JP3291237B2 - Coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma C on a member having an organic surface such as a plastic or a paint-coated iron plate.
The present invention relates to a technique for improving the adhesion between an inorganic protective film and an organic substance on the surface of a member when the inorganic protective film is formed using a VD method. The inorganic protective film to which the present invention is applied is mainly transparent in the visible region, and a transparent plastic member to which the inorganic protective film is applied can be used for a vehicle such as an automobile, a train, and a window of a building or a house. It can be used as an abrasion-resistant film of an automobile body or the like to which a paint is applied.

[0002]

2. Description of the Related Art The use of plastic materials such as acryl and polycarbonate has been studied for windows for vehicles such as automobiles and trains in view of demands for weight saving and easy shape design for energy saving. The problem is that the light transmittance is reduced due to the severe environment exposed to wind and rain and the generation of small scratches due to sand and dust, and in the case of a front window of a car, scratching by a wiper has been a problem. In addition, the body for automobiles is also used in a severe environment, so that the appearance is deteriorated due to the occurrence of scratches on the painted surface. Therefore, the present inventors conducted an experiment to increase the mechanical strength and improve the scratch resistance by forming a transparent carbon film having a high hardness on the surface of the plastic having a low mechanical strength and on the painted surface of the body. The effect was confirmed ("Member covered with carbon film and method of making the same", Patent Application Showa 63-
233166 and "Chassis or part covered with carbon film", Japanese Patent Application No. 63-230787).

[0003] However, when environmental tests under high temperature and high humidity were carried out over a long period of time on these members, such as plastics and paint films, provided with these scratch-resistant films, it was found that there was a problem in the adhesiveness of the films. This is due to the fact that the plastic and the coating film are organic substances, impregnated with moisture and expanded to increase the stress of the coating and cause peeling, or the adhesion between the organic substance as the substrate and the coating is not enough, and the minute It is considered that peeling occurred due to the intrusion of water into the gap and the reduction of van der Waals' attractive force.

[0004]

As described above, if the above-mentioned coating is applied to windows for vehicles such as automobiles and trains, automobile bodies, etc., which can be exposed to the weather, the abrasion resistance is improved. Further improvement in adhesiveness was being pursued.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides an organic composite in which a film is formed on a substrate having an organic material such as plastic or paint by using a plasma CVD method. In the bonding region, there is provided an organic composite characterized in that the organic substance and the coating are each mixed, and the manufacturing method thereof is to use power or bias voltage to form the coating. The method is characterized in that a strong voltage is applied in the initial stage, thereby partially melting (partial melt) the organic substance on the substrate surface.

Generally, before forming a film by the plasma CVD method, a plasma is generated with an inert gas such as argon as a pretreatment, and the substrate is sputtered with ions of the inert gas to clean the surface of the substrate, thereby bonding the substrates. Techniques for improving the performance are known. This is a substance that does not easily desorb from the substrate even if it is in a reduced pressure state, such as a substance with a low vapor pressure or water molecules attached to the substrate surface. It is intended for the removal of. There is also known a method of reducing a surface oxidized by plasma such as hydrogen and activating the surface to improve adhesiveness. These are all effects on deposits on the substrate surface or several molecular layers on the substrate surface, and a clear boundary is formed at the interface between the substrate and the coating. On the other hand, the substrate surface has irregularities of about 0.1 μm or less, and a film is selectively formed on the protrusions,
The contact between the substrate and the coating at this boundary is a point contact, and there is a gap of several tens to several hundreds of squares other than the contact part, and the adhesive force of the coating is the van der Waals attractive force or covalent bonding of the contact part. It is known that it is determined by the total area number of the chemical bonding force such as force and the contact area at the protrusion. Therefore, in order to increase the adhesive strength of the coating, it is effective to increase the chemical bonding force between the substrate and the coating and the contact area.

In the present invention, in consideration of the above, in the initial stage of film formation, the substrate surface is heated for a short period of time by plasma, and only the surface portion is melted (partial melt) to reduce the chemical bonding force between the substrate and the coating and the contact area. It has been increased. This has been made effective by using a non-thermosetting organic substrate or a substrate having an organic surface having a low melting point (in some cases, a softening point and a glass transition point). FIG. 1 shows a conceptual diagram of the organic composite of the present invention. An organic substance (101) as a substrate and a film (1) formed by plasma CVD.
02), a partial melt region (103) is formed.

