JPH0620975A - Carbon film manufacturing method - Google Patents

Abstract

PURPOSE:Not to mix re-released impurities into a carbon film on a substrate by a method wherein an inner wall of a reaction container or a substrate holder is plasma-cleaned when the carbon film is formed on the substrate. CONSTITUTION:When a silicon carbide film is formed on the surface to be formed by using reactive vapor tetramethylsilane having a carbon-silicon coupling, in order to remove a reaction product adhered to an inner wall or the surface of a reaction cylinder 25 or a holder 2, fluoric compound vapor, for example mixed vapor with CF4 or oxygen, is introduced from an introducing inlet 17 and electromagnetic energy is applied thereto to perform vapor phase etching by generating fluoric radical and oxygen radical. Further, in this plasma discharge, after the reactive vapor is mixed through a mixture chamber 8, it is dissolved or acts in an exciting chamber 26, and a space reaction is mainly used in which the reaction product is formed on a substrate. Thus, a carbon film in which unnecessary impurities are not mixed can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is based on the plasma vapor phase method.
The present invention relates to a method for producing carbon or a film containing carbon as a main component, which has good reproducibility and characteristics.

According to the present invention, after P-type and N-type layers are formed on a substrate provided in a reaction furnace by a plasma vapor phase method,
This N or P type impurity is re-emitted by the inner wall of the reactor or the holder of the substrate into the P or N type semiconductor layer to be produced next, and this is mixed in at a concentration of 10 ¹⁵ to 10 ¹⁸ cm ^-3. In order to prevent the intrinsic or substantially intrinsic (hereinafter I
The process of forming a coating film (referred to as a layer) (in this case, the film formed at the beginning of the next process may be coated) substantially removes the past history. To aim.

In addition, or in the previously formed layers, those adhering to the inner wall of the reactor, the surface of the holder of the substrate and the like are removed by converting hydrogen and a fluorine compound reactive gas such as CF ₄ into plasma. The purpose is to provide a process.

By doing so, the RUN-T can be reproduced with good reproducibility.
The O-RUN has a characteristic that variations in characteristics can be reduced and the obtained characteristics can be made extremely excellent.

Further, according to the present invention, in a semiconductor device having at least one junction, particularly PIN, PI, NI or PN junction on a substrate provided in the reaction furnace, the inner wall of the reaction furnace, particularly plasma atoms or reactive gas, collides. In order to prevent impurities, particularly oxygen and alkali metal atoms, from being released from the inner wall, it is intended to form carbon or a film containing carbon as a main component in advance on the surface thereof.

[0006]

2. Description of the Related Art Conventionally, with respect to the plasma CVD method, a semiconductor device having a PIN junction or the like has been manufactured in one reaction furnace. However, if this bonding is repeated, it suffers from completely indefinite deterioration and variation, and only the reliability as a semiconductor device is unsuitable.

As a result of investigating the cause, the most probable cause is that oxygen and alkali metals adhering to the inside of the reaction furnace are mixed in the semiconductor layer to cause a decrease in electric conductivity. Even if 1PPM is mixed, the dark conductivity of 10 ^-6 (Ωcm) ^-1 is 10 ^-8 (Ωcm) ^-1 and 1/1
It had been lowered to 00. Further, even in the case of an alkali metal, when 5PPM is mixed, the conductivity of P-type and I-type is lowered or the conductivity of the transparent conductive film is lowered.

In order to prevent these from being mixed, the semiconductor layer is preliminarily 0.2 to 2 .mu.m on the inner wall of the reaction furnace or the portion of the holder (also called "boat") of the substrate, which is sputtered by the reactive gas due to the plasma. It was extremely important that the film be formed to a thickness of 10 mm and coated. Furthermore, for the deterioration of reproducibility characteristics, for the fabrication of one semiconductor device,
When the last step is to make an N or P type semiconductor layer and the next first step is to make a P or N type semiconductor layer, the first impurity such as phosphorus is ^{added at} a concentration of 10 ¹⁵ -10 ¹⁸ cm ^-3. It is mixed in the P-type semiconductor layer. For this reason, even if boron is added to the P-type semiconductor layer at a concentration of, for example, 10 ¹⁸ to 10 ²¹ cm ⁻³ , its electrical conductivity is extremely poor because the recombination centers increase due to the incorporation of phosphorus.
When there is no mixture: 10 ^-2 to 10 ⁺¹ (Ωcm) ^-1 against 1
0 ^-6 to 10 ^-4 (Ωcm) ^-1 and 1/100 to 1/1000
I only got it.

