CN113667952A - Magnetron sputtering flexible copper-clad substrate and preparation method thereof - Google Patents
Magnetron sputtering flexible copper-clad substrate and preparation method thereof Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a magnetron sputtering flexible copper-clad substrate, and particularly relates to the technical field of flexible copper-clad plates. According to the invention, the structure of a coarse structure is carried out on the surface of the first transition layer by using an electrolytic method, then the polyether resin solution is dripped after surface modification to form a smooth polyether resin film as a second transition layer, the copper foil layer is sputtered on the surface of the smooth second transition layer, the adhesive force of the copper foil layer can be effectively improved, the peeling strength between the copper foil layer and the sputtered layer is higher, and the flexible copper-clad substrate with lower thickness can be prepared.
Description
Technical Field
The invention relates to the technical field of flexible copper clad laminates, in particular to a magnetron sputtering flexible copper clad laminate 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. The flexible copper clad laminate is widely applied to electronic products such as aerospace equipment, navigation equipment, aircraft instruments, military guidance systems, mobile phones, digital cameras, digital video cameras, automobile satellite direction positioning devices, liquid crystal televisions, notebook computers and the like. The flexible copper clad laminate has the advantages of thinness, lightness and flexibility, and the flexible copper clad laminate using the polyimide base film also has the characteristics of excellent electrical property, thermal property and heat resistance. Its low dielectric constant allows for rapid transmission of electrical signals. Good thermal performance can make the subassembly easily cool down. Higher glass transition temperatures may allow the assembly to perform well at higher temperatures.
At present, there are two main methods for bonding copper foil to the surface of an insulating substrate. The first method is to bond a copper foil on the surface of an insulating base material through an adhesive to prepare the flexible copper clad laminate, and the second method is to directly deposit copper on the surface of the insulating base material, such as electrolytic copper deposition to prepare the copper foil layer. Compared with the first method, the copper foil layer is directly prepared on the surface of the insulating base material, so that the production cost can be reduced, the thickness of the obtained flexible copper clad laminate is lower, and the thickness of the thinnest copper foil layer can be controlled to be about 6 mu m. However, when copper is directly deposited on the surface of the insulating substrate, the peel strength between the copper foil and the substrate is too low to prepare a copper foil having a low thickness.
Disclosure of Invention
In order to overcome the above defects in the prior art, embodiments of the present invention provide a magnetron sputtering flexible copper-clad substrate and a preparation method thereof, and the problem to be solved by the present invention is: how to improve the peeling strength between the copper foil layer and the base material and reduce the thickness of the flexible copper-clad base material.
In order to achieve the purpose, the invention provides the following technical scheme: the utility model provides a flexible copper-clad base plate of magnetron sputtering, includes the substrate rete, at least one surface of substrate rete is provided with first transition layer, one side that the substrate rete was kept away from to first transition layer is provided with the second transition layer, one side that first transition layer was kept away from to the second transition layer is provided with the copper foil layer, first transition layer is the metal sputtering layer, the second transition layer is polyether resin film layer.
In a preferred embodiment, the substrate film layer is one of PI, PE, PP, PTEE, PS, PPA, PTO, PEEK, PC, PA, PSU, PET, PPs, PEN, PEs, and the thickness of the substrate film layer is 50 to 70 um.
In a preferred embodiment, the first transition layer is an alloy of one or more of titanium, zinc, iron, nickel, chromium, cobalt, copper, silver, and gold, the thickness of the first transition layer is 40 to 120nm, and copper particles are provided inside the first transition layer.
In a preferred embodiment, the thickness of the second transition layer is 10-30nm, and the thickness of the copper foil layer is 2-5 um.
