CN102717554B - A kind of two stratotype flexibility coat copper plates - Google Patents
A kind of two stratotype flexibility coat copper plates Download PDFInfo
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- CN102717554B CN102717554B CN201210228020.5A CN201210228020A CN102717554B CN 102717554 B CN102717554 B CN 102717554B CN 201210228020 A CN201210228020 A CN 201210228020A CN 102717554 B CN102717554 B CN 102717554B
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Abstract
The present invention relates to a kind of two stratotype flexibility coat copper plates, it comprises organic macromolecule membrane and covers the layers of copper on this machine macromolecule membrane, it is characterized in that, peel strength between described layers of copper and described organic polymer film is higher than 0.6N/mm, and the preparation method of described two stratotype flexibility coat copper plates comprises the step of by ion beam sputtering, organic high molecular polymer film being carried out to metal lining; Wherein, the parameter of described ion beam sputtering comprises: ion beam and be 20-70 ° by the angle between the metallic plates plane normal that bombards, described plasma sputter source and described metallic plates be 20-40 centimetre by the distance between the position bombarded; It is 10-30 centimetre that described metallic plates is received by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Peel strength between the layers of copper of two stratotype flexibility coat copper plates provided by the invention and organic polymer film is high, and Thickness Ratio is thinner, thinner than 18 microns.
Description
Technical field
The present invention relates to a kind of two stratotype flexibility coat copper plates.
Background technology
Flexibility coat copper plate FCCL (Flexible Copper Clad Laminate) refers to the single or double at flexible insulating material such as polyester film (PET) or Kaptons (PI), by certain PROCESS FOR TREATMENT, to bond together the formed copper-clad plate with good flexural property with certain thickness Copper Foil.Flexibility coat copper plate FCCL is divided into the two-ply (2L-FCCL) of three ply board (3L-FCCL) and the non-adhesive having adhesive.Compared to three stratotype flexibility coat copper plates (3L-FCCL), two stratotype flexibility coat copper plates (2L-FCCL) are not owing to containing epoxy adhesive or acrylate adhesive, the various aspects of performance such as its heat resistance, dimensional stability, ageing resistance, reliability are all better than three stratotype flexibility coat copper plates (3L-FCCL), are thus developed rapidly.
At present, the method preparing two stratotype flexibility coat copper plates (2L-FCCL) mainly contains: (1) rubbing method (also claiming casting, Casting), (2) pressing method (being also laminating, Lamination).
1. rubbing method (casting, Casting):
Early stage rubbing method is that the performed polymer of polyimides (PI) (polyamic acid, PAA) one side is coated on copper foil surface, prepares through super-dry removal solvent and high temperature imidization.This method processing procedure is relatively simple, easily implements.But the cohesive in goods between layers of copper and polyimides and the poor stability of product size.
Industry develops multi-layer coated method in recent years, its processing procedure is: be first coated with (cast) one deck thermoplasticity PI (TPI) resin at copper foil surface, and then be coated with PI (low CTE-PI) resin of one deck low thermal coefficient of expansion, finally be coated with one deck thermoplasticity PI (TPI) resin again, after high temperature imidization again with Copper Foil pressing, make product.
Adopt multi-layer coated method (casting) that the effect of two aspects can be obtained:
(1) cohesive of goods and dimensional stability are in good unification;
(2) keep integrally-built symmetry, reduce goods curling.
But multi-layer coated method (casting) also has the place of blemish in an otherwise perfect thing, the problems such as complicated in processing procedure, equipment investment cost is larger, and because prepare the technical problem existing for thin copper foil, this method is difficult to produce the 2L-FCCL that copper thickness is less than 18 microns thickness.This method is mainly used to manufacture order panel.
2. pressing method (laminating, Lamination): pressing method be development in recent years than faster more a kind of process, it is on the basis of low-expansion coefficient PI (CTE-PI) film, two-sided or one side is coated with a kind of performed polymer (polyamic acid, PAA) with outstanding fusible thermoplasticity PI resin, after drying and imidization, make composite membrane.Again at high temperature under high pressure, the product of single or double is made after thermoplastic resin again melting with Copper Foil pressing.
Existing basement membrane manufacturer provides this composite membrane at present, and composite membrane on the PI film of high-dimensional stability, applies one deck thermoplasticity PI resin (TPI) form, and composite membrane and Copper Foil directly can be hot pressed into plate by FCCL producer.
The feature of pressing method (laminating):
(1) processing procedure is relatively simple, but cost compares, rubbing method wants high;
(2) production model of small lot multi items is applicable to;
(3) one side and two-sided product all can be produced;
(4) product has cohesive and dimensional stability and to hold concurrently excellent combination property.
Because prepare the technical problem existing for thin copper foil, this method is equally also difficult to produce the 2L-FCCL that copper thickness is less than 18 microns thickness.
The 2L-FCCL that rubbing method and pressing method are produced, the adhesion of Copper Foil and polyimides (PI) matrix is good, and namely peel strength is high, but its complex manufacturing technology, high to equipment requirement, cause with high costs.More owing to will use ready-made Copper Foil (rolled copper foil and electrolytic copper foil), and be limited to the reason of technique, rolled copper foil and electrolytic copper foil are all difficult to make less than 18 microns thickness, as 12 microns, 9 microns, 7 microns equal thickness.It is made to receive certain restriction with the application in the medium-to-high grade precise electronic product such as liquid crystal (plasma) display, liquid crystal (plasma) TV based on HDI (high density interconnect substrate) technology and COF (Chip on Flex, flexible chip) technology.
Summary of the invention
The present invention, in order to overcome in prior art existing technological deficiency, provides adhesion (peel strength) between a kind of Copper Foil and organic polymer film higher and be two ultra-thin stratotype flexibility coat copper plates.
