TWI852435B - A method and equipment for producing a heterogeneous dopant containing plasma organic compound thin film - Google Patents

Abstract

The present invention provides a method and equipment for producing a heterogeneous dopant containing plasma organic compound thin film. The plasma organic compound thin film comprises a matrix film generated by the plasma chemical reaction device and a doped material as a heterogeneous material produced by hollow cathode device. As such, the present invention provides a combined process, in terms of plasma chemical reaction device and hollow cathode device, to form the heterogeneous dopant containing plasma organic compound thin film. The method of the present invention comprises introducing a precursor into a plasma reaction chamber for plasma chemical reaction, and using a hollow cathode device in the same plasma reaction chamber to sputter the cathode material through the hollow cathode discharge reaction. The sputtering species is introduced to the plasma reaction chamber by using an inert gas to form the heterogeneous dopant containing plasma organic compound thin film. By utilizing combined process, the present invention is able to produce silver doped parylene film and silver doped diamond-like carbon film to provide its antibacterial function. Therefore, the present invention is able to prepare the heterogeneous dopant containing plasma organic compound thin film and provide multifunctional properties.

Description

A method and apparatus for manufacturing heterogeneous doped plasma organic thin film

A method for manufacturing an organic thin film and an apparatus thereof, in particular, a method for manufacturing a heterogeneous doped plasma organic thin film and an apparatus thereof.

Surface modification technology refers to the technology that only processes the surface of materials, such as carburizing, nitriding, boronizing, laser treatment, ion implantation, roughening, functionalization and coating. Among them, the use of coating technology to modify the surface of materials has been widely used in the fields of civil industry, optoelectronics, semiconductors and biomedicine.

In addition to the choice of coating materials determining the surface properties that coating can impart, with the increasing demand for multifunctional and unique surface properties, concepts such as composite materials, control of surface structure, or development of advanced coating technologies have been proposed one after another.

Taking various medical catheters as an example, silicone is widely used because of its biological inertness, softness and high flexibility. However, due to its easy adhesion and high friction, silicone needs to be modified on the surface in actual clinical applications. It is coated with Parylene film with good biocompatibility, no cytotoxicity and dry lubricity to reduce the pain and foreign body sensation of the patient.

However, it is not uncommon for patients to contract bacterial infections from the use of medical equipment. Severe bacterial infections may lead to sepsis and multiple organ failure, which may lead to the patient's death. The reasons include that various medical catheters are in direct contact with human soft tissues and body fluids for a long time, making them the medical products with the highest chance of bacterial infection. The antibacterial effect of polyparaxylene film is limited, and at most it can only achieve the effect of bacteria inhibition.

If silver metal with antibacterial properties is doped into the polyparaxylene film, it will give the polyparaxylene film additional antibacterial properties, thereby effectively reducing the risk of patients undergoing invasive medical procedures and postoperative bacterial infections.

Among the process options for introducing silver metal doping sources into plasma polyparaxylene film, the use of organic metal compounds is an effective precursor for providing silver metal, but the cost of organic metal compounds is relatively high and they are usually highly toxic compounds, so they are not suitable for medical devices that come into contact with the human body. If you consider using magnetron sputtering with silver metal targets for doping, it is known that the process pressure of magnetron sputtering is ~10 ^-3 Torr, which is very different from the process pressure of ~10 ^-1 Torr commonly used in plasma polymerization processes, so it is not suitable as a process method for introducing silver metal.

Although silver metal can be grown on the surface of plasma polyparaxylene film using wet chemical process, it requires a two-stage process, and the silver metal grown by wet chemical process has poor adhesion, so there is a risk of falling off and even causing toxicity to human cells.

In view of this, there is an urgent need for a technology that can dope the polyparaxylene film with silver metal that has antibacterial properties and has process and equipment advantages.

