WO2014208943A1 - Plasma chemical vapor deposition device - Google Patents

Abstract

The present invention relates to a plasma chemical vapor deposition device, comprising: a vacuum chamber having a plurality of vacuum spaces which are partitioned so as to be independent from each other; a vacuum control unit for controlling the degrees of vacuum for the vacuum spaces; circular electrodes which are rotationally provided in each vacuum space one by one in the shape where at least a part of each outer circumferential surface is positioned in each vacuum space, and of which the outer circumferential surfaces are surrounded with a base material; at least one magnetic field generating member for forming a magnetic field toward the base material surrounding each circular electrode; and a gas supply unit for supplying a process gas to the inside of the vacuum spaces. Thus, provided is the plasma chemical vapor deposition device which can independently and continuously perform a plurality of processes and can obtain process stability and quality improvement even in a high-speed process.

Description

Plasma chemical vapor apparatus

The present invention relates to a plasma chemical vapor apparatus, and more particularly, to a plasma chemical vapor apparatus capable of performing a plurality of processes independently and continuously, and improving process stability.

In the field of semiconductor, display, solar cell or packaging paper manufacturing, etc., it is applied to a process of forming a thin film or etching a thin film on a substrate, or a surface treatment for changing the surface characteristics of the substrate. PVD method), chemical vapor deposition (CVD), and the like.

Among them, the plasma chemical vapor apparatus based on chemical vapor deposition (CVD) may be applied to a method of performing a series of processes as described above on the surface of a substrate by decomposing the process gas by plasma, and the process speed and The process quality is superior to devices using the PVD method and is widely used in recent years.

An example of such a conventional plasma chemical vapor apparatus has been disclosed in Japanese Unexamined Patent Publication No. 2011-80104 (hereinafter referred to as "prior patent").

The prior patent discloses an example of a film forming apparatus in which a process gas decomposed in a process of passing a film forming region of a vacuum chamber while a substrate is wound around a pair of circular electrode surfaces as a substrate is transferred in a roll-to-roll manner is formed on the substrate.

A magnetic field generating member is provided inside both circular electrodes, and the magnetic field formed by these magnetic field generating members densifies the plasma in the deposition region adjacent to the substrate.

On the other hand, this prior patent has been to minimize the deposition material deposition in other areas other than the surface of the substrate during the film forming process by placing a portion of the outer peripheral surface of the both circular electrodes in the film forming region blocked from other areas.

However, such a conventional plasma chemical vapor apparatus has a form in which a pair of circular electrode portions are positioned in a region blocked from other regions of the vacuum chamber, so that the deposition process performed at both circular electrodes cannot be independently controlled.

In addition, the conventional plasma chemical vapor apparatus has a problem that only a single film forming process is performed in a single film forming region, and a plurality of different processes cannot be performed continuously.

In addition, a pair of circular electrodes are arranged in a single film forming region, which limits the process stability between the two circular electrodes. That is, the process gas decomposed by the plasma generated from the circular electrode on one side may be unstablely deposited on the circular electrode on the other side and the substrate, and thus, there is a limit in improving process safety. This limitation of process stability is emerging as a problem that can not perform high-speed process and the limit of quality improvement.

This problem also applies to the case where the conventional plasma chemical vapor apparatus is used for the purpose of performing an etching process or a surface treatment process in addition to the film forming process.

Accordingly, an object of the present invention is to provide a plasma chemical vapor apparatus that can perform a plurality of processes independently and continuously, and can ensure process stability and quality improvement even at a high speed process.

According to the present invention, there is provided a plasma chemical vapor apparatus, comprising: a vacuum chamber having a plurality of independent vacuum spaces separated from each other; A vacuum controller for adjusting the vacuum degree of the vacuum spaces; A circular electrode having at least a portion of an outer circumferential surface disposed in each of the vacuum spaces so as to be rotatable in each of the vacuum spaces, and having a substrate wound around the outer circumferential surface; At least one magnetic field generating member which forms a magnetic field toward the substrate to wind the circular electrodes; It is achieved by a plasma chemical vapor apparatus comprising a gas supply for supplying a process gas into the vacuum spaces.

Here, a plurality of guide rolls are rotatably provided in adjacent areas of the circular electrodes, and the substrate is not wound or rolled selectively when the process for the substrate is a process for one surface or a process for both surfaces of the substrate. It is preferable to further include.