By forming the partial melt region as described above at the beginning of the film formation, the unevenness of the substrate is eliminated.
Therefore, selective film growth due to electric field concentration or the like on the protrusion is eliminated, and as a result, the contact area between the film and the substrate increases. Further, the coating substance (nucleus) grown to a certain size in the gas phase enters the melt region at a speed corresponding to the energy in the plasma, and the coating grows around the nucleus.
Therefore, in the partial melt region, the organic substance as the substrate and the substance constituting the coating film are mixed, and there is almost no substantially non-contact portion, and the adhesive strength increases. Further, the material constituting the substrate is activated by melting, and as a result, a chemical reaction with the substance constituting the film is promoted,
A chemical bonding force such as a covalent bonding force is increased, and the adhesive force is increased.

The partial melt region can be formed by heating with plasma. The plasma heating can be performed simultaneously with the film forming reaction using the plasma of the material gas. There is also a method in which plasma is generated by an inert gas such as argon, xenon, krypton, or the like, a partial melt region is formed on the substrate surface by the inert gas plasma, and then a source gas is introduced to start film formation. In the case of this method, since the raw material gas is introduced after the partial melt portion is formed by the inert gas plasma, the coating material (nucleus) grown to a certain size in the gas phase penetrates deeply into the partial melt portion. And
A film having higher adhesiveness can be obtained.

[0010] Heating of the substrate surface by plasma can be realized by increasing the electric power applied to the plasma. The power applied in the initial stage of film formation is 0.1 W / cm ² or more,
Preferably, it is 1 W / cm ² or more, and the duration of application of electric power applied in the initial stage of film formation is 1 msec.
10 min or less, preferably 100 msec or more and 1
min or less is appropriate. This is because if the applied power is too low, the substrate surface will not melt, and if the applied power is too high, the reaction speed in space will be too high, and the film material will become too large before it becomes a film, and it will become powder. And the duration of application is 1 msec or more, preferably 100 msec or more. The time required for the plasma gas temperature to rise from plasma generation to a sufficient gas temperature, that is, the time required for the plasma to stabilize and the plasma The energy given by the gas is transferred as thermal energy from the substrate surface to conduct as thermal energy, and it is necessary as the time until the substrate surface is melted.The upper limit is not physically significant, but from the demand of tact time, It is not needed.

When starting film formation by introducing a raw material gas after forming a partial melt region on the substrate surface with an inert gas plasma, the plasma of the inert gas is supplied for 1 msec or more prior to the introduction of the raw material gas. 10 min or less,
Preferably a time of 100 msec or more and 1 min or less,
It is preferable to apply power of 0.1 W / cm ² or more, preferably 1 W / cm ² or more. After forming the partial melt region on the substrate surface in this manner, a raw material gas is introduced without stopping the plasma of the inert gas to form a film. Even in the initial stage of the film formation, 0.1 W / cm ² or more is formed. When a high electric power of preferably 1 W / cm ² or more is applied, the energy of the plasma maintains a high energy state corresponding to the electric power, and thus, the speed of the particles generated in the plasma increases, and the particles become in the partial melt region. Will penetrate deeply. A film grows with the particles that have penetrated into the partial melt region as nuclei, and when the film has been formed into a layer of several atoms to several tens of atoms, the power is reduced to normal power, and the film is grown to a predetermined thickness. The adhesive strength of the coating is very strong because the core of the coating that has penetrated deep into the partial melt region acts like an anchoring. Needless to say, since there is a nucleus that penetrates into the partial melt region without applying high power in the early stage of film formation, the presence or absence of high power application in the early stage of film formation does not limit the present invention, The application of high power during the initial stage of film formation is advantageous for adhesion.

The region to be melted by heating has a depth from the surface of 0.01 μm to 1 mm, preferably 0.1 μm.
１００100 μm is appropriate. The lower limit is due to the requirement for obtaining sufficient strength, and the upper limit is due to the problem that if a melt region of 1 mm or more is provided, crystallization of the plastic as a substrate will occur and cloudiness will occur. Even if the melt area is 1 mm or less, crystallization of the plastic occurs, but this is not a problem because the crystal grains are not so large.

