser galvanometer (or dynamic focusing mirror), these positions are processed；Processed table
The roughness in face will dramatically increase, to strengthen the bond strength in next step chemical deposit between metal and matrix material；Together
When metal or metallic compound be introduced into and be embedded into these positions, the catalytic active center as next step chemical plating；
Such as by a synchronization feeding device, layer of metal, metallic compound are covered or coat in polymer surface,
At the same time, these positions are processed using laser aid so that can be realized in the three-dimensional surface of high polymer material
The introducing and insertion of fixed powder.
The surface of high polymer material is cleaned, the metal of excessive residual or metallic compound are cleaned up；By what is cleaned
High polymer material, which is put into chemical plating fluid, implements chemical plating, you can obtains stereoscopic circuit board.
Preferably, the solid powder be containing in element palladium, silver, platinum, gold, nickel, copper, zinc, aluminium, tin, chromium, iron extremely
Few a kind of simple substance, compound and/or mix powder.It is preferred that the particle diameter of the solid powder is 5nm~100 μm.It is preferred that institute
The thickness for stating solid powder covering is 10nm~100 μm.Described high polymer material is isoprene rubber, butadiene-styrene rubber, poly- carbonic acid
Ester, poly- titanate esters, polybutylene terephthalate (PBT), polymethyl methacrylate, liquid crystal polymer, nylon, acrylic nitrile-butadiene
Styrene plastics, vinyon, polystyrene plastics, polystyrene-acrylonitrile plastics, polypropylene plastics, PC-
In glass fiber compound material, epoxy-fiberglass composite, Melamine-glass fiber compound material at least
It is a kind of.
Embodiment 1
Under the cooperation of linkage work-table and synchronous powder feeding system device, in makrolon (polycarbonate, PC) material table
The line pattern position covering last layer silver nitrate powder that face is pre-designed；At the same time, using laser, by laser galvanometer,
These positions are processed；The surface of cleaning material afterwards is clean by the powder cleaning of excessive residual；By what is cleaned
Workpiece, which is put into chemical plating fluid, implements electroless copper, nickel, silver and/or gold, you can obtains conducting wire.The conductive line surfaces of gained connect
It is continuous, uniformly, the defects of pore-free, crackle, good conductivity, and with substrate combinating strength height.
Embodiment 2
Under the cooperation of linkage work-table and synchronous powder feeding system device, in styrene-butadiene-acrylonitrile (ABS) plastics
The line pattern position covering last layer palladium bichloride powder that surface is pre-designed；At the same time, using laser, dynamic Laser is passed through
Focus lamp, these positions are processed；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；Will
The workpiece cleaned, which is put into chemical plating fluid, implements electroless copper, nickel, silver and/or gold, you can obtains conducting wire.Gained is led
Line surface is continuous, uniformly, the defects of pore-free, crackle, good conductivity, and it is good with basal body binding force.
Embodiment 3
Under the cooperation of linkage work-table and synchronous powder feeding system device, in the line map that PC- glass fiber materials surface is pre-designed
Shaped position covers last layer silver oxide powder；At the same time, using laser, by laser galvanometer, these positions are processed
Processing；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；The workpiece cleaned is put into chemical plating fluid
Implement electroless copper, nickel, silver and/or gold, you can obtain conducting wire.The conductive line surfaces of gained are continuous, uniform, pore-free, split
The defects of line, good conductivity, and it is good with basal body binding force.
Embodiment 4
Under the cooperation of linkage work-table and synchronous powder feeding system device, it is pre-designed on epoxy resin-glass fiber material surface
Line pattern position covers last layer argent powder；At the same time, using laser, by dynamic Laser focus lamp, to these
Position is processed；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；The workpiece cleaned is put
Enter and implement electroless copper, nickel, silver and/or gold in chemical plating fluid, you can obtain conducting wire.The conductive line surfaces of gained are continuous, equal
It is even, the defects of pore-free, crackle, good conductivity, and with substrate combinating strength height.
Embodiment 5
Under the cooperation of linkage work-table and synchronous powder feeding system device, in the line pattern position that PC material surfaces are pre-designed
Cover last layer metallic nickel powder；At the same time, using laser, by dynamic Laser focus lamp, these positions are processed
Processing；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；The workpiece cleaned is put into chemical plating fluid
Implement electroless copper, nickel, silver and/or gold, you can obtain conducting wire.The conductive line surfaces of gained are continuous, uniform, pore-free, split
The defects of line, good conductivity, and with substrate combinating strength height.
Embodiment 6
Under the cooperation of linkage work-table and synchronous powder feeding system device, covered in the line pattern position that ABS surface is pre-designed
Cover layer of metal platinum powder end；At the same time, using laser, by laser galvanometer, these positions are processed；Afterwards
The surface of plastics is cleaned, the powder cleaning of excessive residual is clean；The workpiece cleaned is put into chemical plating fluid and implements chemistry
Copper facing, nickel, silver and/or gold, you can obtain conducting wire.The conductive line surfaces of gained are continuous, uniformly, the defects of pore-free, crackle,
Good conductivity, and with substrate combinating strength height.
Embodiment 7
Under the cooperation of linkage work-table and synchronous powder feeding system device, it is pre-designed on epoxy resin-glass fiber material surface
Line pattern position covers last layer gold trichloride powder；At the same time, using laser, by dynamic Laser focus lamp, to this
A little positions are processed；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；The workpiece that will be cleaned
It is put into chemical plating fluid and implements electroless copper, nickel, silver and/or gold, you can obtains conducting wire.The conductive line surfaces of gained are continuous,
Uniformly, the defects of pore-free, crackle, good conductivity, and with substrate combinating strength height.