In addition, it is effective that the process gas is any one of an etching gas, a film forming gas, and a surface treatment gas.

In addition, the gas supply unit is effective to independently control the process gas supplied to each of the vacuum space.

In this case, the process gas supplied to each vacuum space from each gas supply unit may be a process gas of a different material.

In addition, it is more preferable that the vacuum control unit independently controls the degree of vacuum of each vacuum space.

At this time, the diameter of the circular electrodes are all the same or at least one of the circular electrodes may have a different diameter than the other circular electrode, the diameter of the circular electrode is effective to be 100mm to 2000mm.

On the other hand, the magnetic field generating member may be provided inside or outside each circular electrode.

In addition, the magnetic field generating member may be installed to adjust the rotation angle.

In addition, the magnetic field generating member may be provided in plurality.

According to the present invention, it is possible to perform a plurality of processes independently and continuously, and there is provided a plasma chemical vapor apparatus capable of ensuring process stability and quality improvement even at a high speed process.

1 is a schematic diagram of a plasma chemical vapor apparatus according to an embodiment of the present invention,

2 is a schematic diagram of a plasma chemical vapor apparatus according to another embodiment of the present invention;

3 is a schematic diagram of a plasma chemical vapor apparatus according to another embodiment of the present invention;

4 is a schematic diagram of a plasma chemical vapor apparatus according to another embodiment of the present invention;

5 and 6 are enlarged views of one example of a circular electrode of the plasma chemical vapor apparatus according to the present invention,

7-9 are schematic diagrams of a plasma chemical vapor apparatus according to another embodiment of the present invention.

As shown in FIG. 1 and FIG. 2, the plasma chemical vapor apparatus 1 according to the present invention has a vacuum chamber 10 having a plurality of independent vacuum spaces 11, and corresponding to each vacuum space 11. Circular electrodes 20 disposed one by one and wound around the substrate S, the magnetic field generating member 30 forming a magnetic field toward the substrate S positioned in the vacuum space 11, and the substrate S includes the circular electrodes ( 20) the substrate transfer unit 40 to be transported in a continuous winding form, the vacuum control unit 50 for adjusting the degree of vacuum of the vacuum space 11, and supplying the process gas into the vacuum space (11) And a gas supply unit 60 and a power supply unit 70 for supplying power to the circular electrode 20 and the like.

The vacuum chamber 10 is manufactured to have a plurality of independent vacuum spaces 11 which are separated from each other by using a plate-like member such as a metal or an alloy having excellent pressure resistance and heat resistance and a frame. The independent sections of these vacuum spaces 11 may be made of partition members 13 such as shield covers. Here, the vacuum spaces 11 are preferably located adjacent to.

Each of the circular electrodes 20 is rotatably installed in a form in which some outer peripheral surfaces thereof are located in the vacuum spaces 11, and the substrate S forms an outer peripheral surface of the circular electrodes 20 located in the vacuum spaces 11. It may be partially wound in a wound form and transported by the substrate transfer part 40.

The circular electrode 20 is rotated to prevent deterioration and stable plasma generation during plasma generation, and the rotation of the circular electrode 20 may be rotated using a driving means (not shown) such as a separate driving motor. It may be rotated by the driving force generated in the sending section 40.

The circular electrode 20 is preferably made of a metal material having excellent plasma resistance, excellent heat resistance, cooling efficiency and thermal conductivity, and excellent workability as a nonmagnetic material. Specifically, aluminum, iron, copper, stainless steel, magnesium It may be provided with a metal material such as, MO, Ti. In addition, the cooling water or the heating water for cooling or heating the circular electrode 20 may flow through the inside of each circular electrode 20.

In addition, the diameter of the circular electrode 20 may be variously changed according to the conditions, such as the area or type of the substrate (S), the diameter may be appropriately selected from 100mm to 2000mm. Of course, the circular electrodes 20 corresponding to the respective vacuum spaces 11 may have the same diameter, as shown in FIGS. 1 and 2, and although not shown, each circular electrode 20 may have a different diameter. . In addition, at least some of the circular electrodes 20 of the plurality of circular electrodes 20 may have the same diameter and the remaining circular electrodes 20 may have different diameters.

