JPH10265958A - Production of tubular body film-formed in inner peripheral surface and production device therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a film can be formed on the inner peripheral surface of a tubular body having a small inside diameter with uniformity or with uniform shape even in the case of such tubular body and the tubular body film-formed on the inner peripheral surface thereof can be obtained with high productivity by using a device having simple structure and a device which can execute the manufacturing method of the tubular body and has a simple structure. SOLUTION: A gaseous starting material for film-forming is introduced inside the tubular body S from an edge part of the tubular body S via a member 4 for introducing gas in a state where the outside of the tubular body S to be film-formed made of a conductive material is covered with an electrical insulating member a. Then high frequency power in a state where amplitude modulation is applied to fundamental high frequency power having a prescribed frequency of >=13.56 MHz by 2a modulation frequency of >=1/10<7> to <=1/10<3> of the prescribed frequency is supplied to the tubular body S to convert the introduced gaseous starting material for film-forming into plasma and a film is formed on the inner peripheral surface of the tubular body S to be formed with the film under an atmosphere of the plasma.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to various glass pipes,
The present invention relates to a method and an apparatus for forming a predetermined film on the inner peripheral surface of a tubular body such as a thin tube for passing cooling water or a medical catheter of a nuclear power plant for the purpose of protecting the inner peripheral surface of the tubular body.

[0002]

2. Description of the Related Art Generally, a film is formed on the inner peripheral surface of a tube by vacuum evaporation. When performing such vacuum deposition, a deposition material such as a linear or rod-like material having a length substantially the same as the tubular body is disposed in a film-forming tube installed in a vacuum vessel, and both ends of the deposited material are disposed. Is supplied with a DC power, whereby the deposition material is heated and vacuum-deposited on the inner peripheral surface of the film-forming tube, thereby forming a desired film on the inner peripheral surface of the tube.

According to Japanese Patent Application Laid-Open No. Sho 62-173091, there is provided an apparatus for performing laser processing such as laser CVD on the inner and outer surfaces of a tube, and a laser beam focusing system for obtaining a predetermined energy density. It is disclosed that a film can be uniformly formed on the inner peripheral surface of a tube by using a laser processing apparatus that synchronously moves a reflecting mirror of a focused laser beam for irradiation to a predetermined processing position. I have.

Japanese Patent Application Laid-Open No. 63-26373 discloses a method of forming a film on the inner peripheral surface of a conductive film-forming tube by a plasma CVD method. A gas introduction pipe having substantially the same length as that described above is installed inside the tubular body, and a raw material gas for film formation is introduced into the tubular body to be film-formed. It is disclosed that a film can be uniformly formed on the inner peripheral surface of the tube by applying a high voltage to the tube.

[0005]

However, in the film formation using the above-described vacuum deposition apparatus, when the inner diameter of the tube is small, the diameter of the vapor deposition material must be small in accordance with the small inner diameter. The evaporation material is liable to be cut off in the course of evaporation. In this case, since the film cannot be formed on the inner surface of the tube, it must be replaced with a new vapor deposition material. In this case, the inside of the container must be again set to a predetermined degree of vacuum, which is troublesome and lowers productivity.

The device disclosed in Japanese Patent Application Laid-Open No. 62-173091 has a complicated structure. In addition, Japanese Patent Application Laid-Open No.
According to the method described in Japanese Patent Application Laid-Open No. 3-26373, a gas introduction tube must be disposed in a film-forming tube, so that film formation can be performed only on a tube having an inner diameter of about 10 mm at most. It is difficult to form a film on the inner peripheral surface. Therefore, the present invention is capable of forming a film evenly or evenly on the inner peripheral surface of a tube having a small inner diameter, and furthermore, using a device having a simple structure, a vacuum in a container where the film is formed. It is an object of the present invention to provide a method capable of adding a film-forming raw material as needed without breaking, thereby obtaining a pipe having a film formed on the inner peripheral surface with high productivity.

Further, the present invention is capable of forming a film evenly or evenly on the inner peripheral surface of a tube having a small inner diameter, and is required without breaking a vacuum in a container where the film is formed. It is an object of the present invention to provide an apparatus having a simple structure capable of adding a film-forming raw material in accordance therewith and thereby obtaining a pipe having a film formed on an inner peripheral surface with high productivity.

[0008]

In order to solve the above-mentioned problems, the present invention provides a method of manufacturing a tube having a film formed on the inner peripheral surface and a method of manufacturing the tube having a film formed on the inner peripheral surface as shown in FIG. Provide a manufacturing device. A film-forming source gas is introduced from the end of the film-forming tube through the conductive gas introducing member into the inside of the tube, and
The gas introduction member is supplied with a basic high frequency power of a predetermined frequency of 13.56 MHz or more at a frequency of 1/10000 of the predetermined frequency.
By supplying high frequency power in a state where amplitude modulation is performed at a modulation frequency of not more than 1/1000 or less, the introduced film-forming raw material gas is turned into plasma, and a film is formed on the inner peripheral surface of the tube under the plasma. A method for producing a tubular body having a film formed on an inner peripheral surface thereof. (A) A vacuum container for performing film formation, an exhaust unit provided for the vacuum container, a holder for supporting a film-forming pipe in the vacuum container, and a film formation supported by the holder A gas introduction member for introducing a film-forming material gas from the end of the tube into the inside, and a film-forming material gas for supplying the film-forming material gas into the film-forming tube through the gas introduction member. Gas supply means, and the gas introduction member is supplied with a basic high frequency power of a predetermined frequency of 13.56 MHz or more by 100% of the predetermined frequency.
A high-frequency power supply means capable of supplying high-frequency power in a state where amplitude modulation is performed at a modulation frequency of 1 / 1,000 or more and 1/1000 or less; Manufacturing equipment.

