Surface treatment method of a polymer for 5G

Abstract

The present application discloses a surface treatment method of a polymer for 5G, belonging to the technical field of surface treatment of polymer. By injecting and adding the oxygen elements to the polymer, the polymer matrix elements and the injected atoms can form a blend structure, which can increase the surface roughness of the polymer, improve its bonding strength with the metal, and thus enhance its anti-peel strength. The surface treatment method of the application has the surface resistivity, surface roughness, water absorption and tensile properties of the polymer all considered. The equipment used in the invention has long service life and low cost, and can realize large-scale roll-to-roll production. The method can be popularized in polymer surface treatment.

Claims

1. A surface treatment method of a polymer for 5G, comprising the steps of: S1. proceed oxygen insertion by using a Penning ion source on the surface of the polymer, controlling a roughness of the polymer surface to change greater than 0 ?m and less than or equal to 0.1 ?m, obtaining a first polymer; S2. proceed oxygen addition by using a Kaufman ion source on a surface of the first polymer, controlling a roughness of the first polymer surface to change greater than 0 ?m and less than or equal to 0.1 ?m, obtaining a second polymer; S3. repeat steps S1 and S2 until the surface resistance of the second polymer is less than or equal to 10.sup.15?; S4. proceed hydrogen abstraction by using a Hall ion source on the surface of the second polymer, obtaining a third polymer; S5. repeat steps S1-S4 until the surface roughness of the third polymer is 0.1?0.4 ?m; wherein the oxygen insertion in S1 has an oxygen flow ranging from 5 sccm to 80 sccm, a voltage ranging from 20 kV to 40 kV, and a beam intensity ranging from 1 mA to 50 mA, the oxygen addition in S2 has an oxygen flow ranging from 20 sccm to 100 sccm, a voltage ranging from 10 kV to 20 kV, and a beam intensity ranging from 5 mA to 150 mA, and the hydrogen abstraction has an argon flow ranging from 50 sccm to 150 sccm, a voltage ranging from 0.1 kV to 1 kV, and a beam intensity ranging from 200 mA to 1000 mA.

2. The surface treatment method according to claim 1, wherein the polymer in S1 is selected from polyimide, liquid crystalline polymer, modified polyimide, polyethylene terephthalate and polytetrafluoroethylene.

3. The surface treatment method according to claim 1, wherein the polymer after the surface treatment has a dielectric constant greater than 3.0, a surface water absorption greater than 10%, a surface resistance greater than 1014?, a surface roughness ranging from 0.1 ?m to 0.4 ?m, a hydrophilic contact angle ranging from 40? to 80?, a 5 GHz high frequency dielectric loss equal to or less than 0.004.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flow chart of the method of an embodiment;

(2) FIG. 2 is an impedance test diagram of ion-treated MPI and pristine MPI in Example 1.

(3) FIG. 3 is a SEM diagram of the polymer in Example 1 before treatment.

(4) FIG. 4 is a surface hydrophilic angle diagram of the polymer in Example 1 before treatment.

(5) FIG. 5 is a SEM diagram of the polymer in Example 1 after treatment.

(6) FIG. 6 is a surface hydrophilic angle diagram of the polymer in Example 1 after treatment.

(7) FIG. 7 is a surface XPS diagram of the polymer in Example 1 after treatment.

(8) FIG. 8 is a binding force test diagram of the pristine polymer and the polymers after treatment in Examples 1?2.

(9) FIG. 9 is a schematic diagram of a polymer combining with copper film.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(10) The present application provides a surface treatment method of a polymer for 5G, comprising the steps of:

(11) S1. a Penning ion source is used to proceed oxygen insertion on the surface of a polymer, the roughness of the polymer surface is controlled to change less than or equal to 0.1 ?m, and a first polymer is obtained;

(12) S2. a Kaufman ion source is used to proceed oxygen addition on the surface of the first polymer, the roughness of the first polymer surface is controlled to change less than or equal to 0.1 ?m, and a second polymer is obtained;

(13) S3. a Hall ion source is used to proceed hydrogen abstraction on the surface of the second polymer, and a third polymer is obtained;

(14) S4. S1?S3 are repeated when the surface roughness of the third polymer is greater than 0.4 ?m or less than 0.1 ?m until the surface roughness of the third polymer is 0.1?0.4 ?m.

(15) In the present application, unless otherwise specified, the required equipments or polymers are well known and commercial available to those skilled in the art.

(16) The Penning ion source is used to proceed oxygen insertion on the surface of the polymer, and the roughness of the polymer surface is controlled to change less than or equal to 0.1 ?m, resulting with a first polymer. In the embodiments, the polymers preferably include polyimide (PI), liquid crystalline polymer (LCP), modified polyimide (MPI), polyethylene terephthalate (PET) and polytetrafluoroethylene (PTFE). In the embodiments, the oxygen flow rate of oxygen insertion preferably ranges from 5 to 80 sccm, more preferably 10 to 60 sccm, and further preferably 30 to 50 sccm; the voltage preferably ranges from 20 to 40 KV, and more preferably 25 to 35 KV; the beam intensity preferably ranges from 1 to 50 mA, more preferably 10 to 40 mA, and further preferably 20 to 30 mA. The embodiments realize the oxygen insertion on the surface of the polymer through a Penning ion source, and facilitate the combination of O and H because of the high oxygen ion energy, thus forming OH radical.

