JP2005330542A - Plasma cvd film deposition system, method for confirming ignition of plasma, method for confirming property of cvd film and method for confirming stain of system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plasma CVD (Chemical Vapor Deposition) system where, at the time when the nonignition or the defect of ignition in plasma is generated, all the numbers thereof can be detected, to provide a method for confirming the ignition of plasma therefor, to provide a method for confirming the properties of a CVD film, and to provide a method for confirming the stain of the system. <P>SOLUTION: The plasma CVD film deposition system at least comprises: a vacuum chamber having a storage space for a plastic vessel; a gaseous starting material feeding means for feeding a gaseous starting material to at least either the internal space or the external space of the vessel arranged in the storage space; a plasma generating means for feeding high frequency or microwaves for making the gaseous starting material into plasma; and an exhausting means for exhausting the gaseous starting material, and wherein a CVD film is deposited on at least either the inner surface or the outer surface of the vessel. It is characterized in that a grounded electrically conductive member is arranged at the inside of the vessel so as to freely be inserted into and withdrawn from a mouth, and also, a first ammeter for measuring electric current flowing through the grounding conductor of the electrically conductive member is connected. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is for coating a gas barrier film such as a CVD film, for example, a DLC (Diamond Like Carbon) film, on at least one of an inner surface and an outer surface of a plastic container by a CVD (Chemical Vapor Deposition) method. The present invention relates to a plasma CVD film forming apparatus, a plasma ignition confirmation method, an apparatus contamination confirmation method, and a CVD film property confirmation method in the apparatus.

  In order to deposit a DLC film on the inner surface of a plastic container for the purpose of improving gas barrier properties, etc., there is a disclosure of an invention of a vapor deposition apparatus using a CVD method, particularly a plasma CVD method (see, for example, Patent Document 1). In the apparatus described in Patent Document 1, a plastic container is disposed in a vacuum chamber, and a high frequency is applied to an external electrode that constitutes a part of the vacuum chamber in a state in which a raw material gas is allowed to flow inside the container. As a result, a bias voltage is generated between the internal electrode and the external electrode arranged inside the container, and the source gas is turned into plasma, and a CVD film is formed on the inner surface of the container. The raw material that has been converted to plasma is exhausted out of the vacuum chamber by the exhaust means of the vacuum chamber.

There is also a disclosure of a technique relating to a mass-production film forming apparatus in which a vacuum chamber is placed on a turntable and a film is formed every time the turntable makes one turn (see, for example, Patent Document 2).
JP-A-8-53117 JP 2004-27271 A

  In a plasma CVD film forming apparatus that forms a CVD film on the wall surface of a plastic container, using the CVD film forming apparatus of Patent Document 1 as an example, the material gas is converted into plasma inside the plastic container and film formation is performed. If a large number of films are formed here, carbon-based foreign substances, which are insulators, adhere to and accumulate on the internal electrodes. In addition, the raw material gas remaining without being consumed as a CVD film or a raw material gas containing a carrier gas such as argon is exhausted from a vacuum chamber which is a film forming chamber. However, these exhaust gases still have residual energy due to plasmatization, and carbon-based foreign substances are attached to the wall surface of the exhaust path from the film formation chamber to the vacuum pump.

  In the apparatus of Patent Document 1, a high frequency is applied to an external electrode surrounding a container, and a raw material plasma is generated between the internal electrode arranged inside the container. However, since the plasma leaks to the exhaust path, the impedance is not determined only by the external electrode and the internal electrode, but actually the impedance is determined by the external electrode, other vacuum chamber members, exhaust pipe members, and the internal electrode. it is conceivable that. Therefore, in the mass-production film forming apparatus exemplified in Patent Document 2, the carbon-based foreign material that is an insulator adheres each time the film is formed, so that the impedance gradually increases.

  In the film forming apparatuses disclosed in Patent Document 1 and Patent Document 2, the high-frequency power source is connected to the external electrode via an automatic matching unit without being directly connected to the external electrode. This is because the automatic matching unit can match the impedance by the inductance L and the capacitance C so that the reflected wave from the entire electrode supplying the output is minimized.

  Since the carbon-based foreign matter is gradually deposited on the wall, the impedance change between the two before and after the film formation is considerably small. Therefore, in such a case, the automatic matching device is used in almost the same way as the fixed matching device. On the other hand, long-term changes in impedance are handled by automatic matching.

  However, the carbon-based foreign matter may become thick and peel from the wall due to internal stress. When such peeling occurs, the impedance changes abruptly. However, the matching speed of the automatic matching device takes about 0.4 seconds at the fastest. On the other hand, in consideration of manufacturing efficiency in the apparatus of Patent Document 2, it is desirable that the plasma generation time, that is, the actual film formation time, be several seconds or less, for example, 2 seconds or less. Therefore, when a large change in impedance occurs due to the separation of carbon-based foreign matter, in the worst case, the plasma is not ignited and the film is not formed at all, or even if the film is ignited, the film formation time is predetermined. It becomes half. In this case, a bottle with insufficient gas barrier properties cannot be predicted and is generated.

  In a CVD film deposition system on the surface of a plastic container, it is necessary to surround the container with external electrodes, so check whether or not plasma has been ignited and whether plasma is being generated stably even if ignited. Confirmation is difficult, and the present inventors have inevitably determined the quality of the film formation by measuring the gas barrier properties of the plastic container on which the film has been formed. However, in this determination method, (1) it takes several days to measure the gas barrier property, and (2) even if a film formation failure occurs suddenly because the total inspection cannot be performed. There is a problem that it is difficult to reliably detect this.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a plasma CVD film forming apparatus that can detect all the occurrences of plasma non-ignition or ignition failure. It is another object of the present invention to provide a plasma ignition confirmation method capable of easily and completely confirming the presence or absence of plasma non-ignition or ignition failure. Another object of the present invention is to provide a CVD film property confirmation method capable of confirming film quality such as gas barrier properties and / or film thickness of a CVD film formed on a container for each container. It is another object of the present invention to provide an apparatus contamination confirmation method for knowing an index of timing of cleaning of carbon-based foreign matter adhering to an internal electrode or an exhaust path that causes plasma ignition failure.

