JP2008218369A - Surface treatment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment device capable of carrying out an inner surface treatment of various treatment objects including long narrow tubes. <P>SOLUTION: The surface treatment device is provided with a vacuum pump 32 for generating gas flow by evacuating treatment gas introduced from an end of a tubular treatment object 21 to the other end of the same 21, excited particle supplying systems 16, 17, 18 disposed at one end side of the treatment object 21 and supplying initial plasma to the gas flow at an initial period of start of discharge, a first main electrode 11 as well as a second main electrode 12 disposed opposite to each other with the treatment object to be pinched therebetween, and a pulse power source 14 maintaining the initial plasma and impressing electric pulse (main pulse) of a duty ratio of 10<SP>-7</SP>to 10<SP>-1</SP>to generate plasma flow inside the treatment object 21 between the first main electrode 11 and the second main electrode 12, whereby, an inner surface of the treatment object 21 is treated by radicals contained in the plasma flow. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a surface treatment apparatus, and more particularly to a surface treatment apparatus capable of treating an inner surface of a long dielectric tubule (inner diameter: several mm, length: several meters) with non-thermal equilibrium low-temperature plasma.

  The liquid in the narrow tube forms a contact angle with the surface of the narrow tube, and its value depends on the properties of the wall surface such as hydrophobicity and hydrophilicity, or the shape of the wall surface such as smooth and concave. The upward force in the capillary tube depends on the product of surface tension, cosine of contact angle, and hole circumference. Since the downward force depends on the product of pressure, gravity, liquid specific gravity, liquid height, etc., the liquid height in the capillary can be calculated by equalizing the upward and downward forces. For example, in a conduit element with an inner diameter of 20 μm, the water column rises about 0.75 m at atmospheric pressure. However, it is difficult to transport the liquid at high speed to the inside of such a thin tube. Therefore, it is extremely difficult to sterilize, sterilize, and wash the inside (inner surface) of the long thin tube by wet processing.

  For this reason, dry treatment (dry process) is suitable for treating the inside (inner surface) of the narrow tube, and inner surface treatment of a long thin tube with non-thermal equilibrium low-temperature plasma rich in radicals is expected.

  As a dry treatment of the inside (inner surface) of the narrow tube, generation of a plasma jet using high-frequency inductive coupling has been attempted (see Non-Patent Document 1). In this case, the plasma length is at most about several centimeters.

  Although an example in which a metal electrode is inserted into a thin tube and performing pulse discharge has been reported, it is extremely difficult to insert a metal electrode into a thin tube having an inner diameter of several mm or less (see Non-Patent Document 2). ).

  In particular, medical instruments having long tubules such as endoscopes contain very finely processed optical systems and metals, so even if it is a low-temperature plasma, the metal part is considerable when sterilized or sterilized with plasma. There is also a problem that the temperature rises and the optical system goes wrong. Therefore, at present, in order to remove microorganisms adhering to the endoscope, etc., a method in which the endoscope is soaked in a predetermined disinfectant and the nurse carefully divides it into several stages is used. The situation is unavoidable.

For this reason, a glass tube filled with water is placed in a plasma atmosphere container generated by a low-temperature plasma generator, and a long thin tube is placed in the glass tube to cover the glass tube. There has also been proposed a sterilization method characterized by performing cleaning and sterilization of long thin tubes simultaneously (see Patent Document 1).
JP 200621027 A Takanori Ichiki et al., “Localozed and ultrahigh-rate etching of silicon wafers using atmospheric-pressure microplasma jet”, Journal Of Applied Physics, Vol. 95, 2004, p. 35-39 H. Fujiyama, “Inner coating of long-narrow tube by plasma sputtering”, Surface and Coating Technology, Vol. 131, 2000, p.278-283

As described above, there has been no effective electrodeless plasma generation method in a long thin tube having a length of several meters and an inner diameter of several millimeters. In particular, as shown in Table 1, the dissociation energy of nitrogen molecules is larger than that of other gas molecules, and it has been difficult for nitrogen plasma to generate a stable plasma.

  Further, in the method proposed in Patent Document 1, the water in the immersion water pipe is agitated by the plasma irradiation generated in the plasma reaction tube, and the inside of the pipe is washed by the movement of the water that has entered the long thin tube. Since plasma is irradiated on almost the entire surface of the long tubule, it is intended to sterilize or remove microorganisms and bacteria attached to the long tubule such as an endoscope. Its ability to sterilize is limited.

  An object of the present invention is to provide a surface treatment apparatus capable of treating an inner surface of various objects to be processed including long narrow tubes having an inner diameter of several millimeters and a length of several meters. Here, “inner surface treatment” means surface treatment of the inner surface of the workpiece. “Surface treatment” means, for example, a treatment such as sterilization, sterilization or improvement of wettability of the inner or outer surface of the object to be treated, and in a broad sense, organic or inorganic substances on the inner or outer surface of the object to be treated. It means removal of adhered substances such as, and change of physical or chemical properties of the inner or outer surface of the object to be treated. “Change of physical property or chemical property” includes processes such as deposition (deposition) and etching using a plasma reaction. Therefore, the process of depositing a thin film made of a material different from the object to be processed on the inner surface of the object to be processed also corresponds to the “inner surface processing of the object to be processed”.

In order to achieve the above object, according to a first aspect of the present invention, (a) a processing gas introduced from one end of a tubular workpiece is exhausted from the other end of the workpiece to generate a gas flow. And (b) an excited particle supply system that is arranged on one end side of the object to be processed and supplies initial plasma to the gas flow at the beginning of discharge, and (c) opposite each other so as to sandwich the object to be processed. (D) an electric pulse with a duty ratio of 10 ⁻⁷ to 10 ⁻¹ (main pulse) that maintains the initial plasma and generates a plasma flow inside the workpiece. And a pulse power source that applies between the first main electrode and the second main electrode, and a surface treatment apparatus that treats the inner surface of the object to be treated with radicals contained in the plasma flow.

In the second aspect of the present invention, (a) the processing gas introduced at a constant flow rate from the introduction pipe provided at the other end of the tubular workpiece to be sealed at one end is exhausted from the exhaust pipe provided at the other end. A vacuum pump that maintains the pressure of the processing gas inside the processing object at the processing pressure, and (b) an excited particle supply that is arranged in a part of the introduction pipe and supplies initial plasma to the processing gas at the beginning of discharge. And (c) a first main electrode and a second main electrode arranged to face each other so as to sandwich the object to be processed, and (d) maintaining an initial plasma and generating a plasma state inside the object to be processed And a pulse power source for applying an electric pulse (main pulse) with a duty ratio of 10 ⁻⁷ to 10 ⁻¹ between the first main electrode and the second main electrode, and the inner surface of the object to be processed by radicals contained in the plasma The gist is that it is a surface treatment apparatus to be treated.

According to a third aspect of the present invention, (a) is connected to the other end of a tubular object to be processed whose one end is sealed, and for sealing a processing gas from the other end into the object to be processed at a predetermined pressure. A vacuum manifold unit, (b) an excited particle supply system that is arranged on the other end side of the workpiece, and injects excited particles into the processing gas at the beginning of discharge, and (c) faces each other so as to sandwich the workpiece. The first main electrode and the second main electrode arranged in this manner, and (d) a duty ratio of 10 ⁻⁷ to 10 to maintain the initial plasma excited by the injection of excited particles and generate a plasma state inside the object to be processed A surface treatment apparatus comprising a pulse power source for applying a 10 ⁻¹ electric pulse (main pulse) between a first main electrode and a second main electrode, and processing an inner surface of an object to be processed with radicals contained in plasma. This is the gist.

According to a fourth aspect of the present invention, (i) in a workpiece having a tubular trunk and a branch pipe branched from the trunk, a processing gas introduced from one end of the trunk is supplied to the other end of the trunk and the end of the branch pipe. (B) an excited particle supply system that is arranged on one end side of the object to be processed and supplies initial plasma to the gas flow at the beginning of discharge; A first main electrode and a second main electrode arranged to face each other so as to sandwich the object to be processed; and (d) a duty ratio of 10 ⁻⁷ for maintaining an initial plasma and generating a plasma flow inside the object to be processed. And a pulse power supply for applying an electric pulse (main pulse) of 10 ⁻¹ between the first main electrode and the second main electrode, and a surface processing apparatus for processing the inner surface of the object to be processed by radicals contained in the plasma flow It is a summary.

According to a fifth aspect of the present invention, (a) in an object to be processed having a tubular trunk and a branch pipe branched from the trunk, the processing gas introduced from one end of the trunk and the end of the branch pipe is transferred to other parts of the trunk. A vacuum pump for evacuating from the end to generate a gas flow; and (b) excited particles that are arranged on one end side of the workpiece and on the end side of the branch tube, and inject the excited particles into the gas flow at the beginning of discharge. And (c) maintaining the initial plasma excited by the injection of the excited particles, and (c) the first main electrode and the second main electrode arranged to face each other so as to sandwich the object to be processed. A pulse power source for applying an electrical pulse (main pulse) having a duty ratio of 10 ⁻⁷ to 10 ⁻¹ for generating a plasma flow inside the workpiece to be applied between the first main electrode and the second main electrode, and included in the plasma flow Surface treatment equipment that treats the inner surface of the object to be treated with radicals And summary that is.

According to a sixth aspect of the present invention, (a) a processing gas is introduced from one end of a tubular object to be processed having a length of 10 cm or more, and a gas flow is formed inside the object to be processed. Adjusting the pressure of the flow to a processing pressure in the range of 20 kPa to 100 kPa, (b) supplying an initial plasma to the gas flow at the beginning of discharge from one end side of the processed object, and (c) the processed object Applying an electrical pulse (main pulse) having a duty ratio of 10 ⁻⁷ to 10 ⁻¹ to electrodes arranged to face each other so as to sandwich the electrode, and generating a plasma flow excited by an initial plasma, The gist of the present invention is a surface treatment method for treating the inner surface of an object to be treated with radicals contained in the plasma flow.

  According to the present invention, a surface treatment apparatus that can effectively generate radical-rich non-thermal equilibrium low-temperature plasma and can treat the inner surface of various objects to be processed including, for example, long tubes with a length of several meters and an inner diameter of several millimeters. Can be provided.

  Next, first to tenth embodiments of the present invention will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, specific thicknesses and dimensions should be determined in consideration of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

  Further, the following first to tenth embodiments exemplify apparatuses and methods for embodying the technical idea of the present invention, and the technical idea of the present invention is a component part. The material, shape, structure, arrangement, etc. are not specified below. The technical idea of the present invention can be variously modified within the technical scope described in the claims.

(First embodiment)
As shown in FIGS. 1 and 2, the surface treatment apparatus according to the first embodiment of the present invention exhausts a processing gas introduced from one end of a tubular object 21 made of a dielectric, In order to set the pressure of the gas flow inside the object 21 to the processing pressure, a vacuum pump 32 provided at the other end of the object to be processed 21 and one end of the object to be processed 21 are disposed at the beginning of discharge. An excited particle supply system (16, 17, 18) for supplying an initial plasma to the flow, and a first main electrode (anode) 11 which is arranged to face each other so as to sandwich the workpiece 21 and constitutes a parallel plate electrode; An electric pulse (main pulse) that maintains the initial plasma and forms a plasma flow inside the workpiece 21 is applied between the first main electrode 11 and the second main electrode 12 with the second main electrode (cathode) 12. And a pulse power source 14.

  In FIG. 1 and FIG. 2, the second main electrode (cathode) 12 described below is grounded as a cathode, and the first main electrode (anode) 11 described above is used as an anode, and a high voltage is applied as an example. ing. However, the drawings are schematic, and the vertical and horizontal relationships in the drawings can be arbitrarily selected and expressed. For example, a display in which the second main electrode 12 described on the lower side is the anode and the first main electrode 11 described on the upper side is the cathode is theoretically possible. If the polarity of the output pulse of the power supply is simply reversed while the second main electrode 12 is grounded, the first main electrode 11 can be made a cathode. Further, if the first main electrode 11 is grounded and a high voltage is applied to the second main electrode 12 without inverting the output pulse of the power source, the first main electrode 11 can be used as a cathode.

  In the surface treatment apparatus according to the first embodiment, the tubular workpiece 21 can be a long tube having a length of 4 to 7 m or more and a thin tube having an inner diameter of 7 to 5 mm or less, but the length is 4 m. Hereinafter, it can be understood from the following explanation that processing is possible even if the inner diameter is 7 mm or more. In particular, since the length of the microplasma jet described in Non-Patent Document 1 is several cm at most, the surface treatment apparatus according to the first embodiment is described in Non-Patent Document 1 even if the length is about 10 cm. It is possible to obtain a sufficiently advantageous effect as compared with the conventional method. That is, in view of the technique described in Non-Patent Document 1, in the field of plasma, if the inner diameter is 7 to 5 mm or less, the workpiece 21 having a length of about 10 cm or more can be defined as a “long tubule”. . Note that the cross-sectional shape of the workpiece 21 is not limited to a circle, and may be a polygon including a rectangle or the like, but in the case of a long thin tube, industrially, there are many cases of a circular cross-section. Let's go. In addition, there is a medical device such as an endoscope (fiberscope) as a typical “long tubule”, but there are various other types such as a tubule for passing drinking water used in vending machines. Tubules are included.

  When the workpiece 21 is a flexible long tubule having an inner diameter of about several mm or less and a length of about several meters or more, and the length of the workpiece 21 is known (constant), as shown in FIG. A second main electrode covering insulating film 23 such as high-purity quartz glass is provided on the second main electrode 12 used as the cathode, and the upper surface of the second main electrode covering insulating film 23 is shown in FIG. A meandering workpiece guide groove 22 as shown may be provided. That is, as shown in FIG. 3B, the flexible workpiece 21 may be stored in the meandering workpiece guide groove 22 so as to be folded and embedded at one place or a plurality of places according to the length. . The meandering workpiece guide groove 22 shown in FIG. 3 (a) may be designed according to the length of the workpiece 21, so that the length of the workpiece 21 is the same as in the case of a medical instrument or the like. If a plurality are defined, the second main electrode covering insulating film 23 having the workpiece guide groove 22 may be prepared in accordance with each length. However, the workpiece guide groove 22 shown in FIG. 3 is an example, and a structure such as a hook structure for fixing the workpiece 21 at a plurality of locations on the upper surface of the flat second main electrode covering insulating film 23 is provided. Various structures such as a screw fixing structure and the like can be adopted.

  If the workpiece 21 is a flexible long thin tube, the first and second reels for winding the workpiece 21 are provided at one end and the other end of the workpiece 21 instead of the structure shown in FIG. The workpiece 21 may be rewound from one reel, the workpiece 21 may be wound up by the second reel, and the surface treatment inside the workpiece 21 may be partially performed sequentially. Therefore, in FIG. 1, the length of the workpiece 21 is illustrated as if the lengths of the first main electrode 11 and the second main electrode 12 are substantially equal. The relationship between the total length of the workpiece 21 and the lengths of the first main electrode 11 and the second main electrode 12 can be arbitrarily designed according to material properties such as flexibility and stretchability.