In order to improve the existing preparation of silver-doped polyparaxylene film, the cost of using organic metal compounds is relatively high and may be highly toxic. The process pressure of magnetron sputtering and plasma polymerization is very different. The wet chemical process is relatively complicated and the silver metal adhesion is poor. The present invention provides a heterogeneous doped electroplating film. A plasma organic film manufacturing device comprises a plasma reaction chamber, a plasma chemical reaction power supply, a hollow cathode discharge unit and a vacuum unit, wherein: The plasma reaction chamber is a vacuum sealable chamber, in which two parallel electrode plates are arranged, divided into a first electrode plate and a second electrode plate, the plasma chemical reaction power supply and the second The electrode plate is electrically connected; the hollow cathode discharge unit includes a fixed insulating sleeve, a vacuum sealing mechanism, a flange, a cathode sputtering tube, an anode shielding cover and a hollow cathode discharge power supply; the cathode sputtering tube is a tubular structure, which is electrically connected to the hollow cathode discharge power supply, and the cathode sputtering tube includes a gas inlet and a hollow cathode Plasma outlet; the fixed insulating sleeve is sleeved on the cathode sputtering tube at the gas inlet, and the cathode sputtering tube is fixed on the flange by the fixed insulating sleeve; the cathode sputtering tube uses the vacuum sealing mechanism to vacuum seal the cathode sputtering tube and the flange; and the anode shielding cover is sleeved on the outside of the cathode sputtering tube and fixed on the flange.

Wherein, the first electrode plate and the second electrode plate are arranged face to face in parallel up and down.

Among them, the plasma chemical reaction power supply and the hollow cathode discharge power supply include a direct current power supply, a pulsed direct current power supply, a radio frequency power supply or an ultra-high frequency power supply.

Wherein, the first electrode plate includes a gas diffusion plate.

The anode shielding cover is sleeved on the outside of the cathode sputtering tube, and there is a gap of 1mm~5mm between the two tube walls.

Among them, the inner diameter of the cathode sputtering tube is between 1mm and 100mm, and the material includes metal, ceramic or a combination thereof.

The vacuum unit reduces the pressure in the plasma reaction chamber.

The present invention further provides a method for manufacturing heterogeneous doped plasma organic thin films using the aforementioned manufacturing equipment, the steps of which include: Placing a substrate on the second electrode plate; passing a reaction precursor through the first electrode plate into the plasma reaction chamber; using the second electrode plate to generate plasma in the plasma reaction chamber using the plasma chemical reaction power supply, and allowing the reaction precursor to undergo a plasma chemical reaction to form a plasma organic thin film species in the plasma reaction chamber; placing the cathode sputtering tube using the hollow cathode The power supply excites a hollow cathode plasma and sputters the cathode sputtering tube to form a sputtering species; and an inert gas is introduced into the cathode sputtering tube from the gas inlet, so that the sputtering species of the hollow cathode plasma in the cathode sputtering tube is transferred from the hollow cathode plasma outlet to the plasma chemical reaction environment of the plasma reaction chamber outside the tube, so as to be mixed with the plasma organic film species to form a heterogeneous doped plasma organic film species, and grow on the surface of the substrate to obtain the heterogeneous doped plasma organic film.

The hollow cathode discharge unit and the plasma reaction chamber operate simultaneously, independently or alternately to perform the overall doping or partial doping of the sputtering species into the plasma organic film species.

The gas of the reaction precursor is flow-controlled by a gas flow meter.

Wherein, the reaction precursor comprises polyparaxylene or diamond-like carbon precursor; the metal target is a silver target; and the inert gas comprises helium, argon and/or krypton.

The inert gas is flow-controlled by a gas flow meter.

From the above description, it can be seen that the present invention proposes a method for preparing a heterogeneous doped plasma organic film, which utilizes a composite plasma coating technology to dope silver metal into a plasma polyparaxylene film and a diamond-like carbon film to make it have antibacterial properties. Therefore, this heterogeneous doped plasma organic film process will be able to achieve the preparation of a composite composition film and provide multifunctional surface properties.

