CN117467929B - Surface metallization treatment method for high polymer material - Google Patents
Surface metallization treatment method for high polymer material Download PDFInfo
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- 238000001465 metallisation Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000011282 treatment Methods 0.000 title claims abstract description 31
- 239000002861 polymer material Substances 0.000 title claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 35
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 32
- 238000005468 ion implantation Methods 0.000 claims abstract description 31
- 238000001659 ion-beam spectroscopy Methods 0.000 claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 101
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 101
- 239000000758 substrate Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 19
- 238000002513 implantation Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 230000001133 acceleration Effects 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000009713 electroplating Methods 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000003475 lamination Methods 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 52
- 150000002500 ions Chemical class 0.000 description 44
- 238000010884 ion-beam technique Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000003672 processing method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000004643 cyanate ester Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
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- 239000011159 matrix material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/48—Ion implantation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Physical Vapour Deposition (AREA)
Abstract
The invention relates to the technical field of surface treatment of high polymer materials, and particularly discloses a surface metallization treatment method of a high polymer material, which comprises the following steps: s1, ion beam sputtering cleaning of the surface of a polymer substrate: performing ion beam sputtering cleaning on the surface of the high polymer substrate by adopting a low-energy radio-frequency gas ion source; s2, high-energy gas ion implantation on the surface of the polymer substrate: high-energy gas ion implantation is carried out on the surface of the high-molecular base material by adopting a high-energy gas ion source; s3, surface metallization treatment of the polymer substrate. The invention adopts the high-energy and low-energy gas ion sources to comprehensively treat the polymer substrate, can greatly improve the surface free energy of the polymer substrate, ensures that the surface metal film layer and the polymer substrate have higher peel strength and adhesive force, ensures that the treated polymer substrate has high bonding strength and stable performance, and has the advantages of simple process, high production efficiency and low cost.
Description
Technical Field
The invention relates to the technical field of surface treatment of high polymer materials, in particular to a surface metallization treatment method of a high polymer material.
Background
PTFE has the advantages of excellent electrical property, chemical corrosion resistance, good heat resistance, low water absorption and the like. Among all resin matrixes for high-frequency copper-clad plates, PTFE has the smallest and most stable dielectric constants and dielectric losses, and is very suitable for being used as a PCB base material of a high-frequency circuit. Although possessing the above-mentioned excellent properties, PTFE is a polymer compound composed of carbon and fluorine, has strong hydrophobicity and surface chemical inertness, has small surface tension and low surface energy, and is difficult to bond and complex with a surface conductive layer material, thus limiting its application in high-frequency microelectronic circuits.
In order to improve the adhesive property of PTFE, the PTFE needs to be subjected to surface modification, so that the free energy and the surface activity of the PTFE are improved, and the bonding strength between the PTFE and a surface conductive layer is improved. The PTFE modification techniques commonly used at present mainly include chemical treatment, plasma treatment, radiation treatment, etc., and the main purpose of these treatments is to introduce polar groups, to increase the surface energy and roughness thereof. The method is characterized in that the chemical treatment is most mature, electroplating or chemical plating is carried out after chemical corrosion, the method relates to harmful chemical agents, the operation risk is high, environmental pollution is easy to cause, a large amount of waste liquid needs to be treated, the purity of a subsequently deposited metal conductive layer is poor, and the electrical property of a device is influenced; plasma treatment is one of the common techniques for modifying the surface of a polymer, is widely applied to the surface treatment of a material, has the advantages of low treatment temperature, short time, no influence on the inherent characteristics of a matrix and no pollution, and is one of the most promising techniques for modifying the surface of PTFE, but has the defects of poor timeliness and limited improvement of adhesion, and the active groups on the surface gradually decrease until the surface returns to the original state along with the increase of the time, so that the application of the surface is limited to a certain extent, and the durability of the surface is required to be improved by combining other treatment methods. In the aspect of improving the surface activity of PTFE, although the radiation treatment is simple to operate, the PTFE matrix is easy to damage, the mechanical property of the PTFE matrix is reduced, and the improvement of the adhesive force is limited.
In summary, several PTFE surface modification methods commonly used at present have problems of operational risk and environmental pollution, or limited improvement of adhesion and unstable performance, and development of a novel surface treatment technology with low cost, fast treatment speed, high adhesion strength and stable performance, which is suitable for large-scale industrial production and application, is urgently needed.
