KR100897323B1 - Method for coating thin film on material by Plasma-enhanced chemical vapor deposition and physical vapor deposition - Google Patents

Abstract

The present invention relates to a thin film coating method of a combination of plasma chemical vapor deposition and physical vapor deposition to ensure corrosion resistance and electrical conductivity properties by combining PECVD method and arc discharge method, and a product thereof.

To this end, an inert gas for activating the substrate surface and removing residual organic matter is pretreated in the chamber to pretreat the substrate surface, and a reaction gas for inducing arc discharge is introduced into the chamber to perform arc discharge of the target. At the same time, the electrons of the target induced by arc discharge are collected on the anode to promote decomposition of the reaction gas, and the decomposed reaction gas is adsorbed on the surface of the substrate by applying a bias voltage to the substrate and inflow from the target in this process. Forming a thin film of conductive and corrosion-resistant on the substrate by containing a metal ion to be characterized in that the coating of the thin film on the substrate.

According to the above-described configuration, since the thin film is coated on the substrate by the arc discharge method and the PECVD method, the electrical conductivity and the corrosion resistance are improved, which is excellent in producing fuel cell separator products, and the substrate and the intermediate layer are coated on the substrate surface. There is also an effect that can improve the adhesion between the coating layer.

Plasma chemical vapor deposition, arc discharge, fuel cell, separator, Me-C: H layer.

Description

Method for coating thin film on material by Plasma-enhanced chemical vapor deposition and physical vapor deposition}

1 is a photograph illustrating a graphite separator that is generally used,

Figure 2 is a photograph illustrating a metal separator plate that is generally used,

Figure 3 is a schematic diagram schematically showing a coating apparatus used for the plasma chemical vapor deposition invented by the present applicant,

4 is a perspective view schematically illustrating a structure in which a DLC layer is coated on a substrate through the coating apparatus of FIG. 3;

5 is a schematic diagram schematically showing a coating apparatus for coating a thin film on a substrate by the plasma chemical vapor deposition method and the arc discharge method according to the present invention;

6 is a block diagram sequentially listing one embodiment of the coating method according to the present invention;

7 is a perspective view schematically illustrating a structure in which a Me-C: H layer is coated on a substrate through the coating method of FIG. 6;

8 is a block diagram sequentially listing another embodiment of the coating method according to the present invention;

9 is a perspective view schematically showing a structure in which an intermediate layer and a Me-C: H layer are coated on a substrate through the coating method of FIG. 8;

10 is a bonding structure and the surface photograph comparing the coating layer using the coating method of the present invention and the coating layer using the PECVD method,

Figure 11a is a table showing the characteristics of the coating layer coated through the coating method of the present invention,

Figure 11b is a table comparing the characteristics of the coating layer having the intermediate layer and the coating layer not forming the intermediate layer according to the present invention,

12 is a surface and cross-sectional photograph of the product formed Me-C: H layer according to the present invention and the actual photograph of the product,

13 is a graph diagram and a table comparing the corrosion resistance characteristics of the coating layer coated by the present invention and the coating layer using the PECVD method.

* Description of Major Symbols in Drawings *

100 substrate 110 substrate

200: intermediate layer 300: Me-C: H layer

400: chamber 410: vacuum pump

420: gas inlet device 430: arc gun

435: shielding film 440: anode

P100: Plasma Pretreatment Process P200: Arc Discharge Process

P200 ': Interlayer Coating Process P300: Coating Process

The present invention relates to a method for coating a thin film on a substrate and a product thereof, and more particularly, by applying a coating technique using arc discharge to a DLC film by plasma chemical vapor deposition (PECVD), high electrical conductivity characteristics with corrosion resistance The present invention relates to a thin film coating method and a product, which are a combination of plasma chemical vapor deposition and physical vapor deposition.

In general, a fuel cell converts chemical energy generated by oxidation of a fuel directly into electrical energy. Recently, research has been focused on CO ₂ emission control and fossil fuel alternative energy to prevent global warming.

In particular, among the fuel cell parts, the separator is an important core part of the fuel cell together with the membrane electrode assembly, which requires excellent cell conductivity, thermal conductivity, gas sealing property, and corrosion resistance, and has low process cost, miniaturization, and light weight in manufacturing. Is one of the required items.