  For example, in the film forming apparatus described in Patent Document 1, an internal electrode that also serves as a raw material supply pipe that supplies a raw material gas to the inside of the container is grounded. The present invention has been completed by finding that the flowing current reflects the plasma generation state indirectly but accurately. That is, the plasma CVD film forming apparatus according to the present invention supplies a source gas to at least one of a vacuum chamber having an accommodation space for a plastic container and an internal space or an external space of the plastic container disposed in the accommodation space. Source gas supply means, plasma generation means for supplying a high frequency for converting the source gas into plasma, and exhaust means for exhausting the source gas, and at least an inner surface or an outer surface of the plastic container In a plasma CVD film forming apparatus for forming a CVD film on at least one of the electrodes, a grounded conductive member is disposed in the plastic container so as to be detachable from a mouth, and is connected to a ground line of the conductive member. A first ammeter for measuring a flowing current is connected.

  In the plasma CVD film forming apparatus according to the present invention, a second ammeter is connected to ground the exhaust path between the housing space and the exhaust unit, and to measure the current flowing through the ground line of the exhaust path. Preferably it is. Since plasma is also generated in the exhaust path as described above, in addition to measuring the current flowing through the ground line of the conductive member, the current flowing through the ground line of the exhaust path is also measured. In addition to this, it becomes an apparatus capable of grasping the entire plasma generation state.

  Furthermore, in the plasma CVD film forming apparatus according to the present invention, it is preferable that a plasma shield made of a conductive material having air permeability is disposed in the exhaust path. The volume of the plasma generation space can be determined by this plasma shield. Therefore, it contributes to stabilization of plasma generation, and it becomes difficult for carbon-based foreign matter to adhere to the exhaust path after the plasma shield.

  In the plasma ignition confirmation method according to the present invention, a plastic container is accommodated in an accommodating space provided in a vacuum chamber, and a grounded conductive member is detachably disposed in the plastic container from the mouth, A raw material gas is supplied to at least one of the internal space and the external space, and the raw material gas is plasmatized by high frequency or microwave to form a CVD film on at least one of the inner surface and the outer surface of the plastic container. A method for confirming plasma ignition when a film is formed, and when the source gas is turned into plasma by supplying a high frequency or microwave, the current flowing through the ground line of the conductive member is measured to determine whether or not there is a current. It is characterized by confirming the ignition of plasma. By measuring the current flowing through the ground line of the conductive member, for example, it can be confirmed that the plasma is not ignited if no current flows.

  In the plasma ignition confirmation method according to the present invention, when the source gas is turned into plasma by supplying a high frequency or microwave, a plasma is obtained by obtaining a profile of current and time flowing in the ground line of the conductive member. It is preferable to confirm the ignition stability. By obtaining a profile indicating the relationship between the current flowing through the ground line of the conductive member and time, it can be confirmed whether the plasma is stably generated from on to off. For example, (1) If the current is equal to or greater than a predetermined value, the plasma is normally ignited and film formation is performed. (2) If no current flows, the plasma is not ignited. (3) The current is a predetermined value. If it is less than that, it can be confirmed that the plasma is ignited but is about to be ignited, and the quality of the film can also be judged.

  Furthermore, in the plasma ignition confirmation method according to the present invention, when the source gas is turned into plasma by supplying a high frequency or microwave, the charge flowing in the ground line of the conductive member is measured to determine the plasma ionization rate. It is preferable to confirm. The charge flowing through the ground line of the conductive member corresponds to the integral value of the profile, and the quality of the film can be judged by confirming that the charge of a predetermined value or more has flowed.

  In the CVD film property confirmation method according to the present invention, a plastic container is accommodated in an accommodating space provided in a vacuum chamber, and a grounded conductive member is detachably disposed in the plastic container from the mouth, and the plastic container A source gas is supplied to at least one of the internal space and the external space, and the raw material gas is plasmatized by high frequency or microwave to form a CVD film on at least one of the inner surface and the outer surface of the plastic container. A CVD film property confirmation method for forming a film, wherein when the source gas is turned into plasma by supplying a high frequency or microwave, the current value flowing through the ground line of the conductive member and the discharge time The product is obtained, and the film quality and / or film thickness of the CVD film is confirmed. The product of the current value flowing through the grounding wire and the discharge time is a value that approximates the ionization rate. If the value is equal to or greater than a predetermined value, the film quality and film thickness are ensured. It can be confirmed that the film thickness is thin and the film quality is insufficient.

  In the apparatus contamination check method according to the present invention, a plastic container is accommodated in an accommodating space provided in a vacuum chamber, and a grounded conductive member is disposed in the plastic container so that it can be inserted and removed from the mouth. A raw material gas is supplied to at least one of the internal space and the external space, and the raw material gas is plasmatized by high frequency or microwave to form a CVD film on at least one of the inner surface and the outer surface of the plastic container. A method for confirming device contamination when forming a film, wherein when the source gas is turned into plasma by supplying a high frequency or microwave, the current flowing through the ground line of the conductive member is measured to determine the device contamination state. It is characterized by confirming. When carbonaceous foreign matter adheres to a conductive member, the impedance increases and the current flowing through the grounding wire of the conductive member decreases, so that the amount of carbonaceous foreign matter attached to the conductive member can be known. it can.

  In the apparatus contamination confirmation method according to the present invention, the exhaust path between the housing space and the exhaust means is grounded, and the current flowing through the ground line of the exhaust path is measured and flows through the ground line of the exhaust path. It is preferable to measure the total current of the current and the current flowing through the ground line of the conductive member to confirm the degree of device contamination. When carbon-based foreign matter adheres to the wall surface of the device in contact with the plasma, the total amount of carbon-based foreign matter attached to the device can be known by utilizing the fact that the impedance increases and the total current decreases.

  The apparatus contamination confirmation method according to the present invention is an apparatus contamination confirmation method for a mass production apparatus for continuously forming the CVD film, wherein the current flowing through the ground line of the conductive member or the value of the total current is It is preferable to set the cleaning time of the apparatus when it falls to a predetermined rate compared to the initial value. The amount of carbon-based foreign matter attached to the conductive member can be known from the current flowing through the ground wire of the conductive member, and the total amount of carbon-based foreign matter attached to the device can be known from the total current. Therefore, it is possible to know the cleaning timing of the apparatus by comparison with the respective initial values.

  According to the present invention, it is possible to detect the total number of the presence or absence of plasma non-ignition or poor ignition. The quality of the CVD film can also be judged. Further, it is possible to know the timing of cleaning of the carbon-based foreign matter adhering to the internal electrode or the exhaust path that causes the plasma ignition failure. Thereby, even if it performs long-term continuous operation, the container which has gas barrier property more than fixed quality always can be manufactured.

Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these embodiments. Moreover, the same code | symbol was attached | subjected when the member was common in each drawing. Hereinafter, embodiments of the present invention will be described with reference to FIGS.
(First embodiment)

  FIG. 1 is a conceptual diagram showing a first embodiment of a plasma CVD film forming apparatus according to the present invention. A plasma CVD film forming apparatus 100 according to the present invention includes a vacuum chamber 3 having an accommodation space 23 for a plastic container 7 and a source gas supply means 22 for supplying a source gas to the internal space of the plastic container 7 disposed in the accommodation space 23. And a plasma generating means 15 for supplying a high frequency or microwave for turning the raw material gas into plasma, and an exhaust means 37 for exhausting the raw material gas, and forming a CVD film on the inner surface of the plastic container 7 This is a plasma CVD film forming apparatus.

  In this plasma CVD film forming apparatus 100, a grounded conductive member 9 is disposed in the plastic container 7 so as to be detachable from the mouth, and a first current that measures a current flowing through the ground line 43 of the conductive member 9 is measured. An ammeter 28 is connected. Further, in the plasma CVD film forming apparatus 100, a second ammeter 41 is connected to ground the exhaust path between the accommodation space 23 and the exhaust unit 37 and measure the current flowing through the ground line 42 of the exhaust path. Yes. Here, the exhaust path includes a space 11, a space 12, and a pipe 30 communicating in series.

  The vacuum chamber 3 also serves as an external electrode. The external electrode (vacuum chamber) 3 includes an upper external electrode 2 and a lower external electrode 1 and accommodates a plastic container 7. The upper part of the lower external electrode 1 is detachably attached to the lower part of the upper external electrode 2 via an O-ring 8. The plastic container 7 can be mounted by detaching the upper external electrode 2 and the lower external electrode 1. A space is formed inside the external electrode 3, and this accommodation space 23 is an accommodation space for accommodating a plastic container 7 to be coated, for example, a PET bottle which is a container made of polyethylene terephthalate resin. The accommodation space 23 of the external electrode 3 is sealed from the outside by an O-ring 8 disposed between the upper external electrode 2 and the lower external electrode 1. A shield cover 10 is provided around the external electrode 3. The shield cover can be divided into an upper shield cover 10a and a lower shield cover 10b, and the divided portions have the same height corresponding to the divided portions of the upper external electrode 2 and the lower external electrode 1.

  The external electrode 3 is electrically insulated from other members by an insulating member 4. That is, the insulating member 4 b is interposed between the external electrode 3 and the shield cover 10. An insulating member 4 a is applied to the upper part of the external electrode 3. The insulating member 4a is provided with an opening 35 having the same diameter as that of the mouth at a position above the mouth of the plastic container 7.

  The upper part of the insulating member 4 a is attached to the base 5. The base 5 supports the internal electrode 9 that also serves as a raw material supply pipe and is connected to the exhaust means 37, and the accommodation space 23 including the internal space of the plastic container 7 is exhausted. Here, the base 5 is electrically insulated from the external electrode 3 by the insulating member 4. In addition, the base body 5 is provided with a space 11 and a space 12 communicating therewith. An opening 34 is provided in the lower portion of the space 11. The opening 34 has substantially the same diameter as the opening 35 provided in the insulating member 4a, and is provided at a position where the openings overlap each other. The space 11 and the accommodation space 23 are connected by the opening 34 and the opening 35. The base 5 also serves as a lid for sealing the accommodation space 23 in the external electrode 3 that also serves as a vacuum chamber. By sealing with the base 5, the external electrode 3 becomes a vacuum chamber. Further, the base 5 is also preferably grounded. Further, a pressure gauge 17 is attached to the base body 5 via a vacuum valve 16 in order to measure the pressure in the space 11 of the base body 5.

  The internal electrode 9 is detachably disposed in the external electrode 3 and disposed in the plastic container 7. That is, one end of the internal electrode 9 is supported by the conductive lid 27 that seals the space 11 with a part of the base body 5 so as to be disposed in the space 11, while the opening 34 and the insulating member of the base body 5 are supported. The other end is inserted into the accommodating space 23 of the external electrode 3 through the opening 35 of 4a. In the film forming apparatus of FIG. 1, the internal electrode 9 also serves as a conductive member. However, a conductive member may be provided separately from the internal electrode, and disposed inside the plastic container 7 so as to be detachable. The conductive lid 27 is insulated from the base body 5 by the insulating member 26. Thereby, the internal electrode 9 is electrically floated from the base 5. The other end of the internal electrode 9 is disposed inside the plastic container 7. The internal electrode 9 has a tube shape whose inside is hollow. The internal electrode 9 also serves as a source gas supply nozzle. That is, a gas outlet 9 a is provided at the tip of the internal electrode 9. Further, the internal electrode 9 is grounded. A gas outlet may be provided on the side cylinder of the internal electrode 9.

  In this embodiment, it is preferable to provide the internal electrode cleaning means described in International Publication WO03 / 104523, International Publication WO03 / 086878, or Japanese Patent Application Laid-Open No. 2003-268550. Thereby, the carbon-type foreign material adhering to the internal electrode 9 can be removed, and discharge can be stabilized.

  The first ammeter 28 detects a weak current flowing through the ground wire 43 when plasma is generated in the plastic container 7, and the ammeter method is not limited. In order to protect the first ammeter 28, a noise cut filter (not shown) may be connected between the first ammeter 28 and the conductive lid 27. When carbon-based foreign matter that is an insulator adheres to and accumulates on the internal electrode 9, the generation of plasma is not stable, and the current detected by the first ammeter 28 becomes weaker. Further, no current flows in the case of plasma non-ignition. Therefore, by measuring the current flowing through the ground wire 43 with the first ammeter 28, it can be used as an indicator of the ignition state of the plasma generated in the plastic container 7.

  The raw material gas supply means 22 introduces the raw material gas supplied from the raw material gas generation source 21 into the plastic container 7. That is, one end of the pipe 18 passing through the inside of the conductive lid 27 is connected to one end of the internal electrode 9, and the other side of the pipe 18 is connected to one side of the mass flow controller 20 via the vacuum valve 19. ing. The other side of the mass flow controller 20 is connected to the source gas generation source 21 via a pipe. The source gas generation source 21 generates hydrocarbon gas such as acetylene.

  As the source gas, for example, when a DLC film is formed, aliphatic hydrocarbons, aromatic hydrocarbons, oxygen-containing hydrocarbons, nitrogen-containing hydrocarbons, etc. that are gaseous or liquid at room temperature are used. In particular, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexane and the like having 6 or more carbon atoms are desirable. When used for food containers, aliphatic hydrocarbons from the viewpoint of hygiene, especially ethylene hydrocarbons such as ethylene, propylene or butylene, or acetylene hydrocarbons such as acetylene, arylene or 1-butyne Is preferred. These raw materials may be used alone, or may be used as a mixed gas of two or more. Further, these gases may be diluted with a rare gas such as argon or helium. In addition, when a silicon-containing DLC film is formed, a Si-containing hydrocarbon gas is used.