According to the above method and the apparatus of (a),
By performing such a modulation on the high-frequency power supplied to convert the film-forming raw material gas into plasma, a high-density and uniform plasma can be obtained. Despite the supply of the film material gas, the film can be uniformly formed on the inner peripheral surface of the tube.
In addition, by adjusting the modulation frequency and the like, the consumption rate of the source gas for film formation can be controlled, and the control of the film formation rate and the like becomes easy. In addition, a raw material gas for film formation can be supplied as necessary without breaking the vacuum in a vacuum chamber for film formation, so that productivity is high. Further, the device (a) has a relatively simple structure.

When the film-forming tube is made of a conductive material, the gas introducing member to which high-frequency power is supplied and the film-forming tube are electrically insulated and the tube is grounded. Thus, a voltage may be applied between the gas introduction member and the tube. In this case, by covering the outside of the tube with an electrically insulating member, discharge outside the tube is suppressed, and plasma can be efficiently generated inside the tube. When the film-forming tube is made of an electrically insulating material, the vacuum vessel may be grounded so that a voltage is applied between the gas introduction member and the vacuum vessel.

Further, in order to solve the above-mentioned problems, the present invention provides the following method for manufacturing a tube having a film formed on the inner peripheral surface, and (b) an apparatus for manufacturing a tube having a film formed on the inner peripheral surface. I do. In a state in which the outside of the tube to be formed of a conductive material is covered with an electrically insulating member, a source gas for film formation is introduced from the end of the tube into the inside of the tube via a gas introduction member. At the same time, the basic high-frequency power having a predetermined frequency of 13.56 MHz or more is supplied to the tube body at a ratio of at least one tenth to one tenth of the predetermined frequency.
By supplying high frequency power in a state where amplitude modulation is performed at a modulation frequency of 1/000 or less, the introduced film-forming raw material gas is turned into plasma, and a film is formed on the inner peripheral surface of the tube under the plasma. A method for producing a tube having a film formed on an inner peripheral surface thereof. (B) a vacuum vessel for performing film formation, an exhaust means provided for the vacuum vessel, a holder for supporting a film-forming tube made of a conductive material in the vacuum vessel, and a supporter for the holder. An electrically insulating member for covering the outside of the film-forming tube to be formed, and a gas introducing member for introducing a film-forming raw material gas from an end of the film-forming tube supported by the holder into the inside thereof. Gas supply means for supplying a film-forming source gas into the film-forming tube via the gas introducing member, and 13.56 MHz or more to the film-forming tube supported by the holder. To the basic high frequency power of the predetermined frequency of 1000
A high-frequency power supply means capable of supplying high-frequency power in a state where amplitude modulation is performed at a modulation frequency of 1/1000 or more and 1/1000 or less. Manufacturing equipment.

According to the above method and the apparatus of (b),
According to the above-described method and the apparatus shown in FIG. In addition, by supplying high-frequency power for gas plasma formation to the film-forming tube in a state where the outside of the tube is covered with an electrically insulating member, discharge outside the tube is suppressed, and Plasma can be efficiently generated inside the body.

In this case, the vacuum vessel may be grounded so that a voltage is applied between the tube and the vessel. Further, in order to solve the above-mentioned problems, the present invention provides the following method for manufacturing a tube having a film formed on the inner peripheral surface and apparatus (c) for manufacturing a tube having a film formed on the inner peripheral surface. The outside of the film-forming tube made of an electrically insulating material is covered with an auxiliary electrode, and the outside of the auxiliary electrode is covered with an electrically insulating member. A film-forming source gas is introduced into the tube, and a fundamental high-frequency power of a predetermined frequency of 13.56 MHz or more is applied to the auxiliary electrode at a modulation frequency of 1/10000 to 1/1000 of the predetermined frequency. By supplying high-frequency power in a modulated state, the introduced film-forming raw material gas is turned into plasma, and a film is formed on the inner peripheral surface of the tube under the plasma. A method for producing a tube formed with a film. (C) a vacuum vessel for forming a film, an exhaust means provided for the vacuum vessel, a holder for supporting a film-forming tube made of an electrically insulating material in the vacuum vessel, An auxiliary electrode that covers the outside of the supported film-forming tube;
An electrically insulating member for covering the outside of the auxiliary electrode, a gas introduction member for introducing a film-forming material gas from an end of the film-forming tube supported by the holder into the inside thereof, 13.56 gas supply means for supplying a film-forming source gas into the film-forming tube through the film-forming member;
High-frequency power supply means capable of supplying high-frequency power in a state where amplitude modulation is performed on a basic high-frequency power of a predetermined frequency of not less than 1 MHz and a modulation frequency of 1/10000 to 1/1000 of the predetermined frequency. An apparatus for manufacturing a tubular body having a film formed on an inner peripheral surface thereof.

