CN109862689A - A kind of flexible copper-clad plate and preparation method thereof - Google Patents
A kind of flexible copper-clad plate and preparation method thereof Download PDFInfo
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- CN109862689A CN109862689A CN201910117749.7A CN201910117749A CN109862689A CN 109862689 A CN109862689 A CN 109862689A CN 201910117749 A CN201910117749 A CN 201910117749A CN 109862689 A CN109862689 A CN 109862689A
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- copper
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Abstract
The present invention provides a kind of flexible copper-clad plates and preparation method thereof.The flexible copper-clad plate includes the insulating substrate, nickel layer and layers of copper set gradually；Nickel layer is divided into discontinuous body by the copper particle and copper particle being equipped in the nickel layer through nickel layer, and the copper particle contacts with insulating substrate through one end of nickel layer and forms copper dental structure in insulating substrate surface, and the other end of the copper particle, which supports, is set to layers of copper.The method of the above-mentioned flexible copper-clad plate copper plate again of ion implanting after first sputtering, to have high peel strength, excellent resistance to ion transport and low signal transmission attenuation.
Description
Technical field
The present invention relates to technical field of copper clad laminate, in particular to a kind of flexible copper-clad plate and preparation method thereof.
Background technique
Flexible copper-clad plate (FCCL) is processing raw material for flexible circuit board (FPC).It includes at least two materials, one is
Insulating substrate, such as polyimides (PI) film, liquid crystal polymer (LCP) film；Another kind is metallic conductor foil, predominantly copper
Foil.
Flexible copper-clad plate main preparation methods have: pressing method, rubbing method, sputtering galvanoplastic, ion implanting galvanoplastic.
When sputtering galvanoplastic prepare flexible copper-clad plate, need to carry out insulating substrate surface specially treated strong to improve removing
Degree.Nevertheless, its peel strength is usually 0.6N/mm.
Ion implantation is widely used in the technical fields such as semiconductor doping, material surface modifying.Chinese invention patent
CN1952209A discloses the ion implanting treatment process before a kind of plating of polymer surfacesization, to improve coating and polymeric matrix
Between peel strength.
Ion implanting galvanoplastic prepare flexible copper-clad plate, are that the ion beam mutation insulating body of high-energy is formed doping
Layer, then plasma-deposited a thin layer conductive layer, plating thicken copper.Chinese invention patent CN101956171B discloses one
The method of kind of ion implanting and plasma deposition apparatus and corona treatment film, may be implemented it is roll-to-roll carry out from
Son injection.
In flexible copper-clad plate field, although the ion implanting of high-energy can improve peel strength, insulation base can be also given
Material brings irradiation damage, substrate carbonization, degradation, penalty.Especially, if ion implanting is too deep, metallic can be in base
It is remained in material, it is difficult to which etching is clean.This brings a negative impact the Df performance of substrate, in addition, can also reduce flexible circuit board
Resistance to Ion transfer performance.If ion implanting is excessively shallow, peel strength is not obviously contributed again.Since there are the above contradiction, mesh
The preceding flexible copper-clad plate for COF, still based on sputtering method technique.
For sputtering method or ion implantation, in order to improve the peel strength of layers of copper and substrate and meet heat resistanceheat resistant performance,
It would generally be using nickel layer as prime coat.However, nickel layer carrys out certain negative effect to the transmission belt of high-frequency signal, it is primarily due to
Pure-nickel-layer has magnetism, has shielding action to signal.
It is mainstream technology route using mSAP technique with the demand higher and higher to HDI wiring board.This is strong to height removing
Degree, the thin copper flexible copper-clad plate demand of high reliability are strong.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of resistance to Ion transfer with high peel strength, excellent
Property and the low flexible copper-clad plate of signal transmission attenuation and preparation method thereof.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of flexible copper-clad plate, including the insulating substrate, nickel layer and layers of copper set gradually；
Nickel layer is divided into discontinuous body, the copper particle by the copper particle and copper particle being equipped in the nickel layer through nickel layer
It is contacted through one end of nickel layer with insulating substrate and forms copper dental structure in insulating substrate surface, the other end of the copper particle supports
Set on layers of copper.
In order to solve the above technical problems, another technical solution used in the present invention are as follows:
A kind of preparation method of above-mentioned flexible copper-clad plate, includes the following steps；
Nickel layer is formed on insulating substrate using sputtering method；
Copper particle is injected in nickel layer using ion implantation；
The plating layers of copper in one side of the nickel layer far from insulating substrate；Obtain the flexible copper-clad plate.
