JP6383910B2 - Plasma CVD apparatus and film manufacturing method - Google Patents

Description

  The present invention relates to a plasma CVD apparatus and a film manufacturing method.

  Diamond-like carbon (DLC) films have been used in many fields because they have excellent properties such as high hardness, wear resistance, and low friction coefficient.

  However, the DLC film is usually an insulator having no electrical conductivity, and since it is a highly insulating film electrically, it is limited to use as an insulating film, and its application field is limited. Is the current situation. If the electrical conductivity can be freely set by adding the conductivity function to the DLC film in addition to the mechanical and chemical properties, it is expected that various application fields in the mechanical and electrical fields will be greatly expanded. For example, it can be used for an electrode. In particular, since a DLC film containing carbon as a main constituent element is a material with a low environmental load, it may be a substitute for a conductive material such as gold or copper.

  Usually, in order to give conductivity to the insulating DLC film, measures such as a method of adding a second element such as nitrogen, boron, and titanium, a method of performing an annealing process after film formation, etc. are taken (for example, patents). References 1-4).

  However, the above-described method requires a plurality of raw materials and requires post-treatment, so that the original characteristics of the DLC film such as high hardness, wear resistance, and low friction coefficient are changed. Many problems occur, such as inferiority.

  On the other hand, the present inventors have newly developed a plasma CVD method capable of manufacturing a high-hardness DLC film at a high speed and at a low cost so that the formation of a DLC film on a large area and a three-dimensional complex shape is inexpensive. Patent Document 5 clarifies that this can be achieved with a system and running cost.

JP 2008-189997 A Japanese Patent No. 4704453 Japanese Patent No. 4134315 JP 2002-025346 A JP 2008-038217 A

An object of one embodiment of the present invention is to provide a method for manufacturing a conductive DLC film.
Another object of one embodiment of the present invention is to facilitate plasma holding even when the frequency of a high-frequency output is lowered.

  One embodiment of the present invention is a method for manufacturing a DLC film having conductivity by a plasma CVD method using a high-frequency power source for the purpose of expanding a use range of a DLC film close to an insulator.

  In one embodiment of the present invention, conventionally, a plurality of raw materials and post-treatments are required to manufacture a conductive DLC film, whereas a conductive DLC film is formed in a single process. It is possible to adjust the strength of the conductivity.

  Another embodiment of the present invention is a conductive DLC film formed by a low-frequency plasma CVD method without using an additive element or post-treatment such as annealing.

  Another embodiment of the present invention is a plasma CVD method in which plasma can be easily held even at a low frequency by applying a low frequency in a pulsed manner to a substrate with a high-frequency power source having a low frequency. It becomes possible to manufacture a DLC film having high conductivity by this plasma CVD method. In other words, the lower the frequency of the voltage applied to the substrate, the higher the conductivity of the DLC film, but it becomes difficult to maintain the plasma when the frequency is low. Therefore, by applying a low frequency to the substrate in a pulse form by a low frequency power source, the plasma can be continuously maintained even if the frequency is low.

Further, various aspects of the present invention will be described below.
[1] a chamber;
A substrate holder disposed in the chamber and holding the substrate;
A gas introduction path connected to the chamber and introducing a source gas into the chamber;
An output supply mechanism for supplying a high frequency output of 5 kHz or more and 500 kHz or less into the chamber in a pulse form having a duty ratio of 10% or more and 90% or less in a cycle of 0.02 ms or more and 20 ms or less;
Comprising
The DUTY ratio is a ratio of a period during which a high frequency output is applied to the substrate holder during one cycle,
A plasma CVD apparatus characterized in that a plasma is generated in the chamber by the high-frequency output supplied from the output supply mechanism to form a film on the substrate.

[2] In the above [1],
The plasma CVD apparatus, wherein the frequency of the high-frequency output is 50 kHz or more and 300 kHz or less.

[3] In the above [1] or [2],
A temperature adjusting mechanism for adjusting the temperature of the substrate held by the substrate holder;
The source gas has at least one of a chain hydrocarbon and a cyclic hydrocarbon,
The film is a DLC film having conductivity,
A plasma CVD apparatus, wherein a temperature at which the DLC film is formed on the substrate is 100 ° C. or higher.

[4] In the above [3],
The chain hydrocarbon is one or more hydrocarbons selected from the group of methane, ethane, acetylene, propane and butane;
The plasma CVD apparatus, wherein the cyclic hydrocarbon is at least one of benzene and toluene.

