JP3118085B2 - Plasma generating method, plasma activating method, plasma processing method, and their devices - 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 for generating plasma, a method for activating the plasma, a method for treating a substrate using the plasma, and an apparatus for treating the same. According to the present invention, the plasma can be generated under atmospheric pressure, and can be similarly activated under atmospheric pressure and used for substrate processing.

[0002]

2. Description of the Related Art Conventionally, low-temperature plasma treatment has been known as one of means for modifying a surface of a polymer material or the like. However, in order to perform the process using the low-temperature plasma, 1 × 10 ⁻⁵ Torr to 1 × 10 ⁻³ Torr (T
In order to satisfy this condition, not only expensive equipment is required, but also the processing operation is complicated, and most of the conventional low-temperature plasma processing apparatuses are required to satisfy this condition. Since the electrodes are mounted, there is a problem that only a material that is sufficiently thin compared to the distance between the electrodes can be processed. As means for solving these problems, JP-A-1-306569 and JP-A-2-15171 disclose the use of an electrode composed of a plurality of fine wires or an electrode provided with a solid dielectric.
A method for exciting plasma under atmospheric pressure is disclosed. According to this method, the apparatus is simpler and the operation is simpler than the conventional method, but the method is the same as the conventional method in that the electrodes must still be used. Only thin materials can be processed, and the conventional problems have not been completely solved.

[0003]

SUMMARY OF THE INVENTION By using a specific energy converter, the present inventor can generate plasma at atmospheric pressure without using electrodes, and furthermore, an electric field is applied to the generated plasma. It has also been found that the plasma can be activated by applying a magnetic field. Further, they have found that the surface modification of materials having various thicknesses can be performed by using these plasmas. Accordingly, the present invention provides a novel method capable of generating plasma at atmospheric pressure without using an electrode by using a specific energy converter, a method for activating the plasma, and a method for activating the plasma. It is an object of the present invention to provide a method of treating a base material to be used, and further provide each of these devices.

[0004]

SUMMARY OF THE INVENTION According to the present invention, there is provided a container in which an energy converter for converting an emitted electromagnetic wave into electric energy and emitting the same is disposed in the presence of a rare gas.
The present invention relates to a method for generating plasma, which comprises irradiating the energy converter with an electromagnetic wave. Also, the present invention
In a container in which an energy converter that converts irradiated electromagnetic waves into electric energy and emits the same is disposed, in the presence of a rare gas, a substrate is formed using plasma generated by irradiating the energy converter with the electromagnetic waves. And a plasma processing method. Further, the present invention provides
An energy converter that converts the irradiated electromagnetic waves into electric energy and emits the energy, and a container in which a load is disposed, introduces a rare gas from the energy converter into the load, and converts the electromagnetic waves into the energy converter. To generate a plasma by irradiating the plasma and applying an electric field or a magnetic field formed by the load to the plasma. Still further, the present invention provides an energy converter that converts irradiated electromagnetic waves into electric energy and emits the same, and in a container in which a load is arranged, a rare gas is introduced from the energy converter into the load. A plasma processing method comprising: irradiating the energy converter with an electromagnetic wave to generate plasma; and processing the substrate using plasma activated by an electric or magnetic field formed by the load. .

Further, the present invention is characterized in that an energy converter for converting irradiated electromagnetic waves into electric energy and emitting the same is disposed in a container provided with an electromagnetic wave generator and a gas introduction unit. The present invention relates to a plasma generator. Further, the present invention provides a plasma processing apparatus, comprising: a container provided with an electromagnetic wave generator and a gas introduction unit; and an energy converter that converts the irradiated electromagnetic wave into electric energy and emits the same. About. Still further, the present invention provides
An energy converter that converts the irradiated electromagnetic waves into electric energy and emits the energy into a container provided with an electromagnetic wave generator and a gas introduction unit, and a downstream of the gas flow introduced from the gas introduction unit (the energy conversion unit). And a load forming an electric or magnetic field. Further, the present invention provides an energy converter for converting an applied electromagnetic wave into electric energy and emitting the same in a container provided with an electromagnetic wave generator and a gas introduction unit, and a gas flow introduced from the gas introduction unit. And a load that forms an electric or magnetic field disposed downstream (with respect to the energy converter) of the plasma processing apparatus.

