JP4195941B2 - Film forming apparatus, film forming method and film forming member - Google Patents

Description

The present invention relates to a film forming member such as a substrate on which a film is formed, a film forming apparatus and a film forming method for forming a film on the surface of the film forming member, and in particular, a high voltage is applied between electrodes. The present invention relates to a film forming member, a film forming apparatus, and a film forming method in which a powder material film is formed by reciprocating powder between electrodes.

It has been widely used to form a coating of various materials on the surface of a member in order to form an electric circuit on the surface of the substrate, or to improve the protection, lubricity, and abrasion of the member surface. Has been done. As a method for forming the film, electroplating (electroplating), electroless plating, vacuum deposition, or the like is mainly performed.
In electroplating and electroless plating, a film-forming member (substrate, etc.) to form a film is immersed in a solution containing a film material, and a film is formed by depositing metal (coating is performed). . However, since this method uses a solution, it is difficult to recover and reuse the coating material contained in the solution. Also, when using a harmful plating solution, it is necessary to perform a post-treatment of the waste solution. There is a problem. In addition, electroplating consumes a large amount of power when depositing metal and requires a large-scale facility.

In vacuum deposition, the coating material is evaporated in vacuum by laser irradiation or heating with a heat source, and the coating material is aggregated and deposited on the coating forming member. There is also a problem that facilities are required and the cost becomes high. Furthermore, there is a problem that the adhesion between the film forming substrate and the film is not so high in electroplating or vacuum deposition.
In order to solve such a problem, the following prior art (J01) is known.
(J01) Patent Document 1 (Japanese Patent Laid-Open No. 6-158350), Patent Document 2 (Japanese Patent Laid-Open No. 2000-1)
In the patent documents 1 and 2, the powder is accommodated in a sealed space formed between a pair of opposed electrodes.
The powder was supported on the electrode or the electrode surface by applying a high voltage (about 25 kV) in which the discharge was not generated between the electrodes while the sealed space was evacuated and the powder reciprocated between the electrodes. A technique is described in which a film of powder material is formed by embedding a part of the powder by colliding the powder with a film forming member. Patent Document 2 describes that the powder can be reciprocated without being evacuated.

JP-A-6-158350 ("0029" to "0030") JP 2000-17455 A ("0018", "0026")

(Problems of conventional technology)
In the prior art (J01), since the coating film to be formed is limited to the powder material film, whether or not the pressure is reduced, it is necessary to prepare a powder having the material composition of the coating film to be formed. There is a problem that the material of the possible coating is limited.

In view of the circumstances described above, the present invention has a technical problem of forming a film made of a material different from the powder material to be used in the technique of forming a film by reciprocating powder between electrodes. .

In view of the above technical problems, the inventors of the present application have conducted intensive experiments and studies, and as a result, the present inventors have previously filed a metal film creation device (see JP-A-6-158350 and JP-A-2000-17455). Even if gas is supplied to the decompressed space and the pressure is increased, if discharge does not occur continuously, the knowledge that the coating can be formed as in the case of decompression and the material composition of the formed coating The knowledge that it changed was obtained, and it came to make this invention.

(Invention)
(First invention)
In order to solve the above technical problem, the film forming apparatus of the first invention is:
At least a pair of electrodes;
An insulating member disposed between the electrodes;
Powder accommodated in a space formed by the electrode and the insulating member;
The gas supply device for supplying a medium gas having a gas pressure higher than atmospheric pressure and altering powder into the space;
A power supply device for reciprocating the powder between the electrodes without applying a voltage to the electrodes without discharging in the space ;
It is provided with.

(Operation of the first invention)
In the film forming apparatus according to the first aspect of the present invention having the above-described constituent elements, powder is accommodated in a space formed by at least a pair of electrodes and an insulating member disposed between the electrodes. The gas supply device supplies a medium gas having a gas pressure higher than atmospheric pressure and denatures the powder to the space. The power supply device applies a voltage to the electrodes to reciprocate the powder between the electrodes without discharging in the space . Accordingly, the coating film is formed in such a manner that the powder reciprocating in the space supplied with the medium gas is embedded when colliding. At this time, since the powder material is altered by the medium gas, a coating film made of a material different from the powder material to be used can be formed.

Furthermore, in the film forming apparatus of the first invention,
A film-forming member on which the electrodes are supported, and the film is formed;
Can also be provided.
In this case, the coating film can be formed on the coating film forming member supported on the surface where the electrodes face each other.

In the film forming apparatus of the first invention,
A gas supply device for supplying the medium gas composed of dry air;
Can also be provided.
In this case, the coating can be formed using dry air that is easily available at low cost.