[5] a chamber;
A substrate holder disposed in the chamber and holding the substrate;
A temperature adjustment mechanism for adjusting the temperature of the substrate held by the substrate holder;
A gas introduction path connected to the chamber for introducing chain hydrocarbons into the chamber;
A high frequency power source for supplying a high frequency output of 5 kHz to 500 kHz in the chamber;
Comprising
A plasma CVD apparatus characterized in that plasma is generated in the chamber by a high-frequency output supplied from the high-frequency power source to form a conductive DLC film on the substrate at a temperature of 100 ° C. or higher.

[6] In the above [5],
The plasma CVD apparatus, wherein the chain hydrocarbon is one or a plurality of hydrocarbons selected from the group of methane, ethane, acetylene, propane, and butane.

[7] a chamber;
A substrate holder disposed in the chamber and holding the substrate;
A temperature adjustment mechanism for adjusting the temperature of the substrate held by the substrate holder;
A gas introduction path connected to the chamber for introducing cyclic hydrocarbons into the chamber;
A high frequency power source for supplying a high frequency output of 5 kHz to 500 kHz in the chamber;
Comprising
A plasma CVD apparatus, wherein plasma is generated in the chamber by a high-frequency output supplied from the high-frequency power source, and a conductive DLC film is formed on the substrate at a temperature of 200 ° C. or higher.

[8] In the above [7],
The plasma CVD apparatus, wherein the cyclic hydrocarbon is at least one of benzene and toluene.

[8-1] In any one of [1] to [8] above,
A vacuum evacuation mechanism having a pressure of 0.6 Pa or less (preferably 0.015 to 0.526 Pa, more preferably 0.037 to 0.301 Pa, and still more preferably 0.150 Pa) in the chamber is provided. A plasma CVD apparatus.

[9] By generating source gas plasma by supplying a high frequency output of 5 kHz or more and 500 kHz or less to the substrate in a pulse form having a duty ratio of 10% or more and 90% or less in a cycle of 0.02 ms or more and 20 ms or less. , To form a film on the substrate,
The DUTY ratio is a ratio of a period during which a high-frequency output is applied to the substrate during one period.

[10] In the above [9],
The method for producing a film, wherein the frequency of the high-frequency output is 50 kHz or more and 300 kHz or less.

[11] In the above [9] or [10],
The source gas has at least one of a chain hydrocarbon and a cyclic hydrocarbon,
The film is a DLC film having conductivity,
The method for producing a film, wherein a temperature at which the DLC film is formed on the substrate is 100 ° C. or higher.

[12] In the above [11],
The chain hydrocarbon is one or more hydrocarbons selected from the group of methane, ethane, acetylene, propane and butane;
The method for producing a film, wherein the cyclic hydrocarbon is at least one of benzene and toluene.

[13] A DLC film having conductivity on a base material is formed at a temperature of 100 ° C. or higher by generating a plasma of a raw material gas with a high frequency output of 5 kHz to 500 kHz,
The method for producing a film, wherein the source gas contains chain hydrocarbons.

[14] In the above [13],
The method for producing a film, wherein the chain hydrocarbon is one or a plurality of hydrocarbons selected from the group consisting of methane, ethane, acetylene, propane and butane.

[15] A DLC film having conductivity on a base material is formed at a temperature of 200 ° C. or higher by generating a plasma of a source gas with a high frequency output of 5 kHz or more and 500 kHz or less,
The method for producing a film, wherein the source gas has a cyclic hydrocarbon.

[16] In the above [15],
The method for producing a film, wherein the cyclic hydrocarbon is at least one of benzene and toluene.

[17] In any one of the above [11] to [16],
A volume resistivity of the DLC film is 0.001 Ω · cm or more and 50 Ω · cm or less.

[18] In the above [11] to [17],
A method for producing a film, comprising forming a film on the substrate and then performing a heat treatment on the film at 300 ° C. or higher (preferably 450 ° C. or higher).
Note that this heat treatment is preferably performed in a vacuum atmosphere.

By applying one embodiment of the present invention, a method for manufacturing a conductive DLC film can be provided.
Further, by applying one embodiment of the present invention, plasma can be easily held even when the frequency of the high-frequency output is lowered.

(A) is a block diagram schematically showing a plasma CVD apparatus according to one embodiment of the present invention, and (B) is a diagram for explaining a case of a DUTY ratio of 50%. It is a figure which shows the relationship between the volume resistivity of the DLC film formed into a film at 150 degreeC by Example 1, a power supply frequency, and a gas kind. It is a figure which shows the relationship between the volume resistivity of the DLC film by Example 2, the base-material temperature at the time of film-forming, and a power supply frequency.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it is easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments below.