The DLC film referred to in the present invention is a film called i-carbon film or hydrogenated amorphous carbon film (aC: H), and includes a hard carbon film. The DLC film is an amorphous carbon film and also has SP ³ bonds. A hydrocarbon gas such as acetylene gas is used as a source gas for forming the DLC film, and a Si-containing hydrocarbon gas is used as a source gas for forming the Si-containing DLC film. By forming such a DLC film on the inner surface of a plastic container, a container that can be used in a one-way and returnable manner as a container for carbonated beverages, sparkling beverages, and the like is obtained.

  The DLC film is an example of a gas barrier thin film obtained by CVD, and the CVD film may be a gas barrier film such as a SiOx film (silicon oxide film), an alumina film, or an AlN film.

  The exhaust means 37 is connected to the space 12 of the base 5 and exhausts the source gas. The space 12 is connected to one side of a pipe 30 constituting an exhaust path, and the other side of the pipe 30 is connected to a vacuum pump 32 via a vacuum valve 31. The vacuum pump 32 is further connected to an exhaust duct 33. A plasma shield 29 made of a conductive material having air permeability is disposed in an exhaust path that connects the exhaust unit 37 including the vacuum pump 32 and the exhaust duct 33 and the accommodating space 23.

  The plasma shield 29 has a role of preventing the attack to piping parts such as a joint of the piping 30 serving as an exhaust path and making the volume of the plasma space constant. The main place of the plasma space is the internal space of the plastic container 7, but since the exhaust gas is still converted into plasma, the space 11 and the space 12 connected thereto are also plasma spaces.

  Examples of the plasma shield 29 include wire mesh, punching metal, and expanded metal as illustrated in FIGS. FIG. 2 is a schematic view showing a form example when a plasma shield is arranged in the exhaust path, and shows a case where three metal meshes are stacked. FIG. 3 is a schematic view showing a configuration example when a plasma shield is arranged in the exhaust path, and shows a case where two punching metals are stacked. FIG. 4 is a schematic view showing a form example when a plasma shield is arranged in the exhaust path, and shows a case where two expanded metals are stacked. When the plasma shield 29 is a metal mesh, punching metal, or expanded metal, the number of stacked layers is preferably 2-10. If the number is one, the residual energy of the exhaust gas cannot be removed sufficiently. At this time, there is a method of reducing the mesh of the wire mesh in order to reduce the residual energy, but the exhaust resistance due to pressure loss increases. On the other hand, if the number exceeds 10, the exhaust resistance increases and the capacity of the exhaust means 37 needs to be significantly increased. Further, it is preferable that the punching metal or the expanded metal be spaced apart from each other without being in contact with each other, and this spacing is preferably at least larger than the hole diameter of the plasma shield 29. By providing a space between the plasma shields 29, the exhaust gas is agitated in the piping of the exhaust path to increase the chance of contact. When the plasma shield 29 is a metal mesh, punching metal, or expanded metal, the characteristics are determined by the hole shape such as round, square, and rectangle, the hole diameter, the aperture ratio, the material thickness, or the thickness of the metal wire. In the plasma shield 29 of the present embodiment, a metal mesh, punching metal, or expanded metal having the same characteristics may be arranged side by side, or a metal mesh, punching metal, or expanded metal having different characteristics may be arranged side by side. The combination can be changed as appropriate. For example, as shown in FIG. 2, a wire mesh 29a with a sparse eye size d1 with respect to the exhaust gas flow, a metal wire 29b with a denser mesh size d2 and a wire mesh with a sparse eye size d1. The wire nets 29 having different eye sizes may be alternately arranged in parallel with 29c. Further, as shown in FIG. 3, the plasma shield 29 may be formed by arranging a punching metal 22d punched into a round shape with a hole diameter φ and a punching metal 22e punched into a rectangle having sides d1 and d2. Further, as shown in FIG. 4, the plasma shield 29 is configured by arranging an expanded metal 29f provided with holes having a center distance d1 in the long direction and a center distance d2 in the short direction and an expanded metal 29g identical to the expanded metal 29g. May be. The plasma shield 29 may be fixed to the holding frame so that the plasma shields are held at predetermined intervals, and the holding frame may be locked in the space 12. The hole diameter d of the plasma shield is 1 to 10 mm, preferably 1.5 to 5 mm. If the hole diameter is less than 1 mm, the exhaust resistance is increased. On the other hand, if the hole diameter exceeds 10 mm, the chance of contact with the exhaust gas decreases, and the residual energy of the exhaust gas cannot be removed sufficiently. In addition, when the shape of the hole is a square, the center distance in the short direction is 1 to 5 mm, the center distance in the long direction is 3 to 10 mm, preferably the center distance in the short direction is 1.5 to 3 mm, and long. The center distance between the eyes is 3 to 5 mm. The expanded metal includes both the standard type and the grating type.

  Further, as the plasma shield 29, as shown in FIG. 5, a metal ribbon shaped metal ribbon wound irregularly can be exemplified. FIG. 5 is a schematic view showing another embodiment when a plasma shield is arranged in the exhaust path, and shows a case where a metal ribbon is irregularly wound. In the case where the plasma shield 29 is an irregularly wound metal ribbon shaped metal ribbon, its characteristics are determined by the thickness and width of the metal ribbon and the method of winding the metal ribbon. Since the plasma shield 29, which is an irregularly wound metal ribbon, has a thickness with respect to the flow direction of the exhaust gas, a plurality of plasma shields 29 may be arranged. However, only one plasma shield 29 should be arranged so as not to increase the exhaust resistance. Is preferred. In this case, the average hole diameter of the plasma shield is 1 to 10 mm, preferably 1.5 to 5 mm.

  Further, as shown in FIG. 6, the plasma shield 29 can be exemplified by an assembly of a plurality of irregular metal fillers, Raschig Super Ring (Rashihi, registered trademark). Typical examples of metal irregular packings are packings used in absorption towers (physical absorption, chemical absorption), stripping towers and distillation towers. Can pass through. FIG. 6 is a schematic view showing another embodiment when a plasma shield is arranged in the exhaust path, and shows a case where an assembly of metal irregular fillers is arranged. When the plasma shield 29 is an irregularly deformed hollow tube-like metal irregular filler, its characteristics are the tube diameter, length and tube thickness of the metal irregular filler, and the metal irregular filler. Determined by the shape. In this case, the average hole diameter of the plasma shield, that is, the tube diameter is 1 to 10 mm, preferably 1.5 to 5 mm.