The invention provides a kind of two stratotype flexibility coat copper plates, it comprises organic macromolecule membrane and covers the layers of copper on this machine macromolecule membrane, it is characterized in that, peel strength between described layers of copper and described organic polymer film is higher than 0.6N/mm, and the preparation method of described two stratotype flexibility coat copper plates comprises the step of by ion beam sputtering, organic high molecular polymer film being carried out to metal lining; Wherein, the parameter of described ion beam sputtering comprises: ion beam and be 20-70 ° by the angle between the metallic plates plane normal that bombards, described plasma sputter source and described metallic plates be 20-40 centimetre by the distance between the position bombarded; It is 10-30 centimetre that described metallic plates is received by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.
Peel strength between the layers of copper of two stratotype flexibility coat copper plates provided by the invention and organic polymer film is high, and Thickness Ratio is thinner, thinner than 18 microns.In addition, significantly, the preparation method preparing two stratotype flexibility coat copper plates provided by the present invention is the method for continuous seepage two stratotype flexibility coat copper plate, the method can not only to of a film substrate face, and can operate the two sides of film substrate, that is, can continuous seepage two stratotype single-face flexibility copper-clad board; simultaneously simultaneously also can continuous seepage two stratotype double side flexible copper coated board, therefore highly efficient in productivity.
Accompanying drawing explanation
Fig. 1 is a preferred embodiment schematic diagram of the present invention.
Fig. 2 is ion beam sputtering schematic diagram of the present invention.
Detailed description of the invention
The invention provides a kind of two stratotype flexibility coat copper plates, it comprises organic macromolecule membrane and covers the layers of copper on this machine macromolecule membrane, it is characterized in that, peel strength between described layers of copper and described organic polymer film is higher than 0.6N/mm, and the preparation method of described two stratotype flexibility coat copper plates comprises the step of by ion beam sputtering, organic high molecular polymer film being carried out to metal lining; Wherein, the parameter of described ion beam sputtering comprises: ion beam and be 20-70 ° by the angle between the metallic plates plane normal that bombards, be preferably 30-60 °, described plasma sputter source and described metallic plates be 20-40 centimetre by the distance between the position bombarded, be preferably 25-35 centimetre; Described metallic plates is received by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film be 10-30 centimetre, be preferably 15-25 centimetre.
Ion beam sputtering schematic diagram of the present invention as shown in Figure 2, under lower air pressure (being usually less than 1.0 × 10-2Pa), bombard so that shape is at a certain angle between the normal d of metallic plates plane c through the ar-ion beam b focused in a of sputter gas source, make target material surface atom generation cascade collision.In collision process, a large amount of atoms departs from target material surface, becomes sputter particles.These sputter particles greatly mainly with straight path arrive organic polymer film surperficial e and above being deposited on.
Present inventor finds, only has and adopts ion beam sputtering under these conditions, can obtain two stratotype flexibility coat copper plates of higher peel strength.
Ion beam sputtering is that (under normal circumstances, low vacuum is in 2 × 10 under vacuum conditions
-3handkerchief), then pass into argon gas, make vacuum drop to 0.5-5 × 10
-2handkerchief, is preferably 1 × 10
-2about handkerchief, then switch on power, sputter gas ion gun is started working, and makes argon gas be ionized into plasma, forms ion beam and draws.Under the effect of accelerating potential, ion beam high velocity bombardment target (such as copper, nickel, chromium, molybdenum, or its alloy), make target atom (such as copper atom, nickle atom, chromium atom, molybdenum atom, or its alloy atom) be sputtered out, be deposited on organic film, form the nano level metal film of one deck.Direction homogeneity when sputtered metallic atom contacts with organic film is good, thus is conducive to the uniformity improving adhesion.
Of the present invention one preferred embodiment as shown in Figure 1, organic high molecular polymer film from unreeling machine 3s, successively through regulating wheel 5 and regulating wheel 4, cold water drum 6, regulating wheel 5 and regulating wheel 4 to winder 7.Described organic high molecular polymer film is in running, and first one surface experiences ion implantation 1 and carry out ion implantation, then experiences ion beam sputtering 2 and carries out 2 secondary ion beam sputterings.Then, another surface of described organic high molecular polymer film experiences ion implantation 1 successively and carries out ion implantation, then experiences ion beam sputtering 2 and carries out 2 secondary ion beam sputterings.
In the present invention, operating parameter during ion beam sputtering can adopt conventional numerical value.But in order to obtain better adhesion at described organic high molecular polymer film and by between the metallic atom that pounds, in a preferred embodiment, gas ion source heater current is 6-15 ampere, is preferably 8-12 ampere.In another preferred embodiment, arc voltage is 50-80 volt, is preferably 60-70 volt.In another preferred embodiment, suppress voltage to be 100-200 volt, be preferably 120-150 volt.In another preferred embodiment, accelerating potential is 1-2 kilovolt, is preferably 1.2-1.5 kilovolt, and accelerating electric current is 50-200 milliampere, is preferably 100-150 milliampere.
In order to improve the homogeneity of adhesion between metallic atom and organic high molecular polymer film further, in a preferred embodiment, described organic high molecular polymer film surface is deposited on by the metallic atom pounded with the direction being basically perpendicular to described organic high molecular polymer film surface.
In order to be conducive to continuous seepage, in a preferred embodiment, described organic high molecular polymer film is placed on unreeling machine.In a preferred embodiment, in order to be convenient to continuous seepage further, described organic high molecular polymer film is placed in after on unreeling machine, by one or more governing mechanism of tension, this governing mechanism of tension can be the various governing mechanism of tension in this area, but in another preferred embodiment, described governing mechanism of tension is made up of two transition wheels, a tension adjustment wheel and a traction wheel, and referring to application number is CN2010105103595.
