CN104372295B - The preparation method and equipment of flexible parent metal circuit board and metal pinning layer - Google Patents

The preparation method and equipment of flexible parent metal circuit board and metal pinning layer Download PDF

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CN104372295B
CN104372295B CN201410494856.9A CN201410494856A CN104372295B CN 104372295 B CN104372295 B CN 104372295B CN 201410494856 A CN201410494856 A CN 201410494856A CN 104372295 B CN104372295 B CN 104372295B
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metal
pinning layer
layer
preparation
flexible parent
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CN104372295A (en
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廖斌
吴先映
张旭
张荟星
陈琳
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Beijing Normal University
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Beijing Normal University
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Abstract

The invention discloses the preparation method and equipment of a kind of flexible parent metal circuit board and metal pinning layer, wherein, the preparation method of the metal pinning layer includes：Using metal vapor vacuum arc (MEVVA) ion gun, basad layer injects the first metallic element, and the basalis is cleaned；Deposit to obtain the first metallic diaphragm using filtered cathodic vacuum arc (FCVA) ion gun, substrate surface after cleaning, Magnetic filter；Using the MEVVA ion guns, the second metallic element is injected to first metal film layer surface, forms metal pinning layer.Therefore, the metal pinning layer and flexible parent metal circuit board being prepared using the preparation method and equipment of the present invention have very high-bond and stripper-resistance.

Description

The preparation method and equipment of flexible parent metal circuit board and metal pinning layer
Technical field
The present invention relates to electronic technology field, the preparation side of more particularly to a kind of flexible parent metal circuit board and metal pinning layer Method and equipment.
Background technology
Originally, FPC (FPC) is only applied to the special industries such as military affairs, space flight, but with scientific and technological progress and a variety of The development of information terminal apparatus, FPC are gradually applied to the fields such as civilian and business, and as rigid line plate, FPC is achieved Greatly development.But rigid line plate is compared, FPC volume is smaller, and weight is lighter, it is possible to achieve bending flexure, stereoscopic three-dimensional Assembling.
With the continuous progress of science and technology, FPC demand is also increased therewith.At present, generally use adhesive is by copper Paper tinsel is affixed on flexible plastic substrates, to prepare FPC.But the inventors found that：
The base material that adhesive is formed can not meet that highdensity assembling requires.Also, used by existing FPC It is follow-up by circuit pattern formation process or electrowinning process between each film layer (such as film base material and conductive layer) in substrate circuit plate During process, the problems such as bond strength declines and easily peeled off often occurs.It can be seen that the film layer that existing manufacture method is formed combines Power deficiency, peel strength are weaker, it is difficult to suitable for harsh and unforgiving environments.Therefore, substrate circuit plate needs further to improve each film layer Between adhesion.
The content of the invention
In view of this, the first purpose of the embodiment of the present invention is to propose a kind of preparation method of metal pinning layer and set It is standby, the metal pinning layer with very high-bond and stripper-resistance can be prepared.
For further, the preparation method of the metal pinning layer includes：Utilize metal vapor vacuum arc (MEVVA, Metal Vapor Vacuum Arc) ion gun, the first metallic element of basad layer injection, is cleaned, and formed to the basalis Metal-doped layer；Using filtered cathodic vacuum arc (FCVA) ion gun, deposited on the metal-doped layer by Magnetic filter Obtain the first metallic diaphragm；Using the MEVVA ion guns, the second metallic element is injected to first metal film layer surface, Form metal pinning layer；Using the FCVA ion guns, on the metal pinning layer, Magnetic filter deposits 10~30nm gold Belong to coating.
Alternatively, in certain embodiments, the basalis is polyimide polymer；And/or first metal film Layer is Ni film layers or Cu film layers；The thickness of first metallic diaphragm is more than or equal to 3nm, and is less than 10nm.
Alternatively, in certain embodiments, first metallic element is Ni or Cu, and its injecting voltage is 4~8kV, Beam intensity is 1~4mA, and implantation dosage is 1 × 1015~1 × 1016/cm2, injection depth is 70~120nm.
Alternatively, in certain embodiments, second metallic element is Ni or Cu, and its injecting voltage is 10~15kV, Injection metal beam intensity is 1~4mA, and implantation dosage is 1 × 1015~5 × 1015/cm2。
Alternatively, in certain embodiments, the metallic element of the metal cladding is Ni or Cu, and thickness be 10~ 30nm；During the Magnetic filter deposition, arc stream is 90~150A, and bend pipe field supply is 1.0~4.0A.