(Second invention)
In order to solve the technical problem, the film forming method of the second invention comprises:
In a space formed by at least a pair of electrodes and an insulating member disposed between the electrodes, a medium gas having a gas pressure higher than atmospheric pressure and denatured the powder is accommodated between the electrodes. In addition, a film of powder material combined with the medium gas is formed by applying a voltage for reciprocating the powder without discharging in the space .

(Operation of the second invention)
In the film forming method according to the second aspect of the present invention having the above structural requirements, the space formed by at least the pair of electrodes and the insulating member disposed between the electrodes has a gas pressure higher than the powder and atmospheric pressure and A coating of a powder material combined with the medium gas by containing a medium gas for modifying the powder and applying a voltage between the electrodes to reciprocate the powder without discharging in the space. Form. Accordingly, a film made of a material different from the powder material to be used can be formed by the film forming method of the second invention.

In the film forming method of the second invention, it is also possible to form a film on a film forming member supported on the surface on which the electrodes face each other.
That is, no film is formed on the electrode itself, and a film made of a material different from the powder material can be formed on a film forming member on which a film such as a substrate is to be formed.

The above-mentioned present invention can form a film made of a material different from the material of the powder to be used.

Next, specific examples (examples) of the embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following examples.
In the following description using the drawings, illustrations other than members necessary for the description are omitted as appropriate for easy understanding.

FIG. 1 is an overall explanatory view of a film forming apparatus according to a first embodiment of the present invention.
In FIG. 1, a film forming apparatus 1 according to a first embodiment of the present invention is a plate-like member supported in a film forming chamber R to which a gas supply device D1 for supplying a medium gas and an exhaust device (vacuum pump) D2 are connected. The base 2 is provided. A first electrode member 3 is supported on the base 2, and a second electrode member 4 is disposed above the first electrode member 3 so as to face the first electrode member 3. In Example 1, the electrode members 3 and 4 are made of brass, and the distance between the electrodes 3 and 4 is set to 10 mm (= 1 cm). However, the materials and distances are designed and specified. It can be arbitrarily changed according to the above.
A power supply device E is connected to the pair of electrode members 3 and 4. Each of the electrode members 3 and 4
Non-conductive plate-like film forming members (materials to be coated) 6 and 7 are fixedly supported on the surfaces on the opposite sides.

A ring-shaped insulating member 8 is sandwiched between the pair of the film forming members 6 and 7. A powder storage space 9 in which the powder F is stored is constituted by a space surrounded by the pair of electrode members 3 and 4 (more precisely, the film forming members 6 and 7) and the insulating member 8. In Example 1, the insulating member 8 is formed in a ring shape having an inner diameter of 25 cm, but the diameter can be arbitrarily changed according to the design or the like. Further, glass is used as the insulating member 8, but the material is not particularly limited, and any insulating member (ceramic, resin, etc.) can be employed.

A column 11 is supported at the end of the base 2, and an arm 12 extending to the second electrode member 4 side is screwed to the tip of the column 11. A shaft member 13 is supported at the tip of the arm 12 so as to be movable in the vertical direction. A plate-like pressing member 14 that contacts the upper surface of the second electrode member 4 is supported at the lower end of the shaft member 13. A spring 16 is mounted on the shaft member 13 between the pressing member 14 and the arm 12 to constantly urge the pressing member 14 downward. Accordingly, the second electrode member 4 is pressed toward the first electrode member 3 by the pressing member, and the powder containing space 9 is sealed so that the powder F does not leak to the outside.

(Operation of Example 1)
In the film forming apparatus 1 according to the first embodiment having the above-described configuration, the film forming chamber R is evacuated by the exhaust apparatus D2 in a state where the powder F is accommodated in the powder accommodating space 9, and then the gas is supplied by the gas supply apparatus D1. Then, the pressure in the film forming chamber R, that is, the powder containing space 9 is increased to a predetermined pressure. In this state, a high voltage equal to or higher than a predetermined voltage value that does not discharge is applied between the electrodes 3 and 4 by the power supply device E, and the powder F is vibrated (reciprocated) between the electrodes 3 and 4. Since the powder F reciprocally moved by the electrodes 3 and 4 collides with the film forming members 6 and 7 with high energy, the powder F is embedded in the surface of the film forming members 6 and 7 in a semi-molten state at the time of collision. At this time, the powder F becomes the electrodes 3 and 4.
Due to the collision of the powders during reciprocation between them, the powder has a velocity component in a plane perpendicular to the reciprocating direction, and thus diffuses almost uniformly into the powder accommodating space 9.
As a result, the film to be formed has a high adhesion force due to embedding, and is formed to have a substantially uniform film thickness over the entire surface of the film forming members 6 and 7 by the linear movement of the powder F between the counter electrodes. The principle that the powder F vibrates and a film is formed when a high voltage is applied is conventionally known as described in Patent Documents 1 and 2, and detailed description thereof is omitted. Further, as described in Patent Documents 1 and 2, the voltage applied by the power supply device E is the powder F.
The applied voltage is gradually increased in order to accelerate the speed (for example, 0. 1 per minute).
1 kV / cm) is desirable.

