CN109862689B - Flexible copper-clad plate and preparation method thereof - Google Patents
Flexible copper-clad plate and preparation method thereof Download PDFInfo
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- CN109862689B CN109862689B CN201910117749.7A CN201910117749A CN109862689B CN 109862689 B CN109862689 B CN 109862689B CN 201910117749 A CN201910117749 A CN 201910117749A CN 109862689 B CN109862689 B CN 109862689B
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Abstract
The invention provides a flexible copper clad laminate and a preparation method thereof. The flexible copper clad laminate comprises an insulation base material, a nickel layer and a copper layer which are sequentially arranged; the nickel layer is internally provided with copper particles penetrating through the nickel layer, the copper particles separate the nickel layer into discontinuous bodies, one end of each copper particle penetrating through the nickel layer is in contact with the insulating base material and forms a copper tooth structure on the surface of the insulating base material, and the other end of each copper particle is abutted against the copper layer. The flexible copper clad laminate has high peel strength, excellent ion migration resistance and low signal transmission loss by using the method of firstly sputtering, then ion implantation and then copper plating.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a flexible copper-clad plate and a preparation method thereof.
Background
The Flexible Copper Clad Laminate (FCCL) is a processing raw material of a Flexible Printed Circuit (FPC). It comprises at least two materials, one of which is an insulating substrate such as a Polyimide (PI) film, a Liquid Crystal Polymer (LCP) film, etc.; the other is a metal conductor foil, mainly a copper foil.
The main preparation method of the flexible copper-clad plate comprises the following steps: a press method, a coating method, a sputtering plating method, an ion implantation plating method.
When the flexible copper clad laminate is prepared by a sputtering electroplating method, special treatment needs to be carried out on the surface of the insulating base material to improve the peeling strength. Nevertheless, the peel strength is usually 0.6N/mm.
The ion implantation method is widely applied to the technical fields of semiconductor doping, material surface modification and the like. Chinese patent CN1952209A discloses an ion implantation treatment process before polymer surface chemical plating to improve the peel strength between the plating and the polymer matrix.
The ion implantation electroplating method for preparing the flexible copper-clad plate is to implant high-energy ion beams into an insulating matrix to form a doped layer, then deposit a thin conductive layer by plasma, and electroplate to thicken copper. Chinese invention patent CN101956171B discloses an ion implantation and plasma deposition apparatus and a method for processing a film by plasma, which can realize roll-to-roll ion implantation.
In the field of flexible copper clad plates, high-energy ion implantation can improve the peeling strength, but can also bring radiation damage to an insulating base material, carbonize and degrade the base material, and the performance is deteriorated. In particular, if the ion implantation is too deep, metal particles remain in the substrate, and it is difficult to etch clean. This adversely affects the Df properties of the substrate and, in addition, reduces the ion migration resistance of the flexible wiring board. If the ion implantation is too shallow, no significant contribution to the peel strength is made. Due to the contradiction, the flexible copper clad laminate used for COF at present still mainly adopts the sputtering process.
For sputtering or ion implantation, a nickel layer is usually used as a primer layer to improve the peel strength of the copper layer from the substrate and to satisfy thermal resistance. However, the nickel layer has a certain negative effect on the transmission of high-frequency signals, mainly because the pure nickel layer has magnetism and has a shielding effect on signals.
With the increasing demand of HDI circuit boards, the adoption of the mSAP process is a mainstream technical route. The copper clad laminate has strong demand on the thin copper flexible copper clad laminate with high peel strength and high reliability.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the flexible copper clad laminate has high peel strength, excellent ion migration resistance and low signal transmission loss and the preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a flexible copper clad laminate comprises an insulation substrate, a nickel layer and a copper layer which are sequentially arranged;
the nickel layer is internally provided with copper particles penetrating through the nickel layer, the copper particles separate the nickel layer into discontinuous bodies, one end of each copper particle penetrating through the nickel layer is in contact with the insulating base material and forms a copper tooth structure on the surface of the insulating base material, and the other end of each copper particle is abutted against the copper layer.