Correspondingly, the Preparation equipment for the metal pinning layer that the embodiment of the present invention proposes is used to implement any of the above-described described gold Belong to the preparation method of pinning layer, the Preparation equipment of the metal pinning layer includes：Injection device, it is configured to utilize metallic vapour vacuum Arc (MEVVA) ion gun, basad layer inject the first metallic element, the basalis are cleaned, and is formed metal-doped Layer；Precipitation equipment, it is configured to utilize the FCVA, deposits by Magnetic filter to obtain the first metal film on the metal-doped layer Layer, wherein, the thickness of first metallic diaphragm is more than or equal to 3nm and is less than 10nm；The injection device, is additionally configured to profit The second metallic element is injected to first metal film layer surface with the MEVVA ion guns, forms metal pinning layer.
Alternatively, in certain embodiments, the precipitation equipment is additionally configured to：Using the FCVA, in the peg Prick on layer and deposit 10~30nm metal cladding.
Relative to prior art, various embodiments of the present invention have the advantage that：
The preparation method and equipment for the metal pinning layer that the embodiment of the present invention proposes, on the base layer, are first passed through by MEVVA First metallic element of ion gun injection, is cleaned and is infiltrated to basalis, then the base by FCVA ion guns after treatment The first metallic diaphragm deposited on bottom, then the second metallic element of higher energy is injected using MEVVA ion guns, makes to gather The thin metallic atom of acid imide film surface deposition obtains recoil energy and entered in basalis, forms the metal mixed with basalis Pinning Rotating fields, the metal pinning Rotating fields and the adhesion of basalis so formed are very good, so that its peel strength It is enhanced.
The another object of the embodiment of the present invention is to propose a kind of preparation method and equipment of flexible parent metal circuit board, can The flexible parent metal circuit board with very high-bond and stripper-resistance is prepared.
The preparation method of the flexible parent metal circuit board includes：Clean flexible parent metal；On the flexible parent metal surface, foregoing A kind of preparation method of described metal pinning layer prepares metal pinning layer；Deposited in the enterprising row metal of the metal pinning layer, Form metal cladding；Required circuit is etched on the metal cladding.
Correspondingly, the Preparation equipment for the flexible parent metal circuit board that the embodiment of the present invention proposes includes：Foregoing any gold Belong to the Preparation equipment of pinning layer；Etching device, it is configured to etch required circuit on the metal cladding.
The preparation method and equipment for the flexible parent metal circuit board that the embodiment of the present invention proposes, it is clear by being carried out to flexible parent metal Wash and infiltrate, then by the way that the metallic element of higher energy is injected, obtain the thin metallic atom that polyimide film surface deposits Recoil energy enters in basalis, forms the metal pinning Rotating fields mixed with basalis, the metal pinning layer so formed Structure and the adhesion of basalis are very good, so that its peel strength is enhanced.
In addition, the embodiment of the present invention also proposes a kind of flexible parent metal circuit board according to any of the above-described kind of technical scheme Preparation method and device fabrication flexible parent metal circuit board；Wherein, the flexible parent metal circuit board includes：Basalis, gold Belong to film layer, metal pinning layer, the metal cladding being deposited on the metal pinning layer and on the metal cladding Circuit layer.
In addition, a further object of the embodiment of the present invention is to propose a kind of terminal device, the terminal device is provided with above-mentioned Flexible parent metal circuit board described in one technical scheme.
Because the preparation method and equipment of any of the above-described kind of flexible parent metal circuit board have above-mentioned technique effect, therefore, make The flexible parent metal circuit board that is obtained with the preparation method and equipment of above-mentioned flexible parent metal circuit board and it is provided with the flexible parent metal The terminal device of circuit board should also possess corresponding technique effect, not repeat hereby.
Brief description of the drawings
The accompanying drawing for forming a part of the embodiment of the present invention is used for providing further understanding the embodiment of the present invention, the present invention Schematic description and description be used for explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the schematic flow sheet of the preparation method of metal pinning layer provided in an embodiment of the present invention；
Fig. 2 is the structural representation of metal pinning layer provided in an embodiment of the present invention；
Fig. 3 is the structural representation of FCVA depositing systems provided in an embodiment of the present invention；
Fig. 4 is the structural representation of MEVVA injected systems provided in an embodiment of the present invention；
Fig. 5 be three kinds of different situations provided in an embodiment of the present invention under the adhesion of conductive copper layer and polyimide substrate and Surface energy schematic diagram；
Fig. 6 is the elemental composition schematic diagram of polyimide film surface after MEVVA ion implantings provided in an embodiment of the present invention.