Thus, as a conventional separator, as shown in FIG. 1, a graphite separator manufactured by machining graphite or molding graphite and a composite material was used, and until recently, automobiles have excellent electric conductivity, thermal conductivity, and chemical stability. And it is in the situation that is mainly used for domestic fuel cells.

However, the graphite separation plate by machining of the graphite separation plate has a disadvantage in that a high manufacturing cost is a problem in the nature of manufacturing the separation plate by machining. Therefore, although some problems that require high cost in manufacturing the separator through extrusion / injection molding of the graphite / resin composite material are solved, it is fatal that the strength of the separator is lowered due to the material characteristics of the composite material including carbon. A problem occurred.

Figure 2 is an example of a metal separator for solving the problems described above, due to the characteristics of a metal material having excellent strength and ductility is in the situation that the development of a metal separator using a metal material is being actively made. In particular, the development of metal separators using stainless steel and titanium alloys, which has the advantage of using a thin plate of 0.2 mm or less with low manufacturing cost and low hydrogen transmittance, has been highlighted.

However, in the metal separator, the dissolution of SO ₃ ⁻ and F ⁻ present in the electrolyte and water in the battery by the fuel cell reaction proceeds together, and the fuel cell operation temperature is operated at a high temperature of about 80 ° C., There is a closure that creates a very corrosive environment.

In addition, since the dissolution of the metal due to corrosion contaminates the electrolyte and the coating is insulated due to the continuous growth of the passivation film on the metal surface, an increase in contact resistance also causes a problem of degrading the performance of the fuel cell.

Therefore, a coating technology for securing excellent electrical conductivity and corrosion resistance at the same time has been developed and applied to the metal separator plate. Table 1 below shows examples of coating materials applicable to the metal separator plate and the characteristics of the coating technology. And disadvantages.

Coating material Characteristic Remarks ◆ Precious Metals-Au, Pt, etc. -Excellent corrosion resistance-Excellent electrical conductivity: Suppression of oxidizing passivation film -High raw material price ◆ metal compound-nitride-carbide-boride -Excellent corrosion resistance compared to metal-Excellent electrical conductivity compared to oxide-Excellent mechanical surface properties can be secured simultaneously -Limited to dry method-Difficult to secure mass production. -Low adhesion ◆ Carbon / Graphite -Excellent corrosion resistance and heat conductivity. Chemical Stability-Excellent Electrical Conductivity ◆ polymer coating -Securing corrosion resistance using polymer-Securing conductivity through dispersion of carbon (graphite) particles in polymer coating layer -Deterioration of conductivity due to difficulty in dispersing carbon-based particles

That is, as the coating material, noble metals, metal compounds, carbon / graphite, polymers, and the like are applied, and the coating material is deposited by a wet method and a sputtering method. However, precious metals have a disadvantage of being expensive, and metal compounds and carbon-based films have a problem that it is difficult to secure mass productivity, and polymer coating has a closed end due to difficulty in dispersing carbon-based particles.

On the other hand, Figure 3 is a patent application No. 2006-84713 "Applicant's Patent Application No. 2006-84713" thin film coating method and the product by the plasma chemical vapor deposition, which the applicant filed on September 4, 2006, the surface of the substrate 10 is activated And pre-treat the surface of the substrate 10 by introducing a reaction gas for removing residual organic matter into the chamber 40, and adding a reaction gas for improving adhesion to the DLC layer 30 in the chamber 40. Coating the intermediate layer 20 on the surface of the substrate 10 and injecting a reaction gas for improving corrosion resistance and mold release property and lubricity into the chamber 40 to form a DLC (Diamond Like Carbon) layer on the surface of the intermediate layer 20. Coating.

That is, aC: H (DLC, Diamond Like Carbon) layer coated on the surface of the metal material by the plasma chemical vapor deposition (PECVD) as described above contains a large amount of hydrogen in the coating film using a hydrocarbon gas. The DLC layer has excellent corrosion resistance to SO ₃ ⁻ and F ⁻ present in the fuel cell electrolyte as compared to the metal compound, and the fuel operated at 80 ° C. because the oxidation temperature of the DLC layer is 400 ° C. or lower. Chemical stability can be ensured even in a battery.