1 and 2, the magnetic field generating member 30 may be provided inside the circular electrode 20 to form a magnetic field toward the substrate S located in the vacuum space 11. In this case, the magnetic field generating member 30 has a central magnet 33 having a length corresponding to the length of the circular electrode 20, and has a polarity different from that of the central magnet 33 and is disposed in a track shape around the central magnet 33. It is desirable to have an outer magnet 35 to be used. The structure of the magnet 31 is a structure for generating a race track-shaped plasma track on the outside of the circular electrode (20).

In this case, the polarity of the magnet 31 may be arranged in various forms in a range capable of stably dense the plasma in the surface region of the substrate (S).

In this case, the magnetic field generating member 30 may be provided in plural in the circular electrode 20 according to the conditions such as the size of the circular electrode 20, although not shown, depending on the type or process conditions of the substrate (S) The direction of the magnetic field may be adjusted by adjusting the rotation angle of the generating member 30.

Of course, the magnetic field generating member 30 may be provided outside the circular electrode 20, as shown in FIG. 3, may be provided inside the vacuum space 11 or outside the vacuum space 11 as shown in FIG. 4. In this case, the magnetic field generating member 30 may be provided in plural, and the direction of the magnetic field may be adjusted by adjusting the rotation angle.

The rotation angle adjustment of the magnetic field generating member 30 may be a manual or automatic configuration by power supply, and in the case of the automatic configuration, the rotation angle of the magnetic field generating member 30 is adjusted by using a driving motor and a controller not shown. I can regulate it.

The rotation angle control of the magnetic field generating member 30, when the magnetic field generating member 30 is provided inside the circular electrode 20, as shown in Figure 5, the rotation axis 37 in the center of the circular electrode 20 Of the magnetic field generating member 30 by rotating the rotary shaft 37 manually or automatically by providing a rotating support member 39 supporting the magnetic field generating member 30 on the rotating shaft 37. The angle of rotation can be adjusted. 3 and 4 in which the magnetic field generating member 30 is provided outside the circular electrode 20, the rotation angle of the magnetic field generating member 30 may be provided with a rotating shaft and a rotation support member.

Here, in the case where the rotation angle adjustment of the magnetic field generating member 30 is automatically performed, the rotating shaft 37 may be rotated using a driving motor (not shown). In this case, the driving motor may be a clutch (not shown). In addition to adjusting the rotation angle of the magnetic field generating member 30, it can also be used for the purpose of rotating the circular electrode 20.

On the other hand, the plasma chemical vapor apparatus 1 according to the present invention, as shown in Figure 6, to enable the reciprocating movement to a position spaced apart from the position that the magnetic field generating member 30 approaches the inner peripheral surface of the circular electrode 20 It may be installed.

This can be implemented by a configuration including a distance adjusting means 76 for reciprocating the magnet 31 constituting the magnetic field generating member 30 in the radial direction of the circular electrode 20, the distance adjusting means 76 ) May be provided as a guide portion 77 for supporting the reciprocating movement of the magnet 31, and a distance adjusting portion 78 for moving the magnet 31 so as to adjust the moving distance with respect to the guide portion 77.

At this time, the guide portion 77 supports the fixed guide 77a toward one side of the inner circumferential surface of the circular electrode 20 from the inner central region of the circular electrode 20 and the magnet 31 while being opposed to the fixed guide 77a. It may be provided as a fixed guide 77b for moving, and rolling means such as rolling rollers or bearings for smooth relative movement may be interposed between the fixed guide 77a and the fixed guide 77b.

In addition, the distance adjusting unit 78 provides a driving force for relatively moving the fixed guide 77b with respect to the fixed guide 77a, and the inner circumferential surface of the circular electrode 20 to adjust the moving distance of the fixed guide 77b. As a driving force transmission means for pushing or pulling to a position spaced apart from an approaching position, the motor includes a solenoid or a cylinder, a motor, a motor, a motor, or the like, driven by a motor, including a driven gear or cam, and a driven gear or cam. It can be provided with an automatic configuration such as configuration.

Of course, the distance adjusting unit 78 forms a stopper structure between the fixed guide 77a and the fixed guide 77b, and the operator opens the circular electrode 20 to adjust the moving distance of the fixed guide 77b by several species. It may be a passive configuration.

On the other hand, the substrate transfer part 40, as described above, the take-up roll 41 for unwinding the base material S, the winding roll 43 for winding the last base material S while winding all the cylindrical electrodes, and winding A guide roll 45 and a tension adjusting means (not shown) may be provided to guide the substrate S unwound from the roll 41 to be wound into the take-up roll 43 through the circular electrodes 20 at an appropriate tension. have.

