JP2003226955A - Method and apparatus for modification surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a surface modification method and apparatus by which a surface is homogeneously and uniformly modified and easily treated even at an atmospheric pressure. <P>SOLUTION: In the surface modification method, a monomer 22 of a gaseous starting material and a carrier gas 23 for diluting the monomer gas are introduced into a casing, a pair of discharge electrodes are provided at a fixed interval inside the casing, a material 16 to be treated is arranged on one of the discharge electrodes, laser beams 13 are emitted into a space provided in parallel to the surface of the material to be treated with a certain distance from the surface to generate ionized plasma, and the monomer and the carrier gas are made into ionized gas 15 by the ionized plasma 14. Thus a film is formed on the surface of the material to be treated by causing the drift action of the ionized gas and impressing bias voltage between the discharge electrodes to attract the ionized gas on the surface of the material to be treated. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface reforming method and apparatus for performing a surface treatment on an object to be treated such as improving the surface hardness, forming a film such as a photocatalyst, improving wettability, degreasing, and forming a rough surface. Regarding

[0002]

2. Description of the Related Art There are roughly two types of conventional surface modification methods and apparatuses: a wet process (wet method) and a dry process (dry method). Above all, the technological shift to a dry process that does not discharge waste such as a harmful solvent after the surface modification treatment is widely performed. These processes are the method of making the target surface by changing the surface of the base material, the method of making the target surface by coating other substances without changing the surface of the base material, the former and the latter. Depending on the purpose, there are methods of compounding, such as heat treatment method such as ion implantation or etching method, PVD method (physical vapor deposition method) or C
VD method (chemical vapor deposition method), plasma polymerization method and the like can be mentioned. For example, in the plasma polymerization method, film formation is performed by the apparatus shown in FIG. In the figure, 16 is an object to be processed,
17 is a treated surface, 19 is a high voltage electrode, 20 is a low voltage electrode,
21 is a housing, 22 is a monomer, 23 is a carrier gas, 2
4 is a mass flow meter, 25 is an exhaust device, 28 is RF (radio
frequency) plasma, 29 is an RF generator, and 30 is a matching device. The film formation is performed as follows. The low-voltage electrode 20 in which the object 16 to be processed is arranged inside the housing 21.
Is provided with a high-voltage electrode 19 which is disposed opposite to the housing 21 with a certain distance, and the inside of the housing 21 is temporarily evacuated by an exhaust device 25 to remove impurities inside the housing 21, and then the monomer 22 and the carrier gas 23 are removed. The gas pressure to several tens of P
At a, an appropriate amount is supplied to the housing 21 by the mass flowmeter 24, and an RF generator 29 of 13.56 MHz is used to pass RF between the high voltage electrode 19 and the low voltage electrode 20 via the matching device 30.
Ionized gas is generated by generating plasma 28,
A film is formed by covering the object 16 to be processed. In the surface modification method and apparatus as described above, the surface modification is performed at a very low gas pressure of several tens of Pa, so that ionized plasma can be easily generated and many high-energy electrons can be supplied. The reactivity of reforming can be improved. Also,
By changing the kind of the monomer, the surface modification treatment for directly changing the surface of the object to be treated 16 can be performed.

[0003]

However, in the conventional method and apparatus for surface modification, a means for uniformly supplying the monomer into the RF plasma is required, and a uniform and uniform surface modification treatment is required. It was difficult to do. Further, since a vacuum exhaust device is required, the housing becomes large in size, and the surface modification treatment cannot be performed under high atmospheric pressure such as atmospheric pressure. Therefore, it takes a long treatment time to reach a vacuum state.
Further, although it is suitable for the surface modification treatment of the planar object, it is difficult to uniformly perform the surface treatment on the inside of the cylindrical shape such as the cylindrical tube or the uneven surface such as the ripple shape. Therefore, the present invention has been made in consideration of the above points, and provides a surface modification method and apparatus capable of uniform and uniform surface modification and capable of easily performing surface treatment even in an atmosphere of atmospheric pressure. The purpose is to provide.