(17) After the first polymer is obtained, the Kaufman ion source is used to proceed oxygen addition on the surface of the first polymer, and the roughness of the first polymer surface is controlled to change less than or equal to 0.1 ?m, resulting with a second polymer. In the embodiments, the oxygen flow rate of oxygen addition preferably ranges from 20 to 100 sccm, more preferably 40 to 80 sccm, and further preferably 50 to 60 sccm; the voltage preferably ranges from 10 to 20 KV, and more preferably 12 to 15 KV; the beam intensity preferably ranges from 5 to 150 mA, more preferably 20 to 120 mA, and further preferably 50 to 100 mA. In an embodiment, when the second polymer has a surface resistance greater than 10.sup.15?, preferably returning to S1, until the surface resistance is less than or equal to 10.sup.15?. The embodiments realize: the oxygen addition on the surface of the first polymer through the Kaufman ion source; forming of CO bond by the combination of oxygen with carbon on the surface of the first polymer, facilitating the increase of surface energy; Penning ion source treatment (oxygen insertion) is repeated when the surface resistance is greater than 10.sup.15?. The higher resistance means less CO key, OH radical and carbon, which can affect the surface hydrophilicity of the polymer.

(18) After the second polymer is obtained, the Hall ion source is used to proceed hydrogen abstraction on the surface of the second polymer, resulting with a third polymer. In the embodiments, the argon flow rate of hydrogen abstraction preferably ranges from 50 to 150 sccm, more preferably 60 to 120 sccm, and further preferably 80 to 100 sccm; the voltage preferably ranges from 0.1 to 1 KV, more preferably 0.3 to 0.8 KV, and further preferably 0.5 to 0.6 KV; the beam intensity preferably ranges from 200 to 1000 mA, more preferably 400 to 800 mA, and further preferably 500 to 600 mA. The embodiments realize the hydrogen abstraction on the surface of the second polymer through the Hall ion source, and realizes at the same time the roughness ranging from 0.1 ?m to 0.4 ?m. In the embodiments, the Ar ions, used in the Hall ion source, are used for hydrogen abstraction and surface micro-etching. The micro-etching nano-structure has a hydrophilic structure with large specific surface area, which can significantly improve the surface energy of the polymer.

(19) In the embodiments, when the surface roughness of the third polymer is greater than 0.4 ?m or less than 0.1 ?m, S1?S3 are repeated until the surface roughness of the third polymer is 0.1?0.4 ?m. If the surface roughness is too small, it means low surface energy and poor hydrophilic, so the combination of high bonding strength cannot be achieved; if the surface roughness is too large, the high frequency loss is large during transmission, so the application of 5G communication cannot be realized. By repeating the Penning ion source-Kaufman ion source-Hall ion source process, a polymer with surface roughness Ra0.1?0.4 ?m is obtained, which has a strong bonding strength with metal. The surface energy of the polymer is proportional to the roughness. The larger the surface roughness is, the larger the surface area of the polymer matrix material is, so that the surface energy of the polymer matrix material is higher, and the bonding strength with other materials is better. On the contrary, the bonding strength is poor. Due to the skin effect, high frequency loss happens easily for the substrate material with high roughness. The embodiments have both the roughness and the bonding strength considered, and realize the regulation of the polymer on high-energy transmission signal loss by controlling the roughness of polymer matrix surface.

(20) In the embodiments, the principles of oxygen insertion, oxygen addition and hydrogen abstraction are as follows:

(21) ##STR00001##

(22) In the embodiments, the polymer after the surface treatment has a dielectric constant greater than 3.0, a surface water absorption greater than 10%, a surface resistance greater than 10.sup.14?, a surface roughness ranging from 0.1 ?m to 0.4 ?m, a hydrophilic contact angle ranging from 40? to 80?, and a 5 GHz high frequency dielectric loss equal to or less than 0.004. The Hall ion source treatment in S3 has a large beam current, which implements etching easily. The large beam current has an influence on the surface roughness of the polymer, and leads to a fever, thus influencing the oxygen insertion and oxygen addition. By controlling the parameters in S1?S3, the polymer realizes the self-healing, and has excellent surface properties.

(23) FIG. 1 is the flow chart of the surface treatment method of the polymer used for 5G of an embodiment. As shown in the FIG. 1, firstly the oxygen insertion is carried out on the surface of the polymer by using a Penning ion source, so that the roughness change of the polymer surface is ?0.1 ?m, and a first polymer is obtained. Then, the Kaufman ion source is used to add oxygen to the surface of the first polymer, so that the roughness change of the surface of the first polymer is less than or equal to 0.1 ?m, and a second polymer is obtained. When the surface resistance of the second polymer is higher than 10.sup.15?, preferably go back to oxygen insertion step, until the surface resistance of the second polymer ?10.sup.15?; Finally, a third polymer is obtained by hydrogen abstraction on the surface of the second polymer using Hall ion source. When the surface roughness of the third polymer is greater than 0.4 ?m or less than 0.1 ?m, S1?S3 are repeated until the roughness of the polymer surface is 0.1?0.4 ?m.