At this time, the base material (S) may be provided with various synthetic resin materials such as PET, PEN, PES, polycarbonate, polyolefin, polyimide, or the like as a synthetic resin film or sheet which is a flexible material. In addition, the base material S may be a conductive material such as metal foil, Cu foil, stainless steel foil, or the like.

In addition, when the process to be performed is an etching process, the surface of the substrate S may be transferred in a form including a pattern forming sheet such as a mask for forming an etching pattern, and the pattern forming sheet may be transferred to a substrate (S) in a previous process. ) It may be attached to the surface or provided with a separate pattern-forming sheet supply in the process of performing the process to be transported with the substrate (S).

In addition, the unwinding roll 41, the winding roll 43, and the guide roll 45 may have the base material S according to the number and size of the circular electrodes 20 provided in the number corresponding to the vacuum space 11. The arrangement can be changed into various forms depending on the conditions in the range that is stably wound on the take-up roll 43 through the).

On the other hand, the vacuum control unit 50 may control the vacuum degree of each vacuum space 11 at the same degree of vacuum at the same time, or may independently control the vacuum degree of each vacuum space (11). The former may be applied when the same process is repeatedly performed in each vacuum space 11 continuously, and the latter may be applied when different processes are continuously performed in each vacuum space 11. To this end, the vacuum control unit 50 is provided with a plurality of vacuum control unit 50 corresponding to each vacuum space 11, as shown in Figure 2, or, as shown in Figure 1, a single vacuum control unit 50 The degree of vacuum of the vacuum spaces 11 may be controlled as described above.

The configuration of the vacuum control unit 50 may be made in various forms. For example, like the general plasma chemical vapor apparatus 1, the vacuum control unit 50 may include a configuration in which a configuration such as a vacuum pump and a valve is connected in various forms. Preferably, the low vacuum pump 51 and the high vacuum pump 53 and the plurality of valves 55 and the pressure control so that the vacuum exhaust may be performed in the order of low vacuum to high vacuum in the process of adjusting the degree of vacuum in the vacuum space 11. Configurations such as the valve 57 and the high vacuum valve 59 may be included in an appropriate number and form.

Meanwhile, the gas supply unit 60 may include a gas supply source 61 for supplying process gas into the vacuum space 11, and a gas supply flow path extending from the gas supply source 61 into the vacuum space 11 (not shown). And a gas flow controller 65, a vacuum gauge 67, a valve 68, and the like, as a gas supply controller 63 for opening and closing a gas supply passage (not shown).

Here, the gas supply passage (not shown) may extend from the gas supply source 61 to a plurality of regions inside the vacuum space 11. For example, the gas supply passage may be an area adjacent to the surface side of the substrate S where the plasma is concentrated. However, it can be extended to a region desired for high quality film formation. A gas supply passage extending to each region may be provided with a nozzle 69 for injecting the corresponding gas.

The gas supply unit 60 may also control the process gas supplied to each vacuum space 11 to be simultaneously supplied to the same process gas, so that the process gas supplied to each vacuum space 11 may be supplied to different process gases. It can also be controlled independently. The former may be applied when the same process is repeatedly performed in each vacuum space 11 continuously, and the latter may be applied when different processes are continuously performed in each vacuum space 11. To this end, the gas supply unit 60 is provided as a single gas supply unit 60 as shown in FIG. 1, or as shown in FIG. 2, provided as a plurality of gas supply units 60 corresponding to the respective vacuum spaces 11. As described, the process gas supply can be controlled.

Here, when the plasma chemical vapor apparatus 1 according to the present invention is a film forming apparatus performing a film forming process, the film forming gas is HMDSO, TEOS, SiH ₄ , dimethylsilane, trimethylsilane, tetramethylsilane containing Si as a source gas. , HMDS, TMOS and the like, and may be C containing methane, ethane, ethylene, acetyrene and the like. Moreover, various source gases can be suitably selected according to the kind of film-forming, including titanium tetrachloride containing Ti, etc. As the reaction gas, oxygen, ozone, nitrous oxide, or the like can be used for forming the oxide, and for forming nitride, nitrogen, ammonia, or the like can be appropriately selected depending on the type of film formation. In addition, as the auxiliary gas, Ar, He, H _2, etc. may be selectively used, and various auxiliary gases may be selectively used depending on the type of film formation. In addition, the film forming gas suitable for the film forming process to be performed is not limited.