The film to be formed is preferably Si _X C _{1 -X} (0 ≦ X ≦ 1) containing a halogen element such as hydrogen or fluorine. The coating is transparent from the visible region to the infrared region and has a high hardness of 1500 kg / mm ² or more, so that it is convenient as a protective film for a transparent member. In addition, since ultraviolet light is absorbed, organic substances on the substrate can be protected from deterioration due to ultraviolet rays.

Further, impurities such as P, B, and N may be added to the formed film at a rate of 10 ppm to 10% (atomic%). The film to which these impurities are added generates carriers of electrons or holes in accordance with the amount of the added impurities, and exhibits a resistivity of 1 × 10 ¹³ to 1 × 10 ⁵ Ωcm. These films having a certain degree of conductivity can be used as protective films for electrophotographic photoreceptors. In addition, since static electricity that is always generated on insulators such as plastics can be prevented, dust and dust can be prevented from being adhered to the insulators. Can be reduced. Also,
When used for an automobile body, it is possible to produce a product that does not attract dust and is less likely to become dirty. Hereinafter, the present invention will be described in detail with reference to examples.

[0015]

【Example】

Embodiment 1 In this embodiment, an example of a front window of an automobile in which a partial melt region is formed by using a substrate bias type positive column plasma CVD method will be described. FIG. 3 shows an outline of a plasma CVD apparatus for performing a thin film forming method on a substrate or a member such as a front window of an automobile.

In the drawing, a reaction vessel (7) of a plasma CVD apparatus is separated from the outside by a gate valve (9). In the gas system (30), argon as an inert gas is converted from hydrocarbon gas (e.g., a saturated hydrocarbon such as methane or ethylene or an unsaturated hydrocarbon) such as methane and ethylene, and silane, disilane or the like from (31). From (32), the silicon-based gas is converted into an additive gas (NF ₃ , NH _3, etc. when the additive is nitrogen, PH ₃ etc. when the additive is P, and B when the additive is B).
₂ H _6, B a (CH _{3) 3} or the like from (33), an etching gas in the reaction vessel CF _4, SF _6, NF ₃ or the like from (34), the valve (28), flow meter (29) And introduced into the reaction system (50) through the nozzle (25). When the flow rate of the silicon-based gas is made lower than that of the carbon-based gas, the Si content in the film becomes lower, and a film containing carbon as a main component is formed. Usually, a film containing carbon as a main component and having a large number of SP ³ bonds is called a diamond-like carbon film. The film of the present invention is similar to the diamond-like carbon film, but further contains Si. As a result, the SP ³ bond is present in a larger amount than the SP ² bond, so that the SP ³ bond is harder, has higher translucency, and the impurity is added in an activated state. This means that carbon can be in either an SP ² or SP ³ bond, while silicon
Promotes SP ³ binding because it can only take SP ³ binding,
This is because it functions as an additive promoter for additives.

The first and second electrodes (3-1) and (3-1) are formed by forming a first pair of electrodes having the same shape above and below the reaction vessel (7).
(3-2) is made of aluminum metal mesh.
The reactive gas is discharged downward from the nozzle (25). Further, third electrodes (13-1), (13-2),... (13-n) (collectively referred to as third electrodes) are arranged in contact with the back surface of the base or the member. The bases or members (1-), (1-2), (1-n) are insulating materials. Here, a second alternating voltage is applied, and a bias is applied in a substantially AC-conducting manner.

A blocking capacitor (61) was inserted between the second alternating voltage source and the substrate or member. A plasma atmosphere or a positive sheet is formed on the organic substance forming surface (1 ') on the substrate or member (1), and a negative self-bias is applied. In order to positively generate the negative self-bias, the frequency of the second alternating voltage is set to 10 kHz to 100 KHz, which is a frequency at which electrons follow an electric field but ions cannot follow a change in the electric field. The substrate or member (1) is the surface on which the organic material is to be formed.
The reactive gas having (1 ') and turned into a glow discharge plasma by the first high frequency alternating voltage is uniformly dispersed in the reaction space (8), and makes the plasma potential in the reaction space uniform.