Disclosure of Invention
The invention aims to provide a high polymer material surface metallization treatment method, which adopts high-energy and low-energy gas ion sources to comprehensively treat a high polymer substrate, can greatly improve the surface free energy of the high polymer substrate, ensures that a surface metal film layer and the high polymer substrate have higher peel strength and adhesive force, ensures that the treated high polymer substrate has high bonding strength and stable performance, and has the advantages of simple process, high production efficiency and low cost.
The invention is realized by the following technical scheme:
a high polymer material surface metallization processing method comprises the following steps:
s1, ion beam sputtering cleaning of the surface of a polymer substrate: performing ion beam sputtering cleaning on the surface of the high polymer substrate by adopting a low-energy radio-frequency gas ion source;
s2, high-energy gas ion implantation on the surface of the polymer substrate: high-energy gas ion implantation is carried out on the surface of the high-molecular base material by adopting a high-energy gas ion source;
s3, surface metallization treatment of the polymer substrate.
The invention adopts the low-energy radio frequency gas ion source to carry out ion beam sputtering cleaning on the surface of the high-molecular substrate, then adopts the high-energy gas ion source to carry out high-energy gas ion implantation on the surface of the high-molecular substrate, realizes the comprehensive treatment of the surface of the high-molecular substrate by adopting the high-energy gas ion source and the low-energy gas ion source, greatly improves the free energy of the surface of the high-molecular substrate, ensures that the surface metal film layer and the high-molecular substrate have higher peel strength and adhesive force after surface metallization, ensures that the treated high-molecular substrate has high bonding strength and stable performance, and has the advantages of simple process, high production efficiency and low cost; is suitable for large-scale industrial production and application.
Further, in step S1, the acceleration voltage of the low-energy RF gas ion source is 100-2000V. Preferably 500 to 1500V.
Further, in step S1, the ion beam sputter cleaning process gas at least includes Ar, kr, xe, he, ne, N 2 、H 2 、O 2 One of the following; the vacuum degree of the ion beam sputtering cleaning is 0.001 to 10Pa, preferably 0.01 to 1.0Pa.
In step S2, the high-energy gas ion implantation working gas at least comprises Ar, kr, xe, he, ne, N 2 、H 2 、O 2 One of them. The vacuum degree of the high-energy gas ion implantation is 0.001 to 1Pa, preferably 0.01 to 0.5Pa.
Further, in step S2, the acceleration voltage of the high-energy gas ion source is 10-50 kV, and the implantation dosage is 1.0X10 12 ～1.0×10 18 ion/cm 2 。
Preferably, in step S2, the acceleration voltage of the high-energy gas ion source is preferably 20-30 kV, and the implantation dosage is 1.0X10 14 ～1.0×10 16 ion/cm 2 。
Further, in step S3, the surface metallization treatment method includes sequentially performing vacuum plating, electroplating thickening to achieve surface metallization, coating a high-frequency adhesive on the surface of the polymer substrate, and then performing copper foil lamination to achieve surface metallization, or coating a high-frequency adhesive on the surface of the polymer substrate and then coating nano metal slurry to achieve surface metallization.
Wherein, vacuum coating and electroplating are the prior art, the high-frequency adhesive is the prior product, and the coating nano metal slurry comprises nano gold slurry, nano silver slurry, nano copper slurry, nano nickel slurry and other conductive materials.
Further, the polymer base material includes a film or plate material such as PTFE (polytetrafluoroethylene), PI (polyimide), LCP (liquid crystal polymer), CF (carbon fiber), CE (cyanate ester), PC (polycarbonate), PS (polystyrene), PE (polyethylene) or PET (polyethylene terephthalate).
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention adopts the high-energy and low-energy gas ion sources to comprehensively treat the surface of the polymer substrate, greatly improves the surface free energy of the polymer substrate, and has higher peel strength and adhesive force with the polymer substrate after surface metallization. The treatment method has the advantages of simple process, high production efficiency, low cost, high membrane base bonding strength, stable performance and the like, and is suitable for large-scale industrial production and application.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic illustration of the vacuum plating+electroplating thickening of PTFE surface metallization (sputtering) of examples 1 and 4 of the present invention;
FIG. 3 is a schematic diagram of the invention in which the PTFE substrate surface of examples 2 and 5 is coated with a high frequency adhesive and then copper foil lamination is performed to achieve PTFE surface metallization (coating method);
FIG. 4 is a schematic diagram of the invention in which the PTFE substrate surface of examples 3 and 6 is coated with a high frequency adhesive and then coated with nano silver paste to achieve the surface metallization of PTFE (coating method);
FIG. 5 is an SEM image (10 KX) of an untreated PTFE surface;
FIG. 6 is an SEM image (10 KX) of a PTFE surface that has been cleaned and implanted by Ar ion beam sputtering;
FIG. 7 is a graph of N 2 SEM image of ion beam sputter cleaned and implanted PTFE surface (10 KX).
