JP3236569B2 - Coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for coating carbon or a carbon-based film having an optical energy bandwidth of 1.0 eV or more, particularly 1.5 to 5.5 eV, on a surface of a member for electric use. These solid surface reinforcements,
Alternatively, the present invention relates to a composite for obtaining a protective material against mechanical stress.

[0002]

2. Description of the Related Art Regarding the coating of a carbon film, a patent application “composite having a carbon film and a method for producing the same” filed by the present inventor (Japanese Patent Application No. 56-146930, filed on Sep. 17, 1981) It has been known. In addition, the carbon film has many characteristics such as high smoothness and high thermal conductivity at the same time as being a wear-resistant material, and is expected to be applied to electric parts and the like.

[0003] Carbon or carbon having an amorphous (amorphous) structure having hardness similar to diamond or a semi-amorphous (semi-amorphous) structure having microcrystallinity of 5 to 200 mm on a surface to be formed is mainly used. In the case of forming a film as a component, in the vicinity of a high-frequency application electrode provided with a substrate having a surface to be formed, positive ions accelerated by self-bias caused by accumulation of electrons in the plasma at the high-frequency application electrode (for example, H ⁺ ) collides with the carbon or carbon-based film being formed to form a carbon film with a greater hardness and a structure close to diamond, with the carbon or carbon-based film as the main component. Have done that. This eliminates the hydrogen atoms bonded to increase the carbon or, or a carbon atom having a bond of C-C to reduce the proportion of carbon having a double bond such as C = C by colliding positive ions This is because the so-called three-way carbon having sp ² hybrid orbitals and the so-called two-way carbon having sp hybrid orbitals are eliminated, and the ratio of so-called tetragonal carbon having sp ³ hybrid orbitals is increased so that diamond bonding is easily caused. Therefore, when an attempt is made to form carbon having a higher hardness or a coating containing carbon as a main component, the self-bias generated between the electrodes must be increased to increase the acceleration of positive ions. As a method for increasing the self-bias, first, a first method is used.
There is a method for reducing the reaction pressure. This is because the number of hydrocarbon gas molecules contained in a unit volume is reduced by reducing the pressure of carbon or a hydrocarbon gas used to form a film containing carbon as a main component. This is based on the fact that the output of the high-frequency energy applied to the plasma increases to increase the electrons in the plasma and accumulate in the high-frequency application electrode, thereby increasing the self-bias.

There is also a method of increasing the output of high-frequency energy. However, as described above, when the energy for decomposing gas increases, the electrons in the plasma increase. This is because the self-bias increases due to the increase.

[0005] However, when carbon or a film containing carbon as a main component is formed on the surface to be formed by such a method, the film is formed by increasing the self-bias. Positive ions having a large kinetic energy accelerated by self-bias collide with carbon or a film containing carbon as the main component, and also collide with the surface to be formed and sputter the surface to be formed. However, it has been difficult to form carbon or a coating containing carbon as a main component without damaging the surface to be formed. In addition, a film having high hardness has poor consistency with the surface to be formed due to expansion, shrinkage, stress, or the like of the surface to be formed or carbon or a film containing carbon as a main component, and causes peeling or detachment. It was bad.

[0006]

SUMMARY OF THE INVENTION The adhesion to the surface to be formed is improved.
It is an object to obtain an excellent carbon film.

[0007]

In order to achieve the above object, the present invention has first and second electrodes, and the first and second electrodes are provided.
The pole and the second electrode face each other, and the first electrode area is
An inert gas in a reaction system smaller than the second electrode area;
Alternatively, the first electrode of the reaction system having a hydrogen atmosphere
After arranging the substrate having the surface to be formed on the pole,
A method for forming a coating film, comprising forming a carbon film on a surface.
It is.

In addition, the semiconductor device has a first electrode and a second electrode.
The first electrode and the second electrode face each other, and the first electrode area
Is inactive in a reaction system smaller than the second electrode area.
The reaction system having an atmosphere of a reactive gas or hydrogen
Disposing a substrate having a surface to be formed on one of the electrodes;
A contaminant or foreign matter on the formed surface is removed, and a carbon film is formed on the formation surface.
Is formed.