[0004]

In order to solve the above problems, the present invention has the following structure. (1) In a surface modification method for modifying the surface of an object to be processed by ionizing plasma generated by various discharges, a visible region is formed in a space parallel to the surface of the object to be processed and at a constant distance from the surface. A laser beam having the following wavelength is irradiated to locally generate the ionized plasma in the laser optical axis direction. According to this configuration, since it is possible to obtain substantially uniform plasma generation in the ionized plasma region generated in the laser light oscillation direction, it is possible to perform uniform and uniform treatment surface modification of the object to be treated. Further, since the ultraviolet light generated from the ionized plasma can be used for modifying the surface of the object to be processed, the surface modification reaction can be promoted. (2) A monomer of a raw material gas and a carrier gas for diluting the raw material gas are introduced into the housing, and the monomer and the carrier gas are ionized by a plasma in the vicinity of a processing surface of an object to be processed arranged inside the housing. In a surface reforming method of forming a film on the object to be processed by ionizing gas and modifying the surface thereof, a laser is provided in a space provided parallel to the surface of the object to be processed and at a constant distance from the surface. By irradiating light, the ionized plasma is locally generated in the laser optical axis direction.
According to this configuration, it is possible to obtain substantially uniform plasma generation in the ionized plasma region generated in the laser light oscillation direction, and therefore it is possible to form a uniform and uniform film on the surface of the target object. Further, since the monomer for directly modifying the treated surface only needs to be present only in the portion where the ionized plasma is generated, the apparatus can be downsized, and the amount of gas used for film formation can be reduced. . (3) As a pretreatment, the material properties of the surface of the object to be treated are directly modified by using ultraviolet light generated by ionized plasma to modify the surface of the object to be treated, and as a post-treatment, the drift action of the ionized gas is used. To form a film on the object to be processed. According to this configuration, after the surface composition of the object to be treated itself is modified, the composite type surface treatment is performed to modify the surface by film formation, so excellent film formation characteristics not seen by each surface treatment alone. Can be obtained. (4) The object to be processed is arranged on one of a high-voltage electrode and a low-voltage electrode provided at a predetermined distance, and an ionized plasma generated by laser light irradiation and a bias voltage applied between the electrodes. Is used. According to this configuration, the ion species in the ionized plasma depending on the polarity of the bias voltage can be accelerated, and the ion species can further penetrate into the depth direction of the processing surface of the object to be processed. (5) The gas pressure inside the casing is at least atmospheric pressure or higher. According to this configuration, since it is not necessary to perform the surface modification treatment under high vacuum, a large exhaust facility or the like is not required and the device can be downsized. Further, since the ionized gas having a high particle density can be used by performing the surface modification under the normal pressure, the processing time can be shortened. (6) In a surface reforming device that reforms the surface of an object to be processed by generating ionized plasma, the surface of the object is parallel to the surface of the object to be processed in a space provided at a constant distance from the surface of the object. A laser device for irradiating the laser beam is provided outside the casing, and a transparent window for transmitting the laser beam is provided in the casing. According to this configuration, since the laser device and the condenser lens are arranged outside the housing, maintainability can be improved. Also, since it is not necessary to evacuate, it is possible to prevent the case from becoming large, and it is sufficient to have a monomer for surface modification only in the part where ionized plasma is generated, so the amount of gas used should be reduced. You can (7) The casing is provided with an introduction part for introducing a monomer as a raw material gas and a carrier gas for diluting the monomer, and an exhaust part for discharging the gas inside the casing. According to this configuration, since the introduction part and the exhaust part are arranged,
Since the residual gas after the treatment can be immediately removed from the treated surface, a uniform and uniform film can be easily formed. Further, since it is sufficient that the monomer and the carrier gas exist only in the portion where the ionized plasma is generated, the amount of gas used can be suppressed. (8) The laser device includes a condenser lens that forms a focal point of the laser light, and condenser lens moving means that moves the focal point while maintaining a constant distance from the surface of the object to be processed. It is a thing. According to this configuration, it is possible to form a uniform film over a wide area and to modify the surface of the object to be processed. (9) A power supply for applying a bias voltage to the object to be processed,
A high-voltage electrode and a low-voltage electrode connected to the power source and connected to one of the objects to be processed are provided, and a steep pulse high voltage having a short rise time is applied from the power source to the both electrodes. . According to this configuration, the particles in the ionized gas generated by the ionized plasma can be rapidly accelerated and can be attracted to the surface of the object to be processed, so that the adhesion to the surface to be processed of the object to be processed can be further improved. it can.
Further, since high energy electrons generated by the pulsed high voltage and ultraviolet light generated by the laser can be supplied before the film component is coated, pretreatment of the treated surface can be performed and the adhesion can be improved. (10) The object to be processed has an uneven structure such as a cylindrical shape or a ripple shape. According to this configuration, the ionized plasma locally generated by the laser can be moved while maintaining a constant distance. Therefore, not only the flat surface treatment but also the inner wall surface or the uneven surface of the cylindrical pipe or the like which is difficult to perform by the normal surface treatment. The surface treatment can be easily performed. (11) The high-voltage electrode is arranged on the central axis portion of the cylindrical object, and the low-voltage electrode is arranged on the outer periphery of the object, and the laser beam is applied to the inner peripheral surface of the object. It is designed to irradiate in the vicinity. According to this configuration,
Since ionized plasma can be generated in the vicinity of the object to be processed, surface treatment efficiency can be improved. Further, the surface treatment of the object to be processed can be uniformly performed by moving the laser light while keeping a constant distance with respect to the inner surface of the object to be processed. Further, by applying a bias voltage between both electrodes, the film strength of the film can be increased.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION A laser, which is the center of the technology of the present invention, has a photoelectron effect in which electrons are emitted from fine particles to irradiate other fine particles with irradiation of laser light, and the energy density is further increased, and gas is emitted. It does not utilize the phenomenon of plasma destruction due to the high ionization degree of laser, which occurs when the energy absorbed by the molecule is transferred to gas heating.It has a relatively high energy density and many high-energy photons directly transfer to atoms or molecules. The ionized plasma is generated by being absorbed by the electrons and generating electrons by photoionization. INDUSTRIAL APPLICABILITY The present invention utilizes the above-described effect of ionized plasma generation to generate ionized plasma by irradiating a space parallel to the surface of the object to be processed and a space provided with a certain distance from the processing surface. The surface modification treatment is performed by forming a film on the surface of the object to be processed or modifying the surface of the object to be processed. Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.