[0006] The energy converter used in the present invention excites the rare gas by absorbing the energy of the electromagnetic wave and then releasing the plasma generation energy, that is, the electrical energy. The energy converter that can be used in the present invention is made of at least one material selected from the group consisting of ceramics and carbon materials. As the ceramic energy converter, those having a defect in the crystal lattice and easily absorbing and releasing energy can be suitably used, and examples thereof include oxides, carbides, nitrides, borides, and silicides. As specific examples of them,
General formula ^{_{M I O · Fe 2 O 3}} ( where, M ^I is a divalent metal ion, for example, Mn ^2+, F
^{e 2+, Co 2+, Ni 2+} , Cu 2+, ferrites represented by Zn ^2+), the general formula _{^{mM II O · M II Cl 2}} · nH 2 O ( wherein, M ^II is a divalent Metal ions such as Mg ²⁺ , Zn
²⁺ , m is an integer of 1 to 10, for example, 3, 5 or 8
And n is an integer of 5 to 20, for example, 15) cements such as magnesia cement, glasses such as oxide glass, SiO ₂ , Al ₂
O ₃ , Na ₂ O, K ₂ O, Fe ₂ O ₃ , FeO, Ca
O, MgO, and crockery comprising at least one component in the ZrO _2, BeO, YBC (yttrium - barium - Copper) superconducting material such as oxides,

The general formula ABO ₃ [where A and B are monovalent and pentavalent, divalent and tetravalent or 3
A combination of trivalent and trivalent metal ions, or B is 6
(A is absent), A is Na ⁺ ,
K ⁺ , Li ⁺ , Rb ⁺ , Ag ⁺ , Ba ²⁺ , Sr ²⁺ , Cd
²⁺ , Pb ²⁺ , Ca ²⁺ , La ³⁺ , Y ³⁺ , Sm ³⁺ , Lu ³⁺ ,
Gd ³⁺ , Pr ³⁺ , Nd ³⁺ , Bi ³⁺ , Ce ⁴⁺ , Th ⁴⁺ , and B is Mo ⁶⁺ , W ⁶⁺ , Re ⁶⁺ , Ta ⁵⁺ , N
b ⁵⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Sn ⁴⁺ , Ce ⁴⁺ , Cr ⁴⁺ , Mn
⁴⁺ , Hf4 ⁺ , ^{V4 +} , Mo4 ⁺ , Fe4 ⁺ , Ru4 ⁺ , Ir4 ⁺ ,
Pt ⁴⁺ , Sc ³⁺ , Ti ³⁺ , Ru ³⁺ , Rh ³⁺ , Mn ³⁺ , C
r ³⁺ , Ni ³⁺ , Co ³⁺ , Y ³⁺ , V ³⁺ , Fe ³⁺ , Mg ³⁺ ,
The perovskite-type composite oxide represented by Cu ²⁺ in which] can be used. Among these, perovskite-type composite oxides emit electric energy and easily generate plasma, and therefore can be suitably used. Among these perovskite-type composite oxides, some of the metal ions constituting the A site and the B site are included. Can be more preferably used because it has a defect in the crystal lattice and easily emits electric energy to generate plasma.

[0008] An energy converter made of a carbon material also absorbs the energy of an electromagnetic wave and then emits electric energy to excite a rare gas. This is considered to be because the carbon material has a layered structure and vibrates between layers, or a defect in the layered structure causes strain between the layers to easily release energy. Examples of the carbon material include amorphous carbon such as gas carbon, soot, charcoal, animal charcoal, and coke, and graphite or activated carbon obtained by graphitizing a substance containing a carbon atom or amorphous carbon. It is more preferable that the surface of the carbon material is coated with a compound having a high melting point, such as iron, nickel, chromium, tungsten, a stainless alloy, or titanium nitride, because there is no loss of the carbon material. The energy converter is the material 1
It may be formed not only from types, but also by combining two or more types.

The energy converter is disposed at a position where the electromagnetic wave can be irradiated. The energy converter may be in a direction perpendicular to the direction of the electromagnetic wave irradiation, in a parallel direction, or at an angle. Is more preferable because it is possible to efficiently absorb the energy of the electromagnetic wave and easily discharge the electric energy.