Description of the embodiments
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
As shown in FIG. 1, the surface metallization treatment method of the high polymer material comprises the following steps:
s1, ion beam sputtering cleaning of the surface of a polymer substrate: performing ion beam sputtering cleaning on the surface of the high polymer substrate by adopting a low-energy radio-frequency gas ion source; the working gas may be Ar, kr, xe, he, ne, N 2 、H 2 、O 2 Other inert gases or mixtures thereof, the vacuum degree is 0.001 to 10Pa, preferably 0.01 to 1.0Pa, and the acceleration voltage is 100 to 2000V, preferably 500 to 1500V.
S2, high-energy gas ion implantation on the surface of the polymer substrate: high-energy gas ion implantation is carried out on the surface of the high-molecular base material by adopting a high-energy gas ion source; the working gas may be Ar, kr, xe, he, ne, N 2 、H 2 、O 2 Other inert gases or mixtures thereof, the vacuum degree is 0.001 to 1Pa, preferably 0.01 to 0.5Pa, and the acceleration voltage is 10 to 50kV, preferably 20 to 30kV. The implantation dose is 1.0X10 12 ～1.0×10 18 ion/cm2, preferably 1.0X10 14 ～1.0×10 16 ion/cm 2 。
S3, carrying out surface metallization treatment on the polymer substrate; the surface metallization can be carried out in three ways according to the product requirement: (1) vacuum coating and electroplating thickening are carried out for PTFE surface metallization (sputtering method). (2) The surface of the PTFE substrate is coated with a high-frequency adhesive, and then copper foil lamination is carried out to realize the surface metallization of PTFE (coating method). (3) The surface of PTFE substrate is coated with adhesive, and then coated with nano gold paste, nano silver paste, nano copper paste, nano nickel paste and other conductive materials to realize surface metallization (coating method)
The polymer substrate in this embodiment includes a film or plate material such as PTFE (polytetrafluoroethylene), PI (polyimide), LCP (liquid crystal polymer), CF (carbon fiber), CE (cyanate ester), PC (polycarbonate), PS (polystyrene), PE (polyethylene), or PET (polyethylene terephthalate).
The embodiment adopts the low-energy radio frequency gas ion source to carry out ion beam sputtering cleaning on the surface of the high-molecular substrate, and then adopts the high-energy gas ion source to carry out high-energy gas ion implantation on the surface of the high-molecular substrate, thereby realizing the comprehensive treatment of the surface of the high-molecular substrate by adopting the high-energy gas ion source and the low-energy gas ion source, greatly improving the free energy of the surface of the high-molecular substrate, and after the surface metallization, leading the surface metal film layer and the high-molecular substrate to have higher peel strength and adhesive force, leading the treated high-molecular substrate to have high bonding strength and stable performance, and the treatment method has the advantages of simple process, high production efficiency and low cost; is suitable for large-scale industrial production and application.
The present technology is further illustrated with reference to the following specific examples.
Example 1:
a high polymer material surface metallization processing method comprises the following steps:
s1, cleaning a PTFE substrate by low-energy ion beam sputtering:
s11, stretching a long film with the specification of PTFE base material of 0.03mm thick and 300mm wide and 1000mm wide on a cold drum with the diameter of 32 cm;
s12, vacuumizing, and starting the cold drum to rotate at the rotating speed of 5r/min;
and S13, when the vacuum degree is better than 0.001Pa, introducing Ar gas to 0.01Pa, starting a low-energy radio-frequency gas ion source to perform ion beam sputtering cleaning on the PTFE surface for two minutes, wherein the incident power of the radio-frequency power supply is 800W, the accelerating voltage is 1200V, and the current is 1000mA.