(Experimental example)
Next, an experiment was conducted on a film actually obtained by using the film forming apparatus 1 of Example 1.
(Experimental example 1)
In Experimental Example 1, the coating film forming apparatus 1 of Example 1 was used, and chromium (C
r) 40 mg of metal was used. Further, dry air of 3 atm was used as the medium gas, and the applied voltage was 24 kV. And the film formation apparatus 1 was operated for 25 hours.
(Experimental example 2)
In Experimental Example 2, Experimental Example 1 was the same as Experimental Example 1 except that the vacuum was evacuated to about 10 ⁻³ torr.
The experiment was carried out under the same conditions as above.
(Experimental example 3)
In Experimental Example 3, the experiment was performed under the same conditions as in Experimental Example 1 except that the sample (powder F) used was 10 mg of carbon (C) powder and the operation time of the apparatus 1 was 7 hours.
(Experimental example 4)
In Experimental Example 4, the experiment was performed under the same conditions as in Experimental Example 3, except that in Example 3, the vacuum was exhausted to 10 ⁻³ torr.

FIG. 2 is a list of results of Experimental Examples 1 to 4.
In FIG. 2, when the experimental examples 1 and 2 are compared, a metal chromium (Cr) film having a metallic luster is formed when evacuated, but a high-pressure medium gas (3 atmospheres of dry air) is used. In this case, a dark blue film was observed. The amber film is irradiated with an α ion beam from an accelerator, and the generated X-rays are measured with a high-resolution Si semiconductor detector. The elements of Cr (chromium), O (oxygen), and N (nitrogen) The peak spectrum was observed, and it was confirmed that the film was a film of these compounds (or a film in which each element was dispersed). Therefore, it is considered that a film in which chromium of powder F and oxygen (O ₂ ) or nitrogen (N ₂ ) in the air reacted or contained was formed.

In addition, when Experimental Examples 3 and 4 are compared, when evacuated, black carbon (carbon, C
When a high-pressure medium gas (3 atm dry air) was used, a metallic luster (metal color) film was formed. When the film was detected with a silicon semiconductor detector, C (carbon), O (oxygen), and N (nitrogen) were observed, and the film was confirmed to be a film of these compounds.
In Experimental Examples 1 to 4, a bakelite plate having a size of 1 cm × 1 cm × 1 cm with a hook attached to the surface of the coating was bonded with an adhesive (Aron Alpha (registered trademark) or Araldite (
(Registered Trademark))) and a hook with a weight of 70 kg was suspended, and none of the coating films were peeled off, showing high adhesion.
Further, it was confirmed that the frictional resistance of the surface of the coating formed in Experimental Examples 1 and 3 was smaller than that in Experimental Examples 2 and 4, and the wear resistance was also the same as in Experimental Examples 1 and 3. It was confirmed that it was better.

Therefore, in the film forming apparatus 1 of Example 1, by using the high-pressure medium gas, a film having a material composition having characteristics different from the material of the powder F is formed by the action of the medium gas on the powder material F. be able to.
Moreover, in the film forming apparatus 1 of Example 1, since a film is formed by the reciprocation between the electrodes 3 and 4, a solution etc. are not required like electroplating, and it is environmentally friendly. Further, since no large electric power is required for depositing the plating, power saving and cost reduction can be achieved. Furthermore, since the powder storage space 9 is hermetically sealed, the remaining powder F has little loss, and a film is formed at room temperature, so that it can be quickly and easily recovered and reused relatively easily. Moreover, in the film forming apparatus 1 of Example 1, since the film is formed in a state in which the material is embedded by the collision of the powder F,
A film having high adhesion can be formed. In particular, a voltage is applied between the electrodes 3 and 4, and the material of the film forming members 6 and 7 is not limited to conductivity, non-conductivity, etc., and any material (metal,
Non-metal, resin, ceramic, wood, rubber, etc.), and thus a film can be formed on the surface of the film forming members 6 and 7 made of any material.