  The excited particle supply system (16, 17, 18) is arranged to face each other so as to sandwich the upstream side of the workpiece 21, and includes a first auxiliary electrode 17 and a second auxiliary electrode 18 that constitute parallel plate electrodes, An auxiliary pulse power supply 16 that applies an electric pulse (auxiliary pulse) that causes initial plasma between the first auxiliary electrode 17 and the second auxiliary electrode 18 is provided. The excited particle supply system (16, 17, 18) supplies initial plasma in order to reduce the discharge start voltage and facilitate plasma generation in the workpiece 21. The plasma, charged particles, and the like generated by the excited particle supply system (16, 17, 18) not only reach the workpiece 21 due to diffusion and the flow of the processing gas, but also the excited particle supply system (16, 17, It can also be expected that the radiation from the plasma generated in 18) photoelectrically neutralizes the neutral particles in the workpiece 21. Once the plasma is generated in the workpiece 21 and the density of the charged particles is sufficiently large, the discharge can be realized only by the electric field in the workpiece 21 and the plasma can be maintained. In this situation, the excited particle supply system (16, 17, 18) is no longer needed. Therefore, the excited particle supply system (16, 17, 18) may be used only at the start of plasma generation.

  The excited particle supply system only needs to be able to supply the initial plasma to the gas flow at the beginning of discharge, and is not necessarily limited to the parallel plate electrode structure illustrated in FIG. The initial plasma may be excited by another structure such as a source.

After the excitation of the initial plasma, the surface treatment apparatus shown in FIG. 1 treats the inner surface of the workpiece 21 with radicals contained in the plasma generated by the discharge. In the surface treatment apparatus according to the first embodiment, a high-purity nitrogen gas is supplied as a treatment gas from upstream to the workpiece 21, but the “treatment gas” is not necessarily limited to nitrogen gas. . For example, for the purpose of sterilization and sterilization of the inner surface of the workpiece 21, various active gases such as chlorine (Cl ₂ ) or a compound gas containing chlorine, more generally a halogen-based compound gas, etc. Alternatively, another gas such as a mixed gas of any of these active gases and nitrogen gas may be used. The other gas may be oxygen (O ₂ ) or a compound gas containing oxygen depending on the purpose of the surface treatment. What is necessary is just to select suitably the purity, dew point, etc. of process gas according to the objective of surface treatment.

  In the surface treatment apparatus according to the first embodiment, as shown in FIG. 1, a treatment gas is supplied to the workpiece 21 from upstream, and the treatment gas is treated by a vacuum pump 32 provided downstream. While flowing in the object 21, the inside of the object 21 is kept at a processing pressure equal to or lower than the atmospheric pressure. For this reason, although not shown in FIG. 1, it will be easily understood by those skilled in the art that a pressure gauge and a variable conductance valve for adjusting the exhaust conductance may be provided in detail. For example, a pressure gauge and a mass flow controller for controlling the flow rate may be provided in the intake adapter 24 shown in FIG. 2, and a variable conductance valve for adjusting the exhaust conductance may be provided in the exhaust adapter 28 shown in FIG. A pressure gauge may be provided on the exhaust adapter 28 side.

  The intake adapter 24 shown in FIG. 2 is a pipe such as a connection joint that connects a supply source of a processing gas such as a gas cylinder (not shown) and one end of the workpiece 21 while maintaining vacuum confidentiality. Further, the exhaust adapter 28 is a pipe such as a connection joint for connecting the vacuum pump 32 shown in FIG. 1 and the other end of the workpiece 21 while maintaining vacuum confidentiality. The intake adapter 24 and the exhaust adapter 28 may be designed by appropriately changing known gas pipe joints, vacuum parts, and the like according to the material, shape, and dimensions of the workpiece 21.

  A high-repetition high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11b and the second main electrode 12. FIG. 4A illustrates the case where the half width is 300 ns as the pulse width of the electric pulse (main pulse). However, the half width is preferably about 50 to 300 ns as the pulse width of the main pulse. In the surface treatment apparatus according to the first embodiment, when the distance between the first main electrode 11 and the second main electrode 12 constituting the parallel plate electrode is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, the voltage wave A high value of about 24 kV is suitable. Further, the pressure in the workpiece 21 is preferably about 30 kPa, and the nitrogen gas flow rate is about 1 SLM. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006 as shown in FIG. Is generated stably and efficiently. In the surface treatment apparatus according to the first embodiment of the present invention, the duty ratio can be set to about. When the duty ratio is 0.001 or less, the discharge becomes unstable, and when the duty ratio is 0.02 or more, the influence of thermal plasma becomes visible. The duty ratio is preferably about 0.003 to 0.01. In order to generate a low temperature plasma in the workpiece 21, barrier discharge by a low frequency AC electric field is possible, but a large input cannot be expected.

  According to the surface treatment apparatus according to the first embodiment, since the duty ratio can be set to about ~, even a medical instrument such as an optical system or a metal-containing endoscope that has been subjected to very fine processing. In addition, problems such as the metal part rising to a considerably high temperature and causing the optical system to go wrong can be avoided.

When the workpiece 21 made of a dielectric is placed in parallel with the electrode surface in the first main electrode 11 and the second main electrode 12 constituting the parallel plate electrode, the dielectric constant ε ₂ of the dielectric is the dielectric constant of the gas If it is larger than ε ₁ (relative permittivity 1), the approximate electric field distribution is as shown in FIG. The electric field strength in the vicinity (center portion) of the center line passing through the centers of the first main electrode 11 and the second main electrode 12 in FIG. 5 can be shown by a substantially parallel straight line shown in FIG. This is the same inside and outside the workpiece 21. Since the dielectric breakdown electric field also depends on the size of the space, or if the atmospheric pressure inside and outside the workpiece 21 is the same, the dielectric breakdown electric field increases within the workpiece 21. Therefore, in order to cause discharge inside the workpiece 21 made of a dielectric, it is necessary to lower the dielectric breakdown voltage inside the workpiece 21 by some method. One method is to lower the gas pressure inside the workpiece 21 in the case of discharge in the right region of the Paschen curve.

(Second Embodiment)
As shown in FIG. 6, the surface treatment apparatus according to the second embodiment of the present invention is disposed so as to face each other so as to sandwich a tubular object 21 made of a dielectric, and has parallel plate electrodes as a whole. An electric pulse (main pulse) that causes fine streamer discharge in a sealed space including the outer surface of the first main electrode 11b and the second main electrode 12 and the outer surface of the workpiece 21 is formed between the first main electrode 11b and the second main electrode 12. And a pulse power supply 14 to be applied. As shown in FIG. 6, “the entire plate is formed as a parallel plate electrode” is because the first main electrode 11 b is not a plate structure, and T-shaped convex portions are periodically arranged, and each T-type This is because the tip of the electrode is used as a discharge location. In this case, the first main electrode 11b is equivalent to a ladder-type electrode in which a plurality of rod-shaped (line-shaped) electrodes are periodically arranged in parallel, but the whole of the first main electrode 11b and the second main electrode 12 is formed. This means that it can be approximated as a “parallel plate electrode”.

  The surface treatment apparatus according to the second embodiment includes a treatment chamber (23, 53, 54, 62) that forms a sealed space surrounding the outer surface of the tubular workpiece 21, and the first main electrode 11b side as an anode. From the inside of the processing chamber (23, 53, 54, 62) to the second main electrode 12 side as a cathode, and the other end (downstream side) of the workpiece 21. The surface treatment apparatus according to the first embodiment is further provided with atmosphere adjusting means (62, 65, 66b, 25b) for exhausting the processing gas from the processing chambers (23, 53, 54, 62) near the side. Is different. The exhaust side pipe 63 of the processing chamber (23, 53, 54, 62) is not limited to the vicinity of the other end (downstream side) side of the workpiece 21 shown in FIG. 53, 54, 62) may be another place. As shown in FIG. 6, the atmosphere adjusting means (62, 65, 66b, 25b) is provided on the intake side adjustment chamber 62, the gas supply layer 65 in contact with the intake side adjustment chamber 62, and the surface of the gas supply layer 65. The first electrode (first main electrode) protective layer 25b having the gas supply hole 66b is provided. The gas supply layer 65 is made of a porous ceramic so that the processing gas from the intake side adjustment chamber 62 is uniformly distributed and permeated. The intake side adjustment chamber 62 has a flat rectangular parallelepiped shape, and five of the six surfaces of the rectangular parallelepiped are made of metal, and the remaining one surface (the left surface in the cross-sectional view of FIG. 6) is closed by the gas supply layer 65. . The plurality of gas supply holes 66 are tapered through holes penetrating the first electrode (first main electrode) protective layer 25b, and are arranged in a two-dimensional matrix at a constant pitch as shown in FIG. . On the other hand, a second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  The processing chamber (23, 53, 54, 62) is a rectangular parallelepiped made up of the second electrode (second main electrode) covering insulating film 23, the processing chamber bottom lid 53, the processing chamber top lid 54, and the intake side adjustment chamber 62. Side plates (not shown) that constitute four sides and are arranged opposite to each other in front of and behind the sheet of FIG. 6 constitute two sides of the rectangular parallelepiped. That is, the processing chamber upper lid 54 and the processing chamber bottom lid 53 are respectively disposed so as to face the second electrode (second main electrode) covering insulating film 23, the suction side adjustment chamber 62, and the front and back of the paper of FIG. The side plates (not shown) of the sheets are in close contact with the upper and lower ends of a box-shaped space to form a sealed space. An upper workpiece holder 52 that holds one end (upstream side) of the workpiece 21 in a sealed state is connected to the processing chamber upper lid 54, and the other end ( A bottom workpiece holder 51 that holds the downstream side in a sealed state is connected. For the upper workpiece holder 52 and the lower workpiece holder 51, the structure used for a well-known gas pipe joint or vacuum component is appropriately changed according to the material, shape, and dimensions of the workpiece 21. And design.

  Further, as shown in FIG. 6, the surface treatment apparatus according to the second embodiment includes a gas source 33 such as a gas cylinder for storing process gas, an intake side pipe 61 connected to the gas source 33, and an intake side. And an intake side valve 41 connected to the pipe 61. It is preferable to employ a needle valve or the like that allows easy adjustment of the gas flow rate for the intake side valve 41. Although not shown, a gas introduction valve may be provided on at least one of the upper workpiece holder 52 and the lower workpiece holder 51.

  The processing chambers (23, 53, 54, 62) are supplied from the atmosphere adjustment means (62, 65, 66 b, 25 b) from the gas source 33 through the intake side pipe 61, the intake side valve 41, and the intake side adjustment chamber 62. The processing gas is supplied in a uniform shower shape. The processing gas supplied from the atmosphere adjusting means (62, 65, 66b, 25b) to the inside of the processing chamber (23, 53, 54, 62) is the exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). Exhausted from. For this reason, as shown in FIG. 6, in the surface treatment apparatus according to the second embodiment, the treatment chambers (23, 53, 54, 62) on the other end (downstream side) side of the tubular workpiece 21 are disposed. The exhaust pipe 63 is provided with a vacuum pump 31 for depressurizing the processing chamber (23, 53, 54, 62). The vacuum pump 31 is connected to the processing chambers (23, 53, 54, 62) via the exhaust side pipe 63 and the exhaust side valve 42. The exhaust side valve 42 is preferably a variable conductance valve whose exhaust conductance can be adjusted.

  FIG. 6 illustrates a case where the second main electrode 12 is grounded and functions as a cathode, and correspondingly, a high voltage is applied to the first main electrode 11b and functions as an anode. The polarity of the pulse power supply 14 may be reversed so that the second main electrode 12 is an anode and the first main electrode 11b is a cathode. When the first main electrode 11b is a cathode, the first main electrode 11b is grounded as a plate electrode, a high voltage is applied using the second main electrode 12 as a ladder-type electrode, and atmosphere adjusting means (62, 65, 66b, 25b) is provided on the second main electrode 12 side.

  Similarly to the first embodiment, in the surface treatment apparatus according to the second embodiment, the tubular workpiece 21 is a long tube having a length of 4 to 7 m or more and a narrow tube having an inner diameter of 7 to 5 mm or less. However, it can be processed even if the length is 4 m or less and the inner diameter is 7 mm or more. Further, as described in the first embodiment, the cross-sectional shape of the workpiece 21 is not limited to a circle. Although illustration is omitted, if the workpiece 21 is a flexible long thin tube, the first and the second workpiece 21 are wound around one end (upstream side) and the other end (downstream side) of the workpiece 21. A second reel is provided, the workpiece 21 is rewound from the first reel, the workpiece 21 is wound up by the second reel, and the surface treatment of the outer surface of the workpiece 21 is partially performed sequentially. In this case, however, a structure in which the first and second reels are accommodated in the processing chambers (23, 53, 54, 62) is preferable.

  In the surface treatment apparatus according to the second embodiment, high-purity nitrogen gas is supplied as a treatment gas to be supplied in a shower form via the atmosphere adjusting means (62, 65, 66b, 25b). "Is not necessarily limited to nitrogen gas. For example, for the purpose of sterilization and sterilization of the outer surface of the workpiece 21, various active gases such as a halogen-based compound gas, or a mixed gas of any of these active gases and nitrogen gas can be used. Other gases can be employed.

  A high-repetition high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11b and the second main electrode 12. FIG. 4A illustrates the case where the half width is 300 ns as the pulse width of the electric pulse (main pulse), but the pulse width of the main pulse is preferably about 10 to 500 ns. In the surface treatment apparatus according to the second embodiment, when the distance between the first main electrode 11b and the second main electrode 12 constituting the parallel plate electrode as a whole is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, A voltage peak value of about 24 kV is suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006 as shown in FIG. Is generated stably and efficiently. The pulse width is closely related to the distance between the anode and the cathode. The voltage application is started between the discharge electrodes, and the discharge goes from glow discharge to streamer discharge and further through fine streamer discharge to arc discharge as the voltage application time elapses from the start of discharge. Discharge that maximizes plasma input power without leading to arc discharge with current, heat loss, and electrode wear is considered fine streamer discharge. For this purpose, an appropriate pulse width exists. Ideally, it is set according to the distance between the anode and the cathode and the discharge state so that the pulse voltage is not applied before the arc discharge.

In order to cause discharge in a sealed space surrounding the outer surface of the workpiece 21, the gas pressure P ₂ inside the processing chamber (23, 53, 54, 62) is equal to the atmospheric pressure P ₃ = 101 kPa or 80˜ The intake side valve 41 and the exhaust side valve 42 may be adjusted so as to be lowered to a value slightly lower than the atmospheric pressure P ₃ to about 90 kPa. In the processing chambers (23, 53, 54, 62), the processing gas is showered from the atmosphere adjusting means (62, 65, 66 b, 25 b) from the gas source 33 through the intake side pipe 61 and the intake side valve 41. When a high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11b and the second main electrode 12 in a state of being supplied in a shape, non-thermal equilibrium low-temperature plasma is generated by fine streamer discharge. The surface treatment of the outer surface of the workpiece 21 is achieved by forming the inside of the processing chamber (23, 53, 54, 62).