However, there are many crosslinkings between the mixture of SP ³ and SP ² and the carbon clusters, so that the electrical characteristics of the DLC film show the characteristics of the insulator.

The present invention has been made to solve the conventional problems as described above, by applying a coating technology using arc discharge to the DLC layer by the plasma chemical vapor deposition (PECVD) to secure high electrical conductivity characteristics with corrosion resistance. It is to provide a thin film coating method and a product of a combination of plasma chemical vapor deposition and physical vapor deposition.

Another object of the present invention is to perform a surface coating to improve the conductivity and corrosion resistance of metal materials through PECVD method and arc discharge method, thereby enabling a low-cost coating process, and plasma chemical vapor deposition that enables mass production of products. It is to provide a thin film coating method and a product of the composite of physical vapor deposition.

The thin film coating method of the present invention for achieving the above object comprises a plasma pretreatment step of pretreating the substrate surface by injecting an inert gas into the chamber to activate the substrate surface and remove residual organic matter; An arc discharge step of injecting a reaction gas for inducing arc discharge into the chamber to perform arc discharge of the target and at the same time collecting electrons of the target induced by arc discharge on the anode to promote decomposition of the reaction gas; And applying a bias voltage to the substrate to adsorb the decomposed reaction gas on the surface of the substrate, and in the process, a coating process for forming a conductive and corrosion-resistant thin film on the substrate by containing metal ions flowing from the target. It is done.

On the other hand, the thin film coating substrate produced by the thin film coating method of the present invention, the surface is activated by the plasma pre-treatment and the residual organic material is removed; Me-C: H layer coated on the surface of the substrate by the chemical vapor deposition method using the arc discharge method and the reaction gas using a target to improve the conductivity and corrosion resistance.

In addition, another thin film coating substrate produced by the thin film coating method of the present invention includes a substrate on which the surface is activated by the plasma pretreatment and residual organics are removed; An intermediate layer coated on the surface of the substrate by an arc discharge method using a target to improve conductivity and adhesion to a Me-C: H layer; Me-C: H layer coated on the surface of the intermediate layer by the chemical vapor deposition method using the arc discharge method and the reaction gas using a target to improve the conductivity and corrosion resistance.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The thin film coating method combining the plasma chemical vapor deposition and the physical vapor deposition of the present invention comprises a plasma pretreatment step (P100), an arc discharge step (P200), and a coating step (P300).

First, in the plasma pretreatment process (P100), the reaction gas for activating the surface of the substrate 100 and removing residual organic matter is introduced into the chamber 400 to pretreat the surface of the substrate 100.

5 to 7, after loading the substrate 100 into the chamber 400, the pressure inside the chamber 400 is 10 ⁻⁵ Torr or less using the vacuum pump 410. The vacuum state is maintained and Ar and H ₂ , which are inert gases, are introduced into the chamber 400 through the gas inlet device 420. Here, the surface of the substrate 100 may be pretreated by further adding N ₂ together with Ar and H ₂ as the reaction gas, and in some cases, plasma pretreatment may be performed using N ₂ or He.

In addition, by generating and maintaining a plasma by applying a pulsed bias voltage to the substrate 100 through a power supply device, a chemical reaction occurs in the plasma, thereby activating (etching) the surface of the substrate 100 and treating it by organic cleaning. Residual organic matter on the surface of the substrate 100 failed to be removed (cleaned).

In addition, as another method for pretreating the surface of the substrate 100, metal ions among the discharge particles discharged through arc discharge of the target may be pretreated by reaching the surface of the substrate 100.

In the arc discharge process (P200), a reaction gas for inducing arc discharge is introduced into the chamber 400 to perform arc discharge of the target, and at the same time, electrons of the target induced by arc discharge are collected on the anode 440. Promote decomposition of the reaction gas.

In more detail with respect to the arc discharge process (P200), a reaction gas such as a carbon compound is introduced into the chamber 400. Then, a cathode power is applied to the arc gun 430 to arc discharge the target installed in the arc gun 430 to draw electrons, while an anode power is applied to the anode 440 to anode electrons of the target induced by arc discharge. Collect at 440. In this case, electrons are continuously released into the chamber 400 to improve electron density and electron temperature, thereby facilitating decomposition of the carbon compound in the chamber 400.