A preparation method of a magnetron sputtering flexible copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: selecting a proper substrate film layer as a substrate of the flexible copper clad laminate, carrying out corona treatment on the surface of the selected substrate, preparing a first transition layer on at least one surface of the substrate by using a magnetron sputtering method after the corona treatment is finished, and then uniformly injecting copper particles into the first transition layer by using an ion injection method;
step two: placing the material obtained in the step one in perchloric acid and ethanol solution for electrochemical polishing treatment, placing the material in electrolyte of 0.4M oxalic acid aqueous solution for anodic oxidation after the polishing treatment is finished, preparing a rough oxidation film on the surface of the first transition layer, placing one side containing the rough oxidation film after the anodic oxidation in the ethanol solution containing 8-12% of trifluoro octyl triethoxysilane for contact reaction for 5-8min, and taking out the material for drying treatment at the temperature of 135-145 ℃ for 5-10 min;
step three: dropwise adding a polyether resin solution to the surface containing the rough oxide film obtained in the step two, standing for 2-4h, forming a smooth polyether resin film on the surface of the first transition layer by virtue of the capillary action of the microstructure, and then fixedly arranging the polyether resin film on the outer side of the first transition layer in a hot-pressing manner to form a second transition layer;
step four: and depositing a copper foil layer on the surface of the second transition layer by using a magnetron sputtering method, thereby obtaining the magnetron sputtering flexible copper-clad substrate.
In a preferred embodiment, the power for corona treatment in the first step is 2.5-4kw, copper and nickel are used as targets under vacuum condition during magnetron sputtering in the first step, and the ion source parameters are set as follows: 1500-4200W, 0.1-0.25A, 0.2-0.4Pa, the inflow rate of argon gas is 180-230sccm, the outflow rate of argon gas is 30-50sccm, and the injection amount of copper particles in the first step is 2 × 1017-1018cm-2。
In a preferred embodiment, the polishing voltage of the electrochemical polishing treatment in the second step is 10-15V dc voltage, the polishing time is 2-3 minutes, and the volume ratio of perchloric acid to ethanol in the perchloric acid-ethanol solution is 1: (4-5), in the second step, stainless steel is used as a cathode during anodic oxidation, and 70-80V direct current voltage is applied between the anode and the cathode, and the oxidation time is 2-4 minutes.
In a preferred embodiment, during the electrochemical polishing and anodic oxidation in the second step, the first transition layer is placed in an electrolyte of perchloric acid and ethanol solution or oxalic acid aqueous solution, and the substrate film layer is not in contact with the perchloric acid and ethanol solution or oxalic acid aqueous solution.
In a preferable embodiment, before the polyether resin solution is dripped on the surface of the rough oxide film of the first transition layer in the third step, the first transition layer is preheated, the preheating temperature is 40-60 ℃, the polyether resin solution is dripped and then cooled to room temperature to obtain the polyether resin film, the hot-pressing temperature in the third step is 160-.
In a preferred embodiment, in the step four, the copper target with the purity of 99.99% is obtained by magnetron sputtering under vacuum condition, and the ion source parameters are set as follows: 1300-4000W, 0.15-0.25A and 0.1-0.4Pa, the inflow rate of argon gas is 180-230sccm, and the outflow rate is 30-50 sccm.
The invention has the technical effects and advantages that:
1. the magnetron sputtering flexible copper-clad substrate prepared by the process is provided with the first transition layer and the second transition layer, the magnetron sputtering method is utilized to sputter the metal layer on the surface of the substrate film layer, the smooth polyether resin film layer is arranged on the surface of the metal layer, the magnetron sputtering method is utilized to sputter the copper foil layer, the substrate film layer is subjected to corona treatment and then sputtered with the first transition layer, the adhesive force on the surface of the substrate film layer can be effectively improved, so that the effect of enhancing the bonding force between the first transition layer and the substrate film layer is achieved, the electrolytic method is utilized to carry out the rough structure on the surface of the first transition layer, then the polyether resin solution is dripped after the surface modification to form the smooth polyether resin film as the second transition layer, the copper foil layer is sputtered on the surface of the smooth second transition layer, and the adhesive force of the copper foil layer can be effectively improved, the peeling strength between the copper foil layer and the sputtering layer is high, and the flexible copper-clad substrate with low thickness can be prepared;
2. according to the invention, the copper particles are injected into the first transition layer by using an ion injection method, so that no residual copper particles are left in the insulating base material after etching, and excellent ion migration resistance is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a magnetron sputtering flexible copper-clad substrate which comprises a substrate film layer, wherein a first transition layer is arranged on at least one surface of the substrate film layer, a second transition layer is arranged on one side, away from the substrate film layer, of the first transition layer, a copper foil layer is arranged on one side, away from the first transition layer, of the second transition layer, the first transition layer is a metal sputtering layer, and the second transition layer is a polyether resin film layer.