The energy converter itself may be formed into a lattice shape, a shape having protrusions or a honeycomb shape, or the energy converter may be supported on a support such as a porous woven fabric, knitted fabric, nonwoven fabric, or felt. It can be further processed into a porous woven fabric, knitted fabric, nonwoven fabric or felt-like carbon material energy converter using carbon fiber. For example, the energy converter can be formed into the shape shown in FIG. 2 or FIG. The energy converter 1 of FIG. 2 is a lattice-like converter having a gap 1a, and the energy converter 1 of FIG. 3 is a converter having a gap 1a and a convex portion 1b (a sharp needle-like projection may be used). is there. When these energy converters are used, electric energy is efficiently received from the energy converter when the rare gas passes through a honeycomb body, a porous converter, or a porous support. Is easy to occur. In addition, when such a honeycomb body, a porous converter, or a porous support is used, plasma is generated on the surface of the energy converter opposite to the electromagnetic wave irradiation surface. The substrate to be processed can be continuously processed without disturbing the irradiation.

The rare gas used in the present invention is excited by electric energy released from the energy converter,
Generates plasma. As a rare gas, argon, helium, neon, or the like can be used, and argon is easily used as a plasma and is excellent in cost, and helium can be preferably used because the plasma state is easily continuous. . In addition, argon has a specific gravity closer to air than helium and is easy to handle under atmospheric pressure, so that argon can be used more preferably. Noble gas concentration is 50%
When the concentration is less than 50%, plasma is hardly generated. Therefore, the concentration is preferably 50% or more, more preferably 90% or more.

In the present invention, when plasma is generated by introducing only a rare gas, the surface of the substrate to be treated can be etched to improve the adhesiveness and the like. If ammonia, nitrogen, oxygen, or the like is introduced as a reactive gas in addition to the rare gas, a functional group such as a hydroxyl group, a carbonyl group, a carboxyl group, or an amino group can be provided on the surface of the substrate to be treated. Further, for example, a saturated hydrocarbon compound such as methane or ethane, an unsaturated hydrocarbon compound such as ethylene or acrylonitrile, an aromatic compound such as benzene, an alicyclic compound such as cyclohexane, or ethylene tetrafluoride or 6 When a fluorohydrocarbon compound molecule such as ethane fluoride is polymerized, water repellency can be imparted to the surface of the substrate to be treated, and the adhesion and the like can be improved.

When a reactive gas is mixed with a rare gas, the concentration of the reactive gas is preferably less than 50%, more preferably less than 10%. Reactive gas concentration of 50
%, The concentration of the rare gas becomes low, no plasma is generated, and no polymerization of the reactive gas occurs.

The electromagnetic wave used in the present invention is applied to an energy converter as electromagnetic wave energy and emitted as electric energy converted by the energy converter, and has a frequency of several kilohertz (KHz) to several hundred gigahertz (GHz). Microwaves having a frequency of 1 to several tens of gigahertz (GHz) emit sufficient electric energy from the energy converter, and can be suitably used.

According to the present invention, the plasma generated as described above can be activated by applying an electric field and / or a magnetic field to the plasma. A load connected to a power supply and applying an electric and / or magnetic field to the plasma is provided downstream of the energy converter in the flow path of the rare gas (and, optionally, a mixed gas with a reactive gas). Therefore,
A rare gas is introduced under atmospheric pressure into a container in which an energy converter and a load are arranged downstream thereof, and an electric field and / or a plasma generated by irradiating the energy converter with electromagnetic waves are formed by the load. By activating the plasma by applying a magnetic field, the surface of the substrate to be treated can be more efficiently modified, and in particular, a wider substrate can be treated. The same applies when a reactive gas is introduced into the container in addition to the rare gas.

The direction in which the electric and / or magnetic field acts may be parallel, perpendicular or at an angle to the direction of the gas flow (plasma flow). It is preferable to apply an electric field and a magnetic field simultaneously, since the plasma is more activated. The plasma generated at atmospheric pressure and optionally activated by the method of the invention can be used for treating various substrates in exactly the same way as plasma according to conventional methods, for example, metals, alloys, ceramics, glass Surface modification of various materials such as plastics, fibers, fabrics and films.