Therefore, in the PIN photoelectric conversion device, an efficiency of 2 to 4% was obtained only with a variation of ± 200% for each run, which was not preferable.

However, in the method of the present invention, 8-10%
It has become possible to obtain a conversion efficiency as high as about 3 to 5 times that of.

Further, in order to reduce the effect of the impurity oxygen doping, a patent application filed by the present inventor, a semiconductor device manufacturing method, patent application 56-55608 (original display 53-1).
52887, filed on Dec. 10, 1978) is known. For example, when a PIN semiconductor device is to be manufactured, each P layer, I layer, and N layer is made into an independent reaction furnace, and the substrate is moved between the layers. This method can have the same measures as those of the present invention, and can obtain extremely preferable electric characteristics. However, in that case, the apparatus is three times as expensive as the one-chamber method, and the manufacturing cost is 2.5 to 3 times more expensive. Further, it has a defect that it is not suitable for mass production.

[0012]

The present invention is particularly effective in such a reactor, particularly in a horizontal reactor.
In addition, it is particularly effective when trying to make a large number of semiconductor devices on a substrate, and has a major feature that the manufacturing cost including depreciation of each semiconductor device can be reduced to 1/100 of that of a vertical reactor. ing.

[0013]

According to the present invention, when a carbon film is formed on a substrate provided in a reaction vessel by a plasma vapor phase method, hydrogen, oxygen, a fluorine compound or a mixture gas thereof made into plasma is used. Plasma cleaning a carbon film or a film containing carbon as a main component formed on the inner wall of the reaction container or the substrate holder, and thereafter, disposing the substrate in the reaction container, the carbon or A method for producing a carbon film, characterized in that a film containing carbon as a main component is formed, and the carbon film or the carbon is mainly formed on a substrate arranged in a reaction furnace by a plasma vapor phase method. When forming a film as a component, an intrinsic or substantially intrinsic carbon film is formed on the inner wall of the reaction furnace or the surface of the substrate holder before forming the carbon film, and thereafter, a base film is formed in the reaction furnace. Carbon film manufacturing method characterized by forming a film mainly containing carbon or carbon and arranged,
Is a second invention.

According to the present invention, a reactor or a reaction cylinder (10 to 30 cmφ, length 1 to 1) arranged horizontally for such mass production is used.
The method using 5 m) will be mainly described. An electrode for supplying electromagnetic energy for converting a pair of reactive gases into plasma is provided outside the reaction tube, and a heating device is provided outside the electrode to surround the reaction tube and the electrode, and the inside of the reaction furnace is directed toward the furnace. A reactive gas is caused to flow, and the substrate is arranged along the flow of this gas.

Further, substrates are arranged in the apparatus in a direction perpendicular or parallel to the electromagnetic field generated by a pair of electrodes, and the substrates are arranged in a plurality of stages or a plurality of rows to form a substrate of 2 to 20 cm square, for example, 20 stages of 10 cm square substrate. The description will focus on forming a film, particularly a carbon or silicon carbide film, on one surface of 400 sheets of 20 columns in total.

The present invention uses non-single-crystal carbon or carbon on the surface to be formed by using a reactive gas composed of a hydride or a halide (carbide silicide gas) having a carbon-silicon bond, or a hydrocarbon such as acetylene. A film whose main component is 0.05
The present invention relates to a plasma vapor phase method in which a reaction pressure of ˜1 torr and a temperature of 100 to 400 ° C. are formed.

The present invention further provides that the reactive gas contains an impurity gas containing trivalent impurities such as B, Al, Ga and In, such as diborane (B ₂ H ₆ ), and an impurity gas containing pentavalent impurities such as Phoshin (PH). ₃ ) or arsine (As
H ₃ ) is gradually added to closely form a P-type layer, an I-type layer and an N-type layer in the order of PIN on a substrate having a surface to be formed, and these steps are repeated to stably produce the layer. Is intended. Further, according to the power of the electromagnetic energy to be turned into plasma, the present invention is a semiconductor having an amorphous structure (referred to as AS), a semi-amorphous (semi-amorphous, hereinafter referred to as SAS) having a crystallinity of 5 to 100Å, or 5 to It is intended to produce a film having a structure of a polycrystal (polycrystal, hereinafter referred to as PC) having a size of 200Å. 200 to 500 for plasma reaction
Even when a high energy of W is required, the distance for obtaining the substantial plasma energy of the spine on the formation surface is controlled by the distance between the substrates.