Further, in order to make the potential distribution in the plasma reaction space more uniform, alternating voltages of two independent frequencies can be applied to the power supply system (40). First
The alternating voltage is a high frequency of 1 to 100 MHz, for example, 13.56 MHz, and is obtained from a pair of two power supplies (15-1), (15-2), that is, (15).
It reaches the matching boxes (16-1) and (16-2) made of LCR circuits. The mutual phases of the matching boxes are adjusted by a phase adjuster (26) so that they can be supplied at 180 ° or 0 ° from each other. It has a symmetric or in-phase output, and has one end (4) of each of the power supplies (15-1) and (15-2).
-1) and (4-2) are a pair of first and second electrodes (3-1) and (3-2)
Respectively. In addition, each power supply (15-
The other ends of 1) and (15-2) are grounded (5-1) and (5-2). Second
10 kHz to 100 KHz, for example, an alternating voltage of 50 kHz is connected from the power supply (17) to the third electrodes (13-1),... (13-n) and is applied.

The exhaust system (25) includes a pressure adjusting valve (21),
Unnecessary gas is exhausted through a molecular pump (22) and a rotary pump (23). These reactive gases enter the reaction space (60).
0.001 to 1.0 torr For example, 0.05 torr.

The present invention is characterized in that plasma is generated in such a space, and the surface of the organic substrate is melted by the energy of the plasma. In this embodiment, a case is described in which a substrate surface is first melted with argon plasma before the start of film formation, and then a raw material gas is introduced to form a film. FIG. 2A is a time chart of the flow rates of the argon and the source gas, and FIG. 2B is a time chart of the input power. Time t ₀
At time t ₁ , the flow of argon was started, and at time t ₁ ,
5-1), (15-2) a pair of first and second electrodes (3-1), (3
-2), a high-frequency electric field is applied, and the power at this time is 1
0 kW (6 W / cm ² per unit area). This power is much larger than a normal power density of about 0.5 W / cm ² . Therefore, at this time, the organic material surface is melted by the argon plasma. t ₁ to t ₂
The time required until the surface of the organic material melts is sufficient. In this case, the time is set to 3 seconds. Introducing a raw material gas at the time t _2, the film forming from this point is started.

At the same time, the application of an AC bias by the second alternating voltage is started, spatter is generated by the self-bias electric field, and a dense film having high hardness is formed. Time t
_{In step 3} , the flow of argon is stopped, and thereafter, the plasma is made only of the source gas. Thereby, a high film forming speed can be realized. At time t ₄ , the applied power is
Until the power is reduced to kW, the temperature of the plasma is kept high, and the precursor or nucleation particles present in the plasma penetrate deeply into the partial melt region at a high speed, thereby achieving good adhesion. I can do it. t ₂ to t
The time up to ₄ may be 60 seconds in this embodiment, as long as nuclei are generated in the partial melt region and several tens of mm of the film are formed. The time from t ₂ to t ₃ is a transition period from an argon plasma to the source gas plasma, but it is not matter at 0 seconds and 10 seconds in the present embodiment. Time t ₄
Thereafter, a normal film forming process is performed. That is, 0.5 to 5 KW of the frequency of 13.56 MHz (0.03 to 3 W / cm ² per unit area) For example, 1.2 K
By applying a first high-frequency voltage of W (high energy of 0.7 W / cm ² per unit area) and applying an AC bias by a second alternating voltage, -200 to -600 V (for example, An output is applied with a negative self-bias voltage of 1 KW, and the reactive gas accelerated by the negative self-bias voltage is sputtered onto the substrate or member surface to form a film, thereby forming a dense film.

The source gas is, for example, a mixed gas of ethylene, silane and hydrogen. The ratio is typically 1/1/1. Further, fluorine may be added by C ₂ F ₆ or the like. The temperature of the substrate or member (1) is maintained at ~ 150 ° C, typically at room temperature without external heating. Thus, the specific resistance on the surface to be formed has 1 × 10 ⁶ Ωcm, and the main component is carbon or carbon to which hydrogen, nitrogen, and silicon having an amorphous structure or a crystal structure transparent to visible light are added. 0.1 to 8 μm, for example 0.5 μm (planar part), 1 to 3 μm
m (convex portion), a film could be formed on the organic resin with very good adhesion. The deposition rate was 100-1000 ° / min.