(First Embodiment) FIG. 1 shows a first embodiment of the present invention.
And 2 are shown. FIG. 1 is a cross-sectional view showing a surface modification device of the present invention, and FIG. 2 is a cross-sectional view of FIG. 1 seen from a direction perpendicular to a laser optical axis. This example is a method of forming a film on a planar object to modify the surface. In the figure,
The same reference numerals are used for common parts, 10 is a laser device, 11 is a condenser lens, 12 is a transmission window, 13 is laser light, 14 is ionized plasma, 15 is ionized gas, 16 is an object to be treated, 17 Is a processing surface, 18 is a power source, 19 is a high voltage electrode,
20 is a low voltage electrode, 21 is a housing, 22 is a monomer, 23
Is a carrier gas, 24 is a mass flow meter, 25 is an exhaust device,
Reference numeral 31 is a condenser lens moving means. As the object 16 to be processed, a 100 mm square SUS304 plate having a thickness of 2 mm was used. Perfluorobenzene (PFB) was used as the monomer 22 and nitrogen was used as the carrier gas 23. Laser device 1
0, Nd: YAG laser (3rd harmonic, λ = 355n
m) was used and the gas pressure was atmospheric pressure (about 0.1 MPa). Next, a method of surface modification by forming a film according to this embodiment will be described. The laser light 13 oscillated by the laser device 10 is 1 mm from the surface of the object 16 to be processed which is arranged on the low voltage electrode 20 provided in the housing 21 through the condenser lens 11 and the transmission window 12. The position is illuminated. Then, ionized plasma 14 is generated in the direction along the axis of the laser beam 13 with the focus of the condenser lens 11 as the center.
At this time, the monomer 22 and the carrier gas 23 are supplied to the inside of the housing 21 by the mass flow meter 24. The generation of the ionized plasma 14 brings the monomer 22 into an activated state, and the ionized gas 15 having a very high reactivity is formed together with the surrounding carrier gas 23, so that the film formation is performed. In this state, the high-voltage electrode 19 and the object 1 to be processed
6 from the power source 18 between the low voltage electrodes 20
A bias voltage of 25 kV is applied. Then, the activated monomer 22 in the ionized gas 15 is treated with the treated surface 17
By being accelerated toward, the object 16 is attracted onto the object 16 to be processed, the depth of the processed surface 17 in the depth direction increases, and a film is formed by deposition. When enlarging the film formation region, the condenser lens moving means 31 is driven to move the focus of the laser light 13 horizontally and vertically with respect to the axial direction. Next, the formed film was evaluated. That is, the surface state of the treated surface was measured with a scanning tunneling microscope (STM), and the surface of the film was analyzed with an X-ray photoelectron analyzer (ESCA). As a result, it was found that the entire surface of the moving area of the ionized plasma 14 generated by the laser beam 13 was a high density fluorine-containing polymer film (C _k F _l ) _m having a three-dimensional crosslinked structure. In addition, after the surface treatment, the carrier gas 2
It was found that the carrier gas 23 entered into the voids in the lattice of the fluorine-containing polymer film by leaving it in the No. 3 for a certain time, and the fluorine-containing polymer film became stronger. Further, by applying the bias voltage, the film thickness was increased in the order of several μm. According to this embodiment, it is possible to form a uniform and uniform film on the surface of the object to be processed 16 under normal pressure. Further, since the monomer 22 and the carrier gas 23 only need to exist in the part where the ionized plasma 15 is generated, the apparatus can be downsized, and the amount of gas used for film formation can be reduced. Since it is not necessary to perform the surface modification treatment under high vacuum as in the conventional case, a large exhaust facility is not required, and the ionized gas 15 having a high particle density is used by carrying out the surface modification under normal pressure. Therefore, the processing time can be shortened. By applying a bias voltage from the power supply 18, the activated monomer 22 is treated 1
By accelerating toward 7, the depth can be increased and the film thickness can be increased.