The present inventor finds, if carry out to matrix material the two stratotype flexibility coat copper plates that surface modification treatment can obtain better high peel strength.In a preferred embodiment, the method of ion implantation is adopted to carry out modification to matrix: by metal ion implantation PI film matrix surface, form the transition zone of a kind of " PI-metal+PI-metal ", by controlling dosage and the energy of ion implantation, thus form a kind of novel, fine and close " PI+ metal " transition zone.
The present inventor finds, organic high molecular polymer film is carried out to the step of metal ion implantation before the step of by ion beam sputtering organic high molecular polymer film being carried out to metal lining, adhesion between layers of copper and organic high molecular polymer film can be improved further.
The equipment that the step of described metal ion implantation adopts can carry out in the ion implantation described in another section of application and/or plasma-deposited equipment for the applicant, it is CN2010105103595 that details refers to application number, and denomination of invention is the method for ion implantation and plasma deposition apparatus and using plasma process film.The parameter adopted in the step of described ion implantation can be that in another section of application (application number is CN2010105103580, and denomination of invention is a kind of method of continuous seepage flexibility coat copper plate) of CN2010105103595 and the applicant, disclosed parameter is carried out with reference to application number equally.Described condition can be for: the vacuum in described vacuum chamber can be the vacuum that this area adopts, and is preferably 2 × 10
-3-5 × 10
-5handkerchief; The thickness of described organic high molecular polymer film is 3-150 micron, is preferably 10-50 micron; The condition of described ion implantation comprises: the described organic high molecular polymer film speed of service is 0.3-2 m/min, and ion implantation voltage is 1-10 kilovolt, and be preferably 5-10 kilovolt, ion implantation dosage is 0.5 × 10
13-1 × 10
17individual atom/centimetre
2, be preferably 0.5 × 10
14-5.0 × 10
16individual atom/centimetre
2.
Make the ion implantation degree of depth be approximately 1-10 nanometer like this, implantation dosage can reach 10 at most as required
17individual atom/centimetre
2magnitude, (1 gram of copper nearly 9.48 × 10
21individual atom).This is just equivalent to " foundation pile " of in base film, having laid One's name is legion.And then " ion beam sputtering " method is applied again, in its surface deposition skim layers of copper, the layers of copper of base film surface deposition and these " foundation piles " embedding base film inside are combined, thus the adhesion (peel strength) on metal film layer and the base film surface deposited is greatly improved.
In order to improve the adhesion between the metal film layer of deposition and base film further, in another preferred embodiment, the vacuum in described vacuum chamber is 2 × 10
-3-5 × 10
-5handkerchief; The thickness of described organic high molecular polymer film is 10-50 micron; The condition of described ion implantation comprises: the described organic high molecular polymer film speed of service is 0.3-2 m/min, and ion implantation voltage is 5-10 kilovolt, and ion implantation dosage is 0.5 × 10
14-5.0 × 10
16individual atom/centimetre
2.
In the preferred embodiment of another kind, the material of described ion implantation is metal, and this metal is one or more in chromium, nickel, copper and molybdenum.
When the metal adopting ion implantation to inject is not copper, preferred ion beam sputtering two kinds of metal levels, wherein the Metal Phase of a kind of metal and ion implantation is same, and another kind is copper.
Although, the thickness of the metallic atom deposited on organic high molecular polymer film by ion beam sputtering is not particularly limited, but in a preferred embodiment, described step of organic high molecular polymer film being carried out to metal lining by ion beam sputtering deposits the metal level of 10-100 nanometer thickness on organic high molecular polymer film, is preferably the metal level of 20-50 nanometer thickness; Like this can by the thickness that follow-up plating makes metal level reach required after ion beam sputtering, and can be cost-saving.
In a preferred embodiment, described metal level, by 5-100 nanometer, is preferably nickel dam and the 10-100 nanometer of 10-80 nanometer, is preferably the layers of copper composition of 10-80 nanometer, can effectively be covered completely by macromolecule organic polymer thin film, surface does not have pin hole.In a preferred embodiment, described nickel dam directly with described organic polymer film contacts, and layers of copper covers on described nickel dam.In another preferred embodiment, first ion injection method implantation dosage on organic polymer film is adopted to be 0.5 × 10
14-5.0 × 10
16individual atom/centimetre
2nickel, then adopt the nickel dam of ion beam sputter depositing one deck 5-100 nanometer finally to adopt the layers of copper of ion beam sputter depositing one deck 10-100 nanometer.
In order to reduce production cost, the described preparation method step of electroplating after being included in and by ion beam sputtering the step of metal lining being carried out to organic high molecular polymer film in a preferred embodiment.The conventional method that described plating can adopt this area to adopt is carried out, and such as, carries out in the continuous electroplating apparatus mentioned in CN101350315A; But (application number is CN2010105103580 to preferred two sections of earlier applications according to the applicant, and denomination of invention is a kind of method of continuous seepage flexibility coat copper plate; Be CN2010105103576 with application number, denomination of invention for for film continuous electroplating apparatus and film is carried out to the method for continuous electroplating) disclosed in electroplanting device in carry out, and during these two sections can be adopted to invent, disclosed parameter is carried out.
Technological parameter during described plating can conventionally carry out, but in a preferred embodiment, the step of described plating comprises preplating and main plating; Described preplating condition can be any adoptable preplating condition in this area, and preferably including electroplating temperature is 20-28 DEG C, and average cathode current density is 10-40 ampere/decimetre
2, be preferably 15-25 ampere/decimetre
2; The speed that described film runs is 10-50 m/h, is preferably 15-30 m/h; Described main plating conditions can be any adoptable main plating condition in this area, and preferably including electroplating temperature is 20-28 DEG C, and average cathode current density is 2-15 ampere/decimetre
2, be preferably 5-10 ampere/decimetre
2; The speed that described film runs is 10-50 m/h, is preferably 15-30 m/h.This embodiment is adopted to electroplate, the very all even densification of the copper clad layers deposited on the membrane.