  Further, as shown in FIG. 7, the plasma shield 29 can be exemplified by a columnar metal provided with a plurality of thin tubes 40 having openings at the upper and lower bases. FIG. 7 is a schematic view showing another form when the plasma shield is arranged in the exhaust path, and a case where a columnar metal having a plurality of thin tubes having openings at the upper and lower bases is arranged. Show. When the plasma shield 29 is a columnar metal having a plurality of thin tubes 40 having openings at the upper and lower bases, the characteristic is the height of the medium metal (distance between the upper and lower bases). It is determined by the hole diameter of the opening of the thin tube 40. In this case, the hole diameter of the opening is 1 to 10 mm, preferably 1.5 to 5 mm.

  Examples of the material of the plasma shield described above include stainless steel, aluminum, titanium, gold, silver, and copper. In the same plasma shield, the hole diameter may be the same, but in order to increase the opening area ratio, holes having different hole diameters may be provided in combination. The opening area ratio of the plasma shield is preferably 40% to 70% in order to suppress an increase in ventilation resistance.

  The inner wall 24b of the pipe 30 is the inner wall of the exhaust path, like the inner wall 24a, but is on the downstream side of the plasma shield 29, so that the adhesion of carbon-based foreign matter is prevented.

  The second ammeter 41 detects a weak current flowing through the ground line 42 when plasma is generated in the space 11 and the space 12, and the current system is not limited. In order to protect the second ammeter 41, a noise cut filter (not shown) may be connected between the second ammeter 41 and the base 5. When carbon-based foreign matter that is an insulator adheres to and accumulates on the inner wall 25 and the inner wall 24a, the plasma generated in the space 11 and the space 12 is not stable, and the current detected by the second ammeter 41 becomes weaker. Further, no current flows in the case of plasma non-ignition. Therefore, by measuring the current flowing through the ground wire 42 with the second ammeter 41, it can be used as an indicator of the ignition state of the plasma generated in the space 11 and the space 12.

  By calculating the total current of the current detected by the first ammeter 28 and the current detected by the second ammeter 41, ignition of the entire plasma generated in the plastic container 7 and the spaces 11 and 12 connected thereto is performed. It can be an indicator of the condition.

  The plasma generation means 15 is a high frequency generator or a microwave generator, and in the case of the first embodiment, is a high frequency supply means. This high-frequency supply means supplies a high frequency to the external electrode 3 to turn the source gas into plasma. The plasma generating means 15 includes a high frequency power supply 14 and an automatic matching device 13 connected to the high frequency power supply 14, and the high frequency power supply 14 is connected to the external electrode 3 via the automatic matching device 13. The high-frequency power source 14 generates a high-frequency voltage between the ground potential and the high-frequency voltage is applied between the internal electrode 9 and the external electrode 3. As a result, the raw material gas supplied into the plastic container 7 is turned into plasma. The frequency of the high-frequency power source is 100 kHz to 1000 MHz, and for example, an industrial frequency of 13.56 MHz is used.

  The vacuum chamber 3 is connected to a leak pipe 38, and the pipe 38 communicates with a leak source (open to the atmosphere) via a vacuum valve 39.

  The container according to the present invention includes a container that is used with a lid, a stopper, or a seal, or a container that is used without being used. The size of the opening is determined according to the contents. The plastic container includes a plastic container having a predetermined thickness having moderate rigidity and a plastic container formed by a sheet material having no rigidity. Examples of the filling material of the plastic container according to the present invention include beverages such as carbonated beverages, fruit juice beverages, and soft drinks, and pharmaceuticals, agricultural chemicals, and dry foods that dislike moisture absorption.

Resin used when molding the plastic container of the present invention is polyethylene terephthalate resin (PET), polyethylene terephthalate copolyester resin (copolymer using cyclohexane dimethanol instead of ethylene glycol as the alcohol component of polyester) Called Eastman Chemical), polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin (PP), cycloolefin copolymer resin (COC, cyclic olefin copolymer), ionomer resin, poly-4-methyl Pentene-1 resin, polymethyl methacrylate resin, polystyrene resin, ethylene-vinyl alcohol copolymer resin, acrylonitrile resin, polyvinyl chloride resin, polyvinyl chloride Resins, polyamide resins, polyamide-imide resins, polyacetal resins, polycarbonate resins, polysulfone resins, or ethylene tetrafluoride resin, acrylonitrile - styrene resins, acrylonitrile - butadiene - styrene resin, can be exemplified. Among these, PET is particularly preferable.
(Second Embodiment)

The present embodiment is not limited to the plasma CVD film forming apparatus of the type that supplies a high frequency to the external electrode shown in FIG. Instead of the internal electrode facing the external electrode, a ground electrode serving also as a raw material gas supply nozzle is arranged inside the plastic container, and the microwave (for example, frequency 2450 MHz) is directly applied to the raw material gas supplied into the plastic container. It is within the scope of the present invention to use a CVD film-forming apparatus that irradiates the source gas into plasma by irradiating the material gas and provide a first ammeter on the ground wire of the ground electrode. Here, the ground electrode also serves as a conductive member. Similarly, the case where a second ammeter is provided on the ground line of the exhaust path is also within the scope of the present invention. In the case of this film forming apparatus, the plasma generating means is a microwave generator, and the microwave is introduced into the accommodation space 23 through the waveguide. Further, instead of the automatic matching unit 13, a microwave matching unit is arranged at a position opposite to the waveguide for introducing the microwave. In this film forming apparatus, a CVD film can be formed on the inner surface of the plastic container.
(Third embodiment)

  The film forming apparatus according to the first and second embodiments is a type of plasma CVD film forming apparatus that forms a CVD film on the inner surface of a plastic container, but forms a CVD film on the outer surface of the plastic container. It may be a type of plasma CVD film forming apparatus. In other words, a source gas supply nozzle serving as a ground electrode is arranged outside the plastic container, and a CVD film forming apparatus that directly irradiates the source gas supplied to the outside of the plastic container with microwaves to convert the source gas into plasma is provided. The case where the first ammeter is provided on the electrode ground wire is also within the scope of the present invention. Here, the ground electrode also serves as a conductive member. Similarly, the case where a second ammeter is provided on the ground line of the exhaust path is also within the scope of the present invention.