Thus, a coating containing carbon as a main component in the front window and other members which are members, in particular, contains not more than 30 atomic% of hydrogen in carbon, and contains 0.1 to 10 atomic% of nitrogen and 10 atomic% or less of silicon. Could be formed. A first carbon consisting of only ethylene was formed on the organic material to a thickness of 100 to 2000 mm, and a multilayer film mainly composed of carbon to which fluorine and hydrogen were added could be formed thereon. FIG. 4 shows a film containing carbon as a main component, which is formed on the main part of the light-transmitting organic material.

FIG. 4A is a longitudinal sectional view of a front window (1) of an automobile. The cross section is shown in FIG. In FIGS. 4A and 4B, the light-transmitting plastics (1) is lightweight, and is made of, for example, an acrylic resin. On the substrate or member (1) having the surface to be formed, carbon or a wear-resistant protective film (45) containing carbon as a main component is applied to the substrate or member (1).
The thickness was set to 1 to 8 μm.

In this embodiment, the partial melt region is formed by introducing argon before the start of film formation. However, the partial melt region may be formed by using only the source gas plasma without introducing argon. And a strongly applied power from the power supplies (15-1) and (15-2).
-1) and (3-2), but the third electrode (13-
(1),... (13-n) may be strongly applied to form a partial melt region. It goes without saying that an inert gas such as xenon or krypton may be used in addition to argon.

Embodiment 2 In this embodiment, a method of providing a partial melt region in a film forming method by atmospheric pressure discharge will be described. FIG. 5 shows a sectional view of the apparatus and a system diagram of a gas system and an electric system at the same time. The center conductor (201), the cylindrical insulator (202), and the purge gas nozzle (203) are coaxially arranged,
The center conductor (201) is supported on an insulating support (204).
Center conductor (201), purge gas nozzle (203) is stainless steel, cylindrical insulator (202) is quartz glass, insulating support (204)
Is composed of Teflon. Purge gas nozzle (203)
Has a double structure of a coaxial cylinder, in which a purge gas is introduced at about 1 atm between the double structures, and the purge gas is ejected from an outlet (206). The outlet (206) is directed outward so as to blow in the outer peripheral direction. Discharge occurs between the central conductor (201) and the cylindrical insulator (202), generating radicals. The generated radicals are carried by the gas flow in the direction of the substrate (271), and in the present invention, the solenoid (261) and the permanent magnet (262) are further provided on the outer periphery of the apparatus and the substrate holder (270), respectively.
Arranged on the back side, radicals are drawn out along the magnetic flux in the direction of the substrate (271). The outer diameter of the central conductor (201) is 1 mm, and the inner and outer diameters of the cylindrical insulator (202) are 1.7 mm and 2, respectively.
5 mm. The length of the discharge space was 20 mm.

The substrate (271) was made of polycarbonate and set on a substrate holder (270) made of a paramagnetic material, stainless steel. The substrate (271) is not actively heated. The distance from the end of the discharge space to the substrate surface was 1 mm.

The gas introduced into the discharge space is regulated by a pressure regulator (221) from a source gas cylinder (211), and the flow rate of the source gas is controlled by a flow controller (241) via a stop valve (231). And similarly helium gas cylinder (212)
The pressure is regulated by the pressure regulator (222) and the stop valve (23
Helium gas whose flow rate is controlled by the flow rate controller (242) via 2) is mixed and introduced into the discharge space.
The raw material gas cylinder (211) contains hydrogen gas balanced 1
It is filled with 0% methane gas. The mixing ratio of helium and the source gas was 99: 1 (source gas 1%). The total flow rate of helium and the source gas is 100 sccm.

The power supplied to the central conductor (201) is supplied from a high frequency power supply (251) via a blocking capacitor (253). The power supply frequency was 13.56 MHz, and the effective input power was 20 W. The bias voltage, which is a feature of the present invention, is supplied from the bias power supply (252) to the high-frequency blocking coil 1 (25).
5) The voltage was applied through the high frequency blocking coil 2 (256). The bypass capacitor (254) has a role of releasing high-frequency power passing through the high-frequency blocking coil 1 (255) and protecting the bias power supply (252).