In a preferred embodiment, the substrate film layer is PI, and the thickness of the substrate film layer is 60 um.
In a preferred embodiment, the first transition layer is nickel, the thickness of the first transition layer is 50nm, and copper particles are disposed inside the first transition layer.
In a preferred embodiment, the thickness of the second transition layer is 15nm, and the thickness of the copper foil layer is 4 um.
A preparation method of a magnetron sputtering flexible copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: selecting a PI material as a substrate of the flexible copper clad laminate, carrying out corona treatment on the surface of the selected substrate, preparing a first transition layer on at least one surface of the substrate by using a magnetron sputtering method after the corona treatment is finished, and then uniformly injecting copper particles into the first transition layer by using an ion injection method;
step two: placing the material obtained in the first step into a perchloric acid and ethanol solution for electrochemical polishing treatment, placing the material into an electrolyte of a 0.4M oxalic acid aqueous solution for anodic oxidation after the polishing treatment is finished, preparing a rough oxidation film on the surface of the first transition layer, placing one side containing the rough oxidation film after the anodic oxidation into an ethanol solution containing 10% trifluoro octyl triethoxysilane for contact reaction for 6min, and taking out the material and drying the material for 8min at the temperature of 140 ℃;
step three: dropwise adding a polyether resin solution to the surface containing the rough oxide film obtained in the step two, standing for 3 hours, forming a smooth polyether resin film on the surface of the first transition layer by virtue of the capillary action of the microstructure, and then fixedly arranging the polyether resin film on the outer side of the first transition layer by utilizing a hot-pressing manner to form a second transition layer;
step four: and depositing a copper foil layer on the surface of the second transition layer by using a magnetron sputtering method, thereby obtaining the magnetron sputtering flexible copper-clad substrate.
In one kind excellenceIn a selected embodiment, the power during the corona treatment in the first step is 3.5kw, copper and nickel are used as targets under a vacuum condition during the magnetron sputtering in the first step, and the ion source parameters are set as follows: 3500W, 0.2A and 0.3Pa, the inflow rate of argon gas is 210sccm, the outflow rate of argon gas is 40sccm, and the injection amount of copper particles in the first step is 2 x 1017cm-2。
In a preferred embodiment, the polishing voltage of the electrochemical polishing treatment in the second step is 13V dc voltage, the polishing time is 2.5 minutes, and the volume ratio of perchloric acid to ethanol in the perchloric acid-ethanol solution is 1: and 4.5, in the second step, stainless steel is used as a cathode during anodic oxidation, 75V direct current voltage is applied between the anode and the cathode, and the oxidation time is 3 minutes.
In a preferred embodiment, during the electrochemical polishing and anodic oxidation in the second step, the first transition layer is placed in an electrolyte of perchloric acid and ethanol solution or oxalic acid aqueous solution, and the substrate film layer is not in contact with the perchloric acid and ethanol solution or oxalic acid aqueous solution.
In a preferred embodiment, in the third step, the first transition layer is preheated before the polyether resin solution is dripped on the rough oxide film surface of the first transition layer, the preheating temperature is 50 ℃, the polyether resin solution is dripped and then cooled to room temperature to obtain the polyether resin film, the temperature of hot pressing in the third step is 140 ℃, the pressure is 4MPa, and the time of hot pressing is 4 min.
In a preferred embodiment, in the step four, the copper target with the purity of 99.99% is obtained by magnetron sputtering under vacuum condition, and the ion source parameters are set as follows: 2500W, 0.2A and 0.3Pa, the inflow rate of argon gas was 210sccm, and the outflow rate was 40 sccm.
Example 2:
the invention provides a magnetron sputtering flexible copper-clad substrate, wherein a first transition layer is titanium, and the thickness of the first transition layer is 50 nm.
Example 3:
different from the embodiments 1 and 2, the invention provides a magnetron sputtering flexible copper-clad substrate, wherein the first transition layer is copper, and the thickness of the first transition layer is 50 nm.
Example 4:
different from the embodiments 1 to 3, the present invention provides a magnetron sputtering flexible copper-clad substrate, wherein the first transition layer is a chromium-nickel alloy, the content of nickel in the chromium-nickel alloy is 70%, the content of chromium in the chromium-nickel alloy is 30%, and the thickness of the first transition layer is 50 nm.