[Embodiment 1]
FIG. 1A is a schematic diagram illustrating a plasma CVD apparatus according to one embodiment of the present invention.

  The plasma CVD apparatus has a processing chamber 1, and a base material holder 3 for holding a base material 2 is disposed in the processing chamber 1. The substrate holder 3 also functions as an RF electrode, and an output supply mechanism 4 is connected to the substrate holder 3. The output supply mechanism 4 supplies a high frequency output of 5 kHz or more and 500 kHz or less to the substrate holder 3 in a pulse shape with a duty ratio of 10% or more and 90% or less in a cycle of 0.02 ms or more and 20 ms or less. .

  The DUTY ratio is a ratio of a period during which a high frequency output is applied to the substrate holder 3 during one cycle. For example, in the case of a DUTY ratio of 10%, a period of 10% of one cycle is a period during which high-frequency output is applied to the substrate holder 3 (high-frequency output on period), and 90% of one cycle is a substrate This is a period during which no high frequency output is applied to the holder 3 (high frequency output off period). Specifically, for example, in the case of 10% DUTY ratio in a period of 1 ms, a period of 0.1 ms of 10% of 1 ms (1 period) is a period in which the high frequency output is on, and 0 of 90% of 1 ms (1 period). .9 ms period is the high frequency output off period.

  Further, for example, FIG. 1B shows a case of 50% DUTY ratio, in which 50% of one cycle is a high frequency output on period, and the remaining 50% of one cycle is a high frequency output off. It becomes the period.

  The plasma CVD apparatus supplies a high-frequency output of 5 kHz or more and 500 kHz or less to the base material 2 through the base material holder 3 by the output supply mechanism 4 through the base material holder 3, and generates plasma of the source gas above the base material 2. It is supposed to be generated.

  In the present embodiment, the high-frequency output when the high-frequency output is supplied to the substrate holder 3 in a pulsed manner by the output supply mechanism 4 is set to 5 kHz or more and 500 kHz or less, but the high-frequency output is set to 50 kHz or more and 300 kHz or less. More preferably, it is less than 250 kHz, More preferably, it is 100 kHz or less. The lower the frequency of the high-frequency output, the more charge is accumulated in the base material 2, so that the discharge is less likely to occur and the plasma is less likely to be generated, but the plasma is reliably generated by supplying it in pulses.

  Further, in the present embodiment, when the high-frequency output is supplied in a pulse form to the substrate holder 3 by the output supply mechanism 4, the pulse form is 10% or more and 90% or less in a cycle of 0.02 ms or more and 20 ms or less. The ratio is preferably a DUTY ratio of 10% to 90% with a period of 0.2 ms to 10 ms. The reason for setting the DUTY ratio to 10% or more is that if it is less than 10%, plasma is hardly generated, and even if plasma is generated, it is easy to disappear. The reason why the DUTY ratio is set to 90% or less is that if it exceeds 90%, the charge is accumulated on the base material 2 and is not easily removed, so that the plasma is easily extinguished. In other words, by supplying the high-frequency output in a pulse shape, the charge accumulated when the high-frequency output is in the off state is removed from the base material 2, and plasma can be generated reliably.

  A heater 5 as an example of a temperature adjustment mechanism for adjusting the temperature of the substrate 2 is arranged around the substrate holder 3, and the substrate 2 is heated by the heater 5. . In addition, the base material 2 can use various materials and various shapes.

  The processing chamber 1 is provided with a gas inlet 10 for introducing a source gas such as hexamethyldisilazane or hexamethyldisiloxane (hereinafter collectively referred to as HMDS), hydrocarbons, and argon. A gas introduction path (not shown) for introducing these gases into the processing chamber 1 is connected to the gas introduction port 10. The gas introduction path has a gas pipe (not shown). The gas pipe is provided with a flow meter (not shown) for measuring the gas flow rate and a gas flow controller (not shown) for controlling the gas flow rate. Appropriate amounts of argon gas, HMDS, and hydrocarbon gas are supplied into the processing chamber 1 from the gas inlet by the flow meter.

  The hydrocarbon-based gas may include at least one of a chain hydrocarbon and a cyclic hydrocarbon. The chain hydrocarbon may be, for example, one or more hydrocarbons selected from the group of methane, ethane, acetylene, propane and butane, and the cyclic hydrocarbon is, for example, at least one hydrocarbon of benzene and toluene It is good to be.