S2, high-energy ion implantation of PTFE base material:
s21, closing a radio frequency gas ion source;
s22, ar ion implantation is carried out for two minutes, the acceleration voltage of the high-energy gas ion source is 25kV, and the implantation dosage is about 2.0x10 15 ion/cm 2 。
S3, surface metallization treatment of the PTFE substrate:
s31, vacuum coating of a PTFE substrate:
s311, introducing Ar gas to 0.2Pa;
s312, starting a Ni target magnetron sputtering power supply to deposit for two minutes, sputtering current 1A, and depositing a Ni film with the thickness of 120nm on the surface of PTFE;
s313, starting a Cu target magnetron sputtering power supply to deposit for two minutes, sputtering current 1A, and depositing a 136nm Cu film on the surface of PTFE;
s32, electroplating a thickened copper film:
the copper film was thickened by 9 μm by the sulfate bright copper plating method.
Example 2:
a high polymer material surface metallization processing method comprises the following steps:
s1, cleaning a PTFE substrate by low-energy ion beam sputtering:
s11, tightly winding a long film with the specification of PTFE base material of 0.05mm thick and 300mm wide and 1000mm on a cold drum with the diameter of 32 cm;
s12, vacuumizing, and starting the cold drum to rotate at the rotating speed of 5r/min;
and S13, when the vacuum degree is better than 0.001Pa, introducing Ar gas to 0.01Pa, starting a low-energy radio-frequency gas ion source to perform ion beam sputtering cleaning on the PTFE surface for two minutes, wherein the incident power of the radio-frequency power supply is 800W, the accelerating voltage is 1200V, and the current is 1000mA.
S2, high-energy ion implantation of PTFE base material:
s21, closing a radio frequency gas ion source;
s22, ar ion implantation is carried out for two minutes, the acceleration voltage of the high-energy gas ion source is 25kV, and the implantation dosage is about 2.0x10 15 ion/cm 2 。
S3, surface metallization treatment of the PTFE substrate:
and coating a high-frequency adhesive on the surface of the PTFE substrate subjected to ion implantation, and pressing the PTFE substrate with a copper foil with the thickness of 9 mu m.
Example 3:
a high polymer material surface metallization processing method comprises the following steps:
s1, cleaning a PTFE substrate by low-energy ion beam sputtering:
s11, tightly winding a long film with the specification of PTFE base material of 0.05mm thick and 300mm wide and 1000mm on a cold drum with the diameter of 32 cm;
s12, vacuumizing, and starting the cold drum to rotate at the rotating speed of 5r/min;
and S13, when the vacuum degree is better than 0.001Pa, introducing Ar gas to 0.01Pa, starting a low-energy radio-frequency gas ion source to perform ion beam sputtering cleaning on the PTFE surface for two minutes, wherein the incident power of the radio-frequency power supply is 800W, the accelerating voltage is 1200V, and the current is 1000mA.
S2, high-energy ion implantation of PTFE base material:
s21, closing a radio frequency gas ion source;
s22, ar ion implantation is carried out for two minutes, the acceleration voltage of the high-energy gas ion source is 25kV, and the implantation dosage is about 2.0x10 15 ion/cm 2 。
S3, surface metallization treatment of the PTFE substrate:
and coating a high-frequency adhesive on the surface of the PTFE substrate after ion implantation, and then coating nano silver paste with the thickness of 10 mu m.
Example 4:
a high polymer material surface metallization processing method comprises the following steps:
s1, cleaning a PTFE substrate by low-energy ion beam sputtering:
s11, stretching a long film with the specification of PTFE base material of 0.03mm thick and 300mm wide and 1000mm wide on a cold drum with the diameter of 32 cm;
s12, vacuumizing, and starting the cold drum to rotate at the rotating speed of 5r/min;
s13, when the vacuum degree is better than 0.001Pa, introducing N 2 And starting a low-energy radio-frequency gas ion source to perform ion beam sputtering cleaning on the PTFE surface for two minutes until the pressure reaches 0.01Pa, wherein the incident power of the radio-frequency power source is 600W, the accelerating voltage is 1200V, and the current is 1000mA.