According to the above method and the apparatus of (c),
According to the above-described method and the apparatus shown in FIG. In addition, high-frequency power for gas plasma is supplied to the auxiliary electrode provided outside the film-forming tube, and the outside of the auxiliary electrode is covered with an electrically insulating member, so that the outside of the tube is covered with the insulating material. Is suppressed, and plasma can be efficiently generated inside the tubular body.

In this case, the vacuum vessel may be grounded so that a voltage is applied between the auxiliary electrode and the vessel.
Further, in any of the devices (a), (b) and (c), the exhaust means provided for the vacuum vessel may include:
Depending on the degree of air permeability between the inside of the tube installed in the vacuum vessel and the outer region of the tube, etc., the gas is exhausted from a region outside the tube in the vacuum container. Either exhausting from the inside of the tube at the end opposite to the gas supply side of the installed tube, or exhausting from both the outside region of the tube and the inside of the tube may be used. When exhausting air from both the outer tube region and the inner tube, exhaust means may be provided for each of them.

The method (a) and the method (a),
In the apparatuses (b) and (c), the material of the film-forming tube is not limited to this, but stainless steel, titanium, copper, or the like can be used as the conductive material. As the electrically insulating material, rubber, resin, ceramic, or the like can be used. The thickness of the film to be formed is a thickness that can be formed with good adhesion on the inner peripheral surface of the film-forming tube according to the purpose of the film formation.

As the basic high-frequency power before the modulation, those having various waveforms such as a sine wave, a rectangular wave, a sawtooth wave, and a triangular wave can be used. Further, the amplitude modulation may be a pulse modulation by turning on / off the power application, and may be a pulse-like modulation. The use of a frequency of 13.56 MHz or more as the frequency of the basic high-frequency power is as follows.
This is because if it is smaller than this, the plasma density tends to be insufficient. Further, the frequency of the basic high-frequency power may be up to about 500 MHz in view of the high-frequency power supply cost and the like.

The reason why the modulation frequency in the above range is used is that the modulation frequency is one of the frequency of the basic high frequency power.
This is because the film forming rate is sharply reduced when the film thickness becomes smaller than 1 / 100,000, and it becomes difficult to obtain matching when the film thickness becomes larger than 1/1000, and the film thickness uniformity is reduced. Further, the duty ratio (on time / on + off time) of the pulse modulation may be about 20 to 90%. This is because if it is less than 20%, the film forming rate decreases, and if it is more than 90%, it becomes difficult to adjust the consumption rate of the film forming material gas.

The following Table 1 shows film-forming raw material gases that can be used for film formation by the method and apparatus of the present invention, films formed by the same, and uses of the films. Table 1 Raw material gas for film formation Film Use CH ₄ carbon Wear resistance, lubrication, hardness enhancement, gas barrier TiCl ₄ , H ₂ , NH ₃ titanium nitride Wear resistance, corrosion resistance, decoration TiCl ₄ , H ₂ , CH ₄ titanium carbide resistance Abrasion and corrosion resistance SiCl ₄ , H ₂ , CH ₄ silicon carbide Abrasion and corrosion resistance SiCl ₄ , H ₂ , NH ₃ Silicon nitride Abrasion and corrosion resistance TiCl ₄ and SiCl _{4 in} Table 1 are liquid at room temperature. It is a compound which is used after being vaporized by bubbling using hydrogen gas or the like at a predetermined temperature.

In the method and apparatus according to the present invention, it is conceivable to form a carbon film on the inner peripheral surface of the film-forming tube. At this time, in addition to methane (CH ₄ ) shown in Table 1 above, ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane ( C
₄ H ₁₀ ), acetylene (C ₂ H ₂ ), benzene (C ₆ H
₆ ) Carbon tetrafluoride (CF ₄ ), carbon difluoride (C ₂
A carbon compound gas such as F ₆ ) can be used. If necessary, a mixture of such a carbon compound gas with a hydrogen gas, an inert gas, or the like as a carrier gas can be used.

In particular, one or more characteristics such as abrasion resistance, lubricity, water repellency, and gas barrier properties are excellent on the inner peripheral surface of a film-forming tube made of a polymer material such as rubber or resin. It is conceivable to form a carbon film. Examples of the rubber include natural rubber, butyl rubber, ethylene propylene rubber, chloroprene rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, acrylic rubber, nitrile rubber, urethane rubber, silicone rubber, and fluorine rubber.

When the film-forming surface of the film-forming tube is formed of a resin, the thermosetting resin may be a phenol-formaldehyde resin, a urea resin, a melamine-formaldehyde resin, an epoxy resin, a furan resin, a xylene resin, Examples thereof include an unsaturated polyester resin, a silicone resin, and a diallyl phthalate resin. In addition, in the thermoplastic resin, vinyl resins (polyvinyl chloride, polyvinyl dichloride, polyvinyl butyrate, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, etc.), polyvinylidene chloride,
Chlorinated polyether, polyester resin (polystyrene, styrene / acrylonitrile copolymer, etc.), AB
S, polyethylene, polypropylene, polyacetal,
Acrylic resin (polymethyl methacrylate, modified acrylic, etc.), polyamide resin (nylon 6, 66, 61)
0, 11 etc.), cellulosic resins (ethyl cellulose,
Cellulose acetate, propylcellulose, cellulose acetate / butyrate, cellulose nitrate, etc., polycarbonate, phenoxy resin, fluorine resin (ethylene trifluoride chloride,
(Tetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene, vinylidene fluoride, etc.), polyurethane and the like.