Therefore, in the present invention, when an attempt is made to produce silicon carbide containing carbon as a main component in the reactive gas as the starting material, a material having a carbon-silicon bond is used.
That is, a hydride or a halide having a carbon-silicon bond, such as tetramethylsilane (Si (CH ₃ ) ₄ )
(Simply called TMS), tetraethylsilane (Si (C
₂ H ₅ ) ₄ ), Si (CH ₃ ) xCl _4- x (1 ≦ x ≦
3), Si (CH ₃ ) xH ₄ -x (1 ≦ x ≦ 3) and other reactive gases are used to facilitate obtaining Si—C bonds in the reaction product.

When trying to obtain carbon, acetylene (C
₂ H ₂ ) or ethylene (C ₂ H ₄ ) were mainly used. By doing so, silicon carbide (SixC _1- x)
(0 ≦ x <0.5) or carbon (C) (when these are combined, it can be shown as SixC ₁₋ x (0 ≦ x <0.5). Therefore, hereinafter, when silicon carbide is referred to, SixC ₁₋ x ( 0 ≦ x
<0.5) shall be produced).

Further, a trivalent or pentavalent impurity is added here to obtain P-type or I-type (intrinsic or auto-doped) from the surface to be formed.
Further, an N-type semiconductor or a semi-insulator was manufactured by substantially artificially adding impurities such as ping).

Further, when such a reactive gas is used, the electromagnetic energy of 50 W or less at a pressure of 1 atm or less, particularly 0.01 to 10 torr, typically 0.3 to 0.6 torr, is applied to the reactor, for example. 0.01-100MHz
In particular, it is possible to form a coating at 500 KHz or 13.56 MHz. That is, a low energy plasma CVD apparatus could be obtained.

When a high energy plasma atmosphere of 50 to 500 W is further applied, the formed silicon carbide is crystallized, and as a result, 0.1 to 5% of boron or phosphorus is added in the P or N type (here, (B ₂ H ₆ or PH ₃ )
In the case of the addition of / (the ratio of the carbide gas or the silicon carbide gas is expressed as a percentage), the electrical conductivity is 1 at low energy.
What was 0 ^-9 to 10 ^-3 (Ωcm) ^-1 was 10 ^-6 to 10
We were able to increase it to ⁺² (Ωcm) ^-1 , approximately 1000 times.

Furthermore, the silicon carbide obtained by using this high energy method was able to have a microcrystalline structure with a size of 5 to 200 Å. In such a structure, the ionization rate of the P or N type impurity as an acceptor or a donor was 97 to 100%, and all the added impurities could be activated.

[Embodiment] An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 shows plasma CVD using the present invention.
An outline of the device is shown. In FIG. 1, a substrate (1) having a surface to be formed is held by a square quartz holder, and in the drawing, a total of 14 sheets of 7 rows and 2 columns is used. The substrate and the holder are placed in advance in a separate chamber (29) in front of the reactor through an inlet (30), and a vacuum is drawn by a valve (32) and a rotary pump (33). Further, the opening / closing door (34) is opened and introduced into the reaction furnace by an automatic feeder, and further, the mixer mixing plate (35) is also arranged at the same time. These were performed in a vacuum state in both the reaction furnace and the separate room, and efforts were made to prevent oxygen (air) from entering the reaction furnace at all. Further, by closing the opening / closing door (34), the substrate was placed between the electrodes (9) and (10) as shown in the drawing.

The drawing shows the structure of the reaction system viewed from above, and the substrates (1) are arranged vertically with their back surfaces aligned with each other. As described above, it is very important to remove the flakes to the lower part by utilizing gravity when considering the mass production yield. Further, in the reaction furnace (25) in which the substrate (1) is inserted, an electric field of electromagnetic energy is perpendicular to or parallel to the substrate (especially if it is parallel, it is easy to obtain film uniformity). (B) In particular, a pair of electrodes (9) and (10) are arranged vertically or horizontally so as to be added as shown in (B). An electric furnace (5) is provided outside this electrode, and the substrate (1) is 100 to 400.
C. Typically, it is heated to 300.degree.

Reactive gases are hydrogen or helium carrier gas such as helium (13), trivalent impurity diborane (14), pentavalent impurity foshin (15), and tetravalent. Silica gas silane, which is an additive, was introduced from (16).