A plasma generating / processing apparatus 1 according to the present invention
The embodiment is schematically shown in FIG. The atmospheric pressure plasma generator of the present invention includes at least the electromagnetic wave generator 8 and the gas introduction unit 6.
The energy converter 1 is arranged in the container 7 to which is connected. This container 7 can be of any shape and size as long as the energy converter 1 can be arranged and the electromagnetic wave can be irradiated to the energy converter 1, but it is preferable to cover the container with a protective material such as aluminum that reflects the electromagnetic wave. .

The electromagnetic wave generator 8 is not particularly limited as long as it can generate an electromagnetic wave having a frequency of several kilohertz (KHz) to several hundred gigahertz (GHz). , A magnetron, or a BK tube can be used. In addition, gas introduction section 6
There is no limitation, and for example, a quartz glass tube can be used. The container 7 includes a three-stub tuner 9 for matching impedance, an isolator (not shown) for separating reflected waves, a power monitor (not shown) for measuring the intensity of electromagnetic waves, a rare gas and unreacted gas. A gas discharge unit 10 for discharging the reactive gas of the above or a circulating device (not shown) for circulating a rare gas or an unreacted reactive gas can be appropriately connected. Further, in the plasma processing apparatus of the present invention, the substrate to be processed 5a is provided downstream of the energy converter 1, and the substrate to be processed 5 is disposed on the table 5a to perform surface treatment. No airtight means is required.

One embodiment of the plasma activation device according to the present invention is schematically shown in FIGS. The atmospheric pressure plasma activating device of the present invention is the same as the atmospheric pressure plasma generating / processing device of the present invention shown in FIG. 1 except that a load 3 connected to a power source is disposed downstream of the energy converter 1 (with respect to the gas flow path). Do it. In the atmospheric pressure plasma activation device of FIG. 4, the energy converter 1 supported on the support 2 is shown. In the apparatus of FIG. 4, means corresponding to the means shown in FIG. 1 are denoted by the same reference numerals.

In the plasma activating device shown in FIGS. 4 and 5, the electrodes are arranged in parallel to the gas flow direction. However, as shown in FIGS. 6 and 7, the electrodes are arranged in the rare gas flow direction. The electric field and / or the magnetic field can be made to act on the plasma efficiently by arranging at right angles to and changing the size of the adjacent upper and lower electrodes. As shown in FIGS. 8 and 9, a coil may be arranged as the load 3. The load 3 is a plasma
May be arranged at a position where the treatment is not hindered, and may be arranged outside the container.

As shown in FIGS. 4 to 7, when an electric field and / or a magnetic field is generated by the electrodes arranged in the container, if the distance between the electrode and the container 7 is shorter than the distance between the electrodes, the electrode Since an electric and / or magnetic field is generated between the electrode and the container 7, it is preferable to make the distance between the electrode and the container 7 longer than between the electrodes. Therefore, it is preferable that the electrode is supported by the holder 4 made of an insulator or the like.

[0022]

According to the present invention, the energy converter 1 disposed in the container 7 is irradiated with an electromagnetic wave, and
The rare gas introduced into the container 7 is excited by the electric energy released from the, and plasma is generated. When the surface of the substrate 5 to be treated is modified by the plasma, the thickness of the substrate 5 to be subjected to the surface modification is not limited because there is no conventional electrode, and the modification can be performed under atmospheric pressure. Since there is no need to create a vacuum state, a large-scale and expensive device is not required, and a complicated operation is not required. When an electric field and / or a magnetic field is applied to the generated plasma by the load 3, the plasma is activated.
The substrate 5 to be processed can be processed more efficiently, and the substrate 5 to be processed having a wide width can be processed.

[0023]

EXAMPLES The present invention will be described below in more detail with reference to examples, but these examples do not limit the scope of the present invention. Note that the contact angle in the example was measured at a temperature of 20 ° C. and a humidity of 65% using a contact angle measuring device (CA-DS manufactured by Kyowa Chemical Co., Ltd.) 30 seconds after the ion-exchanged water was dropped on the substrate 5. Is a value measured under the conditions of The thickness of the film formed on the surface of the substrate is a value measured by an electron microscope.