Example 5:
the invention provides a magnetron sputtering flexible copper-clad substrate which comprises a substrate film layer, wherein at least one surface of the substrate film layer is provided with a transition layer, one side of the transition layer, which is far away from the substrate film layer, is provided with a copper foil layer, and the transition layer is a metal sputtering layer.
In a preferred embodiment, the substrate film layer is PI, and the thickness of the substrate film layer is 60 um.
In a preferred embodiment, the transition layer is nickel, the thickness of the transition layer is 50nm, and the first transition layer is internally provided with copper particles.
In a preferred embodiment, the copper foil layer has a thickness of 4 um.
A preparation method of a magnetron sputtering flexible copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: selecting a PI material as a substrate of the flexible copper clad laminate, carrying out corona treatment on the surface of the selected substrate, preparing a first transition layer on at least one surface of the substrate by using a magnetron sputtering method after the corona treatment is finished, and then uniformly injecting copper particles into the first transition layer by using an ion injection method;
step two: and depositing a copper foil layer on the surface of the transition layer by using a magnetron sputtering method, thereby obtaining the magnetron sputtering flexible copper-clad substrate.
In a preferred embodiment, the power for corona treatment in the first step is 3.5kw, copper and nickel are used as targets under vacuum condition during magnetron sputtering in the first step, and the ion source parameters are set as follows: 3500W, 0.2A and 0.3Pa, the inflow rate of argon gas is 210sccm, the outflow rate of argon gas is 40sccm, and the injection amount of copper particles in the first step is 2 x 1017cm-2。
In a preferred embodiment, in the step two, the copper target with the purity of 99.99% is obtained by magnetron sputtering under vacuum condition, and the ion source parameters are set as follows: 2500W, 0.2A and 0.3Pa, the inflow rate of argon gas was 210sccm, and the outflow rate was 40 sccm.
Example 6:
the invention provides a magnetron sputtering flexible copper-clad substrate which comprises a substrate film layer, wherein a first transition layer is arranged on at least one surface of the substrate film layer, a second transition layer is arranged on one side, away from the substrate film layer, of the first transition layer, a copper foil layer is arranged on one side, away from the first transition layer, of the second transition layer, the first transition layer is a metal sputtering layer, and the second transition layer is a polyether resin film layer.
In a preferred embodiment, the substrate film layer is PI, and the thickness of the substrate film layer is 60 um.
In a preferred embodiment, the first transition layer is nickel, the thickness of the first transition layer is 50nm, and copper particles are disposed inside the first transition layer.
In a preferred embodiment, the thickness of the second transition layer is 10nm, and the thickness of the copper foil layer is 4 um.
A preparation method of a magnetron sputtering flexible copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: selecting a PI material as a substrate of the flexible copper clad laminate, carrying out corona treatment on the surface of the selected substrate, preparing a first transition layer on at least one surface of the substrate by using a magnetron sputtering method after the corona treatment is finished, and then uniformly injecting copper particles into the first transition layer by using an ion injection method;
step two: placing the material obtained in the first step into a perchloric acid and ethanol solution for electrochemical polishing treatment, placing the material into an electrolyte of a 0.4M oxalic acid aqueous solution for anodic oxidation after the polishing treatment is finished, preparing a rough oxidation film on the surface of the first transition layer, placing one side containing the rough oxidation film after the anodic oxidation into an ethanol solution containing 10% trifluoro octyl triethoxysilane for contact reaction for 6min, and taking out the material and drying the material for 8min at the temperature of 140 ℃;
step three: dropwise adding a polyether resin solution to the surface containing the rough oxide film obtained in the step two, standing for 3 hours, forming a smooth polyether resin film on the surface of the first transition layer by virtue of the capillary action of the microstructure, and then fixedly arranging the polyether resin film on the outer side of the first transition layer by utilizing a hot-pressing manner to form a second transition layer;
step four: and depositing a copper foil layer on the surface of the second transition layer by using a magnetron sputtering method, thereby obtaining the magnetron sputtering flexible copper-clad substrate.