S2, high-energy ion implantation of PTFE base material:
s21, closing a radio frequency gas ion source;
s22, N ion implantation is carried out for two minutes, the acceleration voltage of the high-energy gas ion source is 20kV, and the implantation dosage is about 3.2 multiplied by 10 15 ion/cm 2 。
S3, surface metallization treatment of the PTFE substrate:
s31, vacuum coating of a PTFE substrate:
s311, introducing Ar gas to 0.2Pa;
s312, starting a Ni target magnetron sputtering power supply to deposit for two minutes, sputtering current 1A, and depositing a Ni film with the thickness of 120nm on the surface of PTFE;
s313, starting a Cu target magnetron sputtering power supply to deposit for two minutes, sputtering current 1A, and depositing a 136nm Cu film on the surface of PTFE;
s32, electroplating a thickened copper film:
the copper film was thickened by 9 μm by the sulfate bright copper plating method.
Example 5:
a high polymer material surface metallization processing method comprises the following steps:
s1, cleaning a PTFE substrate by low-energy ion beam sputtering:
s11, stretching a long film with the specification of PTFE base material of 0.03mm thick and 300mm wide and 1000mm wide on a cold drum with the diameter of 32 cm;
s12, vacuumizing, and starting the cold drum to rotate at the rotating speed of 5r/min;
s13, when the vacuum degree is better than 0.001Pa, introducing N 2 And starting a low-energy radio-frequency gas ion source to perform ion beam sputtering cleaning on the PTFE surface for two minutes until the pressure reaches 0.01Pa, wherein the incident power of the radio-frequency power source is 600W, the accelerating voltage is 1200V, and the current is 1000mA.
S2, high-energy ion implantation of PTFE base material:
s21, closing a radio frequency gas ion source;
s22, N ion implantation is carried out for two minutes, the acceleration voltage of the high-energy gas ion source is 20kV, and the implantation dosage is about 3.2 multiplied by 10 15 ion/cm 2 。
S3, surface metallization treatment of the PTFE substrate:
and coating a high-frequency adhesive on the surface of the PTFE substrate subjected to ion implantation, and pressing the PTFE substrate with a copper foil with the thickness of 9 mu m.
Example 6:
a high polymer material surface metallization processing method comprises the following steps:
s1, cleaning a PTFE substrate by low-energy ion beam sputtering:
s11, stretching a long film with the specification of PTFE base material of 0.03mm thick and 300mm wide and 1000mm wide on a cold drum with the diameter of 32 cm;
s12, vacuumizing, and starting the cold drum to rotate at the rotating speed of 5r/min;
s13, when the vacuum degree is better than 0.001Pa, introducing N 2 To 0.01Pa, start low energy radio frequency gas ionizationIon beam sputtering cleaning is carried out on the PTFE surface by the sub-source for two minutes, the incident power of the radio frequency power supply is 600W, the accelerating voltage is 1200V, and the current is 1000mA.
S2, high-energy ion implantation of PTFE base material:
s21, closing a radio frequency gas ion source;
s22, N ion implantation is carried out for two minutes, the acceleration voltage of the high-energy gas ion source is 20kV, and the implantation dosage is about 3.2 multiplied by 10 15 ion/cm 2 。
S3, surface metallization treatment of the PTFE substrate:
and coating a high-frequency adhesive on the surface of the PTFE substrate after ion implantation, and then coating nano silver paste with the thickness of 10 mu m.
Examples 1 to 3 and examples 4 to 6 of the present invention are different in that: examples 1-3 were Ar ion beam sputter cleaning and implantation of PTFE substrate surfaces, and examples 4-6 were N ion beam sputter cleaning and implantation of PTFE substrate surfaces.
In both examples 1 and 4, the surface metallization of PTFE was performed by vacuum plating and electroplating thickening (sputtering method), as shown in FIG. 2;
in both the embodiment 2 and the embodiment 5, the high-frequency adhesive is coated on the surface of the PTFE substrate, and then copper foil lamination is performed to realize the surface metallization (coating method) of the PTFE, as shown in fig. 3;
in both examples 3 and 6, the surface of the PTFE substrate was coated with a high-frequency adhesive, and then coated with a nano silver paste to effect the surface metallization of PTFE (coating method), as shown in FIG. 4.
Test results:
(1) The untreated PTFE surface is visually bright, and the PTFE surface after ion beam treatment is in a matte state. The untreated PTFE, the PTFE that was sputter cleaned and infused with Ar ion beam (example 1-example 3), and the PTFE surface that was sputter cleaned and infused with N ion beam (example 4-example 6) were observed using SEM (scanning electron microscope). Fig. 5 is a metallographic microscope image of untreated PTFE, fig. 6 is a metallographic microscope image of a PTFE surface (example 1-example 3) subjected to Ar ion beam sputter cleaning and implantation, and fig. 7 is a metallographic microscope image of a PTFE surface (example 4-example 6) subjected to N ion beam sputter cleaning and implantation. As can be seen from fig. 5-7, the untreated PTFE surface was flat; the PTFE surface spinous processes subjected to Ar ion beam sputtering cleaning and injection are densely distributed in a high-rise manner; PTFE surface spinous processes cleaned and implanted by N-beam sputtering are densely packed but weaker than PTFE cleaned and implanted by Ar-beam sputtering.