10: Manufacturing equipment for heterogeneous doped plasma organic films

11: Plasma reaction chamber

111: Plate electrode

111A: First electrode plate

111B: Second electrode plate

12: Plasma chemical reaction power supply

13: Hollow cathode discharge unit

131:Fixed insulation sleeve

132: Vacuum sealing mechanism

133:France

134: Cathode sputtering tube

134A: Gas inlet

134B: Hollow cathode plasma outlet

135: Anode shield

136: Hollow cathode discharge power supply

14: Vacuum unit

20: Reaction precursors

30: Heterogeneous doped plasma organic film

40: Base material

50: Plasma organic film species

60: Splash species

70: Heterogeneous doped plasma organic film species

80: Inert gas

S1~S5: Steps

In order to more clearly explain the technical solution of the embodiment of the present invention, the following will briefly introduce the drawings required for the description of the embodiment. Obviously, the drawings described below are only some examples or embodiments of the present invention, and are not absolutely used to limit the technical scope of the present invention. Unless it is obvious from the previous and following texts or otherwise explained, the same reference numerals in the figures represent the same structure or operation. Among them: Figure 1 is a schematic diagram of a preferred embodiment of the manufacturing equipment of the heterogeneous doped plasma organic film of the present invention.

Figure 2 is a schematic diagram of a preferred embodiment of the hollow cathode discharge unit of the present invention.

Figure 3 is a flow chart of a preferred embodiment of the heterogeneous doped plasma organic film manufacturing method of the present invention.

Figures 4A and 4B show the cross-sectional microscopic morphology of plasma polyparaxylene film and silver-doped plasma polyparaxylene film grown by composite plasma plating technology in Example 1 of the present invention.

Figures 4C and 4D show the cross-sectional microscopic morphology of plasma diamond-like carbon film and silver-doped plasma diamond-like carbon film grown by composite plasma plating technology in the second embodiment of the present invention.

Figure 5 shows the compositional depth analysis of the silver-doped plasma polyparaxylene film in Example 1 of the present invention using an X-ray photoelectron spectrometer.

Figure 6 shows the analysis of the silver doping content of the silver-doped plasma diamond-like carbon film grown at different silver metal hollow cathode powers using energy dispersive X-ray spectroscopy in the present invention.

Figures 7A and 7B show the growth of E. coli colonies on plasma polyparaxylene films and silver-doped plasma polyparaxylene films grown by the composite plasma coating technology of the present invention after 24 hours of plate culture.

The present invention will be described in detail below with several preferred embodiments. The attached diagrams are only some exemplary representatives or embodiments of the present invention. For those with ordinary knowledge in the field to which the present invention belongs, the present invention can also be applied to other similar situations based on these attached diagrams without making any progressive efforts.

The "system", "device", "unit" and/or "module" used in the present invention below are a method for distinguishing different components, elements, parts, parts or assemblies at different levels. However, if other words can achieve the same purpose, the words can be replaced by other expressions. As shown in the present invention, unless the context clearly indicates an exception, the words "one", "a", "a kind" and/or "the" do not specifically refer to the singular, but may also include the plural. Generally speaking, the terms "including" and "comprising" only indicate that the steps and elements that have been clearly identified are included, and these steps and elements do not constitute an exclusive list. The method or device may also include other steps or elements.

Flowcharts are used in the present invention to illustrate the operations performed by the system according to the embodiments of the present invention. It should be understood that the preceding or succeeding operations are not necessarily performed in exact order. Instead, the steps may be processed in reverse order or simultaneously. At the same time, other operations may be added to these processes, or one or more operations may be removed from these processes.

<Equipment for manufacturing heterogeneous doped plasma organic thin films>

Please refer to FIG. 1 , the present invention discloses a heterogeneous doped plasma organic thin film manufacturing device 10, which includes a plasma reaction chamber 11, a plasma chemical reaction power supply 12, a hollow cathode discharge unit 13 and a vacuum unit 14.