Further, in the coating film forming apparatus 1 of Example 1, when the powder F reciprocates between the electrodes 3 and 4, the powder F collides with each other, friction, and collision with the film forming members 6 and 7 cause the powder. F can be deformed or rounded and processed into a spherical shape. Therefore, it is also possible to create spherical fine particles, which are the remaining powder, while forming a film.

FIG. 3 is an explanatory diagram of the film forming apparatus of Example 2, FIG. 3A is an explanatory diagram of a state before starting voltage application by the power supply device, and FIG. 3B is an explanatory diagram of a state after starting voltage application by the power device.
In the description of the second embodiment, components corresponding to the components of the first embodiment are denoted by the same reference numerals in the last digit, and detailed description thereof is omitted.
The second embodiment is different from the first embodiment in the following points, but in other points, the first embodiment.
It is configured in the same way.

In FIG. 3, the film forming apparatus 21 according to the second embodiment includes a tube-shaped (cylindrical) first electrode member 22 and a wire-shaped (columnar) arranged along the axis of the cylinder of the first electrode member 22. And a second electrode member 23. Non-conductive film forming members 26 and 27 are supported on the inner peripheral surface of the first electrode member 22 and the outer peripheral surface of the second electrode member 23, respectively. The electrode member 22,
One end wall 28 as an insulating member is fixedly supported at one axial end portion of 23. Further, the other end wall 29 as an insulating member is detachably supported at the other end in the axial direction.
Sealing packings 31 and 32 are arranged at the connecting portions between the electrode members 22 and 23. A screw is formed at the other end of the second electrode member 23, and a nut 33 is attached to and detached from the screw at the other end of the second electrode member 23 that penetrates the other end wall 29. 29 can be attached and detached. A power supply device E is connected to the first electrode member 22 and the second electrode member 23, and a high voltage is applied thereto. Therefore, in the second embodiment, the electrodes 22 and 23 are arranged to face each other, and the electrode 2
2 and 23 (more precisely, the film forming members 26 and 27) and the space surrounded by the both end walls 28 and 29 form a powder storage space 34 for storing the powder F.

(Operation of Example 2)
In the film forming apparatus 21 of Example 2 having the above-described configuration, the other end wall 29 is removed in a state where the other end wall 29 is removed and the powder F is accommodated in the other end portion of the powder accommodating space 34 (see FIG. 3A). When a high voltage is applied by the power supply device E after supplying the gas, the powder F starts to reciprocate between the electrodes 22 and 23. At this time, due to collisions between the powders F, the powder F is in a donut-shaped powder storage space 34.
It quickly diffuses in the axial direction and circumferential direction. And the film formation member 26,2 of the powder F
7, the film can be formed on the film forming members 26 and 27. Accordingly, in the film forming apparatus 21 of the second embodiment, not only the flat film forming members 6 and 7 as in the first embodiment, but also the tube-shaped film forming member 26 or the wire tube-shaped film forming member 27 is coated. Can be formed. In addition, the film forming apparatus 21 of Example 2 has the same operations and effects as the film forming apparatus 1 of Example 1.

(Example of change)
As mentioned above, although the Example of this invention was explained in full detail, this invention is not limited to the said Example, A various change is performed within the range of the summary of this invention described in the claim. It is possible. Examples of modifications of the present invention are illustrated below.
(H01) In the above-described embodiment, the case where dry air is supplied as the medium gas to the powder accommodating spaces 9 and 34 is exemplified. However, the present invention is not limited to dry air, and the powder F may vary depending on the material of the powder F. It is also possible to supply a gas (O ₂ , N ₂ , cyanogen gas, ammonia gas, etc., or a mixed gas thereof) that reacts. Further, the pressure of the medium gas can be arbitrarily changed and can be set to a pressure lower than the atmospheric pressure. However, the pressure is higher than the atmospheric pressure and does not discharge in relation to the applied voltage (for example, 15 Atmospheric pressure).

(H02) In the above examples, Cr (chromium) or C (carbon) is exemplified as the powder, but is not limited thereto, and any metal material, metal compound, nonmetal material, nonmetal compound, or
Any material that reciprocates when a voltage is applied, such as an organic material, a resin material, and ceramics, can be used. For example, Mo (molybdenum), W (tungsten), Hf (hafnium), Ta (
Tantalum), Si (silicon), Ti (titanium), Be (beryllium), B (boron),
Al (aluminum), V (vanadium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Ge (germanium), Rb (rubidium),
Y (yttrium), Zr (zirconium), Nb (niobium), Ru (ruthenium), R
Examples include h (rhodium), Pd (palladium), Sn (tin), Re (rhenium), Os (osmium), Ir (iridium), Pb (lead), Bi (bismuth), and the like. The compound, _{stainless, Cr 2 N, TiN, TiC} , CoCr, CoNi, Al 2 O
₃ , TaN, NiCr, SiC, TiCr, TiFe and the like. It is also possible to use a plurality of materials at the same time to form a layered film in which a plurality of materials and a medium gas compound or each material is mixed.