<First Modification of Second Embodiment>
As shown in FIG. 8, the surface treatment apparatus according to the first modification of the second embodiment of the present invention is disposed so as to face each other so as to sandwich a tubular object 21 made of a dielectric material, As the first main electrode 11c and the second main electrode 12 constituting parallel plate electrodes, and an electric pulse (main pulse) that causes fine streamer discharge in the processing chambers (23, 53, 54, 62) The structure shown in FIG. 6 is the same as that shown in FIG. 6 in that a pulse power supply 14 is applied between the second main electrodes 12. As described in FIG. 8, the first main electrode 11c has a ladder-type structure in which a plurality of rod-shaped (linear) electrodes are periodically arranged in parallel, as shown in FIG. However, it means that the entire structure formed by the first main electrode 11c and the second main electrode 12 can be approximated to a “parallel plate electrode”. As in FIG. 6, the processing chambers (23, 53, 54, 62) include the second electrode (second main electrode) covering insulating film 23, the processing chamber bottom lid 53, the processing chamber top lid 54, and the intake side adjustment. The chamber 62 constitutes four surfaces of a rectangular parallelepiped, and side plates (not shown) opposed to the front and back of the paper surface of FIG. 8 constitute the remaining two surfaces of the rectangular parallelepiped.

  The surface treatment apparatus according to the first modification of the second embodiment supplies the processing gas from the first main electrode 11c as the anode toward the second main electrode 12 as the cathode in a shower shape. The structure of the atmosphere adjusting means (62, 27, 66c) for exhausting the processing gas from the exhaust side pipe 63 of the processing chamber (23, 53, 54, 62) is different from the structure shown in FIG. As shown in FIG. 8, the atmosphere adjusting means (62, 27, 66c) includes the intake side adjusting chamber 62 and the processing chamber side wall 27 for supplying the processing gas from the intake side adjusting chamber 62 through the plurality of gas supply holes 66c. Although there are a plurality of rod-shaped (linear) first main electrodes 11c made of a metal such as tungsten (W) or inconel, the metal is contaminated by the point that it is exposed to the discharge space. If it is a use which does not consider contamination, there exists an advantage which can be manufactured more simply and cheaply than the structure shown in FIG. The plurality of gas supply holes 66c are through holes penetrating the processing chamber side wall 27, and are arranged in a two-dimensional matrix at a constant pitch in accordance with the fine streamer discharge distribution, as shown in FIG. However, in practice, it may be adjusted to the pitch of the arrangement of the first main electrodes 11c. On the other hand, a second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  Further, as shown in FIG. 8, the surface treatment apparatus according to the first modification of the second embodiment includes a gas source 33 such as a gas cylinder for storing a processing gas, and an intake side pipe connected to the gas source 33. 61 and an intake side valve 41 connected to the intake side pipe 61. It is preferable to employ a needle valve or the like that allows easy adjustment of the gas flow rate for the intake side valve 41.

  In the processing chambers (23, 53, 54, 62), the processing gas from the atmosphere adjusting means (62, 27, 66 c) is made uniform in a shower shape from the gas source 33 through the intake side pipe 61 and the intake side valve 41. Supplied. The processing gas supplied from the atmosphere adjusting means (62, 27, 66c) is exhausted from the exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). For this reason, as shown in FIG. 8, in the surface treatment apparatus according to the first modification of the second embodiment, the treatment chamber (23, 53, 54, 62) is provided with a vacuum pump 31 for reducing the pressure inside. The vacuum pump 31 is connected to the processing chambers (23, 53, 54, 62) via the exhaust side pipe 63 and the exhaust side valve 42. The exhaust side valve 42 is preferably a variable conductance valve whose exhaust conductance can be adjusted.

  Connected to the processing chamber upper lid 54 is an upper processing object holder 52 for holding one end (upstream side) of the tubular processing object 21 in a sealed state. A bottom workpiece holder 51 that holds the end (downstream side) in a sealed state is connected. For the upper workpiece holder 52 and the lower workpiece holder 51, the structure used for a well-known gas pipe joint or vacuum component is appropriately changed according to the material, shape, and dimensions of the workpiece 21. And design.

  FIG. 8 illustrates a case where the second main electrode 12 is grounded and used as a cathode, and a high voltage is applied to the first main electrode 11c and used as an anode. The main electrode 12 may be an anode, and the first main electrode 11c may be a cathode. When the first main electrode 11c is a cathode, the first main electrode 11c is grounded as a plate-like electrode, a high voltage is applied with the second main electrode 12 as a ladder electrode, and atmosphere adjusting means (62, 27, 66c) Is provided on the second main electrode 12 side.

  Similarly to the first embodiment, in the surface treatment apparatus according to the first modification of the second embodiment, the tubular workpiece 21 has a length of 4 to 7 m or more and an inner diameter of 7 It can be processed even with a thin tube of ˜5 mm or less, but can be processed even with a length of 4 m or less and an inner diameter of 7 mm or more. Further, as described in the first embodiment, the cross-sectional shape of the workpiece 21 is not limited to a circle. Although illustration is omitted, if the workpiece 21 is a flexible long thin tube, the first and the second workpiece 21 are wound around one end (upstream side) and the other end (downstream side) of the workpiece 21. A second reel is provided, the workpiece 21 is rewound from the first reel, the workpiece 21 is wound up by the second reel, and the surface treatment of the outer surface of the workpiece 21 is partially performed sequentially. In this case, however, a structure in which the first and second reels are accommodated in the processing chambers (23, 53, 54, 62) is preferable.

  In the surface treatment apparatus according to the first modification of the second embodiment, high-purity nitrogen gas is supplied as a treatment gas to be supplied in a shower form via the atmosphere adjustment means (62, 27, 66c). The “processing gas” is not necessarily limited to nitrogen gas. For example, for the purpose of sterilization and sterilization of the inner and outer surfaces of the tubular object 21, various active gases such as halogen-based compound gas, or a mixture of any of these active gases with nitrogen gas Various other gases, such as gas, can be employed.

  A high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11 c and the second main electrode 12. FIG. 4A illustrates the case where the pulse width of the electric pulse (main pulse) is 300 ns as the half width, but the pulse width of the main pulse is preferably about 10 to 500 n as the half width. In the surface treatment apparatus according to the first modification of the second embodiment, when the distance between the first main electrode 11c and the second main electrode 12 constituting the parallel plate electrode as a whole is 15 mm, the high voltage pulse A repetition frequency of 2 kHz and a voltage peak value of about 24 kV are suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006 as shown in FIG. Is generated stably and efficiently.

In order to cause discharge inside the processing chamber (23, 53, 54, 62), the gas pressure P ₂ inside the processing chamber (23, 53, 54, 62) is equal to the atmospheric pressure P ₃ = 101 kPa. The intake side valve 41 and the exhaust side valve 42 may be adjusted so as to be lowered to a value slightly lower than the atmospheric pressure P ₃ to about 80 to 90 kPa. In the processing chambers (23, 53, 54, 62), the processing gas flows from the gas source 33 through the intake side pipe 61 and the intake side valve 41 into a shower shape from the atmosphere adjusting means (62, 27, 66 c). When a high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11c and the second main electrode 12 in the supplied state, non-thermal equilibrium low-temperature plasma is processed by fine streamer discharge. Formed inside the chamber (23, 53, 54, 62), the surface treatment of the outer surface of the workpiece 21 is achieved.

<Second Modification of Second Embodiment>
As shown in FIG. 9, the surface treatment apparatus according to the second modification of the second embodiment of the present invention is disposed so as to face each other so as to sandwich a tubular object to be treated 21 made of a dielectric. The first main electrode (anode) 11d and the second main electrode 12 constituting the parallel plate electrode and the electric pulse (main pulse) causing fine streamer discharge in the processing chamber (23, 53, 54, 62) as the first main electrode. The structure shown in FIG. 6 is the same as that shown in FIG. 6 in that a pulse power supply 14 applied between the electrode 11d and the second main electrode 12 is provided. As shown in FIG. 9, the first main electrode 11d does not have a flat plate structure, and T-shaped convex portions are periodically arranged, as shown in FIG. This is because the tip of the electrode is used as a discharge location. In this case, the first main electrode 11d is equivalent to a ladder-type electrode in which a plurality of rod-shaped (line-shaped) electrodes are periodically arranged in parallel. However, the first main electrode 11d and the second main electrode 12 are entirely formed. This means that it can be approximated as a “parallel plate electrode”.

  The surface treatment apparatus according to the second modification of the second embodiment supplies the processing gas from the first main electrode 11d as the anode toward the second main electrode 12 as the cathode in a shower shape. The structure of the atmosphere adjusting means (62, 25d, 66d) for exhausting the processing gas from the exhaust side pipe 63 of the processing chamber (23, 53, 54, 62) is different from the structure shown in FIG. In the first modified example shown in FIG. 8, metal contamination is a problem because a plurality of rod-shaped (linear) first main electrodes 11c made of a metal such as W are exposed to the discharge space. However, in the surface treatment apparatus according to the second modification of the second embodiment of the present invention, the surface of the first main electrode 11c is covered with a first electrode (first main electrode) protective layer 25d such as alumina. Therefore, contamination with metal is suppressed. For this reason, the atmosphere adjusting means (62, 25d, 66d) receives the processing gas from the intake side adjustment chamber 62, the first electrode (first main electrode) protective layer 25d, and the intake side adjustment chamber 62 as shown in FIG. The first electrode (first main electrode) includes a plurality of gas supply holes 66d provided in the protective layer 25d. The plurality of gas supply holes 66d are arranged in a two-dimensional matrix at a constant pitch in accordance with the fine streamer discharge distribution, as shown in FIG. 7, but at the pitch of the arrangement of the first main electrodes 11c. Just add. A second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  Others are substantially the same as those of the surface treatment apparatus according to the second embodiment, and a duplicate description is omitted.

(Third embodiment)
As shown in FIG. 10, the surface treatment apparatus according to the third embodiment of the present invention exhausts a processing gas introduced from one end (upstream side) of a tubular object 21 made of a dielectric, A vacuum pump (first pump) 32 provided at the other end (downstream side) of the workpiece 21 and one end of the workpiece 21 in order to set the pressure of the gas flow inside the workpiece 21 to the processing pressure. It is arranged on the (upstream side) side, arranged opposite to each other so as to sandwich the workpiece 21 and the excited particle supply system (17, 18) for supplying the initial plasma to the gas flow at the beginning of discharge, and parallel as a whole. The first main electrode 11b and the second main electrode 12 constituting the flat plate electrode, and the electric pulse (main pulse) that maintains the initial plasma and causes the plasma flow inside the workpiece 21 are supplied to the first main electrode 11b and the second main electrode 11b. A pulse power source 14 applied between the main electrodes 12; Obtain. Here, it is described that “a parallel plate electrode is configured as a whole” because, as shown in FIG. 10, the first main electrode 11b is not a plate structure, and T-shaped convex portions are periodically arranged, This is because the tip of the T type is used as the discharge location. In this case, as described in the second embodiment, the first main electrode 11b can be regarded as equivalent to a ladder-type electrode in which a plurality of rod-shaped (linear) electrodes are periodically arranged in parallel. This means that the entire structure formed by the electrode 11b and the second main electrode 12 can be approximated as a “parallel plate electrode”.

  Similar to the surface treatment apparatus according to the second embodiment, the surface treatment apparatus according to the third embodiment uses the processing gas from the first main electrode 11b side as the anode and the second main electrode 12 as the cathode. It further includes atmosphere adjusting means (62, 65, 66b, 25b) that supply air in a shower shape toward the side and exhaust the processing gas from the second exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). This is different from the surface treatment apparatus according to the first embodiment. The processing chamber (23, 53, 54, 62) is a rectangular parallelepiped made up of the second electrode (second main electrode) covering insulating film 23, the processing chamber bottom lid 53, the processing chamber top lid 54, and the intake side adjustment chamber 62. Side plates (not shown) that constitute four sides and are opposed to each other in front of and behind the sheet of FIG. 10 constitute two sides of the rectangular parallelepiped. The intake side adjustment chamber 62 has a flat rectangular parallelepiped shape, and five of the six surfaces of the rectangular parallelepiped are made of metal, and the gas supply layer 65 is closed on the remaining surface (the left surface in the cross-sectional view of FIG. 10). .

  As shown in FIG. 10, the atmosphere adjusting means (62, 65, 66b, 25b) is a gas supply made of porous ceramic that allows the processing gas from the intake side adjustment chamber 62 and the intake side adjustment chamber 62 to be uniformly distributed and permeated. The first electrode (first main electrode) protective layer 25b is provided on the surface of the layer 65 and the gas supply layer 65 and has a plurality of gas supply holes 66b. The plurality of gas supply holes 66 are tapered through holes penetrating the first electrode (first main electrode) protective layer 25b, and are arranged in a two-dimensional matrix at a constant pitch as shown in FIG. . On the other hand, a second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  Furthermore, as shown in FIG. 10, the surface treatment apparatus according to the third embodiment includes a gas source 33 such as a gas cylinder that stores a processing gas, a first intake side pipe 67 connected to the gas source 33, and a first gas source 33. A second intake side pipe 61; a first intake side valve 43 connected to the first intake side pipe 67; and a second intake side valve 41 connected to the second intake side pipe 61. For the first intake side valve 43 and the second intake side valve 41, it is preferable to employ a needle valve or the like that allows easy adjustment of the gas flow rate.

  A processing gas is supplied from the upstream side to the inside of the tubular workpiece 21 from the gas source 33 via the first intake side pipe 67 and the first intake side valve 43, and a vacuum pump (second pump) provided downstream. The processing gas flows through the workpiece 21 by the pump 31, and the inside of the workpiece 21 is close to the atmospheric pressure of about 20 to 30 kPa, but is maintained at a processing pressure equal to or lower than the atmospheric pressure.

  On the other hand, the process chambers (23, 53, 54, 62) are supplied from the atmosphere adjusting means (62, 65, 66 b, 25 b) from the gas source 33 through the second intake side pipe 61 and the second intake side valve 41. The processing gas is supplied in a uniform shower shape. The processing gas supplied from the atmosphere adjusting means (62, 65, 66b, 25b) is exhausted from the second exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). For this reason, as shown in FIG. 10, in the surface treatment apparatus according to the third embodiment, the space surrounding the outer surface of the workpiece 21 is decompressed on the other end (downstream side) side of the tubular workpiece 21. A second vacuum pump (second pump) 31 is provided. The second vacuum pump (second pump) 31 is connected to the processing chamber (23, 53, 54, 62) via the second exhaust side pipe 63 and the second exhaust side valve 42. On the other hand, the first vacuum pump (first pump) 32 is connected to the other end (downstream side) of the workpiece 21 via the first exhaust side pipe 68 and the first exhaust side valve 44. The first exhaust side valve 44 and the second exhaust side valve 42 are preferably variable conductance valves whose exhaust conductance can be adjusted.

  Connected to the processing chamber upper lid 54 is an upper processing object holder 52 for holding one end (upstream side) of the tubular processing object 21 in a sealed state. A bottom workpiece holder 51 that holds the end (downstream side) in a sealed state is connected. For the upper workpiece holder 52 and the lower workpiece holder 51, the structure used for a well-known gas pipe joint or vacuum component is appropriately changed according to the material, shape, and dimensions of the workpiece 21. And design.