In a preferred embodiment, the power for corona treatment in the first step is 3.5kw, copper and nickel are used as targets under vacuum condition during magnetron sputtering in the first step, and the ion source parameters are set as follows: 3500W, 0.2A and 0.3Pa, the inflow rate of argon gas is 210sccm, the outflow rate of argon gas is 40sccm, and the injection amount of copper particles in the first step is 2 x 1017cm-2。
In a preferred embodiment, the polishing voltage of the electrochemical polishing treatment in the second step is 13V dc voltage, the polishing time is 2.5 minutes, and the volume ratio of perchloric acid to ethanol in the perchloric acid-ethanol solution is 1: and 4.5, in the second step, stainless steel is used as a cathode during anodic oxidation, 75V direct current voltage is applied between the anode and the cathode, and the oxidation time is 3 minutes.
In a preferred embodiment, during the electrochemical polishing and anodic oxidation in the second step, the first transition layer is placed in an electrolyte of perchloric acid and ethanol solution or oxalic acid aqueous solution, and the substrate film layer is not in contact with the perchloric acid and ethanol solution or oxalic acid aqueous solution.
In a preferred embodiment, in the third step, the first transition layer is preheated before the polyether resin solution is dripped on the rough oxide film surface of the first transition layer, the preheating temperature is 50 ℃, the polyether resin solution is dripped and then cooled to room temperature to obtain the polyether resin film, the temperature of hot pressing in the third step is 140 ℃, the pressure is 4MPa, and the time of hot pressing is 4 min.
In a preferred embodiment, in the step four, the copper target with the purity of 99.99% is obtained by magnetron sputtering under vacuum condition, and the ion source parameters are set as follows: 2500W, 0.2A and 0.3Pa, the inflow rate of argon gas was 210sccm, and the outflow rate was 40 sccm.
Example 7:
the invention provides a magnetron sputtering flexible copper-clad substrate which comprises a substrate film layer, wherein a first transition layer is arranged on at least one surface of the substrate film layer, a second transition layer is arranged on one side, away from the substrate film layer, of the first transition layer, a copper foil layer is arranged on one side, away from the first transition layer, of the second transition layer, the first transition layer is a metal sputtering layer, and the second transition layer is a polyether resin film layer.
In a preferred embodiment, the substrate film layer is PI, and the thickness of the substrate film layer is 60 um.
In a preferred embodiment, the first transition layer is nickel, the thickness of the first transition layer is 50nm, and copper particles are disposed inside the first transition layer.
In a preferred embodiment, the thickness of the second transition layer is 30nm, and the thickness of the copper foil layer is 4 um.
A preparation method of a magnetron sputtering flexible copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: selecting a PI material as a substrate of the flexible copper clad laminate, carrying out corona treatment on the surface of the selected substrate, preparing a first transition layer on at least one surface of the substrate by using a magnetron sputtering method after the corona treatment is finished, and then uniformly injecting copper particles into the first transition layer by using an ion injection method;
step two: placing the material obtained in the first step into a perchloric acid and ethanol solution for electrochemical polishing treatment, placing the material into an electrolyte of a 0.4M oxalic acid aqueous solution for anodic oxidation after the polishing treatment is finished, preparing a rough oxidation film on the surface of the first transition layer, placing one side containing the rough oxidation film after the anodic oxidation into an ethanol solution containing 10% trifluoro octyl triethoxysilane for contact reaction for 6min, and taking out the material and drying the material for 8min at the temperature of 140 ℃;
step three: dropwise adding a polyether resin solution to the surface containing the rough oxide film obtained in the step two, standing for 3 hours, forming a smooth polyether resin film on the surface of the first transition layer by virtue of the capillary action of the microstructure, and then fixedly arranging the polyether resin film on the outer side of the first transition layer by utilizing a hot-pressing manner to form a second transition layer;
step four: and depositing a copper foil layer on the surface of the second transition layer by using a magnetron sputtering method, thereby obtaining the magnetron sputtering flexible copper-clad substrate.