In another preferred embodiment, it is 20-25 DEG C that described preplating condition comprises electroplating temperature, and average cathode current density is 15-25 ampere/decimetre
2, the speed that described film runs is 15-30 m/h; It is 20-25 DEG C that described main plating conditions comprises electroplating temperature, and average cathode current density is 5-10 ampere/decimetre
2, the speed that described film runs is 15-30 m/h.Electroplate under this condition, the more all even densification of the copper clad layers deposited on the membrane.
In another preferred embodiment, it is 20-28 DEG C that described preplating condition comprises electroplating temperature, and average cathode current density is 10-40 ampere/decimetre
2, the speed that described film runs is 10-50 m/h; It is 20-28 DEG C that described main plating conditions comprises electroplating temperature, and average cathode current density is 2-15 ampere/decimetre
2, the speed that described film runs is 10-50 m/h.The more all even densification of the copper clad layers being very beneficial for like this depositing on the membrane.
In one embodiment of the invention, any electrolytic copper plating solution that the electroplate liquid that described plating adopts can adopt for this area, but preferably comprise copper sulphate 60-150 grams per liter, sulfuric acid 60-150 grams per liter, hydrochloric acid 0.1-0.3 milliliter/liter, and 5-15 milliliter/liter additive.The additive that described additive can use for this area, is preferably such as called the acid bright copper plating additive of 210, has good planarization and pliability to make the copper clad layers of deposition by the commodity of Guangzhou Atotech sold.
In another embodiment of the invention, the method carries out the step of passivation after being also included in plating, described passivating conditions can be any adoptable passivating conditions in this area, preferably including passivation temperature is 20-30 DEG C, the described film speed of service is 10-50 m/h, any passivating solution that the passivating solution that described passivation adopts can adopt for this area, but the aqueous solution preferably comprised containing BTA 0.2-5 grams per liter, the antirust passivator of LT-02 of Chemical Co., Ltd.'s production that such as Guangzhou is bright.
Clean after described thin film electroplating, the solution of cleaning can be any solution for cleaning in this area, but is preferably water.After film is washed, naturally can dry, the temperature of this area dry film also can be adopted dry, but preferably dry at 100-120 DEG C.
Described organic high molecular polymer film can be any organic high molecular polymer film in this area, such as: polyimides (PI) film, polyphenylene oxide (PTO) film, Merlon (PC) film, polysulfones (PSU) film, polyether sulfone (PES) film, polyphenylene sulfide (PPS) film, polystyrene (PS) film, polyethylene (PE) film, polypropylene (PP) film, PEI (PEI) film, polytetrafluoroethylene (PTFE) (PTFE) film, polyether-ether-ketone (PEEK) film, polyamide (PA) film, PET (PET) film, the organic high molecular polymer films such as liquid crystal polymer (LCP) film or polyparabanic acid (PPA) film.Be preferably: the suitable film as flexibility coat copper plate dielectric material such as polyimides (PI) film, PET (PET) film, liquid crystal polymer (LCP) film or polyparabanic acid (PPA) film.In a preferred embodiment, described organic high molecular polymer film is Kapton, polyethylene terephthalate thin film, liquid crystal polymer film or polyparabanic acid film.
Ion implantation of the present invention is carried out in the equipment of a kind of ion implantation and plasma-deposited film, and this equipment is disclosed in another section of patent of the applicant, and application number is CN2010105103595.Wherein, the vacuum chamber of this equipment as shown in Figure 2.Vacuum chamber part 8, is provided with let off roll 81, transition wheel 82, dance roller 83, traction wheel 84, wind-up roll 85, chill roll 86, the opening 87 for ion implantation, the opening 88 for plasma-deposited, vacuum orifice 9 in this vacuum chamber.At opening 87 and the voltage (not drawing) also between 88 and B with the ion beam current that applying acceleration is sent by described ion gun.Described opening is rectangle, and the size 50 millimeters on wherein axially vertical with described chill roll limit, the limit of other direction is of a size of 265 millimeters.The diameter of described cooling roll shaft is 70 millimeters, and the distance between described opening described chill roll axis is corresponding thereto 85 millimeters; Distance 105 millimeters between adjacent two described openings on same wall.
The step of plating of the present invention is carried out in following electroplanting device, and this electroplanting device is disclosed in another section of patent application of the applicant, and application number is CN2010105103576.As shown in Figure 3, it comprises pre-galvanized groove ampere, main electroplating bath B, main electroplating bath C, rinsing bowl D, deactivation slot E and rinsing bowl F; Unreeling machine 1, winder 2, the 4th orienting roll 3, the 3rd orienting roll 4, the 6th orienting roll 5, the 7th orienting roll 6, the 7th orienting roll 7, the 8th orienting roll 8, first orienting roll group 9, first orienting roll group 10, between winder 2 and the 8th orienting roll 8, there is drying baker 26; Second guide roller 11, the 4th guide roller 12, the 4th guide roller 14, the 5th guide roller 13, the 3rd guide roller 15; Second plate group 16, first anode group 17, first anode group 18, first anode group 19, first anode group 20; Second conductive rollers group 21, first conductive rollers group 22, first conductive rollers group 23, first conductive rollers group 24 and the first conductive rollers group 25.
During plating, pending film is placed on unreeling machine 1, then one end of film is made to sequentially pass through the 3rd guide roller 15, second guide roller 11, second conductive rollers group 21, 4th orienting roll 3, first conductive rollers group 22, first orienting roll group 9, first conductive rollers group 23, 3rd orienting roll 4, first conductive rollers group 24, first orienting roll group 10, first conductive rollers group 25, 6th orienting roll 5, 4th guide roller 12, 7th orienting roll 6, 5th guide roller 13, 7th orienting roll 7, 4th guide roller 14, 8th orienting roll 8, drying baker 26 and being finally wound on winder 2.With electroplating bath and each main electroplating bath in inject electroplate liquid and electroplate liquid, start each motor, regulate the rotating speed of motor, film is run with required speed.