Description of reference numerals
100 polyimide film substrates
110 metal pinning layers
120 metal claddings
200 FCVA negative electrodes
210 trigger electrodes
220 anodes
230 conduits
240 magnetic fields
300 MEVVA negative electrodes
310 extraction electrodes
320 suppress secondary electron electrode
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made Embodiment, belong to the scope of protection of the invention.
It should be noted that in the case where not conflicting, the feature in the embodiment of the present invention and embodiment can be mutual group Close.
Below in conjunction with the accompanying drawings, each preferred embodiment of the present invention is described further：
Embodiment of the method
With the extensive use of FPC, the requirement more and more higher to performances such as peel strengths, high knot is prepared Close following development of the transition zone of intensity to FPC and seem extremely important.Here, there is provided one kind can be in harsh ring The manufacture method of the metal pinning layer of the high bond strength used under border.
It should be noted that in the present embodiment, metal pinning layer is prepared on the base layer, the basalis of selection can be polyamides Imine polymer, such as polyimide film (PI film, polyimide film).Herein, substrate is polyimide polymer, is gathered Acid imide is heat resistance highest kind in current industrialized high polymer material, due to superior combination property. Kapton is a kind of new high temperature resistant organic polymer thin film again, is by pyromellitic acid anhydride (PMDA) and diamino Yl diphenyl ether (ODA) through polycondensation and salivates film forming in extremely strong property solvent dimethyl acetamide (DMAC), then is formed through imidization.
Reference picture 1, it illustrates the preparation method of the metal pinning layer of the present embodiment, the preparation method includes following step Suddenly：
S100：Using metal vapor vacuum arc (MEVVA) ion gun, basad layer injects the first metallic element, to substrate Layer is cleaned.
Wherein, this step is metal ion implantation cleaning treatment process early stage, sub- using high-energy metals ion implanting polyamides Amine film, can sputter away makes its adsorption micronic dust gas etc., improves the cleanliness factor on its surface.Also, MEVVA ion guns are to poly- Acid imide carries out metallic element injection, because metallic element has certain energy can be to polyimide film table in injection process The physical absorption in face or the impurity of chemisorbed have certain sputtering effect, and can form the metal-doped layer of shallow implant.
In addition, before deposited metal pinning layer, by that by high-energy metals Ion Implanted Polyimide Against Steel film layer, can make to gather Acid imide film surface part organic group interrupts, and improves its surface energy, strengthens its surface wettability, can make subsequent deposition Thin metal can be close to polyimide surface to greatest extent.
It is pointed out that in S100, the first metallic element can use Ni or Cu.As a kind of optional embodiment, The injecting voltage of first metallic element is 4~8kV, and beam intensity is 1~4mA (containing end value), and implantation dosage is 1 × 1015~1 × 1016/cm2(containing end value), injection depth are 70~120nm (containing end value).
S102：Utilize filtered cathodic vacuum arc (FCVA) ion gun, substrate surface after cleaning, Magnetic filter deposition Obtain the first metallic diaphragm.
In this step, optionally, the first metallic diaphragm can be Ni film layers or Cu film layers, and thickness is 3~10nm.
S104：Using MEVVA ion guns, the second metallic element is injected to the first metal film layer surface, forms metal pinning Layer.
In this step, by using MEVVA ion guns, the ion implanting of higher energy can be made into polyimide film surface The thin metallic atom of deposition obtains recoil energy and entered in polyimide film, can form being mixed with polyimides for 50nm or so Metal pinning Rotating fields, so formed pinning Rotating fields and polyimide film substrate caking power it is very good.
So, above-mentioned metal pinning layer is using polyimide film as substrate, by preparing metal transfer on polyimide film Layer --- metal pinning layer：A kind of Ni of element and FCVA ion source deposit in the Ni and Cu that injected by MEVVA ion guns and One or two kinds of element is formed in Cu, so as to improve the bond strength between polyimide film and metal pinning layer, makes it anti- Peel strength is enhanced.
In S104, as an alternative embodiment, the second metallic element can use Ni or Cu.Second metal member The injecting voltage of element be 10~15kV (contain end value), and it is 1~4mA (containing end value) to inject metal beam intensity, implantation dosage for 1 × 1015~5 × 1015/cm2(containing end value).
Based on the various embodiments described above and each optional embodiment, the preparation method of above-mentioned metal pinning layer may also include with Lower step：
S106：Using the FCVA ion guns, on metal pinning layer, Magnetic filter deposits metal cladding.Wherein, it is golden The metallic element for belonging to coating is Ni or Cu, and thickness can be 10~30nm (containing end value).