Alternatively, when the plasma chemical vapor apparatus 1 according to the present invention is an etching apparatus that performs an etching process, the etching gas as the process gas may be formed according to the material of the substrate S and the thin film deposited on the substrate S. Can vary. For example, the etching gas may be a Cl-based gas such as Cl2 or BCl3 and an F-based gas such as CF4, SF6, or NF3. In addition, various etching gases such as HF, hfacH, XeF2, Acetone, NH3, and CH4 may be selected. That is, the etching gas suitable for the etching process to be performed is not limited. In the etching process, a mask corresponding to the etching pattern may be included on the surface of the substrate S.

Alternatively, when the plasma chemical vapor apparatus 1 according to the present invention is a surface treatment apparatus that performs a surface treatment process, various process gases may be used in the use for changing the surface characteristics of the substrate S as the process gas. For example, gas for pre-treatment use may use gases such as Ar, H2, O2, N2, He, CF4, NF3, and gas for ashing use may use gas such as Ar, O2, CF4, and the like. In addition, a process gas suitable for the surface treatment process to be performed is not limited.

Meanwhile, the power supply unit 70 may supply the high frequency AC power to the circular electrode 20 as a power source for generating plasma. Here, the high frequency AC power source may use a high frequency (AC) power source or a high frequency (VHF) power source (VHF) for forming a high density plasma. The polarity may be selectively connected to the positive electrode (+) or the negative electrode (−) to the circular electrode 20 depending on the conditions.

An example of applying the plasma chemical vapor apparatus 1 according to the present invention having such a configuration to perform an etching process will be briefly described.

After loading the substrate S in the form of winding the circular electrode 20 positioned in each vacuum space 11 inside the vacuum chamber 10, the vacuum control unit 50 plasmas each vacuum space 11. Vacuum to a vacuum suitable for etching. At this time, the vacuum degree of each vacuum space 11 may be the same as described above and may be different. In the former case, the same etching pattern is continuously etched in each vacuum space 11 in the same region of the substrate S, so that the etching rate can be significantly improved, or the etching method can be used as a method for precise etching. It can be used as a method for independently etching different etching patterns in each vacuum space 11 in different regions of the substrate S, or a method for sequentially etching thin film layers formed in multiple layers on the substrate S. .

After the substrate S is loaded, the etching gas is introduced into each vacuum space 11 at an appropriate flow rate in the gas supply unit 60, and the vacuum degree of each vacuum space 11 is properly maintained as described above.

In this case, the etching gas supplied from the gas supply unit 60 to each vacuum space 11 may be supplied with the same etching gas or different etching gas for each vacuum space 11 according to the above-described etching method.

At this time, when power is supplied from the power supply unit 70 to each of the circular electrodes 20, the circular electrodes 20 are rotated and positioned in each vacuum space 11 by the magnetic field generated by the magnetic field generating member 30. The plasma of the outer surface of the circular electrode 20 is formed.

On the other hand, the substrate (S) is moved through each vacuum space 11 in the form of winding each circular electrode 20 as described above, the substrate (S) by the plasma in the process of passing the region where the plasma is formed The etching gas converted into the active species form is strongly induced in the direction of the substrate S, so that the etching process of the substrate S is performed.

In this process, the substrate S, which has been etched, is finally recovered to the winding roll 43 as described above, and when the recovery of the substrate S is completed, the power supply unit 70 cuts off the power, and the gas supply unit ( At 60), the etching gas supply is stopped. Then, the vacuum in the vacuum control unit 50 discards the vacuum of each vacuum space (11).

When the vacuum is broken, the etching process according to the present invention is completed by drawing the substrate S on which the etching is completed to the outside.

Even if the process to be performed is a film formation process or a surface treatment process, it may be easily applied to performing a film formation or surface treatment process by plasma by changing the type of process gas and the degree of vacuum.

In the plasma chemical vapor apparatus 1 according to the present invention, the vacuum spaces 11 are each formed as independent spaces, and the single circular electrode 20 and the magnetic field generating member 30 correspond to each vacuum space 11. Arrangement may be performed to continuously and independently move the substrate (S) in each vacuum space (11).