The forms of the film forming apparatus of the second embodiment and the third embodiment are exemplifications, and any apparatus that converts the raw material gas into plasma by microwaves is within the scope of the present invention. Even in the case of using microwaves, plasma can be easily ignited by inserting a conductive member serving also as a ground electrode inside the container.
(Fourth embodiment)

  In this embodiment, a film forming apparatus for forming a CVD film on the inner surface, the outer surface, or both surfaces of the container, specifically, International Publication WO 03, by converting both the gas in the inner space and the gas in the outer space of the plastic container into plasma. It is also within the scope of the present invention to provide a first ammeter on the ground line of the internal electrode of the film forming apparatus described in Japanese Patent No. 085165. Similarly, the case where a second ammeter is provided on the ground line of the exhaust path is also within the scope of the present invention.

The present invention is not limited by whether a CVD film is formed on the inner surface, outer surface, or both surfaces of the container, or whether the method of converting the raw material into plasma uses high frequency or microwaves. In any embodiment, it is preferable to arrange a plasma shield in the exhaust path.
(CVD film formation method)

  Next, before explaining the plasma ignition confirmation method and the apparatus contamination confirmation method, a method for forming a DLC film inside the container using the plasma CVD film formation apparatus 100 shown in FIG. 1 will be described. Here, the case where the film forming apparatus according to the first embodiment is used will be described on behalf of the first to fourth embodiments. In addition, you may supply a microwave instead of a high frequency with the film-forming apparatus of other embodiment. The inside of the accommodation space 23 is opened to the atmosphere by opening the vacuum valve 39, and the lower external electrode 1 of the external electrode 3 is removed from the upper external electrode 2. The plastic container 7 is inserted into the accommodation space 23 in the upper external electrode 2 from the lower side of the upper external electrode 2 and installed. At this time, the internal electrode 9 is inserted into the plastic container 7. Next, the lower external electrode 1 is attached to the lower part of the upper external electrode 2, and the external electrode 3 is sealed with an O-ring 8.

  Next, the inside of the plastic container 7 is replaced with a raw material gas and adjusted to a predetermined film forming pressure. That is, as shown in FIG. 1, after the vacuum valve 39 is closed, the vacuum valve 31 is opened and the vacuum pump 32 is operated. As a result, the inside of the vacuum chamber (external electrode) 3 including the inside of the plastic container 7, the inside of the space 11, and the inside of the space 12 are exhausted through the pipe 30 to become a vacuum. The pressure in the vacuum chamber 3 at this time is 2.6 to 66 Pa.

  Next, the vacuum valve 19 is opened, a hydrocarbon gas such as acetylene gas is generated in the source gas generation source 21, and the flow rate of the hydrocarbon gas is controlled by the mass flow controller 20 to flow through the pipe 18. Further, the raw material gas is blown out from the gas blowing port 9 a through the internal electrode 9. As a result, hydrocarbon gas is introduced into the plastic container 7. The plastic container 7, the space 11, and the space 12 are maintained at a pressure suitable for DLC film formation (for example, about 6.6 to 665 Pa) and stabilized by the balance between the controlled gas flow rate and the exhaust capacity. Let

  Next, a high frequency output is supplied to the external electrode 3 to make the source gas into plasma in the plastic container 7 to form a DLC film on the inner surface of the plastic container 7. That is, the vacuum chamber 3 is supplied with RF output (for example, 13.56 MHz) by the plasma generating means 15. As a result, a bias voltage is generated between the external electrode 3 and the internal electrode 9 and the raw material gas in the plastic container 7 is turned into plasma to generate hydrocarbon-based plasma, and a DLC film is formed on the inner surface of the plastic container 7. Is done. At this time, the automatic matching unit 13 matches the impedance by the inductance L and the capacitance C so that the reflected wave from the entire electrode supplying the output is minimized.

  Here, by arranging the plasma shield 29 as shown in FIG. 1, the volume of the plasma generation space becomes constant, which contributes to the stabilization of the plasma and the stabilization of the impedance.

  In the case of a mass production apparatus, it is desirable that the high frequency supply time from the plasma generating means 15 to the external electrode 3 be 2 seconds or less. The DLC film is formed to have a thickness of 5 to 40 nm, for example.

  After the film formation time has elapsed, the RF output from the plasma generating means 15 is stopped, the plasma is extinguished, and the film formation of the DLC film is completed. Almost simultaneously, the vacuum valve 19 is closed to stop the supply of the raw material gas.

  Next, in order to remove the hydrocarbon gas remaining in the apparatus, the vacuum valve 31 is opened and the vacuum pump 32 is evacuated. Thereafter, the vacuum valve 31 is closed and the exhaust is finished. The pressure in the vacuum chamber 3 at this time is 6.6 to 665 Pa. Thereafter, the vacuum valve 39 is opened. Thereby, the vacuum chamber 3 is opened to the atmosphere. Then, the plastic container 7 is taken out.

By repeating these steps, a DLC film is formed in new plastic containers one after another.
(Plasma ignition confirmation method)

  Next, a method for confirming plasma generation while supplying high frequency or microwave will be described. A current flowing through the ground line 43 of the internal electrode 9 that is a conductive member when high frequency or microwave is supplied is measured using the first ammeter 28. At this time, when the source gas is turned into plasma, a current flows through the ground line 43 of the conductive member 9. Whether or not plasma is ignited inside the plastic container 7 can be confirmed by the presence or absence of an electric current.

At the same time, a profile of current and time flowing through the ground line 43 of the conductive member 9 is obtained. An example of the profile obtained at this time is shown in FIG. (A) is a profile when no carbon-based foreign matter is attached to the apparatus, (b) is a profile 1 when carbon-based foreign matter is deposited on the apparatus, and (c) is when a carbon-based foreign substance is deposited on the apparatus. Profiles 2 and (d) are profiles 3 when carbon-based foreign matters are deposited on the apparatus, and (e) are profiles when a large amount of carbon-based foreign substances are deposited on the apparatus. In addition, the electric current value in the case of (a) was made into 100, and (b)-(e) was written together. Here, the integral value of the current indicated by the area surrounded by the time axis indicates the charge flowing through the ground line 43 of the conductive member 9. This charge can be used as an indicator of the ionization rate of plasma inside the plastic container 7. Therefore, in the film forming process in which the profile of (a) is obtained, a current flows stably during film formation and the ionization rate is high, so that a film with a desired film thickness is formed and the gas barrier property is also good. It is. In the film forming process in which the profile of (b) is obtained, since the ionization rate of the current flowing stably during film formation is lower than that in (a), a film thinner than the desired film thickness is formed, Gas barrier properties also deteriorate. In the film forming process in which the profile of (c) is obtained, current does not flow in the first half during film formation, but flows stably in the second half. That is, it can be determined that the film formation time is short. At this time, since the ionization rate is lower than (a), a film thinner than a desired film thickness is formed, and the gas barrier property is also lowered. In the film forming process in which the profile of (d) is obtained, current flows and plasma is ignited in the first half during film formation, but current does not flow and plasma disappears in the second half. That is, also in this case, it can be determined that the film formation time is short. At this time, since the ionization rate is lower than (a), a film thinner than a desired film thickness is formed, and the gas barrier property is also lowered. The cases (c) and (d) are not ignited, and the ignition is poor. In the film forming process in which the profile (e) is obtained, no current flows during film formation, and the plasma is not ignited. That is, also in this case, it can be determined that the film formation time is substantially zero. At this time, the ionization rate is also zero, and no film is formed.
(CVD film property confirmation method)