EXAMPLES 1 TO 6 AND COMPARATIVE EXAMPLE An apparatus similar to the apparatus schematically shown in FIG. 1 (however, the energy converter 1 was carried on the support 2) was used. In an aluminum container 7 connected to a magnetron as an electromagnetic wave generator 8, 1 g of a 20-60 mesh energy converter made of various materials shown in Table 1 is sintered on a support 2 made of cordierite. And placed in the container 7. In addition, the substrate 5 to be treated
A polyethylene terephthalate film (referred to as PET film) was placed in the container 7. The distance between the PET film and the energy converter was 5 cm. 200 ml / min of argon (100%) gas from gas inlet 6
And the output from the magnetron is 60
A microwave having a frequency of 2.45 gigahertz (GHz) was irradiated to various energy converters to generate plasma, and a PET film (contact angle 78 °) was treated for 5 minutes. Thereafter, the contact angle of the treated PET film was measured. Table 1 shows the results. In addition, as a comparative example, the contact angle was measured after performing the same operation also when the energy converter 1 was not used. The results are also shown in Table 1.

[0025]

[Table 1]

Examples 7 to 10 Except that an energy converter composed of various materials shown in Table 2 was used and that a mixed gas of argon (190 ml / min) and oxygen (10 ml / min) was used. Plasma treatment was performed in the same manner as in Nos. 1 to 6. afterwards,
The contact angle of the treated PET film was measured. Table 2 shows the results.

[0027]

[Table 2]

Examples 11 to 14 The use of energy converters made of various materials shown in Table 3, the use of a mixed gas of argon (280 ml / min) and carbon tetrafluoride (20 ml / min), and the use of a magnetron The plasma processing was performed in exactly the same manner as in Examples 1 to 6, except that the output of the laser was set to 100 W, microwaves having a frequency of 2.45 gigahertz (GHz) were irradiated, and the processing time was set to 1 hour. . Thereafter, the contact angle of the PET film and the film thickness of the polytetrafluoroethylene and polytetrafluoroethylene-like film formed on the surface of the PET film were measured. Table 3 shows the results.

[0029]

[Table 3]

Examples 15 to 18 Energy converters composed of various materials shown in Table 4 were used, and argon (280 ml / min) and methane (20
(ml / min), and a plasma treatment was performed in exactly the same manner as in Examples 11 to 14, except that the substrate was a polytetrafluoroethylene film (referred to as a PTFE film). Then, the film thickness of the polyethylene and polyethylene-like film formed on the surface of the PTFE film was measured. Table 4 shows the results.

[0031]

[Table 4]

Examples 19 to 24 were carried out using an apparatus similar to the apparatus schematically shown in FIG. Made of aluminum connected to a magnetron,
In the container 7 whose widest cross section is 30 cm x 30 cm,
20-60 mesh La _0.8 Sr _0.2 CoO ₃ (1
g) was placed in a container 7 by holding the energy converter 1 held by sintering the support 2 made of cordierite. And below the energy converter 1,
Electrodes at intervals of 10 mm connected to a power supply as a load 3 were supported by a support 4 made of ceramics, and were arranged parallel to the flow of the rare gas. Further, a PET film as a substrate 5 was placed in the container 7 below the electrode. Argon (100%) gas is introduced at a flow rate of 150 ml / min from the gas introduction unit 6, and a microwave having a frequency of 2.45 GHz (GHz) is output from the magnetron to the energy converter 1 at various outputs shown in Table 5. After irradiation and generation of plasma, various electromagnetic fields were formed by the load 3, and the plasma was activated to treat the PET film (contact angle 78 °) for 5 minutes. Thereafter, the contact angle of the treated PET film was measured. Table 5 shows the results.

[0033]

[Table 5]

Example 25 A PET film was treated in exactly the same manner as in Examples 19 to 24 except that the load 3 was not provided and the microwave output was 400 W, and the contact angle of the treated PET film was changed. Was measured. The results are also shown in Table 5 above.

Examples 26 to 31 were carried out using an apparatus similar to the apparatus schematically shown in FIG. That is, a coil having a diameter of 15 cm and six turns connected to a power supply was arranged below the energy converter 1 as the load 3, various microwaves shown in Table 6 were irradiated, and the load 3 was shown in Table 6 Except that various magnetic fields were formed,
The PET film was treated in exactly the same manner as in Examples 19 to 24, and the contact angle of the treated PET film was measured. Table 6 shows the results.