(24) The technical scheme of the application will be described clearly and completely in combination with the embodiments in the application. Obviously, the embodiments described are only part of the embodiments of the application, not all of them. Based on the embodiments in the application, all other embodiments obtained by ordinary technicians in the field without creative labor shall be covered by the protection of the application.

Example 1

(25) S1. The oxygen insertion on the surface of the MPI matrix was carried out by using the Penning ion source. The voltage was 30 KV, the oxygen flow was 60 sccm, and the beam intensity was 25 mA, so that the roughness changes of the polymer surface was less than or equal to 0.1 ?m, and a first polymer was obtained;

(26) S2. The oxygen addition on the surface of the first polymer was carried out by using the Kaufman ion source. The voltage was 15 KV, the oxygen flow was 50 sccm, and the beam intensity was 150 mA, so that the roughness changes of the polymer surface was less than or equal to 0.1 ?m, and a second polymer was obtained. The surface resistance of the second polymer was 2?10.sup.15?, and thus returning to S1 to proceed oxygen insertion and oxygen addition in order, until the resistance of the second polymer was less than 10.sup.15?;

(27) S3. The hydrogen abstraction was carried out on the surface of the second polymer by using the Hall ion source. The voltage was 800V, the gas flow was 100 sccm, the beam intensity was 800 mA, and a third polymer was obtained. The surface roughness of the third polymer is 0.5 ?m, and thus repeating S1?S3, until the roughness of the polymer treated was in a range from 0.1 ?m to 0.4 ?m. The roughness of the polymer in this embodiment was 0.3 ?m after the treatment.

Example 2

(28) S1. The oxygen insertion on the surface of the MPI matrix was carried out by using the Penning ion source. The voltage was 20 KV, the oxygen flow was 60 sccm, and the beam intensity was 25 mA, so that the roughness changes of the polymer surface was less than or equal to 0.1 ?m, and a first polymer was obtained;

(29) S2. The oxygen addition on the surface of the first polymer was carried out by using the Kaufman ion source, the voltage was 10 KV, the oxygen flow was 50 sccm, and the beam intensity was 100 mA, so that the roughness changes of the polymer surface was less than or equal to 0.1 ?m, and a second polymer was obtained. The surface resistance of the second polymer was 2?10.sup.15?, and thus returning to S1 to proceed oxygen insertion and oxygen addition in order, until the resistance of the second polymer was less than 10.sup.15?;

(30) S3. The hydrogen abstraction on the surface of the second polymer was carried out by using the Hall ion source. The voltage was 500V, the gas flow was 110 sccm, and the beam intensity was 800 mA, and a third polymer was obtained. The surface roughness of the third polymer was 0.5 ?m, and thus repeating S1?S3, until the roughness of the polymer treated was in a range from 0.1 ?m to 0.4 ?m. The roughness of the polymer in this embodiment was 0.2 ?m after the treatment.

(31) Performance Test and Verification

(32) 1) Impedance test (15 KV) was performed on pristine MPI and the treated MPI in Example 1. The results were shown in FIG. 2. It can be seen from the FIG. 2 that the impedances of MPI polymer before and after treatment are basically the same at 10.sup.6 high frequency, indicating that ion implantation has no effect on the electrical properties of the substrate material itself.

(33) 2) The surface hydrophilic angle and the surface morphology of the polymer before and after the treatment of Example 1 were tested, and the results were shown in FIGS. 3?6. As can be seen from FIGS. 3-6, the hydrophilicity of the treated polymer surface is significantly enhanced, and the hydrophilic angle changes from 75? to 40?, with a significant decrease and a significant treatment effect. After the treatment, the roughness of the polymer surface increases from 0.12 ?m to 0.23 ?m.

(34) 3) The polymer surface treated and untreated of Example 1 were characterized by XPS, and the results were shown in FIG. 7. As can be seen from FIG. 7, the CF bond on the surface of the polymer untreated is dominating obviously, and the treated polymer is divided into two peaks. It can be seen that the number of CO bond and C?O bond on the surface of the polymer treated increase significantly, and the appearance of CO single bond and C?O double bond are able to significantly increase the surface energy and hydrophilic properties of the polymer.

(35) 4) The pristine MPI and the treated polymer in Examples 1?2 were tested for binding force, and the results were shown in FIG. 8.

(36) The test method was as follows: the pristine polymer and the treated polymer in Examples 1?2, respectively, was attached to the surface of the copper film by compression method (as shown in FIG. 9), and the binding force was tested.

(37) As can be seen from FIG. 8, the binding strength between the treated polymer and the copper film increases significantly, up to 0.9 KG/cm, and the surface treatment effect is obvious.

(38) The above described are only preferred embodiments of the present application, It should be understood by those skilled in the art that, without departing from the principle of the present application, any variations and modifications fall into the scope of the present application.