JPH0762546A - Atmospheric plasma surface treating device - Google Patents

Abstract

PURPOSE:To provide a plasma surface treating device of a blow off-type capable of preventing the diffusion of the remaining part of the reactive gas blowing off after the end of a treatment and their by-products to the circumference or at least decreasing the amt. of diffusion. CONSTITUTION:This atm. plasma surface treating device is constituted by providing the outer periphery of a reaction vessel 1 consisting of a dielectric having electrodes 2a, 2b with a box body 10 forming a space to suck blow-off gases, further, providing the outer periphery thereof with an outside box body 11 forming another space on the outer periphery thereof and introducing an inert gas therein so as not to introduce the air into the reaction vessel. The device as another embodiment is constituted by providing the opposite side of the reaction vessel with respect to the work with a receiving boxy body having an opening slightly larger than a discharge port for the blow-off and treated gases and the inert gas from the outside box when the work is fibrous.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment method or a thin film formation method and an apparatus therefor, and more particularly to a plasma surface treatment method or a film formation method using atmospheric pressure glow discharge plasma.

[0002]

2. Description of the Related Art In order to form a carbon film, a fluorocarbon film or the like on the surface of a solid material such as a metal or a ceramic material, conventionally, a gas such as a fluorocarbon-based or hydrocarbon-based substance as a reaction gas and helium, A rare gas such as argon or neon or a mixed gas of an inert gas such as N ₂ is converted into plasma by a high frequency electric field in a vacuum chamber for coating treatment or thin film formation. With the demand for an atmospheric pressure plasma surface treatment method and a thin film forming method that do not require a container or the like, development has been promoted and technical contents have been disclosed. As a typical example, Japanese Patent Application No. 63-1
66599 (JP-A-2-15171), Japanese Patent Application No. 61-1
93934 (Japanese Patent Laid-Open No. 63-50478), Japanese Patent Application No. 63-
138630 (JP-A-1-306569). FIG. 7 is a schematic elevational view schematically showing the thin film forming apparatus used in these inventions, and FIG. 8 is a sectional view taken along line AA of FIG. This device has a structure in which a dielectric rectangular box-shaped (or cylindrical) reaction vessel 1 is formed, and the outer surfaces of side walls 1a and 1b (left and right side walls in FIG. 8) facing each other vertically or horizontally are formed. , The electrodes 2a and 2b are attached,
Inlet port 1c of the reaction vessel 1 connected to a high frequency and high voltage power source
From a rare gas such as helium (He), neon (Ne) or argon (Ar) or an inert gas such as N ₂ and C
A mixed gas with a reaction gas of a fluorocarbon-based or hydrocarbon-based substance such as F ₄ is flown as shown by an arrow C, and the inlet 1c
The object 5 to be processed is positioned below the outlet 1d on the opposite side of the above, and is placed so as to move in the direction of arrow B. When a high-frequency high voltage is applied to the electrodes 2a, 2b by flowing the mixed gas with such a structure, the mixed gas is turned into plasma by the glow discharge 7 and flows as shown by an arrow D, and radicals generated there are blown out. The surface of the object 5 to be processed is reformed or a thin film is formed on the surface by being blown out from the mouth 1d.

[0003]

The gas blown out from the above-mentioned outlet treats the surface of the object to be treated and diffuses into the atmosphere. This diffused gas reacts with the above-mentioned surface to produce solids and solids. By-products as gases are produced which can pollute the surrounding environment and become harmful. Therefore, there has been a demand for preventing blowout gas and by-products (solid and gas) from diffusing into the surroundings, or at least reducing the amount of diffusion. The present invention aims to provide a device that meets these needs.

[0004]

The present invention has solved this problem by the following means. (1) Around a box-shaped reaction container made of a dielectric material with electrodes,
A box body is provided to form a space for sucking the gas blown out as exhaust gas after the mixed gas comes into contact with the surface of the object to be treated from the outlet and finishes the treatment, and another space is provided on the outer periphery of the box body. The outer box body that forms the
The structure is such that an inert gas such as r or N ₂ is introduced and blown out from the lower end toward the object to be processed. Further, when the object to be processed is moved, the front end portions of the side walls of the reaction container and the box body facing the object to be processed are inclined toward the vertical central axis surface side. (2) When the object to be treated is a fibrous material such as a breathable woven fabric, an inert gas such as Ar or N ₂ is applied to the object to be treated around a dielectric box-shaped reaction container having an electrode. A box that defines a space to be blown out is provided, and a separate space for gas suction that has an opening area slightly larger than the total blowing area of the reacted mixed gas and the inert gas is provided on the side opposite to the reaction container with respect to the object to be processed. The structure is such that a receiving box body that defines the space is provided. In the case of a moving object to be processed, the structure conforms to the item (1).