In a preferred embodiment, the power for corona treatment in the first step is 3.5kw, copper and nickel are used as targets under vacuum condition during magnetron sputtering in the first step, and the ion source parameters are set as follows: 3500W, 0.2A and 0.3Pa, the inflow rate of argon gas is 210sccm, the outflow rate of argon gas is 40sccm, and the injection amount of copper particles in the first step is 2 x 1017cm-2。
In a preferred embodiment, the polishing voltage of the electrochemical polishing treatment in the second step is 13V dc voltage, the polishing time is 2.5 minutes, and the volume ratio of perchloric acid to ethanol in the perchloric acid-ethanol solution is 1: and 4.5, in the second step, stainless steel is used as a cathode during anodic oxidation, 75V direct current voltage is applied between the anode and the cathode, and the oxidation time is 3 minutes.
In a preferred embodiment, during the electrochemical polishing and anodic oxidation in the second step, the first transition layer is placed in an electrolyte of perchloric acid and ethanol solution or oxalic acid aqueous solution, and the substrate film layer is not in contact with the perchloric acid and ethanol solution or oxalic acid aqueous solution.
In a preferred embodiment, in the third step, the first transition layer is preheated before the polyether resin solution is dripped on the rough oxide film surface of the first transition layer, the preheating temperature is 50 ℃, the polyether resin solution is dripped and then cooled to room temperature to obtain the polyether resin film, the temperature of hot pressing in the third step is 140 ℃, the pressure is 4MPa, and the time of hot pressing is 4 min.
In a preferred embodiment, in the step four, the copper target with the purity of 99.99% is obtained by magnetron sputtering under vacuum condition, and the ion source parameters are set as follows: 2500W, 0.2A and 0.3Pa, the inflow rate of argon gas was 210sccm, and the outflow rate was 40 sccm.
The high thermal conductivity ceramic copper-clad substrates prepared in the above examples 1 to 7 were respectively used as an experimental group 1, an experimental group 2, an experimental group 3, an experimental group 4, an experimental group 5, an experimental group 6, and an experimental group 7, and the peel strength resistance and the surface roughness of the contact between the copper foil layer and the substrate were measured for the selected flexible copper-clad plate. The test results are shown in table one:
watch 1
As shown in the table I, the flexible copper clad laminate produced by the invention has better peel strength, can effectively reduce the thickness of the copper foil layer, the sputtering surface roughness of the copper foil layer is lower, different sputtering metal layers are respectively adopted in the embodiments 1 to 4, the effect is better when the sputtering layers are made of chromium-nickel alloy, the embodiment 5 is used as a comparison group, the copper foil layer is subjected to magnetron sputtering on the traditional sputtering layer, compared with the embodiment 1, the peel strength of the flexible copper clad laminate is lower, the polyether resin film layers with different thicknesses are adopted in the embodiments 6 and 7 to be contacted with the copper foil layer, the effect is better when the thickness of the polyether resin film layer is 15nm, the invention utilizes the magnetron sputtering method to sputter the metal layer on the surface of the substrate film layer by the first transition layer and the second transition layer, the smoother polyether resin film layer is arranged on the surface of the metal layer, and then the copper foil layer is sputtered by the magnetron method, and the substrate rete sputters first transition layer again after corona treatment, can effectively improve the adhesive force on the surface of substrate rete, thereby play the effect of the bonding force between first transition layer of reinforcing and the substrate rete, utilize the electrolysis method to carry out coarse structure's structure on first transition layer surface, then drop polyether resin solution can form glossy polyether resin film as the second transition layer after the surface modification, sputter the copper foil layer on comparatively smooth second transition layer surface, can effectively improve the adhesive force of copper foil layer, make peel strength between copper foil layer and the sputtering layer higher, can prepare the lower flexible copper-clad base plate of department's thickness.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The utility model provides a flexible copper-clad base plate of magnetron sputtering, includes the substrate rete, its characterized in that: at least one surface of the substrate film layer is provided with a first transition layer, one side of the substrate film layer, which is far away from the first transition layer, is provided with a second transition layer, one side of the second transition layer, which is far away from the first transition layer, is provided with a copper foil layer, the first transition layer is a metal sputtering layer, and the second transition layer is a polyether resin film layer.
2. The magnetron sputtering flexible copper-clad substrate according to claim 1, characterized in that: the base material film layer is one of PI, PE, PP, PTEE, PS, PPA, PTO, PEEK, PC, PA, PSU, PET, PPS, PEN and PES, and the thickness of the base material film layer is 50-70 um.