It should be noted that in the various embodiments described above, when performing Magnetic filter deposition operation, arc stream is 90~150A, curved Pipe field supply is 1.0~4.0A.Optionally, arc stream can use 100A, and bend pipe field supply can be 2.0A.
In the various embodiments described above, a kind of element and FCVA ion source deposit in the Ni and Cu that injected by MEVVA ion guns Ni and Cu in one or two kinds of element form the metal pinning layer of strong adhesion on polyimide substrate, it is as shown in Figure 2 Metal pinning layer, is prepared on polyimide substrate, and has following structure：Base polyimide film 100, metal pinning Layer 110 and metal cladding 120.Wherein, base polyimide film 100 is formed integrated with metal pinning layer 110, the two it Between there is higher adhesion, peel strength is high.
Below, an example is being combined, in specific implementation process, the preparation method of above-mentioned metal pinning layer is being made into one Walk explanation：
First, in polyimide film layer surface, inject Ni or Cu elements using high pressure MEVVA sources, injecting voltage 4~ Between 8kV, for beam intensity in 1~4mA, implantation dosage is 1 × 10 during injected with metallic elements15~1 × 1016/cm2Between, injection Depth is in 70~120nm.
Then, recycle FCVA systems to deposit one layer very thin of Ni or Cu film layers on surface, thickness 3~10nm it Between, the polyimide film surface of FCVA systems after the implantation deposits the Ni that a layer thickness is about 3~10nm or so or (no group of Cu Conjunction order) in one kind.
It should be noted that the thickness of this layer of Ni or Cu film layers is unsuitable blocked up, too it is thick can cause polyimide film/ The metallic atom of metal interface can not obtain enough recoil energies and enter inside polyimide film.
Then, MEVVA ion guns are recycled to inject Ni or Cu metallic elements on deposition film surface, injecting voltage is 10 Between~15kV, implantation dosage is 1 × 1015~5 × 1015/cm2Between, inject 1~4mA of metal beam intensity.
Finally, metal cladding is formed using FCVA ion source deposits Ni or Cu.So, formed using aforesaid way Intermediate metal and polyimide film form integration, thus intermediate metal and polyimide film peel strength can be made It is obviously improved, job stability and reliability are higher under various rigor conditions.
In addition, the embodiment of the present invention also proposes a kind of preparation method of flexible parent metal circuit board, the flexible parent metal circuit board Preparation method include：
S200：Clean flexible parent metal；
S202：On the flexible parent metal surface, the preparation method of the metal pinning layer according to foregoing any embodiment Prepare metal pinning layer；
S204：In the enterprising row metal deposition of the metal pinning layer, metal cladding is formed；
S206：Required circuit is etched on the metal cladding.
Above-described embodiment to flexible parent metal by being cleaned and infiltrated, then by the way that the metallic element of higher energy is noted Enter, the thin metallic atom for depositing polyimide film surface obtains recoil energy and entered in basalis, and formation mutually mixes with basalis The metal pinning Rotating fields of conjunction, the metal pinning Rotating fields and the adhesion of basalis so formed are very good, so that it is anti- Peel strength is enhanced.
Apparatus embodiments
To realize the preparation method of above-mentioned metal pinning layer, based on the various embodiments described above, the present embodiment proposes a kind of metal The Preparation equipment of pinning layer, the Preparation equipment include following device：Injection device and precipitation equipment.
Wherein, injection device is used to utilize MEVVA ion guns, the first metallic element is injected to the basalis, to described Basalis is cleaned.
It should be noted that MEVVA ion guns mainly produce area by plasma and ion beam draw-out area forms, plasma Body produces area i.e. metal vapor vacuum arc region of discharge.MEVVA ion implantings are exactly using load energy caused by MEVVA ion guns Ion beam bombardment material surface, to workpiece surface carry out ion implanting, so as to change the physics of material surface, chemical property mistake Journey so that film can be securely joined with workpiece substrate.
Precipitation equipment is used to utilize the FCVA, and substrate surface after cleaning deposits to obtain the first metallic diaphragm.Note Enter device to be additionally operable to inject the second metallic element to first metal film layer surface using the MEVVA ion guns, form gold Belong to pinning layer.
In the Preparation equipment of above-mentioned metal pinning layer, precipitation equipment is additionally operable to：Using the FCVA ion guns, in the gold Belong to deposited metal coating on pinning layer.