In addition, the semiconductor device has first and second electrodes,
The first electrode and the second electrode face each other, and the first electrode area
Is inactive in a reaction system smaller than the second electrode area.
Said reaction system having an atmosphere of an inert gas or hydrogen
After arranging a substrate having a formation surface on one electrode,
Sp is formed on the surface to be formed. ^Three Forming carbon films with hybrid orbitals
This is a method for forming a coating film.

In addition, the semiconductor device has first and second electrodes,
The first electrode and the second electrode face each other, and the first electrode area
Is inactive in a reaction system smaller than the second electrode area.
The reaction system having an atmosphere of a reactive gas or hydrogen
Disposing a substrate having a surface to be formed on one of the electrodes;
Remove contaminants or foreign matter on the surface, The surface to be formed is sp ^Three
Forming a carbon film having hybrid orbitals;
This is a film formation method.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention solves the above-mentioned problems and has an optical energy bandwidth (Eg) of 1.0 eV or more, preferably 1.5 to 5.5 eV, and a hardness in Vickers hardness.
2000 kg / mm ² or more, preferably 4500 kg / mm ² or more, ideally amorphous with microcrystalline size of the amorphous or 5~20Å having insulation properties and hardness similar to diamond that 6500Kg / mm ² ( (Semi-amorphous) Carbon having a structure, hydrogen or a halogen element is added at a concentration of 25 atomic% or less or a trivalent or V-valent impurity is added at a concentration of 5 atomic% or less, and nitrogen is added at a concentration of N / C ≦ 0.05. In addition, carbon having so-called carbon as a main component is provided on the formation surface with good adhesion and good consistency with the formation surface.

Direct current or high frequency energy is applied between the first electrode and the second electrode provided in contact with the substrate having a surface to be formed, and the generated plasma causes the hydrocarbon gas and / or the hydrocarbon gas to be applied thereto. A method of forming a film containing carbon or carbon as a main component on the surface to be formed by causing a decomposition reaction with an additive gas to reduce the reaction pressure when forming a film containing carbon or carbon as a main component. Increasing the high-frequency energy, changing the amount of additive gas added, or using a combination of these conditions increases the hardness of carbon or a carbon-based film formed from the surface to be formed toward the surface. It was decided to let it.

That is, the present invention is intended to coat carbon or a film containing carbon as a main component on the surface to be formed, and to reinforce mechanical strength such as abrasion resistance on the surface.
For this purpose, instead of directly forming a carbon film having a hardness similar to diamond or a film containing carbon as a main component on the surface to be formed, the hardness is gradually increased from a portion close to the surface to be formed, and a desired hardness is obtained. It is characterized in that the reaction pressure is reduced, the high-frequency energy is increased, or the amount of additive gas is changed so that carbon or a carbon-based film having a desired hardness can be obtained when the film thickness is large.

In order to form a film having hardness similar to diamond directly on the surface to be formed, the self-bias must be increased to form a film containing carbon or carbon as a main component. Sputtering on the surface to be formed cannot be avoided, but carbon or a film containing carbon as a main component that is close to the surface to be formed has a hardness of carbon that can be formed with a self-bias that does not damage the surface to be formed. Alternatively, a film containing carbon as a main component is formed, and a film whose hardness is gradually increased is laminated, and a carbon film having a desired hardness or a film containing carbon as a main component is formed on the surface. Carbon or a coating containing carbon as a main component, which has good close contact with carbon and has high hardness.

In this case, as shown in FIG. 6 (A), a method of laminating a film having a small hardness from a film having a high hardness into several layers, and a method of continuously increasing the hardness as shown in FIG. 6 (B). Alternately, there is a method of forming a carbon or a coating containing carbon as a main component whose hardness continuously changes in a single layer. In the present invention, as a method of increasing the self-bias, a method of reducing the reaction pressure, a method of increasing the high-frequency energy, a method of changing the amount of the additive gas, and a method of combining two or three of the above three methods There is.