[0005]

In the case of the above (1), the reaction gas entering from the introduction port is turned into plasma, and the object to be treated is processed into unreacted gas, byproduct gas, etc., and sucked into the space outside the reaction container. , When it is recovered by an external recovery device, etc., but when the components in the air are mixed during this suction and affect the above-mentioned processing, another external box body is provided to prevent mixing, and Ar,
An inert gas such as N ₂ is blown onto the object to be treated. The outer box body can be omitted when the components in the air do not affect the treatment. Further, in the case of a moving object to be processed, by tilting the tip of the box and the wall of each space facing the object to be processed, it becomes difficult for the atmosphere to be entrapped, and the unreacted gas and the inert gas are collected. Definitely done. In the case of the above item (2) in which the object to be processed is made of a breathable fiber material, the sprayed plasma processes the object to be processed, and unreacted gas and by-product gas pass through the object to be processed. It does not contaminate the environment by coming out to the side opposite to the spraying side and being sucked into the receiving box body. The case where the object to be processed moves is the same as in the case of the above item (1).

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A vertical cross-sectional view of a first embodiment of an atmospheric pressure plasma surface treatment apparatus according to the present invention is shown in FIG. 1 (B), and FIG.
An arrow view is shown in FIG. In these figures, the same members as those in FIGS. 7 and 8 shown as the prior art are designated by the same reference numerals. Electrodes 2a and 2b are attached to the outer surfaces of the left and right side walls 1a and 1b of the reaction box 1 made of a dielectric box having a rectangular shape in a plan view. The electrodes 2a and 2b are high-frequency and high-voltage. Is connected to the power supply 3 of. Box-shaped reaction vessel 1
Is composed of the side walls 1a and 1b, front and rear peripheral walls 1f connecting left and right side walls in the figure, and a pair of side walls and an upper wall 1e covering the upper surface of the peripheral wall. A round-hole-shaped reaction gas inlet 1c is provided, and the lower surface is opened to form a gas outlet 1d.
An object 5 to be processed is horizontally placed below 1b with a predetermined distance. A dielectric rectangular box 10 having side walls 10a and 10b so as to form a space S ₁ is provided on the outer periphery of the reaction container 1, and the structure of the container itself is almost the same as the structure of the reaction container. Box 1 without description
Outlet ports 10c and 10'c are provided on both left and right sides of the upper end of 0 on both outer sides of the inlet port 1c of the reaction vessel 1, and the lower end portions of the side walls 10a and 10b are the side wall 1a of the reaction vessel 1. Between the lower end portions of the side walls 1a and 10a, 1b and 10b, which are located above the upper surface of the object 5 to be processed and which are on the same side in the left and right relations, at substantially the same height as the lower end portion of 1b. The suction ports 10d and 10'd are formed in each of them. On the outer periphery of the box body 10, a quadrangular outer box body 11 made of a conductor is provided so as to form a space S ₂ on the outer side, and inlets 11c and 11'c are formed on the left and right outer sides of the upper surface thereof.
However, the lower ends of both side walls 11a and 11b provided outside the discharge ports 10c and 10'c are located above the upper surface of the object 5 to be processed by substantially the same height as the lower ends of the side walls 10a and 10b. Located on the side walls 10a and 11a, 10
The outlets 11d and 11 'are provided between b and 11b, respectively.
form d. When there is no problem in this process even when the outside air is mixed, the outer box body 11 shown in FIG. 1B can be omitted as shown in FIG.