The plasma reaction chamber 11 is a vacuum sealable chamber, in which two parallel electrode plates 111 are arranged, as shown in FIG1 . A preferred embodiment of the two electrode plates 111 is to be arranged face to face in parallel, and to be divided into a first electrode plate 111A and a second electrode plate 111B. The plasma chemical reaction power supply 12 is preferably electrically connected to the second electrode plate 111B with a negative electrode. Preferably, the first electrode plate 111A and the second electrode plate 111B are arranged face to face in parallel up and down.

The plasma chemical reaction power supply 12 can be a DC power supply, a pulsed DC power supply, a radio frequency power supply or an ultra-high frequency power supply, etc.

The first electrode plate 111A is preferably a gas diffusion plate to evenly pass the gas of a reaction precursor 20 into the plasma reaction chamber 11.

Further with FIG. 2 , the hollow cathode discharge unit 13 includes a fixed insulating sleeve 131, a vacuum sealing mechanism 132, a flange 133, a cathode sputtering tube 134, an anode shielding cover 135 and a hollow cathode discharge power supply 136.

The cathode sputtering tube 134 is a tubular structure, which is electrically connected to the hollow cathode discharge power supply 136. The cathode sputtering tube 134 includes a gas inlet 134A and a hollow cathode plasma outlet 134B.

The fixed insulating sleeve 131 is sleeved on the cathode sputtering tube 134 at the gas inlet 134A; and the cathode sputtering tube 134 is fixed on the flange 133 by the fixed insulating sleeve 131 to achieve electrical insulation. The cathode sputtering tube 134 uses the vacuum sealing mechanism 132 to vacuum seal the cathode sputtering tube 134 and the flange 133.

The anode shielding cover 135 is sleeved on the outside of the cathode sputtering tube 134 and fixed on the flange 133. There is preferably a gap of 1mm~5mm between the two tube walls for electrical insulation. The cathode sputtering tube 134 of the present invention preferably has an inner diameter of 1mm~100mm, and the material includes metal, ceramic or a combination thereof.

The hollow cathode discharge power supply 136 includes a DC power supply, a pulsed DC power supply, a radio frequency power supply or an ultra-high frequency power supply. The vacuum unit 14 reduces the pressure in the plasma reaction chamber 11, preferably to a decompression environment with a pressure lower than one atmosphere.

<Method for manufacturing heterogeneous doped plasma organic film>

Referring to FIG. 3 , the present invention uses the above-mentioned heterogeneous doped plasma organic film manufacturing equipment 10 to prepare a manufacturing method of a heterogeneous doped plasma organic film 30, and the steps include: step S1) placing a substrate 40 on the second electrode plate 111B; step S2) passing the reaction precursor 20 through the first electrode plate 111A into the electrode plate 111B; In the plasma reaction chamber 11; Step S3) the second electrode plate 111B is used to generate plasma in the plasma reaction chamber 11 by using the plasma chemical reaction power supply 12, and the reaction precursor 20 is subjected to a plasma chemical reaction to form a plasma organic thin film species 50 in the plasma reaction chamber 11; Step S4) the cathode sputtering tube In step S5), an inert gas 80 is introduced into the cathode sputtering tube 134 from the gas inlet 134A to make the hollow cathode discharge plasma 137 in the cathode sputtering tube 134. The sputtering species 60 of the plasma 137 is transferred from the hollow cathode plasma outlet 134B to the plasma chemical reaction environment of the plasma reaction chamber 11 outside the tube to be mixed with the plasma organic film species 50 to form a heterogeneous doped plasma organic film species 70, and grows on the surface of the substrate 40 to obtain the heterogeneous doped plasma organic film 30.

Preferably, the gas of the reaction precursor 20 in the aforementioned step S2 is preferably flow-controlled by a gas flow meter. The reaction precursor 20 includes polyparaxylene or a diamond-like carbon precursor, such as paraxylene or a hydrocarbon. The inert gas 80 includes helium, argon and/or krypton, preferably argon. The inert gas 80 is preferably flow-controlled by a gas flow meter.