(Second Embodiment) This embodiment is a method for directly modifying the surface of a flat object to be processed. The surface modification device is the same as that used in the first embodiment. As the object 16 to be processed, a polytetrafluoroethylene plate (PTFE,) having a thickness of 2 mm and a size of 100 mm square, a monomer 22
Was used as methane (CH ₄ ). The laser device and gas pressure are the same as in the first embodiment. Bias voltage is 3
It was set to ˜20 kV. Next, the method of surface modification by the direct treatment of this embodiment will be described. It is parallel to the processing surface 17 of the object to be processed 16 and is 1 to 2 m from the processing surface 17.
The space is irradiated with the laser light 13 at the position of m. The monomer 2 introduced into the housing 21 by the generated ionized plasma 14.
2 is converted into ionized gas 15 by ionized plasma 14, and the surface of the object 16 to be processed is destroyed by the high-energy electrons generated by the ionized plasma 14 and the ultraviolet light generated from the laser beam 13 to destroy the composition of the constituent material of the object 16 to be activated. By doing so, the activated treated surface 17 and the monomer 22 cause a chemical reaction, and the surface is modified. Next, the surface condition of the produced surface was measured by a scanning tunneling microscope (STM), and the surface of the film was analyzed by an X-ray photoelectron analyzer (ESCA) for evaluation. As a result, ionized plasma 14 generated by the laser beam 13 causes the dissociation component of CH ₄ to combine and P.
The elimination of fluorine atoms on the TFE surface causes the structure of -CF _2-, which is a PTFE structure, to be -CF or -CF.
It was found that the structure changed to a new structure such as H. Further, in the present embodiment, when the processing area is increased, the ionized plasma 14 may be moved by moving the laser moving means in the direction perpendicular to the laser optical axis. By doing so, it is not necessary to separate the condenser lens 11 and the transmission window 12, and the condenser lens 11 can be directly attached to the housing 21 for surface treatment. According to this embodiment, it is possible to uniformly and uniformly modify the surface 17 of the object 16 to be processed. Further, since the monomer 22 for directly modifying the treated surface 17 only needs to be present only in the portion where the ionized plasma 14 is generated, the apparatus can be downsized and the amount of gas used for the monomer 22 can be reduced. it can. Further, the ultraviolet light generated from the ionized plasma 14 is applied to the object 1 to be processed.
Since it can be used to modify the surface, the reaction can be promoted.