  Further, the processing chamber 1 is connected with a vacuum pump 13 which is an evacuation mechanism for evacuating the inside of the processing chamber 1.

  The high-frequency power source of 5 to 500 kHz in the plasma CVD apparatus has the advantages of a direct-current power source and a high-frequency power source, and has an advantage of using a frequency that is easy to handle industrially of 5 to 500 kHz. Further, in the case of a high frequency power source of 5 to 500 kHz, there is an advantage that the bias effect to the substrate is enhanced as compared with the conventional high frequency power source of 13.56 MHz.

  Next, a method for forming a DLC film on the surface of the substrate 2 using the plasma CVD apparatus of FIG. 1 will be described.

  First, the base material 2 made of, for example, SUS304 is mounted on the base material holder 3. Next, the substrate 2 is heated to 150 ° C. with a heater, the inside of the processing chamber 1 is evacuated to 0.6 Pa or less by the vacuum pump 13, and then argon gas is introduced into the processing chamber 1. Next, by continuously supplying a high frequency current of 250 kHz to the substrate holder 3 using the output supply mechanism 4 with an output of 50 W, argon plasma is formed in the vicinity of the substrate 2 to clean the surface of the substrate 2. Ion bombard for 1 minute. Thereby, the surface of the base material 2 is ion-etched by the action of strong ions, and the oxide layer on the surface of the base material 2 is removed.

  Thereafter, the temperature of the substrate 2 is maintained at 100 ° C. or higher by the heater 5, and the pressure in the processing chamber 1 is maintained at 0.6 Pa or lower by the vacuum pump 13. Subsequently, a high frequency output of 5 kHz to 500 kHz (preferably 50 kHz to 300 kHz, more preferably less than 250 kHz, more preferably 100 kHz or less) is applied to the substrate holder 3 using the output supply mechanism 4 at an output of 300 W for 0.02 ms. While supplying the substrate holder 3 in a pulse shape with a duty ratio of 10% or more and 90% or less at a cycle of 20 ms or less (preferably a cycle of 0.2 ms or more and 10 ms or less), HMDS is supplied into the processing chamber 1 at a flow rate of 5 ccm. After the intermediate layer is formed on the surface of the substrate 2 for 3 minutes, at least one hydrocarbon gas of chain hydrocarbon gas and cyclic hydrocarbon gas is used as the hydrocarbon-based gas at a flow rate of 5 ccm. A DLC film is formed on the intermediate layer for 60 minutes after being introduced into 1.

  As described above, when a DLC film is formed by a plasma CVD method in which a high frequency output of 5 kHz or more and 500 kHz or less is supplied in a pulse shape, the DLC film formed by a plasma CVD method using a conventional high frequency power supply with a frequency of 13.56 MHz is formed on the DLC film. In comparison, a DLC film having higher conductivity (for example, a DLC film having a volume resistivity of 0.001 Ω · cm to 50 Ω · cm) can be obtained.

  Further, in the above DLC film manufacturing method, the lower the frequency of the high-frequency output, the stronger the bias to the substrate 2 during film formation, and thus the lower the resistivity of the DLC film. Moreover, since it is thought that the resistivity of the DLC film | membrane falls so that the temperature of the base material 2 at the time of film-forming is high, 300 degreeC or more is preferable, More preferably, it is 450 degreeC or more.

  Further, the DLC film manufactured by the above manufacturing method may be subjected to heat treatment at 300 ° C. or higher (preferably 450 ° C. or higher). Thereby, the resistivity of the DLC film can be further reduced. Note that the heat treatment here is more preferably performed in a vacuum atmosphere.

[Embodiment 2]
In the description of the present embodiment, the description of the same parts as those of the first embodiment will be omitted, and different parts will be described.

  The output supply mechanism 4 of the first embodiment supplies the high frequency output to the base material 2 in a pulsed manner, but the output supply mechanism of the present embodiment does not provide a pulse shape but continuously outputs the high frequency output to the base material 2. The frequency of the high frequency output is the same as that of the first embodiment.

  The method for producing a DLC film according to the present embodiment generates a chain hydrocarbon gas plasma with a high-frequency output of 5 kHz or more and 500 kHz or less, whereby a DLC film having conductivity on a substrate is formed at a temperature of 100 ° C. or more. It is preferable to form a film.