The formation surface used in the present invention is P
ET (polyethylene terephthalate), PES, PMM
A, an organic resin substrate such as Teflon, epoxy, polyimide or the like, a metal mesh carrier, a tape carrier such as paper, glass, metal, ceramic, semiconductor, a member for a magnetic head, a magnetic disk, and the like.

FIG. 1 shows an outline of a plasma CVD apparatus for forming carbon or a film containing carbon as a main component according to the present invention. In the drawing, in the doping system (1), hydrogen as a carrier gas is converted from (2) to hydrocarbon gas as a reactive gas such as methane and ethylene from (3) to diborane (diluted with hydrogen) (III), ), V-impurity ammonia or phosphine from (5) to valve (6), flow meter
After passing through (7), it is introduced into the reaction system (8) through the nozzle (9).
Before reaching the nozzle, it is effective to add microwave energy (10) to excite the reactive gas to activate it in advance.

The reaction system (8) was provided with a first electrode (11) and a second electrode (12). In this case, the condition of (first electrode area / second electrode area) <1 was satisfied. A pair of electrodes (1
A high frequency power supply (13) and a matching transformer (1)
4) Electric energy is applied from the DC bias power supply (15), and plasma is generated. Exhaust system (16) is pressure regulating valve
(17), unnecessary gas is exhausted through the turbo molecular pump (18) and the rotary pump (19). The reaction space (2
0) pressure is 0.001 ~ 10torr typically 0.01 ~ 0.5t
0 due to high frequency or direct current energy under orr
An energy of 1-5 KW is applied. Especially the excitation source is 1GHz
As described above, for example, at the frequency of 2.45 GHz, hydrogen is separated from the CH bond, and the frequency source is 0.1 to 50 MHz, for example.
At a frequency of 13.56 MHz, CC bonds and C = C bonds are decomposed to form -CC- bonds, and unpaired carbon atoms collide with each other to form a covalent bond to locally form a stable diamond structure. It can be made to have the structure.

DC bias is -200 to 600V (effectively -4
00 to + 400V). This is because when the DC bias is zero, the self-bias has -200 V (the second electrode is at the ground level). The reactive gas was partially diluted with hydrogen. For example, methane: hydrogen = 1: 1. The first electrode has a cooling means, and controls the temperature on the formation surface.
It was kept at 250--100 ° C.

In the present invention, the surface to be formed is placed on the cathode electrode. This is because when comparing the film quality of the carbon film formed when the surface to be formed is placed on the anode side and when the film surface is placed on the cathode side, the direction when the surface to be formed is placed on the cathode side as shown in FIG. This is because a carbon film having high hardness can be obtained at a high film forming rate. In FIG. 2, ○ indicates a stylus type surface roughness meter,
Indicates a film thickness measured by an ellipsometer, and △ indicates a refractive index of the film measured by an ellipsometer. The experimental conditions were as follows: high frequency energy 60 W, pressure 0.015 torr Methane flow rate 100 SCC
M, the substrate temperature was room temperature, and the film formation time was 180 minutes.

As described above, while having a Vickers hardness of 2000 kg / mm ² or more on the surface to be formed by the plasma,
Amorphous carbon with a large number of CC bonds with thermal conductivity of 2.5 W / cm deg or higher was formed. In addition, this electromagnetic energy is 50
Supplying W ~1KW, it was added plasma energy 0.03~3W / cm ² per unit area.

FIG. 3 shows the film forming speed and the Vickers hardness of the film when the carbon film was formed by changing the high-frequency energy applied in the apparatus used in the present invention. The higher the applied high frequency energy, the harder the film is formed. FIG. 4 shows the film forming speed and the Vickers hardness of the film when the carbon film was formed by changing the reaction pressure. The smaller the reaction pressure, the harder the film is formed. FIG. 5 shows the relationship between the applied high frequency energy, the reaction pressure, and the self-bias. The higher the high-frequency energy, the greater the self-bias, and the lower the reaction pressure, the greater the self-bias. From FIG. 5, FIG. 3, and FIG. 4, it can be seen that the larger the self-bias, the harder the carbon film formed.