  FIG. 10 illustrates a case where the second main electrode 12 is grounded and used as a cathode, and a high voltage is applied to the first main electrode 11b and used as an anode, but the polarity of the pulse power supply 14 is reversed, The second main electrode 12 may be an anode and the first main electrode 11b may be a cathode. When the first main electrode 11b is a cathode, the first main electrode 11b is grounded in the shape of a plate electrode, a high voltage is applied with the second main electrode 12 as a ladder electrode, and atmosphere adjusting means (62, 65). , 66b, 25b) are provided on the second main electrode 12 side.

  As in the first embodiment, in the surface treatment apparatus according to the third embodiment, the tubular workpiece 21 is a long tube having a length of 4 to 7 m or more and a narrow tube having an inner diameter of 7 to 5 mm or less. However, it can be processed even if the length is 4 m or less and the inner diameter is 7 mm or more. Further, as described in the first embodiment, the cross-sectional shape of the workpiece 21 is not limited to a circle. Although illustration is omitted, if the workpiece 21 is a flexible long thin tube, the first and the second workpiece 21 are wound around one end (upstream side) and the other end (downstream side) of the workpiece 21. A second reel is provided, the workpiece 21 is rewound from the first reel, the workpiece 21 is wound up by the second reel, and the surface treatment of the inside of the workpiece 21 is partially performed sequentially. In this case, however, a structure in which the first and second reels are accommodated in the processing chambers (23, 53, 54, 62) is preferable.

  In FIG. 10, the excited particle supply system (17, 18) is a first parallel plate electrode that sandwiches the introduction pipe 60 on the upstream side of the workpiece 21, as described in the first embodiment. The auxiliary electrode 17 and the second auxiliary electrode 18, and an auxiliary pulse power source (not shown) for applying an electric pulse (auxiliary pulse) causing initial plasma between the first auxiliary electrode 17 and the second auxiliary electrode 18 are provided. The introduction pipe 60 is a pipe made of a dielectric. The excited particle supply system is not limited to the parallel plate electrode structure as illustrated in FIG. 10 as long as it can supply the initial plasma to the gas flow at the beginning of discharge, and is not necessarily limited to an inductive plasma source or the like. The initial plasma may be excited with another structure as in the case of the surface treatment apparatus according to the first embodiment.

  After the excitation of the initial plasma, the surface treatment apparatus shown in FIG. 10 treats the inner surface and the outer surface of the tubular workpiece 21 with radicals contained in the plasma. In the surface treatment apparatus according to the third embodiment, high-purity nitrogen gas is supplied to the workpiece 21 as a treatment gas from upstream, but the “treatment gas” is not necessarily limited to nitrogen gas. . For example, for the purpose of sterilization and sterilization of the inner and outer surfaces of the workpiece 21, various active gases such as halogen-based compound gas, or a mixed gas of any of these active gases and nitrogen gas, etc. Various other gases can be employed.

  A high-repetition high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11b and the second main electrode 12. Although FIG. 4A illustrates the case where the half width is 300 ns as the pulse width of the electric pulse (main pulse), the half width is preferably about 10 to 500 ns as the pulse width of the main pulse. In the surface treatment apparatus according to the third embodiment, when the distance between the first main electrode 11b and the second main electrode 12 constituting the parallel plate electrode as a whole is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, A voltage peak value of about 24 kV is suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006 as shown in FIG. Is generated stably and efficiently.

<Three operation modes>
The surface treatment apparatus according to the third embodiment has three operation modes. That is, a mode in which discharge is caused only inside the tubular workpiece 21, a mode in which discharge is caused only outside the workpiece 21, and a mode in which discharge is caused both inside and outside the workpiece 21. .

(A) Mode in which discharge is caused only inside the workpiece 21:
As described in the surface treatment apparatus according to the first embodiment, the workpiece 21 made of a dielectric material parallel to the electrode surface in the first main electrode 11b and the second main electrode 12 constituting the parallel plate electrode. When the dielectric constant ε ₂ of the dielectric is larger than the dielectric constant ε _{1 of the} gas, the approximate electric field distribution is as shown in FIG. 5, and the dielectric breakdown electric field is increased in the workpiece 21. Therefore, in order to cause discharge inside the workpiece 21 made of a dielectric, the gas pressure P ₁ inside the workpiece 21 is set to about ₁₀ to 40 kPa, and the gas pressure P ₂ outside the workpiece 21 is set. It is preferable to lower it. The gas pressure P ₂ outside the workpiece 21 is preferably equal to the atmospheric pressure P ₃ = 101 kPa or slightly lower than the atmospheric pressure P ₃ to about 80 to 90 kPa. That is,
P ₁ <P ₂ ≦ P ₃ (1)
The first intake side valve 43, the second intake side valve 41, the first exhaust side valve 44, and the second exhaust side valve 42 may be adjusted so that Alternatively, the gas pressure P ₁ inside the workpiece 21 is set to about ₁₀ to 40 kPa, and the gas pressure P ₂ outside the workpiece 21 is set to a pressure of 10 ⁻³ Pa to 10 ⁻⁵ Pa or less:
P ₂ << P ₁ <P ₃ (2)
The first intake side valve 43, the second intake side valve 41, the first exhaust side valve 44, and the second exhaust side valve 42 may be adjusted so that For this reason, for example, pressure gauges are provided in the first exhaust side pipe 68 and the second exhaust side pipe 63, and the first intake side valve 43, the second intake side valve 41, the first exhaust side valve 44, and the 2 The exhaust side valve 42 may be adjusted. Alternatively, a mass flow controller for controlling the flow rate may be provided in the first intake side pipe 67 and the second intake side pipe 61. The pressure gauge may be provided on the downstream side of each of the first intake side valve 43 and the second intake side valve 41.

  After setting the pressure condition represented by the expression (1) or (2), the second intake side valve 41 and the second exhaust side valve 42 are closed, the gas flow outside the object 21 is stopped, and the object 21 is processed. A gas flow is formed only in the interior. Then, the excited particle supply system (17, 18) is activated to supply the initial plasma to the gas flow, and between the first main electrode 11b and the second main electrode 12, a high repetition rate as shown in FIG. When the high voltage pulse is applied, the non-thermal equilibrium low-temperature plasma flow is transported inside the workpiece 21 and the surface treatment of the inner surface of the workpiece 21 is achieved.

(B) Mode in which discharge is caused only outside the workpiece 21:
In order to cause discharge only outside the workpiece 21, the gas pressure P ₁ inside the workpiece 21 is set to a relatively high value of about 70 to 90 kPa, and the gas pressure outside the workpiece 21 is set. It is slightly lower than P ₂ or approximately the same level. Then, the gas pressure P ₂ outside the workpiece 21 may be made to be slightly lower than the atmospheric pressure P ₃ to be equal to the atmospheric pressure P ₃ = 101 kPa or about 80 to 90 kPa. That is,
P ₁ ≦ P ₂ ≦ P ₃ (3)
The first intake side valve 43, the second intake side valve 41, the first exhaust side valve 44, and the second exhaust side valve 42 may be adjusted so that However, the gas pressure P ₁ inside the workpiece 21 is not necessarily lower than the gas pressure P ₂ outside the workpiece 21, and the gas pressure P ₁ inside the workpiece 21 is equal to the atmospheric pressure P ₃ = The gas pressure P ₂ outside the workpiece 21 is approximately equal to 101 kPa or higher than the atmospheric pressure P ₃ , and the atmospheric pressure P ₃ is also equal to the atmospheric pressure P ₃ or slightly lower than the atmospheric pressure P ₃ to about 80 to 90 kPa:
P ₂ ≤ P ₁ ≒ P ₃ (4)
P ₂ ≦ P ₃ <P ₁ (5)
It is also good. Alternatively, the gas pressure P ₁ inside the workpiece 21 is set to a pressure of 10 ⁻³ Pa to 10 ⁻⁵ Pa or less, and the gas pressure P ₂ outside the workpiece 21 is equal to the atmospheric pressure P ₃ = 101 kPa or 80 As a pressure of about ~ 90 kPa:
P ₁ << P ₂ ≤P ₃ (6)
The first intake side valve 43, the second intake side valve 41, the first exhaust side valve 44, and the second exhaust side valve 42 may be adjusted so that After setting the pressure conditions shown in the formulas (3), (4), (5), or (6), the first intake side valve 43 and the first exhaust side valve 44 are closed, and the inside of the workpiece 21 Stop the gas flow. The processing chambers (23, 53, 54, 62) are supplied from the atmosphere adjusting means (62, 65, 66 b, 25 b) from the gas source 33 through the second intake side pipe 61 and the second intake side valve 41. When a high-repetitive high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11b and the second main electrode 12 in a state where the processing gas is supplied in a shower shape, non-flow is caused by fine streamer discharge. Thermal equilibrium low temperature plasma is formed outside the workpiece 21, and surface treatment of the outer surface of the workpiece 21 is achieved. Of course, the excited particle supply system (17, 18) is not activated in the mode in which the discharge is caused only outside the workpiece 21.

(C) Mode in which discharge is caused both inside and outside the workpiece 21:
In order to cause electric discharge both inside and outside the workpiece 21, the gas pressure P ₁ inside the workpiece 21 is set to about ₁₀ to 40 kPa, and is higher than the gas pressure P ₂ outside the workpiece 21. It is preferable to keep it down. The gas pressure P ₂ outside the workpiece 21 is equal to the atmospheric pressure P ₃ = 101 kPa or slightly lower than the atmospheric pressure P ₃ to about 80 to 90 kPa, and is expressed by the above equation (1). The first intake side valve 43, the second intake side valve 41, the first exhaust side valve 44, and the second exhaust side valve 42 are adjusted so as to satisfy the conditions.

  After setting the pressure condition shown by the equation (1), the excited particle supply system (17, 18) is activated to supply the initial plasma to the gas flow, and between the first main electrode 11b and the second main electrode 12. If a high-repetitive high-voltage pulse as shown in FIG. 4 is applied, the non-thermal equilibrium low-temperature plasma flow is transported inside the workpiece 21 and the surface treatment of the inner surface of the workpiece 21 is achieved. At the same time, since the processing gas is supplied to the processing chambers (23, 53, 54, 62) from the atmosphere adjusting means (62, 65, 66b, 25b) in a shower form, fine streamer discharge occurs and non-thermal equilibrium occurs. The low temperature plasma is formed outside the workpiece 21 and the surface treatment of the outer surface of the workpiece 21 is achieved at the same time.

(Fourth embodiment)
As shown in FIG. 11, the surface treatment apparatus according to the fourth embodiment of the present invention prepares a storage tube 71 that houses a tubular workpiece 21 that is a long thin tube, and the inside of the workpiece 21. In addition, a plasma flow may be flowed to both the outside and the outside, and the inner surface and the outer surface of the workpiece 21 may be processed simultaneously. That is, as shown in FIG. 11, the surface treatment apparatus according to another embodiment is connected to a gas source 33 such as a gas cylinder for storing a processing gas, and the gas source 33 via a first intake side pipe. A first intake side valve 43 and a second intake side valve 41 connected via a second intake side pipe are provided. Processing gas is supplied from the upstream side to the inside of the tubular workpiece 21 through the first intake side valve 43 from the gas source 33, and the processing gas is supplied by a vacuum pump (first pump) 32 provided downstream. Flows in the workpiece 21, and the inside of the workpiece 21 is maintained at a processing pressure of about 20 to 30 kPa, which is close to atmospheric pressure, but less than atmospheric pressure. On the other hand, the processing chamber (23, 53, 54, 62) constituted by the storage tube 71 is supplied with processing gas from the upstream side through the second intake side valve 41 from the gas source 33 and is provided downstream. Further, the processing gas flows through the storage tube 71 by the vacuum pump (second pump) 31, and the processing tube 71 is maintained at a processing pressure equal to or lower than atmospheric pressure, although it is close to atmospheric pressure of about 80 to 90 kPa.

  In order to evacuate the sealed space between the storage tube 71 and the outer surface of the tubular workpiece 21, the storage tube upper cap 73 and the storage tube bottom cap 72 are in close contact with the upper end and the lower end of the storage tube 71, respectively. It constitutes a sealed space with a double pipe structure.

  Further, the first main electrode 11b and the second main electrode 12 which are arranged to face each other so as to sandwich the storage tube 71 storing the tubular workpiece 21 and constitute parallel plate electrodes, and the upstream side of the storage tube 71 A first auxiliary electrode 17 and a second auxiliary electrode 18 that constitute parallel plate electrodes with the electrode interposed therebetween.

In order to cause discharge both inside and outside the tubular workpiece 21, the gas pressure P ₁ inside the workpiece 21 is set to about ₁₀ to 40 kPa, and between the storage tube 71 and the workpiece 21. it is preferable to be lower than the gas pressure P _2. The gas pressure P ₂ between the storage tube 71 and the workpiece 21 is equal to the atmospheric pressure P ₃ = 101 kPa or about 80 to 90 kPa so as to be slightly lower than the atmospheric pressure P _3. The valve 43, the second intake side valve 41, the first exhaust side valve 44, and the second exhaust side valve 42 may be adjusted. After setting to a predetermined pressure condition, the excited particle supply system (17, 18) is started, and the gas flow in both the processing object 21 and the sealed space between the storage tube 71 and the outer surface of the processing object 21 is performed. In addition, if an initial plasma is supplied and a high voltage pulse as shown in FIG. 4 is applied between the first main electrode 11b and the second main electrode 12, a non-thermal equilibrium low temperature plasma flow is obtained. The inside and outside of the workpiece 21 are respectively transported, and the surface treatment of the inner surface and the outer surface of the workpiece 21 is achieved at the same time.

(Fifth embodiment)
In the surface treatment apparatus according to the fifth embodiment of the present invention, as shown in FIG. 12, a neck adapter 19 is provided at the neck of a bowl-shaped workpiece 21 made of a dielectric material. An introduction pipe 60 penetrating the neck adapter 19 and an exhaust side pipe 68 are provided substantially in parallel. The introduction pipe 60 is a pipe made of a dielectric. A processing gas is introduced into the bowl-shaped workpiece 21 from the introduction pipe 60, and the processing gas is discharged from the exhaust side pipe 68. The first main electrode 11 and the second main electrode 12 constituting the parallel plate electrode are arranged so as to face each other so as to sandwich the workpiece 21. A part of the introduction pipe 60 is provided with an excited particle supply system (16, 17, 18) for supplying initial plasma to the gas flow introduced from the introduction pipe 60 at the beginning of discharge. The excited particle supply system (16, 17, 18) includes a first auxiliary electrode 17 and a second auxiliary electrode 18 that form parallel plate electrodes across a part of the introduction pipe 60, and an electric pulse (auxiliary pulse) that causes initial plasma. ) Is applied between the first auxiliary electrode 17 and the second auxiliary electrode 18. On the other hand, each of the first main electrode 11 and the second main electrode 12 maintains an initial plasma generated by the excited particle supply system (16, 17, 18), and causes electricity to cause a plasma flow inside the workpiece 21. A pulse power supply 14 for applying a pulse (main pulse) between the first main electrode 11 and the second main electrode 12 is connected.