[0036]

[Table 6]

Examples 32 to 37 The use of the energy converter 1 made of various materials shown in Table 7 and the use of a mixed gas of argon (450 ml / min) and carbon tetrafluoride (50 cc / min) Magnetron output 300W, frequency 2.45 GHz (GH
Plasma treatment was carried out in exactly the same manner as in Examples 19 to 24, except that the microwave irradiation of z) was performed and the outputs of various loads 3 shown in Table 7 were used. Then, PET
The contact angle of the film and the film thickness of polytetrafluoroethylene and a polytetrafluoroethylene-like film formed on the PET film surface were measured. Table 7 shows the results.

[0038]

[Table 7]

Example 38 An experiment was performed using an apparatus similar to the apparatus schematically shown in FIG. In a container made of aluminum connected to a magnetron, a honeycomb-shaped graphitized molded product made of pitch coke as shown in FIG. Also,
A PET film was placed in the container 7 as the substrate 5. Argon (100%) gas is supplied from the gas inlet 6 at 200 ml / m.
in at a flow rate of 60 in.
W, a microwave having a frequency of 2.45 gigahertz (GHz) is irradiated on the carbon material 1 to generate plasma, and PE
The T film (78 ° contact angle) was treated for 5 minutes. The measured contact angle of the treated PET film was 68 °.

Example 39 The same carbon material 1 as in Example 38 was used except that a mixed gas of argon (190 ml / min) and oxygen (10 ml / min) was used. Plasma treatment was performed. The measured contact angle of the treated PET film was 67 °.

EXAMPLE 40 Argon (280 ml / min) and carbon tetrafluoride (20 ml
/ min), a magnetron output of 100 watts (W), and a frequency of 2.45 GHz (GHz).
) And the processing time was 1
A carbon material 1 similar to that of Example 38 except that the time was
And plasma treatment was performed in exactly the same manner as in Example 38. The contact angle of the treated PET film was 99 °, and the thickness of the polytetrafluoroethylene and polytetrafluoroethylene-like coating formed on the surface of the PET film was 50 μm.

Example 41 Argon (280 ml / min) and methane (20 ml / min)
A plasma treatment was performed in exactly the same manner as in Example 40, except that the same carbon material 1 as in Example 38 was used, except that the mixed gas of Example 1 was used, and that the base material 5 was a PTFE film. The thickness of the polyethylene and polyethylene-like film formed on the surface of the PTFE film was 59 μm.

Examples 42 to 47 Apparatus similar to the apparatus schematically shown in FIG. 4 (however, a honeycomb-like graphitized molded product made of pitch coke as a raw material as shown in FIG. (Support 2 was not used). The honeycomb-shaped graphitized molded body 1 is placed in an aluminum container connected to a magnetron, and a load 3 is placed downstream of the carbon material 1.
The electrodes connected at 10 mm intervals connected to a power source were supported by a holder 4 made of ceramics, and were arranged in parallel with the flow of the rare gas. Further, a PET film as a substrate 5 was placed in the container 7 downstream of the electrode. Gas inlet 6
(100%) gas was introduced at a flow rate of 150 ml / min., And a microwave having a frequency of 2.4 GHz (GH _Z ) was output from the magnetron at various outputs shown in Table 8.
After irradiating the carbon material 1 to generate plasma, the load 3
Thus, various electromagnetic fields shown in Table 8 were formed, plasma was activated, and the PET film was treated for 5 minutes. Thereafter, the contact angle of the treated PET film was measured. Table 8 shows the results.

[0044]

[Table 8]

Examples 48 to 53 Apparatus similar to the apparatus schematically shown in FIG. 8 (however, a honeycomb-like graphitized molded article using pitch coke as a raw material as shown in FIG. (Support 2 was not used). As shown in FIG. 8 and FIG.
m, a coil having six turns was arranged downstream of the carbon material 1, irradiation was performed with various microwave outputs shown in Table 9, and various magnetic fields shown in Table 9 were formed on the load 3. The PET films were treated exactly as in Examples 42-47, and the contact angles of the treated PET films were measured. Table 9 shows the results.