In order to solve the technical problem, the invention adopts another technical scheme as follows:
the preparation method of the flexible copper-clad plate comprises the following steps;
forming a nickel layer on the insulating base material by a sputtering method;
injecting copper particles into the nickel layer by adopting an ion injection method;
plating a copper layer on one side of the nickel layer away from the insulating base material; and obtaining the flexible copper-clad plate.
The invention has the beneficial effects that: the process of firstly sputtering to form a nickel layer, then injecting copper particles by ions and then plating a copper layer is adopted, so that the following steps can be realized:
1. the copper tooth structure ensures high peel strength;
2. the copper teeth are connected with the copper layer, so that no residual copper particles are left in the insulating base material during etching, and excellent ion migration resistance is ensured;
3. the copper particles separate the nickel layer into discontinuous bodies, so that the signal transmission loss is reduced.
Drawings
FIG. 1 is a schematic structural diagram of a cross section of a flexible copper clad laminate of the present invention;
description of reference numerals:
101. an insulating base material; 102. a nickel layer; 103. a copper tooth structure; 104. a copper-nickel alloy layer; 105. a copper layer.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The most key concept of the invention is as follows: the method of sputtering, ion implantation and copper plating is used, so that the copper-plated copper-clad laminate has high peel strength, excellent ion migration resistance and low signal transmission loss.
Referring to fig. 1, the invention provides a flexible copper clad laminate, which comprises an insulating base material 101, a nickel layer 102 and a copper layer 105, which are sequentially arranged;
the nickel layer 102 is internally provided with copper particles penetrating through the nickel layer 102, the nickel layer 102 is divided into discontinuous bodies by the copper particles, one end of each copper particle penetrating through the nickel layer 102 is in contact with the insulating base material 101, a copper tooth structure 103 is formed on the surface of the insulating base material 101, and the other end of each copper particle is abutted to the copper layer 105.
The invention also provides a preparation method of the flexible copper-clad plate, which comprises the following steps;
forming a nickel layer 102 on an insulating base material 101 by a sputtering method;
injecting copper particles into the nickel layer 102 by adopting an ion injection method;
plating a copper layer 105 on one side of the nickel layer 102 away from the insulating base material 101; and obtaining the flexible copper-clad plate.
From the above description, the beneficial effects of the present invention are: the process of firstly sputtering to form a nickel layer, then injecting copper particles by ions and then plating a copper layer is adopted, so that the following steps can be realized:
1. the copper tooth structure ensures high peel strength;
2. the copper teeth are connected with the copper layer, so that no residual copper particles are left in the insulating base material during etching, and excellent ion migration resistance is ensured;
3. the copper particles separate the nickel layer into discontinuous bodies, so that the signal transmission loss is reduced.
Further, a copper-nickel alloy layer 104 is disposed between the nickel layer 102 and the copper layer 105, the copper-nickel alloy layer 104 is non-ferromagnetic, and the other end of the copper particles abuts against the copper-nickel alloy layer 104.
As can be seen from the above description, by providing the copper-nickel alloy layer 104, the signal transmission loss can be further reduced.
Further, the thickness of the nickel layer 102 is 2nm to 100 nm.
Further, the depth of the copper tooth structure 103 is 5nm to 500 nm.
Further, the diameter of the copper particle is 1nm to 200 nm.
Further, the insulating substrate 101 is composed of an organic polymer thin film.
Further, a copper layer 105 is plated on the nickel layer 102 by electroplating or electroless plating.
As can be seen from the above description, in addition to electroplating and electroless plating, other composite processes can be applied to the present solution.
Further, the method also comprises the following steps: a copper-nickel alloy layer 104 is formed between the nickel layer 102 and the copper layer 105 by ion implantation.