It is pointed out that in the various embodiments described above, precipitation equipment can use FCVA ion source deposits system as shown in Figure 3 System, the FCVA ion source deposit systems include：FCVA negative electrodes 200, trigger electrode 210, anode 220, conduit 230 and magnetic field 240。
In addition, in the various embodiments described above, injection device can use MEVVA ion gun injected systems as shown in Figure 4, should MEVVA ion gun injected systems include：MEVVA negative electrodes 300, extraction electrode 310 and suppression secondary electron electrode 320.
With reference to the fabrication processing of metal pinning layer, above-mentioned Preparation equipment is described further：
1st, basalis detects：
In above-described embodiment, substrate can be polyimide polymer, and before preparation starts, detection means is carried out to basalis Confirm, prepare to start the preparation of metal pinning layer.
2nd, metal ion implantation early stage cleans：
Injection device can use MEVVA ion gun injected systems, and it carries out metallic element using MEVVA sources to polyimides Injection, because metallic element has the physical absorption or change that certain energy can be to polyimide film surface in injection process Learning the impurity of absorption has certain sputtering effect, and can form the metal-doped layer of shallow implant.
3rd, metal pinning Rotating fields are formed：
Precipitation equipment can use FCVA ion source deposit systems, and it is left using FCVA sources 3~10nm of deposition Cu or Ni films It is right.
Then, Cu or Ni is either injected on Ni films using Cu of the MEVVA ion guns injected system in 3~10nm, is formed With the sub- integrated metal pinning Rotating fields of polyimide film.
4th, metal cladding structure：
The metal cladding deposited using FCVA ion source deposits system, metal cladding element is that Ni and Cu thickness is 10 ~30nm.
To realize the preparation method of above-mentioned flexible parent metal circuit board, based on the various embodiments described above, the present embodiment proposes a kind of The Preparation equipment of flexible parent metal circuit board, the Preparation equipment include：Injection device and precipitation equipment and etching device.Wherein：
Injection device is used to clean flexible parent metal, and prepares metal pinning layer on the flexible parent metal surface.
Precipitation equipment is used to, in the enterprising row metal deposition of the metal pinning layer, form metal cladding.
Etching device is used to etch required circuit on the metal cladding.
Optionally, in above-described embodiment, above-mentioned injection device can further comprise：First injection device and the second injection Device.
Wherein：
First injection device is used to utilize metal vapor vacuum arc (MEVVA) ion gun and filtered cathodic vacuum arc (FCVA) ion gun, Cu or Ni is injected to the basalis, the basalis is cleaned；Wherein, Cu or Ni note It is 4~8kV to enter voltage, and beam intensity is 1~4mA, and implantation dosage is 1 × 1015~1 × 1016/cm2, injection depth be 70~ 120nm。
Second injection device be used for using the MEVVA ion guns to the Cu either Ni film surfaces inject Cu or Ni, form metal pinning layer；Wherein, Cu or Ni injecting voltage is 10~15kV, and injection metal beam intensity is 1~4mA, Implantation dosage is 1 × 1015~5 × 1015/cm2。
As an alternative embodiment, above-mentioned precipitation equipment can further comprise：
First precipitation equipment, for utilizing the FCVA ion guns, on the metal pinning layer, Magnetic filter deposits gold Belong to coating；Wherein, the metallic element of the metal cladding is Ni or Cu, and thickness is 10~30nm；
Second precipitation equipment, for utilizing FCVA ion guns, flexible parent metal surface after cleaning, Magnetic filter deposits to obtain Cu film layers or Ni film layers；Wherein, the thickness of the Ni film layers or Cu film layers is 3~10nm.
It is pointed out that in the various embodiments described above, precipitation equipment can use FCVA ion source deposits system as shown in Figure 3 System, the FCVA ion source deposit systems include：FCVA negative electrodes 200, trigger electrode 210, anode 220, conduit 230 and magnetic field 240。
In addition, in the various embodiments described above, injection device can use MEVVA ion gun injected systems as shown in Figure 4, should MEVVA ion gun injected systems include：MEVVA negative electrodes 300, extraction electrode 310 and suppression secondary electron electrode 320.
By being cleaned and infiltrated to flexible parent metal in above-described embodiment, then by the way that the metallic element of higher energy is noted Enter, the thin metallic atom for depositing polyimide film surface obtains recoil energy and entered in basalis, and formation mutually mixes with basalis The metal pinning Rotating fields of conjunction, the metal pinning Rotating fields and the adhesion of basalis so formed are very good, so that it is anti- Peel strength is enhanced.