Further, a reactive gas T having a carbon-silicon bond.
When MS (20) is used, it is stored in the stainless steel container (21) because it is a liquid in the initial state. This container is controlled at a predetermined temperature by an electronic thermostat (22).

This TMS has a boiling point of 25 ° C., the rotary pump (12) is evacuated through the valve (11),
0.01 to 10 torr, especially 0.02 to 0.
It was kept at 4 torr. By doing this, the pressure lower than 1 atm results in no TM
S can be vaporized. This vaporized TMS is 1
Introducing into the reaction furnace at a concentration of 00% via a flow meter enables the flow rate to be controlled more accurately than in the conventional method in which the container (21) is bubbled to release the reactive gas. , Technically important. When the flow meter was clogged for practical use, helium was introduced from (24) in the drawing.

When the reaction product attached to the inner wall or surface of the reaction tube (25) or the holder (2) is to be removed, the fluorine compound gas CF ₄ or the mixed gas CF ₄ + O ₂ (2) with oxygen is obtained from (17). ˜5%) was introduced, and by applying electromagnetic energy, fluorine radicals and oxygen radicals were generated and removed by vapor phase etching.

Further, in this plasma discharge, after the reactive gas is mixed into the mixing chamber (8), the excitation chamber (2
In 6), a spatial reaction in which decomposition or reaction was caused and a reaction product was formed on the substrate was mainly used. As the electromagnetic energy, DC or high frequency was mainly used from the power source (4).

In this way, a silicon carbide film was formed on the formation surface. For example, the substrate temperature was 300 ° C., the high-frequency energy output was 25 W, silane or TMS was 50 cc / min, and He as a carrier gas was 250 cc / min. With (reactive gas / He) 5, a film growth rate of 160Å / min could be obtained.

Further, for this film formation, a PIN junction, a PN
Bonding, PI, NI bonding, PINPIN bonding, etc. were formed by gradually laminating reaction products required to have the required thickness on the substrate.

After the film has been formed on the surface to be formed in this manner, the reactive gas is sufficiently purged from the reaction tube, and then the opening / closing door (34) is opened and the mixer mixing plate (3).
5), the substrate on the jig (3) is evacuated (0.01 t) to the separate chamber (29) by an automatic drawing tube for both the reaction cylinder and the separate chamber.
or or below) and moved. Further open / close door (34)
After closing (1), the valve was opened from (31) in another room to fill it with air to bring it to atmospheric pressure, and then the substrate on which the jig and the film were formed was taken out.

As is clear from the above examples, according to the present invention, after the reactive gas is mixed in the mixer (8), the exhaust gas (6) is randomly moved in a layered state (microscopically in a plasmaized state). The film was formed on the surface to be formed to a thickness of 0.1 to 3 μ with a variation of ± 5% or less on the surface to be formed. There is.

FIG. 2 shows the relationship between the arrangement of the substrate (1) and the electrodes (9) and (10) as seen from the direction of the exhaust port (6) in the drawing of FIG. In the drawing, (A) shows the substrates arranged horizontally and the electromagnetic fields of the electrodes (9) and (10) arranged horizontally. In this case, the number of substrates that can be introduced at one time can be increased.

In FIG. 2B, the electromagnetic fields by the electrodes (9) and (10) and the substrate (1) are vertically arranged, and the number of substrates arranged is twice that of (A). FIG. 3 shows an operation procedure chart of the semiconductor device manufacturing method of the present invention.

In the drawing, "49", which is "0", indicates the retention of 0.01 torr or less by evacuation of the reaction furnace. Further, the "1" (40) indicates the coating of carbon or silicon carbide on the reactor or reactor and the holder according to the present invention.

The details of this coating are shown in FIG.
(B) and (C). FIG. 3 (B) shows vacuum evacuation (49)
To 0.01 torr or less and hold for 10 to 30 minutes, and then hydrogen for 0 to 30 minutes, 30 to 5 by electromagnetic energy.
Plasma cleaning by the output of 0 W, adsorption,
Water and oxygen were removed. After further removing the hydrogen,
By (51), helium was simultaneously turned into plasma by the output of 30 to 50 W for 10 to 30 minutes to further remove hydrogen on the surface. The hydrogen plasma generation (50) is performed by adding HCl or Cl at a concentration of 1 to 5% in hydrogen, chlorine radicals are simultaneously generated, and the radicals exist inside the holder such as quartz. It has the effect of sucking out alkali metals such as sodium. Therefore, the concentration of sodium, water, and oxygen at the background level can be reduced to 10 ¹⁴ cm ^-3 or less in the formed film, which was a very important pretreatment step.