  From the pulse power supply 14, a high voltage pulse of high repetition as described in the first embodiment (see FIG. 4) is applied between the first main electrode 11 and the second main electrode 12. Although FIG. 4A illustrates the case where the half width is 300 ns as the pulse width of the electric pulse (main pulse), the half width is preferably about 10 to 500 ns as the pulse width of the main pulse. FIG. 12 illustrates a case where the second main electrode 12 is grounded and used as a cathode, and a high voltage is applied to the first main electrode 11 and used as an anode, but the polarity of the pulse power supply 14 is reversed, The second main electrode 12 may be an anode, and the first main electrode 11 may be a cathode.

  Furthermore, in the surface treatment apparatus according to the fifth embodiment, an intake side valve 43 is connected to the introduction pipe 60, and an intake side pipe 67 is connected to the intake side valve 43. Is connected to a gas source 33 such as a gas cylinder for storing the processing gas. It is preferable to employ a needle valve or the like that allows easy adjustment of the gas flow rate for the intake side valve 43.

  On the other hand, in order to exhaust the processing gas introduced from the introduction pipe 60 and set the pressure of the gas flow inside the workpiece 21 to the processing pressure, the exhaust side pipe 68 is connected via the exhaust side valve 44. A vacuum pump 32 is connected. The exhaust side valve 44 is preferably a variable conductance valve whose exhaust conductance is adjustable. With this configuration, the processing gas is supplied from the gas source 33 through the intake side pipe 67 and the intake side valve 43 to the inside of the bowl-shaped workpiece 21 from the introduction pipe 60 provided at the neck. By exhausting the processing gas from the exhaust side pipe 68 provided at the neck portion by the vacuum pump 32, the inside of the workpiece 21 is close to the atmospheric pressure of about 20 to 30 kPa, but the processing pressure is kept below the atmospheric pressure. It is.

  In the surface treatment apparatus according to the fifth embodiment, when the distance between the first main electrode 11 and the second main electrode 12 constituting the parallel plate electrode is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, the voltage wave A high value of about 24 kV is suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006 as shown in FIG. Is generated stably and efficiently.

  In the surface treatment apparatus according to the fifth embodiment, high-purity nitrogen gas is supplied from the neck to the object 21 as a treatment gas, but the “treatment gas” is not necessarily limited to nitrogen gas. . For example, for the purpose of sterilization and sterilization of the inner surface of the workpiece 21, various active gases such as a halogen-based compound gas, a mixed gas of any of these active gases and nitrogen gas, etc. Other gases can be employed. Further, as described in the first embodiment, the cross-sectional shape of the workpiece 21 is not limited to a circle but may be a rectangle or the like. In addition, the concept of “a bowl-shaped workpiece” in the fifth embodiment includes not only a bottle shape as shown in FIG. 12 but also a structure in which one end of a long thin tube is closed.

  FIG. 12 shows an example in which the first auxiliary electrode 17 and the second auxiliary electrode 18 constituting the excited particle supply system (16, 17, 18) are provided at positions that do not overlap the exhaust side pipe 68. As shown in FIG. 13, the first auxiliary electrode 17 and the second auxiliary electrode 18 may be disposed at a position sandwiching both the exhaust side pipe 68 and the introduction pipe 60. Furthermore, as shown in FIG. 14, the first auxiliary electrode 17 and the second auxiliary electrode 18 may be arranged at positions sandwiching the neck adapter 19. Furthermore, the excited particle supply system is not necessarily limited to the parallel plate electrode structure as illustrated in FIGS. 12 to 14, as long as it can supply initial plasma to the gas flow at the beginning of discharge. The initial plasma may be excited by another structure such as an inductive plasma source, as in the case of the surface treatment apparatus according to the first and third embodiments.

(Sixth embodiment)
As shown in FIG. 15, the surface treatment apparatus according to the sixth embodiment of the present invention is made of a dielectric and has the other end (FIG. 15) of a tubular object 21 having one end (the upper end in FIG. 15) sealed. , A vacuum manifold unit (43, 44, 45, 60, 64, 69, 70) for sealing a processing gas inside the workpiece 21 at a predetermined processing pressure is provided.

  The vacuum manifold unit (43, 44, 45, 60, 64, 69, 70) includes an introduction pipe 60 connected to the other end of the workpiece 21, a manifold valve 45 connected to the introduction pipe 60, and a manifold. A T-type pipe 64 connected to the valve 45, a first intake-side valve 43 and a first exhaust-side valve 44 connected to the T-type pipe 64, and an intake-side pipe 70 connected to the first intake-side valve 43; And an exhaust side pipe 69 connected to the first exhaust side valve 44. The introduction pipe 60 is a pipe made of a dielectric. The gas source 33 is connected to the intake side pipe 70, and the vacuum pump 30 is connected to the exhaust side pipe 69. The gas source 33 is a gas cylinder or the like that stores processing gas. As the first intake side valve 43, a needle valve or the like that can easily adjust the gas flow rate can be adopted.

  The processing chambers (23, 53, 54, 62) are connected to the intake side piping 70 via the second intake side valve 41, and the processing chambers (23, 53, 54, 62) are processed from the gas source 33 into the processing chambers (23, 53, 54, 62). The gas can be supplied. Here, as in the third embodiment, the processing chambers (23, 53, 54, 62) include the second electrode (second main electrode) covering insulating film 23, the processing chamber bottom lid 53, and the processing chamber. The upper lid 54 and the intake side adjustment chamber 62 constitute four surfaces of a rectangular parallelepiped, and side plates (not shown) arranged oppositely in front of and behind the paper surface of FIG. 15 constitute two surfaces of the rectangular parallelepiped. The intake side adjustment chamber 62 has a flat rectangular parallelepiped shape, and five of the six surfaces of the rectangular parallelepiped are made of metal, and the gas supply layer 65 is closed on the remaining surface (the left surface in the cross-sectional view of FIG. 15). . A second exhaust side pipe 63 is connected to the processing chamber (23, 53, 54, 62), a second exhaust side valve 63 is connected to the second exhaust side pipe 63, and a second exhaust side valve 42 is connected to the second exhaust side valve 42. The vacuum pump 30 is connected via an exhaust side pipe 69. The first exhaust side valve 44 and the second exhaust side valve 42 are preferably variable conductance valves whose exhaust conductance is adjustable.

First, with the first intake side valve 43 closed, the manifold valve 45 and the first exhaust side valve 44 are opened, and the inside of the workpiece 21 reaches about 10 ⁻¹ Pa to 10 ⁻⁶ Pa by the vacuum pump 30. Evacuate to pressure (background pressure). After reaching the ultimate pressure, the first exhaust-side valve 44 is closed and the first intake-side valve 43 is opened, so that the first intake-side valve 43, T-type piping from the gas source 33 is introduced into the tubular workpiece 21. 64, process gas is supplied from the other end side through the manifold valve 45 and the introduction pipe 60. Although the inside of the workpiece 21 is close to the atmospheric pressure of about 20 to 30 kPa, the manifold valve 45 is closed when the processing pressure reaches the atmospheric pressure or lower, and the inside of the workpiece 21 is maintained at the processing pressure.

  On the other hand, in the processing chamber (23, 53, 54, 62), the processing gas is supplied from the gas source 33 to the atmosphere adjusting means (62, 65, 66b, 25b) via the intake side pipe 70 and the second intake side valve 41. Is supplied at a constant flow rate. As in the third embodiment, the atmosphere adjusting means (62, 65, 66b, 25b) uniformly distributes the processing gas from the intake side adjustment chamber 62 and the intake side adjustment chamber 62 as shown in FIG. The first electrode (first main electrode) protective layer 25b having a plurality of gas supply holes 66b is provided on the surface of the gas supply layer 65 and the gas supply layer 65 made of porous ceramic. The plurality of gas supply holes 66 are tapered through holes penetrating the first electrode (first main electrode) protective layer 25b, and are arranged in a two-dimensional matrix at a constant pitch as shown in FIG. . On the other hand, a second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  For this reason, the processing gas from the atmosphere adjusting means (62, 65, 66b, 25b) is made uniform in a shower-like shape, and in the space surrounding the outer surface of the workpiece 21 inside the processing chamber (23, 53, 54, 62). Supplied. The processing gas supplied from the atmosphere adjusting means (62, 65, 66b, 25b) is exhausted from the processing chamber (23, 53, 54, 62) through the second exhaust side pipe 63.

  The surface treatment apparatus according to the sixth embodiment is further provided with excited particles that are arranged on the other end side of the workpiece 21 and inject active particles into a treatment gas sealed at the beginning of discharge to excite plasma. The first main electrode 11b and the second main electrode 12 which are arranged to face each other so as to sandwich the system (16, 17, 18) and the workpiece 21 and constitute parallel plate electrodes as a whole, and injection of active particles A pulse power supply 14 that maintains an initial plasma more excited and applies an electric pulse (main pulse) between the first main electrode 11 b and the second main electrode 12 to cause a plasma state inside the workpiece 21 is provided. Here, “the parallel plate electrode as a whole is configured” is described, as in the second and third embodiments, the first main electrode 11b is not a flat plate structure, and the T-shaped convex portion has a period. This is because the tips of the respective T-shapes are used as discharge locations. In this case, as described in the second embodiment, the first main electrode 11b can be regarded as equivalent to a ladder-type electrode in which a plurality of rod-shaped (linear) electrodes are periodically arranged in parallel. This means that the entire structure formed by the electrode 11b and the second main electrode 12 can be approximated as a “parallel plate electrode”.

  An upper workpiece holder 52 that holds one end (upper end in FIG. 15) side of the tubular workpiece 21 is connected to the processing chamber upper lid 54, and other objects to be processed 21 are connected to the processing chamber bottom lid 53. A bottom workpiece holder 51 that holds the end (lower end in FIG. 15) in a sealed state is connected. The bottom workpiece holder 51 may be designed by appropriately changing the structure used for a well-known gas pipe joint, vacuum component, etc., depending on the material, shape, and dimensions of the workpiece 21. .

FIG. 15 illustrates a case where the second main electrode 12 is grounded and used as a cathode, and a high voltage is applied to the first main electrode 11b and used as an anode, but the polarity of the pulse power supply 14 is reversed, The second main electrode 12 may be an anode and the first main electrode 11b may be a cathode. When the first main electrode 11b is a cathode, the first main electrode 11b is grounded in the shape of a plate electrode, a high voltage is applied with the second main electrode 12 as a ladder electrode, and atmosphere adjusting means (62, 65). , 66b, 25b) are provided on the second main electrode 12 side. The cross-sectional shape of the workpiece 21 is not limited to a circle, as described in the first and third embodiments. The excited particle supply system (16, 17, 18) is not shown in FIG. In the same manner as described in the first embodiment, the first auxiliary electrode 17 and the second auxiliary electrode 18 that constitute parallel plate electrodes across the introduction pipe 60 of the workpiece 21 and the electricity that excites the active particles An auxiliary pulse power supply (not shown) for applying a pulse (auxiliary pulse) between the first auxiliary electrode 17 and the second auxiliary electrode 18 is provided. The excited particle supply system only needs to be able to inject active particles into the processing gas sealed at the beginning of discharge. Therefore, the excited particle supply system is not necessarily limited to the parallel plate electrode structure illustrated in FIG. The active particles may be excited by another structure such as a plasma source, as in the case of the surface treatment apparatus according to the first embodiment.

  After the excitation of the initial plasma by the injection of the active particles, the surface treatment apparatus shown in FIG. 15 treats the inner surface and the outer surface of the tubular object 21 with one end sealed by radicals contained in the plasma. In the surface treatment apparatus according to the sixth embodiment, high-purity nitrogen gas is supplied as the processing gas, but the “processing gas” is not necessarily limited to nitrogen gas. For example, for the purpose of sterilization and sterilization of the inner and outer surfaces of the workpiece 21, various active gases such as halogen-based compound gas, or a mixed gas of any of these active gases and nitrogen gas, etc. Various other gases can be employed.

  A high repetitive high voltage pulse as described in the first embodiment is applied between the first main electrode 11b and the second main electrode 12 (see FIG. 4). FIG. 4A illustrates the case where the half width is 300 ns as the pulse width of the electric pulse (main pulse). However, the half width is preferably about 50 to 300 ns as the pulse width of the main pulse. In the surface treatment apparatus according to the sixth embodiment, when the distance between the first main electrode 11b and the second main electrode 12 constituting the parallel plate electrode as a whole is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, A voltage peak value of about 24 kV is suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006 as shown in FIG. Is generated stably and efficiently.

  The surface treatment apparatus according to the sixth embodiment also has the three operation modes described in the third embodiment. That is, a mode in which discharge is caused only inside the tubular workpiece 21 sealed at one end, a mode in which discharge is caused only outside the workpiece 21, and a discharge is caused both inside and outside the workpiece 21. These modes can be controlled by the pressure conditions indicated by the equations (1) to (6) as in the third embodiment. Since the content is substantially the same as the description in the third embodiment, a duplicate description is omitted.

(Seventh embodiment)
16 and 17 are cross-sectional views seen from directions orthogonal to each other. As shown in FIGS. 16 and 17, the surface treatment apparatus according to the seventh embodiment of the present invention is made of a dielectric and has one end of a tubular workpiece 21 having a branch at the downstream branch portion 10 ( A vacuum pump provided at the other end (downstream side) of the workpiece 21 in order to exhaust the processing gas supplied from the upstream side and set the pressure of the gas flow inside the workpiece 21 to the processing pressure. (First pump) 32, an excited particle supply system (17, 18) that is disposed on one end (upstream side) side of the workpiece 21 and supplies initial plasma to the gas flow at the beginning of discharge, and the workpiece 21 The first main electrode 11b and the second main electrode 12 that are arranged to face each other and constitute parallel plate electrodes as a whole, and the electricity that maintains the initial plasma and causes a plasma flow inside the workpiece 21 A pulse (main pulse) is applied to the first main electrode 11. And a pulse power supply 14 applied between the second main electrode 12. An example of “a tubular object to be processed having a branch” is an endoscope. Here, “the parallel plate electrode as a whole is described” is described in the same manner as in the second, third, and sixth embodiments, that the first main electrode 11b is not a flat plate structure but is a T-shaped protrusion. The parts are periodically arranged, and the tips of the respective T-shapes are used as discharge points, but the whole structure can be approximated as “parallel plate electrodes”.

  Similar to the surface treatment apparatuses according to the second, third, and sixth embodiments, the surface treatment apparatus according to the seventh embodiment uses the process gas as a cathode from the first main electrode 11b side as the anode. Atmosphere adjusting means (62, 65, 66b) for supplying air in the form of a shower toward the second main electrode 12 side and exhausting the processing gas from the second exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). 25b). The processing chamber (23, 53, 54, 62) is a rectangular parallelepiped made up of the second electrode (second main electrode) covering insulating film 23, the processing chamber bottom lid 53, the processing chamber top lid 54, and the intake side adjustment chamber 62. Side plates (not shown) that constitute four sides and are opposed to each other in front of and behind the sheet of FIG. 16 constitute two sides of the rectangular parallelepiped. The intake side adjustment chamber 62 has a flat rectangular parallelepiped shape, and five of the six surfaces of the rectangular parallelepiped are made of metal, and the remaining one surface (the left surface in the cross-sectional view of FIG. 16) is closed by the gas supply layer 65. .