Example 1 In the apparatus shown in FIG. 1, a carbon film was formed on a substrate having a surface to be formed by the method of the present invention. First, methane to which hydrogen was added was introduced into the reaction system from the nozzle at a flow rate of 100 SCCM, the pressure was maintained at 0.03 torr, and 50 W
And a film was formed for 150 minutes on a Si substrate kept at room temperature under the condition of self-bias of -150 V to form a first layer. Next, methane to which hydrogen was added was introduced from the nozzle at a flow rate of 100 SCCM, and the pressure was reduced to 0.01.
A high-frequency energy of 100 W was applied to methane while maintaining the pressure at 5 torr, and the surface to be formed was maintained at 150 ° C. under the condition of self-bias of −200 V to form a film for 150 minutes to form a second layer. Then, methane to which hydrogen was added was introduced from the nozzle at a flow rate of 100 SCCM onto the second layer, and the reaction system was set to 0/015 t.
A high-frequency energy of 200 W was applied to methane while maintaining the temperature at orr, and the surface to be formed was maintained at room temperature under the condition of self-bias of -280 V to form a film for 60 minutes to form a third layer.
When the Vickers hardness of these three layers was measured,
Layer is 2200 kg / mm ² , the second layer is 3500 kg / mm ² , the third layer is 4200 kg / mm ² , and the carbon film having a hardness similar to diamond on the surface is adhered to the surface to be formed. Was formed well.

Example 2 Hydrogen-added methane was introduced at a flow rate of 100 SCCM into a reaction system on which a substrate having a surface to be formed was placed, and the pressure was reduced to 0.03 ton.
While maintaining the pressure at rr, a high-frequency energy of 50 W was applied to methane, and a film was formed for 150 minutes to form a first layer. Next, on the first layer, the high-frequency energy for methane is 1
The second layer was formed under the same conditions as the first layer except that the power was 50 W. The film formation was performed on the second layer under the same conditions as the first layer except that the high-frequency energy was set to 300 W and the film was formed for 60 minutes. As a result, 2200 kg / mm ² , 3800
^{Kg / mm 2, 5000Kg / mm} 2, a first layer having a Vickers hardness of the second layer, it was possible to form a carbon film comprising a third layer. This carbon film has a surface hardness of 5000 kg
/ mm ² and hardness similar to diamond, and excellent in wear resistance, high thermal conductivity and high smoothness.

In this embodiment, the hardness of the carbon film is increased by increasing only the output of the high-frequency energy, but the same effect can be obtained by decreasing only the reaction pressure as described above. In this embodiment, each carbon film layer is formed using one reaction chamber. However, each layer may be formed in a different reaction chamber by connecting a plurality of reaction chambers.

[Embodiment 3] In this embodiment, instead of laminating layers having different hardnesses on the surface to be formed, the carbon whose hardness continuously changes by continuously increasing the high-frequency energy is used. A film was formed. First, film formation is started under the same conditions as those for forming the first layer in Example 1, and then high-frequency energy is applied.
The carbon film was formed on the surface to be formed by increasing the power at a rate of 0.7 to 2 W / min until the power became 300 W. The formed carbon film had a Vickers hardness of 4000 Kg / mm ^{2 on} the surface and was excellent in wear resistance, high thermal conductivity, and high smoothness.

In this embodiment, only the high-frequency energy is continuously increased, but only the reaction pressure may be continuously reduced. Alternatively, the high-frequency energy may be continuously increased and the reaction pressure may be continuously reduced. May be. Further, the amount of the additive to be added to the reactive gas may be continuously changed, and the method of the present invention can be carried out by combining the change of the additive with an increase in the high-frequency energy or a decrease in the reaction pressure. .