  In addition, the method for manufacturing a DLC film according to the present embodiment generates a cyclic hydrocarbon gas plasma with a high-frequency output of 5 kHz or more and 500 kHz or less, thereby forming a conductive DLC film at 200 ° C. or higher. The film is preferably formed at a temperature.

  Also in the present embodiment, the same effect as in the first embodiment can be obtained.

[Relationship between power frequency and gas type]
The conductive DLC film of this example was formed using the plasma CVD apparatus shown in FIG. The high frequency output supplied to the base material 2 by the output supply mechanism 4 was 13.56 MHz, 250 kHz or 100 kHz, and the temperature of the base material 2 was 150 ° C. As the source gas, argon gas, hexamethyldisilazane (HMDS) and hydrocarbon gas (methane, acetylene, toluene) were supplied from the gas inlet 10 by a flow meter.

  A 4-inch silicon wafer was mounted on the substrate holder 3 in the processing chamber 1 as a material to be coated (substrate 2). The inside of the processing chamber 1 is evacuated to 0.6 Pa or less using a mechanical booster pump and an oil rotary pump, and then argon gas is introduced to form argon plasma at an output of 50 W using a high-frequency power source of the output supply mechanism 4 to be coated. The surface of the material was ion etched for 1 minute. Thereafter, 5 ccm of HMDS was introduced to form an intermediate layer for 3 minutes, and then 5 ccm of toluene was introduced to form a DLC film for 60 minutes. Further, in place of toluene, methane and acetylene were similarly treated to form a DLC film.

  The results of measuring the volume resistivity of the DLC film obtained at a temperature of 150 ° C. of the substrate 2 using a high-precision resistivity meter are shown in Table 1 and FIG. FIG. 2 is a bar graph showing the results shown in Table 1.

  It can be seen that any gas species is an insulator at a frequency of 13.56 MHz of an industrial high-frequency power source generally used in a plasma CVD apparatus. On the other hand, methane and acetylene show that the volume resistivity is low at low frequencies of 250 kHz and 100 kHz. However, toluene is an insulator at any frequency. From this, it was confirmed that a conductive DLC film can be produced by using low-frequency power sources of 250 kHz and 100 kHz for chain hydrocarbons such as methane and acetylene at 150 ° C.

  In this case, when 100 kHz was continuously applied to the substrate, the plasma became unstable and the film could not be formed. This phenomenon is observed only at 100 kHz and is not observed at 13.56 MHz and 250 kHz.

  Therefore, the film formation at 100 kHz shown in Table 1 is a result of applying a pulsed high-frequency output to the base material as described in the first embodiment, thereby stabilizing the plasma and forming the DLC film. Became possible. Specifically, in the film formation at 100 kHz shown in Table 1, a high frequency output of 100 kHz is supplied to the base material holder 3 in a pulse shape of 50% DUTY ratio at a cycle of 2.0 ms. In addition, the film formation at 13.56 MHz and 250 kHz shown in Table 1 is the one in which the high frequency output is continuously supplied to the substrate holder 3 instead of the pulse shape.

[Influence of substrate temperature and power supply frequency]
The conductive DLC film of this example was formed using the plasma CVD apparatus shown in FIG. 1, and the film formation conditions were the same as those of Example 1.

  Specifically, the high frequency output supplied to the substrate 2 by the output supply mechanism 4 is 13.56 MHz, 250 kHz, or 100 kHz, and the temperature of the substrate 2 is 150 ° C., 300 ° C., or 450 ° C. As the source gas, argon gas, hexamethyldisilazane (HMDS) and hydrocarbon gas (acetylene, toluene) were supplied from the gas inlet 10 by a flow meter.

  A 4-inch silicon wafer was mounted on the substrate holder 3 in the processing chamber 1 as a material to be coated (substrate 2). The inside of the processing chamber 1 is evacuated to 0.6 Pa using a mechanical booster pump and an oil rotary pump, and then argon gas is introduced to form argon plasma at an output of 50 W using a high-frequency power source of the output supply mechanism 4. The surface of was ion-etched for 1 minute. Thereafter, 5 ccm of HMDS was introduced to form an intermediate layer for 3 minutes, and then 5 ccm of toluene was introduced to form a DLC film for 60 minutes. In addition, a DLC film was formed in the same manner with acetylene instead of toluene.

  In the film formation at 100 kHz shown in Table 2, a high-frequency output of 100 kHz is supplied to the substrate holder 3 in a pulse shape with a duty ratio of 50% at a cycle of 2.0 ms. In addition, the film formation at 13.56 MHz and 250 kHz shown in Table 2 is the one in which a high frequency output is continuously supplied to the substrate holder 3 instead of a pulse shape.