The beneficial effects of the present invention are: nickel layer, rear ion implanting copper particle are formed using first sputtering, then plate layers of copper
Technique, it can be achieved that:
1, copper dental structure guarantees high peel strength；
2, copper tooth is connected with layers of copper, guarantees that etching noresidue copper particle inside insulating substrate, guarantees excellent resistance to ion
Migration；
3, nickel layer is separated into discontinuous body by copper particle, reduces signal transmission attenuation.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flexible copper-clad plate cross section of the invention；
Label declaration:
101, insulating substrate；102, nickel layer；103, copper dental structure；104, albata layer；105, layers of copper.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The most critical design of the present invention is: with the method for ion implanting copper plate again after first sputtering, to have high
Peel strength, excellent resistance to ion transport and low signal transmission attenuation.
Fig. 1 is please referred to, the present invention provides a kind of flexible copper-clad plate, including insulating substrate 101, the nickel layer 102 set gradually
With layers of copper 105；
Nickel layer 102 is divided into discontinuous body by the copper particle and copper particle being equipped in the nickel layer 102 through nickel layer 102,
The copper particle contacts with insulating substrate 101 through one end of nickel layer 102 and forms copper dental structure in 101 surface of insulating substrate
103, the other end of the copper particle, which supports, is set to layers of copper 105.
The present invention also provides a kind of preparation methods of above-mentioned flexible copper-clad plate, include the following steps；
Nickel layer 102 is formed on insulating substrate 101 using sputtering method；
Copper particle is injected in nickel layer 102 using ion implantation；
The plating layers of copper 105 in one side of the nickel layer 102 far from insulating substrate 101；Obtain the flexible copper-clad plate.
As can be seen from the above description, the beneficial effects of the present invention are: nickel layer, rear ion implanting copper particle are formed using first sputtering
Son, then plate layers of copper technique, it can be achieved that:
1, copper dental structure guarantees high peel strength；
2, copper tooth is connected with layers of copper, guarantees that etching noresidue copper particle inside insulating substrate, guarantees excellent resistance to ion
Migration；
3, nickel layer is separated into discontinuous body by copper particle, reduces signal transmission attenuation.
Further, albata layer 104, the copper-nickel alloy-layer 104 are equipped between the nickel layer 102 and layers of copper 105
For nonferromagnetic, the other end of the copper particle, which supports, is set to albata layer 104.
Seen from the above description, by the way that albata layer 104 is arranged, signal transmission attenuation can be further decreased.
Further, the nickel layer 102 with a thickness of 2nm~100nm.
Further, the depth of the copper dental structure 103 is 5nm~500nm.
Further, the diameter of the copper particle is 1nm~200nm.
Further, the insulating substrate 101 is made of organic polymer thin film.
Further, using plating or chemical plating plating layers of copper 105 on nickel layer 102.
Seen from the above description, in addition to plating and chemical plating, other combination process can also be applied in this programme.
Further, further comprising the steps of: cupro-nickel is formed between nickel layer 102 and layers of copper 105 using ion implantation
Alloy-layer 104.
Please refer to Fig. 1, specific preparation flow of the invention are as follows: in magnetron sputtering apparatus, select pure nickel target, sputtering
Air pressure is 0.1Pa~5Pa, and sputtering voltage is that 100V~800V sputters insulating substrate 101.Control sputtering time obtains institute
Need the nickel layer 102 of thickness.
The insulating substrate 101 is organic polymer thin film, is included at least any in PI, LCP, PEI, PAEK, PTFE.
102 thickness range of nickel layer is 2nm~100nm, and when being lower than 2nm, the stability of peel strength is bad；When higher than 100nm, to signal
Transmission loss is larger.
By the insulating substrate 101 of Ni plated layer 102 in metal vapor vacuum arc source (MEVVA) type ion implantation apparatus
Carry out ion injecting process.It will be on the nickel layer 102 of copper ion implantation to 101 surface of insulating substrate.First control acceleration voltage is 10
~50kV, implantation dosage are 2 × 1017~1018cm-2, film is with 1 μm~50 μm of the intermittent movement of step pitch progress.Copper ion
When being injected into nickel layer 102, the energy of the nickle atom absorbing copper ions of nickel layer 102 makes it obtain kinetic energy, moves towards insulating substrate 101
It is dynamic, and then form copper dental structure 103.On the other hand, the injection of copper ion is so that nickel layer 102 generates vacancy, and accumulation of vacancies is at sky
Hole, so that nickel layer 102 is separated into discontinuous body.The depth of the copper dental structure 103 is 5nm~500nm, diameter 10nm
~200nm.Copper dental structure 103 formed after, adjust ion implanting acceleration voltage be 0.5kV~10kV, implantation dosage be 1 ×
1015~1 × 1017cm-2, insulating substrate 101 at the uniform velocity moves, and is uniformly injected into one layer of copper on 102 surface of nickel layer of insulating substrate 101
Layer 105, copper ion forms doped structure in nickel layer 102, and spreads under Implantation Energy, forms albata layer 104.