Describe the present invention in detail by the following examples.
Embodiment 1: the copper film being deposited 10 nanometer thickness by ion beam sputtering in every side of polyimides (PI) film, then electroplating deposition 12 micron thickness layers of copper
Experimentation: (1) is by volume polyimides (PI) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, by one end of PI film successively by governing mechanism of tension, governing mechanism of tension, is finally fixed on wrap-up.Ion beam sputtering equipment (Xinan Nuclear Physics Research Academy) is adopted to carry out ion beam sputtering, when vacuum is lower than 8.0 × 10
-4after handkerchief, then pass into argon gas, make vacuum drop to 1 × 10
-2about handkerchief, then switch on power, gas ion source is started working.The parameter of described ion beam sputtering comprises: the angle between ion beam and the plane normal residing for the metallic plates (copper coin) that bombards is 50 °, described ion beam source and described metallic plates be 20 centimetres by the distance between the position bombarded; It is 10 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 6 amperes, and argon flow amount is 4 ml/min.Arc voltage is 50 volts, and arc current is 0.8 ampere.Suppress voltage to be 120 volts, suppress electric current to be 2 milliamperes.Accelerating potential is 1 kilovolt, and accelerating electric current is 80 milliamperes.The copper film of 10 nanometers is deposited in every side of polyimides (PI) film.
(2) electroplate: above-mentioned polyimides (PI) film that deposited copper film is electroplated.In pre-galvanized groove, the temperature of pre-plating solution is 25 DEG C, and average cathode current density is 15 amperes/decimeter
2, pre-plating solution is: copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.2 milliliter/liter, Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 25 DEG C, and average cathode current density is 3.9 amperes/decimeter
2, plating solution is for comprising copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.15 milliliter/liter, and Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.The speed that film runs is 10 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 100 DEG C, carries out drying to film.It is 25 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 10 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 0.2 grams per liter BTA.
Electroplating deposition 12 micron thickness layers of copper, layers of copper is dense smooth.
Embodiment 2: the copper film being deposited 100 nanometers by ion beam sputtering in every side of polyimides (PI) film, then electroplating deposition 7 micron thickness layers of copper
Experimentation: (1) is by volume polyimides (PI) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, by one end of PI film successively by governing mechanism of tension, governing mechanism of tension, is finally fixed on wrap-up.Ion beam sputtering instrument (Xinan Nuclear Physics Research Academy) is adopted to carry out ion beam sputtering, when vacuum is lower than 8.0 × 10
-4after handkerchief, then pass into argon gas, make vacuum drop to 0.5 × 10
-2about handkerchief, then switch on power, gas ion source is started working.The parameter of described ion beam sputtering comprises: the angle between ion beam and the plane normal residing for the metallic plates (copper coin) that bombards is 20 °, described ion beam source and described metallic plates be 40 centimetres by the distance between the position bombarded; It is 30 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 15 amperes, and argon flow amount is 8 ml/min.Arc voltage is 80 volts, and arc current is 1.5 amperes.Suppress voltage to be 180 volts, suppress electric current to be 8 milliamperes.Accelerating potential is 2 kilovolts, and accelerating electric current is 150 milliamperes.The copper film of 100 nanometers is deposited in every side of polyimides (PI) film.
(2) electroplate: above-mentioned polyimides (PI) film that deposited copper film is electroplated.In pre-galvanized groove, the temperature of pre-plating solution is 20 DEG C, and average cathode current density is 25 amperes/decimeter
2, pre-plating solution is copper sulphate 150 grams per liter, sulfuric acid 60 grams per liter, hydrochloric acid 0.1 milliliter/liter, open cylinder agent 5 milliliters/liter, Atotech 210A:0.5 milliliter/liter, Atotech 210B:0.3 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 20 DEG C, and average cathode current density is 15 amperes/decimeter
2, plating solution is for comprising copper sulphate 120 grams per liter, sulfuric acid 80 grams per liter, hydrochloric acid 0.15 milliliter/liter, and Atotech 210 open cylinder agent 7 milliliters/liter, Atotech 210A:0.6 milliliter/liter, Atotech 210B:0.5 milliliter/liter.The speed that film runs is 50 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 110 DEG C, carries out drying to film.It is 20 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 50 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 1 grams per liter BTA.
Electroplating deposition 7 micron thickness layers of copper, layers of copper is very fine and close smooth.
Embodiment 3: the copper film being deposited 50 nanometers by ion beam sputtering in every side of polyimides (PI) film, then electroplating deposition 9 micron thickness layers of copper
Experimentation: (1) is by volume polyimides (PI) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, by one end of PI film successively by governing mechanism of tension, governing mechanism of tension, is finally fixed on wrap-up.Ion beam sputtering instrument (Xinan Nuclear Physics Research Academy) is adopted to carry out ion beam sputtering, when vacuum is lower than 8.0 × 10
-4after handkerchief, then pass into argon gas, make vacuum drop to 5 × 10
-2about handkerchief, then switch on power, gas ion source is started working.The parameter of described ion beam sputtering comprises: the angle between ion beam and the plane normal residing for the metallic plates that bombards is 40 °, described ion beam source and described metallic plates (copper coin) be 30 centimetres by the distance between the position bombarded; It is 20 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 10 amperes, and argon flow amount is 6 ml/min.Arc voltage is 65 volts, and arc current is 1.2 amperes.Suppress voltage to be 140 volts, suppress electric current to be 6 milliamperes.Accelerating potential is 1.5 kilovolts, and accelerating electric current is 120 milliamperes.The copper film of 50 nanometers is deposited in every side of polyimides (PI) film.
