JPH07166355A - Surface treatment of substrate - Google Patents

Abstract

PURPOSE:To provide a surface treatment method for substrates by a glow discharge plasma method under an atm. pressure capable of by which gases for reaction are uniformly diffused and supplied to a plasma region, the use efficiency thereof is improved and substrate surfaces can be partially treated. CONSTITUTION:One surface of a metallic electrode 4 is provided with a first solid dielectric substance 6; a perforated metallic electrode 3 is disposed opposite to the first solid dielectric substance 6; the perforated metallic electrode 3 is so formed as to enable the supply of the gases for reaction and the space between the first solid dielectric substance 6 and the perforated metallic electrode 3 is divided by a second solid dielectric substance 8 in such a manner that desired surface treated patterns are obtd., by which a plasma generator is constituted. The part desired to be partially treated of the substrate 7 is installed in the space divided by the second solid dielectric substance of such plasma generator and an inert gas is supplied to the substrate; in addition, the gases for reaction are supplied to the substrate via the perforated metallic electrode. Glow discharge plasma is generated under the pressure near the atm. pressure and excited active species are brought into contact with the substrate surface. As a result, the cost is reduced and handling is facilitated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating the surface of a substrate made of, for example, plastic, paper, metal, glass, ceramics, or the like, and more particularly to a method for treating the surface of a substrate with plasma at atmospheric pressure.

[0002]

2. Description of the Related Art Conventionally, for example, plastic, paper,
As a method for controlling the wettability of the surface of a substrate such as metal, glass, ceramics or the like, a surface treatment method using low-voltage glow discharge plasma of about 0.1 to 10 Torr is widely known, and is also applied industrially. ing. In this surface treatment method, when the pressure becomes higher than the above pressure, the discharge locally becomes an arc discharge,
Since it is difficult to apply to substrates such as plastic and paper having poor heat resistance, the above pressure range is usually selected so that it can be applied to all substrates. Therefore, in order to make a vacuum (or low pressure), the processing container requires an expensive vacuum chamber, and a vacuum exhaust device is required. Further, when processing a large-area substrate for processing in a vacuum, a large-capacity vacuum container is required and a large vacuum exhaust device is also required. Therefore, there is a problem that the equipment cost becomes high. In addition, when the surface treatment of a substrate having a high water absorption rate is performed, it takes a long time to evacuate, and there is a problem that the cost of the treated product becomes high.

Therefore, in order to overcome the above-mentioned various problems, it has been proposed to reduce the cost of the apparatus and equipment and glow discharge plasma under atmospheric pressure capable of processing a large area substrate. For example, Japanese Patent Application Laid-Open No. 2-15171 discloses a method of disposing a solid dielectric on the surface of an electrode.
Japanese Patent Laid-Open No. 48626 proposes a surface treatment method of performing glow discharge plasma under atmospheric pressure by a method using a thin wire type electrode. In these proposals, a method of supplying a mixed gas of an inert gas mainly containing helium and a reaction gas to a plasma region near the substrate from a porous tube having a plurality of openings is used. However, there is a problem that it is difficult to uniformly diffuse and supply the gas when the substrate has a large area.

Further, Japanese Patent Laid-Open No. 2-73979 discloses that
A substrate is placed between two electrodes, one of which is a metal electrode capable of supplying a surface-treating reaction gas having a porous plate-shaped solid dielectric disposed on the opposite surface and the other of which is a metal electrode. An inert gas and a reaction gas are supplied to the space between them, and a voltage is applied to the electrodes to cause glow discharge plasma under a pressure near atmospheric pressure, and active species excited by the plasma are brought into contact with the substrate surface. Therefore, a thin film forming method has been proposed. However, this method has a problem that the ratio of the gas actually used for the surface treatment to the reaction gas is small, a large amount of unused gas is generated, and the use efficiency (yield) of the reaction gas is poor. there were.

Further, in these conventional techniques, when a surface of only a part of the substrate is partially surface-treated or a pattern of the processed portion is formed, a photosensitive resin or the like is used to remove unnecessary portions. It is general to employ a method of masking the mask and removing the mask after the treatment, and therefore there is a problem that two or more steps are required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glow under atmospheric pressure in which a reaction gas is uniformly diffused and supplied to a plasma region, its use efficiency is high, and a substrate surface can be partially treated. It is an object of the present invention to provide a surface treatment method for a substrate by a discharge plasma method.

[0007]

According to the method of treating a surface of a substrate of the present invention, a first solid dielectric is provided on one surface of a metal electrode, and a porous metal electrode is provided opposite to the first solid dielectric. , The porous metal electrode is capable of supplying a reaction gas,
Of the plasma generator in which the space between the solid dielectric and the porous metal electrode is divided by the second solid dielectric so as to obtain a desired surface treatment pattern, and is divided by the second solid dielectric. Place the part to be processed of the substrate in the space, supply the inert gas to the substrate, supply the reaction gas to the substrate through the porous metal electrode, and apply the voltage to the electrode under the pressure near atmospheric pressure. It is characterized in that a glow discharge plasma is generated and the active species excited by the plasma are brought into contact with the substrate surface.

In the present invention, the surface treatment of the substrate mainly means the formation of a surface functional group layer, the formation of a free radical layer, the formation of a hydrophilic or water-repellent thin film, and the like.
By controlling the surface energy of the substrate and modifying the wettability and adhesiveness of the substrate, or by forming an inorganic or organic thin film on the substrate surface, chemical, mechanical, optical, electrical properties, etc. It means to give.

In the present invention, the reaction gas selected according to the purpose of the surface treatment is supplied to the plasma region from the porous metal electrode to perform the surface treatment. As the reaction gas, for example, when fluorine is chemically bonded to the surface of the substrate to reduce the surface energy and impart water repellency, a gas containing fluorine is used. As the fluorine-containing gas, carbon tetrafluoride (C
F ₄ ), saturated fluorocarbon gas such as carbon hexafluoride (C ₂ F ₆ ) and sulfur fluoride gas such as sulfur hexafluoride (SF ₆ ).

On the contrary, in the case of increasing the surface energy and imparting hydrophilicity, a hydrocarbon compound gas is used to form a layer having a functional group such as a carbonyl group, a hydroxyl group and an amino group on the surface. use. Examples of the hydrocarbon compound include alkanes such as methane, ethane, propane, butane, pentane and hexane; ethylene,
Alkenes such as propylene, butene, pentene; Alkadienes such as pentadiene and butadiene; Acetylene,
Alkynes such as methylacetylene; aromatic hydrocarbons such as benzene, toluene, xylene, indene, naphthalene, phenanthrene; cycloalkanes such as cyclopropane and cyclohexane; cycloalkenes such as cyclopentene and cyclohexene; methanol, ethanol and the like Examples thereof include alcohols; ketones such as acetone and methyl ethyl ketone; and aldehydes such as methanal and ethanal. These may be used alone or in combination of two or more. Further, in this case, it is also possible to use oxygen gas, a mixed gas of oxygen and hydrogen, steam, ammonia gas, or the like.

In order to impart chemical, mechanical, optical and electrical characteristics to the substrate, SiO ₂ , TiO ₂ and S are added.
When forming a metal oxide thin film of nO ₂ or the like, a gas or vapor of a metal organic compound such as a metal hydride gas, a metal halide gas or a metal alcoholate is used.

The material and shape of the substrate used in the present invention are not particularly limited, and examples thereof include plastics, metals, glass, ceramics, papers, fibers and the like, which may be dense or porous. Examples of plastics include polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polystyrene; polyamide; polyvinyl chloride;
Films or sheets of polycarbonate; polyacrylonitrile, etc. can be used. In the case of a film, it may be stretched or unstretched. Further, it may be one which has been subjected to a known treatment such as surface cleaning or surface activation.

The present invention will be described in detail below with reference to the drawings by taking the case of imparting water repellency to the surface of plastics as an example. In addition, in FIGS. 1-3, the same code | symbol is attached | subjected to a mutually corresponding thing. FIG. 1 is a schematic cross-sectional view showing an example of a plasma generator used in the present invention. This apparatus comprises a power supply unit 1, a processing container 2, a porous metal electrode 3 and a metal electrode 4 facing each other, and a plasma processing unit 5 between two facing electrodes. The power supply unit 1 is capable of applying a voltage having a frequency on the order of kHz, and a frequency of 10 to 30 kHz is preferable for imparting water repellency. Plasma formation is performed by applying a high voltage, but if the applied voltage is too low, the plasma density and self-bias will be small, so the process will take time and is inefficient, and if it is too high, the behavior will shift to arc discharge. , Electric field strength 5-40
It is preferable to apply the voltage so as to be about kV / cm.

The processing container 2 has a top surface 2a and a bottom surface 2b made of stainless steel and a side surface 2c made of Pyrex glass, and an insulator 2d is arranged between the top surface 2a and the porous metal electrode 3. The material of the processing container 2 is not limited to this, and all may be made of glass or plastic, or may be made of metal such as stainless steel or aluminum as long as it is insulated from the electrodes.

In the present invention, the plasma treatment part 5 by glow discharge plasma is a space between the first solid dielectric and the porous metal electrode. At least one of the electrodes facing each other is a metal electrode having a first solid dielectric on the facing surface,
At least one of them is a porous metal electrode capable of supplying a reaction gas. That is, there are the following five cases as the configuration of the two electrodes facing each other. Metal electrode with solid dielectric disposed-Porous metal electrode Metal electrode with solid dielectric disposed-Porous metal electrode with solid dielectric disposed Metal electrode-Porous metal electrode with solid dielectric disposed Porous metal with solid dielectric disposed Electrode-porous metal electrode Porous metal electrode with solid dielectric arrangement-porous metal electrode with solid dielectric arrangement

In FIG. 1, the above configuration is shown,
The two electrodes facing each other are composed of a porous metal electrode 3 and a metal electrode 4 on which a first solid dielectric 6 is arranged. The porous metal electrode capable of supplying the reaction gas means that the porous metal electrode itself also serves as a gas supply pipe, and as shown in the porous metal electrode 3 in FIG.
a is provided, and the facing surface for the other facing electrode is a porous surface having a large number of openings 3b serving as gas outlets. The porous metal electrode 3
And the metal electrode 4 are connected such that one of them is on the anode side and the other is on the cathode side. Further, whichever of the two electrodes facing each other in the above-mentioned configurations may be an upper part or a lower part.

A plastic substrate 7 is placed on top of the first solid dielectric 6. If surface treatment of only one side of the substrate is required, one of the above electrode configurations is selected,
If double-sided simultaneous processing is required, the configuration of or is selected.

As the material of the first solid dielectric material 6, ceramics; glass; plastics such as polytetrafluoroethylene and polyethylene terephthalate are used, and are appropriately selected depending on the reactivity with the reaction gas. For example,
Since glass is easily melted by carbon tetrafluoride plasma, it is difficult to use it for imparting water repellency. The shape may be a sheet or a film, but if it is too thin, dielectric breakdown occurs when high voltage is applied and arc discharge occurs,
Further, if it is too thick, it becomes difficult to discharge, so 0.05 to 4
A thickness of mm is preferred. The solid dielectric must be disposed on the entire surface of the opposing surface, because if there is a portion that is not disposed on the surface of the opposing surface, arc discharge will occur at that portion.

The distance between the facing first solid dielectric and the porous metal electrode is appropriately determined depending on the gas flow rate of the reaction gas, the magnitude of the applied voltage, the thickness of the processing substrate, and the like. 1 to 20 because the uniformity of the gas diffusion in the space between the first solid dielectric and the porous metal electrode is impaired, and the unused reaction gas increases, resulting in inefficiency.
mm is preferred.

The arrangement structure of the first solid dielectric and the porous metal electrode facing each other is preferably parallel plate type as shown in FIG.

The material of the metal electrode and the porous metal electrode may be a multi-component metal such as stainless steel or brass, or a pure metal such as copper or aluminum. The materials of the metal electrode and the porous metal electrode may be the same or different.

In the present invention, the space between the opposing first solid dielectric and porous metal electrode is divided by the second solid dielectric 8 so that a desired surface treatment pattern can be obtained. As a method of dividing the space between the first solid dielectric and the porous metal electrode facing each other by the second solid dielectric, for example, as a material for forming the second solid dielectric, the first solid dielectric is used. Prepare a sheet-shaped material that fills the entire space between the dielectric and the porous metal electrode, stack this sheet on the substrate, and then expose only the area to be processed on the substrate, A method of using a sheet obtained by hollowing out is mentioned. When the sheet thus obtained is used as the second solid dielectric and is sandwiched between the first solid dielectric and the porous metal electrode, the substrate surface in contact with the second solid dielectric is not treated. , Only the area to be processed on the substrate is surface-treated. In this case, if the area to be processed on the substrate has a desired pattern, only the pattern portion is processed.

The more the space between the first solid dielectric and the porous metal electrode is sealed by the second solid dielectric, the more efficiently the reaction gas is used, but the inert gas and the reaction gas are used more efficiently. When the gas is supplied to the processing container 2 from different inlets, it is necessary to open a sufficient gap so that the inert gas can be diffused into the plasma processing unit 5. As the method of forming the gap, for example, when the second solid dielectric 8 is the above-mentioned sheet, unevenness is provided on the upper surface or the lower surface of the sheet, and between the sheet and the upper electrode or between the sheet and the substrate. A method for providing a gap or a second solid dielectric 8
There is a method of making a small hole on the side of the.

The material of the second solid dielectric may be the same as the material used for the first solid dielectric described above, but may be the same as or different from the first solid dielectric. Good.

In the present invention, as described above, the substrate 7 is placed between the first solid dielectric and the porous metal electrode,
An inert gas and a reaction gas are supplied to the space, and a voltage is applied to the electrodes to cause glow discharge plasma under a pressure near atmospheric pressure, and active species excited by the plasma are brought into contact with the substrate surface.

The above-mentioned pressure near the atmospheric pressure is 100 to 7
It means 70 Torr, and atmospheric pressure is preferable in view of cost reduction of the device and equipment.

As the inert gas, He, Ne,
A single gas or a mixed gas of a rare gas such as Ar and Xe or a nitrogen gas is used, but it is preferable to use He, which has a long metastable state life and is advantageous in excitating and decomposing the reaction gas. H
When an inert gas other than e is used, it is necessary to mix an organic vapor such as acetone or methanol or a hydrocarbon gas such as methane or ethane within 2% by volume.

When imparting water repellency, a fluorine-containing gas is used as the reaction gas. The mixing ratio of the inert gas and the fluorine-containing gas is such that the fluorine-containing gas concentration is about 1
At 0% by volume or more, glow discharge plasma is less likely to be generated even when a high voltage is applied, so about 10% by volume or less is preferable, and the amount of reaction gas used can be small, and water repellency can be imparted to 0.3 to More preferably between 5.0% by volume.

The flow rate of the reaction gas is controlled by a mass flow controller and introduced into the plasma processing section 5 through the gas introduction port 9 of the porous metal electrode 3. The flow rate of the inert gas is introduced from the gas introduction port 10a of the gas introduction pipe 10 into the processing container 2 with its flow rate controlled by the mass flow controller. As shown in FIG. 1, the gas introducing pipe 10 is configured such that a portion inside the processing container 2 surrounds the periphery of the plasma processing portion 5, and a large number of holes are formed in the inner peripheral surface of the surrounding portion. The hole may be used as the gas outlet 10b, but the inert gas is substantially uniformly diffused into the plasma processing unit 5 without being configured in this way. Further, an inert gas and a reaction gas may be mixed and introduced from the gas introduction port 9, but in order to uniformly impart water repellency, only the reaction gas is introduced from the gas introduction port 9. Is preferred. Unused reaction gas and inert gas are discharged from the gas discharge port 11 of the processing container.

Heating or cooling of the substrate is not particularly necessary for the atmospheric pressure plasma treatment for imparting water repellency, and it is sufficient at room temperature.

The treatment time is determined by the magnitude of the applied voltage. Within the range of the applied voltage, the treatment is made water repellent in about 5 seconds, and even if the treatment is carried out for a longer time, the water repellent effect is improved. No, a short treatment time is sufficient.

[0032]

EXAMPLES Examples of the present invention will be described below. Example 1 The plasma generator shown in FIG. 1 (the metal electrode 4 was made of aluminum and had a disk shape with a diameter of 80 mm, on which polytetrafluoroethylene having a diameter of 90 mm and a thickness of 1 mm was arranged as a first solid dielectric 6). The porous metal electrode 3 is SUS3.
In the case of 04, a disk type with a facing surface having a diameter of 80 mm, a polyester film 80 mm × 80 mm × thickness 100 μm as a substrate 7 (trade name “Lumirror S1” manufactured by Toray Industries, Inc.
0 ") is placed on the first solid dielectric 6, and the second solid dielectric 8 that divides the space between the opposing first solid dielectric and the porous metal electrode is placed on the substrate 7. Diameter 80mm,
Corrugated plate-shaped polytetrafluoroethylene sheet having an inner diameter of 70 mm and a thickness of 5 mm and an outer diameter of 20 mm and a thickness of 5 inside
A corrugated sheet-shaped polytetrafluoroethylene sheet having a diameter of 70 mm is placed as shown in FIG. 1 to form a space having an outer diameter of 70 mm, an inner diameter of 20 mm and a thickness of 5 mm.
Between the substrate 7 and the second solid dielectric 8, and between the porous metal electrode 3 and the second solid dielectric 8), the distance between the substrate 7 and the porous metal electrode 3 is about After setting to 5 mm, the gas was exhausted from the exhaust port 12 up to 1 Torr by an oil rotary pump (not shown. The same applies hereinafter).

Then, a carbon tetrafluoride gas having a gas flow rate of 2 sccm is introduced through the gas inlet 9 and H of 198 sccm.
e gas is introduced into the processing container 2 through the gas inlet 10a,
After setting the atmospheric pressure to 760 Torr, a rectangular wave having a frequency of 15 kHz was applied with electric power of 6.2 kV and 28 mA and left for 10 seconds to perform surface treatment of the substrate. Plasma emission was observed with the application of high voltage.

Next, the contact angle of the treated surface of the treated substrate with pure water was measured. As a result, it was clear that only the region having an outer diameter of 70 mm and an inner diameter of 20 mm showed 100 to 108 degrees and was made water repellent. The contact angle of the substrate used was 65 degrees. Moreover, as a result of analyzing the treated surface by X-ray electron spectroscopy, it was found that 67% of fluorine in atomic ratio was chemically bonded to the surface.

Example 2 The plasma generator shown in FIG. 1 (the metal electrode 4 was made of aluminum and had a disk shape of 80 mm in diameter, and the first solid dielectric 6 was formed on the metal electrode 4 by polytetrafluoro having a diameter of 90 mm and a thickness of 1 mm. Ethylene is provided, and the porous metal electrode 3 is SUS3.
In the case of 04, a disk type with a facing surface having a diameter of 80 mm, a polyester film 80 mm × 80 mm × thickness 100 μm as a substrate 7 (trade name “Lumirror S1” manufactured by Toray Industries, Inc.
0 ”) was placed on the first solid dielectric 6 and the distance between the substrate 7 and the porous metal electrode 3 was set to about 10 mm.

Next, as shown in FIG. 2, as a second solid dielectric 8, a corrugated plate-shaped polytetrafluoroethylene sheet 13 having a size of 60 mm × 60 mm × thickness of 10 mm is provided with a thickness of 20 m.
An mx20 mm square cutout 14 provided with four pieces was prepared and placed on the above-mentioned substrate 7 (since the sheet is corrugated, the substrate 7 and the second solid dielectric 8 are And a small gap is formed between the porous metal electrode 3 and the second solid dielectric 8). Then, it was exhausted to 1 Torr from the exhaust port 12 with an oil rotary pump.

Then, a carbon tetrafluoride gas having a gas flow rate of 6 sccm is introduced from the gas inlet 9 and H of 194 sccm.
e gas is introduced into the processing container 2 through the gas inlet 10a,
After setting the atmospheric pressure to 760 Torr, a rectangular wave with a frequency of 15 kHz is applied at a power of 10.0 kV and 35 mA to 10
The substrate was left to stand for a second for surface treatment. Plasma emission was observed with the application of high voltage.

Next, the contact angle of the treated surface of the treated substrate with pure water was measured. As a result, 20mm × on the substrate
It was clear that the water-repellent property was exhibited at 100 to 108 degrees only in the four 20 mm square regions. The contact angle of the substrate used was 65 degrees. In addition, as a result of analyzing the treated portion by X-ray electron spectroscopy, the atomic ratio was 6
It was found that 5% of fluorine was chemically bonded to the surface.

Example 3 The plasma generator shown in FIG. 1 (the metal electrode 4 was a disc type having a diameter of 80 mm and made of aluminum, and a polytetrafluoro having a diameter of 90 mm and a thickness of 1 mm was used as the first solid dielectric 6 thereon. Ethylene is provided, and the porous metal electrode 3 is SUS3.
In the case of a disc type having a diameter of 80 mm on the opposite surface made of 04), polytetrafluoroethylene having a thickness of 1 mm having an opening in the porous metal electrode 3 is arranged as another first solid dielectric,
A 80 mm × 80 mm × 1 mm thick stainless steel plate (SUS304) was placed on the first solid dielectric 6 as the substrate 7, and the distance between the substrate 7 and the porous metal electrode 3 was set to about 3 mm.

Next, as a second solid dielectric 8, as shown in FIG. 3, a corrugated polytetrafluoroethylene sheet 15 of 60 mm × 60 mm × thickness of 2 mm is provided with a pattern 16 as shown in FIG. A hollowed-out piece was prepared and placed on the above-mentioned substrate 7 (since the sheet is a corrugated plate, it is between the substrate 7 and the second solid dielectric 8 and between the porous metal electrode 3 and the second solid dielectric 8). A slight gap is formed between the solid dielectrics 8). Then, it was exhausted to 1 Torr from the exhaust port 12 with an oil rotary pump.

Then, a mixed gas of titanium tetrachloride having a gas flow rate of 2 sccm and nitrogen gas having a gas flow rate of 2 sccm is introduced into the gas inlet port 9.
In addition, 500 sccm of He gas was introduced into the gas inlet 1
After being introduced into the processing container 2 from 0a and setting the atmospheric pressure to 760 Torr, the frequency is 15 kHz, 10.0 kV, 35 m
The substrate was surface-treated by applying the power of A and leaving it for 10 minutes. Plasma emission was observed with the application of high voltage.

Next, when the processed substrate was observed, it turned into a golden color with a pattern similar to that of FIG. 3, and as a result of analysis by X-ray electron spectroscopy, atomic ratio Ti: N = 57: Four
It was found that the titanium nitride film of No. 3 was formed.

COMPARATIVE EXAMPLE 1 The plasma generator shown in FIG. 1 (the metal electrode 4 was made of aluminum and had a disk shape of 80 mm in diameter, and a first solid dielectric 6 was formed on the metal electrode 4 and had a diameter of 90 mm and a thickness of 1 mm. Ethylene is provided, and the porous metal electrode 3 is SUS3.
In the case of 04, a disk type with a facing surface having a diameter of 80 mm, a polyester film 80 mm × 80 mm × thickness 100 μm as a substrate 7 (trade name “Lumirror S1” manufactured by Toray Industries, Inc.
0 ”) is placed on the first solid dielectric 6 and the second solid dielectric 8 is not set, and the distance between the substrate 7 and the porous metal electrode 3 is set to 2 mm, and then the oil rotary pump is used up to 1 Torr. The gas was exhausted from the exhaust port 12.

Next, carbon tetrafluoride gas with a gas flow rate of 10 sccm was introduced into the processing container 2 through the gas inlet 9 and He gas with 990 sccm through the gas inlet 10a to the atmospheric pressure of 760 Torr. 15kH
Applying a square wave of z at a power of 6.2 kV and 28 mA, 1
The substrate was left to stand for 0 seconds for surface treatment. Plasma emission was observed with the application of high voltage.

Next, the contact angle of the treated surface of the treated substrate with pure water was measured. As a result, it was clear that all treated surfaces exposed to the plasma were 100 to 108 degrees and were made water repellent. The contact angle of the substrate used was 65 degrees. Moreover, as a result of analyzing the treated surface by X-ray electron spectroscopy, it was found that about 63% of atomic ratio of fluorine was chemically bonded to the surface.

[0046]

The structure of the present invention is as described above, and does not require a special vacuum forming device and equipment as compared with the conventional method of surface-treating plastic or the like by low-pressure glow discharge plasma. No special operation is required for that purpose, the cost reduction effect is excellent, and the handling is easy. Moreover, since the reaction gas is uniformly diffused and supplied to the plasma region, it is possible to increase the area of the processing region, which was a problem of atmospheric pressure plasma, and to efficiently use the reaction gas. Further, it is possible to specify the area of the processing surface of the substrate, and it can be used for, for example, a circuit board, a memo pad, etc., and the industrial ripple effect will be great. Further, it can be easily applied to thin film formation.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a plasma generator used in a surface treatment method of the present invention.

FIG. 2 is a plan view of a second solid dielectric used in Example 2.

FIG. 3 is a plan view of a second solid dielectric used in Example 3.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Power supply part 2 Processing container 2a Upper surface 2b Bottom surface 2c Side surface 2d Insulator 3 Porous metal electrode 3a Gas passage 3b Open hole 3c Pipe 3d Fine wire 4 Metal electrode 5 Plasma processing part 6 First solid dielectric 7 Substrate 8 Second Solid dielectric 9 Gas inlet 10 Gas inlet 10a Gas inlet 10b Gas outlet 11 Gas outlet 12 Exhaust outlet 13 Polytetrafluoroethylene sheet 14 Holed-out 15 Polytetrafluoroethylene sheet 16 Pattern

Claims (1)

[Claims] 1. A first solid dielectric is provided on one surface of the metal electrode, and a porous metal electrode is provided opposite to the first solid dielectric, and the porous metal electrode is capable of supplying a reaction gas.
A second solid dielectric of a plasma generator in which a space between the first solid dielectric and the porous metal electrode is divided by the second solid dielectric to obtain a desired surface treatment pattern. Place the scheduled processing part of the substrate in the designated space,
In addition to supplying an inert gas to the substrate, a reaction gas is supplied to the substrate via a porous metal electrode, and a voltage is applied to the electrode to generate glow discharge plasma under a pressure near atmospheric pressure. A method for treating a surface of a substrate, which comprises contacting the excited active species with the surface of the substrate.