The thickness of albata layer 104 is less than the half of 102 thickness of former nickel layer.
The insulating substrate 101 injected ions into, which is placed in electroplating bath or chemical plating bath, carries out copper facing, and layers of copper 105 is increased
Add to required thickness, generally 2 μm~12 μm.
The preparation method of flexible copper-clad plate of the invention, and the flexibility manufactured by these methods is described in detail above
The specific configuration of copper-clad plate.The following are embodiments.
The embodiment of the present invention one are as follows:
The LCP film of 25 μ m-thicks that Kuraray company is produced, model CTQ sputters one layer on magnetron sputtering apparatus
Nickel layer 102, sputtering pressure 0.15Pa, sputtering voltage 400V, nickel layer 102 is with a thickness of 25nm.Then true using metallic vapour
Empty arc ion source (MEVVA) type ion implantation apparatus carries out ion implanting to LCP film.High energy ion injection acceleration voltage be
20kV, implantation dosage are 5 × 1017cm-2, film intermittence moving step pitch is 5 μm, and the depth for being formed by copper dental structure 103 is
200nm, diameter 100nm.The acceleration voltage of low energy ion injection is 5kV, and implantation dosage is 5 × 1016cm-2, measure to obtain copper
Nickel alloy layer 104 with a thickness of 10nm.
Sputtering and the good LCP film of ion implanting are subjected to electroplating copper, copper thickness is 12 microns.
The embodiment of the present invention two are as follows:
The LCP film of 25 μ m-thicks that Kuraray company is produced, model CTQ sputters one layer on magnetron sputtering apparatus
Nickel layer 102, sputtering pressure 0.15Pa, sputtering voltage 400V, nickel layer 102 is with a thickness of 25nm.
The LCP film sputtered is subjected to electroplating copper, copper thickness is 12 microns.
The embodiment of the present invention three are as follows:
The LCP film of 25 μ m-thicks that Kuraray company is produced, model CTQ uses metal vapor vacuum arc source
(MEVVA) type ion implantation apparatus carries out ion implanting nickel layer 102 to LCP film.The acceleration voltage of ion implanting is 20kV, injection
Dosage is 5 × 1017cm-2, then plasma-deposited nickel layer 102 is to a thickness of 25nm.
The LCP film injected ions into carries out electroplating copper, and copper thickness is 12 microns.
The flexible copper-clad plate that above-described embodiment is obtained carries out peel strength test；By the surface layers of copper of flexible copper-clad plate
After 105 etchings, obtained LCP film measures its sheet resistance；Flexible copper-clad plate is prepared into co-planar waveguide sample, in network
Radio frequency transmission performance test is carried out on analyzer.Obtain test result as shown in Table 1.
1 performance test of table
From the test result of table 1 it is found that the prepared flexible copper-clad plate of the present invention, peel strength can reach higher
It is horizontal；The sheet resistance of insulating substrate after the etching of layers of copper 105 is high, has good resistance to Ion transfer performance；Transmission loss is low,
Guarantee high frequency signal transmission performance.
In conclusion the present invention provides a kind of resistance to ion transports with high peel strength, excellent and low
Flexible copper-clad plate of signal transmission attenuation and preparation method thereof.Nickel layer, rear ion implanting copper particle are formed using first sputtering, then plated
The technique of upper layers of copper, it can be achieved that:
1, copper dental structure guarantees high peel strength；
2, copper tooth is connected with layers of copper, guarantees that etching noresidue copper particle inside insulating substrate, guarantees excellent resistance to ion
Migration；
3, nickel layer is separated into discontinuous body by copper particle and surface forms nonmagnetic albata layer, reduces signal
Transmission loss.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (10)
1. a kind of flexible copper-clad plate, which is characterized in that including the insulating substrate, nickel layer and layers of copper set gradually；
Nickel layer is divided into discontinuous body by the copper particle and copper particle being equipped in the nickel layer through nickel layer, and the copper particle runs through
One end of nickel layer contacts with insulating substrate and forms copper dental structure in insulating substrate surface, and the other end of the copper particle, which supports, to be set to
Layers of copper.