Embodiment 4 In this embodiment, before forming a carbon film on a surface to be formed, the surface to be formed is disposed in an atmosphere of an inert gas or hydrogen activated by plasma. After removing contaminants or foreign substances such as oxides, carbides or nitrides, a carbon film was formed. Means for converting inert gas or hydrogen into plasma is 0.1 to 100 MHz. Using a microwave frequency and 1 ~10GH _Z, energy applied is sufficient 10～1000W. The pressure of the reaction system during plasma conversion is 10 ^-3 torr
As described above, it is typically 0.01 to 200 torr, preferably 1 to 10 torr. Under the above conditions, the inert gas or hydrogen is plasma-activated, and the activated hydrogen or the inert gas causes oxides, dirt, hydroxides, and / or the surface of these to be localized on the surface to be formed. Removed tension and physical adsorption force. After such a treatment, a carbon film was formed on the surface to be formed according to Example 1, Example 2, or Example 3. The obtained carbon film was excellent in adhesion to the surface to be formed.

[0029]

As described above, carbon or a film containing carbon as a main component produced by the method of the present invention is in close contact with the surface to be formed.
It was excellent.

Further, the film mainly composed of closely spaced carbon or carbon onto the forming surface, the film containing carbon as a main component or carbon in hardness obtained made by the self-bias so as not to damage to the formation surface And a layer of gradually increasing hardness is laminated, and a film having carbon or carbon as a main component having a desired hardness is formed on the surface, so that excellent adhesion to a surface on which the film is formed is excellent. It has a hardness similar to that of diamond, and has been extremely effective for electric members in which a dissimilar material slides on the surface of a part such as a magnetic head or a magnetic disk.

Particularly, the obtained carbon or a coating containing carbon as a main component has a thermal conductivity of 2.5 W / cm deg or more, typically 4.0 W / cm deg.
~ 6.0W / cm deg and close to 60W / cm deg of diamond, the heat generated by friction can be uniformly dissipated to the whole, and furthermore, the abrasion resistance, high thermal conductivity, high smoothness unique to carbon film, etc. It had characteristics.

Further, the method of the present invention comprises the steps of:
Since a magnetic material, a metal, a ceramic, a semiconductor, or the like can be used as a formation surface, the reaction is immeasurable.

[Brief description of the drawings]

FIG. 1 is a diagram showing an outline of an apparatus used in the present invention.

FIG. 2 is a view showing the film quality of a carbon film.

FIG. 3 is a diagram showing an output of high-frequency energy, a film forming speed, and Vickers hardness.

FIG. 4 is a diagram showing a reaction pressure, a film formation rate, and Vickers hardness.

FIG. 5 is a diagram showing the relationship between high-frequency energy, reaction pressure, and self-bias.

FIG. 6 is a graph showing the relationship between the thickness and hardness of a carbon film.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Doping system 6 ... Valve 7 ... Flow meter 8 ... Reaction system 9 ... Nozzle 10 ... Microwave energy 11 ... 1st electrode 12 ... 2nd Electrode 13 High frequency power supply 14 Matching transformer 15 DC bias power supply 16 Exhaust system 17 Pressure regulating valve 18 Turbo molecular pump 19 Rotary pump 20 Reaction space

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C23C 16/27 C01B 31/02 G11B 5/187 G11B 5/72 G11B 5/84

Claims (18)