Furthermore, the hollow cathode discharge unit 13 of steps S4 and S5 of the present invention can operate simultaneously, independently or alternately with the plasma reaction chamber 11 to perform overall or partial doping of heterogeneous materials into the plasma organic film.

<Implementation examples and validation tests>

In the first embodiment, the heterogeneous doped plasma organic film 30 is a silver doped plasma polyparaxylene film. The plasma polyparaxylene film is obtained by using liquid paraxylene as the reaction precursor 20, using argon to carry its vapor into the plasma reaction chamber 11, using a short pulse plasma power supply as the plasma chemical reaction power supply 12, and performing plasma polymerization chemical reaction. The silver metal doping is to use a silver metal tube as the cathode sputtering tube 134 of the hollow cathode discharge unit 13. In this embodiment, the inner diameter of the silver metal tube is 6 mm. A pulsed DC plasma power supply 136 is used to excite the hollow cathode plasma 137, and argon is used as the inert gas 80 to sputter the silver. The seed 60 is blown out of the tube to be mixed in the plasma polymerization chemical environment of the plasma reaction chamber 11. During the growth process of the plasma polyparaxylene film, the silver metal is doped in the plasma polyparaxylene film. Only in the last 10 minutes of the plasma polymerization chemical reaction growth of the plasma polyparaxylene film, the silver metal hollow cathode device is opened to perform silver metal doping in the extreme surface of the plasma organic film.

Please refer to FIG. 4A and FIG. 4B, which are respectively the cross-sectional microscopic morphologies of a pure plasma polyparaxylene film (comparative example without silver doping) and a silver doped plasma polyparaxylene film of Example 1 of the present invention made by the aforementioned manufacturing apparatus and manufacturing method of the present invention; wherein the parameters of the plasma polyparaxylene film grown by the plasma polymerization chemical reaction are the same. It can be seen from the figure that since silver metal is doped in the plasma polyparaxylene film, the obtained film thickness is thicker. Further analysis of the silver-doped plasma polyparaxylene film using energy dispersive X-ray spectroscopy revealed that the doping amount of silver metal in the plasma polyparaxylene film was 1.15at.%, and it was confirmed that silver metal was indeed doped in the plasma polyparaxylene film.

The present invention provides another preferred embodiment 2, taking the heterogeneous doped plasma organic film 30 as a silver doped plasma diamond-carbon film as an example. The plasma diamond-carbon film is obtained by using acetylene and argon as the reaction precursors 20 and a pulsed DC plasma power supply as the plasma chemical reaction power supply 12 to perform a plasma chemical reaction. The silver metal doping is to use a silver metal tube as the cathode sputtering tube 134 of the hollow cathode discharge unit 13. The inner diameter of the silver metal tube is 6 mm. A pulsed DC plasma power supply 136 is used to excite the hollow cathode plasma 137. Argon is used as the inert gas 80 to sputter the silver. The seed 60 is blown out of the tube to be mixed in the plasma polymerization chemical environment of the plasma reaction chamber 11. During the growth process of the plasma diamond-carbon film, the silver metal is doped in the plasma. Only in the last 10 minutes of the plasma chemical reaction growth of the plasma diamond-carbon film, the silver metal hollow cathode device is opened to perform silver metal doping in the extreme surface of the plasma diamond-carbon film.

Figure 4C and Figure 4D are cross-sectional microscopic morphologies of a plasma diamond-carbon film (comparative example without silver doping) and a silver-doped plasma diamond-carbon film of Example 2 of the present invention respectively produced by the aforementioned production equipment and production method of the present invention; wherein the parameters of the plasma diamond-carbon film grown by plasma chemical reaction are the same. It can be seen from the figure that since silver metal is doped in the plasma diamond-carbon film, the obtained film thickness is thicker.