Substrate embodiment
With extensive use of the polyimide film in FPC, the requirement to performances such as peel strengths is increasingly Height, prepare following development of the transition zone of high bond strength to FPC and seem extremely important.Here, propose a kind of The FPC using polyimide film as substrate for the high bond strength that can be used under harsh and unforgiving environments.
In the present embodiment, the substrate of the flexible PCB is provided with：According to the metal described in any of the above-described embodiment of the method The preparation method of pinning layer and the Preparation equipment using the metal pinning layer described in any of the above-described apparatus embodiments, are prepared into The metal pinning layer arrived.
Wherein, the substrate of the flexible PCB includes：Basalis, metal pinning layer and it is deposited on the metal pinning layer On metal cladding.
Above-mentioned each method embodiment has elaborated to the manufacturing process of metal pinning layer, and here is omitted, related Content participates in foregoing embodiments.
It should be noted that in above-described embodiment, the methods of Cu paper tinsels thickness can pass through plating needed for FPC, is carried out Thicken, this method can manufacture 0~50 micron of Cu paper tinsels on polyimide film, and its great advantage is can be very easily Prepare the copper foil (more than 8 microns Cu paper tinsels can only be prepared in conventional laminate layer method) that less than 8 microns and adhesion is excellent.
In addition, the embodiment of the present invention also proposes a kind of terminal device, the terminal device is provided with any of the above-described embodiment institute The flexible parent metal circuit board stated.
Because the preparation method and equipment of any of the above-described kind of flexible parent metal circuit board have above-mentioned technique effect, therefore, make The flexible parent metal circuit board that is obtained with the preparation method and equipment of above-mentioned flexible parent metal circuit board and it is provided with the flexible parent metal The terminal device of circuit board should also possess corresponding technique effect, and its specific implementation process is similar to the above embodiments, does not go to live in the household of one's in-laws on getting married hereby State.
Below by three contrast tests, metal pinning layer and the flexible PCB for being provided with the metal pinning layer are carried out Performance evaluation：
Example one：(no pinning Rotating fields)
Using the PI 100HN types polyimide films of du pont company's production as base material, in the following manner to polyimides Film layer carries out double treatment：
1) Magnetic filter deposited Cu film transition zone, condition arc stream are 100A, bend pipe field supply 2.0A, deposit thickness 20nm.
2) plating forms the copper film that thickness is 20 μm in copper-bath.
Example two：(selection Cu metals are pinning layer structural element)
1) clean：Implanting C u element conditions：High pressure 6kV is injected, injects beam intensity 3mA, implantation dosage 3 × 1015；
2) Magnetic filter deposited Cu film condition：Arc stream 100A, bend pipe field supply 2.0A, deposit thickness 8nm；
3) Cu ion implantings are carried out to Cu thin layers and forms pinning layer condition：Accelerating potential 12kV, line 5mA, implantation dosage 3 ×1015/cm2；
4) cover：Magnetic filter deposited Cu film coating condition：Arc stream 100A, bend pipe field supply 2.0A, deposit thickness 20nm；
5) finally plating forms the copper film that thickness is 20 μm in copper-bath.
Example three：(selection Ni metal pinning Rotating fields element)
1) ion implanting Ni elements condition：High pressure 6kV is injected, injects beam intensity 3mA, implantation dosage 3 × 1015。
2) Magnetic filter deposition Ni film conditions：Arc stream 100A, bend pipe field supply 2.0A, deposit thickness 8nm.
3) Ni ion implantings are carried out to Ni thin layers and forms pinning layer condition：Accelerate high pressure 12kV, line 5mA, implantation dosage 3 ×1015/cm2。
4) Magnetic filter deposited Cu film coating condition：Arc stream 100A, bend pipe field supply 2.0A, deposit thickness 20nm.
5) plating forms the copper film that thickness is 20 μm in copper-bath.
Below, in the method in IPC-TM-650 (printed circuit TIA of U.S. ortho-test), to determine film base Peel strength between material and conductive layer.Test method is：
Rectangle test bar 200mm × 10mm polyimide film side bonds are fixed on to the periphery of disk, then fixture Peeled off with 10mm/min speed and polyimide film substrate into 90 degree of directions, determine required load-carrying (kg/cm).
Reference picture 5, it illustrates the adhesion and surface energy of three kinds of different tests conductive copper layers and polyimide substrate.Figure In, abscissa is respectively：In three kinds of examples, no pinning Rotating fields PI, Cu are that Cu-PI, Ni of pinning layer structural element are nail Prick the Ni-PI of Rotating fields element.Ordinate is：Surface energy (left side) and adhesion (right side).