2. flexible copper-clad plate according to claim 1, which is characterized in that be equipped with corronil between the nickel layer and layers of copper
Layer, the copper-nickel alloy-layer are nonferromagnetic, and the other end of the copper particle, which supports, is set to albata layer.
3. flexible copper-clad plate according to claim 1, which is characterized in that the nickel layer with a thickness of 2nm~100nm.
4. flexible copper-clad plate according to claim 1, which is characterized in that the depth of the copper dental structure be 5nm~
500nm。
5. according to right to go 1 described in flexible copper-clad plate, which is characterized in that the diameter of the copper particle be 1nm~200nm.
6. flexible copper-clad plate according to claim 1, which is characterized in that the insulating substrate is by organic polymer thin film group
At.
7. flexible copper-clad plate according to claim 6, which is characterized in that the material of the organic polymer thin film includes
Any one in PI, LCP, PEI, PAEK, PTFE.
8. a kind of preparation method of flexible copper-clad plate as claimed in claim 2, which is characterized in that include the following steps；
Nickel layer is formed on insulating substrate using sputtering method；
Copper particle is injected in nickel layer using ion implantation；
The plating layers of copper in one side of the nickel layer far from insulating substrate；Obtain the flexible copper-clad plate.
9. the preparation method of flexible copper-clad plate according to claim 8, which is characterized in that using plating or chemical plating in nickel
Plating layers of copper on layer.
10. the preparation method of flexible copper-clad plate according to claim 8, which is characterized in that further comprising the steps of: using
Ion implantation forms albata layer between nickel layer and layers of copper.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910117749.7A CN109862689B (en) | 2019-02-15 | 2019-02-15 | Flexible copper-clad plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910117749.7A CN109862689B (en) | 2019-02-15 | 2019-02-15 | Flexible copper-clad plate and preparation method thereof |
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| Publication Number | Publication Date |
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| CN109862689A true CN109862689A (en) | 2019-06-07 |
| CN109862689B CN109862689B (en) | 2020-12-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910117749.7A Active CN109862689B (en) | 2019-02-15 | 2019-02-15 | Flexible copper-clad plate and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667952A (en) * | 2021-08-27 | 2021-11-19 | 江苏耀鸿电子有限公司 | Magnetron sputtering flexible copper-clad substrate and preparation method thereof |
| CN113692111A (en) * | 2021-08-24 | 2021-11-23 | 江苏耀鸿电子有限公司 | High-corrosion-resistance flexible copper-clad plate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0257678A (en) * | 1988-02-18 | 1990-02-27 | Hitake Seiko Kk | Formation of patterned substrate |
| JP2002319757A (en) * | 2001-04-20 | 2002-10-31 | Sumitomo Electric Printed Circuit Inc | Flexible copper clad plate |
| CN103222352A (en) * | 2010-11-12 | 2013-07-24 | 国立大学法人东北大学 | Multilayer wiring board |
| CN103813659A (en) * | 2012-11-05 | 2014-05-21 | 三星电机株式会社 | Method of manufacturing printed circuit board |
-
2019
- 2019-02-15 CN CN201910117749.7A patent/CN109862689B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0257678A (en) * | 1988-02-18 | 1990-02-27 | Hitake Seiko Kk | Formation of patterned substrate |
| JP2002319757A (en) * | 2001-04-20 | 2002-10-31 | Sumitomo Electric Printed Circuit Inc | Flexible copper clad plate |
| CN103222352A (en) * | 2010-11-12 | 2013-07-24 | 国立大学法人东北大学 | Multilayer wiring board |
| CN103813659A (en) * | 2012-11-05 | 2014-05-21 | 三星电机株式会社 | Method of manufacturing printed circuit board |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113692111A (en) * | 2021-08-24 | 2021-11-23 | 江苏耀鸿电子有限公司 | High-corrosion-resistance flexible copper-clad plate and preparation method thereof |
| CN113667952A (en) * | 2021-08-27 | 2021-11-19 | 江苏耀鸿电子有限公司 | Magnetron sputtering flexible copper-clad substrate and preparation method thereof |
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| CN109862689B (en) | 2020-12-22 |
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