Referring to fig. 1, the specific preparation process of the present invention is: in the magnetron sputtering equipment, a pure nickel target is selected, and the insulating base material 101 is sputtered under the sputtering pressure of 0.1 Pa-5 Pa and the sputtering voltage of 100V-800V. The sputtering time is controlled to obtain the nickel layer 102 with the required thickness.
The insulating base material 101 is an organic polymer film, and at least includes any one of PI, LCP, PEI, PAEK, and PTFE. The thickness range of the nickel layer 102 is 2 nm-100 nm, and when the thickness is less than 2nm, the stability of the peeling strength is poor; above 100nm, the loss of signal transmission is large.
The insulating base material 101 plated with the nickel layer 102 is subjected to an ion implantation process in a metal vapor vacuum arc ion source (MEVVA) type ion implanter. Copper ions are implanted onto the nickel layer 102 on the surface of the insulating substrate 101. Firstly, the accelerating voltage is controlled to be 10-50 kV, and the injection dosage is controlled to be 2 multiplied by 1017～1018cm-2The film is intermittently moved at a pitch of 1 to 50 μm. When copper ions are implanted into the nickel layer 102, the nickel atoms of the nickel layer 102 absorb the energy of the copper ions, so that the copper ions obtain kinetic energy and move towards the insulating base material 101, thereby forming the copper tooth structure 103. On the other hand, the implantation of copper ions causes vacancies to be generated in the nickel layer 102, and the vacancies are gathered into voids, thereby causing the nickel layer 102 to be separated into discontinuous bodies. The depth of the copper tooth structure 103 is 5 nm-500 nm, and the diameter is 10 nm-200 nm. After the copper tooth structure 103 is formed, the accelerating voltage of ion implantation is adjusted to 0.5kV to 10kV, and the implantation dosage is 1 × 1015～1×1017cm-2The insulating base material 101 moves at a constant speed, a copper layer 105 is uniformly injected on the surface of the nickel layer 102 of the insulating base material 101, copper ions form a doping structure in the nickel layer 102 and are diffused under the injection energy to form a copper-nickel alloy layer 104. The thickness of the copper-nickel alloy layer 104 is less than half of the thickness of the original nickel layer 102.
The ion-implanted insulating base material 101 is placed in an electroplating bath or an electroless plating bath to be plated with copper, and the copper layer 105 is increased to a desired thickness, typically 2 μm to 12 μm.
The preparation method of the flexible copper clad laminate of the invention and the specific construction of the flexible copper clad laminate manufactured by the method are described in detail above. The following are examples.
The first embodiment of the invention is as follows:
a25-micron LCP film with the model of CTQ and the thickness of 25 mu m produced by Kuraray company is sputtered with a nickel layer 102 on a magnetron sputtering device, the sputtering pressure is 0.15Pa, the sputtering voltage is 400V, and the thickness of the nickel layer 102 is 25 nm. The LCP film is then ion implanted using a metal vapour vacuum arc ion source (MEVVA) type ion implanter. The accelerating voltage of high-energy ion implantation is 20kV, and the implantation dosage is 5X 1017cm-2The intermittent moving step pitch of the film was 5 μm, and the depth of the copper tooth structure 103 formed was 200nm and the diameter was 100 nm. The accelerating voltage of low-energy ion implantation is 5kV, and the implantation dosage is 5X 1016cm-2The thickness of the copper-nickel alloy layer 104 was measured to be 10 nm.
And electroplating copper on the sputtered and ion-implanted LCP film, wherein the thickness of the copper is 12 microns.
The second embodiment of the invention is as follows:
a25-micron LCP film with the model of CTQ and the thickness of 25 mu m produced by Kuraray company is sputtered with a nickel layer 102 on a magnetron sputtering device, the sputtering pressure is 0.15Pa, the sputtering voltage is 400V, and the thickness of the nickel layer 102 is 25 nm.
And electroplating copper on the sputtered LCP film, wherein the thickness of the copper is 12 microns.