Here, as the carbon compound, a reaction gas such as propane (C ₃ H ₈ ), acetylene (C ₂ H ₂ ), methane (CH ₄ ) may be used, and in addition to the above-described reaction gas, other gases including hydrocarbons may be used. It can be used that corresponds to the obvious matters in the configuration of the present invention.

The target used for the arc discharge may be any one of transition metals, but it is appropriate to use Ti. In addition, the reaction gas decomposed through the arc discharge process (P200) is divided into neutral hydrocarbons and carbon ions due to the nature of the carbon compound used.

Subsequently, in the coating process P300, a decomposed hydrocarbon and carbon ions are applied to the substrate 100 by applying a bias voltage to the substrate 100, and the metal ions introduced from the target in this process are adsorbed. It is contained on the surface of (100) to form a conductive and corrosion-resistant thin film on the substrate (100).

In this case, the substrate 110 is rotated during the arc discharge process P200 and the coating process P300 to ensure uniformity of the film coated on the substrate 100. The Me-C: H layer 300 is formed on the surface of the substrate 100 through the coating process P300. In addition, the electrical potential of the Me-C: H layer 300 may be improved by increasing the bias potential applied to the substrate 100.

Meanwhile, after the plasma pretreatment process of the present invention and before the arc discharge process (P200), the arc discharge method is applied to the surface of the substrate 100 to improve the adhesion between the substrate 100 and the thin film and to improve the conductivity of the final thin film. It may include an intermediate layer coating process (P200 ') to form the intermediate layer 200 through.

Referring to the method for an embodiment of the above-described intermediate layer coating process (P200 ') through Figures 5 and 8, 9, after the pre-treatment of the surface of the substrate 100, Ti is installed in the arc gun 430 Arc coating is performed by applying an arc power source to the arc gun 430 to coat the intermediate layer 200 containing Ti on the surface of the substrate 100.

In addition, the method for another embodiment of the intermediate layer coating process (P200 ') described above, after pretreatment of the surface of the substrate 100, Cr is installed in the arc gun 430, the arc gun 430 An arc power is applied to the arc discharge to coat the intermediate layer 200 containing Cr on the surface of the substrate 100.

Here, although Ti and Cr are exemplified in the present invention as the metal material used for coating the intermediate layer 200, the present invention is not limited thereto, and any metal material suitable for improving adhesion may be applied to the intermediate layer 200 in the present invention.

On the other hand, a preferred embodiment of the coating substrate is coated by a thin film coating method that is a combination of the plasma chemical vapor deposition and physical vapor deposition as described above, the Me-C: H layer 300 is deposited on the surface of the substrate 100 It is composed.

Referring to Figure 7, the substrate 100 of the present invention is typically applied to a fuel cell separator used in a fuel cell, such as stainless steel, titanium alloys, aluminum alloys, etc. that can be utilized as a metal material of the fuel cell. It is applied as a material that can reduce the weight and manufacturing cost.

The substrate 100 has a surface activated by plasma pretreatment to form a predetermined etching depth and to remove residual organic matter. In addition, the surface of the substrate 100 is coated with a Me-C: H layer 300 by an arc discharge method using a target and a chemical vapor deposition method using a reaction gas to improve conductivity with corrosion resistance.

Subsequently, in another embodiment of the coating substrate of the present invention, the intermediate layer 200 is coated on the surface of the substrate 100, and the Me-C: H layer 300 is deposited on the surface of the intermediate layer 200.

Referring to FIG. 9, the surface of the substrate 100 is activated by plasma pretreatment to form a predetermined etching depth and to remove residual organic material. In addition, the intermediate layer 200 is coated on the surface of the substrate 100 by an arc discharge method using a target to improve the conductivity of the substrate 100 and to improve adhesion to the Me-C: H layer 300. In addition, the surface of the intermediate layer 200 is coated with a Me-C: H layer 300 by an arc discharge method using a target and a chemical vapor deposition method using a reaction gas to improve conductivity along with corrosion resistance.

As described above, the coating apparatus used to coat the Me-C: H layer 300 on the substrate 100 is as shown in FIG. 5. And a gas inlet device 420 through which the inert gas and the reaction gas are introduced, and a substrate 110 is installed at the center of the lower end of the chamber 400, and a substrate to be coated on the substrate 110. The 100 is raised, and a vacuum pump 410 is installed at a lower portion of the chamber 400.