When a carbon film is formed on the inner peripheral surface of a film-forming tube made of such a polymer material, the thickness of the carbon film can be formed with good adhesion on the film-forming tube. Even when the tube is required to have flexibility and flexibility, the flexibility and flexibility are not impaired, as long as the tube can function as a protective film of the film-forming tube. Good. As the carbon film, typically, DLC (Diamond Like Carbon)
Mention may be made of membranes. The DLC film has good lubricity, water repellency, releasability, etc., is hard to be scratched, and by adjusting its thickness, the film-forming tube body has flexibility and flexibility. It is a carbon film that can have a moderate hardness enough to not impair the flexibility and flexibility of the tube covered with the film even when it is required,
Further, the film can be easily formed, for example, the film can be formed at a relatively low temperature.

Prior to the formation of the carbon film, as a pretreatment, a film-forming surface of the film-forming tube is treated with a fluorine (F) -containing gas.
Considering exposure to plasma of at least one gas selected from hydrogen (H ₂ ) gas and oxygen (O ₂ ) gas, at this time, the surface on which the film is to be formed is cleaned or further roughened. The degree improves. These contribute to the improvement of the adhesion and the uniformity of the carbon film.

As the fluorine-containing gas, fluorine (F
₂ ) gas, nitrogen trifluoride (NF ₃ ) gas, sulfur hexafluoride (SF ₆ ) gas, carbon tetrafluoride (CF ₄ ) gas, silicon tetrafluoride (SiF ₄ ) gas, disilicon hexafluoride ( Si ₂
F ₆ ) gas, chlorine trifluoride (ClF ₃ ) gas, hydrogen fluoride (HF) gas and the like. When the fluorine-containing gas plasma is adopted, the film formation surface is terminated with fluorine, and when the hydrogen gas plasma is employed, the film formation surface is terminated with hydrogen. Since the fluorine-carbon bond and the hydrogen-carbon bond are stable, by performing the termination treatment as described above, the carbon atom in the film forms a stable bond with the fluorine atom or the hydrogen atom in the deposition surface portion. From these facts, it is possible to improve the adhesion between the subsequently formed carbon film and the film-forming tube.

When oxygen gas plasma is employed, dirt such as organic substances adhering to the surface on which a film is to be formed can be particularly efficiently removed. Performance can be improved. In the present invention, the pretreatment of the deposition surface with plasma performed prior to the formation of the carbon film may be performed a plurality of times using the same type of plasma or using different types of plasma.
For example, after exposing the surface to oxygen gas plasma, exposing it to a fluorine-containing gas plasma or hydrogen gas plasma, and further forming a carbon film thereon, after the surface is cleaned, the surface may be terminated with fluorine or hydrogen. The adhesion between the carbon film to be formed after the termination and the film-forming tube is very good.

[0027]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a tube manufacturing apparatus 1 according to the present invention.
It is a figure showing the schematic structure of an example. This apparatus is an apparatus for forming a film on the inner peripheral surface of a film-forming tube S made of an electrically insulating material, and has a vacuum chamber 1 in which the film-forming tube S is placed. A supporting holder 3 is provided. The support holder 3 is held in the chamber 1 by a member (not shown). The chamber 1 is set to the ground potential.

A gas introduction member 4 made of a ring-shaped conductive material having a gas passage hole 41 at the center is disposed at one end of the film-forming tube S, and a gas passage hole 51 is disposed at the center at the other end. The exhaust member 5 made of a ring-shaped conductive material having the following structure is disposed. Note that there may be a slight gap between the film-forming tube S supported by the holder 3 and the gas introduction member 4 and between the film-forming tube S and the exhaust member 5, respectively. It does not need to be kept particularly airtight. The gas introduction member 4 and the chamber 1 are insulated by an electrically insulating member 40. The exhaust member 5 and the chamber 1 are electrically connected and at the ground potential.

The gas introduction member 4 and the exhaust member 5
Are provided with pressure gauges P and P ′, respectively, so that the pressure inside the film-forming tube S can be almost measured by measuring the pressure inside the gas passage holes 41 and 51. The vacuum chamber 1 has an exhaust pump 6 through a valve 6a.
b is connected, and the inside of the chamber 1 can be evacuated. The exhaust member 5 has a pressure regulating valve 6.
An exhaust pump 6b 'is connected via a', and the inside of the film-forming tube S is evacuated to a predetermined pressure in accordance with the pressure in the film-forming tube S detected by the pressure gauges P and P '. It can be adjusted.