(2) The free energy of the untreated PTFE and the ion beam treated PTFE surfaces were tested with a dyne pen. The untreated PTFE had a surface energy of less than 20mN/m, the PTFE (examples 1 to 3) which had been subjected to Ar ion beam sputter cleaning and implantation had reached 72 mN/m, and the PTFE (examples 4 to 6) which had been subjected to N ion beam sputter cleaning and implantation had a surface energy of 62mN/m. It can be seen that the surface free energy of PTFE is greatly improved after ion beam sputter cleaning and implantation.
(3) The film base peel strength of example 1, example 2, example 4, example 5 and PTFE film base not treated with ion beam were tested according to CPCA/JCA-BM 03-2005 peel strength test criteria, and the film base adhesion of example 3 and example 6 and film base not treated with ion beam were tested according to GB/T9286-1998 cross-hatch test criteria, the results are shown in Table 1:
TABLE 1
| Film base bonding Strength | Peel strength (N/mm) (CPCA/JCA-BM 03-2005) | Adhesive force (GB/T9286-1998) |
| Untreated by ion beam | 0 (skinning, no binding force) | Grade 5 |
| Example 1 | 0.8 | / |
| Example 2 | 1.0 | / |
| Example 3 | / | Level 1 |
| Example 4 | 0.6 | / |
| Example 5 | 0.9 | / |
| Example 6 | / | Level 1 |
Test results show that the surface free energy of PTFE can be greatly improved by adopting the method to treat PTFE, and after surface metallization, the surface metal film layer and the PTFE substrate have good peel strength and adhesive force.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The surface metallization treatment method of the high polymer material is characterized by comprising the following steps of:
s1, ion beam sputtering cleaning of the surface of a polymer substrate: performing ion beam sputtering cleaning on the surface of the high polymer substrate by adopting a low-energy radio-frequency gas ion source;
s2, high-energy gas ion implantation on the surface of the polymer substrate: high-energy gas ion implantation is carried out on the surface of the high-molecular base material by adopting a high-energy gas ion source;
s3, carrying out surface metallization treatment on the polymer substrate;
in the step S1, the working gas for ion beam sputtering cleaning is Ar; in the step S2, the working gas for ion implantation of the high-energy gas is Ar, the accelerating voltage of the high-energy gas ion source is 10-50 kV, and the implantation dosage is 2.0x10 15 ion/cm 2 。
2. The method for surface metallization of polymer material according to claim 1, wherein in step S1, the acceleration voltage of the low-energy radio-frequency gas ion source is 100-2000V.
3. The method for surface metallization of polymer material according to claim 2, wherein in step S1, the acceleration voltage of the low-energy radio-frequency gas ion source is 500-1500V.
4. The method according to claim 1, wherein in the step S1, the vacuum degree of the ion beam sputtering cleaning is 0.001 to 10Pa, and in the step S2, the vacuum degree of the high-energy gas ion implantation is 0.001 to 1Pa.
5. The method according to claim 4, wherein the vacuum degree of ion beam sputtering cleaning is 0.01-1.0 Pa, and the vacuum degree of high-energy gas ion implantation is 0.01-0.5 Pa in step S2.
6. The method for metallizing a surface of a polymer material according to claim 1, wherein in the step S2, the acceleration voltage of the high-energy gas ion source is 20 to 30kV1.
7. The method according to any one of claims 1 to 6, wherein in step S3, the surface metallization is performed by sequentially performing vacuum plating, electroplating thickening to achieve surface metallization, coating a high-frequency adhesive on the surface of the polymer substrate, and then performing copper foil lamination to achieve surface metallization, or coating a high-frequency adhesive on the surface of the polymer substrate and then coating a nano metal slurry.
8. The method of any one of claims 1 to 6, wherein the polymeric substrate comprises a film or sheet of PTFE, PI, LCP, CF, CE, PC, PS or PET.
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