In addition, an arc device for arc discharge is installed at one side of the chamber 400, an anode device for collecting electrons is installed at the other side of the chamber 400, and a shielding film 435 between the arc device and the substrate 100. This is installed. Here, the shielding film 435 is fixed to the center of the upper end of the chamber 400 is transferred up, down, or is configured to rotate left, right.

In addition, a power supply device for supplying power to the arc gun 430 of the arc device and the anode 440 of the anode device is connected and installed, respectively, and a power supply device for applying bias power to the substrate 110 is connected and installed.

Referring to the operation and effect of the present invention configured as described in detail as follows.

In order to coat the Me-C: H layer 300 on a substrate 100 such as a fuel cell separator plate of a fuel cell component by using a thin film coating method that combines plasma chemical vapor deposition and physical vapor deposition of the present invention, A reaction gas for plasma pretreatment is introduced into the chamber 400 to activate (etch) the surface of the substrate 100, and remove residual organic material on the surface of the substrate 100 that has not been treated by cleaning (organic cleaning).

After the pretreatment, a reaction gas for arc discharge is introduced into the chamber 400 to induce arc discharge. At this time, since the plasma shielding film 435 is installed between the arc gun 430 and the base material 100 where the arc discharge is made, it is appropriate to prevent the discharge particles discharged and drawn out by the arc discharge to reach the base material 100. In some cases, arc discharge may be performed while the plasma shielding film 435 is opened.

However, even when the shielding film 435 is closed, the ions among the discharge particles discharged by the arc discharge may partially reach the base material 100 beyond the shielding film 435, and thus, instead of the plasma pretreatment through the above characteristics, Arc discharge may be performed by another method of cleaning.

Subsequently, when the above-described arc discharge is started to improve conductivity and corrosion resistance, current is applied to the anode 440 on the opposite side to collect electrons induced by the arc discharge. At this time, when the electrons are collected in the anode 440 region, the inflow of the electrons from the arc source into the gas phase of the reactor is continued to maintain an electrically neutral plasma state. The introduced electrons can maintain a very high electron density and electron temperature compared to the conventional single arc discharge method or PECVD method, thereby promoting decomposition of hydrocarbons, which are reaction gases, in the chamber 400.

Subsequently, when a negative voltage bias is applied to the workpiece, a film is formed by adsorption of decomposed neutral hydrocarbons (radicals) and carbon ions, and carbon is formed by ion bombardment of an inert gas ionized from the gas phase in the process of forming the film. The clustering of is suppressed to form nanonized graphite clusters, and the Me-C: H layer 300 is formed on the surface of the substrate 100 through the impact of metal ions flowing from the arc source by the bias and the inclusion in the film. .

As such, the metal-containing and nanonized graphite film is synthesized from the insulating film into a conductive film through the suppression of crosslinking between carbon clusters and metal-containing properties, and a film having excellent adhesion due to collision of metal ions by an arc source and carbon ions is formed. .

However, by forming the intermediate layer 200 before the coating of the Me-C: H layer 300 as described above, better adhesion between the substrate 100 and the Me-C: H layer 300 can be expected. In addition, the electrical conductivity may also be further improved through the coating of the intermediate layer 200.

10 is a comparison of the internal carbon bond structure of the DLC layer by the conventional PECVD method and the Me-C: H layer 300 by the coating method of the present invention through a Raman analysis method, the present invention is Ti arc arc target The experiment was performed.

As a result, the Me-C: H layer 300 of the present invention and the existing DLC layer can be seen that the carbon bond structure is significantly different, more specifically, the Me-C: H layer of the present invention In the structure of 300 and the existing DLC layer, D and G peaks appear respectively. In the conventional DLC layer, the G peak is predominant and the D peak is somewhat weak.

Here, G (Graphite) peak is the "graphite structure with carbon ring" is evidence that there is a carbon bond of the black research tank inside the film, D (Disorder) peak is "incomplete carbon ring and partially broken carbon bond" As the carbon ring means an unfinished bonding state, the carbon bonding state can be known according to their strength and position.