Figure 5 is a compositional depth analysis of the silver-doped plasma polyparaxylene film of the aforementioned Example 1 using an X-ray photoelectron spectrometer. It can be seen from the figure that the surface layer of the obtained coating film has a region rich in silver metal, which is consistent with the coating result of this example.

Figure 6 uses energy dispersive X-ray spectroscopy to analyze the silver doping amount of the silver-doped plasma diamond-carbon film grown at different silver metal hollow cathode powers. It can be seen from the figure that with the increase of the silver metal hollow cathode power, the silver doping amount of the obtained silver-doped plasma diamond-carbon film increases almost linearly; when the silver metal hollow cathode power is 150W, the silver metal doping amount in the plasma diamond-carbon film is 1.60at.%, and it can be confirmed that silver metal is indeed doped in the plasma diamond-carbon film.

FIG7A and FIG7B show the growth of E. coli colonies on a comparative example of a plasma polyparaxylene film grown using a composite plasma coating technology and an example of a silver-doped plasma polyparaxylene film after 24 hours of plate culture. It can be clearly seen in the figure that E. coli colonies are generated on the surface of the plasma polyparaxylene film, but once silver metal doping is performed, the resulting silver-doped plasma polyparaxylene film can significantly reduce the formation of colonies, and no E. coli colonies are generated. Further quantitative antibacterial activity value calculation using JIS Z 2801 shows that the antibacterial activity values of plasma polyparaxylene film and silver-doped plasma polyparaxylene film are 0 and 5.95 respectively. Antibacterial activity value > 2.0 indicates antibacterial efficacy, so it can be seen that this silver-doped plasma polyparaxylene film has excellent antibacterial effect.

In some embodiments, numbers describing the quantity of components and attributes are used. It should be understood that such numbers used in the description of the embodiments are modified by the modifiers "approximately", "approximately" or "substantially" in some examples. Unless otherwise specified, "approximately", "approximately" or "substantially" indicate that the numbers are allowed to vary by ±20%. Accordingly, in some embodiments, the numerical parameters used in the specification and the claim are approximate values, which may vary according to the required features of the individual embodiments. In some embodiments, the numerical parameters should consider the specified significant digits and adopt the general digit retention method. Although the numerical domains and parameters used to confirm the breadth of the scope of the invention in some embodiments are approximate values, in specific embodiments, the settings of such numerical values are as accurate as possible within the feasible range.

Finally, it should be understood that the embodiments described in the present invention are intended only to illustrate the principles of the embodiments of the present invention. Other variations may also fall within the scope of the present invention. Therefore, as an example and not a limitation, alternative configurations of the embodiments of the present invention may be considered consistent with the teachings of the present invention. Accordingly, the embodiments of the present invention are not limited to the embodiments explicitly introduced and described in the present invention.

10: Manufacturing equipment for heterogeneous doped plasma organic films

11: Plasma reaction chamber

111:Electrode plate

111A: First electrode plate

111B: Second electrode plate

12: Plasma chemical reaction power supply

13: Hollow cathode discharge unit

131:Fixed insulation sleeve

132: Vacuum sealing mechanism

133:France

134: Cathode sputtering tube

134A: Gas inlet

134B: Hollow cathode plasma outlet

135: Anode shield

136: Hollow cathode discharge power supply

14: Vacuum unit

20: Reaction precursors

30: Heterogeneous doped plasma organic film

40: Base material

50: Plasma organic film species

60: Splash species

70: Heterogeneous doped plasma organic film species

80: Inert gas

Claims (12)