Embodiment 8
Under the cooperation of linkage work-table and synchronous powder feeding system device, in the line map that PC- glass fiber materials surface is pre-designed
Shaped position covers last layer metallic copper powder；At the same time, using laser, by laser galvanometer, these positions are processed
Processing；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；The workpiece cleaned is put into chemical plating fluid
Implement electroless copper, nickel, silver and/or gold, you can obtain conducting wire.The conductive line surfaces of gained are continuous, uniform, pore-free, split
The defects of line, good conductivity, and with substrate combinating strength height.
Embodiment 9
Under the cooperation of linkage work-table and synchronous powder feeding system device, covered in the line pattern position that ABS surface is pre-designed
Cover layer of metal zinc powder；At the same time, using laser, by laser galvanometer, these positions are processed；Afterwards
The surface of plastics is cleaned, the powder cleaning of excessive residual is clean；The workpiece cleaned is put into chemical plating fluid and implements chemistry
Copper facing, nickel, silver and/or gold, you can obtain conducting wire.The conductive line surfaces of gained are continuous, uniformly, the defects of pore-free, crackle,
Good conductivity, and with substrate combinating strength height.
Embodiment 10
Under the cooperation of linkage work-table and synchronous powder feeding system device, it is pre-designed on epoxy resin-glass fiber material surface
Line pattern position covers last layer metallic aluminium powder；At the same time, using laser, by dynamic Laser focus lamp, to these
Position is processed；The surface of plastics is cleaned afterwards, the powder cleaning of excessive residual is clean；The workpiece cleaned is put
Enter and implement electroless copper, nickel, silver and/or gold in chemical plating fluid, you can obtain conducting wire.The conductive line surfaces of gained are continuous, equal
It is even, the defects of pore-free, crackle, good conductivity, and with substrate combinating strength height.
Although some specific embodiments of the present invention are described in detail by example, the skill of this area
Art personnel it should be understood that example above merely to illustrating, the scope being not intended to be limiting of the invention.The skill of this area
Art personnel to above example it should be understood that can modify without departing from the scope and spirit of the present invention.This hair
Bright scope is defined by the following claims.
Claims (6)
- A kind of 1. method for making in three-dimensional polymer surface or repairing stereo circuit, it is characterised in that including following step Suddenly：A, using synchronous powder feeding system technology, in the line pattern position that polymer surface is pre-designed covering last layer metallization Compound solid powder；B, at the same time, the region covered with metallic compound solid powder is processed using laser, to improve height The roughness of area to be machined on molecular material surface, and the product of metal compound powders and laser reactive can be drawn simultaneously Enter or be embedded into the region being lasered, form the catalytic active center of chemical plating；C, above-mentioned high polymer material is put into chemical plating fluid and carries out chemical plating, you can obtain stereo circuit.
- 2. according to the method for claim 1, it is characterised in that：The metal compound powders be containing element palladium, silver, The compound powder of at least one of platinum, gold, nickel, copper, zinc, aluminium, tin, chromium, iron or the mixed-powder by these powder constituents.
- 3. according to the method for claim 1, it is characterised in that：The particle diameter of the powder is 5nm~100 μm.
- 4. according to the method for claim 1, it is characterised in that：The thickness of the powder bed is 10nm~100 μm.
- 5. according to the method for claim 1, it is characterised in that：Described high polymer material be isoprene rubber, butadiene-styrene rubber, Makrolon, poly- titanate esters, polybutylene terephthalate (PBT), polymethyl methacrylate, liquid crystal polymer, nylon, propylene Nitrile-butadiene-styrene plastics, vinyon, polystyrene plastics, polystyrene-acrylonitrile plastics, polypropylene plastics In material, PC- glass fiber compound materials, epoxy-fiberglass composite, Melamine-glass fiber compound material At least one.
- 6. according to the method for claim 1, it is characterised in that：Between the step b) and step c), in addition to height The surface of molecular material is cleaned, and the metallic compound solid powder of excessive residual is washed.
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| CN109927288B (en) * | 2017-12-18 | 2021-12-03 | 上海微电子装备（集团）股份有限公司 | Additive manufacturing device and manufacturing method |
| JP2020019983A (en) * | 2018-07-31 | 2020-02-06 | セイコーエプソン株式会社 | Wiring substrate and method for manufacturing wiring substrate |
| CN110798990B (en) * | 2019-11-22 | 2020-06-09 | 广东工业大学 | Repair method of fine circuit |
| CN114050422B (en) * | 2021-10-30 | 2023-07-11 | 西南电子技术研究所（中国电子科技集团公司第十研究所） | Self-repairing method for integrated package structure of phased array antenna microsystem |
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| US6238847B1 (en) * | 1997-10-16 | 2001-05-29 | Dmc Degussa Metals Catalysts Cerdec Ag | Laser marking method and apparatus |
| CN101394710A (en) * | 2008-10-10 | 2009-03-25 | 华中科技大学 | Manufacturing and repairing method for conductive circuit of three dimensional mold interconnecting device |
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| JPH02305969A (en) * | 1989-05-18 | 1990-12-19 | Mitsubishi Electric Corp | Pretreatment for electroless plating |
| JPH11775A (en) * | 1997-06-10 | 1999-01-06 | Mitsubishi Heavy Ind Ltd | Laser cladding device |
| WO2010017116A2 (en) * | 2008-08-08 | 2010-02-11 | Med-El Elektromedizinische Geraete Gmbh | Laser-based fabrication of implantable stimulation electrodes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6238847B1 (en) * | 1997-10-16 | 2001-05-29 | Dmc Degussa Metals Catalysts Cerdec Ag | Laser marking method and apparatus |
| CN101394710A (en) * | 2008-10-10 | 2009-03-25 | 华中科技大学 | Manufacturing and repairing method for conductive circuit of three dimensional mold interconnecting device |
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