  The processing chamber upper lid 54 is provided with an upper workpiece holder 52 for holding one end (upstream side) of the tubular workpiece 21 having a branch in a sealed state. On the other hand, as shown in FIG. 17, the processing chamber bottom cover 53 has a bottom processing object holder 81 that holds the other end (downstream side) of the processing object 21 in a sealed state, and a branch portion 10 of the processing object 21. A branch pipe end holder 82 is provided for holding the end of the branch pipe 21b branched in the closed state. The upper workpiece holder 52, the bottom workpiece holder 81, and the branch pipe end holder 82 have structures used for well-known gas pipe joints, vacuum parts, and the like. The design may be made with appropriate changes according to the dimensions. A first exhaust side pipe 68 is connected to the bottom workpiece holder 81, and a branch exhaust pipe 68 b branched from the first exhaust side pipe 68 is connected to the branch pipe end holder 82. A first vacuum pump (first pump) 32 is connected to the downstream side of the first exhaust side pipe 68 via the first exhaust side valve 44. With such a configuration, the first vacuum pump (first pump) 32 evacuates the inside of the workpiece 21 through the first exhaust side pipe 68, the branch exhaust pipe 68 b and the first exhaust side valve 44. Is possible.

  As shown in FIG. 16, the atmosphere adjusting means (62, 65, 66b, 25b) is a gas supply made of porous ceramic that allows the processing gas from the intake side adjustment chamber 62 and the intake side adjustment chamber 62 to be uniformly distributed and permeated. The first electrode (first main electrode) protective layer 25b is provided on the surface of the layer 65 and the gas supply layer 65 and has a plurality of gas supply holes 66b. The plurality of gas supply holes 66 are tapered through holes penetrating the first electrode (first main electrode) protective layer 25b, and are arranged in a two-dimensional matrix at a constant pitch as in the second embodiment. (See FIG. 7). On the other hand, a second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  Furthermore, as shown in FIG. 16, the surface treatment apparatus according to the seventh embodiment includes a gas source 33 such as a gas cylinder for storing a processing gas, a first intake side pipe 67 connected to the gas source 33, and a first gas source 33. A second intake side pipe 61; a first intake side valve 43 connected to the first intake side pipe 67; and a second intake side valve 41 connected to the second intake side pipe 61. For the first intake side valve 43 and the second intake side valve 41, it is preferable to employ a needle valve or the like that allows easy adjustment of the gas flow rate.

  A processing gas is supplied from the upstream side through the first intake side pipe 67 and the first intake side valve 43 from the gas source 33 to the inside of the tubular workpiece 21 having a branch, and a vacuum pump provided downstream. The (second pump) 31 causes the processing gas to flow through the workpiece 21, and the inside of the workpiece 21 is close to an atmospheric pressure of about 20 to 30 kPa, but is maintained at a processing pressure equal to or lower than the atmospheric pressure.

  On the other hand, the process chambers (23, 53, 54, 62) are supplied from the atmosphere adjusting means (62, 65, 66 b, 25 b) from the gas source 33 through the second intake side pipe 61 and the second intake side valve 41. The processing gas is supplied in a uniform shower shape. The processing gas supplied from the atmosphere adjusting means (62, 65, 66b, 25b) is exhausted from the second exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). For this reason, as shown in FIGS. 16 and 17, in the surface treatment apparatus according to the seventh embodiment, the second vacuum pump that depressurizes the space surrounding the outer surface of the workpiece 21 in the second exhaust side pipe 63. A (second pump) 31 is connected. The second vacuum pump (second pump) 31 is connected to the processing chamber (23, 53, 54, 62) via the second exhaust side pipe 63 and the second exhaust side valve 42. The first exhaust side valve 44 and the second exhaust side valve 42 are preferably variable conductance valves whose exhaust conductance can be adjusted.

  FIG. 16 illustrates a case where the second main electrode 12 is grounded and used as a cathode, and a high voltage is applied to the first main electrode 11b and used as an anode, but the polarity of the pulse power supply 14 is reversed, The second main electrode 12 may be an anode and the first main electrode 11b may be a cathode. When the first main electrode 11b is a cathode, the first main electrode 11b is grounded in the shape of a plate electrode, a high voltage is applied with the second main electrode 12 as a ladder electrode, and atmosphere adjusting means (62, 65). , 66b, 25b) are provided on the second main electrode 12 side.

  Similarly to the first embodiment, in the surface treatment apparatus according to the seventh embodiment, the length of the tubular part (stem part) other than the branch is 4 to 7 m as the tubular workpiece 21 having the branch. Processing is possible with the above-mentioned long and narrow tubes having an inner diameter of 7 to 5 mm, but processing is possible even if the length of the trunk is 4 m or less and the inner diameter is 7 mm or more. In addition, as described in the first embodiment, the cross-sectional shape of the workpiece 21 is not limited to a circular shape in any of the branching pipe part and the trunk part.

  In FIGS. 16 and 17, the excited particle supply system (17, 18) configures parallel plate electrodes with the introduction pipe 60 on the upstream side of the object to be processed 21 sandwiched in the same manner as described in the first embodiment. The first auxiliary electrode 17 and the second auxiliary electrode 18 to be applied, and an auxiliary pulse power source (not shown) for applying an electric pulse (auxiliary pulse) that causes initial plasma between the first auxiliary electrode 17 and the second auxiliary electrode 18 are provided. . The introduction pipe 60 is a pipe made of a dielectric. The excited particle supply system only needs to be able to supply the initial plasma to the gas flow at the beginning of discharge, and is not necessarily limited to the parallel plate electrode structure illustrated in FIGS. 16 and 17. The initial plasma may be excited by another structure such as a plasma source as in the case of the surface treatment apparatus according to the first embodiment.

  After the excitation of the initial plasma, the surface treatment apparatus shown in FIGS. 16 and 17 treats the inner surface and the outer surface of the tubular workpiece 21 having a branch with radicals contained in the plasma. In the surface treatment apparatus according to the seventh embodiment, high-purity nitrogen gas is supplied to the workpiece 21 as a treatment gas from upstream, but the “treatment gas” is not necessarily limited to nitrogen gas. . For example, for the purpose of sterilization and sterilization of the inner and outer surfaces of the workpiece 21, various active gases such as halogen-based compound gas, or a mixed gas of any of these active gases and nitrogen gas, etc. Various other gases can be employed.

  A high repetitive high voltage pulse as described in the first embodiment is applied between the first main electrode 11b and the second main electrode 12 (see FIG. 4). In the surface treatment apparatus according to the seventh embodiment, when the distance between the first main electrode 11b and the second main electrode 12 constituting the parallel plate electrode as a whole is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, A voltage peak value of about 24 kV is suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006. For this reason, as in the case of the high frequency discharge, the thermal plasma is not generated, and the non-thermal equilibrium low temperature plasma is generated stably and efficiently.

  The surface treatment apparatus according to the seventh embodiment also has the three operation modes described in the third embodiment. That is, a mode in which discharge is caused only inside the tubular workpiece 21 having a branch, a mode in which discharge is caused only outside the workpiece 21, and a discharge is caused both inside and outside the workpiece 21. Although it is a mode, as in the third embodiment, these modes can be controlled by the pressure conditions indicated by the equations (1) to (6). Since the content is substantially the same as the description in the third embodiment, a duplicate description is omitted.

(Eighth embodiment)
18 and 19 are cross-sectional views seen from directions orthogonal to each other. As shown in FIGS. 18 and 19, the surface treatment apparatus according to the eighth embodiment of the present invention is made of a dielectric material, and the substantially straight trunk portion and the branch pipe merge at the upstream branch portion 9. In order to exhaust the processing gas supplied from the upstream side of the tubular workpiece 21 and set the pressure of the gas flow inside the workpiece 21 to the processing pressure, it is provided downstream of the workpiece 21. A vacuum pump (first pump) 32, an excited particle supply system (85, 91, 92, 93) that is disposed on the upstream side of the workpiece 21 and supplies excited particles to the gas flow at the beginning of discharge; The first main electrode 11b and the second main electrode 12 which are arranged opposite to each other so as to sandwich the processing object 21 and constitute a parallel plate electrode as a whole, and the initial plasma generated by the excited particles are maintained, and the object to be processed Electric pulse that causes plasma flow inside 21 And a pulse power source 14 for applying a (main pulse) between the first main electrode 11b and the second main electrode 12. The endoscope described in the seventh embodiment corresponds to an example of the “tubular object to be processed”, but just upstream and downstream of the endoscope of the seventh embodiment. Corresponds to the topology that is reversed. Here, “the parallel plate electrode is configured as a whole” is described in the same manner as in the second, third, sixth, and seventh embodiments, in which the first main electrode 11b does not have a plate structure, and T The convex portions of the mold are periodically arranged, and the tips of the respective T-shapes are used as discharge locations, which means that the entire structure can be approximated as a “parallel plate electrode”.

  The excited particle supply system (85, 91, 92, 93) includes, for example, as shown in FIGS. 18 and 19, an excited particle generation chamber 85, a first reflecting mirror 92 provided in the excited particle generation chamber 85, and A second reflecting mirror 93 and ultraviolet irradiation means 91 are provided. The first reflecting mirror 92 is a perforated concave mirror having a through hole for irradiating a part thereof with ultraviolet rays. The second reflecting mirror 93 is also a concave mirror. By arranging the first reflecting mirror 92 and the second reflecting mirror 93 so as to face each other, the ultraviolet rays introduced from the through holes of the first reflecting mirror 92 are changed between the first reflecting mirror 92 and the first reflecting mirror 92. A plurality of reflections are performed with the second reflecting mirror 93 to excite the processing gas supplied to the excited particle generation chamber 85 to generate excited particles. As the ultraviolet irradiation means 91, semiconductor light emitting devices such as semiconductor lasers and light emitting diodes using wide band gap semiconductors such as GaN compound semiconductors, ZnSe compound semiconductors, ZnO compound semiconductors, SiC compound semiconductors, etc. are miniaturized. Is preferred. However, a gas laser that emits ultraviolet light, such as an excimer laser, or other solid-state laser may be used. When a large ultraviolet irradiation means 91 such as a gas laser such as an excimer laser is used, the ultraviolet irradiation means 91 is disposed outside the excitation particle generation chamber 85, and excited particles are passed through a window material that transmits ultraviolet rays such as sapphire. Ultraviolet light may be introduced into the generation chamber 85. Even in this case, the ultraviolet rays from the ultraviolet irradiation means 91 arranged outside the excitation particle generation chamber 85 pass between the first reflecting mirror 92 and the second reflecting mirror 93 from the through hole of the first reflecting mirror 92. Introduced, the processing gas can be excited by multiple reflection between the first reflecting mirror 92 and the second reflecting mirror 93.

  Similar to the surface treatment apparatuses according to the second, third, sixth, and seventh embodiments, the surface treatment apparatus according to the eighth embodiment supplies a processing gas from the first main electrode 11b side as an anode. The atmosphere adjusting means (62, 62) supplies air in a shower shape toward the second main electrode 12 as a cathode and exhausts the processing gas from the second exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). 65, 66b, 25b). The processing chamber (23, 53, 54, 62) is a rectangular parallelepiped made up of the second electrode (second main electrode) covering insulating film 23, the processing chamber bottom lid 53, the processing chamber top lid 54, and the intake side adjustment chamber 62. Side plates (not shown) that constitute four sides and are opposed to each other in front of and behind the sheet of FIG. 18 constitute two sides of the rectangular parallelepiped. The intake side adjustment chamber 62 has a flat rectangular parallelepiped shape, and five of the six surfaces of the rectangular parallelepiped are made of metal, and the gas supply layer 65 is closed on the remaining one surface (the left surface in the cross-sectional view of FIG. 18). .

  As shown in FIG. 19, the processing chamber upper lid 54 has an upper workpiece holder 83 that holds one end (upstream side) of the trunk of the workpiece 21 in a sealed state, and a branch branched from the trunk at the branching portion 9. A branch pipe end holder 84 that holds the end of the pipe 21b in a sealed state is provided. The upper workpiece holder 83 and the branch pipe end holder 84 are excited by providing an opening at the bottom of the excited particle generation chamber 85 constituting the excited particle supply system (85, 91, 92, 93). It is connected to the particle generation chamber 85. On the other hand, as shown in FIG. 19, the processing chamber bottom lid 53 is provided with a bottom processing object holder 51 for holding the other end (downstream side) of the processing object 21 in a sealed state. The upper workpiece holder 83, the branch pipe end holder 84, and the bottom workpiece holder 51 have structures used for well-known gas pipe joints, vacuum parts, etc., and the material and shape of the workpiece 21. The design may be made with appropriate changes according to the dimensions. A first exhaust pipe 68 is connected to the bottom workpiece holder 51.

  A first vacuum pump (first pump) 32 is connected to the downstream side of the first exhaust side pipe 68 via a first exhaust side valve 44. With such a configuration, the first vacuum pump (first pump) 32 can evacuate the inside of the workpiece 21 through the first exhaust side pipe 68 and the first exhaust side valve 44. is there.

  As shown in FIG. 18, the atmosphere adjusting means (62, 65, 66b, 25b) is a gas supply made of porous ceramic that allows the processing gas from the intake side adjustment chamber 62 and the intake side adjustment chamber 62 to be uniformly distributed and permeated. The first electrode (first main electrode) protective layer 25b is provided on the surface of the layer 65 and the gas supply layer 65 and has a plurality of gas supply holes 66b. The plurality of gas supply holes 66 are tapered through holes penetrating the first electrode (first main electrode) protective layer 25b, and are arranged in a two-dimensional matrix at a constant pitch as in the second embodiment. (See FIG. 7). On the other hand, a second electrode (second main electrode) covering insulating film 23 such as high-purity quartz glass is provided on the second electrode (second main electrode) 12.

  Furthermore, as shown in FIG. 18, the surface treatment apparatus according to the eighth embodiment includes a gas source 33 such as a gas cylinder for storing a processing gas, a first intake side pipe 67 connected to the gas source 33, and a first gas source 33. A second intake side pipe 61; a first intake side valve 43 connected to the first intake side pipe 67; and a second intake side valve 41 connected to the second intake side pipe 61. For the first intake side valve 43 and the second intake side valve 41, it is preferable to employ a needle valve or the like that allows easy adjustment of the gas flow rate. The first intake side valve 43 is connected to the introduction pipe 60, and the introduction pipe 60 is connected to the ceiling portion of the excited particle generation chamber 85. In the surface treatment apparatus according to the eighth embodiment, the introduction pipe 60 is not necessarily a pipe made of a dielectric.

  Processing gas is supplied into the excited particle generation chamber 85 from the upstream side via the first intake side pipe 67, the first intake side valve 43, and the introduction pipe 60 from the gas source 33. The processing gas supplied to the inside of the excitation particle generation chamber 85 is to be processed through the openings of the upper object holder 83 and the branch pipe end holder 84 provided at the bottom of the excitation particle generation chamber 85, respectively. It is supplied to the trunk of the object 21 and the branch pipe 21b. At this time, excited particles are generated inside the excited particle generation chamber 85, and the generated excited particles together with the processing gas are the upper workpiece holder 83 and the branch pipe end holder at the bottom of the excited particle generation chamber 85. 84, the plasma is injected into the trunk of the workpiece 21 and the branch pipe 21b, respectively, and initial plasma is generated inside the trunk of the workpiece 21 and inside the branch pipe 21b. The processing gas supplied to the trunk of the workpiece 21 and the branch pipe 21b is merged in the branching section 9, and then exhausted by a vacuum pump (second pump) 31 provided downstream of the workpiece 21 to be processed. The inside 21 is close to an atmospheric pressure of about 20 to 30 kPa, but is maintained at a processing pressure equal to or lower than the atmospheric pressure.