During from Fig. 5 it can be found that using Ni as pinning layer structural element, the adhesion of polyimide film and metallic copper is up to 1.1kg/cm, during using Cu as pinning layer structural element, the adhesion of polyimide film and metallic copper is 0.95kg/cm, and without nail When pricking Rotating fields, the adhesion of polyimide film and metallic copper is less than 0.1kg/cm, and adhesion improves can be apparent.And And it can also be seen that also increasing with the Implanted Polyimide surface energy of ion elements from Fig. 5, wellability also improves therewith.
Reference picture 6, is surface-element composition after MEVVA ion implantings, and abscissa is respectively：In three kinds of examples, do not follow closely It is that pinning layer structural element Cu-PI, Ni are pinning layer structural element Ni-PI to prick Rotating fields PI, Cu.Ordinate is Elements C, O, N And metal M content.
From the XPS figures of the polyimide film surface shown in Fig. 6, it can be seen that because the injection of metallic element causes polyamides Imines film surface-element is changed：The increase of C element content, O and N element are reduced, the reduction explanation of element：Polyimide film Phenyl ring or imide ring fracture in layer, while the increase of C and metal ratio illustrates the formation of new keys, and this can be from micro- The increase of adhesion is explained in terms of sight.
To sum up, the good metal of one layer of adhesion is formed on the surface of polyimide film using MEVVA sources and FCVA systems Pinning layer, formed after pinning layer and form required circuit diagram by being electrolysed deposit, the metals for etching accumulation such as plating thereon Case.This class formation adhesion is very good, and reason can be analyzed as follows：
1st, high-energy metals early stage Ion Implanted Polyimide Against Steel film, which can sputter away, makes its adsorption micronic dust gas etc., improves The cleanliness factor on its surface；
2nd, high-energy metals early stage Ion Implanted Polyimide Against Steel film layer can make polyimide film surface portion organic group Interrupt, improve its surface energy, strengthen its surface wettability, the thin metal of subsequent deposition can be enable to be close to gather to greatest extent Acid imide surface.
3rd, the thin metallic atom that the ion implanting of later stage higher energy can deposit polyimide film surface is recoiled Energy enters in polyimide film, can form the pinning Rotating fields that 50nm or so metal and polyimides mix, so this Sample forms metal pinning Rotating fields and polyimide film substrate caking power is fine.
The reason for comprehensive three aspects, the film layer that this manufacture method is formed be not present by circuit pattern formation process or The problem of bond strength during the subsequent handlings such as electrowinning process between polyimide layer and metallic diaphragm declines and easily peeled off.
Further, since the preparation method and equipment of any of the above-described kind of metal pinning layer have above-mentioned technique effect, therefore, make The preparation method of layer and the metal pinning layer of equipment acquisition and the substrate for being provided with the metal pinning layer are pricked with above-mentioned peg Also should possess corresponding technique effect, its specific implementation process is similar to the above embodiments, does not repeat hereby.
Obviously, those skilled in the art should be understood that above-mentioned each module of the invention or each step can be with general Computing device realize that they can be concentrated on single computing device, or be distributed in multiple computing devices and formed Network on, alternatively, they can be realized with the program code that computing device can perform, it is thus possible to they are stored Performed in the storage device by computing device, either they are fabricated to respectively each integrated circuit modules or by they In multiple modules or step be fabricated to single integrated circuit module to realize.So, the present invention is not restricted to any specific Hardware and software combines.The storage device is nonvolatile memory, such as：ROM/RAM, flash memory, magnetic disc, CD etc..
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.

Claims (9)

  1. A kind of 1. preparation method of metal pinning layer, it is characterised in that including：
    Using metal vapor vacuum arc (MEVVA) ion gun, basad layer injects the first metallic element, and the basalis is carried out Cleaning, and form metal-doped layer；Wherein, the injecting voltage of first metallic element is 4~8kV, beam intensity is 1~ 4mA；
    Using filtered cathodic vacuum arc (FCVA) ion gun, deposit by Magnetic filter to obtain 3nm on the metal-doped layer ~10nm the first metallic diaphragm；
    Using the MEVVA ion guns, the second metallic element is injected to first metal film layer surface, forms metal pinning Layer；
    Using the FCVA ion guns, on the metal pinning layer, Magnetic filter deposits 10~30nm metal cladding；Its Described in Magnetic filter deposition when, arc stream is 90~150A, and bend pipe field supply is 1.0~4.0A.