  Next, a CVD film property confirmation method will be described. The product of the current value flowing through the ground line 43 and the discharge time shows a value approximated to the ionization rate. Compared with the case of obtaining the profile shown in FIG. 8, there is an advantage that it can be determined by a numerical value of the product of the current value flowing through the ground line 43 and the discharge time. Is less than the predetermined value, it can be confirmed that the film thickness is thin and the film quality is insufficient. When the plasma is not ignited, the product of the current value flowing through the ground line 43 and the discharge time is zero, and no film is formed.

(Device dirt check method)
Next, an apparatus contamination confirmation method will be described. The device contamination is carbon-based foreign matter adhering to the internal electrode 9, the inner wall 25 of the space 11, or the inner wall 24 a of the space 12. First, a method for confirming the degree of contamination of the internal electrode 9 which is a conductive member will be described. The current flowing through the ground line 43 of the internal electrode 9 is measured using the first ammeter 28 when the source gas is turned into plasma by supplying high frequency or microwave. At this time, when the source gas is turned into plasma, a current flows through the ground line 43 of the conductive member 9. As the amount of carbon-based foreign matter attached to the internal electrode 9 increases, the electrical resistance (impedance) increases and the current measured by the first ammeter 28 decreases. Thus, the amount of carbon-based foreign matter attached to the internal electrode 9 can be confirmed by determining the degree of decrease in the current value with reference to the initial current value before the carbon-based foreign matter is attached. Then, when the value of the current flowing through the ground line 43 is reduced to a predetermined rate, 50 to 90%, for example, 80%, compared to the initial value, the time for cleaning the apparatus is set, so that plasma non-ignition or plasma ignition Defects can be prevented. This ratio can be changed as appropriate.

  Next, a method for confirming the degree of contamination of the inner wall 25 of the space 11 and the inner wall 24a of the space 12 will be described. When the source gas is turned into plasma by supplying high frequency or microwave, the current flowing through the ground line 42 of the base 5 in electrical connection with the exhaust path is measured using the second ammeter 41. At this time, when the source gas is turned into plasma, a current flows through the ground line 42. As the amount of carbon foreign matter attached to the inner wall 25 of the space 11 or the inner wall 24a of the space 12 increases, the electrical resistance (impedance) increases and the current measured by the second ammeter 42 decreases. As a result, the amount of carbon-based foreign matter attached to the inner wall 25 of the space 11 or the inner wall 24a of the space 12 is determined by obtaining the degree of decrease in the current value with reference to the initial current value before the carbon-based foreign matter is attached. Can be confirmed.

  By obtaining the total current of the current flowing through the grounding line 42 and the current flowing through the grounding line 43 obtained as described above, it becomes possible to check the degree of contamination of the entire apparatus. That is, based on the total current of the initial current value, it can be confirmed that the device becomes dirty as the degree of decrease in the total current value increases.

  The device is cleaned when the total current value is reduced to a predetermined ratio of 50 to 90%, for example, 80%, compared to the initial value, thereby preventing plasma non-ignition or plasma ignition failure. can do. This ratio can be changed as appropriate.

  In addition, by providing the 1st ammeter 28 and the 2nd ammeter 41 separately, the necessity for the cleaning of the internal electrode 9 or the inner wall 25 of the space 11, or the inner wall 24a of the space 12 can also be judged separately.

  Using the film forming apparatus of FIG. 1, a DLC film was formed on a 500 ml PET bottle having a thickness of 0.3 mm with a film forming time of 2 seconds. The high frequency output was constant, and the cleaning mechanism for the internal electrode 9 (not shown) was not activated. Assuming that the initial current value of the first ammeter before film formation is 100, the current value of the first ammeter was 60 when the number of film formation was 200. Further, assuming that the initial current value of the second ammeter before film formation is 100, the current value of the second ammeter was 85 when the number of film formation was 200. Assuming that the total current value of the first ammeter and the second ammeter before film formation is 100, the initial total current value was 80 when the number of film formation was 200. The plasma was ignited for 2 seconds. In the first film formation, the film thickness was 30 nm. When the film formation frequency was 200, the film thickness was 20 nm. Thereby, it became clear that the film thickness of the DLC film can be confirmed by the product of the current value of the first ammeter and the discharge time. In addition, the oxygen barrier property of the container with the first film formation is 0.0033 ml / container / day, whereas the oxygen barrier property of the container with the 200th film formation is 0.0080 ml / container / day. It was revealed that the gas barrier property can be relatively confirmed. The oxygen permeability was measured with an Oxtran manufactured by Modern Control under the condition of 22 ° C. × 60% RH.

  Furthermore, when the number of times of film formation was 600, the current value of the first ammeter was zero. At this time, no DLC film was formed on the inner wall surface of the PET bottle. Thereby, it was clarified that the presence or absence of plasma ignition can be confirmed by examining whether or not current flows through the first ammeter.

  Next, the internal electrode 9 was cleaned to remove the carbon-based foreign matter, and the inner wall 25 of the space 11 and the inner wall 24a of the space 12 were cleaned to remove the carbon-based foreign matter. The average current value of the first ammeter when the film was formed five times immediately after the device cleaning was 99 compared with the initial current value. The average current value of the second ammeter was 98 compared with the initial current value. The average of the total current values was 98 compared with the initial total current value.

  From the examples, it was shown that when the amount of carbon-based foreign matter attached was large, the current value and the total current value were reduced, and it became clear that the current value and the total current value returned to the initial values by cleaning. . Therefore, it became clear that the degree of contamination of the apparatus can be confirmed by measuring the current flowing through the first ammeter and the second ammeter.