A source gas supply unit 7 for film formation is connected to the gas introduction member 4, and the source gas for film formation is supplied to the inside of the tube S through the gas passage hole 41 of the member 4. It can be supplied. The gas supply unit 7 includes valves 711 and 721.
.., mass flow controllers 712, 722,.
Valves 711 ', 721' and regulators 713, 723
Are connected to each other through one or more film source gas sources 714, 724,... Further, a high-frequency power supply unit 8 is connected to the gas introduction member 4. The high-frequency power supply unit 8 includes a matching box 8
1. A high-frequency power supply 82 and an arbitrary waveform generator 83 are connected in this order.

In carrying out the method of the present invention using this apparatus, a film-forming tube S made of an electrically insulating material is carried into the chamber 1 and supported by the holder 3 to form the gas introducing member 4 and the exhaust gas. Between the first member 5 and the second member 5. Then
An exhaust pump 6 is provided in the chamber 1 (including the inside of the film-forming tube S).
A predetermined degree of vacuum is set by the operations of b and 6b '. In addition, the film-forming pipe S is formed via the gas introduction member 4 from the gas supply unit 7.
The raw material gas for film formation is introduced therein, and the pulse-modulated high-frequency power generated by the high-frequency power supply 82 and the arbitrary waveform generator 83 is supplied to the gas introduction member 4 via the matching box 81. The pulse-modulated high-frequency power is a high-frequency power obtained by subjecting a basic high-frequency power having a predetermined frequency of 13.56 MHz or more to amplitude modulation at a modulation frequency of 1/10000 to 1/1000 of the predetermined frequency. Also, the duty ratio (ON time / ON time +
OFF time) is determined in the range of 20 to 90%. Thus, the introduced film-forming source gas is turned into plasma, and a desired film is uniformly formed on the inner peripheral surface of the tube S under the plasma.

According to the above-described method and apparatus, a high-density and uniform plasma can be obtained by performing such a modulation on the high-frequency power supplied for converting the source gas for film formation into plasma. Despite supplying the film forming material gas from one end of the film forming tube S, the film can be uniformly formed on the inner peripheral surface of the tube S. Also,
By adjusting the modulation frequency and the like, the consumption rate of the source gas for film formation can be controlled, and the control of the film formation rate and the like becomes easy. In addition, since a film-forming material gas can be supplied as needed without breaking the vacuum in the chamber 1 where the film is formed, productivity is high. Also, the device is relatively simple in construction.

FIG. 2 is a diagram showing a schematic configuration of another example of a tube manufacturing apparatus according to the present invention. This apparatus is an apparatus for forming a film on the inner peripheral surface of a film-forming tube S made of a conductive material, and has an inner diameter equal to or slightly larger than the outer diameter of the film-forming tube S. A tubular insulating member 2 a having substantially the same length as the film-forming tube S is provided supported by the holder 3. The holder 3 includes an insulating member 2a and a film-forming tube S
It is for supporting. Further, a ring-shaped insulating member 2b is disposed between the insulating member 2a and the gas introduction member 4, and a conductive film-forming tube S held inside the insulating member 2a by the holder 3 is provided. The gas introduction member 4 can be electrically insulated from the gas introduction member 4. A ring-shaped insulating member 2b 'is disposed between the insulating member 2a and the exhaust member 5, and the film-forming tube S and the exhaust member 5 are disposed.
And can be electrically insulated from each other. In addition,
The insulating members 2b and 2b 'do not need to keep the airtightness between the film-forming tube S and the gas introduction member 4 and between the film-forming tube S and the exhaust member 5, respectively. . Other configurations are the same as those of the apparatus shown in FIG. 1, and the same parts are denoted by the same reference numerals.

In carrying out the method of the present invention using this apparatus, the film-forming tube S is supported by the holder 3 and disposed inside the insulating member 2a. Further, the film-forming tube S is set to the ground potential, and a high-frequency voltage is applied between the gas introduction member 4 and the tube S. Other operations are shown in FIG.
In the same manner as in the case of using the apparatus, the pulse-modulated high-frequency power is supplied to the film-forming raw material gas to convert the gas into plasma, and under the plasma, the film-forming tube S made of a conductive material is formed. A desired film is uniformly formed on the inner peripheral surface. According to this method and apparatus, the same effect as that of the film formation using the apparatus of FIG. 1 can be obtained. Further, the film-forming tube S made of a conductive material
Is covered with the insulating member 2a, electric discharge outside the film-forming tube S is suppressed, and plasma can be efficiently generated inside the tube S.

FIG. 3 is a view showing a schematic configuration of still another example of the tube manufacturing apparatus according to the present invention. This apparatus is an apparatus for forming a film on the inner peripheral surface of a film-forming tube S made of a conductive material, and has an inner diameter equal to or slightly larger than the outer diameter of the film-forming tube S. A tubular insulating member 2 a having substantially the same length as the film-forming tube S is provided supported by the holder 3. The holder 3 is for supporting the insulating member 2a and the film-forming tube S. Further, a ring-shaped insulating member 2b is disposed between the insulating member 2a and the gas introduction member 4, and a conductive film-forming tube S held inside the insulating member 2a by the holder 3 is provided. The gas introduction member 4 can be electrically insulated from the gas introduction member 4. A ring-shaped insulating member 2b 'is disposed between the insulating member 2a and the exhaust member 5, so that the film-forming tube S and the exhaust member 5 can be electrically insulated. Has become. The insulating members 2b and 2b 'need to keep the airtightness between the film-forming tube S and the gas introduction member 4 and between the film-forming tube S and the exhaust member 5, respectively. There is no. The high-frequency power supply unit 8 is connected to a film-forming tube S supported by the holder 3. The gas introduction member 4 and the exhaust member 5 are both electrically connected to the chamber 1 and are at the ground potential. Other components are the same as those shown in FIG. 1, and the same parts are denoted by the same reference numerals.