In this embodiment, the bias initially applied is set to -1000 V with respect to the substrate holder as a DC voltage. The time is 2 seconds, and then the applied bias voltage is -100 V
Decreased to. The substrate surface was partially melted during the high bias application time at the initial stage of film formation, thereby improving the adhesiveness.

The purge gas was supplied from a cylinder (213) to a pressure regulator (22).
The pressure is adjusted by 3), and the flow rate is controlled by a flow controller (243) via a stop valve (233) to be supplied to a purge gas nozzle. In this embodiment, nitrogen was used as the purge gas. The flow rate is 1000 sccm.

A hard carbon film was formed on a polycarbonate substrate by the above-described apparatus and method. The film was formed at a very high rate of 0.2 μm / min immediately below the opening of the discharge region, but hardly generated powder, and was a good film with few pinholes. The hardness measured by a microindentation hardness meter was about 3000 kgf / mm ² , and the transmittance in the visible region in the spectral transmittance measurement was 90% or more, which was almost transparent. In addition, according to FT-IR, Raman spectroscopy, and the like, it was found that the ratio of sp3 bond to sp2 bond was 1.6 to 1, indicating a structure close to that of diamond.

Although the film forming apparatus was not moved in this embodiment, it is needless to say that a film can be uniformly formed on a large-area substrate by scanning the plane at a constant speed.

Although not described in this embodiment, a hard carbon film can be formed on a cylindrical substrate. In this case, the discharge opening of the donut-shaped film forming apparatus is directed toward the inner periphery, and is moved up and down at a constant speed by a vertical mechanism at a speed corresponding to the film forming speed, so that the film is formed on the surface of the cylindrical substrate set at the center. It can also be formed.

The adhesive strengths of the coatings prepared in Examples 1 and 2 and the coatings prepared by the conventional method (without providing a partial melt area) were compared by the following test methods.

"Adhesion test method" A polycarbonate having a film formed on its surface is immersed in warm water at 50 ° C for 10 days, then left at room temperature for 1 day, and a cellophane tape is adhered and peeled to cause peeling of the film. Check if you want to. "Adhesion Test Results" The results of the above experiments are summarized in Table 1 below.

[0038]

[Table 1]

As described above, the coating provided with the partial melt region has a very good adhesiveness, and the transparent organic composite using the coating has sufficient reliability even in a severe environment where it can be exposed to wind and rain. It was confirmed that it had.

[0040]

The organic composite obtained by providing the partial melt region using the organic substance of the present invention has high practicality and reliability and is industrially useful.

[Brief description of the drawings]

FIG. 1 shows the concept of the organic composite of the present invention.

FIG. 2 shows a time chart of the flow rate and power at the beginning of film formation.

FIG. 3 shows an outline of a plasma CVD apparatus of an embodiment.

FIG. 4 shows an example in which a carbon film or a protective film containing carbon as a main component is coated on a member such as a front window of the embodiment, and an essential part thereof.

FIG. 5 shows a cross-sectional view of a coaxial cylindrical film forming apparatus and a system diagram of gas and electric systems.

[Explanation of symbols]

 Reference Signs List 101 Organic substrate 102 Plasma CVD film 103 Partial melt region

【Reference number】

[Table 1]

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI C30B 29/04 C30B 29/04 R // C08L 101: 00 C08L 101: 00 (56) References JP-A-63-11671 (JP) JP-A-62-157602 (JP, A) JP-A-60-195092 (JP, A) JP-A-1-245562 (JP, A) JP-A-1-201476 (JP, A) 54-85274 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 16/00-16/56 C01B 31/00-31/36 C30B 29/04 C08J 7/00-7 / 04 JICST file (JOIS)

Claims (11)