A manufacturing device for heterogeneous doped plasma organic film comprises a plasma reaction chamber, a plasma chemical reaction power supply, a hollow cathode discharge unit and a vacuum unit, wherein: the plasma reaction chamber is a vacuum sealable chamber, in which two parallel electrode plates are arranged, which are divided into a first electrode plate and a second electrode plate, and the plasma chemical reaction power supply is electrically connected to the second electrode plate; the hollow cathode discharge unit comprises a fixed insulating sleeve, a vacuum sealing mechanism, a flange, a cathode sputtering tube, an anode shielding cover and a hollow cathode discharge power supply. The cathode sputtering tube is a tubular structure, which is electrically connected to the hollow cathode discharge power supply, and includes a gas inlet and a hollow cathode plasma outlet; the fixed insulating sleeve is sleeved on the cathode sputtering tube at the gas inlet, and the cathode sputtering tube is fixed to the flange by the fixed insulating sleeve; the cathode sputtering tube uses the vacuum sealing mechanism to vacuum seal the cathode sputtering tube, the flange and the reaction chamber in the cathode sputtering tube; and the anode shielding cover is sleeved on the outside of the cathode sputtering tube and fixed to the flange. The manufacturing equipment of heterogeneous doped plasma organic film as described in claim 1, wherein: the first electrode plate and the second electrode plate are arranged face to face in parallel up and down. The manufacturing equipment of heterogeneous doped plasma organic thin film as described in claim 1, wherein: the plasma chemical reaction power supply and the hollow cathode discharge power supply include a DC power supply, a pulsed DC power supply, a radio frequency power supply or an ultra-high frequency power supply. The manufacturing equipment of heterogeneous doped plasma organic film as described in claim 1 or 2, wherein: the first electrode plate includes a gas diffusion plate. The manufacturing equipment of heterogeneous doped plasma organic film as described in claim 1, wherein: the anode shielding cover is set on the outside of the cathode sputtering tube, and there is a gap of 1mm~5mm between the two tube walls. The manufacturing equipment of heterogeneous doped plasma organic film as described in claim 1, wherein: the inner diameter of the cathode sputtering tube is between 1mm and 100mm, and the material includes metal, ceramic or a combination thereof. The manufacturing equipment of heterogeneous doped plasma organic thin film as described in claim 1, wherein: the vacuum unit reduces the pressure in the plasma reaction chamber. A method for manufacturing a heterogeneous doped plasma organic film, the steps of which include: providing a manufacturing device for a heterogeneous doped plasma organic film as described in any one of claims 1 to 7; placing a substrate on the second electrode plate; passing a reaction precursor through the first electrode plate into the plasma reaction chamber; the reaction precursor comprises polyparaxylene or diamond-like carbon precursor; using the second electrode plate to generate plasma using the plasma chemical reaction power supply, and causing the reaction precursor to undergo a plasma chemical reaction to form a plasma organic film species in the plasma reaction chamber; sputtering the cathode The hollow cathode discharge power supply of the tube excites a hollow cathode plasma, and sputters the inner wall of the cathode sputtering tube to form a sputtering species, and the sputtering species is silver metal; and an inert gas is introduced into the cathode sputtering tube from the gas inlet, so that the sputtering species of the hollow cathode plasma in the cathode sputtering tube is transferred from the hollow cathode plasma outlet to the plasma chemical reaction environment of the plasma reaction cavity outside the tube, so as to be mixed with the plasma organic film species to form a heterogeneous doped plasma organic film species, and grow on the surface of the substrate to obtain the heterogeneous doped plasma organic film. The manufacturing method of heterogeneous doped plasma organic film as described in claim 8, wherein: the hollow cathode discharge unit and the plasma reaction chamber operate simultaneously, independently or alternately to perform the whole doping or partial doping of the sputtering species into the plasma organic film species. The method for manufacturing a heterogeneous doped plasma organic film as described in claim 8 or 9, wherein: the gas of the reaction precursor is flow-controlled by a gas flow meter. A method for manufacturing a heterogeneous doped plasma organic film as described in claim 8 or 9, wherein: the inert gas is flow-controlled by a gas flow meter. A method for manufacturing a heterogeneous doped plasma organic film as described in claim 8 or 9, wherein: the inert gas comprises helium, argon and/or krypton.