FIG. 3 is a vertical cross-sectional view showing a second embodiment for dealing with the case where the object 5 to be processed is moved (to the left as shown by arrow B in the figure). Wall 21
a, 21b and the lower end portions of both side walls 30a, 30b of the box body 30, respectively, inwardly toward the vertical axis surface side, the outer box body 3
The lower end portions of the both side walls 31a and 31b of No. 1 are inclined outward with respect to the vertical axis surface, but other than that are exactly the same as those in FIG. 1, and there is a problem in processing even if outside air is mixed. If not, the outer box body 11 can be omitted according to FIG.

Next, the operation of the devices of the first and second embodiments will be described. Referring to FIGS. 1 and 2, a reaction gas such as CF ₄ and H 2 which have entered through the inlet 1c of the reaction vessel 1 and H
The mixed gas of the diluent gas such as e is turned into plasma by the glow discharge 7 by the high frequency high voltage applied to the electrodes 2a and 2b, and the generated radicals are blown out from the blowout port 1d to treat the surface of the object 5 to be treated. After reforming, the unreacted gas, by-product gas, etc. enter the space S ₁ through the suction ports 10d, 10'd and are collected in a recovery container (not shown) through the discharge ports 10c, 10'c. Ar, N from the inlets 11c, 11'c (31c, 31'c) of the outer box 11 (31)
Inert gas ₂ or the like is introduced second space S ₂ menstrual and outlet 11d, is blown from 11'd (31d, 31'd) to be treated object 5, some of the suction port 10d, 1
It is sucked in 0'd (30d, 30'd), and most of it is discharged to the outside atmosphere, and the invasion of the atmosphere is blocked so that the components in the atmosphere do not affect the treatment of the above surface modification. . As shown in FIG. 3, when the object 5 to be processed is moved in the direction of the arrow B, the lower ends of the side walls are bent with respect to the surface of the object 5 to be inclined toward the vertical central axis surface side. Therefore, it acts to prevent the entrainment of the atmosphere, and at the same time, ensures the recovery of the processing gas.

Next, referring to FIG. 4, there is shown a vertical cross-sectional view of a third embodiment corresponding to the case where the object to be treated is a fiber having a breathable structure such as a woven or knitted material, and FIG. The A arrow line view of FIG. 4 is shown. In the apparatus of this embodiment, the same members as those in FIGS. 1 and 2 are designated by the same reference numerals, and only different points will be described. The object to be treated 25 is a breathable fiber, and the box body 10 itself has the same structure as in FIGS. 1 and 2,
10f and 10'f are inlets, and 10g and 10'g are outlets. The gas outlet of the reaction container 1 and the first box 10 is on the side opposite to the gas outlet side of the object 25 to be treated. A flat and rectangular cross-section box body 12 having a suction port 12d that is slightly larger than the total area of the mouth is provided upward. The box body 12 is made of a dielectric material and has a discharge port 12c on the lower side. It is provided. If the atmosphere does not affect the processing, the box 10 can be omitted. FIG. 6 shows a fourth embodiment in the case where the fibrous object 25 to be processed is moved (to the left as indicated by arrow B in the figure), and the reaction vessel 21 is the same as the second embodiment.
The lower ends of both side walls 21a and 21b of the box are inclined toward the surface of the object to be processed 25, and both side walls 30a and 30b of the box body 30 are formed.
The lower end portion and both side walls 32a and 32b of the lower receiving box 32 are inclined outward, but if the atmosphere does not affect the processing, the box 10 can be omitted as in the third embodiment.

The operation of the above third embodiment will be described below. Unlike the first embodiment (see FIG. 1), the unreacted gas, the by-product gas, and the like pass through the air-permeable object 25 to be processed, and thus are sucked by the receiving box 12 on the opposite side of the processing apparatus, The invasion of the atmosphere to the fibrous object 25 is prevented by blowing out the inert gas from the outlets 10g and 10'g of the box body 10. As shown in the fourth embodiment of FIG. 6, when the object to be processed 25 moves in the direction of the arrow B, the end portions of the respective side walls are bent to prevent the entrainment of the atmosphere and recover the gas. This is the same as in the second embodiment (see FIG. 3).

[0011]

EFFECTS OF THE INVENTION By providing a suction space around the outlet of plasma, or when the object to be treated is a fibrous object having air permeability, a suction space is formed on the side opposite to the outlet with respect to the object to be treated. When the object to be processed is moved during the process by providing the box body, the end faces of the reaction container, the box body, the outer box body, and the box body facing the object to be processed are inclined in an appropriate direction. By doing so, the treated by-product gas and unreacted gas related to the reaction are released into the atmosphere and adversely affect the environment, and the atmosphere is prevented from flowing into the reaction vessel and adversely affecting the reaction.