(Third Embodiment) FIG. 3 shows a third embodiment of the present invention.
And shown in FIG. FIG. 3 shows a cylindrical surface modifying apparatus of the present invention, and FIG. 4 shows a concavo-convex surface modifying apparatus of the present invention, which is a cross-sectional view perpendicular to the laser optical axis. In the figure, 26 is a high voltage electrode and 27 is a low voltage electrode. The object to be processed 16 has a thickness of 2 mm and an inner diameter of 20.
mm SUS304 tube and thickness 2 mm, 100 mm
A square SUS304 plate was used, perfluorobenzene (PFB) was used as the film forming monomer 22, and nitrogen was used as the carrier gas 23. Laser device and gas pressure is the first
Same as the embodiment. The bias voltage was 5 to 25 kV. Next, the method of surface modification by film formation of this example will be described with reference to FIG. The internal electrode 26 is provided on the central axis of the cylindrical object 16 to be processed, the external electrode 27 is arranged along the outer surface of the object 16 to be processed, and the laser beam 13 is provided in the vicinity of the object 16 to be processed by 1 mm. Illuminate the space. Then, the ionized plasma 14 is generated in the direction along the axis of the laser light 13. At this time, when the monomer 22 and the carrier gas 23 are supplied to the inside of the object 16 to be processed, the monomer 22 is activated due to the generation of the ionization plasma 14, and the highly reactive ionized gas 15 is generated together with the surrounding carrier gas 23. The film is formed. In this state, by applying a bias voltage of 5 to 25 kV from the power source 18 between the internal electrode 26 and the external electrode 27, the activated monomer 22 in the ionized gas 15 is attracted to the object 16 to be treated,
As the depth of the processed surface 17 increases in the depth direction, a film is formed by deposition. Next, the surface-treated state was measured for surface smoothness with a scanning tunneling microscope (STM), and the surface of the film was analyzed with an X-ray photoelectron analyzer (ESCA). As a result, it was found that a fluorine-containing polymer film (C _k F _l ) _m having a high-density three-dimensional crosslinked structure was formed on the entire inner surface of the object to be treated 16. Further, by leaving the carrier gas 23 in the carrier gas 23 or the atmosphere after the surface treatment, the carrier gas 23 enters into the voids in the lattice of the fluorine-containing polymer film, and a stronger fluorine-containing polymer film can be formed. In addition, the film is formed even in the concavo-convex shape as shown in FIG. 4, and when the bias voltage is applied, the voltage from the power source 18 is adjusted so that the electric field strength of the processing surface 17 is constant, and thus the processing surface is adjusted. The depth and film thickness in the depth direction could be increased. According to this embodiment, it is possible to form a uniform and uniform film having an uneven surface shape, and it is possible to easily form a film on the inner surface of the object 16 to be processed, which is difficult to perform by a normal surface treatment. Further, it is possible to prevent the apparatus from increasing in size, and it is sufficient that the monomer 22 and the like are present only inside the object to be processed 16, so that the amount of gas used can be significantly reduced. In addition, since it is not necessary to perform surface modification treatment under high vacuum,
No large-scale exhaust equipment is required, and the ionized gas 15 having a high particle density can be used by performing the surface modification at atmospheric pressure, so that the processing time can be shortened.