3. The magnetron sputtering flexible copper-clad substrate according to claim 1, characterized in that: the first transition layer is an alloy formed by one or more than two of titanium, zinc, iron, nickel, chromium, cobalt, copper, silver and gold, the thickness of the first transition layer is 40-120nm, and copper particles are arranged inside the first transition layer.
4. The magnetron sputtering flexible copper-clad substrate according to claim 1, characterized in that: the thickness of second transition layer is 10-30nm, the thickness of copper foil layer is 2-5 um.
5. A preparation method of a magnetron sputtering flexible copper-clad substrate is characterized by comprising the following steps: the preparation method comprises the following specific steps:
the method comprises the following steps: selecting a proper substrate film layer as a substrate of the flexible copper clad laminate, carrying out corona treatment on the surface of the selected substrate, preparing a first transition layer on at least one surface of the substrate by using a magnetron sputtering method after the corona treatment is finished, and then uniformly injecting copper particles into the first transition layer by using an ion injection method;
step two: placing the material obtained in the step one in perchloric acid and ethanol solution for electrochemical polishing treatment, placing the material in electrolyte of 0.4M oxalic acid aqueous solution for anodic oxidation after the polishing treatment is finished, preparing a rough oxidation film on the surface of the first transition layer, placing one side containing the rough oxidation film after the anodic oxidation in the ethanol solution containing 8-12% of trifluoro octyl triethoxysilane for contact reaction for 5-8min, and taking out the material for drying treatment at the temperature of 135-145 ℃ for 5-10 min;
step three: dropwise adding a polyether resin solution to the surface containing the rough oxide film obtained in the step two, standing for 2-4h, forming a smooth polyether resin film on the surface of the first transition layer by virtue of the capillary action of the microstructure, and then fixedly arranging the polyether resin film on the outer side of the first transition layer in a hot-pressing manner to form a second transition layer;
step four: and depositing a copper foil layer on the surface of the second transition layer by using a magnetron sputtering method, thereby obtaining the magnetron sputtering flexible copper-clad substrate.
6. The method for preparing the magnetron sputtering flexible copper-clad substrate according to claim 5, characterized in that: the power during corona treatment in the first step is 2.5-4kw, copper and nickel are used as targets under a vacuum condition during magnetron sputtering in the first step, and ion source parameters are set as follows: 1500-4200W, 0.1-0.25A, 0.2-0.4Pa, the inflow rate of argon gas is 180-230sccm, the outflow rate of argon gas is 30-50sccm, and the injection amount of copper particles in the first step is 2 × 1017-1018cm-2。
7. The method for preparing the magnetron sputtering flexible copper-clad substrate according to claim 5, characterized in that: and in the second step, the polishing voltage is 10-15V direct current voltage during electrochemical polishing treatment, the polishing time is 2-3 minutes, and the volume ratio of perchloric acid to ethanol in the perchloric acid-ethanol solution is 1: (4-5), in the second step, stainless steel is used as a cathode during anodic oxidation, and 70-80V direct current voltage is applied between the anode and the cathode, and the oxidation time is 2-4 minutes.
8. The method for preparing the magnetron sputtering flexible copper-clad substrate according to claim 5, characterized in that: and in the second step, during electrochemical polishing and anodic oxidation, the first transition layer is placed in electrolyte of perchloric acid and ethanol solution or oxalic acid aqueous solution, and the substrate film layer is not contacted with the perchloric acid and ethanol solution or oxalic acid aqueous solution.
9. The method for preparing the magnetron sputtering flexible copper-clad substrate according to claim 5, characterized in that: and in the third step, before the polyether resin solution is dripped on the surface of the rough oxide film of the first transition layer, the first transition layer is preheated, the preheating temperature is 40-60 ℃, the polyether resin solution is dripped and then cooled to room temperature to obtain the polyether resin film, the hot-pressing temperature in the third step is 120-160 ℃, the pressure is 1-8MPa, and the hot-pressing time is 3-6 min.
10. The method for preparing the magnetron sputtering flexible copper-clad substrate according to claim 5, characterized in that: in the fourth step, the ion source parameters are set as follows according to the copper target with the purity of 99.99 percent under the vacuum condition during magnetron sputtering: 1300-4000W, 0.15-0.25A and 0.1-0.4Pa, the inflow rate of argon gas is 180-230sccm, and the outflow rate is 30-50 sccm.
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