[Brief description of drawings]

FIG. 1A is a schematic vertical sectional view of a simplified type of an embodiment of an atmospheric pressure plasma surface treatment apparatus according to the present invention,
(B) of this figure shows a standard type.

FIG. 2 is a plan view taken along arrow A in FIG.

FIG. 3 is a vertical cross-sectional view of a second embodiment for coping with the case where the object to be processed moves.

FIG. 4 is a vertical cross-sectional view of a third embodiment for coping with the case where the object to be processed is fibrous.

5 is a view on arrow A in FIG. 4. FIG.

FIG. 6 is a vertical cross-sectional view of a fourth embodiment which deals with the case where the object to be processed moves in a fibrous shape.

FIG. 7 is an elevational view showing an outline of a conventional atmospheric pressure plasma surface treatment apparatus.

8 is a cross-sectional view taken along the line AA of FIG.

[Explanation of symbols]

1, 21 Reaction container 1a, 1b, 21a, 21b Side wall 1c of reaction container 1c Inlet port 1d Outlet port 1e, 10e, 11e Upper wall 1f, 11f Peripheral wall 2a, 2b Electrode 3 Power supply 5, 25 Object to be treated 7 Glow discharge 10 , 30 Box 10a, 10b Side wall of the box 10c, 10'c Box outlet 10d, 10'd Box inlet 10f, 10'f Box inlet 10g, 10'g Box outlet Mouth 11,31 Outer box body 11a, 11b, 31a, 31b Side wall of outer box body 11c, 11'c, 31c, 31'c Outer box body inlet 11d, 11'd Outer box body outlet 12, 32 : receiving box body 12a, 12b, 32a, 32b receiving box body suction port B of the outlet 12d receiving boxes of the side wall 12c receiving box body, C arrows S _1, S ₂ space

Claims (5)