  On the other hand, the process chambers (23, 53, 54, 62) are supplied from the atmosphere adjusting means (62, 65, 66 b, 25 b) from the gas source 33 through the second intake side pipe 61 and the second intake side valve 41. The processing gas is supplied in a uniform shower shape. The processing gas supplied from the atmosphere adjusting means (62, 65, 66b, 25b) is exhausted from the second exhaust side pipe 63 of the processing chamber (23, 53, 54, 62). For this reason, as shown in FIGS. 18 and 19, in the surface treatment apparatus according to the eighth embodiment, the second vacuum pump that decompresses the space surrounding the outer surface of the workpiece 21 in the second exhaust side pipe 63. A (second pump) 31 is connected. The second vacuum pump (second pump) 31 is connected to the processing chamber (23, 53, 54, 62) via the second exhaust side pipe 63 and the second exhaust side valve 42. The first exhaust side valve 44 and the second exhaust side valve 42 are preferably variable conductance valves whose exhaust conductance can be adjusted.

  FIG. 18 illustrates a case where the second main electrode 12 is grounded and used as a cathode, and a high voltage is applied to the first main electrode 11b and used as an anode, but the polarity of the pulse power supply 14 is reversed, The second main electrode 12 may be an anode and the first main electrode 11b may be a cathode. When the first main electrode 11b is a cathode, the first main electrode 11b is grounded in the shape of a plate electrode, a high voltage is applied with the second main electrode 12 as a ladder electrode, and atmosphere adjusting means (62, 65). , 66b, 25b) are provided on the second main electrode 12 side.

  Similarly to the first embodiment, in the surface treatment apparatus according to the eighth embodiment, the length of the tubular part (stem part) other than the branch is 4 to 7 m as the tubular workpiece 21 having the branch. Processing is possible with the above-mentioned long and narrow tubes having an inner diameter of 7 to 5 mm, but processing is possible even if the length of the trunk is 4 m or less and the inner diameter is 7 mm or more. In addition, as described in the first embodiment, the cross-sectional shape of the workpiece 21 is not limited to a circular shape in any of the branching pipe part and the trunk part.

  After the excitation of the initial plasma, the inner surface of the surface treatment apparatus shown in FIGS. 18 and 19 is treated with radicals contained in the plasma flowing at a constant flow rate inside the tubular object 21 having a branch. In addition, the outer surface of the tubular workpiece 21 having a branch is also treated by radicals contained in the plasma generated outside the workpiece. In the surface treatment apparatus according to the eighth embodiment, high-purity nitrogen gas is supplied as a treatment gas inside and outside the workpiece 21, but the “treatment gas” is not necessarily limited to nitrogen gas. is not. For example, for the purpose of sterilization and sterilization of the inner and outer surfaces of the workpiece 21, various active gases such as halogen-based compound gas, or a mixed gas of any of these active gases and nitrogen gas, etc. Various other gases can be employed.

  A high repetitive high voltage pulse as described in the first embodiment is applied between the first main electrode 11b and the second main electrode 12 (see FIG. 4). In the surface treatment apparatus according to the eighth embodiment, when the distance between the first main electrode 11b and the second main electrode 12 constituting the parallel plate electrode as a whole is 15 mm, the repetition frequency of the high voltage pulse is 2 kHz, A voltage peak value of about 24 kV is suitable. When the repetition frequency of the high voltage pulse is 2 kHz, the repetition period is 500 μs and the duty ratio is 0.3 / 500 = 0.006. For this reason, as in the case of the high frequency discharge, the thermal plasma is not generated, and the non-thermal equilibrium low temperature plasma is generated stably and efficiently.

  The surface treatment apparatus according to the eighth embodiment also has the three operation modes described in the third embodiment. That is, a mode in which discharge is caused only inside the tubular workpiece 21 having a branch, a mode in which discharge is caused only outside the workpiece 21, and a discharge is caused both inside and outside the workpiece 21. Although it is a mode, as in the third embodiment, these modes can be controlled by the pressure conditions indicated by the equations (1) to (6). Since the content is substantially the same as the description in the third embodiment, a duplicate description is omitted.

(Ninth embodiment)
In the surface treatment apparatuses according to the third and sixth to eighth embodiments, examples in which the three operation modes are controlled according to the pressure conditions indicated by the expressions (1) to (6) have been shown. That is, by selecting the pressure conditions represented by the equations (1) to (6), a mode in which discharge is caused only inside the workpiece 21, a mode in which discharge is caused only outside the workpiece 21, Although the mode in which discharge is caused both inside and outside the workpiece 21 is determined, the three operation modes can be controlled using parameters other than the pressure of the processing gas. One example of another parameter is the temperature of the processing gas described in the surface treatment apparatus according to the ninth embodiment of the present invention.

As shown in FIG. 20, the surface treatment apparatus according to the ninth embodiment of the present invention exhausts a processing gas introduced from one end (upstream side) of a tubular object 21 made of a dielectric, A vacuum pump (first pump) 32 provided at the other end (downstream side) of the workpiece 21 and one end of the workpiece 21 in order to set the pressure of the gas flow inside the workpiece 21 to the processing pressure. It is arranged on the (upstream side) side, arranged opposite to each other so as to sandwich the workpiece 21 and the excited particle supply system (17, 18) for supplying the initial plasma to the gas flow at the beginning of discharge, and parallel as a whole. The first main electrode 11b and the second main electrode 12 constituting the flat plate electrode, and the electric pulse (main pulse) that maintains the initial plasma and causes the plasma flow inside the workpiece 21 are supplied to the first main electrode 11b and the second main electrode 11b. A pulse power source 14 applied between the main electrodes 12; Than obtaining points are the same as the surface treatment apparatus according to the third embodiment. Further, a gas source 33 such as a gas cylinder for storing the processing gas, a first intake side pipe 67 and a second intake side pipe 61 connected to the gas source 33, and a first intake side pipe 67 connected to the first intake side pipe 67. The surface treatment apparatus according to the third embodiment is the same as the surface treatment apparatus according to the third embodiment in that an intake side valve 43 and a second intake side valve 41 connected to the second intake side pipe 61 are provided.
However, the surface treatment apparatus according to the ninth embodiment of the present invention is the third embodiment in that the introduction pipe 86 connected to the first intake side valve 43 includes a preheater 87 as shown in FIG. This is different from the surface treatment apparatus according to the embodiment. In order to increase the heating efficiency of the processing gas, it is preferable that the introduction pipe 86 gains a constant heating distance by a topology such as meander line meandering as shown in FIG. In the introduction pipe 86, the portion where the preheater 87 is arranged does not necessarily need to be a pipe made of a dielectric, but the portion where the excited particle supply system (17, 18) is arranged is made of a dielectric. The

A processing gas is supplied from the upstream side to the inside of the tubular workpiece 21 from the gas source 33 via the first intake side pipe 67 and the first intake side valve 43, and a vacuum pump (second pump) provided downstream. The processing gas flows through the workpiece 21 by the pump 31) and the inside of the workpiece 21 is maintained at a predetermined pressure, but discharge is caused only within the workpiece 21 among the three operation modes. When selecting the mode, the preheater 87 is energized so that the temperature of the processing gas flowing inside the processing target 21 is changed to the outside of the processing target 21 via the atmosphere adjusting means (62, 65, 66b, 25b). By making the temperature 30 to 50 ° C. higher than the temperature of the processing gas flowing in the gas, it is possible to easily cause discharge only inside the workpiece 21. Of course, in order to cause discharge inside the workpiece 21, the gas pressure P ₁ inside the workpiece 21 is set to about ₁₀ to 40 kPa and is lower than the gas pressure P ₂ outside the workpiece 21. It is preferable to keep it. Further, as shown in the equation (1), the gas pressure P ₂ outside the object to be treated 21 should be slightly lower than the atmospheric pressure P ₃ to be equal to the atmospheric pressure P ₃ = 101 kPa or about 80 to 90 kPa. However, by setting the temperature of the processing gas flowing inside the workpiece 21 to be higher by 30 ° C. to 50 ° C. than the temperature of the processing gas flowing outside the workpiece 21, the processing gas is more stably and reliably processed. A mode in which discharge is generated only inside the object 21 can be selected. In addition, even when the gas pressure P ₁ inside the workpiece 21 and the gas pressure P ₂ outside the workpiece 21 are close to each other, a mode in which discharge is generated only inside the workpiece 21 can be selected.

  Since the structures of the processing chambers (23, 53, 54, 62) and the atmosphere adjusting means (62, 65, 66b, 25b) are the same as those of the surface processing apparatus according to the third embodiment, redundant description is omitted. To do.

  Although not shown in the figure, an embedded heater is provided inside the atmosphere adjusting means (62, 65, 66b, 25b), and the temperature of the processing gas flowing outside the workpiece 21 is adjusted. It is also possible to select a mode in which discharge is caused only at the outside of the workpiece 21 by raising the temperature of the processing gas flowing inside the chamber.

  Further, a Peltier cooling unit is provided inside the atmosphere adjusting means (62, 65, 66b, 25b), and the temperature of the processing gas flowing outside the workpiece 21 is controlled by electronic cooling (Peltier effect). The temperature of the processing gas flowing in the interior of the substrate 21 can be set lower than the temperature of the processing object 21 so that the discharge can be suppressed only outside the processing object 21 and the discharge can be caused inside the processing object 21. Instead of the Peltier cooling unit, a refrigerant gas pipe is provided inside the atmosphere adjusting means (62, 65, 66b, 25b), and the temperature of the processing gas flowing outside the workpiece 21 is adjusted to the inside of the workpiece 21. It is also possible to suppress the discharge only outside the workpiece 21 by lowering the temperature of the processing gas flowing through the chamber.

  Others are substantially the same as those of the surface treatment apparatus according to the third embodiment, and a duplicate description is omitted.

(Tenth embodiment)
As described in the ninth embodiment, the three operation modes can be controlled using parameters other than the pressure of the processing gas. One example of the other parameter is the temperature of the processing gas described in the surface treatment apparatus according to the ninth embodiment of the present invention. A trigger gas that facilitates discharge only at a desired discharge location at the beginning of discharge is used. It is also possible to control the three operation modes by the introduced method.

As shown in FIG. 21, the surface treatment apparatus according to the tenth embodiment of the present invention exhausts a processing gas introduced from one end (upstream side) of a tubular object 21 made of a dielectric, A vacuum pump (first pump) 32 provided at the other end (downstream side) of the workpiece 21 and one end of the workpiece 21 in order to set the pressure of the gas flow inside the workpiece 21 to the processing pressure. It is arranged on the (upstream side) side, arranged opposite to each other so as to sandwich the workpiece 21 and the excited particle supply system (17, 18) for supplying the initial plasma to the gas flow at the beginning of discharge, and parallel as a whole. The first main electrode 11b and the second main electrode 12 constituting the flat plate electrode, and the electric pulse (main pulse) that maintains the initial plasma and causes the plasma flow inside the workpiece 21 are supplied to the first main electrode 11b and the second main electrode 11b. A pulse power source 14 applied between the main electrodes 12; Or a gas source 33 such as a gas cylinder for storing process gas; a first intake side pipe 67c and a second intake side pipe 61c connected to the gas source 33; and a first intake side pipe 67c. The surface treatment apparatus according to the third embodiment is the same as the surface treatment apparatus according to the third embodiment in that the first intake side valve 43c and the second intake side valve 41c connected to the second intake side pipe 61c are provided.
However, in the surface treatment apparatus according to the tenth embodiment of the present invention, the first T-type pipe 67t for introducing the trigger gas is connected to the first intake side valve 43c, and the trigger gas is introduced to the second intake side valve 41c. This is different from the surface treatment apparatus according to the third embodiment in that a second T-type pipe 61t is connected. Further, the branch portion of the first T-type pipe 67t is connected to the first trigger gas source 88a via the first trigger gas introduction valve 43b and the first trigger gas introduction pipe 67b. The branch portion of the second T-type pipe 61t is connected to the second trigger gas source 88b via the second trigger gas introduction valve 41b and the second trigger gas introduction pipe 61b. Although the first trigger gas source 88a and the second trigger gas source 88b are illustrated as separate gas sources in FIG. 21, they may be a common gas source. The first trigger gas source 88a and the second trigger gas source 88b are cylinders filled with a gas that can be easily discharged, such as helium (He) and argon (Ar). The first trigger gas introduction valve 43b and the second trigger gas introduction valve 41b are preferably valves having a fast response time (response) such as an electromagnetic valve or a pneumatic valve.

  Furthermore, the downstream side of the first T-type pipe 67t is connected to the introduction pipe 60 via the first manifold valve 43a. The introduction pipe 60 is a pipe made of a dielectric. On the other hand, the downstream side of the second T-type pipe 61t is connected to the atmosphere adjusting means (62, 65, 66b, 25b) via the second manifold valve 41a.

Inside the tubular workpiece 21, from the gas source 33 through the first intake side pipe 67 c, the first intake side valve 43 c, the first T-type pipe 67 t, the first manifold valve 43 a and the introduction pipe 60, from the upstream side. The processing gas is supplied, and the processing gas flows through the workpiece 21 by a vacuum pump (second pump) 31 provided downstream, and the inside of the workpiece 21 is maintained at a predetermined pressure. At this time, when selecting a mode in which the discharge is caused only in the workpiece 21 among the three operation modes, the first trigger gas source 43b is opened for a short time in the initial stage of the discharge. The trigger gas is caused to flow in from 88a, and the trigger gas is introduced into the workpiece 21 through the first T-type pipe 67t, the first manifold valve 43a, and the introduction pipe 60, so that only the inside of the workpiece 21 is discharged. Can easily occur. Of course, in order to cause discharge inside the workpiece 21, the gas pressure P ₁ inside the workpiece 21 is set to about ₁₀ to 40 kPa and is lower than the gas pressure P ₂ outside the workpiece 21. It is preferable to keep it. Further, as shown in the equation (1), the gas pressure P ₂ outside the object to be treated 21 should be slightly lower than the atmospheric pressure P ₃ to be equal to the atmospheric pressure P ₃ = 101 kPa or about 80 to 90 kPa. However, it is possible to select a mode in which discharge is caused only in the workpiece 21 more stably and reliably by introducing the trigger gas instantaneously and in pulses. Further, even when the gas pressure P ₁ inside the workpiece 21 and the gas pressure P ₂ outside the workpiece 21 are close, by introducing a trigger gas, a discharge is caused only inside the workpiece 21. The mode can be selected.