In practicing the method of the present invention using this apparatus, the tube S is disposed in the insulating member 2a, and a high-frequency voltage is applied between the film-forming tube S and the chamber 1. In the same manner as in the case of using the apparatus shown in FIG. 1, a pulse-modulated high-frequency power is supplied to a source gas for film formation, the gas is turned into plasma, and a film is formed from a conductive material under the plasma. A desired film is uniformly formed on the inner peripheral surface of the tube S. According to this method and apparatus, the same effect as that of the film formation using the apparatus of FIG. 1 can be obtained. In addition, since the outside of the film-forming tube S made of a conductive material is covered with the insulating member 2a, the discharge outside the film-forming tube S is suppressed, and the efficiency inside the tube S is reduced. Plasma can be generated well.

FIG. 4 is a view showing a schematic configuration of still another example of the tube manufacturing apparatus according to the present invention. This apparatus is an apparatus for forming a film on the inner peripheral surface of a film-forming tube S made of an electrically insulating material, and has an inner diameter that is the same as or slightly larger than the outer diameter of the film-forming tube S. A tubular auxiliary electrode 9 having substantially the same length as the film-forming tube S and an inner diameter on the outside thereof that is the same as or slightly larger than the outer diameter of the auxiliary electrode 9, and is substantially the same as the film-forming tube S. A tubular insulating member 2 a ′ having the same length is provided supported by the holder 3. The holder 3 is for supporting the film-forming tube S, the auxiliary electrode 9, and the insulating member 2a '. Further, the pulse-modulated high-frequency power supply unit 8 is connected to the auxiliary electrode 9. The gas introduction member 4 and the exhaust member 5 are both insulated from the electrode 9 and are electrically connected to the chamber 1 and are at the ground potential.
Other components are the same as those shown in FIG. 1, and the same parts are denoted by the same reference numerals.

In carrying out the method of the present invention using this apparatus, the tube S is disposed inside the electrode 9 disposed in the insulating member 2a 'and is supported by the holder 3, and the auxiliary electrode 9 and the chamber 1 Except that a high frequency voltage is applied between
As in the case of using the apparatus shown in FIG. 1, a pulse-modulated high-frequency power is supplied to the source gas for film formation to convert the gas into plasma, and the film is formed from an electrically insulating material under the plasma. A desired film is uniformly formed on the inner peripheral surface of the tube S. According to this method and apparatus, the same effect as that of the film formation using the apparatus of FIG. 1 can be obtained. Further, since the outside of the auxiliary electrode 9 disposed outside the film-forming tube S is covered with the insulating member 2a, discharge outside the film-forming tube S is suppressed, and the tube S It is possible to efficiently generate plasma inside the device.

Next, a specific example of the method of the present invention in which a DLC film is formed using the apparatus shown in FIGS. Example 1 (Apparatus in FIG. 1) Film-forming tube S Material Polyimide Size Outer diameter 5 mm (inner diameter 4 mm) × Length 30 cm Gas introduction member 4 Material Stainless steel Gas passage hole 1 mm diameter Gas introduction member 4 and coating the material gas CH ₄ 10 sccm for distance 2mm deposition of the membrane tube high frequency power fundamental frequency power 13.56 MHz, 300 W pulse modulation frequency 1 kHz, 50% duty deposition vacuum 0.01Torr deposition rate 100 Å / min deposition time 30min embodiment Example 2 (apparatus in FIG. 2) Film-forming tube S Material Stainless steel Size Outer diameter 5 mm (inner diameter 4 mm) x length 30 cm Gas introduction member 4 Material Stainless steel Gas passage hole 1 mm diameter Insulation member 2a Material Polytetrafluoroethylene size outer diameter 20 mm (inner diameter of about 5 mm) × 30cm long film-forming raw material gas CH ₄ 10 sccm Frequency power Basic high frequency power 13.56 MHz, 300 W Pulse modulation frequency 1 kHz, duty 50% Deposition vacuum degree 0.01 Torr Deposition rate 100 l / min Deposition time 30 min Example 3 (apparatus in FIG. 3) Stainless steel Size Outer diameter 5 mm (inner diameter 4 mm) x length 30 cm Gas introduction member 4 Material Stainless steel Gas passage hole Diameter 1 mm Distance between gas introduction member 4 and tube to be coated 2 mm Insulation member 2a Material Polytetrafluoroethylene Size Outer diameter 30 mm (inner diameter about 5 mm) x length 30 cm Deposition material gas CH _{4 10} sccm High frequency power Basic high frequency power 13.56 MHz, 300 W Pulse modulation frequency 1 kHz, Duty 50% Deposition vacuum degree 0.01 Torr Deposition rate 100Å / min Film-forming time 30 min Example 4 (the apparatus of FIG. 4) Film-forming pipe S Material Poly D Size Outer diameter 5 mm (inner diameter 4 mm) x length 30 cm Gas introduction member 4 Material Stainless steel Gas passage hole Diameter 1 mm Distance between gas introduction member 4 and deposition target tube 2 mm Auxiliary electrode 9 Material Stainless steel Size Outside diameter 9 mm (inner diameter of about 5 mm) × 30cm long insulating member 2a' material polytetrafluoroethylene size outer diameter 30 mm (inner diameter of about 9 mm) × material gas CH ₄ for a length of about 30cm film 10sccm RF power basic frequency power 13.56 MHz, 300 W Pulse modulation frequency 1 kHz, duty 50% Deposition degree of vacuum 0.01 Torr Deposition rate 100 ° / min Deposition time 30 min Comparative Example 1 (apparatus of FIG. 1) In Example 1, pulse modulation was performed as the high-frequency power for gas plasma formation. 13.56MHZ without frequency
A film was formed for 30 minutes in the same manner as in Example 1 except that a high frequency power of 300 watts was used. The deposition rate is 1
It was 30 ° / min. Comparative Example 2 (Apparatus of FIG. 2) In the above-mentioned Example 2, the frequency was 13.56 MH, without pulse modulation, as the high frequency power for gas plasma formation.
A film was formed for 30 minutes in the same manner as in Example 2 except that a high frequency power of 300 watts was used. The deposition rate is 1
It was 20 ° / min. Comparative Example 3 (Apparatus in FIG. 3) In Example 3, the frequency was 13.56 MH, without pulse modulation, as the high-frequency power for gas plasma formation.
A film was formed for 30 minutes in the same manner as in Example 3 except that a high-frequency power of 300 watts was used. The deposition rate is 1
It was 20 ° / min. Comparative Example 4 (Apparatus of FIG. 4) In the above-mentioned Example 4, the frequency was 13.56 MH, without pulse modulation, as the high frequency power for gas plasma formation.
A film was formed for 30 minutes in the same manner as in Example 4 except that a high frequency power of 300 W was used. The deposition rate is 1
It was 10 ° / min.