(Fourth Embodiment) This embodiment is a method of directly modifying the surface of a cylindrical object to be processed. The surface modification device is the same as that shown in FIG. 3 used in the third embodiment. A borosilicate glass tube having a thickness of 2 mm and an inner diameter of 20 mm was used as the object to be treated 16, and oxygen was used as the monomer 22. The laser device and gas pressure are the same as in the third embodiment. The bias voltage was 3 to 25 kV. Next, the method of surface modification by the direct treatment of this embodiment will be described. A laser beam 13 is irradiated to a space 1 mm from the processing surface 17 in parallel with the processing surface 17 inside the processing object 16, and the monomer 22 introduced into the processing object 16 by the generated ionized plasma 14 is removed. The ionized plasma 14 is changed to an ionized gas 15 and the surface of the object 16 to be processed is destroyed and activated by destroying the composition of the object 16 to be processed by the high energy electrons generated by the ionized plasma 14 and the ultraviolet light generated from the laser beam 13. Then, the activated treated surface 17 and the monomer 22 are activated.
Undergoes a chemical reaction to perform surface modification. Next, the wettability of the surface was measured by a contact angle meter to evaluate the surface. As a result, it was found that the wettability increased and the hydrophilicity increased. That is, it is considered that the hydrophilicity is increased by increasing the oxygen-containing functional groups on the surface of the object to be processed 16 by the generated ionized plasma 14. According to the present embodiment, it is possible to modify the surface of the object 16 to be processed, which is concave and uniform, and to easily modify the inner surface of the object 16 to be processed, which is difficult by the normal surface treatment. be able to. Further, since the monomer 22 for directly modifying the treated surface 17 only needs to be present only in the portion where the ionized plasma 14 is generated, the apparatus can be downsized and the amount of gas used for the monomer 22 can be reduced. it can.
Further, since the ultraviolet light generated from the ionized plasma 14 can be used for modifying the surface of the object 16 to be processed, the reaction can be promoted. In this embodiment, the laser light 1
By moving 3 on the surface of the object to be processed 16 while keeping a constant distance from the surface of the object to be processed 16, the generation part of the ionized plasma 14 locally generated along the laser optical axis is moved. Therefore, it is possible to perform a uniform and uniform surface treatment over a wide area. As a pretreatment, the surface composition itself of the object to be treated is modified, and then the composite type surface treatment is carried out to modify the surface by film formation, to obtain excellent film formation characteristics that did not appear by each treatment alone. I was able to. The bias voltage applied at the time of the surface modification treatment is a steep pulse high voltage having a very short rise time and a short pulse width, whereby the activity in the ionized gas 15 generated by the ionized plasma 14 is increased. The converted monomer 22 particles and the like can be rapidly accelerated and attracted to the surface of the object 16 to be processed, so that the adhesion with the object 16 can be improved. Further, by using a steep pulse high voltage as the bias voltage, high energy electrons and laser light 13
Since the ultraviolet light generated by the above reaches the processing surface 17 before the film forming processing, the pretreatment effect is remarkably exhibited, and the adhesion between the object to be processed and the formed film can be further strengthened. The same effect can be obtained by using other organic substances and inorganic substances for the object to be treated and the monomer, and the irradiation position of the laser beam 13 does not need to be set to the value shown in the embodiment, and the gas pressure and the treatment area are not required. The desired surface treatment can be performed by arbitrarily setting it according to the above conditions.

[0010]

As described above, the surface modification method and apparatus of the present invention have the following effects. (1) Ionized plasma is generated by irradiating a space parallel to the processing surface of the object to be processed and having a certain distance from the processing surface to generate ionized plasma, and drift of ionized gas due to application of a bias voltage. Since the surface of the object to be processed is modified by the action and the ultraviolet light, the ultraviolet light generated from the ionized plasma can be used for modifying the surface of the object to be processed, and the chemical reaction can be promoted. (2) The laser beam is parallel to the surface of the object to be processed, and
By irradiating the space provided with a certain distance from the treated surface, the ionized plasma was generated by the laser beam, and the monomer and carrier gas introduced into the housing were ionized by the ionized plasma, so that the surface of the object to be treated was uniform and uniform. A uniform film can be formed. (3) As a pretreatment, the material properties of the surface of the object to be treated are directly modified by using ultraviolet light generated by ionized plasma to modify the surface of the object to be treated, and as a post-treatment, the drift action of the ionized gas is used. Since the film is formed on the object to be processed, the composite type surface treatment can be performed, and excellent film forming characteristics which cannot be seen by each surface treatment alone can be obtained. (4) Since the plasma generated by the laser and the bias voltage are used together, the ion species in the ionized gas are accelerated toward the processing surface, increasing the depth of the processing surface in the depth direction and increasing the adhesion of the film. can do. Further, the film thickness can be increased. (5) Since the surface modification treatment is performed under normal pressure, the device can be downsized. Moreover, since an ionized gas having a high particle density can be used, the processing time can be shortened. (6) Since the laser light is used, it is possible to prevent the size of the reforming processing apparatus from increasing, and it is sufficient that the monomer and carrier gas are present only in the portion where the ionized plasma is generated, so that the amount of gas used can be suppressed. (7) Since the ionized plasma is moved on the surface of the object to be processed while maintaining a constant distance from the surface of the object to be processed, uniform and uniform film formation and object to be processed over a wide area. The surface can be modified. (8) Since the bias voltage is such that a steep pulse high voltage with a short rise time of voltage is applied, particles in the ionized gas generated by the ionized plasma are rapidly accelerated and attracted to the surface of the object to be processed. It is possible to improve the adhesion to the surface of the object to be processed. Further, since the ultraviolet light generated by the high energy electrons and the laser can be supplied before the film component is coated, the pretreatment of the treated surface can be performed and the adhesion can be further improved. (9) Since the localized ionized plasma is moved according to the shape of the object to be processed, not only the flat surface treatment but also the surface treatment of the inner wall surface of the cylindrical tube or the like, which is difficult by the ordinary surface treatment, and the surface treatment of the uneven surface. It can be done easily.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a surface modification device used in first and second embodiments of the present invention.