  2. 2. the preparation method of metal pinning layer according to claim 1, it is characterised in that：
    The basalis is polyimide polymer；And/or
    First metallic diaphragm is Ni film layers or Cu film layers；The thickness of first metallic diaphragm is more than or equal to 3nm, and Less than 10nm.
  3. 3. the preparation method of metal pinning layer according to claim 2, it is characterised in that：
    First metallic element is Ni or Cu, and its injecting voltage is 4~8kV, and beam intensity is 1~4mA, and implantation dosage is 1×1015~1 × 1016/cm2, injection depth is 70~120nm；
    And/or
    Second metallic element is Ni or Cu, and its injecting voltage is 10~15kV, and injection metal beam intensity is 1~4mA, note Enter dosage for 1 × 1015~5 × 1015/cm2。
  4. 4. the preparation method of the metal pinning layer according to Claims 2 or 3, it is characterised in that the metal cladding Metallic element is Ni or Cu, and thickness is 10~30nm.
  5. A kind of 5. Preparation equipment of metal pinning layer, it is characterised in that including：
    Injection device, it is configured to utilize metal vapor vacuum arc (MEVVA) ion gun, basad layer injects the first metallic element, The basalis is cleaned, and forms metal-doped layer；
    Precipitation equipment, it is configured to utilize FCVA, deposits by Magnetic filter to obtain the first metallic diaphragm on the metal-doped layer； Wherein, the thickness of first metallic diaphragm is more than or equal to 3nm and is less than 10nm；
    The injection device is also configured to：Using the MEVVA ion guns second is injected to first metal film layer surface Metallic element, form metal pinning layer；
    FCVA ion source deposits system configuration be for：10~30nm metal covering is deposited on the metal pinning layer Layer, the FCVA ion source deposits system include FCVA negative electrodes (200), trigger electrode (210), anode (220), conduit (230) with And magnetic field (240).
  6. A kind of 6. preparation method of flexible parent metal circuit board, it is characterised in that including：
    Clean flexible parent metal；
    On the flexible parent metal surface, the preparation method of the metal pinning layer according to any one of Claims 1-4 prepares gold Belong to pinning layer；
    In the enterprising row metal deposition of the metal pinning layer, metal cladding is formed；
    Required circuit is etched on the metal cladding.
  7. A kind of 7. Preparation equipment of flexible parent metal circuit board, it is characterised in that including：
    The Preparation equipment of metal pinning layer according to claim 5；
    Etching device, it is configured to etch required circuit on the metal cladding.
  8. A kind of 8. flexible parent metal circuit board that preparation method using flexible parent metal circuit board as claimed in claim 6 manufactures； Wherein, the flexible parent metal circuit board includes：Basalis, metallic diaphragm, metal pinning layer, be deposited on the metal pinning layer it On metal cladding and the circuit layer on the metal cladding.
  9. 9. a kind of terminal device, it is characterised in that the terminal device is provided with the flexible parent metal circuit board described in claim 8.
CN201410494856.9A 2014-09-23 2014-09-23 The preparation method and equipment of flexible parent metal circuit board and metal pinning layer Active CN104372295B (en)

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CN105773462B (en) * 2016-01-07 2019-03-29 北京师范大学 A kind of method and apparatus in the skive stick service life that polishing optical glass is improved based on ion beam technology
CN105755443B (en) * 2016-02-26 2018-11-09 北京师范大学 The method and apparatus in rod member service life in a kind of raising aerospace relay
CN105908134B (en) * 2016-04-13 2018-11-09 北京师范大学 A kind of method and apparatus preparing polytetrafluoroethylene (PTFE) circuit board
CN107503108A (en) * 2016-06-14 2017-12-22 北京师范大学 The preparation method and equipment of novel environment friendly is seamless wall cloth
CN107236928A (en) * 2017-07-20 2017-10-10 北京师范大学 Flexible parent metal circuit board and preparation method thereof and equipment
CN108456844B (en) * 2018-02-07 2019-11-08 中国原子能科学研究院 A method of it being coated with high-purity N i/Cu bilayer target membrane on high-boron-silicon glass
CN110578124B (en) * 2019-10-22 2021-10-01 北京市辐射中心 Method for preparing hard film on flexible substrate and related product
CN110993886B (en) * 2019-12-26 2021-01-05 北京师范大学 Preparation device for lithium battery current collector
CN114232052B (en) * 2020-09-09 2023-03-10 北京师范大学 Preparation method of high-temperature corrosion resistant composite coating on surface of zirconium alloy cladding

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