Next, the above Examples 1 to 4 and Comparative Examples 1 to 4
Of the DLC film coated tube obtained by the above method, a point A of 1 cm, a point B of 15 cm and a C of 29 cm from one end of the tube.
The film thickness was measured at three points, and the film thickness uniformity was evaluated. The results are shown in Table 2 below. Table 2 Thickness (Å) Thickness uniformity A point B point C point Example 1 0.24 0.22 0.17 ± 11.1% Example 2 0.23 0.21 0.16 ± 17.5 % Example 3 0.25 0.22 0.18 ± 16.2% Example 4 0.22 0.20 0.16 ± 15.5% Comparative Example 1 0.34 0.09 0.04 ± 95. 7% Comparative Example 2 0.33 0.09 0.03 ± 100.0% Comparative Example 3 0.35 0.10 0.05 ± 90.0% Comparative Example 4 0.33 0.08 0.03 ± 102 According to this, it is understood that the use of the high-frequency power subjected to the pulse modulation as the high-frequency power for gas plasma conversion significantly improved the film thickness uniformity as compared with the case where the modulation was not performed.

Next, in the third embodiment, the pulse modulation frequency is set in the range of 10 Hz to 100 kHz (about 1 / 100,000 to about 1/100 of the frequency of the basic high frequency power).
The changes in the film forming speed and film thickness uniformity when the duty was changed at 50% were examined. The results are shown in FIG.
(A) and (B). According to this, in the range of the pulse modulation frequency, as the modulation frequency increases, the film forming speed increases, and as the modulation frequency decreases, the film thickness uniformity improves. Therefore, when the frequency of the basic high-frequency power is 13.56 MHz as in the third embodiment, it is possible to improve both the film forming speed and the film thickness uniformity in a well-balanced manner by setting the pulse modulation frequency to about 1 kHz. I understand.

Here, only the relationship between the pulse modulation frequency and the deposition rate and the relationship between the pulse modulation frequency and the film thickness uniformity when methane gas is used as the source gas for film formation are shown. That is, the pulse modulation frequency that can improve both the film forming rate and the film thickness uniformity in a well-balanced manner can be appropriately determined depending on the type of gas.

[0043]

According to the present invention, it is possible to form a film evenly or evenly on the inner peripheral surface of a pipe having a small inner diameter, and to improve productivity by using a device having a simple structure. A method capable of obtaining a tubular body having a film formed on an inner peripheral surface thereof, and
It is possible to provide an apparatus having a simple structure capable of performing such a pipe manufacturing method.

[Brief description of the drawings]

FIG. 1 is a view showing a schematic configuration of an example of an apparatus for manufacturing a pipe having a film formed on an inner peripheral surface according to the present invention.

FIG. 2 is a view showing a schematic configuration of another example of the apparatus for manufacturing a tubular body having a film formed on an inner peripheral surface according to the present invention.

FIG. 3 is a view showing a schematic configuration of still another example of the apparatus for manufacturing a tubular body having a film formed on the inner peripheral surface according to the present invention.

FIG. 4 is a view showing a schematic configuration of still another example of the apparatus for manufacturing a tubular body having a film formed on the inner peripheral surface according to the present invention.