Thus, looking at the above experimental results, in the structure of the Me-C: H layer 300 of the present invention, it is possible to confirm the graphitization of the carbon bonds and the increase of the clusters by shifting the G peak to the long wavelength, Increasing the intensity and increasing the ratio of the strength can confirm the increase of unfinished carbon ring and the increase of carbon cluster.

Therefore, it can be seen from the surface photograph that the structure of the Me-C: H layer 300 formed through the present invention is more graphitized than the general DLC layer, and is grown to form a collection of very fine carbon clusters. It can be confirmed that a more smooth and beautiful film is formed than the existing DLC layer.

In addition, in the coating process (P300) of the present invention, by applying a lower anode current compared to the current of the arc source, it was possible to form the Me-C: H layer 300 on the substrate 100, It was confirmed that the electrical conductivity could be gradually improved by increasing the anode current for the collection.

11A is an experimental result for explaining the relationship between the properties of the Me-C: H layer 300 containing Ti and electrical conductivity, and FIG. 11B is a Me-C: H layer 300 according to the formation of the intermediate layer 200. Experimental results to explain the relationship between the characteristics of and).

As can be seen from the above experimental results, it can be seen that the Me-C: H layer 300 of the present invention exhibits excellent electrical conductivity as compared to the DLC layer by PECVD method, in particular on a metal plate such as stainless steel In the case of coating the Me-C: H layer 300, the sheet resistance value was measured to be about 7 mΩ / cm 2, indicating that the electrical conductivity was very excellent, and the Me-C: H layer (which formed the intermediate layer 200) ( When the Me-C: H layer 300 without the intermediate layer 200 is formed, the Me-C: H layer 300 having the intermediate layer 200 has better adhesion and electrical conductivity. It can be confirmed.

12 is a cross-sectional photograph of the surface of the silicon and stainless steel plate on which the Me-C: H layer 300 is formed as described above, and the actual photograph synthesized on the metal plate is additionally attached.

13 is an experimental result for confirming the corrosion resistance characteristics of the Me-C: H layer 300 coated on the substrate 100, it was confirmed that the more excellent corrosion resistance characteristics than the DLC layer coating by the conventional PECVD method Could.

On the other hand, the present invention has been described in detail only with respect to the specific examples described above it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, it is natural that such variations and modifications belong to the appended claims. .

As described above, the present invention can further improve the electrical conductivity and corrosion resistance of the substrate by coating the Me-C: H layer on the surface of the substrate subjected to plasma pretreatment by arc discharge and plasma chemical vapor deposition (PECVD). Therefore, it is used as an optimal coating method for parts requiring excellent electrical conductivity and corrosion resistance, such as a fuel cell separator, thereby improving the performance of the fuel cell.

Furthermore, prior to coating the Me-C: H layer on the surface of the substrate, by coating an intermediate layer for improving adhesion, not only the electrical conductivity but also the adhesion between the substrate and the Me-C: H layer are improved. Therefore, the Me-C: H layer can be more firmly coated on the surface of the base material, which also has the effect of blocking the peeling of the coating layer.

In addition, since the Me-C: H layer is easily coated on a substrate such as a fuel cell separator by combining the arc discharge method and the plasma chemical vapor deposition method (PECVD) as described above, more substrates are used than the conventional coating process such as the sputtering process. Charging and coating are done in one step. Therefore, mass production of the product can be realized by increasing the number of parts manufactured by coating per unit time, and through this mass production of products, the cost of coating can be reduced by accounting for more than 95% of the manufacturing process. There is also an effect that can promote.

Claims (24)