It is a conceptual diagram which shows 1st Embodiment of the CVD film-forming apparatus which concerns on this invention. It is the schematic which shows the example of a mode when a plasma shield is arrange | positioned in an exhaust path | route, Comprising: The case where three metal meshes are piled up is shown. It is the schematic which shows the example when a plasma shield is arrange | positioned in an exhaust path, Comprising: The case where two punching metals are piled up is shown. It is the schematic which shows the example of a form when a plasma shield is arrange | positioned in an exhaust path | route, Comprising: The case where two sheets of expanded metals are accumulated is shown. It is the schematic which shows another form when a plasma shield is arrange | positioned in an exhaust path | route, Comprising: The case where what wound the metal ribbon irregularly is shown. It is the schematic which shows another form when a plasma shield is arrange | positioned in an exhaust path | route, Comprising: The case where the aggregate | assembly of metal irregular fillers is arrange | positioned is shown. It is the schematic which shows another form when a plasma shield is arrange | positioned in an exhaust path | route, Comprising: The case where the thing provided with multiple thin tubes which have an opening in the upper bottom and lower bottom is shown is shown. The example of the profile of the electric current which flows into the grounding wire 43 of the electroconductive member 9 and time is shown, (a) is a profile when a carbonaceous foreign material has not adhered to an apparatus, (b) is carbon in an apparatus. Profile 1 when carbonaceous foreign matter is deposited, (c) is profile 2 when carbonaceous foreign matter is deposited on the device, and (d) is profile 3 when carbonaceous foreign matter is deposited on the device. Indicates the profile when a large amount of carbon-based foreign matter is deposited on the apparatus.

Explanation of symbols

100, CVD film forming apparatus 1, lower external electrode 2, upper external electrode 3, external electrode (vacuum chamber)
4, 4a, 4b, insulating member 5, base 7, plastic container 8, O-ring 9, internal electrode (conductive member)
9a, gas outlet 10, shield cover 10a, upper shield cover 10b, lower shield cover 11, 12, space 13, automatic matching unit 14, high frequency power supply 15, plasma generating means 16, 19, 31, 39, vacuum valve 17, Pressure gauges 18, 30, 38, piping 20, mass flow controller 21, source gas generation source 22, source gas supply means 23, storage spaces 24, 24 a, 24 b, 25, inner wall 26, insulating member 27, conductive lid 28, second 1 ammeter 29, plasma shield
32, vacuum pump 33, exhaust ducts 34 and 35, opening 37, exhaust means 40, narrow tube 41, second ammeters 42 and 43, ground wire

Claims (10)

A vacuum chamber having a housing space for the plastic container, a raw material gas supply means for supplying a raw material gas to at least one of an internal space and an external space of the plastic container disposed in the housing space, and the raw material gas is converted into plasma A plasma generating means for supplying a high frequency or microwave to be discharged and an exhaust means for exhausting the source gas, and a CVD film is formed on at least one of the inner surface and the outer surface of the plastic container In the plasma CVD film forming apparatus,
A plasma characterized in that a grounded conductive member is disposed in the plastic container so as to be insertable / removable from the mouth, and a first ammeter for measuring a current flowing through a ground wire of the conductive member is connected. CVD film deposition system.   2. The plasma according to claim 1, wherein a second ammeter is connected for grounding an exhaust path between the housing space and the exhaust means and measuring a current flowing through a ground line of the exhaust path. CVD film deposition system.   The plasma CVD film forming apparatus according to claim 1 or 2, wherein a plasma shield made of a conductive material having air permeability is disposed in the exhaust path. A plastic container is housed in a housing space provided in the vacuum chamber, and a grounded conductive member is disposed in the plastic container so as to be detachable from the mouth, and at least one of the internal space and the external space of the plastic container. This is a method for confirming plasma ignition when supplying a raw material gas to plasmatize the raw material gas by high frequency or microwave to form a CVD film on at least one of the inner surface and the outer surface of the plastic container. And
A plasma characterized in that when the source gas is turned into plasma by supplying a high frequency or microwave, the current flowing through the ground wire of the conductive member is measured to check the ignition of the plasma based on the presence or absence of the current. Ignition confirmation method.   When the source gas is turned into plasma by supplying a high frequency or microwave, the profile of current and time flowing in the ground line of the conductive member is obtained to check the ignition stability of the plasma, The plasma ignition confirmation method according to claim 4.   5. The plasma ionization rate is confirmed by measuring a charge flowing in a ground line of the conductive member when the source gas is turned into plasma by supplying high frequency or microwave. 5. The plasma ignition confirmation method according to 5. A plastic container is housed in a housing space provided in the vacuum chamber, and a grounded conductive member is disposed in the plastic container so as to be detachable from the mouth, and at least one of the internal space and the external space of the plastic container. A CVD film property confirmation method for supplying a raw material gas to a plasma film and forming the CVD film on at least one of an inner surface and an outer surface of the plastic container by converting the raw material gas into plasma by high frequency or microwave. There,
The quality and / or film thickness of the CVD film is obtained by obtaining the product of the current value flowing through the ground line of the conductive member and the discharge time when the source gas is turned into plasma by supplying a high frequency or microwave. The CVD film property confirmation method characterized by confirming. A plastic container is housed in a housing space provided in the vacuum chamber, and a grounded conductive member is disposed in the plastic container so as to be detachable from the mouth, and at least one of the internal space and the external space of the plastic container. This is a method for confirming the contamination of an apparatus when a raw material gas is supplied to the substrate, and the raw material gas is plasmatized by high frequency or microwave to form a CVD film on at least one of the inner surface and the outer surface of the plastic container. And
An apparatus contamination confirmation method, comprising: measuring a current flowing in a ground line of the conductive member to confirm an apparatus contamination condition when supplying a high frequency or microwave to plasma the source gas.   The exhaust path between the housing space and the exhaust means is grounded, and the current flowing through the ground line of the exhaust path is measured, and the current flowing through the ground line of the exhaust path and the ground line of the conductive member are measured. 9. The apparatus contamination confirmation method according to claim 8, wherein the contamination condition of the apparatus is confirmed by measuring a total current with a flowing current.   An apparatus contamination confirmation method for a mass production apparatus for continuously forming the CVD film, wherein a current flowing through a ground line of the conductive member or a value of the total current is a predetermined ratio compared to an initial value. 10. The apparatus contamination check method according to claim 8, wherein the apparatus cleaning time is set when the voltage drops.

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