(H03) In the above embodiment, the film forming members 6, 7, 26 and 27 are preferably provided, but may be omitted. That is, the electrode member itself can be used as a film forming member.
(H04) In the above-described embodiment, the size of the powder F varies depending on the material (specific gravity, etc.) of the powder F, but can be made a size that can be reciprocated by applying a voltage. For example, the size of the powder F can be reduced to about 500 μm or less with an agate mortar or the like.
(H05) In the above embodiment, the size of the device and the voltage to be applied are not limited to the values exemplified in the embodiment, and can be changed according to the design. At this time, since the distance between the electrodes and the voltage are related to the discharge conditions and the reciprocating motion of the powder, it is possible to set the voltage and the distance between the electrodes so as not to discharge and reciprocating.

(H06) In the above-described embodiment, the electrode members 3, 4, 22, and 23 are configured by a pair of opposing flat plates or a combination of a tube and a wire. It is. For example, the tube can be bent into a donut shape, or a flat plate-like first electrode member and second electrode member can be alternately stacked to form a multilayer structure having a plurality of powder containing spaces 9, 34. is there. Thereby, it is also possible to form a film on both surfaces of one substrate at the same time.
(H07) In the above-described embodiment, the voltage to be applied is not limited to a voltage obtained by superimposing an AC voltage on a DC voltage, and may be only an AC voltage or a DC voltage.
(H08) In the above embodiment, the exhaust device can be omitted.

(H09) In the above embodiment, the coating pattern is not limited to a simple coating. For example, a mask pattern is formed by forming a coating film with powder F in a state in which a mask for an electric circuit pattern is applied to the surface of the coating film forming member. It is also possible to form an electric circuit according to the above.
(H010) In the above embodiment, a conductor film is formed on the surface of a thin ceramic plate as a film forming member, and an insulator layer and a conductor layer are alternately laminated, so that a yoke plate of a capacitor or a transformer (transformer) It can also be used for (iron core). It is also possible to coat a high temperature superconductor on a conductor or ceramic substrate.

Such a film-forming device is a highly durable coating for general rust prevention, a coating under high functions such as wear resistance, or a coating for vacuum vessels or pipes, atomic nuclei, synchrotron radiation, nuclear physical properties, It can be used to coat a compound target or the like used in nuclear medicine (medicine using radiation or the like).

FIG. 1 is an overall explanatory view of a film forming apparatus according to a first embodiment of the present invention. FIG. 2 is a list of results of Experimental Examples 1 to 4. FIG. 3 is an explanatory diagram of the film forming apparatus of Example 2, FIG. 3A is an explanatory diagram of a state before starting voltage application by the power supply device, and FIG. 3B is an explanatory diagram of a state after starting voltage application by the power device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 21 ... Film formation apparatus 2 ... Base 3, 22 ... 1st electrode member 4, 23 ... 2nd electrode member 6, 7, 26, 27 ... Film formation member 8, 28, 29 ... Insulation member 9, 34 ... Powder Body housing space 11 ... post 12 ... arm 13 ... shaft member 14 ... pressing member 16 ... springs 31, 32 ... packing 33 ... nut D1 ... gas supply device D2 ... exhaust device F ... powder R ... film formation chamber

Claims (6)

At least a pair of electrodes;
An insulating member disposed between the electrodes;
Powder accommodated in a space formed by the electrode and the insulating member;
The gas supply device for supplying a medium gas having a gas pressure higher than atmospheric pressure and altering powder into the space;
A power supply device for reciprocating the powder between the electrodes without applying a voltage to the electrodes without discharging in the space ;
A film forming apparatus comprising: A film-forming member on which the electrodes are supported, and the film is formed;
The film forming apparatus according to claim 1, further comprising: A gas supply device for supplying the medium gas composed of dry air;
The film forming apparatus according to claim 1, further comprising: A space formed by at least a pair of electrodes and an insulating member disposed between the electrodes contains a powder and a medium gas having a gas pressure higher than atmospheric pressure and denatures the powder. In addition, a coating film of the powder material combined with the medium gas is formed by applying a voltage for reciprocating the powder without discharging in the space . The film forming method according to claim 4 , wherein a film is formed on a film forming member supported on a surface on the side where the electrodes face each other. A film forming member having a film formed by the film forming method according to claim 4 .

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