Plasma pretreatment (P100) for pretreating the surface of the substrate 100 by injecting an inert gas into the chamber 400 to activate the surface of the substrate 100 and remove residual organic matter; Injecting a reaction gas for inducing arc discharge in the chamber 400 to perform arc discharge of the target and at the same time to capture the electrons of the target induced by the arc discharge to the anode 440 to facilitate decomposition of the reaction gas Arc discharge process (P200); By applying a bias voltage to the substrate 100, the decomposed reaction gas is adsorbed onto the surface of the substrate 100, and metal ions flowing from the target in the process are included to form a thin film of conductivity and corrosion resistance in the substrate 100. Thin film coating method comprising a combination of plasma chemical vapor deposition and physical vapor deposition, characterized in that it comprises a coating step (P300) to form. The method of claim 1, wherein the plasma pretreatment step (P100) maintains the pressure inside the chamber 400 at a vacuum of 10 ^-5 Torr or less, and maintains inert gas Ar and H ₂ in the chamber 400. Plasma chemical vapor deposition and physical vapor deposition, wherein the plasma 110 is activated by applying a bias voltage to the substrate 110 to maintain and generate plasma around the substrate 100, thereby activating the surface of the substrate 100 and removing residual organic substances. Composite thin film coating method. 3. The method of claim 2, wherein in the plasma pretreatment step (P100), pretreatment is possible by further adding N ₂ together with Ar and H ₂ . [Claim 2] The plasma chemistry of claim 1, wherein the metal ions of the discharge particles discharged through the arc discharge of the target can be pretreated by reaching the surface of the substrate 100 as a method for pretreating the surface of the substrate 100. Thin film coating method that combines vapor deposition and physical vapor deposition. The method of claim 1, wherein in the arc discharge process (P200), a reaction gas such as a carbon compound is introduced into the chamber 400, and a cathode power is applied to the arc gun 430 to target the target installed in the arc gun 430. At the same time, with the arc discharge, electrons are drawn to the anode 440 to collect the electrons of the target induced by the arc discharge on the anode 440, and the electrons are continuously discharged into the chamber 400 to keep the electron density. And the plasma chemical vapor deposition and physical vapor deposition, characterized in that to improve the electron temperature, thereby promoting the decomposition of the carbon compound in the chamber (400). The method of claim 5, wherein the carbon compound is a combination of plasma chemical vapor deposition and physical vapor deposition, characterized in that any one of propane (C ₃ H ₈ ), acetylene (C ₂ H ₂ ), methane (CH ₄ ). Thin film coating method. 6. The method of claim 5, wherein a shielding film 435 is further provided between the arc gun 430 and the substrate 100 to prevent the metal particles of the arc-discharged target from directly reaching the substrate 100. Thin film coating method that combines plasma chemical vapor deposition and physical vapor deposition. The thin film coating method of claim 5, wherein the target is any one of transition metals. 6. The thin film coating method of claim 8, wherein the target is formed of Ti, using plasma chemical vapor deposition and physical vapor deposition. The thin film coating method according to claim 1 or 5, wherein the reaction gas decomposed through the arc discharge process (P200) is a neutral hydrocarbon and carbon ions. [6] The plasma chemical vapor deposition process according to claim 1 or 5, wherein the conductivity of the finally coated thin film can be improved by increasing the current applied to the anode 440 during the arc discharge process P200. Thin film coating method that combines physical vapor deposition. According to claim 1, Plasma chemical vapor deposition and physical vapor deposition, characterized in that to improve the conductivity of the final coating film by increasing the bias voltage applied to the substrate 100 in the coating process (P300) Composite thin film coating method. The plasma chemical vapor deposition method of claim 1, wherein the substrate 110 is rotated to ensure uniformity of the film coated on the substrate 100 during the arc discharge process P200 and the coating process P300. Thin film coating method that combines physical vapor deposition. 2. The method of claim 1, wherein the thin film formed through the coating process (P300) is a Me-C: H layer (300). The intermediate layer coating process of claim 1, wherein the intermediate layer 200 is formed on the surface of the substrate 100 to improve adhesion between the substrate 100 and the thin film and improve conductivity of the final thin film before the arc discharge process P200. Thin film coating method comprising a plasma chemical vapor deposition and physical vapor deposition characterized in that it further comprises (P200 '). The method of claim 15, wherein the intermediate layer coating process (P200 ') after the pre-treatment of the surface of the substrate 100, Ti is installed in the arc gun 430, the arc power is applied to the arc gun 430 by arc discharge And coating the intermediate layer (200) containing Ti on the surface of the substrate (100). The method of claim 15, wherein the intermediate layer coating step (P200 ') after the pre-treatment of the surface of the substrate 100, Cr is installed in the arc gun 430, arc power is applied to the arc gun 430 by arc discharge Thin film coating method comprising a combination of plasma chemical vapor deposition and physical vapor deposition, characterized in that for coating the intermediate layer (200) containing Cr on the surface of the substrate (100). delete delete delete delete delete delete delete

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