The third embodiment of the invention is as follows:
a25 μm thick CTQ LCP film from Kuraray was ion implanted with nickel layer 102 using a metal vapor vacuum arc ion source (MEVVA) type ion implanter. The accelerating voltage of ion implantation is 20kV, and the implantation dosage is 5 × 1017cm-2The nickel layer 102 is then plasma deposited to a thickness of 25 nm.
And electroplating copper on the ion-implanted LCP film, wherein the thickness of the copper is 12 microns.
Carrying out peel strength test on the flexible copper clad laminate obtained in the embodiment; etching a surface copper layer 105 of the flexible copper clad laminate to obtain an LCP film, and measuring the surface resistance of the LCP film; and preparing the flexible copper clad laminate into a coplanar waveguide sample, and carrying out radio frequency transmission performance test on a network analyzer. The test results shown in table 1 were obtained.
TABLE 1 Performance test
The test results in table 1 show that the peel strength of the flexible copper clad laminate prepared by the invention can reach a higher level; the insulating substrate after the copper layer 105 is etched has high surface resistance and good ion migration resistance; the transmission loss is low, and the transmission performance of high-frequency signals is ensured.
In conclusion, the invention provides the flexible copper clad laminate with high peel strength, excellent ion migration resistance and low signal transmission loss and the preparation method thereof. The process of firstly sputtering to form a nickel layer, then injecting copper particles by ions and then plating a copper layer is adopted, so that the following steps can be realized:
1. the copper tooth structure ensures high peel strength;
2. the copper teeth are connected with the copper layer, so that no residual copper particles are left in the insulating base material during etching, and excellent ion migration resistance is ensured;
3. the nickel layer is separated into non-continuous bodies by the copper particles, and a non-magnetic copper-nickel alloy layer is formed on the surface of the nickel layer, so that the signal transmission loss is reduced.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (9)
1. A flexible copper clad laminate is characterized by comprising an insulating base material, a nickel layer and a copper layer which are sequentially arranged;
the copper-nickel composite material is characterized in that copper particles penetrating through the nickel layer are arranged in the nickel layer and divide the nickel layer into discontinuous bodies, one end of each copper particle penetrating through the nickel layer is in contact with an insulating base material, a copper tooth structure is formed on the surface of the insulating base material, the other end of each copper particle abuts against the copper layer, a copper-nickel alloy layer is arranged between the nickel layer and the copper layer, the copper-nickel alloy layer is non-ferromagnetic, and the other end of each copper particle abuts against the copper-nickel alloy layer.
2. The flexible copper clad laminate according to claim 1, wherein the thickness of the nickel layer is 2nm to 100 nm.
3. The flexible copper clad laminate according to claim 1, wherein the depth of the copper tooth structure is 5nm to 500 nm.
4. The flexible copper clad laminate according to claim 1, wherein the diameter of the copper particles is 1nm to 200 nm.
5. The flexible copper clad laminate according to claim 1, wherein the insulating substrate is composed of an organic polymer film.
6. The flexible copper clad laminate according to claim 5 wherein the material of the organic polymer film comprises any one of PI, LCP, PEI, PAEK and PTFE.
7. The preparation method of the flexible copper-clad plate according to claim 1, which is characterized by comprising the following steps:
forming a nickel layer on the insulating base material by a sputtering method;
injecting copper particles into the nickel layer by adopting an ion injection method;
plating a copper layer on one side of the nickel layer away from the insulating base material; and obtaining the flexible copper-clad plate.
8. The method for preparing the flexible copper clad laminate according to claim 7, wherein the copper layer is plated on the nickel layer by electroplating or electroless plating.
9. The preparation method of the flexible copper clad laminate according to claim 7, further comprising the following steps: and forming a copper-nickel alloy layer between the nickel layer and the copper layer by adopting an ion implantation method.
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| CN113692111B (en) * | 2021-08-24 | 2022-08-23 | 江苏耀鸿电子有限公司 | High-corrosion-resistance flexible copper-clad plate and preparation method thereof |
| 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 |
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 |
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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 |
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