FIG. 5A is a diagram illustrating an example of a relationship between a pulse modulation frequency and a film forming speed, and FIG. 5B is a diagram illustrating an example of a relationship between a pulse modulation frequency and film thickness uniformity. It is.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum chamber 2a, 2a ', 2b, 2b', 40 Insulation member 3 Deposition tube support holder 4 Gas introduction member 41 Gas passage hole 5 Exhaust member 51 Gas passage hole 6a Valve 6a 'Pressure control valve 6b, 6b ′ Exhaust pump 7 Source gas supply unit for film formation 711, 721, 711 ′, 721 ′ Valve 712, 722 Mass flow controller 713, 723 Regulator 714, 724 Source gas source for film formation 8 High frequency power supply unit 81 Matching box 82 High frequency Power supply 83 Arbitrary waveform generator 9 Auxiliary electrode P, P 'Pressure gauge S Tube for film formation

Claims (6)

[Claims] 1. A film-forming raw material gas is introduced from the end of a film-forming tube through a conductive gas-introducing member into the tube, and 13.56 MHz or more is introduced into the gas introducing member. Of the predetermined frequency to the basic high-frequency power of the predetermined frequency.
A high-frequency power in a state where amplitude modulation is performed at a modulation frequency of 1 / 1,000 or more and 1/1000 or less is supplied to convert the introduced film-forming material gas into a plasma, and the plasma is applied to the inner circumference of the tube under the plasma. A method for producing a tubular body having a film formed on an inner peripheral surface, wherein the film is formed on a surface. 2. A method for forming a film on the inside of a tubular body through a gas introduction member from an end of the tubular body while covering the outside of the tubular body made of a conductive material with an electrically insulating member. A high-frequency wave in a state in which the raw material gas is introduced, and the tube is subjected to amplitude modulation of a basic high-frequency power of a predetermined frequency of 13.56 MHz or more at a modulation frequency of 1/10000 to 1/1000 of the predetermined frequency. Producing a tubular body having a film formed on an inner peripheral surface thereof by supplying electric power to convert the introduced film-forming raw material gas into plasma and forming a film on the inner peripheral surface of the tubular body under the plasma; Method. 3. A gas introduction through an end of the tubular body in a state in which the outside of the tubular body made of an electrically insulating material is covered with an auxiliary electrode and the outside of the auxiliary electrode is covered with an electrically insulating member. A raw material gas for film formation is introduced into the tube through a member, and a basic high frequency power of a predetermined frequency of 13.56 MHz or more is supplied to the auxiliary electrode at a frequency of 1 / 10,000,000 to 1/1000 of the predetermined frequency. Supplying high-frequency power in a state where amplitude modulation is performed at a modulation frequency of the introduced film-forming raw material gas, and forming a film on the inner peripheral surface of the tube under the plasma. A method for producing a tubular body having a film formed on an inner peripheral surface thereof. 4. A vacuum vessel for performing film formation, an exhaust unit provided for the vacuum vessel, a holder for supporting a film-forming pipe in the vacuum vessel, and a vacuum chamber supported by the holder. A conductive gas introducing member for introducing a film forming material gas from an end of the film forming tube into the inside thereof, and a film forming material inside the film forming tube through the gas introducing member. 13. gas supply means for supplying gas and the gas introduction member;
High-frequency power supply means for supplying high-frequency power in a state where amplitude modulation is performed on a basic high-frequency power of a predetermined frequency of 56 MHz or more at a modulation frequency of 1/10000 to 1/1000 of the predetermined frequency. An apparatus for manufacturing a tubular body having a film formed on an inner peripheral surface thereof. 5. A vacuum vessel for forming a film, an exhaust means provided for the vacuum vessel, a holder for supporting a film-forming tube made of a conductive material in the vacuum vessel, and the holder An electrically insulating member for covering the outside of the film-forming tube supported by the film-forming member, and a gas inlet for introducing a film-forming material gas from an end of the film-forming tube supported by the holder into the inside thereof 13. a member, gas supply means for supplying a film-forming source gas into the film-forming tube via the gas introducing member, and the film-forming tube supported by the holder. A basic high frequency power of a predetermined frequency of 56 MHz or more
A high-frequency power supply means capable of supplying high-frequency power in a state where amplitude modulation is performed at a modulation frequency of 1 / 1,000 or more and 1/1000 or less; Manufacturing equipment. 6. A vacuum container for forming a film, an exhaust means provided for the vacuum container, a holder for supporting a film-forming tube made of an electrically insulating material in the vacuum container, An auxiliary electrode that covers the outside of the film-forming tube supported by the holder, an electrically insulating member that covers the outside of the auxiliary electrode, and an inner end formed from the end of the film-forming tube supported by the holder; A gas introduction member for introducing a film source gas, a gas supply unit for supplying a film formation source gas into the inside of the film-forming tube via the gas introduction member, and , 1
High-frequency power supply means for supplying high-frequency power in a state where amplitude modulation is performed on a basic high-frequency power of a predetermined frequency of 3.56 MHz or more at a modulation frequency of 1/10000 to 1/1000 of the predetermined frequency; An apparatus for manufacturing a tubular body having a film formed on an inner peripheral surface thereof.