(2) electroplate: above-mentioned polyimides (PI) film that deposited copper film is electroplated.Plating: in pre-galvanized groove, the temperature of pre-plating solution is 22 DEG C, and average cathode current density is 30 amperes/decimeter
2, pre-plating solution is copper sulphate 150 grams per liter, sulfuric acid 80 grams per liter, hydrochloric acid 0.2 milliliter/liter, open cylinder agent 7 milliliters/liter, Atotech 210A:0.7 milliliter/liter, Atotech 210B:0.5 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 22 DEG C, and average cathode current density is 17 amperes/decimeter
2, plating solution is for comprising copper sulphate 100 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.2 milliliter/liter, and open cylinder agent 11 milliliters/liter, Atotech 210A:0.9 milliliter/liter, Atotech 210B:0.7 milliliter/liter.The speed that film runs is 40 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 120 DEG C, carries out drying to film.It is 22 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 40 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 3 grams per liter BTAs.
Electroplating deposition 9 micron thickness layers of copper, layers of copper is dense smooth.
Embodiment 4: adopt ion implantation to be 3 × 10 at every side implantation dosage of polyimides (PI) film
14individual atom/centimetre
2copper ion, then deposited the copper film of 30 nanometers in every side of polyimides (PI) film by ion beam sputtering, last electroplating deposition 12 micron thickness layers of copper
Experimentation: (1) is by volume polyimides (PI) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, governing mechanism of tension is passed through successively in one end of PI film, all chill rolls, governing mechanism of tension, is finally fixed on wrap-up.In chill roll, pass into the cooling water of 0-10 DEG C, vacuumize, make vacuum be 5 × 10
-4handkerchief.Open ion gun and open accelerating potential.The PI film speed of service is made to be 2 ms/min.
(2) ion implantation: all adopt copper ion source.Ion implantation voltage is 5 kilovolts, and implantation dosage is 3 × 10
14individual atom/centimetre
2.
(3) by above-mentioned injected 3 × 10
14individual atom/centimetre
2the film of copper adopts ion beam sputtering instrument (Xinan Nuclear Physics Research Academy) to carry out ion beam sputtering, when vacuum is lower than 8.0 × 10
-4after P ampere, then pass into argon gas, make vacuum drop to 3 × 10
-2about handkerchief, then switch on power, gas ion source is started working.The parameter of described ion beam sputtering comprises: the angle between ion beam and the plane normal residing for the metallic plates (copper coin) that bombards is 60 °, described ion beam source and described metallic plates be 25 centimetres by the distance between the position bombarded; It is 15 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 8 amperes, and argon flow amount is 5 ml/min.Arc voltage is 70 volts, and arc current is 1 ampere.Suppress voltage to be 140 volts, suppress electric current to be 5 milliamperes.Accelerating potential is 1.2 kilovolts, and accelerating electric current is 80 milliamperes.The copper film of 30 nanometers is deposited in every side of polyimides (PI) film.
(4) electroplate: above-mentioned polyimides (PI) film that deposited copper film is electroplated.In pre-galvanized groove, the temperature of pre-plating solution is 25 DEG C, and average cathode current density is 15 amperes/decimeter
2, pre-plating solution is: copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.2 milliliter/liter, Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 25 DEG C, and average cathode current density is 3.9 amperes/decimeter
2, plating solution is for comprising copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.15 milliliter/liter, and Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.The speed that film runs is 10 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 100 DEG C, carries out drying to film.It is 25 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 10 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 0.2 grams per liter BTA.
Electroplating deposition 12 micron thickness layers of copper, layers of copper is dense smooth.
Embodiment 5: adopt ion implantation to be 1 × 10 at every side implantation dosage of polyimides (PI) film
16individual atom/centimetre
2nickel, then successively deposit the nickel film of 5 nanometers and the copper film of 30 nanometers by ion beam sputtering in every side of polyimides (PI) film, last electroplating deposition 12 micron thickness layers of copper
Experimentation: (1) is by volume polyimides (PI) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, governing mechanism of tension is passed through successively in one end of PI film, all chill rolls, governing mechanism of tension, is finally fixed on wrap-up.In chill roll, pass into the cooling water of 0-10 DEG C, vacuumize, make vacuum be 5 × 10
-4handkerchief.Open ion gun and open accelerating potential.The PI film speed of service is made to be 2 ms/min.
(2) ion implantation: all adopt nickel ion source.Ion implantation voltage is 6 kilovolts, and implantation dosage is 1 × 10
16individual atom/centimetre
2nickel.
(3) by above-mentioned injected 1 × 10
16individual atom/centimetre
2the film of nickel adopts ion beam sputtering instrument (Xinan Nuclear Physics Research Academy) to carry out ion beam sputtering, when vacuum is lower than 8.0 × 10
-4after handkerchief, then pass into argon gas, make vacuum drop to 1 × 10
-2about handkerchief, then switch on power, gas ion source is started working.The parameter of described ion beam sputtering comprises: ion beam with by the metallic plates that bombards (first for nickel plate, then be copper coin) residing for plane normal between angle be 70 °, described ion beam source and described metallic plates be 25 centimetres by the distance between the position bombarded; It is 15 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 6 amperes, and argon flow amount is 4 ml/min.Arc voltage is 60 volts, and arc current is 0.9 ampere.Suppress voltage to be 140 volts, suppress electric current to be 5 milliamperes.Accelerating potential is 1 kilovolt, and accelerating electric current is 80 milliamperes.First deposit the nickel film of 5 nanometers in every side of polyimides (PI) film, then deposit the copper film of 30 nanometers.