(57) [Claims] 1. A gas-phase reaction apparatus having a pair of electrodes and a power supply for applying DC or AC power to the electrodes is used to form hydrogen or fluorine on a substrate having an organic material surface. a method of forming a _{Si X C 1-X (0} ≦ X ≦ 1) film containing oxygen, a first step of placing the substrate between the upper or of said electrodes, between the electrodes A second step of introducing an inert gas; and applying a first power from the power supply to the electrode to plasmatize the inert gas between the electrodes, thereby melting the surface of the substrate by the plasma. a third step, a fourth step of introducing a material gas between the electrodes, hydrogen if by applying a second power from the power source to the electrode
Or a fifth step of forming a Si _X C _1-X (0 ≦ X ≦ 1) film containing fluorine on the substrate. 2. A pair of electrodes consisting of first and second electrodes, a third electrode for applying a bias, a first power supply for applying DC or AC power to the pair of electrodes,
Using gas phase reactor having a second power supply for applying a power of DC or AC to the third electrode, organic table
Si _X C containing hydrogen or fluorine on a substrate having a surface
_{1-X (0 ≦ X ≦} 1) A method of forming a coating on the upper or second electrode of the first electrode, or the first placing the substrate between the pair of electrodes A second step of introducing an inert gas between the pair of electrodes; and applying a first power from the first power supply to the pair of electrodes to apply the inert gas between the pair of electrodes. A third step in which the active gas is turned into plasma and the surface of the substrate is melted by the plasma; and a source gas is introduced between the pair of electrodes and a bias is applied to the third electrode from the second power supply. fourth step _{and, Si X C 1-X (} 0 ≦ X ≦ containing hydrogen or fluorine and applying a second power from the first power source to the pair of electrodes for applying
1) A method for forming a film, comprising a fifth step of forming a film on the substrate. 3. A pair of electrodes comprising first and second electrodes, a third electrode for applying a bias, a first power supply for applying DC or AC power to the pair of electrodes,
Using gas phase reactor having a second power supply for applying a power of DC or AC to the third electrode, organic table
Si _X C containing hydrogen or fluorine on a substrate having a surface
_{1-X (0 ≦ X ≦} 1) A method of forming a coating on the upper or second electrode of the first electrode, or the first placing the substrate between the pair of electrodes And a second step of introducing an inert gas between the pair of electrodes; and applying a first power from the second power supply to the third electrode to apply a first power to the third electrode. A third step of turning the inert gas into plasma and melting the surface of the substrate with the plasma; and introducing a source gas between the pair of electrodes and applying a bias to the third electrode. process _{and, Si X C 1-X (} 0 ≦ X ≦ containing hydrogen or fluorine and applying a second power from the first power source to said pair of electrodes
1) A method for forming a film, comprising a fifth step of forming a film on the substrate. 4. The method according to claim 1 , wherein the substrate having an organic material surface has hydrogen or
Forms a Si _X C _1-X (0 ≦ X ≦ 1) film containing fluorine
A first power is applied to convert the inert gas into plasma,
A first step of melting the surface of the substrate, a second step of introducing a source gas, and a step of applying a second power to apply Si _x containing hydrogen or fluorine.
A third step of forming a C _1-X (0 ≦ X ≦ 1) coating on the substrate;
A film forming method, comprising the steps of: 5. The method according to claim 5 , wherein the substrate having an organic material has hydrogen or
Forms a Si _X C _1-X (0 ≦ X ≦ 1) film containing fluorine
A first power is applied to convert the inert gas into plasma,
A first step of melting the surface of the substrate, and applying a second power to apply Si _x containing hydrogen or fluorine.
A second step of forming a C _1-X (0 ≦ X ≦ 1) coating on the substrate;
A film forming method, comprising the steps of: 6. any one smell of claims 1 4
And stopping the introduction of the inert gas after the introduction of the source gas . 7. claimed in any one of claims 1 to 6, the film forming method characterized in that said first power is greater than the second power. 8. according to any one of claims 1 to 6, and the first power greater than said second power,
And the application time of the first power is 1 msec or more and 10 m or more.
a method for forming a coating film, wherein the thickness is not more than in. 9. A any one of claims 1 to 8, the film forming method characterized in that the said first power 0.1 W / cm ² or more. 10. The method according to claim 1, wherein the substrate is from 0.01 μm to 0.01 μm.
Film forming method according to any one of claims 1 9, characterized in that the melt depth in the region of 1 mm. 11. The any one of claims 1 10, wherein the inert gas is argon, the film forming method which is a xenon or krypton.