In addition, the same corresponding process may be performed in each vacuum space 11 or different corresponding processes may be continuously performed.

In addition, process stability is ensured as a single circular electrode 20 is disposed in each vacuum space 11. That is, the process gas decomposed by the plasma generated in the circular electrode 20 of each vacuum space 11 does not affect the other side vacuum space 11, thereby improving process safety.

This process stability improvement provides high speed process performance and quality improvement.

On the other hand, the plasma chemical vapor apparatus 1 according to the present invention, as shown in Fig. 7 to 9, any one of the guide roll 45 and the circular shape of the plurality of guide rolls 45 provided in each vacuum space (11) By adjusting the form in which the substrate S is wound around the electrode 20, one surface process or a two-side process of performing the process on one surface of the substrate S or performing the process on both sides of the substrate S may be selected. .

For example, the form in which the substrate S is wound around the guide roll 45 and the circular electrode 20 selected as shown in FIG. 7 may be any one of a corresponding process (deposition, etching, or surface treatment) on one surface of the substrate S. ) Can be performed. At this time, the magnetic field generating member 30 forms a magnetic field toward the substrate S which winds the circular electrode 20 to condense plasma.

Alternatively, the form in which the substrate S is wound around the guide roll 45 and the circular electrode 20 selected in the form shown in FIGS. 8 and 9 corresponds to both surfaces of the substrate S (deposition, etching or surface treatment process). Can be performed). At this time, the magnetic field generating members 30 of the adjacent circular electrodes 20 form a magnetic field toward the substrate S in opposite directions to densify the plasma.

In the plasma chemical vapor apparatus 1 of this type, the film forming or surface treatment process may be performed on one or both surfaces of the substrate S by changing conditions such as the type and the degree of vacuum of the process gas in various forms as in the above-described embodiments. It can be applied easily.

A plurality of processes can be performed independently and continuously, and a plasma chemical vapor apparatus capable of ensuring process stability and quality improvement even at a high speed process is provided.

Claims (14)

In the plasma chemical vapor apparatus, A vacuum chamber having a plurality of independent vacuum spaces separated from each other; A vacuum controller for adjusting the vacuum degree of the vacuum spaces; A circular electrode having at least a portion of an outer circumferential surface disposed in each of the vacuum spaces so as to be rotatable in each of the vacuum spaces, and having a substrate wound around the outer circumferential surface; At least one magnetic field generating member which forms a magnetic field toward the substrate to wind the circular electrodes; And a gas supply unit for supplying a process gas into the vacuum spaces. The method of claim 1, A plurality of guide rolls are rotatably provided in adjacent areas of the circular electrodes, and the substrate is optionally wound or not wound when the process for the substrate is a process for one side or a process for both sides of the substrate. Plasma chemical vapor apparatus comprising a. The method of claim 2, Wherein said process gas is any one of an etching gas, a film forming gas, and a surface treatment gas. The method of claim 3, The gas supply unit is a plasma chemical vapor apparatus, characterized in that for independently controlling the process gas supplied to each vacuum space. The method of claim 4, wherein And a process gas supplied from each gas supply unit to each vacuum space is a process gas of a different material. The method according to any one of claims 1 to 5, The vacuum control unit is a plasma chemical vapor apparatus, characterized in that for controlling the vacuum degree of each vacuum space independently. The method of claim 6, The diameter of the circular electrodes are all the same or at least any one of the circular electrode has a different diameter than the other circular electrode plasma chemical vapor apparatus. The method of claim 7, wherein The diameter of the circular electrode is a plasma chemical vapor apparatus, characterized in that 100mm to 2000mm. The method of claim 7, wherein The magnetic field generating member is provided in each of the circular electrode plasma chemical vapor apparatus. The method of claim 9, The magnetic field generating member is a plasma chemical vapor apparatus, characterized in that the rotation angle adjustable. The method of claim 9, The magnetic field generating member is a plurality of plasma chemical vapor apparatus, characterized in that provided in the plurality of circular electrodes. The method of claim 7, wherein The magnetic field generating member is provided on the outside of the circular electrode to form a magnetic field toward the substrate side. The method of claim 12, The magnetic field generating member is a plasma chemical vapor apparatus, characterized in that the rotation angle adjustable. The method of claim 12, Plasma chemical vapor apparatus, characterized in that the magnetic field generating member is provided in plurality.

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