(4) electroplate: above-mentioned polyimides (PI) film that deposited copper film is electroplated.In pre-galvanized groove, the temperature of pre-plating solution is 25 DEG C, and average cathode current density is 15 amperes/decimeter
2, pre-plating solution is: copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.2 milliliter/liter, Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 25 DEG C, and average cathode current density is 3.9 amperes/decimeter
2, plating solution is for comprising copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.15 milliliter/liter, and Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.The speed that film runs is 10 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 100 DEG C, carries out drying to film.It is 25 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 10 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 0.2 grams per liter BTA.
Electroplating deposition 12 micron thickness layers of copper, layers of copper is dense smooth.
Embodiment 6: adopt ion implantation to be 1 × 10 at every side implantation dosage of PET (PET) film
15individual atom/centimetre
2, then successively deposit the nickel film of 20 nanometers and the copper film of 10 nanometers by ion beam sputtering in every side of PET (PET) film, last electroplating deposition 12 micron thickness layers of copper
Experimentation: (1) is by volume PET (PET) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, governing mechanism of tension is passed through successively in one end of PET (PET) film, all chill rolls, governing mechanism of tension, is finally fixed on wrap-up.In chill roll, pass into the cooling water of 0-10 DEG C, vacuumize, make vacuum be 5 × 10
-4handkerchief.Open ion gun and open accelerating potential.PET (PET) the film speed of service is made to be 2 ms/min.
(2) ion implantation: all adopt nickel ion source.Ion implantation voltage is 6 kilovolts, and implantation dosage is 1 × 10
15individual atom/centimetre
2nickel.
(3) by above-mentioned injected 1 × 10
15individual atom/centimetre
2nickel film adopt ion beam sputtering instrument (Xinan Nuclear Physics Research Academy) carry out ion beam sputtering, when vacuum is lower than 8.0 × 10
-4after handkerchief, then pass into argon gas, make vacuum drop to 1 × 10
-2about handkerchief, then switch on power, gas ion source is started working.The parameter of described ion beam sputtering comprises: ion beam with by the metallic plates that bombards (first for nickel plate, then be copper coin) residing for plane normal between angle be 50 °, described ion beam source and described metallic plates be 25 centimetres by the distance between the position bombarded; It is 15 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 8 amperes, and argon flow amount is 5 ml/min.Arc voltage is 50 volts, and arc current is 1 ampere.Suppress voltage to be 200 volts, suppress electric current to be 10 milliamperes.Accelerating potential is 1.2 kilovolts, and accelerating electric current is 200 milliamperes.First deposit the nickel film of one deck 20 nanometer in every side of PET (PET) film, then deposit the copper film of one deck 10 nanometer.
(4) electroplate: above-mentioned PET (PET) film that deposited copper film is electroplated.In pre-galvanized groove, the temperature of pre-plating solution is 25 DEG C, and average cathode current density is 15 amperes/decimeter
2, pre-plating solution is: copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.2 milliliter/liter, Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 25 DEG C, and average cathode current density is 3.9 amperes/decimeter
2, plating solution is for comprising copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.15 milliliter/liter, and Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.The speed that film runs is 10 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 100 DEG C, carries out drying to film.It is 25 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 10 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 0.2 grams per liter BTA.
Electroplating deposition 12 micron thickness layers of copper, layers of copper is dense smooth.
Embodiment 7: adopt ion implantation to be 1 × 10 at every side implantation dosage of PET (PET) film
15individual atom/centimetre
2, then successively deposit the nickel film of 10 nanometers and the copper film of 20 nanometers by ion beam sputtering in every side of PET (PET) film, last electroplating deposition 12 micron thickness layers of copper
Experimentation: (1) is by volume PET (PET) film (thickness 0.025 millimeter, width 270 millimeters) be placed on let off roll, governing mechanism of tension is passed through successively in one end of PET (PET) film, all chill rolls, governing mechanism of tension, is finally fixed on wrap-up.In chill roll, pass into the cooling water of 0-10 DEG C, vacuumize, make vacuum be 5 × 10
-4handkerchief.Open ion gun and open accelerating potential.PET (PET) the film speed of service is made to be 2 ms/min.
(2) ion implantation: all adopt nickel ion source.Ion implantation voltage is 6 kilovolts, and implantation dosage is 1 × 10
15individual atom/centimetre
2nickel.
(3) by above-mentioned injected 1 × 10
15individual atom/centimetre
2nickel film adopt ion beam sputtering instrument (Xinan Nuclear Physics Research Academy) carry out ion beam sputtering, the parameter of described ion beam sputtering comprises: ion beam with by the metallic plates that bombards (first for nickel plate, then be copper coin) residing for plane normal between angle be 30 °, described ion beam source and described metallic plates be 25 centimetres by the distance between the position bombarded; It is 15 centimetres that described metallic plates is accepted by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic high molecular polymer film.Gas ion source heater current is 15 amperes, and argon flow amount is 10 ml/min.Arc voltage is 80 volts, and arc current is 1.7 amperes.Suppress voltage to be 190 volts, suppress electric current to be 9 milliamperes.Accelerating potential is 2 kilovolts, and accelerating electric current is 160 milliamperes.First deposit the nickel film of one deck 10 nanometer in every side of PET (PET) film, then deposit the copper film of one deck 20 nanometer.
(4) electroplate: above-mentioned PET (PET) film that deposited copper film is electroplated.In pre-galvanized groove, the temperature of pre-plating solution is 25 DEG C, and average cathode current density is 15 amperes/decimeter
2, pre-plating solution is: copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.2 milliliter/liter, Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.In main electroplating bath, the temperature of electroplate liquid is 25 DEG C, and average cathode current density is 3.9 amperes/decimeter
2, plating solution is for comprising copper sulphate 60 grams per liter, sulfuric acid 100 grams per liter, hydrochloric acid 0.15 milliliter/liter, and Atotech 210 open cylinder agent 10 milliliters/liter, Atotech 210A:0.8 milliliter/liter, Atotech 210B:0.6 milliliter/liter.The speed that film runs is 10 ms/h.