On the other hand, the atmosphere adjusting means (62, 65, 66b, 25b) is connected upstream from the gas source 33 via the second intake side pipe 61c, the second intake side valve 41c, the second T-type pipe 61t, and the second manifold valve 41a. The processing gas is supplied from the side, and the processing gas flows through the processing chambers (23, 53, 54, 62) by the vacuum pump (second pump) 31 provided downstream, and the processing chambers (23, 53, 54, 62) 62) The inside is maintained at a predetermined pressure. At this time, when selecting a mode in which discharge is caused only outside the workpiece 21 among the three operation modes, the second trigger gas introduction valve 41b is opened for a short time in the initial stage of discharge, and the second trigger gas source The trigger gas is caused to flow from 88b and introduced into the processing chamber (23, 53, 54, 62) through the second T-type pipe 61t and the second manifold valve 41a, so that the outside of the object 21 to be processed is introduced. It is possible to make discharge easy to occur. Of course, in order to cause discharge only outside the workpiece 21, it is preferable to set the pressure conditions shown in the formulas (3), (4), (5), or (6). By introducing the trigger gas instantaneously and in a pulsed manner, it is possible to select a mode in which discharge is caused only within the workpiece 21 in a more stable and reliable manner. In addition, even when the gas pressure P ₁ inside the workpiece 21 and the gas pressure P ₂ outside the workpiece 21 are close, the trigger gas is introduced to cause discharge only outside the workpiece 21. The mode can be selected.

  In the mode in which discharge is caused both inside and outside the workpiece 21, the trigger gas may be allowed to flow into both, or the trigger gas may not be allowed to flow into both. Alternatively, the trigger gas may be allowed to flow into one of the conditions where it is difficult to discharge.

  Other configurations, for example, the structures of the processing chambers (23, 53, 54, 62) and the atmosphere adjusting means (62, 65, 66b, 25b) are the same as those of the surface processing apparatus according to the third embodiment. The duplicated explanation is omitted.

(Other embodiments)
As described above, the present invention has been described according to the first to tenth embodiments. However, it should not be understood that the description and drawings constituting a part of this disclosure limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  For example, the technical ideas described in the first to tenth embodiments can be combined with each other. For example, the structure of the first main electrode 11c and the structure of the atmosphere adjusting means (62, 27, 66c) described in the first modification of the second embodiment are the same as those in the third, sixth to tenth embodiments. The structure of the first main electrode 11d and the structure of the atmosphere adjusting means (62, 25d, 66d) described in the second modification of the second embodiment may be applied to the third, sixth to sixth. You may apply to ten embodiment.

  Further, in the first to seventh and ninth to tenth embodiments as the excited particle supply system, the excitation of the plasma discharge by the parallel plate type electrode is explained, and in the eighth embodiment, the excitation by the ultraviolet ray is explained. These are merely examples, and there are various other initial plasma excitation means. For example, as shown in FIG. 22, one electrode (first auxiliary electrode) 17b is circulated around the outside of the introduction pipe 60 in a band shape (flat ring shape), and the other electrode (second auxiliary electrode) 8 is L-shaped. The short needle shape may be provided at the center of the introduction pipe 60 and discharged between the first auxiliary electrode 17 b and the second auxiliary electrode 8.

  Alternatively, as shown in FIG. 23, one electrode (first auxiliary electrode) 17a is formed in a band shape (flat ring shape) around the outside of the introduction pipe 60, and the other electrode (second auxiliary electrode) 18a is formed in a band shape ( A flat ring shape may be used, and the inside of the introduction pipe 60 may be circulated to cause discharge between the first auxiliary electrode 17a and the second auxiliary electrode 18a. In FIG. 23, the current introduction terminal (feedthrough) 7 is used to excite the case where the voltage from the auxiliary pulse power supply 16 is supplied to the other electrode (second auxiliary electrode) 18a. Of course, this is not limited to the illustration of FIG. An external wiring 67 is connected from the auxiliary pulse power supply 16 to the current introduction terminal (feedthrough) 7, and the current introduction terminal (feedthrough) 7 and the other electrode (second auxiliary electrode) 18a are connected by an internal wiring 6c. Yes. The auxiliary pulse power supply 16 and one electrode (first auxiliary electrode) 17a are connected by an external wiring 17a.

  In the eighth embodiment, excitation by ultraviolet rays using multiple reflection has been described. However, it is not always necessary to use multiple reflections, and excitation can also be performed by means of traveling a single ultraviolet beam in the direction of process gas introduction. Particles can be generated.

  The excited particles may be generated using radiation other than ultraviolet rays, for example, radiation by synchrotron radiation.

  Further, in the first to tenth embodiments, the case where there is one object to be processed is illustrated, but the first main electrode 11b and the second main electrode 12 are mutually connected so as to sandwich all the objects to be processed. If they are arranged to face each other, a plurality of objects to be processed can be processed at the same time. In this case, if the inner surfaces of a plurality of objects to be processed are to be processed, it is needless to say that an intake side piping (introduction piping) and an exhaust side piping for the respective processing objects and valves associated therewith are required. is there.

  As described above, the present invention naturally includes various embodiments not described herein. Therefore, the technical scope of the present invention is defined only by the invention specifying matters according to the scope of claims reasonable from the above description.

It is a schematic diagram explaining the principle of the surface treatment apparatus which concerns on the 1st Embodiment of this invention. It is a bird's-eye view for demonstrating a part of surface treatment apparatus concerning a 1st embodiment of the present invention concretely. FIG. 3A is a bird's-eye view for explaining a meandering workpiece guide groove for housing a flexible long thin tube in the surface treatment apparatus according to the first embodiment of the present invention. ) Is a schematic cross-sectional view for explaining a state in which the object to be processed is accommodated in the object to be processed guide groove. FIG. 4A is a voltage waveform of a high voltage pulse applied between the first main electrode and the second main electrode in the surface treatment apparatus according to the first embodiment of the present invention, and FIG. The corresponding current waveform. It is a schematic diagram for demonstrating electric field distribution at the time of putting the to-be-processed object which consists of a dielectric material in parallel with an electrode surface in the 1st main electrode and 2nd main electrode which comprise a parallel plate electrode. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 2nd Embodiment of this invention. It is a typical top view for demonstrating arrangement | positioning of the several gas supply hole of the surface treatment apparatus which concerns on the 2nd Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 1st modification of the 2nd Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 2nd modification of the 2nd Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 3rd Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 4th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 5th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 1st modification of the 5th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 2nd modification of the 5th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus concerning the 6th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus which concerns on the 7th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus concerning 7th Embodiment seen from the direction orthogonal to FIG. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus concerning the 8th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus concerning 8th Embodiment seen from the direction orthogonal to FIG. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus concerning the 9th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the principal part of the surface treatment apparatus concerning the 10th Embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the excitation particle supply system of the surface treatment apparatus which concerns on other embodiment of this invention. It is sectional drawing for demonstrating typically the structure of the excitation particle supply system of the surface treatment apparatus which concerns on other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 8 ... 2nd auxiliary electrode 9 ... Branch part 10 ... Branch part 11, 11b, 11c, 11d ... 1st main electrode 12 ... 2nd main electrode 14 ... Pulse power supply 16 ... Auxiliary pulse power supply 17, 17a, 17b ... 1st auxiliary | assistant Electrodes 18, 18a ... second auxiliary electrode 19 ... neck adapter 20, 21 ... workpiece 21b ... branch pipe 22 ... workpiece guide groove 23 ... second main electrode covering insulating film 24 ... intake adapter 25b, 25d ... first Main electrode protective layer 27 ... Processing chamber side wall 28 ... Exhaust adapter 30 ... Vacuum pump 31 ... Vacuum pump (second pump)
32 ... Vacuum pump (first pump)
33 ... Gas source 41 ... Intake side valve (second intake side valve)
41a ... second manifold valve 41b ... second trigger gas introduction valve 41c ... second intake side valve 42 ... exhaust side valve (second exhaust side valve)
43 ... 1st intake side valve 43a ... 1st manifold valve 43b ... 1st trigger gas introduction valve 43c ... 1st intake side valve 44 ... 1st exhaust side valve 45 ... Manifold valve 51 ... Bottom part workpiece holder 52 ... Top cover Processed object holder 53 ... Processing chamber bottom cover 54 ... Processing chamber upper cover 60 ... Introduction piping 61 ... Suction side piping (second suction side piping)
61b ... second trigger gas introduction pipe 61c ... second intake side pipe 61t ... second T-type pipe 62 ... intake side adjustment chamber 63 ... exhaust side pipe (second exhaust side pipe)
64 ... T-type piping 65 ... Gas supply layer 66, 66b, 66c, 66d ... Gas supply hole 67 ... First intake side piping 67b ... First trigger gas introduction piping 67c ... First intake side piping 67t ... First T-type piping 68 ... First exhaust side pipe 68b ... Branch exhaust pipe 69 ... Exhaust side pipe 70 ... Intake side pipe 71 ... Storage tube 72 ... Storage tube bottom cap 73 ... Storage tube upper cap 81 ... Bottom workpiece holder 82 ... Branch pipe end Holder 83 ... Upper workpiece holder 84 ... Branch pipe end holder 85 ... Excitation particle generation chamber 86 ... Introduction pipe 87 ... Preheater 88a ... First trigger gas source 88b ... Second trigger gas source 91 ... Ultraviolet irradiation means 92 ... 1st reflector 93 ... 2nd reflector

Claims (12)

A gas introduction system for introducing a processing gas from one end of a tubular workpiece;
A vacuum exhaust system for exhausting the processing gas from the other end of the workpiece;
An excited particle supply system that is arranged on the gas supply upstream side of the object to be processed and supplies excited particles that cause an initial discharge in the main body of the object to be processed;
A first main electrode and a second main electrode having a processing region as a main plasma generation region sandwiched between processing regions of the object to be processed, and the excited particle supply system is driven until at least main plasma generation And applying a main pulse having a duty ratio of 10 ⁻⁷ to 10 ⁻¹ between the first main electrode and the second main electrode to generate a non-thermal equilibrium plasma flow inside the object to be processed, A surface treatment apparatus for treating an inner surface of an object. A processing gas introduced at a constant flow rate from an introduction pipe provided at the other end of the tubular workpiece to be sealed at one end is exhausted from an exhaust pipe provided at the other end, and the inside of the workpiece is An evacuation system for maintaining the pressure of the processing gas at the processing pressure;
An excited particle supply system that is arranged on the gas supply upstream side of the object to be processed and supplies excited particles that cause an initial discharge in the main body of the object to be processed;
A first main electrode and a second main electrode having a processing region as a main plasma generation region sandwiched between processing regions of the object to be processed, and the excited particle supply system is driven until at least main plasma generation And applying a main pulse having a duty ratio of 10 ⁻⁷ to 10 ⁻¹ between the first main electrode and the second main electrode to generate a non-thermal equilibrium plasma flow inside the object to be processed, A surface treatment apparatus for treating an inner surface of an object. A vacuum manifold unit for sealing a processing gas at a predetermined pressure from the other end to the inside of the processing object connected to the other end of the tubular processing object sealed at one end;
An excited particle supply system that is disposed on the other end side and supplies excited particles that cause initial discharge in the main body of the workpiece;
A first main electrode and a second main electrode having a processing region as a main plasma generation region sandwiched between processing regions of the object to be processed, and the excited particle supply system is driven until at least main plasma generation And applying a main pulse with a duty ratio of 10 ⁻⁷ to 10 ⁻¹ between the first main electrode and the second main electrode to generate non-thermal equilibrium plasma inside the object to be processed, The surface treatment apparatus characterized by processing the inner surface of. In a workpiece having a tubular trunk and a branch pipe branched from the trunk, the processing gas introduced from one end of the trunk is exhausted from the other end of the trunk and the end of the branch pipe to generate a gas flow Vacuum evacuation system to
An excited particle supply system that is arranged on the gas supply upstream side of the object to be processed and supplies excited particles that cause an initial discharge in the main body of the object to be processed;
A first main electrode and a second main electrode having a processing region as a main plasma generation region sandwiched between processing regions of the object to be processed, and the excited particle supply system is driven until at least main plasma generation And applying a main pulse having a duty ratio of 10 ⁻⁷ to 10 ⁻¹ between the first main electrode and the second main electrode to generate a non-thermal equilibrium plasma flow inside the object to be processed, A surface treatment apparatus for treating an inner surface of an object. In a workpiece having a tubular trunk and a branch pipe branched from the trunk, the processing gas introduced from one end of the trunk and the end of the branch pipe is exhausted from the other end of the trunk to generate a gas flow. Vacuum evacuation system to
An excited particle supply system that is arranged on the gas supply upstream side of the object to be processed and supplies excited particles that cause an initial discharge in the main body of the object to be processed;
A first main electrode and a second main electrode having a processing region as a main plasma generation region sandwiched between processing regions of the object to be processed, and the excited particle supply system is driven until at least main plasma generation And applying a main pulse having a duty ratio of 10 ⁻⁷ to 10 ⁻¹ between the first main electrode and the second main electrode to generate a non-thermal equilibrium plasma flow inside the object to be processed, A surface treatment apparatus for treating an inner surface of an object. A processing chamber constituting a sealed space surrounding the outer surface of the workpiece;
The first main electrode is used as an anode, the second main electrode is used as a cathode, and a processing gas is supplied from the first main electrode side to the second main electrode side in a shower shape inside the processing chamber. And an atmosphere adjusting means for exhausting the processing gas supplied in a shower form from a part of the processing chamber, and applying the main pulse between the first main electrode and the second main electrode. The surface treatment apparatus according to claim 1, wherein the outer surface of the workpiece is further subjected to non-thermal equilibrium plasma treatment.   The pulse width of the main pulse is 10 to 500 ns in half width, and the pulse width is before the elapse of time when the arc discharge current starts flowing from glow discharge to streamer discharge and then fine streamer discharge in plasma generation between the anode and the cathode. The surface treatment apparatus according to claim 1, wherein the surface treatment apparatus is set in accordance with an interval between the anode and the cathode so that no pulse voltage is applied. The atmosphere adjusting means is
The surface treatment apparatus according to claim 6, further comprising a second evacuation system that depressurizes a space surrounding an outer surface of the workpiece. An excited particle supply system that is arranged on the gas supply upstream side of a tubular object to be processed having a length equal to or greater than the outer diameter, and that supplies excited particles that cause an initial discharge in the main body of the object to be processed, which is made of a dielectric,
A first main electrode and a second main electrode having a processing region of the processing object as a main plasma generation region sandwiched between processing regions of the processing object, and introducing a processing gas from one end of the processing object. the gas flow is formed inside of the object to be treated Te, the pressure of the gas flow was adjusted to the process pressure in the range of 20KPa～100kPa, the excited particle supplying system drives at least until the main plasma generation, a duty ratio of 10 ^{- By} applying a main pulse of ⁷ to 10 ⁻¹ between the first main electrode and the second main electrode, a non-thermal equilibrium plasma flow is generated inside the object to be processed, and the inner surface of the object to be processed is processed. The surface treatment apparatus characterized by the above-mentioned.  The excited particle supply system is any one of an ultraviolet light generator, a laser beam generator, an electron beam generator, a radiation generator, and a high-temperature heater. Surface treatment equipment.  The surface treatment apparatus according to claim 1, wherein the discharge of the non-thermal equilibrium plasma is a fine streamer discharge. In the discharge of the non-thermal equilibrium plasma, the maximum rising rate dV / dt of the voltage of the main pulse applied between the first main electrode and the second main electrode is 10 kV / μs to 1000 kV / μs. The surface treatment apparatus according to any one of claims 1 to 10.

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