[0046]

[Table 9]

[0047]

According to the present invention, plasma can be generated under atmospheric pressure, so that the plasma processing apparatus is inexpensive and excellent in workability. When ceramics (particularly perovskite-type composite oxide) and carbon material are used as the energy converter, plasma is easily generated. Further, since it is not necessary to pass the base material between the electrodes as in the conventional case, the surface modification of the base material having various shapes and thicknesses can be performed. In addition, when a substrate is treated by introducing a rare gas to generate plasma, etching of the substrate surface can be performed. When a reactive gas is introduced together with a rare gas to generate plasma and the substrate is treated, Crosslinks to the surface layer of the substrate,
Chemical modification, graft polymerization, coating and the like can also be performed. In the gas flow path, if an electric field and / or a magnetic field is applied to generated plasma by a load arranged downstream of the energy converter, the plasma is activated, and the etching, crosslinking, and chemical reaction are more efficiently performed. Modification, graft polymerization, coating, etc. can be performed.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing one example of an atmospheric pressure plasma processing apparatus of the present invention.

FIGS. 2A and 2B are explanatory diagrams showing an example of the shape of the energy conversion body of the present invention, wherein FIG. 2A is a plan view thereof, and FIG. 2B is a cross-sectional view taken along the line CC ′ of FIG.

3A and 3B are explanatory views showing another example of the shape of the energy conversion body of the present invention, wherein FIG. 3A is a plan view thereof, and FIG.
FIG. 3 is a sectional view taken along line DD ′ of FIG.

FIG. 4 is a cross-sectional view schematically showing one example of the atmospheric pressure plasma activation device of the present invention.

5 is a sectional view of a load portion of the atmospheric pressure plasma activation device of FIG.

FIG. 6 is a cross-sectional view schematically showing another example of the atmospheric pressure plasma activation device of the present invention.

FIG. 7 is a sectional view of a load portion of the atmospheric pressure plasma activation device of FIG. 6;

FIG. 8 is a cross-sectional view schematically showing still another example of the atmospheric pressure plasma activation device of the present invention.

9 is a sectional view of a load portion of the atmospheric pressure plasma activation device of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Energy converter 2 ... Energy converter support 3 ... Load 4 ... Load support 5 ... Substrate 6 ... Gas introduction part 7 ... Container 8 ... Electromagnetic wave generator 9 ・ ・ ・ Three stub tuner 10 ・ ・ ・ Gas discharge part

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H05H 1/24 H05H 1/46

Claims (8)

(57) [Claims] 1. An electromagnetic wave is irradiated to an energy converter in the presence of a rare gas in a container in which an energy converter that converts the irradiated electromagnetic wave into electric energy and emits the energy is disposed. , Plasma generation method. 2. A plasma generated by irradiating an electromagnetic wave to an energy converter in the presence of a rare gas in a container in which an energy converter that converts the irradiated electromagnetic wave into electric energy and emits the energy is disposed. A plasma processing method, wherein a substrate is processed using the method. 3. A rare gas is introduced from the energy converter in the direction of the load into a container in which an energy converter that converts the irradiated electromagnetic wave into electric energy and emits the energy and emits the energy. Irradiating the plasma to the energy converter to generate a plasma, and causing an electric field or a magnetic field formed by the load to act on the plasma. 4. A rare gas is introduced from the energy converter in the direction of the load into a container in which an energy converter for converting the irradiated electromagnetic wave into electric energy and emitting the energy and emitting the energy is introduced. Irradiating the substrate with the energy converter to generate plasma, and treating the substrate using plasma activated by an electric or magnetic field formed by the load. 5. A plasma generator, wherein an energy converter that converts irradiated electromagnetic waves into electric energy and emits the energy is disposed in a container provided with an electromagnetic wave generator and a gas introduction unit. 6. A plasma processing apparatus comprising: a container provided with an electromagnetic wave generation device and a gas introduction unit; and an energy converter for converting irradiated electromagnetic waves into electric energy and emitting the same. 7. An energy converter that converts an applied electromagnetic wave into electric energy and emits it into a container provided with an electromagnetic wave generator and a gas introduction unit, and a gas flow introduced from the gas introduction unit. A plasma activation device, further comprising a load disposed downstream (with respect to the energy converter) and forming an electric or magnetic field. 8. An energy converter that converts an applied electromagnetic wave into electric energy and emits the same in a container provided with an electromagnetic wave generator and a gas inlet, and a gas flow introduced from the gas inlet. A plasma processing apparatus, comprising: a load arranged downstream (with respect to the energy converter) to form an electric or magnetic field.