FIG. 2 is a cross-sectional view in a direction perpendicular to the laser optical axis of FIG.

FIG. 3 is a cross-sectional view of a cylindrical inner surface modifying apparatus used in the third and fourth embodiments of the present invention.

FIG. 4 is a cross-sectional view of an uneven surface modification device used in a third embodiment of the present invention.

FIG. 5 is a cross-sectional view showing a conventional surface modification method and apparatus.

[Explanation of symbols]

10 Laser device 11 Condensing lens 12 transparent window 13 Laser light 14 Ionizing plasma 15 Ionized gas 16 Object to be processed 17 Processing surface 18 power 19, 26 High voltage electrode 20, 27 Low voltage electrode 21 housing 22 Monomer 23 Carrier gas 24 mass flow meter 25 exhaust system 28 RF plasma 29 RF generator 30 Matching device

Claims (11)

[Claims] 1. A surface reforming method for reforming a surface of an object to be treated by ionizing plasma generated by various discharges, comprising: forming a space parallel to the surface of the object to be treated and having a constant distance from the surface. A surface modification method characterized in that the ionized plasma is locally generated in a laser optical axis direction by irradiating a laser beam having a wavelength of a visible region or less. 2. A monomer of a raw material gas and a carrier gas for diluting the monomer are introduced into the housing, and the monomer and the carrier gas are ionized in the vicinity of the processing surface of the object to be processed arranged inside the housing. In a surface reforming method of forming an ionized gas with plasma, forming a film on the object to be processed and modifying the surface thereof, a space provided parallel to the surface of the object to be processed and having a constant distance from the surface. A surface modification method, characterized in that the ionized plasma is locally generated in the laser optical axis direction by irradiating a laser beam on the surface. 3. The surface modification method according to claim 1,
A surface modification method comprising: a step, wherein the surface modification method according to claim 2 is a second step. 4. The object to be processed is arranged on one of a high-voltage electrode and a low-voltage electrode provided at a predetermined distance,
4. The surface modification method according to claim 1, wherein an ionized plasma generated by irradiation with laser light and a bias voltage applied between the electrodes are used. 5. The surface modification method according to claim 1, wherein the gas pressure inside the housing is at least atmospheric pressure or higher. 6. A housing provided with an object to be processed therein, and ionizing plasma generating means for generating ionized plasma. The ionized plasma generated by the ionizing plasma generating means is caused to act on the object to be processed, and its surface is treated. In the surface reforming apparatus for modifying the above, a laser device is provided outside the casing, and a transmission window that transmits the laser light is provided in the casing, and a space provided at a constant distance from the surface of the object to be processed. A surface reforming device, which irradiates a laser beam parallel to the surface of the object to be processed. 7. The housing is provided with an introduction part for introducing a monomer as a raw material gas and a carrier gas for diluting the monomer, and an exhaust part for discharging the gas inside the case. Item 7. The surface modification device according to item 6. 8. The laser device includes a condenser lens that forms a focal point of the laser beam, and a condenser lens moving unit that moves the focal point with a constant distance from the surface of the object to be processed. It has provided, Claim 6 or 7 characterized by the above-mentioned.
The surface modification device described. 9. A power source for applying a bias voltage to the object to be processed, and a high voltage electrode and a low voltage electrode connected to the power source and connected to either one of the object to be processed. 9. The surface modification device according to claim 6, wherein a steep pulse high voltage having a short rise time is applied between the electrodes. 10. The object to be processed has an uneven shape such as a cylindrical shape or a ripple shape.
The surface modification apparatus according to any one of 1. 11. The high-voltage electrode is arranged on the central axis of the cylindrical object, and the low-voltage electrode is arranged on the outer circumference of the object, and the laser beam is applied to the inner circumference of the object. The surface reforming apparatus according to claim 10, wherein irradiation is performed near the surface.