[Claims] 1. A gas such as a fluorocarbon-based or hydrocarbon-based substance as a reaction gas and helium, argon, neon or the like from one end of a gap between a pair of electrodes arranged to face each other under atmospheric pressure. Noble gas or a mixed gas with an inert gas such as N ₂ is introduced, and is sprayed on the surface of the object to be treated, which is placed at the other end between the electrodes, either stationary or movably, under high frequency and high voltage. In the atmospheric pressure plasma surface treatment apparatus for modifying the surface of the object to be treated or depositing and forming, for example, an amorphous carbon film on the surface of the object to be treated by the mixed gas turned into plasma by glow discharge, the surface treatment apparatus has a predetermined interval. And side walls arranged in parallel facing each other,
Each of the pair of electrodes is arranged on the outer surface thereof, and a pair of side walls arranged with a gap of a predetermined distance from the surface of the object to be processed is connected to the front and rear end portions of the both side walls. Having a peripheral wall and an upper wall that covers the upper surfaces of the side wall and the peripheral wall, the introduction port of the mixed gas is opened in the central portion of the upper wall, and between the lower end of the side wall and the object to be processed. A box-shaped or cylindrical dielectric reaction container whose gap forms an outlet for the treated gas, and a reaction chamber that surrounds the reaction container and is arranged on the outer periphery to form a predetermined space between the surfaces of the electrodes. A pair of side walls
It has a peripheral wall connecting the front and rear ends of the both side walls, and an upper wall that covers the upper surfaces of the both side walls and the peripheral wall, and is substantially symmetric with respect to the inlet of the mixed gas of the reaction vessel on the upper wall. Has a pair of treated gas outlets open in position,
The lower end of the side wall has a dielectric box body which is arranged at a predetermined distance from the lower end of the reaction container with respect to the object to be processed, and the processed gas discharged from the lower end of the reaction container. Flows upward in a space between the side wall of the box and the side wall of the reaction vessel, passes through the discharge port, and is collected. 2. The atmospheric pressure plasma surface treatment apparatus according to claim 1, wherein an outer casing made of a conductor is further provided on the outer periphery of the casing, and the outer casing encloses the casing. And a pair of side walls that are arranged on the outer periphery to form a predetermined space between the outer surface of both side surfaces of the box body, a peripheral wall that connects the front and rear end portions of the both side walls, and both sides thereof. A wall and an upper wall that covers the upper surface of the peripheral wall, on which a pair of inert gas is provided outside the pair of treated gas outlets of the box in a substantially symmetrical position. Have an inlet,
The lower end of the side wall is arranged at a predetermined distance from the object to be processed, and the inert gas flows in a space between outer surfaces of both side walls of the box and an inner surface of the outer box, and It flows into the space between the side wall of the box and the side wall of the reaction vessel and is discharged to prevent external air from flowing into the reaction vessel, and flows in the box body together with the treated gas to the upper part thereof. Atmospheric pressure plasma surface treatment apparatus, characterized in that it is passed through the discharge port of and recovered. 3. The atmospheric pressure plasma surface treatment apparatus according to claim 1, wherein the object to be treated is moved and treated in a direction from one electrode of the pair of electrodes toward the other electrode, The lower ends of the pair of side walls of the reaction vessel and the box are inclined inwardly toward the vertical central axis of the pair of electrodes, and the lower ends of the pair of side walls of the outer box are aligned with the vertical central axis. An atmospheric pressure plasma surface treatment apparatus, which is inclined outward. 4. A gas such as a fluorocarbon-based or hydrocarbon-based substance as a reaction gas and helium, argon, neon or the like from one end of a gap between a pair of electrodes arranged to face each other under atmospheric pressure. Noble gas or a mixed gas with an inert gas such as N ₂ is introduced and sprayed on the surface of the object to be treated, which is placed at the other end between the electrodes, either stationary or movably, under high frequency and high voltage. In an atmospheric pressure plasma surface treatment apparatus that modifies the surface of the object to be processed or deposits and forms, for example, an amorphous carbon film on the surface by the mixed gas that has been turned into plasma by glow discharge, the object to be processed is a woven fabric, a knitted fabric, or the like. The surface treatment device is made of a breathable fiber material that allows the mixed gas to pass therethrough, and the surface treatment device is arranged in parallel to face each other with a predetermined interval, and each of the pair of electrodes is provided on the outer surface thereof. A pair of side walls, which are arranged with a predetermined distance from the upper side of the object to be processed, a peripheral wall connecting front and rear end portions of the both side walls, and upper surfaces of the side wall and the peripheral wall. A box-shaped or cylindrical dielectric reaction container having an upper wall for covering, the introduction port of the mixed gas is opened in the central portion of the upper wall, and an outlet for the treated gas is formed at the lower end of the side wall. And a pair of inert gas discharges between the lower end of each side wall of the reaction vessel and a predetermined space formed around the reaction vessel to form a predetermined space with the surfaces of the electrodes. It has a pair of side walls forming a mouth, a peripheral wall connecting front and rear ends of the both side walls, and an upper wall covering upper surfaces of the both side walls and the peripheral wall, and the reaction vessel is mixed on the upper wall. A pair of inert gas inlets are opened at positions approximately symmetrical to the gas inlet. A dielectric made box body which, on the opposite side of the reaction vessel and the box with respect to the object to be processed object,
A dielectric container box having a suction port that is slightly larger than the total area of the gas outlets of the reaction container and the box and that opens upward, and has a rectangular flat cross section and a discharge port at the bottom. The processed gas from the reaction vessel is sucked into the receiving box body through the object to be processed in a sealed state surrounded by the inert gas from the box body flowing outside. Atmospheric pressure plasma surface treatment equipment characterized by being collected and recovered. 5. The atmospheric pressure plasma surface treatment apparatus according to claim 4, wherein the object to be treated is moved and treated in a direction from one electrode of the pair of electrodes toward the other electrode, and the reaction vessel is treated. Lower ends of the side walls of the pair of electrodes are inwardly inclined toward the vertical center axis planes of the pair of electrodes, and lower ends of the pair of side walls of the box body are inclined outwards with respect to the vertical center axis planes of the box body. 2. The atmospheric pressure plasma surface treatment apparatus according to claim 1, wherein the side walls of the box are wider and wider than the lower ends of the pair of side walls of the box body.