When this chlorine was added, it was also effective to remove chlorine adsorbed on the wall surface by sputtering with an inert gas (51). By sufficiently plasma-cleaning the inner wall of such a reaction container such as quartz, a film which can easily release the impurity plasma by plasma can be closely adhered to the inner wall of the container. Thus, even if this film is formed to a thickness of several tens of μm, the protective film is peeled off from the wall surface due to residual stress or the like.
It can be prevented from becoming a powder (powder) and injecting into the coating.

Then, after vacuuming these systems, ethylene which is a carbide gas or TMS which is a silicon carbide.
Is introduced and decomposed by plasma energy,
The thickness of 2 μm is typically 0.2 to 0.5 μm.
When these films are formed, the region where high electromagnetic energy is applied, that is, the region where impurities are likely to be re-emitted, is particularly thick and easy to stick, which gives doubly preferable results.

Even when the complicated pretreatment step of the present invention is not carried out, after vacuuming as shown in FIG.
It was effective to form 1-2 μm and prevent the re-release of oxygen and alkali metal from the reactor wall.

Further, in FIG. 3A, in order to manufacture a semiconductor device, substrate coating and system vacuuming (4
1) Further, a P or N type semiconductor is produced (42), an I type semiconductor layer is produced (43), and an N type layer is produced (44),
A first device was made (48). This device is P
It goes without saying that it must be made according to a device design specification having at least one junction such as I, NI, PIN, PN.

After this, the same layer as the I-type semiconductor layer shown in (46) or the layer shown in (42) for the reaction system in which only the reaction furnace or the reaction furnace and the holder are inserted and installed in this system. The coating was used to prevent the history of the step (44) used in manufacturing the previous device from affecting the next run. The details are shown in FIGS.
Shown in (D) and (E).

That is, FIG. 3 (B) shows a process of forming a semiconductor layer in the first step of vacuuming (49), hydrogen plasma discharge (50), helium plasma treatment (51), and the first run of the semiconductor device, as in the above-mentioned pretreatment. It has (52). However, since (50) and (51) have already been performed in (46) of (A), 0.1 to (52) of (C) is generally used.
It was sufficient to produce a semiconductor layer with a thickness of 2μ.

The plasma etching step shown in (D) and (E) may be carried out in order to eliminate the history of the previous production of the apparatus (40), that is, the previous run. That is, FIG.
In (B), vacuum evacuation (49) CF ₄ or CF ₄ + O (about 5%) was introduced from (17) in FIG. 1, and plasma etching (53) was performed for 20 minutes to 1 hour. Further evacuation is performed, and then hydrogen plasma treatment (50) is performed for 10 to 30 minutes to remove the C and F residues.
A semiconductor layer having a conductivity type and components similar to those of the semiconductor layer (42) of I-type of 0.5 to 0.5 μm or the first run of the next step was manufactured. This method was the most thorough and guaranteed reproducibility.

A simple method is shown in (E) (49).
The steps of evacuation and plasma etching (53) and removal of residual adsorption gas (50) were performed.

As a result, P or N type impurities are separated from each other between the last step (44) of the fabrication (48) of the first semiconductor device and the first step (42) of the next step (48). It was possible to eliminate the possibility of contamination in 42).

FIG. 4 shows the result of evaluation of the effect by the method of the present invention. FIG. 4 shows the result of a photoelectric conversion device manufactured using the method of the present invention. In this case, as a substrate, ITO having a thickness of 500 to 2000 Å on a metal such as a stainless steel substrate or a glass which is a translucent substrate, and a multi-layer electrode having tin oxide or antimony oxide formed thereon to a thickness of 100 to 500 Å are provided. A substrate was used. On top of this, silicon carbide (SixC _1-X 0
≦ X <1) (for example, X = 0.3 to 0.5) is 100 to 3
To a thickness of 00Å and to the upper surface thereof an intrinsic or substantially intrinsic silicon of AS or SAS to a thickness of 0.4 to 0.7 μm, and on this upper surface, a silicon carbide (SixC) containing N-type carbon as a main component. _1−X 0 ≦ X <1 (for example, X = 0.3 to
0.5) PIN with a thickness of 100-300Å
It has a structure. The specifications of the P, I, and N type semiconductors are (42), (43), and (4) in the chart of FIG.
4), (42) ...