  Table 2 and FIG. 3 show the results of measuring the volume resistivity of the DLC film obtained as described above using a high-precision resistivity meter. FIG. 3 is a graph showing the results shown in Table 2.

  From Table 2 and FIG. 3, in toluene, conductivity is recognized if 250 kHz and 100 kHz are 300 ° C. or higher, but in 13.56 MHz, conductivity is not recognized unless it is 450 ° C. It can also be seen that the resistivity at 100 kHz is lower than that at 250 kHz. This shows that the lower the resistivity, the lower the resistivity of the DLC film. Comparing toluene and acetylene, it can be seen that acetylene tends to exhibit lower conductivity at 100 kHz.

DESCRIPTION OF SYMBOLS 1 ... Processing chamber 2 ... Base material 3 ... Base material holder 4 ... Output supply mechanism 5 ... Heater 10 ... Gas inlet 13 ... Vacuum pump

Claims (12)

By generating only the high frequency output of 5 kHz or more and 500 kHz or less to the base material in the form of a pulse having a duty ratio of 10% or more and 90% or less at a cycle of 0.02 ms or more and 20 ms or less, A film is formed on a substrate;
The source gas has a cyclic hydrocarbon;
The film is a DLC film having conductivity,
The temperature when forming the DLC film on the substrate is 100 ° C. or higher and 450 ° C. or lower,
The DUTY ratio is a ratio of a period during which a high-frequency output is applied to the substrate during one period. By generating only the high frequency output of 5 kHz or more and 500 kHz or less to the base material in the form of a pulse having a duty ratio of 10% or more and 90% or less at a cycle of 0.02 ms or more and 20 ms or less, A film is formed on a substrate;
The source gas has at least one of a chain hydrocarbon and a cyclic hydrocarbon,
The film is a DLC film having conductivity,
The temperature when forming the DLC film on the substrate is 100 ° C. or more and 300 ° C. or less,
The DUTY ratio is a ratio of a period during which a high-frequency output is applied to the substrate during one period. In claim 2 ,
The method for producing a film, wherein the chain hydrocarbon is one or a plurality of hydrocarbons selected from the group consisting of methane, ethane, acetylene, propane and butane. In claim 1 or 2 ,
The method for producing a film, wherein the cyclic hydrocarbon is at least one of benzene and toluene. In any one of Claims 1 thru | or 4 ,
The method for producing a film, wherein the frequency of the high-frequency output is 50 kHz or more and 300 kHz or less. A DLC film having conductivity on a base material is formed at a temperature of 100 ° C. or more and 300 ° C. or less by generating a plasma of a raw material gas only by a high frequency output of 250 kHz or more and 500 kHz or less,
The method for producing a film, wherein the source gas contains chain hydrocarbons. In claim 6 ,
The method for producing a film, wherein the chain hydrocarbon is one or a plurality of hydrocarbons selected from the group consisting of methane, ethane, acetylene, propane and butane. A DLC film having conductivity on a base material is formed at a temperature of 200 ° C. or higher and 450 ° C. or lower by generating plasma of a raw material gas only by a high frequency output of 250 kHz or higher and 500 kHz or lower,
The method for producing a film, wherein the source gas has a cyclic hydrocarbon. In claim 8 ,
The method for producing a film, wherein the cyclic hydrocarbon is at least one of benzene and toluene. In any one of Claims 1 thru | or 9 ,
A volume resistivity of the DLC film is 0.001 Ω · cm or more and 50 Ω · cm or less. A plasma CVD apparatus for carrying out the film manufacturing method according to any one of claims 1 to 5,
A chamber;
Disposed in said chamber, and a substrate holder for holding said substrate,
Is linked to the chamber, a gas introduction path for introducing the raw material gas into the chamber,
The high-frequency output in the chamber, and an output supplying mechanism for supplying the pulsed,
A temperature adjustment mechanism for adjusting the temperature of the substrate held by the substrate holder;
Plasma CVD apparatus characterized by comprising a. A plasma CVD apparatus for carrying out the film manufacturing method according to any one of claims 6 to 9,
A chamber;
Disposed in said chamber, and a substrate holder for holding said substrate,
A temperature adjustment mechanism for adjusting the temperature of the substrate held by the substrate holder;
A gas introduction path connected to the chamber and introducing the source gas into the chamber;
A high frequency power source for supplying the high frequency output to the chamber,
Plasma CVD apparatus characterized by comprising a.

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