After plating terminates, the rinsing bowl making film pass through to be equipped with water is washed, passivation in deactivation slot afterwards, washes afterwards at the rinsing bowl by being equipped with water again, by drier, at temperature is 100 DEG C, carries out drying to film.It is 25 DEG C that described passivating conditions comprises passivation temperature, and the speed that film runs is 10 ms/h, and passivating solution is the aqueous solution (LT-02 of the chemical industry that Guangzhou is bright) containing 0.2 grams per liter BTA.
Electroplating deposition 12 micron thickness layers of copper, layers of copper is dense smooth.
Performance test: the adhesion in flexibility coat copper plate prepared by detection embodiment 1-7 between metal level and substrate film and soldering resistance
Experimental technique: according to Chinese printed circuit Association Standard CPCA/JPCA-BM03-2005 printed circuit flexibility coat copper plate " detect, the result of detection is as shown in table 1:
Table 1
Note:
1. peel strength unit is: N/mm;
2. detect by " Chinese printed circuit Association Standard CPCA/JPCA-BM03-2005 printed circuit flexibility coat copper plate ".
As can be seen from Table 1, the thinner thickness of two-layer flexibility coat copper plate provided by the present invention, meets the trend that FPC (FPC) develops, and metal level in flexibility coat copper plate and the adhesion between substrate film is higher, soldering resistance good.
Claims (13)
1. a stratotype flexibility coat copper plate, it comprises organic macromolecule membrane and covers the layers of copper on this organic polymer film, it is characterized in that, peel strength between described layers of copper and described organic polymer film is higher than 0.6N/mm, and the preparation method of described two stratotype flexibility coat copper plates comprises the step of by ion beam sputtering, organic polymer film being carried out to metal lining; Wherein, the parameter of described ion beam sputtering comprises: ion beam and be 20-70 ° by the angle between the metallic plates plane normal that bombards, plasma sputter source and described metallic plates be 20-40 centimetre by the distance between the position bombarded; It is 10-30 centimetre that described metallic plates is received by the distance between the metallic atom place that pounds by the position of ion beam bombardment and described organic polymer film; Described organic polymer film is Kapton, polyethylene terephthalate thin film, liquid crystal polymer film or polyparabanic acid film; Before described preparation method is included in and organic polymer film is carried out to the step of metal lining by ion beam sputtering, organic polymer film is carried out to the step of metal ion implantation.
2. two stratotype flexibility coat copper plates according to claim 1, wherein, in described preparation method, sputtering pressure is argon atmosphere 0.5 × 10
-2-5 × 10
-2handkerchief, gas ion source heater current is 6-15 ampere.
3. two stratotype flexibility coat copper plates according to claim 1, wherein, in described preparation method, arc voltage is 50-80 volt, and arc current is 0.8-2 ampere.
4. two stratotype flexibility coat copper plates according to claim 1, wherein, in described preparation method, suppress voltage to be 100-200 volt, suppress electric current to be 2-10 milliampere.
5. two stratotype flexibility coat copper plates according to claim 1, wherein, in described preparation method, accelerating potential is 1-2 kilovolt, and accelerating electric current is 50-200 milliampere.
6. two stratotype flexibility coat copper plates according to claim 1, wherein, in described preparation method, are deposited on described organic polymer film surface by the metallic atom pounded with the direction being basically perpendicular to described organic polymer film surface.
7. two stratotype flexibility coat copper plates according to claim 1, wherein, the metal ion of described ion beam sputtering comprises one or more in copper ion and optional nickel ion, chromium ion and molybdenum ion.
8. two stratotype flexibility coat copper plates according to any one of claim 1-7, wherein, in the step of described metal ion implantation, ion implantation dosage is 0.5 × 10
14-5.0 × 10
16individual atom/centimetre
2.
9. two stratotype flexibility coat copper plates according to claim 8, wherein, the metal ion injected in the step of described metal ion implantation is one or more of chromium ion, nickel ion, copper ion and molybdenum ion.
10. according to two stratotype flexibility coat copper plates in claim 1-7 described in any one, wherein, described step of organic polymer film being carried out to metal lining by ion beam sputtering deposits the metal level of 10-200 nanometer thickness on organic polymer film.
11. two stratotype flexibility coat copper plates according to claim 10, wherein, described metal level is made up of the nickel dam of 5-100 nanometer and the layers of copper of 5-100 nanometer.
12. according to two stratotype flexibility coat copper plates in claim 1-7 described in any one, wherein, and the step that described preparation method electroplates after being included in and carrying out the step of metal lining by ion beam sputtering to organic polymer film.
13. two stratotype flexibility coat copper plates according to claim 12, wherein, the step of described plating comprises preplating and main plating; It is 20-28 DEG C that described preplating condition comprises electroplating temperature, and average cathode current density is 10-40 ampere/decimetre
2, the speed that described organic polymer film runs is 10-50 m/h; It is 20-28 DEG C that described main plating conditions comprises electroplating temperature, and average cathode current density is 2-15 ampere/decimetre
2, the speed that described organic polymer film runs is 10-50 m/h.
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| CN109097750A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109097726A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109097772A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109097748A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
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| CN109097751A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
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| CN110418507B (en) * | 2019-08-19 | 2020-11-06 | 台山市精诚达电路有限公司 | Manufacturing process of high-frequency high-speed flexible circuit board |
| CN112210760B (en) * | 2020-10-13 | 2021-05-07 | 廖斌 | Surface treatment method of ultrathin polymer |
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| CN113667952B (en) * | 2021-08-27 | 2022-07-12 | 江苏耀鸿电子有限公司 | Magnetron sputtering flexible copper-clad substrate and preparation method thereof |
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