Further, after that, 600 to ITO is added in this step.
A photoelectric conversion device was made to a thickness of 800 Å or an aluminum metal film was formed by vacuum deposition. The conversion efficiency is shown in FIG.

With a cell size of 1 cm ² , AM1 (100
Under the condition of mW / cm ² ), 3% of the case (71) without the pretreatment (40) and the value (70) with the pretreatment were obtained. Furthermore, the change in the efficiency of the run (every production date) due to the addition of the intermediate step (46) (60) resulted in (61) without any addition.

The efficiency of (60) can be 11 to 9%, while the efficiency of (60) is 1 to 4 when the method of the present invention is not used.
There was only%.

Further, when the cell area was set to 100 cm ² , the efficiency of 7 to 9% could be obtained using the method of the present invention, while it was 0 to 3% without the method of the present invention. In particular, those having no diode characteristics had 30% or more and could not be manufactured.

FIG. 4B shows the electric conductivity value when an I-type silicon semiconductor is formed in the process of forming a P-type semiconductor particularly near the surface.

When a P-type semiconductor is produced in the previous step and the pretreatment of the intermediate treatment method of the method of the present invention is not carried out, the electrical conductivity by light irradiation of AM1 is (65). The case opposite to the dark conductivity (64) was also observed, and the value was 10 ⁻⁶ to 10 ⁻⁴ , which was a large variation. On the other hand, when the pretreatment of the present invention was performed, photoconductivity (70) and dark conductivity (70 ') were obtained. Further, when the intermediate treatment was performed, photoconductivity (62) and dark conductivity (63) were obtained. These are the
It clearly shows how important it is to prevent the ping effect.

As is apparent from the above description, the present invention is applicable to the production of not only photoelectric conversion devices or light emitting elements but also various semiconductor devices such as field effect semiconductor devices and photosensor arrays using the same reaction tube. The present invention provides an extremely important manufacturing apparatus and manufacturing method, which allows a non-single crystal semiconductor film to be formed on 100 to 500 substrates in the same time as when four 10 cm squares are formed by a conventional vertical plasma CVD apparatus. Can be made and is very suitable for mass production.
Further, by arranging the electrode structure or the substrate as in the present invention, the photoelectric conversion device having the PIN structure is
A conversion efficiency of 0% or more could be repeatedly and stably obtained, and the film quality was extremely excellent.

In the present invention, silicon carbide (SixC _1-X
The description is centered on 0 ≦ X <0.5). The present invention is shown in FIG.
The horizontal plasma CVD apparatus shown in FIG.
However, the present invention is effective even if the electrode is made in a dielectric type or a plasma CVD apparatus utilizing arc discharge. Further, the method of the present invention can be similarly applied to a vertical or horizontal bell jar type plasma CVD apparatus.

[0057]

[Effect] By adopting the constitution of the present invention, it is possible to efficiently obtain a carbon film having a function of preventing the mixing of unnecessary impurities.

[Brief description of drawings]

FIG. 1 is a plasma vapor phase apparatus used in Examples.

FIG. 2 shows a part of FIG.

3 is a chart using the apparatus of FIG. 1 and using the plasma vapor phase method of the method of the present invention.

4 is another material showing the efficiency of the photoelectric conversion device obtained according to the chart of FIG. 3 and the anti-doping effect of the method of the present invention.

Claims (2)

[Claims] 1. When forming a carbon film on a substrate provided in a reaction vessel by a plasma vapor phase method, an inner wall of the reaction vessel or a substrate holder is formed by plasmatizing hydrogen, oxygen, a fluorine compound or a mixture gas thereof. Plasma cleaning the carbon film or the film containing carbon as the main component formed in the above step, and thereafter disposing the substrate in the reaction vessel, and depositing the carbon or the film containing carbon as the main component by the plasma vapor phase method. A method for producing a carbon film, which comprises forming the carbon film. 2. When forming a carbon film or a film containing carbon as a main component on a substrate arranged in a reaction furnace by a plasma vapor phase method, the inner wall of the reaction furnace or the substrate is formed before forming the carbon film. A carbon film characterized in that an intrinsic or substantially intrinsic carbon film is formed on the surface of the holder, and thereafter a substrate is placed in the reaction furnace to form carbon or a film containing carbon as a main component. Manufacturing method.