(57) [Claims] 1. A carbon film is formed by a plasma CVD apparatus having a reaction system having a first electrode and a second electrode facing each other , wherein the area of the first electrode is smaller than the area of the second electrode.
In the method , after arranging a substrate having a surface to be formed on the first electrode of the reaction system in an atmosphere of an inert gas or hydrogen gasified into plasma , the hardness is changed from the substrate side to the film surface from the substrate side. Direction
A method for forming a film, comprising forming a carbon film that has been continuously increased . 2. A method for forming a carbon film using a plasma CVD apparatus having a first electrode and a second electrode facing each other and a reaction system having an area of the first electrode smaller than an area of the second electrode. After arranging a substrate having a surface to be formed on the first electrode of the reaction system in an atmosphere of an inert gas or hydrogen gasified into plasma , the hardness of the surface to be formed is changed to the substrate side. From to the membrane surface
A method for forming a film, comprising forming a carbon film having a stepwise increase . 3. A method of forming a carbon film using a plasma CVD apparatus having a reaction system having a first electrode and a second electrode facing each other , wherein the area of the first electrode is smaller than the area of the second electrode. A substrate having a surface to be formed is provided on the first electrode of the reaction system in an atmosphere of an inert gas or hydrogen gasified by plasma to remove contaminants or foreign matter on the surface to be formed. After the removal , the hardness of the surface to be formed is continuously increased from the substrate side toward the film surface.
A method for forming a film, comprising: forming a carbon film having an increased amount . 4. A method for forming a carbon film using a plasma CVD apparatus having a reaction system having a first electrode and a second electrode facing each other , wherein the area of the first electrode is smaller than the area of the second electrode. A substrate having a surface to be formed is provided on the first electrode of the reaction system in an atmosphere of an inert gas or hydrogen gasified by plasma to remove contaminants or foreign matter on the surface to be formed. After the removal , the hardness of the surface to be formed is gradually increased from the substrate side toward the film surface.
A method for forming a film, comprising: forming a carbon film having an increased amount . 5. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
After that, while reducing the reaction pressure continuously,
A method for forming a carbon film on a formed surface, wherein the carbon film has a hardness from a surface on which a carbon film is formed to a film surface.
A method for forming a film, wherein the film is continuously increased. 6. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
After that, the reaction pressure is reduced step by step
A method for forming a carbon film on a formed surface, wherein the carbon film has a hardness from a surface on which a carbon film is formed to a film surface.
A method for forming a coating film, wherein the coating film is gradually increased. 7. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
After removing contaminants or foreign matter from the surface to be formed,
While continuously reducing the reaction pressure, a carbon film is formed on the surface to be formed.
A method of forming the carbon film, hardness towards the membrane surface from the forming surface
A method for forming a film, wherein the film is continuously increased. 8. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
After removing contaminants or foreign matter from the surface to be formed,
While gradually reducing the reaction pressure, a carbon film is formed on the surface to be formed.
A method of forming the carbon film, hardness towards the membrane surface from the forming surface
A method for forming a coating film, wherein the coating film is gradually increased. 9. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
And then continuously increasing the high frequency energy
A method of forming a carbon film on the formation surface, wherein the carbon film has a hardness from the formation surface side toward the film surface.
A method for forming a film, wherein the film is continuously increased. 10. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
And then gradually increase the high frequency energy
A method of forming a carbon film on the formation surface, wherein the carbon film has a hardness from the formation surface side toward the film surface.
A method for forming a coating film, wherein the coating film is gradually increased. 11. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
To remove contaminants or foreign matter from the surface to be formed,
While continuously increasing the frequency energy,
A method for forming a carbon film , wherein the carbon film has a hardness from a surface on which a carbon film is formed to a film surface.
A method for forming a film, wherein the film is continuously increased. 12. A semiconductor device having a first electrode and a second electrode facing each other.
And, an area of the first electrode is smaller than the area of the second electrode
To form a carbon film with a plasma CVD system
And the above reaction of an inert gas or hydrogen atmosphere
Disposing a substrate having a surface to be formed on the first electrode of the reactive system
To remove contaminants or foreign matter from the surface to be formed,
While gradually increasing the frequency energy,
A method for forming a carbon film , wherein the carbon film has a hardness from a surface on which a carbon film is formed to a film surface.
A method for forming a coating film, wherein the coating film is gradually increased. 13. any one smell of claims 1 to 12
Te, the carbon film, to characterized in that it has a sp ³ hybrid orbital
Film formation method. 14. any one smell of claims 1 to 12
The carbon film has a hardness similar to that of diamond.
A method for forming a coating film having a fuzz structure. 15. any one smell of claims 1 to 12
The carbon film is formed by using ethylene as a raw material gas . 16. any one smell of claims 1 to 12
The film-forming surface is made of an organic resin substrate such as PET, PES, PMMA, Teflon, epoxy, or polyimide, glass,
A method for forming a coating film, which is a metal, a ceramic, a semiconductor, a member for a magnetic head, or a magnetic disk. 17. any one of claims 1 to 12, bi Vickers hardness of the carbon film, 2000 kg / mm ²
A method for forming a film, characterized by the above. 18. any one smell of claims 1 to 12
Te, when forming the carbon film, changing the addition amount of the additive gas
A method for forming a coating film, comprising: