JP3031219B2 - Article surface treatment method and apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for modifying a surface of an article to be treated using plasma and fine particles.

[0002]

2. Description of the Related Art Conventionally, wear resistance, lubricity,
In order to improve the heat resistance and other properties, it is common to form a film having the desired properties on the article. Examples of such a film forming method include a CVD method such as a thermal CVD method and a plasma CVD method, a vacuum evaporation method, a sputter evaporation method,
A PVD method such as an ion plating method is employed.

[0003]

However, it is difficult to form a film with good adhesion on an article having a high hardness, for example, by the conventional CVD method, PVD method, etc. As a result, the desired properties may not be sufficiently provided. In addition, the conventional CVD method, PV
According to the method D, it is difficult to achieve this when it is desired to form a layer of target particles on an article for modifying the article surface.

Accordingly, the present invention provides a method of forming a film having desired characteristics with good adhesion on the surface of an article to be treated, not only when the surface hardness of the article is not high, but also when the article has high hardness. An article surface modification method capable of modifying or modifying the surface by selectively forming a layer of target particles on the surface of the article to be treated, or modifying the surface by hitting the article surface, and the like. It is an object to provide a device.

[0005]

According to the present invention, there is provided the following method and apparatus. The article to be treated is supported by the article to be treated supporting means provided in the vacuum vessel, and a gas for plasma atmosphere and fine particles corresponding to the intended treatment of the article are introduced into the vessel, and the gas is applied under a predetermined vacuum. Into plasma by applying high frequency power,
While charging the fine particles in the plasma atmosphere, the charged fine particles are accelerated toward the article to be processed by applying a DC voltage having a polarity opposite to the charging polarity of the fine particles to the article supporting means, thereby accelerating the charged particles. An article surface modification treatment method, comprising subjecting a treated article to a target treatment. A vacuum vessel, an article supporting means provided in the vacuum vessel, and an exhaust means, a plasma atmosphere gas supply means, a fine particle supply means, and a plasma atmosphere gas supply means provided in the vessel. A high-frequency power applying means for applying high-frequency power to the plasma atmosphere gas introduced into the gas to convert the gas into plasma and charging the fine particles introduced by the fine particle supply means under the plasma atmosphere; and DC voltage applying means connected to the supporting means for applying a DC voltage having a polarity opposite to the charging polarity of the fine particles to the means to accelerate the charged fine particles toward the article to be processed on the supporting means. An article surface modification treatment device comprising:

According to the method and apparatus for modifying the surface of an article of the present invention, fine particles charged in a plasma atmosphere generated by applying high-frequency power to a gas for a plasma atmosphere are charged to a means for supporting an article to be processed by a charging polarity of the fine particles ( When a DC voltage having a polarity opposite to that of the normal (usually negative) is applied, the object is accelerated toward the article to be processed supported by the support means. When the voltage applied to the supporting means is relatively large, the fine particles are driven into the surface of the article to be processed supported by the supporting means. When the voltage is relatively small, the fine particles hit the surface of the article.

When the fine particles are driven into the surface of the article, the surface of the article is modified by newly imparting a property determined by the material of the fine particles to the article or by improving the properties of the article. can do. As described above, the particle layer formed by being driven into the surface of the article, not simply deposited on the surface of the article, hardly peels off and has good adhesion regardless of the hardness or the like of the article.

When the fine particles are used to strike the surface of the article, the article surface can be cleaned to improve its wettability, or the article surface roughness can be improved. When it is difficult to drive the fine particles into the article due to the combination of the material of the fine particles and the material of the article to be processed, a gas capable of forming a film is used as the gas for the plasma atmosphere, and the acceleration of the fine particles and the film formation are performed simultaneously. This makes it possible to easily form a film in which fine particles are dispersed.

The material of the fine particles in the article surface modification method and apparatus of the present invention may be, but is not particularly limited to, metal, resin, carbon such as diamond and the like. When particles made of resin such as polyimide or carbon are used as the fine particles and the fine particles are driven into the surface portion of the article to be treated, the lubricity of the article surface can be improved.

The surface of the article can be made conductive by using fine particles made of, for example, a conductive metal and driving the fine particles into the surface of an article made of an electrically insulating material such as a resin. . In order to impart conductivity to an article made of an electrically insulating substance, a conductive paint or the like has conventionally been applied to the article. However, the applied layer has poor adhesion and tends to crack due to external force. Was. According to the method and apparatus of the present invention, since conductive fine particles can be driven into an article, it is difficult to fall off even when an external force is applied.

Further, when fine particles made of, for example, diamond are used and the fine particles are driven into, for example, a metal article, the problem of poor adhesion which occurs in the conventional bonding of diamond fine particles onto a metal article does not occur. For example, when diamond particles are driven into a blade substrate such as a metal rotary grindstone substrate, metallization of the blade substrate and the diamond particles, which is generally required when bonding the diamond particles to the blade substrate, becomes unnecessary.

Further, two or more kinds of fine particles may be used. The particle size of the fine particles may be appropriately selected within a range in which a target article surface modification treatment can be performed with the fine particles, but may be approximately in a range of 100 to 5000 °. However, it is not limited to this. The fine particles include, but are not limited to, for example, thermal CVD.
It is obtained by generating and collecting target particles in a gas phase in a predetermined vacuum state by appropriately selecting a raw material gas using a particle generator that applies the apparatus or a particle generator that applies a plasma CVD apparatus. .

The gas for the plasma atmosphere used in the method and apparatus for modifying the surface of an article of the present invention is for charging fine particles (usually negatively charged), and the type thereof is not particularly limited. Further, a plurality of gases may be used. An inert gas such as, for example, argon (Ar) gas can be used to form a layer containing the fine particles on the surface of the article, and oxygen (eg, oxygen) can be used to form a layer containing the oxidized fine particles on the surface of the article. O ₂ ) gas, dinitrogen oxide (N
₂ O) gas can be used. For example, nitrogen (N ₂ ) gas and ammonia (NH ₃ ) gas can be used to form a layer containing nitrided fine particles on the surface of the article. In order to form a layer containing carbonized fine particles, for example, methane (CH ₄ ) gas, ethane (C
₂ H ₆ ) gas and dicarbon hexafluoride (C ₂ F ₆ ) gas can be used.

Further, carbon (C), titanium (Ti), silicon (Si), aluminum (Al)
Methane gas, ethane gas, dicarbon hexafluoride gas, titanium tetrachloride (TiCl ₄ ) gas, silicon tetrachloride (SiCl ₄ ) gas, silicon tetrafluoride (SiF ₄ ) Gas, monosilane (SiH ₄ ) gas, aluminum trichloride (AlCl ₃ )
A compound gas, such as a gas, which is one or more of a gas that is combined with the fine particle constituent material and a part of which is taken into the fine particles, an inert gas, a hydrogen (H ₂ ) gas, and an oxygen (O ₂ )
It is conceivable to use one or more gases (inert gas and / or active gas) selected from a single active gas which is not a compound gas such as gas, fluorine (F ₂ ) gas, chlorine (Cl ₂ ) gas, etc. Can be

The material of the article to be treated used in the article surface modification method and apparatus of the present invention may be a metal, a polymer material, a ceramic or the like, but is not particularly limited. When an article made of an electrically insulating material is used, charging (charging up) of the article surface can be prevented by applying a high frequency voltage together with a DC voltage to the article supporting means to be processed.

In the method and apparatus for modifying the surface of an article of the present invention, the method is not limited thereto. In a preferred embodiment (aspect 1), the method is applied to the surface modification of the article to be treated. The introduction of the fine particles into the vacuum vessel and the application of the DC voltage to the article-to-be-processed supporting means are repeatedly performed intermittently, simultaneously with the introduction of the fine particles, or during the introduction of the fine particles, or An article surface modification method in which the application of each of the DC voltages to the article supporting means to be processed is started after the introduction of the fine particles is stopped, and the application of the DC voltage is stopped before the next introduction of the fine particles is started.

In the apparatus, the fine particle supply means intermittently and repeatedly introduces fine particles into the vacuum vessel in performing a surface modification treatment of the article to be treated, and the DC voltage applying means comprises: In the surface modification treatment, a DC voltage is intermittently and repeatedly applied to the article-to-be-processed supporting means, and the DC voltage applying means is simultaneously with the introduction of the fine particles, or during the introduction of the fine particles, Alternatively, after the introduction of the fine particles is stopped, the application of the DC voltage to the article supporting means to be processed is started, and the application of the DC voltage is stopped before the next fine particle supply is started. Can be mentioned.

In this method and apparatus, the evacuation from the vacuum vessel may be performed continuously. Although the amount of charged fine particles that can be captured in the sheath formed between the article supporting means and the plasma is limited, the supply of the fine particles into the vacuum vessel is intermittently performed at a constant cycle. When performing, unnecessary consumption of fine particles by supplying more fine particles than can be captured in the sheath is avoided.

In this method and apparatus, the application of each DC voltage may be stopped before the start of the supply of the next fine particles, but in any case, the target processing can be performed in the vacuum vessel as much as possible. It is desirable to apply the DC voltage during a period in which a predetermined amount of fine particles exist. If the amount of the fine particles accelerated toward the article to be processed becomes too small, it becomes difficult to perform uniform processing with the fine particles of the article, but the processing is performed in a state where a predetermined amount of the fine particles remains in the vacuum vessel. When the application of the DC voltage to the article supporting means is stopped, a predetermined amount of fine particles is driven into the surface of the article to be processed, a film containing the predetermined amount of fine particles is formed on the article to be processed, Can be beaten with a predetermined amount of fine particles, and as a result, such an article surface modification treatment can be performed uniformly.

In the method and apparatus for modifying the surface of an article according to the present invention, the present invention is not limited thereto, but as a preferred embodiment (aspect 2), the method according to aspect 1 is further described. Performing the high-frequency power application intermittently and intermittently, before starting the introduction of each fine particle, or simultaneously starting the application of the high-frequency power with the start of the introduction of the fine particles, and simultaneously with stopping the application of the DC voltage, Alternatively, there may be mentioned an article surface modification treatment method in which the application of the high-frequency power is stopped thereafter.

In the apparatus, the high-frequency power applying means intermittently and repeatedly applies high-frequency power to the plasma atmosphere gas in the surface modification treatment of the article to be treated. Before the introduction of the fine particles, or simultaneously with the start of the introduction of the fine particles, the application of the high-frequency power is started, and the application of the high-frequency power is stopped simultaneously with or after the stop of the application of the respective DC voltages, or the surface of the article. A reforming treatment device can be mentioned.

In the method and the apparatus, the introduction of the plasma atmosphere gas into the vacuum vessel may be performed intermittently in synchronization with the application of the high-frequency power. Then, since the pressure in the vacuum vessel fluctuates and the plasma generation becomes difficult to stabilize, it is preferable to supply the plasma continuously. By intermittently repeating the application of the high-frequency power at the timing as described above, it is possible to sufficiently charge the fine particles consumed in the reforming process of the article to be processed by the plasma. In addition, a period in which the application of high-frequency power is stopped intermittently without the introduction of fine particles into the vacuum vessel and the application of a DC voltage to the support of the article to be treated is intermittently repeated. The surplus fine particles that are not consumed can be easily discharged out of the vacuum container.

If the surplus fine particles are not once discharged to the outside of the vacuum container, the fine particles are further added to the surplus fine particles by the next introduction of the fine particles, and the amount of the fine particles in the vacuum container is necessary for the article reforming process. The amount may be larger or smaller than the amount, but when such extra fine particles are once discharged out of the container, this can be avoided. As a result, the surface modification treatment of the article to be treated can be performed more uniformly with a predetermined amount of fine particles.

[0024]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a diagram showing a schematic configuration of an example of an article surface modification treatment apparatus according to the present invention. This device has a vacuum vessel 1 to which an exhaust device 11 is attached, and an electrode 2 and an electrode 31 are provided at positions in the vessel 1 facing each other. The electrode 2 is an electrode also serving as an article support holder, and a high-frequency power supply 42 via a matching box 41 and a positive DC power supply 53 via a low-pass filter 51 and an on / off switch 52 are connected in parallel. The electrode 2 is provided with a heater 20. The switch 52 is opened and closed at a predetermined timing, which will be described later, under an instruction from a control unit (not shown).

The electrode 31 is a high-frequency electrode, and is connected to a high-frequency signal generator 34 that can generate an arbitrary waveform via a matching box 32 and a high-frequency power amplifier 33. Further, the container 1 is provided with a fine particle supply unit 6 including a solenoid valve 61 and a fine particle hopper 62 connected via the solenoid valve 61, and a plasma atmosphere gas supply unit 7 is additionally provided. The gas supply section 7 includes mass flow controllers 711, 712,... And one or more plasma atmosphere gas sources 731, 732,... Connected via electromagnetic valves 721, 722. Each solenoid valve is opened and closed at a predetermined timing described below under an instruction from a control unit (not shown).

In carrying out the method of the present invention using this apparatus, the article S to be treated is carried into the container 1 and is supported by the holder 2. Apply vacuum. Next, the container 1 is supplied from the gas supply unit 7.
A gas for plasma atmosphere is introduced into the container, fine particles are introduced into the container 1 from the fine particle supply unit 6, high frequency power is applied from the device 34 to the electrode 31 via the high frequency power amplifier 33 and the matching box 32, and a power source 53 is supplied. , The application of a positive voltage to the electrode 2 via the on / off switch 52 is synchronously repeated and repeatedly started and stopped at a constant cycle.

The fine particles to be introduced are 100 mm in diameter.
Those having a range of up to 5000 ° are used. The supply amount of the fine particles from the fine particle supply unit 62 is adjusted by appropriately determining the size of the opening of the fine particle hopper 62. At this time, the cycle of starting and stopping the application of the high-frequency power to the electrode 31 and the cycle of starting and stopping the application of the positive voltage to the electrode 2 are performed at the same timing. The timing starts at the same time as the turning on of the two parties and stops before the turning off of the two parties.

FIG. 2 shows a pattern (A) for supplying fine particles into the container 1, a pattern (B) for applying high-frequency power to the electrode 31,
And an example of a positive voltage application pattern (C) to the electrode 2 is shown. As described above, in the plasma P generated by applying the high-frequency power to the electrode 31, the fine particles are negatively charged.
At this time, since a positive voltage is applied to the electrode 2, the negatively charged fine particles are captured in a sheath formed between the plasma P and the electrode 2, and further accelerated toward the electrode 2. When the voltage applied to the electrode 2 is relatively large, the fine particles are driven into the article S. When the voltage is relatively small, the fine particles hit the surface of the article S to clean the surface, To improve the degree.

When driving the fine particles into the article S, FIG.
As shown in (A), since the layer S1 containing fine particles is formed on the surface of the article S, the layer is formed with good adhesion regardless of the hardness of the article S or the like. At this time, when a gas that can be combined with a substance constituting the fine particles is used as the plasma atmosphere gas, a layer containing the fine particles made of the compound can be formed on the surface of the article S.

When it is difficult to drive the fine particles into the article S due to the material of the fine particles or the material of the article S, as shown in FIG. A film S2 containing fine particles can be formed on the surface of the article S. Further, since the supply of the fine particles into the container 1 is performed intermittently, the amount of the fine particles accelerated toward the article S exceeds the amount that can be captured in the sheath, and is not wastefully consumed. In addition, although the required charged fine particles are intermittently deficient due to the intermittent supply of the fine particles, a predetermined amount of the fine particles is placed in the vacuum vessel 1 because the positive voltage is applied to the electrode 2 intermittently. Particles can be accelerated toward the article S only in the state where. Further, the application of high-frequency power to the electrode 31 is performed intermittently, and a period in which none of the supply of fine particles, the application of positive voltage, and the application of high-frequency power is performed is intermittently repeated. It is discharged out of the vacuum vessel 1 by continuous operation,
By the next supply of the fine particles, the amount of the fine particles required for processing the article S can be accurately present in the container 1. And
From these facts, it is possible to perform a uniform modification treatment on the surface of the article S.

When the article S is electrically insulating, a positive voltage from the power supply 53 and a high-frequency voltage from the high-frequency power supply 42 can be applied to the electrode 2 in a superimposed manner. Can be prevented from being charged up. Here, as shown in FIG. 1, an article surface modification treatment apparatus to which a parallel plate type plasma CVD apparatus is applied is used. However, when an article S having a three-dimensional structure is used, an inductively coupled plasma CVD apparatus is used. An apparatus to which the apparatus is applied can also be used.

Next, a concrete example of carrying out the method of the present invention using the apparatus shown in FIG. 1 will be described. The apparatus conditions and processing conditions common to each embodiment are as follows. High-frequency electrode 31 size Diameter 270 mm Electrode 2 size Diameter 300 mm Distance between electrodes 30 mm Operating frequency 13.56 MHz Frequency of high-frequency voltage application, positive voltage application 40 kHz, duty ratio 20% Particle supply period 40 kHz, duty ratio 10% Example 1 Processing conditions Fine particle material DLC (Diamond Like Carbon) Size Diameter 1000 mm ± 20% Workpiece S Cutting blade made of stainless steel Size Diameter 100 mm x thickness 5 mm High frequency power 200 W Positive voltage 5 kV On pulse width 5 μsec, Off time 20 μsec Gas for plasma atmosphere Argon (Ar) 200 sccm Processing vacuum degree 0.1 Torr Processing time 5 min As a result, as shown in FIG. 3 (A), fine particles made of DLC are contained on the surface of the blade S made of stainless steel. A layer S1 was formed. As a result, the coefficient of friction of the blade S with respect to the cut object is reduced to one-half that of the case where the layer S1 is not formed, and the conventional blade requires the use of a lubricant, which is no longer necessary. Example 2 Processing Conditions Fine Particle Material Silicon Size Diameter 1000Å ± 30% Treated Article S Plastic Article Size Diameter 100 mm × Thickness 5 mm High Frequency Power 200 W Positive Voltage 5 kV On Pulse Width 5 μsec, Off Time 20 μsec Plasma Atmosphere Gas Argon (Ar) 200 sccm As a result, as shown in FIG. 3 (A), a layer S1 containing fine particles made of silicon is formed on the surface of the article S made of plastic, and the surface hardness of the article S is reduced. 10 times improvement. Example 3 Processing Conditions Fine Particle Material Silicon Size Diameter 1000Å ± 30% Treated Article S Plastic Article Size Diameter 100 mm × Thickness 5 mm High Frequency Power 200 W Positive Voltage 5 kV On Pulse Width 5 μsec, Off Time 20 μsec (High Frequency Voltage Superimposed, 300 W) Gas for plasma atmosphere Argon (Ar) 200 sccm Methane (CH ₄ ) 100 sccm Processing vacuum degree 0.1 Torr Processing time 10 min As a result, as shown in FIG. A layer S1 containing fine particles was formed, the surface hardness of the article S was improved by 15 times, and the coefficient of friction was halved when used by sliding against a counterpart member, compared to the case without the layer S1. . Example 4 Processing Conditions Fine Particle Material Diamond Size Diameter 500 mm ± 20% Article to be Treated S Stainless Steel Cutting Blade Size 100 mm Diameter x 0.5 mm Thickness High Frequency Power 200 W Positive Voltage 5 kV On Pulse Width 5 μsec, Off Time 20 μsec Plasma Atmosphere As a result, as shown in FIG. 3A, a diamond fine particle-containing layer S1 is formed on the surface of the blade article S made of stainless steel, as shown in FIG. What could not be used as a blade before forming S1 became usable as a blade, and its cutting life was 500 hours. Example 5 Processing Conditions Fine Particle Material Stainless Steel Size Diameter 1000Å ± 20% Article to be Treated S Polyethylene Article Size Diameter 100 mm × Thickness 5 mm High Frequency Power 200 W Positive Voltage 5 kV On Pulse Width 5 μsec, Off Time 20 μsec Plasma Atmosphere Gas Argon (Ar) As a result, a layer S1 containing fine particles made of stainless steel is formed on the surface portion of the article S made of polyethylene, as shown in FIG. From 10 × 10 ¹¹ Ω · cm to 10 × 10 ² Ω · cm, and good conductivity was obtained.

[0033]

As described above, according to the present invention, not only when the surface hardness of the article to be treated is not high, but also when the hardness is high, a film having desired properties and good adhesion to the surface of the article is obtained. To improve the surface, or to selectively form a layer of target particles on the surface of the article to be treated to modify the surface, or to modify the surface of the article by hitting the surface. An article surface modification treatment method and apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is a view showing a schematic configuration of an example of an article surface modification treatment apparatus according to the present invention.

FIG. 2 shows the timing of the supply of fine particles into a vacuum vessel (A), the application of high-frequency power to a gas for plasma atmosphere (B), and the application of a positive voltage to article support means (C) in the method of the present invention. It is a figure showing an example.

FIGS. 3A and 3B are enlarged cross-sectional views of a part of an article after a modification treatment obtained by performing the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum container 11 Exhaust apparatus 2 Article support holder and electrode 20 Heater 31 High frequency electrode 32, 41 Matching box 33 High frequency power amplifier 34 High frequency signal generator 42 High frequency power supply 51 Low pass filter 52 On / Off switch 53 DC positive voltage power supply 6 Particle supply part 7 Gas supply section for plasma atmosphere S Article to be processed P Plasma

Claims (8)

(57) [Claims] An article to be processed is supported by means for supporting the article to be processed provided in a vacuum vessel, and a gas for plasma atmosphere and fine particles corresponding to a desired treatment for the article are introduced into the vessel, and The gas is turned into plasma by applying high-frequency power under vacuum, and the fine particles are charged in the plasma atmosphere, and a DC voltage having a polarity opposite to the charging polarity of the fine particles is applied to the article-to-be-processed supporting means. The surface of the article to be treated is subjected to a desired treatment by accelerating the article toward the article to be treated. 2. In the surface modification treatment of the article to be treated, the introduction of the particles into the vacuum vessel and the application of the DC voltage to the article supporting means are intermittently repeated, Simultaneously with the introduction, or during the introduction of the fine particles, or after the introduction of the fine particles is stopped, start applying the DC voltage to the article-to-be-processed supporting means,
2. The method for modifying the surface of an article according to claim 1, wherein the application of the DC voltage is stopped before starting the introduction of the next fine particles. 3. The application of the high-frequency power to the plasma atmosphere gas is intermittently repeated, and the application of the high-frequency power is started before or simultaneously with the start of the introduction of the fine particles, and The article surface reforming method according to claim 2, wherein the application of the high-frequency power is stopped simultaneously with or after each DC voltage application is stopped. 4. The plasma atmosphere gas comprises at least one compound gas which is a compound gas which is combined with a substance constituting the fine particles and a part of which is incorporated into the fine particles, and an inert gas and an active gas. 1 or 2 to be chosen
4. The method according to claim 1, wherein the above gas is used. 5. A vacuum vessel, an article supporting means provided in the vacuum vessel, and an exhaust means attached to the vessel.
Under the plasma atmosphere, high-frequency power is applied to the plasma atmosphere gas introduced into the container by the plasma atmosphere gas supply means, the fine particle supply means, and the plasma atmosphere gas supply means, and the gas is turned into plasma.
A high-frequency power applying means for charging the fine particles introduced by the fine particle supply means; and a DC voltage having a polarity opposite to the charging polarity of the fine particles is applied to the supporting means, so that the fine particles charged on the supporting means are covered with the fine particles. An article surface reforming apparatus, comprising: a DC voltage applying means connected to the support means for accelerating toward a treated article. 6. The fine particle supply means intermittently and repeatedly introduces fine particles into the vacuum vessel upon performing a surface modification treatment of the article to be treated, and the DC voltage applying means comprises: In the reforming treatment, a DC voltage is repeatedly and intermittently applied to the article supporting means, and the DC voltage applying means is simultaneously with the introduction of the fine particles, or during the introduction of the fine particles, or 6. The article surface reforming apparatus according to claim 5, wherein the application of each DC voltage to the article support means is started after the introduction of the fine particles is stopped, and the DC voltage application is stopped before the next supply of the fine particles. . 7. The high-frequency power applying means intermittently and repeatedly applies high-frequency power to the plasma atmosphere gas during the surface modification treatment of the article to be treated, and the high-frequency power applying means is adapted to introduce the fine particles. 7. The method according to claim 6, wherein the application of the high-frequency power is started before the start or simultaneously with the start of the introduction of the fine particles, and the application of the high-frequency power is stopped simultaneously with or after stopping the application of the DC voltage. Surface treatment equipment for goods. 8. The gas supply means for plasma atmosphere,
As the plasma atmosphere gas, at least one compound gas which is a compound gas and is combined with a constituent material of the fine particles supplied by the fine particle supply means and a part of which is taken into the fine particles, and an inert gas and an active gas. A gas for supplying one or more selected gases.
An article surface modification treatment apparatus according to 6 or 7.